The Reactions Parameters of Lime PDF

Copyright by ASTM Int'l (all rights reserved); Wed Aug 1 12:04:31 EDT 2012
Downloaded/printed by
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions authorized.
THE REACTION
PARAMETERS
OF LIME
A symposium
presented at the
Seventy-second Annual Meeting
AMERICAN SOCIETY FOR
TESTING AND MATERIALS
Atlantic City, N. J., 22-27 June 1969
ASTM SPECIAL TECHNICAL PUBLICATION 472
List price $15.25
AMERICAN SOCIETY FOR TESTING AND MATERIALS

1916 Race Street, Philadelphia, Pa. 19103
BY AMERICAN SOCIETY FOR TESTING AND MATERIALS 1970
Library of Congress Catalog Card Number: 75-108623
ISBN 0-8031-0057-4
Printed in Lutherville-Timonium, Md.

June 1970
Foreword
The Symposium on The Reaction Parameters of Lime was presented
during the Seventy-second Annual Meeting of the American Society for
Testing and Materials held in Atlantic City, N. J., 22-27 June 1969. The
symposium was sponsored by Committee C-7 on Lime. V. S. Tadsen,
Chas. Pfizer & Co., Inc., presided as symposium chairman.
Contents
Introduction 1
Characterization of the Properties of Commercial Lime by Surface Area
Measurements and Scanning Electron M i c r o s c o p y - - J . L. LADES
AND P. A. SANDBERG 3
Discussion 24
Phase Equilibria and Thermodynamic Properties of Lime-Iron Oxide
Melts Containing up to 30 Percent S i O 2 : 1 4 5 0 and 1550 C Sec-
tions--M. T I M U C I N AND A. E. MORRIS 25
Discussion 31
X-Ray and Electron Microscope Studies of Calcined and Sulfated Lime-
stones---6, n. M C C L E L L A N , S. R. H U N T E R , AND R. M . SCHEIB 32
Influence of Lime in Mortar on the Expansion of Brick M a s o n r y - -
T. RITCHIE 67
Discussion 81
Testing of Building Mortars Using the New British Standard M e t h o d s - -
R. GILLARD AND H. N. L E E 82
Discussion 114
Effects of Calcination Conditions on the Properties of Lime---g. c.
M U L L I N S AND J . D. H A T F I E L D 117
Discussion 130
Observations on the Solution of Calcium Oxide in Slag Systems----GERhARD
DERGE AND 3 . R. SHEGOG 132
Discussion 141
Characterization of Lime: A Comparison and Scaling Down of the Coarse
Grain Titration Test and the A S T M Slaking Rate T e s t - - w . J.
S C H L I T T AND G. W . H E A L Y 143
Discussion 157
Crucible Test of Lime Reactivity in Slags--R. w, LIMES AND R. O. RUSSELL 161
Discussion 170
Present Status and Technical Advances of Steelworks Lime for Basic
Oxygen Furnaces in Germany--KARL-HEINZ OBST, Jt2RGEN
S T R A D T M A N N , W O L F G A N G U L L R I C H , AND GERT KONIG 173
Discussion 190
Curing of Cement-Lime M o r t a r s - - J . I. DAVISON 193
The Textural Evolution of Limestone Calcines--G. H. MCCLELLAN AND
.l.L. EADES 209
STP472-EB/Jun. 1970
Introduction
Very early in man's development of permanent structures lime was em-

ployed as a cementing agent in mortars to bond stones together. Later it
was used with aggregate and gypsum for surface treatment of structures
and for art work. The Romans, first to build an extensive highway network,
frequently used lime to improve the stability of base courses. Existence of
some of these highways attests to the success of their methods. Chemical
uses for lime developed concurrently with structural uses. The historic uses
of lime continue today with new applications being reported frequently.
Lime is one of the basic materials of our industrial complex. It ranks
essential with salt, sulfur, iron ore, and fossil fuels. The annual world
consumption of lime and its ore, limestone, exceeds two billion tons.
This symposium was organized to present recent findings of pure and
applied research directed toward a better understanding of the funda-
mental properties of lime and the effect variations in these properties have
on certain end uses, and test methods developed to better evaluate this
enigmatic chemical.
Several investigators have used the scanning electron microscope to give
visualization of the time-temperature dependent physical changes occurring
to lime oxide during and after its formation from limestone. With measure-
ments of surface area and pore size distribution these special micrographic
techniques permit anticipation and interpretation of the chemical behavior
of lime oxide under widely varying conditions.
Even though masonry construction represents the oldest known use of
lime, the trend toward thin-wall construction requires a fuller understand-
ing of the short- and long-term properties of lime mortars. The authors of
the papers on mortars report on investigations of lime mortar curing by
current ASTM method of test, field exposure of lime mortar-masonry as-
semblages, and evaluation of mortar specifications by test methods.
The studies of the rate-of-hydration methods used to characterize the
reactivity of lime oxide show good correlation, and the data can be related
to that obtained by more sophisticated means. The hot wire microscope
was designed to study steelmaking oxide reactions in controlled atmosphere
at temperature. Observations of the solution of lime oxide in slags at 1500
to 1650 C strongly suggest a similar rate-controlling mechanism in both
slagging and hydration reactions. The data from crucible scale and produc-
Copyrightby
Copyright 9 ASTM
1970 by
Int'lASTM International
(all rights reserved); Wedwww.astm.org
Aug 1 12:04:31 EDT 2012
2 THE REACTION PARAMETERS OF LIME
tion furnace studies of the rate of solution of lime oxide in slags reinforce
this interpretation. Scanning electron micrographs supply further confirma-
tion with certain limitations established by pore size measurements.
Control of the sulfur dioxide content of the gaseous combustion products
of fossil fuels is a major concern to the industrial community. A number of
continuing research projects in this field are being sponsored by the Fed-
eral Government and industry. Limestone and lime will react with sulfur
dioxide under certain conditions to form stable compounds. The determina-
tion of the parameters controlling these reactions is the subject of several
symposium papers.
The advent of basic pneumatic processes for rapid refining of iron into
steel has emphasized the need for studies of the physical and chemical
properties of lime and, particularly, rate of change of these properties at
steelmaking temperatures. One cannot read this symposium volume without
being impressed by the reinforcement the reported investigations lend to
each other, especially in the area of conditions controlling rates of reaction.
The development and use of lime oxide premixed with either iron or alum-
inum oxide resulting in an increased reaction rate and efficiency is first
reported in this symposium. The subsequent possibility of reducing refining
time is of major economic import.
The recent symposium on soil stabilization, sponsored by ASTM Com-
mittee D-18, precluded related papers in this symposium volume.
It is the sincere hope of the sponsoring Committee that the investiga-
tions reported herein will stimulate additional research on lime and lime-
stone and related end uses.
ASTM Committee C-7 acknowledges with much appreciation the work
of the authors in preparing the papers for this symposium volume. Ac-
knowledgment of and appreciation for the large amount of work and
assistance of the headquarters staff is hereby tendered.
V. S. Tadsen
Research Manager,
Chas. Pfizer & Co., Inc., Toledo, Ohio 43604;
symposium chairman.
J. L. Eades r and P. A. Sandberg 1
Characterization of the Properties of

Commercial Lime by Surface Area
Measurements and Scanning Electron
Microscopy
REFERENCE: Eades, I. L. and Sandberg, P. A., "Characterization o f

the Properties of Commercial Lime by Surface Area M e a s u r e m e n t s and
Scanning Electron Microscopy," The Reaction Parameters of Lime,
A S T M STP 472, American Society for Testing and Materials, 1970, pp.
3-24.
ABSTRACT: Reactivity of lime (CaO, CaO-MgO) is a function of surface

area and pore space which is related to temperature or time of calcination
or both. The development and distribution of pore space in calcined stone
is poorly understood. The scanning electron microscope (SEM) now
allows observation of porosity differences in the oxides calcined from the
same stone at various temperatures and times.
The oxides formed from five limestones calcined in commercial kilns
(four calcitic and one dolomitic) and one dolomitic stone calcined in a
laboratory furnace were examined with the SEM, and their surface areas
were determined by the Brunauer, Emmett, and Teller (BET) method using
Krypton gas.
One of the stones was subjected to several different kiln conditions. The
SEM made it possible to record the changes of the low-porosity quarry
stone to a very porous oxide as it was calcined. However, with increased
kiln time, the resulting CaO crystals coalesce, increasing pore space, and,
with continued calcination, the pore space approached zero.
KEY W O R D S : roasting, calcium oxides, porosity, time dependence, tem-

perature, electron microscopes, scanning, limestone, rocks, oxides, calcite,
dolomite (minerals), tests, evaluation, kilns, refractory materials, furnaces,
area, krypton, gold, palladium, dissociation, pellets, porosity, oxygen-blown
converters, combustion
Research assistant professor and associate professor, respectively, Department of

Geology, University of Illinois, Urbana, I11. 61801. Dr. Eades is a personal member
ASTM.
Copyright
Copyright by9ASTM
1970Int'l
by (all
ASTMrightsInternational
reserved); Wed Augwww.astm.org
1 12:04:31 EDT 2012
Although the art of lime burning has been practiced since ancient times,
it was not until the 18th century that a scientific explanation of calcination
was advanced [1]. 2 As industrial and chemical technology developed, lime
became an increasingly important component in numerous reactions and
processes. For these applications, the lime was judged primarily on its
chemical purity, and minimal amounts of silica, alumina, iron, and other
impurities were desired. In general, reaction rates were not thought
important.
Reaction rates of commercial limes became a matter of considerable in-
terest with the introduction of the basic oxygen converter steel furnace.
Operation costs for such converters are quite high, and steel producers
quickly began investigation of methods to lower the time per heat of steel.
Metallurgists became interested in the relationship between lime reactivity
and slagging time. As a result of these and other studies it quickly became
apparent that in steel making and many other industrial applications reac-
tivity of a lime was a more significant criterion for judging quality and
suitability of a lime than chemical purity.
It is well known [2-10] that pore space and calcium oxide (CaO) crys-
tallite size are the prime factors controlling reactivity of any given lime.
These in turn can be linked to calcining conditions, with low temperature
burning producing a highly porous, highly reactive lime and high tempera-
ture burning producing a shrunken, dense lime with low porosity and low
reactivity. In most attempts to interpret lime structure and its relationship
to kiln conditions, theoretical models have been based on surface area,
reactivity, and density data. Light and transmission electron microscopy
have been used in a few studies [11]'~ of crystallites and pore space and
their relation to reactivity and calcining conditions.
This study makes use of the unique properties of the scanning electron
microscope (SEM) [12-20] for study of surface characteristics of solid
specimens. In contrast to the transmission electron microscope, in which a
thin-film replica (carbon or metal-shadowed carbon) of a relatively low
relief portion of the specimen surface is observed, the SEM allows study
of essentially the entire surface of solid, metal-coated fragments of lime or
other materials. Since the image produced by the SEM in emissive mode
shows the specimen surface as if illuminated by oblique incident reflected
light, interpretation of specimen characteristics is facilitated. For most
manufacturers, users, or researchers the visual representation of lime speci-
men characteristics affecting reactivity is a welcome complement to the
"~T h e italic n u m b e r s in b r a c k e t s refer to the list o f r e f e r e n c e s a p p e n d e d to this

paper.
3 See p. 32.
EADE$ AND SANDBURG ON COMMERCIAL LIME 5
standard, but conceptually abstract notation of total surface area as M~/g

for some of the samples used in this study surface area measurements have
been made and are related to specimen texture in the discussion below.
In the SEM study described below we have seen that differences in
morphology of calcite (CaCO3) grains and intergranular voids in the orig-
inal limestones may explain why resulting limes with similar surface areas
can differ in reactivity. The limestones which serve as quarry stone for the
commercial limes studied differ greatly in their physical makeup, which
may include shell fragments, pellets, oolites, precipitated calcite grains, or
combinations of these, together with crystalline calcite cement between
grains. The results of SEM comparison of shape and size of the CaO crys-
tallites formed from different biogenic or inorganically precipitated calcium
carbonate materials suggest that the form of CaO crystallites is at least
partially influenced by the form type of carbonate grains and relative
arrangement of grains and voids in the parent CaCO3.
Materials and Methods of Calcination

Commercial lime manufacturers supplied samples of their quarry stone
and lime (CaO) derived from the stone. This study includes samples pro-
duced in conventional vertical, rotary, calcimatic, and fluid solids kilns.
The stones represent four types of calcitic limes and one dolomitic. The
samples will be identified by laboratory numbers only.
The construction and operation of vertical or shaft kilns is such that
differences in temperature occur in different parts of the calcining zone.
This results in different degrees of burning or calcination for various parts
of the load. Some of the pieces of stone may be only partially calcined
containing an outer shell of highly reactive lime and retain a core of un-
calcined calcium carbonate. Such pieces are removed in order to meet the
chemical specifications of the buyer. By visual inspection of the lime as it
exits the kiln on a conveyor belt an experienced worker can quickly recog-
nize and remove the uncalcined pieces. Such partially burned fragments
provide excellent materials in which to observe the initial phases of calcina-
tion. One such piece sent to us contained a core of only slightly affected
limestone, surrounded by progressively more calcined material approaching
the outer surface.
A charge of limestone may be subjected to too high a kiln temperature
or too long a retention time for the intended use of the lime, and a very
hard burned or "dead" burned CaO is produced. A sample of such a lime
was supplied and provided a view of the opposite end of the range of cal-
cination from the partially burned sample containing the core of the same
limestone.
Because of the greater uniformity and degree of control of temperature

and retention time in rotary and calcimatic kilns there is a much greater
uniformity of burn in any given load. However, variations of temperature
or retention time could produce loads of partially calcined or of dead
burned lime (as in the case in production of refractory materials from
dolomite).
The precise values of kiln temperatures and retention time for the lime
samples studied were not available to us. The statements supplied by the
companies on degree of burning for each sample were based on experienced
observation of the samples, knowledge of kiln conditions, and reactivity
tests. Because of these limitations on sample data, the exact quantitative
relationships between kiln conditions and resulting lime cannot be given at
this time. Rather this study emphasizes the significance of control of kiln
conditions in the production of commercial lime.
Treatment of Samples
The samples of CaO were shipped to us in sealed dry jars and, upon re-
ceipt, were stored in desiccator vessels. Immediately prior to SEM study
the samples were removed from the desiccator and jars and fractured with
a hammer. Several specimens of fresh internal fracture surfaces were
mounted in Duco cement on standard specimen stubs and coated with a
2:1 mixture of gold and palladium. The metal was deposited from several
angles in order to minimize charging of the rough, porous surfaces of the
specimens. The coated specimens were stored in a small portable desic-
cator, and SEM observation was begun within a few hours at most. Be-
cause of these precautions no hydration products were observed on the
sPeciments studied.
Surface area measurements were made with an Orr surface area pore-
volume analyzer Model 2100. The instrument utilizes the classical
Brunauer, Emmett, and Teller (BET) [21] low-temperature nitrogen ad-
sorption technique. When the lumps of lime were fractured for the SEM
specimens, internal pieces from the lump were ground with mortar and
pestle to pass a No. 100 U.S. standard sieve and be retained on a No. 200.
Approximately 0.5-g samples were heated for 16 h at 150 C in a 0.001-ram
Hg vacuum to clear the sample of adsorbed gas and moisture before sur-
face area measurements were determined. Krypton gas was used with
these low surface area materials.
The reactivities of the oxides were determined by temperature rise as
related to the slaking rate test as described in ASTM Physical Testing of
Quicklime and Hydrated Lime (C 110-67).
EADES AND SANDBURG ON COMMERCIAL LIME 7
Prior Studies
Azbe [3] in 1927 discussed the atomic structure of CaCO3 and CaO
and the changes occurring in limestone during "burning" or calcination.
Although virtually nothing was then known about the microstructure of
limes and limestones, it was possible, on the basis of knowledge of the unit
cells of the two minerals and observations of volume density changes with
calcination, to make a number of inferences as to the microscopic change
in crystaUite form and void space distribution. Azbe [3] stated that, in
CaO, occupied space (space under atomic influence) was 43.4 percent that
of CaCO~ so that "soft-burned, unshrunk lime contains 56.6 percent
voids." KSnig et al [5] indicated a value of 46.5 percent for a soft-burned
rotary kiln lime based on surface area measurement. Azbe suggested that
the cells of CaO aggregated as the lime was hard burned so the voids would
fill in and the lime would become less reactive as a result of decrease in
pore volume into which resulting hydrate could expand. It seems more
likely that the decreased reactivity is due not to absence of space for
hydrate development, but rather to extreme reduction in surface area and
interconnecting voids on which hydration may occur. From Azbe's discus-
sion it appears that the voids he is considering are very minute spaces be-
tween cells which are "several times wider than the molecule of water" [3],
that is, very much smaller than the intergranular spaces we observed in the
SEM. Nevertheless, his generalizations regarding changes in void space and
reactivity with increasing calcination were valid.
More recently, Mayer and Stowe [4] established a hypothetical model
of the transitional state between CaCO3 and CaO and employed this model
in explaining changes in surface area and equivalent pore diameter during
calcination. Hedin's work [11] supplemented and supported such theoret-
ical considerations of unit cell alteration and migration with transmission
electron micrographs of limes calcined under various temperatures and CO,,
pressures. Hedin presented a diagrammatic interpretation of the dissocia-
tion of CaCO~--CaO +CO2 which distinguished two episodes in the de-
velopment of the oxide: (1) the loss of CO2 and development of stable
CaO crystallites through bonding, and (2) the clumping or coalescing of
the resultant crystallites with corresponding decrease in surface area and
pore space.
SEM Observations Correlated with Surface Area

Sample 400, a quarry stone calcined in both rotary and vertical kilns
for making lime with different slaking properties, is a pelletoidal oolitic
limestone with coarse crystalline calcite cement between grains (Fig. 1).
8 THE REACTION PARAMETERSOF LIME
FIG. 1--Pelletoidal limestone with coarse calcite cement: Sample 400 (X94).
All figures are scanning electron micrographs of gold-lead coated fresh fractured
surfaces.
The pellets are composed of closely packed micritic crystallites with very
little pore space (Fig. 2). The diameters of individual crystallites range
approximately from 0.5 to 3/zm.
Samples of only slightly burned lime which contained uncalcined CaCOa
(core) were selected to study the initial phases of calcination which were
observable on the internal fractured surfaces. The fractured lumps revealed
visually a very clear boundary between core of tan, partially reacted stone
and the outer zone of white, soft crystallites of CaO. Small samples 1 cm
in diameter which cut across the calcining boundary were selected with
the aid of a binocular microscope. SEM study of the area on the edge of
the tan zone (Fig. 3) revealed that the micritic pellets had become
rounded, anastomosing "globs." The surfaces show small white points
which are interpreted as points of contact with the adjacent material re-
moved when the specimen was fractured. The exact development of the
rounded globs is uncertain. The differences in average diameters between
the crystallites of the micritic pellet (Fig. 2) and the pellet from the par-
tially calcined core (Fig. 3) may be a function of differences in the two
sampled pellets. However, the rounding of crystallite edges and the anas-
tomosing of adjacent grains still remains unexplained, and we have not
found the phenomenon in the literature.
Eades and McClellan (unpublished) have used the SEM to study par-
ticles of Iceland spar ground to less than No. 20 but greater than No. 24
mesh which were shock calcined at temperatures ranging from 750 to
1400 C, and it was observed that the individual particles retained their
rhombohedral shape, except for a slight rounding on the corners. As the
furnace temperature was increased the soft crystallites of CaO coalesced
in the process of recrystallization of the oxide.
In the case of vertical kilns, the stone is gravity fed into the calcining
zone from above as lime is withdrawn from the bottom. As the stone
moves downward the weight increases as the overlying bed becomes
thicker. Also, the outer surface shrinks due to calcination, the internal
pressure of CO2 increases. It appears (Fig. 3) as if the stone had reached
a plastic state and the individual grains (Fig. 2) had fused together,
FIG. 2--Detail view o[ micritic pellet in center oJ Fig. 1 (X5165).
FIG. 3--Core region of partially burned stone (Sample 400.4 vertical kiln) (X1373).
although CaO has a melting point of 2580 C. Calcite crystals are very
soft crystals and are easily deformed. (Shown by Eades' unpublished pic-
tures of crystals along shear planes of laboratory sheared cores of limestone.)
On close inspection, many of the crystallites in Figs. 3 and 4 appear to be
composed of two or more grains intergrown. Hedin [11] observed physical
changes which occur below the dissociation point in some calcitic lime-
stones. Generally, if the crystallites were small the heating caused expan-
sion. This could be an alternative mechanism producing the grain mor-
phology shown in Fig. 3. As the calcium carbonate grains expanded, they
compressed together, and the surfaces started to dissociate. Newly formed
crystallites of CaO interlocked so that many grain boundaries were almost
obliterated. The loss of CO2 produced shrinkage and the CaO grains were
drawn closer together.
These voids discussed by Azbe [3], resulting from loss of CO2 molecules
from individual CaCO,s unit cells, correspond to the initial voids of the
"transitory phase" mentioned by Mayer and Stowe [4]. Such voids would
not be visible, and the first clearly discernible voids in our SEM micro-
graphs (Fig. 4) are about 0.1 /zm diameter. Mayer and Stowe said crystal-
lites of CaO develop as pseudocarbonate "open" structure (produced by

CO2 loss but prior to readjustment of lattice), and the initial crystal size is
of the order of 10 -~/zm. Subsequently, larger visible pores form with a
rather uniform spacing, cutting up the apparent solid grain surface (Fig.
4). The relative arrangement of pore spaces and crystallites in the oxides
studied suggest that there are preferential sites where CO~ escapes, perhaps
related to lattice defects or cleavage planes in the original carbonate.
The outer portion of the same hand specimen from which Figs. 3 and 4
were taken had the white powdery appearance of calcined lime. A fractured
surface through the outer portion (Fig. 5) revealed a very regular crystal
morphology. The pores were uniformly arranged and had about the same
diameter as pores observed in the outer part of the region of pore develop-
ment (right edge of Fig. 3). The size of the elongated crystallites varied
little (diameters of about 0.5 to 0.6/zm and lengths approximately 1.5 to
2/zm). They were connected with narrow necks or spines to one or more
laterally or terminally adjacent crystals of similar size and shape. The out-
lines or shapes of the initial large scale globs were still evident.
FIG. 4---Region close to outer surface of same partially burned specimen. The lime-
stone core is toward the left; the outer, more cah'ined region toward the right ( X 1836).
FIG. 5--Outer margin o] same partially burned specimen (X1836).
Surface area measurement of the material taken from the boundary zone
between the CaO and the coalescing globs gave a rather low figure (1.62
M2/g), which is an average value, representative of the several stages of
calcination shown in Figs. 3, 4, and 5.
Maximum pore space is developed when the individual grains of CaO
have contracted to their smallest dimension (as a result of total loss of
CO~), but before clumping or coalescing of these grains into larger masses
has begun. In our specimens maximum porosity would be approximately
represented by Figs. 6 (vertical kiln) and 10 (rotary kiln). Earlier stages
of calcination of these two samples show correspondingly smaller pore
space and crystallites which are apparently still losing CO._, and contracting.
Mayer and Stowe [4] stated that the highest activity for a lime developed
immediately after collapse of the "open" structure. They stated that ac-
tivity is a function not of any abnormal lattice but of the very minute
crystal size and very high surface areas. The lime shown in Fig. 3 is prob-
ably of this type. Mayer and Stowe found it impossible even experimentally
to isolate that initial lime state because of the rapid rate of clumping of
the small formless globs into larger ones, so that commercial production of
such a lime is not feasible. In fact, such a lime would not be desirable for
most users since, except by means of disaggregation, the surfaces are not
effectively available for reaction because of the very low permeability.
This clumping and growth of crystals brings about a correlative clump-
ing of pore spaces and an increase in permeability. A practical optimum
activity range, from the standpoint of industry, is reached when pore vol-
umes have grown to form a large interconnecting network, but before fur-
ther crystal clumping and shrinkage of the total volume of the lump begins
to decrease pore volume. The microstructural characteristics of the oxides
(shown in SEM figures), the reactivity, and surface area measurements
reflect this change for the stones studied.
With continued calcination there is a reforming or rearrangement of the
crystallites, and growth of the crystals of CaO occurs. The growth of large
cubic crystals of CaO starts by contracting of the crystallites from the
elongated worm-like structures into bulging, more equidimensional forms
(Fig. 6). Contact surface between the crystallites increases to broad
rounded or elongated areas which increases the pore space at this point
and starts to reduce surface area. As observed in a hard burned vertical
FIG. 6--Normal burned vertical kiln lime, Sample 400A (X4590).
kiln lime, crystal faces, noticeable fiat surfaces begin to develop on the
rounded globs (Fig. 6). This is evidence of the loss of reactivity, not only
because of loss of surface area but because of loss of surface energy [22].
A comparison of structure and surface area measurements of the two limes
shown in Figs. 6 and 10 helps to show why hydrates made from the two
limes are different.
An extra hard burned (dead burned) lime shown in Fig. 7 was made
from the same stone (Figs. 1 and 2) and kiln as the lime in Fig. 6. The
growth of crystals from the size of the crystallites in Fig. 8 to the crystal
size in Fig. 7, requires a tremendous amount of energy. The large crystals
have grown by assimilation of smaller crystals, and the resulting shrinkage
has proceeded until pore space is almost nonexistent.
The nature of the limestone or the form of the CaCO3 crystal seems
to influence the structure, surface area, and porosity of the resulting oxide.
Hedin [11] presented illustrations of oxides produced by calcining cleavage
rhombohedrons of Iceland spar calcite. The crystallites of his soft and normal
burned specimens are nearly equidimensional grains with little intergran-
ular porosity evident, and contrast rather markedly with the elongate,
FIG. 7--Extra hard or dead burned lime from vertical kiln (X 1820).
FIG. 8----Normal rotary kiln lime, Sample 400R (>(4590).
worm-like crystallites and elaborate tunneled voids in comparably treated

specimens of our calcined micritic limestone pellets. SEM micrographs
(Figs. 13 and 14) of low reacting CaO produced commercially from rhombo-
hedral calcite crystals show crystallite and pore structure strikingly similar
to that of Hedin's Iceland spar specimens.
Another calcitic stone (Sample 500) calcined commercially in a rotary
kiln produces a lime (Figs. 9 and 10) which is very similar to the lime
produced from the pelletoidal limestone (Figs. 1 and 2). The crystallites of
the soft burned lime in Fig. 9 are smaller, more elongated particles than
those in Fig. 8. The oxide also fractures along planes having internal voids
which must be related to the structure of the original stone. These charac-
teristics are expressed also in terms of surface area (Table 1 ). The soft
burned lime (500A) has a surface area of 2.07 M2/g as compared to 1.44
M2/g for the rotary kiln lime (400R) of the pelletoidal stone. The two
limes have a temperature rise in 60 s of 50 and 40 C, respectively.
The internal voids of lime No. 500A would allow greater volumes of
liquid to enter the lime and contacting a larger surface area resulting in
greater reactivity than the lime made from stone No. 400.
FIG. 9--Normal rotary kiln lime, Sample 500A (•
FIG. lO--Hard burned rotary kiln lime, Sample 500B (•
TABLE 1--Reactivity and surface areas.
Figure Sample Sample ~ Reactivity, b Surface

Number Number Description deg C Area MVg
1......... 400 stone . . . . . .

2 ......... 400 stone . . . . . .
3......... 400A VK partial B ... 1.62
4 ......... 400A partial B ... 1.62
5......... 400A partial B ... 1.62
6......... 400B VK normal B 32 1.35
7......... 400C VK dead B 1 0.51
8 ......... 400R RK normal B 40 1.44
9......... 500A RK normal B 50 2.07
10 . . . . . . . . . 500B RK hard B 25 1.11
11 . . . . . . . . . 700 stone . . . . . .
12 . . . . . . . . . 700A RK normal 29 5.14
13 . . . . . . . . . 800A FS B 35 1.51
14 . . . . . . . . . 800B FS B 24 1.35
15 . . . . . . . . . 600A V K normal not available 1.44
16 . . . . . . . . . 600B C normal not available 2.08 to 5.47
17 . . . . . . . . . 900 laboratory furnace . .. 12.11 to 15.8
VK = vertical kiln.
R K = rotary kiln.
FS = fluid solids.
C = calcimatic.
B = burned.
b Temperatures rise in 60 s.
T h e h a r d b u r n e d l i m e ( F i g . . 10) p r o d u c e d in a r o t a r y k i l n f r o m S a m p l e
5 0 0 s h o w s a s t r u c t u r e s i m i l a r to t h a t s e e n in S a m p l e 4 0 0 B ( F i g . 6 ) . T h e
s u r f a c e a r e a has b e e n r e d u c e d to 1.11 M 2 / g a n d the r e a c t i v i t y to 25 C.
I f t h e l i m e is o v e r b u r n e d C a O g r a i n f e a t u r e s c h a r a c t e r i s t i c of p a r t i c u l a r
p a r e n t C a C O a t y p e s are o b l i t e r a t e d .
S t o n e N o . 7 0 0 ( F i g . 11 ) is a m e t a m o r p h o s e d l i m e s t o n e . C a l c i n a t i o n of
this m a t e r i a l in a r o t a r y kiln results in a l i m e w h i c h is m a d e u p of d i f f e r e n t
size p a r t i c l e s ( F i g . 1 2 ) . T h e s e d i f f e r e n c e s in p a r t i c l e size are r e l a t e d to the
initial m o r p h o l o g y of the s t o n e r a t h e r t h a n to c o a l e s c i n g of crystallites.
H o w e v e r , o n close e x a m i n a t i o n of Fig. 12, it is e v i d e n t t h a t the crystallites
h a v e s t a r t e d to c o a l e s c e . T h e s u r f a c e a r e a of this l i m e is 5 . 1 4 M 2 / g .
A t t e n t i o n is c a l l e d to the t u n n e l t y p e v o i d s w h i c h are p r o b a b l y d u e t o the
s o l u t i o n v o i d s in the s m a l l calcite c r y s t a l s of the stone.
S a m p l e 8 0 0 is a m a r b l e w h i c h is p r i m a r i l y I c e l a n d s p a r t y p e m a t e r i a l .
G r o u n d r h o m b o h e d r a l c a l c i t e p a r t i c l e s w e r e c a l c i n e d in a fluid solids kiln.
F i g u r e 13 s h o w s the l i m e ( 8 0 0 A ) w i t h a 35 C rise a n d a s u r f a c e a r e a of
1.51 M 2 / g . L i m e m a d e f r o m the s a m e s t o n e in the s a m e kiln c a l c i n e d i n t o
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions author
'1 8 THE REACTION PARAMETERS OF LIME
FIG. ll--Metamorphosed limestone, Sample 700 (X 1400).
FIG. 12--Normal burned rotary kiln lime, Sample 700A (X2592).
FIG. 13--Fluid solids calcined marble, Sample 800A (>(6800).
a less reactive lime (Fig. 14), with only 24 C rise, shows the same coales-
cing effect which was seen in Figs. 6 and 7. Along with the drop in reac-
tivity, the surface area was reduced from 1.51 to 1.35 M2/g.
Samples of stone No. 600 (a dolomite) were calcined in shaft and calci-
matic kilns. The shaft kiln lime (600A) (Fig. 15) shows the coalescing
effect with much larger voids than those shown by the calcimatic limes.
The calcimatic lime (600B) (Fig. 16) shows some clumping as the small,
individual crystallites started to coalesce. The surface area of the shaft kiln
lime is 1.35 M2/g, and the lime from the calcimatic kiln varies from 2.08
to 5.47 M2/g. The high surface area for the dolomitic lime seems to be due
to a combination of the method of calcination and the smaller crystallites
which form from the dolomite.
A fine grained dolomite (900) calcined in a laboratory furnace at 1000 C
(Fig. 17) had a surface area of 12.11 to 15.8 M~/g. The crystallites and
pores of the limes are so very small that it was difficult to metal coat the
crystallites so that they would be conductive without filling the pores.
The photomicrograph of this laboratory prepared sample is included with
this study of commercial limes to show the size of the crystallites and the
type of surface area that may be obtained with the closely controlled
calcining conditions.
FIG. 14--Fluid solids calcined marble, Sample 800B (•
FIG. 15--Vertical kiln calcined dolomitic lime, Sample 600A (>(5865).
FIG. 16--Calcimatic calcined dolomitic lime, Sample 600B (X6162).
FIG, 17--Dolomite calcined at 1000 C in laboratory furnace, Sample 900 (>(22,525),
Discussion and Conclusions
The study of the eleven commercial limes which were calcined from
five different types of stone seem to point to a control exerted by the tex-
ture and grain size of the stone on the size of crystallites and the pore
distribution in early calcination. Figures 8 and 9 representing limes made
in rotary kilns, not that the kiln type matters if the burning process is con-
trolled, show limes that have about the same degree of calcination. Neither
lime shows any coalescing, but the limes differ in surface areas by 0.5
M2/g. Figure 12 clearly shows two distinct size lime crystallites while Fig.
11 shows that the stone is made up of large calcite plates and small frac-
tured interlocking calcite grains.
After the lime is first formed the significance of the original morphology
starts to disappear. With continued calcination the original crystallites start
to coalesce, and larger particles are formed. It appears the softest lime cal-
cined from a stone is not necessarily the most reactive. Sample 700A which
has a surface area of 5.14 M2/g only has a reactivity of 29 C rise in 60 s,
while Sample 500A with a surface area of 2.07 M2/g has a rise of 50 C in
60 s. So it seems that it is necessary for the initial small lime particles to
merge, thus increasing pore space, permeability, and reactivity. As the
crystallites start to coalesce, the new particles seem to start to recrystallize.
It would appear that the most reactive lime for a given stone would be at
the point just before the crystal faces start to emerge.
Commercially it would be difficult to control the burning to such a degree
if the texture and composition varied widely in the quarry stone.
References
[1] Boynton, R. S., Chemistry and Technology o] Lime and Limestones, Wiley, 1966.
[2] Wuhrer, J., "On the Reactivity of Lime from Different Kiln Systems," National
Lime Association, Washington, D. C., 1965.
[3] Azbe, V. J., "Science and Engineering in Lime-Bornings," Industrial and Engi-
neering Chemistry, Vol. 19, No. 5, 1927, pp. 1-10.
[4] Mayer, R. P. and Stowe, R. A., "Physical Characterization of Limestone and
Lime," National Lime Association, Washington, D. C., 1964.
[5] KSnig, G., Rellermeyer, H., and Obst, K. H., "Processes Taking Place in the
Dissolution of Hard and Soft-Burnt Lime in the Slags from the Basic Oxygen
Furnaces," Stahl und Eisen, Vol. 87, No. 18, 1967, pp. 1071-1077.
[6] Clark, G. L., Bradley, W. F., and Azbe, V. J., "Recent Research with X-rays,"
Industrial and Engineering Chemistry, Vol. 32, No. 7, 1940.
[7] Staley, H. R., "Micromeritics of Lime," National Lime Association, Washington,
D. C., 1946.
[8] Staley, H. R., "Calcining and Hydration," National Lime Association, Washing-
ton, D. C., 1950.
[9] Murray, J. A., Fischer, H. C., and Sabean, D. W., "Der Effekt von Brennzeit und
Temperature auf die Eigenschaften von Branntkalk aus Kalzit," National Lime
Association, Washington, D. C., 1950.
[10] Eades, J. L. and Sandberg, P. A., "Scanning Electron Microscope Study of

Development and Distribution of Pore Space in Calcium Oxide," Proceedings,
Symposium on the Scanning Electron Microscopy, Illinois Institute of Tech-
nology, Research Institute, Chicago, 1969, pp. 381-388.
[11] Hedin, R., "Structural Processes in the Dissociation of Calcium Carbonates,"
National Lime Association, Washington, D. C., 1961.
[12] Hay, W. W. and Sandberg, P. A., "The Scanning Electron Miscroscope, a
Major Breakthrough for Micropaleontology," Micropaleontology, Vol. 13, No. 4,
1967, pp. 407-418.
[13] Kimoto, S. and Russ, J. C., "The Characteristics and Applications of the
Scanning Electron Microscope," American Scientist, Vol. 57, No. 1, 1969, pp.
112-133.
[14] Sandberg, P. A. and Hay, W. W., "Application of the Scanning Electron Micro-
scope in Paleontology and Geology," Proceedings, Symposium on the Scanning
Electron Microscopy, Illinois Institute of Technology, Research Institute,
Chicago, 1968, pp. 29-38.
[15] Gillott, J. E., "Study of the Fabric of Fine Grained Sediments with the Scanning
Electron Microscope," Journal of Sedimentary Petrology, Vol. 39, No. 1, 1969,
pp. 90-105.
[16] Willard, R. J., "Scanning Electron Microscope," Geotimes, Vol. 13, No. 7, 1968,
pp. 16-18.
[17] Willard, R. J., "Scanning Electron Microscope Gives Researchers a Clear Look
at Rock Fractures," Mining Engineer, 1969, pp. 88-90.
[18] Pfefferkorn, G. and Blaschke, R., "Raster-Elektronenmikroskop fiir Oberfl~iche-
nuntersuchungen," Umschau in Wissenschaft und Technik, Vol. 18, 1967, pp.
584-590.
[19] Reumuth, H., "Stereoscan----ein neues Zeitalter der Mikroskopie? Das Raster-
Elektronenmikroskop," Mikrokosmos, Vol. 57, No. 1, 1968, pp. 1-9.
[20] Bulba, E., "Scanning Electron Microscopy," Current Laboratory Practice, Vol. 1,
No. 1, 1968, pp. 6-11.
[21] Brunauer, S., Emmett, P. H., and Teller, E., "The Adsorption of Gases in
Multimolecular Layers," Journal of the American Chemical Society, Vol. 60,
1938, pp. 309-319.
[22] Cimino, A., "The Structure of Solids and Liquids," Chemistry Today, Organiza-
tion for Economic Co-operation and Development, 1964, p. 114.
DISCUSSION
G. H. McClellan 1 (written discussion)--The most important contribution

that the scanning electron microscope (SEM) studies Dr. Eades has made
is the demonstration that the actual size and shape of pores and the origin
of the surface area of samples of lime can be more easily seen and under-
stood than ever before. This gives the observer an appreciation for the
meaning of surface area measurements and pore size distributions that
could never be conveyed by a conceptual model or descriptive presentation
where terminology is necessarily nonquantitative. Studies of limes prepared
under different conditions show what is meant by a change in pore size
distribution and how surface areas are decreased by hard burning.
The contrast between the textures of the shaft-kiln lime and the rotary-
kiln lime made from the same stone show that the rate of heating during
calcination has a significant effect on the texture of the calcines. The hard
burned limes from the shaft kiln had the large pores and small surface
areas expected from such an unreactive material. The growth of the oxide
crystals is very apparent. The softer burned limes from the rotary kiln
show the "brain" texture Dr. Eades described and have high porosity
without evidence of oxide crystal morphology. These features are consistent
with the high reactivity of such calcines.
The variation in textures of limes prepared from stones of different tex-
tures has often been discussed, but very few physical data have been ob-
tained on such materials. This work clearly shows that the massive lime-
stones produce calcines with physical properties quite different from those
of calcines of oolitic and pelletoidal limestones. It is also significant that
the many literature descriptions of the radial, fibrous habit of the calcite in
oolites has been shown to be incorrect by SEM studies.
1 Fundamental Research Branch, Division of Chemical Development, Tennessee

Valley Authority, Muscle Shoals, Ala.
24
M. Timucin ~ and A. E. Morris ~
Phase Equilibria and Thermodynamic

Properties of Lime-Iron Oxide Melts
Containing up to 30 Percent Si02:
1450 and 1550 C Sections
REFERENCE: Timucin, M. and Morris, A. E., "Phase Equilibria and

Thermodynamic Properties of Lime-Iron Oxide Melts Containing up to
30 Percent S i O 2 : 1 4 5 0 and 1550 C Sections," The Reaction Parameters
o[ Lime, ASTM STP 472, American Society for Testing and Materials,
1970, pp. 25-31.
ABSTRACT: This paper is a brief presentation of research work on the

effect of lime on the thermodynamic properties of synthetic basic oxygen
steelmaking slags saturated with lime. It provides a basis for understanding
the fluxing behavior of lime and other constituents in such slags. Solid
solutions of ferrous iron in lime also have been investigated, particularly
with respect to an improvement in the resistance of lime to hydration.
KEY WORDS: fluxes, slags, steelmaking, evaluation, tests, calcium

oxides, thermodynamic properties, iron alloys, hydration
In order to provide a basis for understanding the fluxing behavior of

Iime and other constituents in basic oxygen furnace steelmaking slags,
phase equilibria and thermodynamic data were obtained on the system
calcium oxide-ferrous iron-ferric oxide-silicon dioxide (CaO-FeO-Fe2Oa-
SIO2) at 1450 and 1550 C. The investigation was carried out over a large
range of compositions and oxygen partial pressures in the ternary CaO-
FeO-Fe._,O3 system, and at 5, 10, 20, and 30 weight percent SiO2 sections
in the quaternary system. The data were used to calculate the thermody-
Formerly, graduate student, Department of Metallurgical and Nuclear Engineer-

ing, University of Missouri at Rolla, Rolla, Mo. 65401; presently, research associate,
Department of Geochemistry and Mineralogy, Pennsylvania State University, Uni-
versity Park, Pa. 16802.
2 Associate professor, Department of Metallurgical and Nuclear Engineering, Uni-
versity of Missouri at Rolla, Rolla, Mo. 65401.
25
Copyright
Copyright by9 ASTM
1970 by
(all rights reserved); Wed www.astm.org
Aug 1 12:04:31 EDT 2012
1.0 / ' 1
1450"C C~O-FeO-FezO~ SYSTEM % / I
9 Er'7~T ~ E ~ / " '2.
0.6
7 /12
--'o/, 'o~ o.I o.~ o.~ o.~ o.#

NCa0
FIG. 1 - - T h e effect of lime on the relative stability of ferric iron at 1450 C as a
function of the partial pressure o] oxygen.
namic activity of CaO and FeO in the ternary and quaternary melts, and
the activity of SiO2 in the quaternary melts.
Because a highly basic slag is desirable in the steelmaking process, the
data for melts saturated with lime were analyzed in some detail. Figure 1
shows the effect of increasing lime content on the relative stability of ferric
iron (Fe203) with respect to ferrous iron (FeO). At all oxygen pressures,
lime increases the stability of the ferric state. For melts saturated with
lime, the addition of SiO_oon the ferrous-ferric ratio is shown in Fig. 2. The
addition of SiO2 increases the stability of the ferrous state, except where a
small addition of SiO2 has increased the solubility of lime (5 percent
SiO.,). Figure 3 is a representation of the effect of SiO2 on the activity of
FeO in lime-saturated melts. The most pronounced effect of SiO2 occurs
between 0 and 10 percent SiOe.
TIMUCIN AND MORRIS ON LIME-IRON OXIDE MELTS 27
1450 *C LIME SATURATION

0.8
. . ,_.....-..~ 3ox sio,
0.7
s;o~0.6 / / / / / ~,,,Z.,.-- 20%Si 0~

c--TOo5 o '/ 37-32
-/ / "~" ' " "
0,4
03
-- V Y / .....
0.2
OI
~o=,~s-w,,~-~ , , \ \ ,x,, o%s,% ,
QI I0 I0.0
FIG. 2 - - T h e effect o] silica~lime ratio o f lime-saturated slags on the ]errous/]erric

ratio at 1450 C. Lines o] constant POe and Si02 content are shown on the diagram.
601" 'FeO' ACTIVITIES ALONG~

I ,, LIME SATURATION AT ~ I._,,.
Io 1r163 --/'0.7 -""x_IRON SATURATION
S~ .~ /7 -~k o~
/, ~ ~ / / 0.6 \ ~
40/~,, ~ ~ n.5 ~ ,,,
/ ~,,. ~ /- t - - / ". o
1 I i i i I I I I I
0,1 0"2 0.3 SinG4 0.5 0.6 0.7 0.8

w,
0
FIG. 3 - - F e O activities in lime-saturated melts as a ]unction of FeO content. Lines
o f constant Si02 are shown on the diagram.
deg C
2_800 PHASEDIAGRAMOFTHE SYSTEM
CaO-'FeO"IN CONTACTWITHIRON
2400 ~ LIQUID
2000
12DO /~t--~:--'~_-- : ? = ~ WUSTITE

LIME/ LIME-.2CaO.Fe,O, I wUSTITE" ~ II
800 /, . . . . I, +2,ca~176 ,""
C.aO I0 20 30 ~r%FeO~60 70 80 90 FeO
F I G . 4--Phase diagram o] the system CaO-FeO in equilibrium with metallic iron.
The system is not a true binary because o] the existenee o] some ]erric iron.
Y' XI= SOLUBILITY Of WUSTITE IN LI~

'X~ LIQUID-CaOssEQM.
a X--'---LIOUID -~ ~Fe'CAIO"EQM.
9
\ .... ~- ~EQM--
,o -
~'J'~ ~o~. I- \
13
14
~ FeOI
F I G . 5 - - T h e solubility of FeO in lime as a function of PO~ at 1200, 1300, and
1400 C.
TIMUCIN AND MORRIS ON LIME-IRON OXIDE MELTS 29
In addition to a study of completely liquid solutions, we also have in-

vestigated completely solid solutions. As shown in Fig. 4, solid lime can
dissolve up to a maximum of about 15 percent FeO at about 1050 C. We
have studied the effect of temperature and oxygen pressure on the thermal
stability of these CaO-FeO solid solutions. A summary of the results is
shown in Fig. 5. At temperatures above 1200 C, if one exceeds the solu-
bility of iron oxide under slightly oxidizing conditions, a liquid oxide is
formed. But if the solubility of iron oxide is exceeded under reducing con-
ditions, metallic iron is formed.
Figure 6 shows how the activity of FeO and CaO vary with composition
and temperature, up to the solubility limit. The data points are from the
J.O~ 1400%.
CaO
1300(; .1090"C
0.9t
0.SL
o,t ',eO"_/"./
l . . _ - t 3 o o "c
0.6
ai
o.51- /// ,~,;5o~
0.4
FeO and CaO ACTIVITIES

0.3 IN LIME SOLID 50LUTIONS
0.2
0.'
' o.dz o.~, o.~6 o68 o.to

NFe Ot
FIG. 6 - - T h e activity of FeO and CaO in CaO solid solutions saturated with FeO
at P02 in equilibrium with metallic iron.
I I
I0o_ TEMP: II00*C
90- Pn_RH : 55*/.~lO_B.5~tm

d 0 -- "2
70
Pure cao
10 TIME,hr5 . 100 1000

FIG. 7--Hydration of CaO and FeO solid solutions at room temperature after
sintering 36 h at 1100 C.
phase equilibrium calculations made from 1450 and 1550 C diagrams.

The curve at 1090 C was obtained from literature data.
In our experiments on the CaO-FeO solid solutions, it was noticed that
the addition of FeO to lime had a stabilizing effect on it with respect to
hydration by moisture in the air. In order to examine this effect more care-
fully, pressed pellets of CaO and several CaO-FeO solid solutions were
sintered for 36 h at 1100 C, and then allowed to hydrate at room tempera-
ture, in air of 55 percent relative humidity. The data are shown in Fig. 7.
Acknowledgment
This research work was sponsored by the National Lime Association.
DISCUSSION
G. Derge ~ (written discussion)--It has been my privilege to have visited

Professor Morris while this work was in progress at Rolla and to have read
the thesis of Timucin upon which this brief presentation is based. The
value of the presentation cannot be appreciated fully without some under-
standing of the large amount of high caliber experimental work upon which
the presentation is based. The authors are to be congratulated on this effec-
tive and useful representation of their work.
For the purposes of this meeting it is worth noting that the boundaries
shown for liquid slag in Fig. 1 are all very real. The function of the slag
in any particular steelmaking process is related to the restraints and im-
posed forces which control the shift from one boundary condition to
another. In the relatively stagnant electric furnace the transfer of oxygen
from the slag-gas interface at the top of the diagram to the slag-metal
interface at the bottom is slow and protects easily oxidized alloys. The
violent convection resulting from the lance action contributes to the speed
of the basic-oxygen process, and the upper boundary is extended to still
higher pressures. The authors have shown the influence of silicon dioxide
(SiO2) on this basic diagram, and of course it would be interesting to have
similar information for manganese oxide (MnO), phosphoric pentoxide
(P205), and all of the other components of operating slags.
The influence of dissolved ferrous oxide (FeO) in improving the re-
sistance of lime to hydration has many implications which offer an incen-
tive for preparing such materials. For example, this should minimize hydro-
gen problems in quality steelmaking.
We look forward to the complete presentation of this work.
M. Timucin and A. E. Morris (authors' closure)---The authors appre-
ciate the kind remarks of Professor Derge and are continuing the work to
include other components and higher temperatures.
1 Professor, Metals Research Laboratory, Carnegie-Mellon University, Pittsburgh,
Pa. 15213.
31
G. H. McClellan,' S. R. Hunter/ and R. M. Scheib 1
X-Ray and Electron Microscope Studies

of Calcined and Sulfated Limestones*
REFERENCE: McClellan, G. H., Hunter, S. R., and Scheib, R. M.,

" X - R a y a n d E l e c t r o n Microscope Studies o f Calcined a n d Sulfated
L i m e s t o n e s . " The Reaction Parameters o / L i m e , A S T M STP 472, American
Society for Testing and Materials, 1970, pp. 32-66.
ABSTRACT: Calcitic limestone and Iceland spar were shock calcined

at temperatures in the range 750 to 1300 C, and the products were examined
by electron microscopy and X-ray diffraction to determine the pore size,
structure, and crystallite size of the calcines. The calcination took place in
two stages: dissociation of the calcium carbonate and recrystallization of the
oxide.
Samples of the same materials, with and without prior calcination, were
treated with a gas containing 4 percent sulfur dioxide at 750, 1050, and
1200 C, and examined as before to determine the degree and manner of sulfa-
tion. The limestone calcines were consistently more reactive with sulfur
dioxide than were those of the Iceland spar; the difference is attributed
to the larger crystallite size of the initial Iceland spar and an unfavorable
distribution of pores in the spar calcines. Sulfation occurs in two stages: a
general surface reaction of the sulfur dioxide and oxygen with the calcium
oxide, and a subsequent diffusion-controlled reaction through the sulfate-
covered outer surface to the unreacted lime core.
Calcite calcines react best with sulfur dioxide at temperatures below
1050 C. Simultaneous calcination-sulfation, as in the injection into the
furnace of a coal-burning power plant, takes place best at temperatures of
1050 C or higher.
KEY W O R D S : calcite, limestone, calcium carbonates, calcium oxides,

calcium sulfates, electric power plants, flue gases, sulfur dioxide, air pollu-
tion, injection, X-ray diffraction, electron microscopes, roasting, sulfation,
crystallites, density ( m a s s / v o l u r a e ) , porosity, evaluation, tests
Of the several processes proposed for the removal of sulfur dioxide

from power plant stack gases, injection of limestone into the furnace is the
simplest. The limestone is calcined to calcium oxide which reacts with
1 Research chemists, Division of Chemical Development, Tennessee Valley Author-
ity, Muscle Shoals, Ala. 35660.
* Work performed under contract TV-29232A with the National Air Pollution
Control Administration of the U.S. Public Health Service.
32
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
McCLELLAN ET AL ON CALCINED AND SULFATED LIMESTONES 33
sulfur dioxide to form calcium sulfate that can be removed in the usual
dust-collecting system. Of the many parameters that affect the efficiency
of the injected limestone, the more important are the physical properties
of the limestone that influence the characteristics of the calcines, the
temperature at the point of injection, the particle size, the retention time
in the reaction zone, the distribution of the particles in the gas stream,
and the rate of oxidation of sulfur dioxide. A study was made by X-ray
diffraction and electron microscopy of the influence of the physical prop-
erties of the limestone and the temperature of injection on the properties
of calcines and their reaction with sulfur dioxide.
Hyatt et al [1] 2 have reviewed the literature on the general subject of
calcination. Fischer [2,3] presented data on the crystallite size and pore
volume of calcines prepared under different conditions. No previous studies,
however, have dealt with the reactions of sulfur dioxide with lime or the
effect that differences in physical properties resulting from differences in
temperature of calcination have on the reactivity of the calcine with sulfur
dioxide. The present study was intended to describe the changes in pore
volume and crystallite size that occur on calcination and the effects of these
changes on the subsequent reactivity of the calcines with sulfur dioxide.
Materials
Data from fixed-bed tests on the reactivity of sulfur dioxide with cal-
cined limestones showed that calcitic stones were generally more reactive
than dolomitic stones. The materials selected for this study were a high-
purity calcitic limestone (USDA Reference Sample 89) and clear crystals
of Iceland spar (Ward's Scientific Company). Both materials were crushed
and screened to produce a minus 20 plus 24-mesh fraction from which
hand-picked samples could be obtained to minimize the effect of minor
accessory minerals.
X-ray and petrographic examinations showed the hand-picked samples
to be free of detectable accessory minerals. The cell constants of both
materials showed that there had been no significant isomorphism and that
both materials were pure calcites as defined by Goldsmith and Graf [4].
Experimental Procedure
A 3-g sample of each calcite was calcined in a platinum boat for 16 h at
constant temperatures in the range 750 to 1300 C. The samples were in-
serted into the preheated furnace to effect initial shock calcination; the long
retention time was sufficient for complete calcination at each temperature.
The italic n u m b e r s in brackets refer to the list of references appended to this
paper.
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions authorize
The calcined samples were placed immediately in a drying oven at 110 C

to prevent hydration and recarbonation. Samples for study by X-ray dif-
fraction at room temperature were ground to minus 200-mesh under nitro-
gen in a dry box. The samples for electron microscopy were replicated
immediately upon removal from the drying oven. All the electron micro-
graphs were prepared by two-step replication that yielded platinum-
shadowed carbon replicas. Each sample was replicated in triplicate to
minimize sampling and observational errors.
A series of calcination studies was made on minus 200-mesh samples
of each material with a high-temperature X-ray diffractometer furnace
which permits the examination of hot calcines. The results were compared
with those obtained with the shock-calcined samples.
X-ray examination, which can detect residual or uncalcined calcium
carbonate, was used to determine the degree of calcination of the samples.
X-ray line broadening was used to determine the mean crystallite size by
the Scherrer equation
D = k X / f l cos O. . . . . . . . . . . . . . . . . . . . . . . . (1)
where:
D = mean crystallite size,
k = constant of about unity,
/3 = pure diffraction broadening, and
0 = Bragg angle.
In this study, the value of k was 0.90 as determined by Rau [5] for cubic
crystals. Both Sherrer and Rau define r, the broadening caused by small
erystallites, as the difference between the total diffraction breadth, flob~,
and the instrumental breadth, fli,,~t, or
/3 .... = ~o|lS -- /31nst ....................... (2)

Klugg and Alexander [6] discuss other forms for the evaluation of P~orr
that have been proposed, and the form presented by Azaroff [7]
/3. . . . = ~ / ~ - /3J,~, V//3o,,~ 2 - / 3 ~ t 2. . . . . . . . . . . . . . (3)
was used in this study. This form is compatible with the Fourier transforms
used in line profile analysis and with it the probable error of/3 .... is 5 to 15
percent, much smaller than that with other forms. The crystallite sizes were
determined for the shock-calcined products, the products of the high-
temperature X-ray studies, and the calcium sulfate reaction products. Only
the relative sizes of crystallites are important in these studies, and the
values reported may not have real physical significance.
TABLE 1--Statistical summary of pore-size distributions of calcines.

Prepared by shock calcination and heating for 16 h.
Pore sizes determined by electron microscopy.
Mean Median Mode of

Calcination Pore Standard Pore Pore Number
Temperature, Size, Deviation, Size, Size, of Pores Skew-
deg C -~ ~, A ~, Measured hess t-Value ~
CALCITIC LIMESTONE
750 635 269 600 400 246 2.19 ...
850 1 188 627 1 100 1 300 252 0.97 12.78
900 1 194 588 1 100 1 100 253 1.05 0.11
950 1 404 658 1 300 1 300 210 1.17 3.63
1 000 2 183 1 183 2 000 2 100 250 1.55 8.52
1 050 1 998 920 1 800 1 500 250 0.90 1.96
1 100 1 958 963 1 800 1 500 201 0.87 0.44
1 200 1 655 1 021 1 400 1 300 254 1.19 3.23
1 300 1 489 837 1 300 1 300 254 1.13 2.02
ICELAND SPAR
750 720 349 600 400 251 1.12 ...
850 1 291 645 1 200 1 300 254 1.04 12.38
900 1 238 623 1 200 1 300 252 0.92 0.95
950 1 744 1 093 1 500 1 300 253 1.72 6.40
1 000 1 602 897 1 500 1 700 250 1.21 0.69
1 050 1 775 971 1 500 1 300 257 1.25 1.11
1 100 1 882 1 069 1 700 1 700 251 1.58 1.19
1 200 3 102 2 224 2 600 3 400 98 2.90 6.91
1 300 2 974 1 931 2 500 2 500 96 1.56 0.43
a Value for comparing confidence between means of arrays of different sizes; applicable
only to pairs of adjacent arrays (750 versus 850 C, 850 versus 900 C, etc.).
Results
T h e statistical s u m m a r y of the p o r e size d i s t r i b u t i o n s of t h e c a l c i n e d
calcitic limestone and Iceland spar that were determined by electron micros-
c o p y a r e p r e s e n t e d in T a b l e 1. A l l t h e statistical v a l u e s w e r e c a l c u l a t e d b y
t h e m e t h o d s d e s c r i b e d in A S T M Manual on Quality Control of Materials
( S T P 1 5 c ) e x c e p t f o r the t-test f o r c o m p a r i n g the m e a n s of d a t a f r o m
a r r a y s of d i f f e r e n t sizes. T h e v a l u e of t was c a l c u l a t e d f r o m t h e e x p r e s s i o n
d e s c r i b e d b y S n e d e c o r [8]
t = (2~ -- 2z)x/n~n2(n~-+- n2 ~ 2)
(nl q- n~)Zx = " ................ (4)
w h e r e ~1 - ~2 is the difference b e t w e e n the g r o u p m e a n s , a n d ~ x 2 is the
p o o l e d s u m o f s q u a r e s . All the d a t a s h o w positive s k e w n e s s coefficients,
i n d i c a t i n g t h a t the d a t a tail off in the d i r e c t i o n o f large pores.
The change in mean pore size with rising temperature of calcination is

shown in Fig. 1. The mean pore size of the calcitic limestone increases
irregularly to a maximum at about 1000 C and then decreases at higher
temperatures. The t-values show no statistical difference between the mean
pore sizes of 850 and 900 C calcines or between those of 1050 and 1100 C
calcines. The probability of significant differences among the means of all
other calcines is at least 95 percent.
The mean pore sizes of the Iceland spar apparently change in a different
manner. The mean pore size initially is larger than that of the limestone
and increases at approximately the same rate as that of the limestone be-
tween 750 and 950 C. A small inflection in the curve between 950 and
1100 C indicates a change in the rate of growth of the mean pore size of
the limestone. Above 1100 C, the mean pore size of the Iceland spar con-
tinues to increase with no evidence of the decrease seen in the limestones;
the difference between the mean pore sizes of the calcines at 1200 and
1300 C is not significant.
Selected cumulative frequency curves for the pore sizes of the limestone
and Iceland spar are shown in Figs. 2 and 3. The data in Fig. 2 show
' ' ' I

3000
*'~. 2 0 0 0
i,i.I
ba
w
llc
0
z
i,/.I
I 000
i
A: ICELAND SPAR ]
I I
800 I000 1200
TEMPERATURE, DEG C
FIG. 1--Mean pore size o/ 16-h calcines.
~10
~[00/ I I ~ ~ "
o
60 r~o ,3, OOl/iOO,O
-OO
c
a.
I' 200 400 600 I000 2000 4000 6000

PORE SIZE,
FIG. 2--Frequency distribution of pores in 16-h limestone calcines.
changes in pore size of the limestone calcines as indicated in the statistical

summary of these data. Between 750 and 1000 C there is a general in-
crease of pore sizes with rising temperature, but at temperatures above
1000 C this trend is reversed, and the fraction of small pores increases with
rise in calcination temperature. This trend in the formation of pores was
unexpected and in marked contrast with the behavior of Iceland spar.
The development of pores in the Iceland spar, Fig. 3, shows a continuous
increase in pore size with rising temperature of calcination. The data are
grouped around three temperature ranges and indicate a soft burn below
900 C, a medium burn below 1100 C, and a hard burn above 1100 C.
The observed decrease in porosity is consistent with the observations of
Hedin [9] who calcined Iceland spar at different temperatures.
The distribution of pores in some calcines was determined by mercury
porosimetry. Raising the temperature of calcination decreased the total
pore volume and shifted the distribution toward larger pores in all the lime-
stone calcines except that made at 1100 C (Fig. 4). This sample showed a
higher pore volume and a more even distribution of pores in the 17.5 to
0.175-/zm region than the 1000 C calcine. The Iceland spar data (Fig. 5)
show less than half the total pore volume of equivalent limestone calcines,
and almost all the pores in the 750 and 850 C calcines are less than 0.2
/zm. The total pore volume of the spar calcines decreases, and the pore
distribution shifts toward larger values with rising calcination temperature
~
ttJ
lO0! i ~ ~ ~ - - "
~
400 600 I000 2000 4000 6000 I0,000
PORE SIZE,
F I G . 3--Frequency distribution of pores in 16-h Iceland spar calcines.
except for the 1200 C calcine. The total pore volume of this calcine was
larger than that of the 1100 C Iceland spar calcine; this may have resulted
from the mechanism that caused the larger pore volume in the 1100 C
limestone calcine. The bulk densities determined by mercury displacement
are presented in Table 2.
T A B L E 2--Bulk densities o f calcines.

Prepared by shock calcination and heating for 16 h.
Bulk density determined by mercury displacement with
all pores larger than 17.5 ~m filled with mercury.
Density, g / c m 3, of Calcine
from Indicated Calcite
Calcination
Temperature, Calcitic Iceland
deg C Limestone Spar
750 . . . . . . . 1.50 1.66

850 . . . . . . . 1.51 1.78
950 . . . . . . . 1.96 ...
1 000 . . . . . . . 2.02 2.68
1 100 . . . . . . . 2.32 3.06
1 200 . . . . . . . 2.56 2.64
1 300 . . . . . . . . . . 3.03
McCLELLAN ET AL ON CALCINEDAND SULFATEDLIMESTONES 39
I I 1 I 1 I I I I 75(~
0.6
X
E
r
.~0.4 I I00
I000 -
o
f 1 2 0 0
0.2
~ R V E S DENOTE
0
I00 50 20 I0 5 2 I 0.5 0.2 0.1 0.05
PORE DIAMETER, MICRONS
FIG. 4--Pore volumes o] 16-h limestone calcines.
The crystallite sizes determined by X-ray of the shock calcines after

quenching in air are shown in Fig. 6. The calcitic limestone had larger
calcium oxide (CAD) crystallites than the Iceland spar at temperatures
below 950 C. Between 950 and 1050 C both materials show a decrease in
I I I I I I I I I I [
~ NUMBERSON CURVES DENOTE //~
0.3 TEMPERATURE,DEG C, OF CALCINATION 7501
Z
e,.
(.9
r
r
8Sq
hi 0.2
Z
.J
o
tel
f, 0.1
a.
0~
I00 50 20 I0 5 2 I 0.5 0.2 0.1 0.05
FIG. 5--Pore volumes o] 16-h Iceland spar calcines.
I I I
2000
Ul
I.--
-l
I.--
1000
n,.
Z
O- LIMESTONE
O I 1 I
800 IOOO 12OO
TEMPERATURE, DE6 C
FIG. 6--Mean crystal/ite sizes o[ 16-h calcines.
crystallite size with a minimum at 1000 C. Further rise in calcination tem-

perature effects the expected increase in crystallite size with that of the
Iceland spar reaching a maximum at 1100 C and then decreasing, whereas
the limestone calcine increases in crystallite size up to 1200 C before de-
creasing. Mayer and Stowe [10] studied a lime prepared in a rotary kiln
at 1350 C and found that the crystallite size of the calcium oxide ranged
from 0.1 /zm ( 1000 A) to 100/zm.
The decrease in crystallite size of the shock-calcined materials at tem-
peratures above 1200 C was considered a result of the experimental pro-
cedure of quenching the heated samples. Samples of both calcites were
then heated in a high-temperature diffractometer furnace over the same
temperature range so that the phase changes and crystallite growth could
be studied without quenching the samples. Several samples of each mate-
rial were ground to minus 200-mesh, and a portion of each sample was
placed on the stage, heated rapidly to 600 C, and there stabilized for 1 h.
The temperature programmer then was started, and the sample was heated
at 6 C/rain to 1400 C with continuous recording of the diffraction maxima
from which the crystallite size was determined. The results in Fig. 7 showed
that the continuously rising temperature caused a continuous increase in
crystallite size when there was no quenching, from which it was concluded
that either the shock calcination or the rapid air quenching after heating
for 16 h either shattered the crystals or highly strained them. The effects
of shock calcination are not well known, and they are difficult to reproduce
for direct X-ray study. The long period of calcination after rapid dissocia-
tion should effectively anneal the sample. Quenching, however, probably
had a major effect on the crystallite size, and attempts were made to eval-
uate its importance. A sample of each material was heated to 1400 C with
the temperature programmer and held there for 4 h, by which time crystal-
lite growth had ceased. The power was turned off, and each sample was
cooled to room temperature in less than 4 min. The X-ray maxima of the
undisturbed sample after cooling showed the same relative decrease in
crystaUite size as in Fig. 6. Quenching of the sample thus is one cause of
the inflection in the crystallite-size curves observed at high temperature.
5000t , , Jl
0
3000
N
o
Id
I.-
.J o
._1
2000 - -
>-
o
A~// o
o
IO00 - -
~ o.~" o
"~I LIMESTONE
ICELAND SPAR
I I
600 800 IOOO 1200
TEMPERATURE, DEG C
FIG. 7--Crystallite sizes o[ calcines heated continously at 6 deg C/min.
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions authori
'4.2 THE REACTION PARAMETERSOF LIME
The rapid crystallite growth, particularly at temperatures above 1100 C,

seems to follow the exponential growth curve proposed by Fischer [3]. Be-
cause of experimental limitations, however, Fischer's data were collected
at temperatures below 875 C and on quenched samples. His maximum rate
of crystallite growth is about 100 A/h, whereas values calculated from Fig.
7, with a heating rate of 6 C/min, can be more than 1000 A/h.
The reaction of the calcines with sulfur dioxide was investigated at 750,
1050, and 1200 C under two different experimental conditions: calcination
for 16 h and subsequent sulfation, and simultaneous calcination and sulfa-
tion. The calcination-sulfation tests were a logical extension of the calcina-
tion study and provided data for comparison with other fixed-bed tests.
The simultaneous calcination-sulfation reactions have been studied in
fixed-bed tests, and the combination of shock calcination with sulfation was
thought to be the most realistic laboratory simulation of dry limestone in-
jection that could be obtained without specialized equipment. The tempera-
tures of the tests were selected to produce soft-, medium-, and hard-burned
limes and hence differences in reactivity with sulfur dioxide.
The calcines for the consecutive tests were prepared by shock calcina-
tion and further heating for 16 h. The hot calcines then were subjected for
15 min to a mixture of air and 4 percent sulfur dioxide (SO~) by volume.
The samples calcined at 1050 C were exposed to the SO., for 5 and 30 min
also to measure the rate of change of the crystallite size of the reaction
product and to prepare samples at different stages of sulfation for study
in the electron microscope. The crystallites of the calcium sulfate grew
larger with rising temperature, and those on the limestone calcines were
consistently larger than those on Iceland spar, as shown in Table 3.
The samples simultaneously calcined and sulfated at 750 C for 15 min
were calcined incompletely; neither lime nor calcium sulfate was detectable
by X-ray in the treated Iceland spar, but both were present in the treated
limestone.
The sulfated samples were examined in the electron microscope in an
attempt to gather fundamental data on the reaction and to obtain a qualita-
tive comparison of the results of consecutive and simultaneous treatments.
Initially, the sulfur dioxide reacts with lime to form individual crystals of
calcium sulfate (CaSO4) that form interlocking aggregates, as shown in
Fig. 8a. On further sulfation these crystallites cover the entire surface of
the particles, and the growth of adjacent crystals results in a general
smoothing of the surface as the crystals form larger aggregates, as in Fig.
8b. These larger aggregates continue to grow and form the tight smooth
surface seen in Fig. 8c that was produced at temperatures above 1050 C.
It is apparent that, even with similar thicknesses of sulfated layers, the
TABLE 3--Properties of sulfation products.
Sulfation Conditions
Crystallite Ratio of Areas of
Temperature, Time, Size of
deg C min CaSO4, A CaCOa CaO CaSO4
SULFATION OF LIMESTONE CALCINES

750 15 1 725 0 1.00 2.20
1 050 5 2 950 0 1.00 0.35
1 050 15 2 325 0 1.00 0.42
1 050 30 2 450 0 1.00 0.68
1 200 15 3 075 0 1.00 0.13
SULFATION OF ICELAND SPAR CALCINES
750 15 1 350 0 1.00 0.48
1 050 5 1 600 0 1.00 0.05
1 050 15 2 050 0 1.00 0.03
1 050 30 1 950 0 1.00 0.35
1 200 15 2 275 0 1.00 0.07
SIMULTANEOUS CALCINATION AND SULFATION OF LIMESTONE
750 15 2 400 1.00 0.02 0.07
1 050 15 2 550 1.00 0.03 0.65
1 200 15 3 150 0 1.00 1.73
SIMULTANEOUS CALCINATION AND SULFATION OF ICELAND SPAR
750 15 0 1.00 0 0
1 050 15 2 825 1.00 0.24 0.19
1 200 15 1 950 0 1.00 0.33
p e r m e a b i l i t y of the surface changes c o n s i d e r a b l y as the surface texture

develops. O n c e the surface coating forms, diffusion processes are influenced
b y the texture.
A second general c o n s i d e r a t i o n was the m e c h a n i s m of the sulfation r e a c -
tion. T w o p r i n c i p a l m o d e l s have b e e n p r o p o s e d : c o n t i n u o u s r e a c t i o n a n d
u n r e a c t e d core. I n the c o n t i n u o u s - r e a c t i o n m o d e l , the sulfation r e a c t i o n is
thought to o c c u r t h r o u g h o u t the internal structure of the lime particles a n d
n o t just on the external surface. In the u n r e a c t e d - c o r e m o d e l , the sulfur
d i o x i d e reacts initially with the e x t e r n a l o r g e o m e t r i c surface of the lime
particles a n d forms a coating. This initial p h a s e is f o l l o w e d b y a r e a c t i o n
b e t w e e n sulfur d i o x i d e that has diffused t h r o u g h the o u t e r surface l a y e r of
c a l c i u m sulfate to the lime in the u n r e a c t e d core. T o d e c i d e which of these
m e c h a n i s m s is correct, s a m p l e s were c a l c i n e d a n d sulfated c o n s e c u t i v e l y
a n d simultaneously, and the sulfated grains were split a n d e x a m i n e d in the
electron m i c r o s c o p e . A typical result is shown in Fig. 9 in which the cal-
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions authoriz
44 THE REACTION PARAMETERSOF LiME
FIG. 8a--Individual calcium sulfate crystals Jormed in initial surface reaction of

lime and sulJur dioxide (X 16,500).
cium sulfate appears at the upper right and the unreacted lime, here
showing shrinkage cracks, is at the left. The sulfation appears to be pro-
ceeding by advance of the sulfate front, and no diffusion reaction is appar-
ent along the shrinkage cracks. The unreacted-core or shell model thus
appears to be correct.
The surface of a particle of calcitic limestone simultaneously calcined
and sulfated at 750 C for 15 min is shown in Fig. 10a. The surface is
FIG. 8b--Lime surJace coated with calcium sulfate, showing development of

smoothed surface texture as the crystals grow together (X 12,000).
covered completely with the calcium sulfate, but the individual crystals are
still discrete. The surface sulfation of material calcined at 750 C and then
sulfated is shown in Fig. 10b. The difference between the two products is
that the crystals of calcium sulfate formed by consecutive reactions are
smaller than those formed by simultaneous reactions, an observation in
agreement with the X-ray crystallite-size data on the samples.
In contrast to the well-sulfated surface of the limestone calcine, the sur-
face of Iceland spar simultaneously calcined and sulfated at 750 C in Fig.
1 la shows only slight sulfation. X-ray examination did not detect any lime
FIG. 8c--Well-reacted lime surface showing the large aggregates of intergrown

calcium sul]ate crystals (•
or sulfate in the sample, although slight reaction was shown by the electron
microscope. The surface of a particle of calcined and subsequently sulfated
Iceland spar is shown in Fig. 1 lb in which the sulfation is readily apparent,
although less than that of the limestone. The comparatively small size of
the crystals of the sulfate is in agreement with the X-ray crystallite-size
data.
At 750 C, the limestone reacts better with sulfur dioxide than does Ice-
land spar under either consecutive or simultaneous conditions. The lime-
McCLELLAN ET AL ON CALCINED AND SULFATED LIMESTONES 4.7
stone behaved about the same under the two conditions, but the Iceland
spar sulfated better when it had been calcined because the dissociation was
complete after 16 h at 750 C, whereas there was no detectable calcination
in the 15-min exposure under the simultaneous reaction conditions.
The limestone calcined and sulfated simultaneously for 5 min at 1050 C
had surfaces like those in Fig. 12a in which the reaction had proceeded to
the extent that the surface had become quite smooth and was composed
of large aggregates of crystallites. The calcined material also sulfated quite
FIG. 9 - - C a l c i u m sulfate reaction ]ront (upper right) and unreacted lime core
(left) showing shrinkage cracks in the oxide (X7,500).
48 TIlE REACTION PARAMETERS OF LIME
FIG. lOa~Sur[ace o] limestone simultaneously calcined and sul[ated at 750 C

( X 12,000).
well in 5 min, but its textural development indicated less sulfation of the
oxide than in the simultaneous reactions, Fig. 12b.
The surface of Iceland spar simultaneously calcined and sulfated for 15
rain at 1050 C, shown in Fig. 13a, indicates a greater degree of reaction
than that at 750 C. The surface is covered completely by the sulfate, and
intergrowth of crystals has smoothed the surface. An Iceland spar sample
calcined at 1050 C and then sulfated for 5 min is shown in Fig. 13b; it had
FIG. lOb--Sur]ace of calcined limestone after reaction with sulfur dioxide at

750 C (•
undergone a good surface reaction, as shown by the unusual development

of a few large single crystals of CaSO4.
The data indicate that at 1050 C the Iceland spar is beginning to sulfate
quite well but still is less reactive than the limestone. These results are in
agreement with the X-ray crystallite-size data which show that the crystal-
lites of the calcium sulfate on the Iceland spar calcines are consistently
smaller than those on limestone calcines. Samples prepared at 1200 C
FIG. l la--Surface of Iceland spar simultaneously calcined and sulfated at

750 C (X12,000).
were generally too featureless to warrant presentation, although the general

conclusions are applicable in that region with one important exception.
Thermal etching of the sulfation product at 1200 C indicated simultaneous
formation and decomposition of the calcium sulfate.
A comparison of the reactivities of the two calcites with sulfur dioxide
can be made from the areas of the X-ray maxima. The relative area ratios
for some sulfated samples, presented in Table 3, show that limestone cal-
cines react with sulfur dioxide better than the Iceland spar calcines under
FIG. 11b--SurIace o] calcined Iceland spar alter reaction with sullur dioxide
at 750 C (•
the conditions tested. Calcined materials showed a general decrease in re-

activity with sulfur doxide as the temperature was raised. When simul-
taneously calcined and sulfated, both materials reacted better at the higher
temperatures because of the increased degree of calcination during the
short 15-min retention time. The Iceland spar sample calcined at 1050 C
shows a relatively large amount of unreacted calcium oxide compared to
the limestone sample prepared under the same conditions. The Iceland spar
oxide must be inactive because of extensive recrystallization of the lime,
FIG. 12a---Surface o/ limestone simultaneously calcined and sulfated at 1050 C

( X 12,000).
or because its poor pore size distribution causes it to be unavailable for

reaction, or because of both of these interrelated factors. The 1200 C
samples were completely calcined in the 15-min calcination-sulfation
experiments.
Discussion of Results
All the isothermal shock-calcination data show that the properties of the
calcined products of the limestone and Iceland spar are distinctly different,
FIG. 12b--Sur[ace o[ calcined limestone alter reaction with sul]ur dioxide at

1050 C (•
even when prepared under the same experimental conditions. The only
significant difference in the starting materials was the crystallite size of the
uncalcined stones. The mean crystallite size of the Iceland spar was 7125 A
and that of the limestone 3875 A. The higher thermal stability of the Ice-
land spar undoubtedly reflects its larger crystallite size. The low-tempera-
ture calcinations (below 950 C) completely dissociated the spar, but only
very slowly, and produced a lime with small pores and small crystallite
sizes. The unfavorable pore-size distribution would require that reactions
5zj. THE REACTION PARAMETERSOF LIME
FIG. 13a Sur]ace of Iceland spar simultaneously calcined and sulfated at 1050 C
( X 12,000).
of lime with sulfur dioxide take place as the gas diffused into the small
pores or through the sulfate layer formed during the early stages of
sulfation.
The limestone calcines prepared at temperatures below 950 C had
larger crystallite sizes than the spar calcines but tended to have larger pore
volumes (generally about twice as large) and a more favorable distribution
of pore sizes. Potter [11] and others have shown that pores between 17.5
and 0.3 /zm are the most favorable for reaction with sulfur dioxide. It
FIG. 13b---Surface o] calcined Iceland spar alter reaction with sul[ur dioxide at
1050 C (•
appears that smaller pores require diffusion times too long to be of practical
significance in actual injection tests.
During calcination at temperatures below 1000 C, the pores grow by the
coalescing of small pores to form larger pores, as can be seen in Fig. 14a.
This coalescing of pores causes the large pores to grow at the expense of
small pores, as can be seen by the porosimetry data (Figs. 4 and 5), and
reach a maximum at about 1000 C, as shown in Fig. 14b. Between 1000
and 1100 C, both materials show a decrease in crystallite size and a mini-
mum in total pore volume. The coincidence of these changes in physical

properties is interpreted as the end of sintering of the oxide, as described
by Hedin [9], and the beginning of recrystallization reactions. The small
crystallites initially formed during calcination have grown by encompassing
oxide forming at sites within a limited domain. The size of the region
FIG. 14a--Scanning electron micrograph o] limestone calcined at 750 C, showing

coalescing pores (X7,000). Insert (upper left) shows replicated detail o[ pore evolu-
tion (X 12,000).
increases with rising temperature and gives rise to larger crystallites. This
type of growth reaches a maximum at about 950 C, and a second type of
growth begins that is characterized initially by the development of smooth
areas containing large oxide crystals that show evidences of growth spirals
and oxide crystal morphology (Fig. 15a). As temperature continues to
FIG. 14b--Scanning electron micrograph o] limestone calcined at 1000 C, show-

ing maximum coalescence o] pores (X2,640). Insert (upper left) shows replicated
detail o[ surface (X12,000).
FIG. 15a--Developing calcium oxide crystals, showing growth spirals and local
smoothing of the surface (•
rise, geometrically outlined pores (Fig. 15b) and massive oxide single
crystals develop (Fig. 15c), as evidenced by the exponential growth of
crystallite size at temperatures above 1100 C noted in continuously heated
samples.
Fischer [2] observed that his limestone calcines showed a minimum
porosity at 1200 C, an increased porosity at 1320 C, and then a decrease
in porosity. In this study, the limestone showed a minimum porosity at
1000 C and the spar a minimum at 1100 C. The pores in these samples
are distributed so that big pores have become quantitatively the most sig-
McCLELLAN ET At ON CALCINED AND SULFATED LIMESTONES 59
FIG. 15b--Geometric pores developed during recrystallization of calcium oxide

( • 12,000).
nificant, and the small pores are those interstitial or geometric pores that
form as the calcium oxide crystals grow. In the electron microscope study,
the emphasis is upon these small pores, so that the decrease in mean pore
size observed in the limestone calcined at temperatures above 1000 C is
consistent with the interpretation of the calcination process presented pre-
viously. A final decrease in porosity occurs as Fischer [2] reported, re-
emphasizing the insignificant contributions the small pores make to the
total pore volume in calcines that are largely recrystallized.
The Iceland spar calcines show trends different from those of the lime-
stone calcines, and their interpretation is less apparent. The principal dif-
FIG. 15c~Massive calcium oxide single crystals formed by recrystallization

(• 12,000).
ference between the high-temperature recrystallizations of Iceland spar and

of limestone appears between 1050 and 1100 C where the relative crystal-
lite size of the oxide produced from the limestone increases 10 percent,
which is only slightly greater than the mensuration error, whereas the crys-
tallite size of the Iceland spar oxide increases more than 60 percent. Over
the same temperature range the mean pore size of the Iceland spar calcine
increases to 1882 A but that of the limestone calcine decreases from
2182 A at 1000 C to 1958 A at 1100 C. These data indicate that Iceland
spar calcined for 16 h at 1100 C is almost completely recrystaUized but the

limestone is not. This interpretation is supported by the physical appear-
ance of the surfaces of the samples as well as by a minimum in the total
pore volume. In Fig. 16a the limestone shows some straight-edged geo-
metric pores characteristic of samples undergoing recrystallization but only
minor growth spirals and little development of oxide crystal morphology.
In contrast to the limestone, the Iceland spar surface, shown in Fig. 16b,
shows good growth spirals and marked development of crystal morphology
in addition to numerous geometric pores.
The limestone crystallite size is maximum in the 1200 C calcine. The
limestone recrystallizes over a wider range of temperature (I000 to 1200
C) and forms smaller crystallites than does the Iceland spar. No physical
evidence has been gathered that can explain this difference, but it must be
related to the nucleation of the oxide during recrystallization and to the
texture of the calcine formed.
The final decrease in crystallite size of the 16-h calcines can result from
too rapid cooling of the samples. In an attempt to confirm this observa-
tion, samples were cooled very slowly in the tube and X-ray furnaces from
1400 C to near room temperature. All these samples showed a very re-
producible decrease in crystallite size, as shown in Fig. 6. No satisfactory
explanation for this observation has been proposed, but the effect is real.
The sulfation reaction of lime with sulfur dioxide has been described in
terms of continuous-reaction and of unreacted-core models. Borgwardt
[12] has presented data for the continuous-reaction model that indicates
that the sulfation reaction takes place throughout the interior of the par-
ticle and not just on the outer surface. The data of Hatfield and Kim [13]
support the unreaeted-core or shell-formation model as the mechanism of
the sulfation reaction. As indicated in Fig. 9, the electron microscope
studies show that in a fixed-bed test the reaction proceeds by the unre-
acted-core mechanism. Examination of a number of particles shows that
the shell seldom is thicker than 70 /xm, even after exposure for several
hours, and the crystallite size of the sulfate is generally larger at the outer
surface than at the reaction front. Calcines treated with sulfur dioxide form
such an impervious surface coating that they can be stored for months at
room temperature with no detectable hydration or recarbonation of the
lime in the unreacted core (Fig. 17).
The limestone calcines had a greater reactivity with sulfur dioxide than
the Iceland spar calcines under all the experimental conditions tested. The
relative difference in reactivity may be a function of the difference in cal-
cination behavior, the pore volume and size distribution of the calcine, and
the temperature at which recrystallization is complete. The data in Table 3
FIG. 16a--Sur]ace of limestone calcined at 1100 C, showing straight-edged pores

and growth spirals ( X 12,000).
show that at 750 C the precalcined limestone is more than four times as
reactive as the Iceland spar calcine. At 1050 C, the reactivity of the Ice-
land spar calcine has dropped by a factor of ten and that of the limestone
calcine has dropped by a factor of five. This decreased reactivity probably
indicates a higher degree of recrystallization of the Iceland spar calcine.
At 1200 C, both calcines lose reactivity.
The difference between the two materials is especially marked in the
simultaneously calcined and sulfated samples. After 15 min at 1050 C in an
McCL[LLAN ET AL ON CALCINED AND SULFATED LIMESTONES 63
FIG. 16b--Surface of Iceland spar calcined at 1100 C, showing well-developed

geometric pores and growth spirals ()< 12,000).
atmosphere containing 4 percent SO._,, the ratio of areas CaSO4:CaCO3:

CaO is 0.19:1.00:0.24 for the Iceland spar and 0.65:1.00:0.03 for the
limestone. The lime produced from the Iceland spar does not react with
sulfur dioxide as well as the lime produced from the limestone, as can be
seen by comparing the relative areas of CaS04 and CaO in the three-
component samples. This may reflect diffusion problems resulting from the
pore-size distribution in the samples, or from the recrystallization of the
lime which decreases its reactivity.
FIG. 17--Scanning electron micrograph of impervious calcium sulfate coating on

calcined limestone surface ( X 2,850).
Finally, it should be noted that although both stones were screened to

minus 20 plus 24-mesh at the beginning of the experiment, no attempt was
made to control the particle size of the limes. The Iceland spar showed
exceptional physical stability on heating, and there was practically no de-
crepitation of the material on shock calcining at any temperature. The
limestone dusted badly during calcination at all temperatures. The surface
area contributed by the decrepitation of the limestone was probably a fac-

tor in its higher reactivity with sulfur dioxide and may indeed be a desir-
able property of stones selected for injection.
Conclusions
The physical and chemical properties of a calcine are influenced m a r k -
edly by the crystallite size of the parent limestone. The high thermal sta-
bility of Iceland spar reflects its relatively large crystallite size, and its
calcines react slowly with sulfur dioxide.
In addition to the decomposition of the calcium carbonate, calcination
effects a recrystallization of the resultant calcium oxide which is accel-
erated by rising temperature and which decreases the reactivity of the
calcine with sulfur dioxide.
Sulfation of lime takes place in two stages: reaction of sulfur dioxide
and oxygen with the exposed surface of lime, followed by diffusion of the
gaseous reactants through the resultant shell of calcium sulfate to the core
of unreacted lime. Pores in the calcine smaller than about 0.1 /zm do not
admit sulfur dioxide rapidly enough to have significant effect on the sulfa-
tion reaction at short retention times.
Calcines react best with sulfur dioxide at temperatures below 1050 C,
but simultaneous calcination and sulfation, which is required when
powdered limestone is injected into power plant furnaces, occurs best at
temperatures of 1050 C and above.
References
[1] Hyatt, E. P., Cutler, I. B., and Wadsworth, M. E., "Calcium Carbonate Decom-
position in Carbon Dioxide Atmosphere," Journal of the American Ceramic
Society, Vol. 41, No. 2, 1958, pp. 70-74.
[2] Fischer, H. C., "Calcination of Calcite. I. Effect of Heating Rate and Tempera-
ture on Bulk Density of Calcium Oxide," Journal o/ the American Ceramic
Society, Vol. 38, No. 7, 1955, pp. 245-251.
[3] Fischer, H. C., "Calcination of Calcite. II. Size and Growth Rate of Calcium
Oxide Crystallites," Journal o/ the American Ceramic Society, Vol. 38, No. 8,
1955, pp. 284-288.
[4] Goldsmith, J. R. and Graf, D. I., "Relation Between Lattice Constants and
Composition of the Ca-Mg Carbonates," American Mineralogist, Vol. 43, 1958,
pp. 84-101.
[5] Rau, R. C., "Routine Crystallite-Size Determination by X-ray Diffraction Line
Broadening," Advances in X-ray Analysis, Vol. 5, 1962, pp. 104-116.
[6] Klug, H. P. and Alexander, L. E., X-Ray Diffraction Procedures, Wiley, New
York, 1954, pp. 494-511.
[7] Azaroff, L. V., "X-Ray Diffraction Methods," 56th Norelco X-Ray Analytical
School, Philips Electronics Instruments, Mr. Vernon, N. Y., 1967, p. 3.
[8] Snedecor, G. W., Statistical Methods, Iowa State College Press, Ames, Iowa,
1956, p. 91.
[9] Hedin, R., "Investigation of the Lime-Burning Processes," Handlingar Proceed-

ings, No. 32, Stockholm, Sweden, 1961.
Lime," Azbe Award No. 4, National Lime Association, Washington, D. C., 1964.
[11] Potter, A. E., "Sulfur Oxide Capacity of Limestones," U.S. Public Health
Service Symposium on Limestone-Sulfur Dioxide Reaction Kinetics and Mecha-
nisms, National Air Pollution Control Administration, Cincinnati, Ohio, 1969,
(abstract).
[12] Borgwardt, R. H., "Kinetics of Reaction of SO2 with Calcined Limestone,"
U.S. Public Health Service Symposium on Limestone-Sulfur Dioxide Reaction
Kinetics and Mechanisms, National Air Pollution Control Administration, Cincin-
nati, Ohio, 1969, (abstract).
[13] Hatfield, J. D. and Kim, Y. K., "Limestone Calcination and Sulfation Investiga-
tions," U.S. Public Health Service Symposium on Limestone-Sulfur Dioxide
Reaction Kinetics and Mechanisms, National Air Pollution Control Administra-
tion, Cincinnati, Ohio, 1969, (abstract).
T. Ritchie 1
Influence of Lime in Mortar on the

Expansion of Brick Masonry*
REFERENCE. Ritchie, T., "Influence of Lime i n M o r t a r o n the Expan-

sion o f B r i c k Masonry," The Reaction Parameters of Lime, A S T M STP
472, American Society for Testing and Materials, 1970, pp. 67-81.
ABSTRACT: Mortars containing normally hydrated dolomitic lime caused

greater expansion of brickwork piers than other mortars. Because the
expansion of brickwork was much greater in the vertical direction than
horizontally, however, and because the expansion was inhibited greatly by
a relatively slight load, mortars containing normally hydrated dolomitic lime
did not damage the brickwork from their expansion. The results of this
study offer an explanation for the satisfactory performance of brick buildings
with mortars containing normally hydrated dolomitic lime even though
such mortars have great capacity for expansion.
KEY WORDS: mortars (materials), masonry, expansion, evaluation,

tests, calcium oxides, brick structures, cements, mechanical properties
Normally hydrated dolomitic lime, produced in the Toronto, Ontario,

area since before 19202 and extensively used as an ingredient of cement:
lime:sand mortars for masonry, has the effect of rendering such mortars
grossly expansive on autoclaving, undoubtedly because in the process of
preparing the lime some of its magnesium oxide remains unhydrated, later
to hydrate, accompanied by great expansion, in the autoclave. As the ex-
cessive expansion of cements and mortars on exposure to steam at high
pressure and temperature in the autoclave generally is considered to indi-
cate their excessive expansion in service, this study was undertaken to de-
termine if mortars containing normally hydrated dolomitic lime cause
* This paper is a contribution from the Division of Building Research of the
National Research Council of Canada and is published with the approval of the
Director of the Division.
1Research officer, Building Materials Section, Division of Building Research,
National Research Council of Canada, Ottawa, Ont., Canada.
-~Ontario Department of Mines, Annual Report, Vol. 34, Part 1, 1925. (This
report gives production figures for hydrated lime in 1920 and states that four lime
plants in Ontario, three in the Toronto area, were equipped to produce hydrated
lime, the major portion of the production being consumed by the building trades.)
67
Copyrightby
Copyright 9 ASTM
1970 by
(all rights reserved); Wedwww.astm.org
Aug 1 12:04:31 EDT 2012
mortar and brickwork to expand, and, if so, to what extent such expan-
sion damages the brickwork and hence the building it forms.
Brick Piers
The dimensional changes of brickwork were studied by using 26 brick
piers constructed with nine masonry mortars of various compositions and
amounts of autoclave expansion and three types of bricks. Each pier was
about 3 ft wide, 1 ft thick, and 3 ft high, and was designed as a hollow
structure of walls one brick (approximately 4 in.) thick. The pier was
constructed on a brick foundation almost 1 ft high and was separated from
it by a flashing material. The top of the pier was covered by a roof with
a slight overhang.
On both the east- and west-facing walls of the piers metal pins were
used to measure vertical and horizontal dimensional changes. These pins,
spherically ended and projecting about 1 in. from the brick surface, were
fastened in the bricks before the walls were laid; they were approximately
16 in. apart horizontally and 17 in. apart vertically. To measure the dis-
tance between the pairs of pins a gage was used that consisted of a microm-
eter head, reading to one ten-thousandth part of an inch, mounted in a
frame of Invar metal. The measurements of the piers were compared with
those of an Invar standard to determine pier dimensional changes. Initial
readings for each pier were taken as soon as possible after construction
was completed; frequent readings were taken in the first few weeks follow-
ing construction, but then were taken only twice each year, in the summer
months.
Bricks
Of the three types of bricks used to construct the piers two were clay
(A and B) and one was concrete (C). Their absorption, strength, and
durability properties are listed in Table 1. Measurements also were made
of the length changes of the bricks using a Whittemore gage and metal
reference pins attached to both faces of the brick. Two samples of each
brick were stored under three different conditions: indoors at 50 percent
relative humidity and 73 F; indoors at 100 percent relative humidity and
73 F; and outdoors exposed to rain and snow.
The length changes of the bricks in six years are shown in Fig. 1. The
two clay bricks stored at 50 percent relative humidity gradually ex-
panded while the concrete brick shrank. Storage at 100 percent relative
humidity caused slightly greater expansion of the clay bricks, but the con-
crete brick reversed its previous behavior and expanded. In six years the
clay bricks stored in high humidity expanded about 0.03 percent, while
RITCHIE ON INFLUENCEOF LIME IN MORTAR 69
TABLE 1--Range of values of properties of the bricks (20 samples tested for water
absorption and 5 samples tested for strength and durability).
Brick A Brick B Brick C

Property (Clay) (Clay) (Concrete)
Initial rate of absorption,

g/min/30 in ~. . . . . . . . . . . . 14.9 to 32.4 50.0 to 77.4 53.8 to 166.7
Absorption, ~o, 24 h . . . . . . . 5.7 to 8.5 9.8 to 13.1 6.7 to 10.2
Absorption, 7o, boil . . . . . . . 7.9 to 10.1 13.0 to 16.0 10.2 to 12.6
Saturation coefficient . . . . . . 0.73 to 0.84 0.74 to 0.82 0.64 to 0.81
Compressive strength, psi.. 11,600 to 18,100 7,000 to 11,700 2,600 to 2,900
Weight loss after 50 freeze-
thaw cycles, 7o . . . . . . . . . . 0.01 to 0.08 0.14 to 0.25 broke between 35
and 50 cycles
the expansion of the concrete brick was approximately 0.1 percent. All the
samples stored outdoors expanded, the concrete brick even more than it
had in storage at 100 percent relative humidity. After three years' outdoor
exposure both clay bricks showed considerable cracking indicating the
effects of frost action.
Mortars
The compositions of the nine mortars used to construct the piers are
given in Table 2. Four of the mortars were prepared from masonry
O. 20
I I I I [ I
Stored at 50% RH Stored at 100% RH Stored Outdoors
73 F 73F
0.15 - Brick C - ~
Brick~
O. l O -
c
o
~Cracked
0"05 I- Brick A~
0 - - -
Brick B
" 0.05 [ Briclk C-/ I
I I I I
,,, 0 lOOO 2000 0 1000 2000 0 1000 2000 3000
9L..
- bays Days Days
FIG. 1--Length changes o] bricks under various storage conditions.
T A B L E 2--Mortars used in the piers.
Mortar Proportions, Autoclave

No. Constituents by v o l u m e Expansion,
1. MC: S 1: 3 0.08
2. MC: S 1: 3 0.10
3. PC:L:S 1:1:6 0.13
5. L:S 1:3 0.10
8. L: S I :3 no test
9. M C : S" 1 : 1 : 6" 4.6
10. MC:S b 1:2:8 b 5.0
11. PC:clay:sand 1 : 1:4-1/2 0.09
12.. P C : S q- organic additive 1 : 3 + 15 7o 0.09
NOTE--MC = m a s o n r y cement,
S = sand,
PC = portland cement, a n d
L = lime.
a M a s o n r y c e m e n t c o m p o s e d o f portland c e m e n t a n d normally hydrated dolomitic lime;

with s a n d it produces m o r t a r o f c o m p o s i t i o n 1 : 1 : 6 P C : L : S .
b M a s o n r y c e m e n t c o m p o s e d o f portland c e m e n t a n d normally hydrated dolomitic lime;
with s a n d it produces m o r t a r o f c o m p o s i t i o n 1 : 2 : 8 P C : L : S .
cements; two of them (in mortars Nos. 1 and 2) were of the portland
cement: limestone type and their mortars were low in autoclave expan-
sion, as shown in the table. The other two masonry cements (in mortars
Nos. 9 and 10) were composed of portland cement and normally hydrated
dolomitic lime blended together in such proportions that when these
masonry cements were mixed with sand the resulting mortars were equiv-
alent in volume proportions to 1 : 1 : 6 cement :lime: sand and 1 : 2: 8 cement:
lime:sand; these mortars were relatively high in autoclave expansion (ap-
proximately 5 percent), as indicated in the table.
Mortar No. 3, a cement:lime:sand mortar of volume proportions 1 : 1:6,
was prepared from lime obtained as putty from the slaking of quicklime;
this mortar was low in autoclave expansion. The same lime putty was used
to prepare mortar No. 5, a lime:sand mix with no cement; the autoclave
expansion of this mortar was also small. A second lime:sand mortar (No.
8) was prepared from normally hydrated dolomitic lime obtained from the
plant which produced the masonry cement for mortars Nos. 9 and 10. Bars
of this lime:sand mortar could not be prepared for autoclave tests because
of the difficulty in de-moulding them.
Two additional mortars of small autoclave expansion were included in
the study. Mortar No. 11 was composed of portland cement, a proprietary
RITCHIE ON INFLUENCE OF LIME IN MORTAR 71
clay material, and sand, while mortar No. 12 was prepared from portland
cement and sand with a proprietary organic additive designed to produce
high strength of bond between brick and mortar.
In addition to the bars for autoclave expansion tests, mortar bars were
prepared for measurements of length changes. Some of them were stored in
a room at 50 percent relative humidity and 73 F, while others were stored
outdoors in a container with open sides but covered on top in such a way
that the bars could not be wetted by rain or snow. All the mortar bars
shrank under both storage conditions, the amount of shrinkage for each
mortar being approximately the same. In six years the shrinkage among
the various mortars varied from 0.07 to 0.20 percent.
Dimensional Changes of the Piers

Six years after their construction all the piers had expanded, as shown
in the graphs of Fig. 2, which refer to the changes in the vertical dimension
of the west walls of the piers. In a few cases, particularly piers of mortar
No. 5, a lime:sand mortar, there was an initial vertical shrinkage of the
brickwork which was recovered within the first year and was followed by
expansion.
With the exception of the piers of mortars Nos. 8, 9, and 10, which con-
tained normally hydrated dolomitic lime, the same general pattern of ex-
pansion took place and was generally of the same magnitude. The maxi-
mum vertical expansion of all these piers did not exceed 0.05 percent after
six years. Much greater vertical expansion occurred in the piers of mortars
Nos. 8, 9, and 10; the least vertical expansion was about 0.12 percent,
while the maximum was about 0.48 percent.
Expansion of the piers in the horizontal direction was considerably less
than that in the vertical direction. A comparison of the expansions in these
two directions, given in Fig. 3, clearly shows the difference; the points
plotted refer to the maximum amount of expansion, vertically and hori-
zontally, that has taken place in each pier in the six years since its con-
struction. In several cases the vertical expansion was three times as large
as that which occurred in the horizontal direction; in one case it was more
than five times as great.
Previous studies 3, 4 have shown that a restraining force of small magni-
tude greatly affects the amount of expansion and shrinkage of masonry
mortars. The difference in horizontal and vertical expansions of the brick
piers can be attributed to the restraining effect of the bond between brick
"~Ritchie, T., "Effect of Restraining Forces on the Expansion of Masonry Mortars,"
Materials Research & Standards, Vol. 4, No. 1, Jan. 1964, pp. 15-19.
' Ritchie, T., "Effect of Restraint on the Shrinkage of Masonry Mortars," Materials
Research & Standards, Vol. 6, No. 1, Jan. 1966, pp. 13-16.
0.5
I I I I
Piers of B r i c k A
0.4
i
0.3
M o r t a r 180
9~ 0 . 2
got
Lo M o r t a r s 1, 2, 3, 5]
O. 1 ) I I I 11,12
c
o
0.4 i i I 1
== 0.3 Piers of B r i c k ~.....~ M o r t a r 10 -

E
r J Mortar 9 _
9;, 0.2
m
u
50.1
•
M o r t a r s 1 ,2 ,3 .5 J
c:
0.1 I I I I 11, 12 -
0.3
I I I I
Mortar 8
'~ 0.2 _ Piers of B r i c k C Mortar 9 -
go. 1 - tar 10 -
20
M o r t a r s 1, 3, 5 J
O. 1 I I I I 11, 12
0 500 i000 1500 2000 2500
Time (Days) After Construction of Pier
F I G . 2 - - V e r t i c a l movements o] west walls of piers.
and mortar. Figure 4, which represents a vertical section through brick

masonry, shows that each brick is bonded to the surrounding mortar. If the
mortar of the horizontal joints attempts to expand it is restrained in the
horizontal direction because of the bond with the brick, but it is not re-
strained in the vertical direction; the mortar of the horizontal joints, there-
fore, is free to expand vertically but not horizontally. The mortar of the
vertical joints, similarly bonded to the brick, cannot expand in the vertical
direction nor can it expand across the width of the joint as it cannot dis-
place the bricks on either side of it because of their bond to the horizontal
mortar joints.
The piers of mortars Nos. 8, 9, and 10 containing normally hydrated

dolomitic lime expanded horizontally (as they had vertically) more than
the piers of the other mortars. The maximum horizontal expansion of the
piers of these three mortars was 0.114 percent in six years, whereas the
maximum horizontal expansion of the other piers was only 0.056 percent.
If, in order to allow for these maximum expansions of 0.114 and 0.056
percent in a wall, a vertical expansion joint of V2 in. width was incor-
0.50
I I I I
East W a l l s I West W a l l s 9 I
I I
l I
I I
I I
I I
I I
0.40 I I
I I
I I
I I
I I
E I
"I I
E I "
tD I !
0.30 I I -
I I
I I
9 I I
I !
I I
I 9
x I !
I % ! _
~' O. 20
I I
o/o 9 I
I I 9
I I 9
I /' I //
/ I /
I /
/ I / /
9 to / 1~ /
0.10 / ! // --
/
I I /
I /
91 //
",9 11'/
.,4 \
L i n e of #' 9 , / 9 L i n e of
Equal ~," Equal
.,Z Expansions / Expansions
o L I /" I L
0 0.05 0.10 0.15 0 O, 05 O. 10 0. 15
Horizontal Expansion, %, Maximum
F I G . 3--Relationship between vertical and horizontal expansion (maximum values
in six years).
Brick
Mortar
li lit t l
Elevation
of Brick
Wall
Brick Brick
It ll I M?tit
Brick
Represents Brick: Mortar Bond
No Expansion in Direction of Arrows
Expansion Occurs in Direction of Arrows
FIG. 4--Influence o] brick: mortar bond on vertical and horizontal expansion o]

mortar.
porated into the brickwork it is calculated that such a joint would have to
be provided every 36 ft in the wall where the expansion was 0.114 percent,
and every 74 ft in the wall where the expansion was 0.056 percent.
Influence of the Direction of Exposure o n Expansion

Measurements of dimensional changes were made on the east- and west-
facing walls of the piers, but as these walls were linked by short adjoining
walls the movements of the one undoubtedly influenced the other. The ex-
pansions of the east- and west-facing walls of each pier (maximum
amount measured in six years) are compared in Fig. 5; the scatter of re-
sults and the lack of any consistent pattern make it impossible to define
the influence of direction of exposure on expansion.
Influence of the Brick on the Expansion of the Piers

The expansion which took place in the three bricks during their long-
term storage indicated that the bricks would have an effect on the expan-
sion of the piers. As the horizontal movement of a pier was probably more
influenced by the brick than its vertical movement, horizontal expansion

was used in an attempt to determine the influence of the bricks on the ex-
pansion of the piers. The values of the maximum horizontal expansions
measured in all the piers are plotted in Fig. 6 which illustrates eight groups
of three piers, each group representing one of the mortars used with the
three bricks. In an additional group (of mortar No. 2) only two bricks
were used, and this group was not considered in regard to the bricks'
influence on expansion.
0.50
I [ l I /'
x" Line of Equal //
Expansion%//
0.40
-.7
/
/
/e
"~ 0.30
/
/
/
o 9 /
'~ 0 . 2 0 ~ 9
9 /
/o
/
"~ 0 . 1 0 /
9 /
L, I
O. i0 O. 20 0.30 0.40 0.50
Vertical Expansion, East Wall, Max,

I
0.12 I I I I I /~
Line of Equal /
. 0.10 Expansion--, / / -
/
~ 0.08 /
/
/
/
E 0.06 9 /
9 /
~- 0.04
o
0.02
.,t.*
/
/
o 0 1 I I I )
0.02 0.04 0.06 0.08 0.10 0.12
Horizontal Expansion, East Wall, Max, %
F I G . 5--Comparisons of expansion o/ east and west walls.
---'m
m
0.12
c:--
0.08
= E"
o 0.04
• m
E
0
'-" ~ B r i c k
M0rta
BC AB
I 2
ABC ABC
3 5
ABC ABC ABC
8 9 10
l In Inn
ABC ABC
ii 12
(m . 0.12
o un
0.08
E -
111 !
o E 0.04
m ~
= E
Q.X
x ~ 0
Brick ABC AB ABC ABC ABC ABC ABC ABC ABe
Mortar I 2 3 5 8 9 10 11 12
FIG. 6---Influence of the brick on the horizontal expansion of the piers.
Figure 6 indicates that the influence of the brick was not consistent but
appeared to depend on the direction of exposure of the wall. For the east-
facing walls, in five of the eight groups of piers, the maximum expansion
occurred in piers of Brick B, but for the west-facing walls, in seven of the
eight groups of piers, the maximum expansion occurred in piers of
Brick C.
Influence o f a S t r u c t u r a l L o a d o n E x p a n s i o n
When measurements of the piers indicated that larger vertical expan-
sions were taking place in those piers of the three mortars containing nor-
mally hydrated dolomitic lime than in the others, additional piers were
built with these mortars to determine the influence on their expansion of a
load applied to them soon after construction. In this later study Brick A
was used to construct six piers, two each of mortars Nos. 8, 9, and 10.
One of the piers was unloaded (corresponding to the original piers), while
the other had a vertically acting load applied to it that provided a pressure
of 15 psi on the brickwork.
The load considerably reduced the vertical expansion as indicated by
Fig. 7 which shows the vertical movements of the west wall of each of the
O. 25
I I I I I
Z
0.20
Mortar 9
No Load--~ / Mortar 8 _.
| 0.15 - Mortar 10 Loadedq ~....,.....-~ oN Load~ .-~'"
NO Load~ ~ Loaded~ ~. ~
~ o. lo
E
~ o. o5
u x
> 0
0.05 I I I I I
200 d00 600 800 1000 1200
Days After Construction of Pier
FIG. 7--Influence of load on vertical expansion of piers.
six piers in the three years after construction. The pressure on the brick-
work had a different effect on various piers. The ratio of the amounts of
expansion of the unloaded and loaded piers was about six for the pier of
mortar No. 8 (composed of lime and sand), it was about three for the pier
of mortar No. 10 (containing two parts lime to one part cement), and about
two for the pier of mortar No. 9 (equal volumes of lime and cement).
The vertically applied pressure on the brickwork reduced the horizontal
expansion (Fig. 8), but the effect was much less pronounced than for the
vertical expansion.
Chemical Effects on Mortar Expansion

As the expansiveness of mortars containing normally hydrated dolomitic
lime appears to be caused by their magnesia content and because magnesia
reacts with chloride compounds to form magnesium oxychloride, a few
tests were made to determine the effect of chloride additives in mortar on
their expansion.
Certain bars of mortar No. 9, prepared from the masonry cement con-
taining equal parts by volume of portland cement and lime, had an auto-
clave expansion of 2.5 percent. Companion bars, some made with mag-
nesium chloride and others with calcium chloride dissolved in the mixing
water in amounts of 4.8 and 5.5 percent of the weight of the masonry
cement, had reduced autoclave expansions of 0.35 and 0.16 percent,
respectively.
Vertical Horizontal
0.30
----
r 0.25 -
on
a~
0.20 -
E
0.15
"x
m
~" 0.10
o
c~.
x 0.05
o
Mortar 8
El
I
10 9 8 10 9
Composition 1:3 1:2:8 1:1:6 1:3 1:2:8 1:1:6
(by v o l u m e ) L:S C:L:S C:L:S L:S C:L:S C:L:S
(L = Lime, C = P o r t l a n d Cement, S = Sand)
I 1 No Load r ~ Loaded
F I G . 8--Effect of load on horizontal and vertical expansions of piers.
Additional tests were made on brick piers, three of which (two of mortar
No. 9 and one of mortar No. 10) were constructed of mortars containing
calcium chloride and magnesium chloride additions. The vertical expan-
sions of these piers are shown in Fig. 9 beside the expansions of piers of
the same mortars without the additives. The values plotted represent the
maximum expansions of the piers in three years.
Even though the autoclave expansion of mortar No. 9 was much reduced
by additions of calcium and magnesium chlorides, the expansion of the
piers of mortar No. 9 containing these additives was little reduced over that
of the pier of the same mortar without the additives. The pier of mortar
No. 10 containing calcium chloride, however, underwent much less ex-
pansion than its companion pier of the same mortar without the chloride
additive.
Performance of Buildings
Examination of a number of buildings constructed of mortar containing
normally hydrated dolomitic lime failed to reveal indications of masonry
Piers of Mortar 9 Piers of Mortar 10

0.30
...."
'~ 0.25
o
_ o
- 0.20
E
c~a
.1
x :~ < 7`
0.15 -= 7"
o
o
u~
0.10
L
0.05
1
(*) 5.5% of Weight of Masonry Cement
(**) 4.8% of Weight of Masonry Cement
FIG. 9.--Effect of chloride additions to m o r t a r on vertical expansion of piers.
distress such as cracking, displacement, or bulging, any of which could be

attributed to the expansion of the mortar. Some of the buildings examined
were 30 years old.
Conclusions
Three mortars containing normally hydrated dolomitic lime, two of which
were shown to be and the third assumed to be highly expansive on auto-
claving, produced a greater amount of expansion of brickwork piers than
six other mortars that expanded less on autoclaving.
The effect on the brickwork of the expansion of the three mortars was,
to a considerable degree, directional in that the piers expanded more in
the vertical direction than in the horizontal. This directional difference was
attributed to the restraint on the horizontal but not vertical expansion of
the horizontal mortar joints, the restraint resulting from the bond between
the mortar and the brick. A load applied to the brickwork reduced the
amount of expansion especially in the vertical direction; a relatively slight
pressure (15 psi) was sufficient to reduce significantly the vertical expan-
sion of the brickwork.
The results of this study, when applied to the practical situation of the
brick masonry walls of buildings, appear to offer an explanation for the
successful use of mortars containing normally hydrated dolomitic lime.
Even though such mortars tend to expand in service, the resulting direc-
tional nature of the expansion and the fact that the expansion is inhibited
by relatively slight loads on the brickwork renders the expansion non-
damaging to the structure. It should be noted, too, that mortar alone does
not determine the dimensional changes of brickwork; the three bricks used
in constructing the piers of this study underwent long-term expansion and
so must have contributed to the expansion of the piers.
The influence, if any, of the direction (east-west) of exposure of brick
walls on their expansion was not established in this study because the piers
were poorly designed to measure possible directional effect. The addition
of calcium and magnesium chloride to mortars containing normally
hydrated dolomitic lime reduced the expansion of the brickwork.
DISCUSSION
Byron Powell 1 (written discussion)--This paper adds to the results

of the author's long term study of the effects of each of the components in
masonry construction.
In prior papers the author has shown the effects of: (1) dimensional
instability or unsoundness of the various brick units and mortars, (2) the
effects of restraining forces on expansion of masonry mortars, and (3) the
effect of restraining forces on shrinkage of masonry mortars.
In this paper the author concludes that mortars made with normal
hydrated lime contribute to but are not totally responsible for expansion of
brickwork. He further concludes that mortars containing normal hydrated
lime show satisfactory performance in field use. Although reasonable ex-
planations for this satisfactory performance are given, the question of
whether normal hydrated lime should or should not be used in masonry
mortar remains unanswered.
T. Ritchie (author's closure)--The question of whether normally hy-
drated dolomitic lime should be used in masonry mortar has been an-
swered if one accepts what must be the final criterion of assessment, its
satisfactory long-term performance in buildings, which was reported to be
the case for the limes of Toronto, Ontario. The results of the paper merely
provide, as Mr. PoweU states, reasonable explanations for this satisfactory
performance, in spite of potential expansions of mortars and bricks which
theoretically must produce cracking of a wall. Whether differences in
dolomitic limes and in building practices between those of Toronto and of
other areas would result in a difference in the performance of buildings is
not known, but it is considered unlikely to be the case.
This study has indicated what is generally well recognized, that it is ex-
tremely difficult to predict the behavior of brickwork from a study of the
properties of the individual bricks and mortar, and when the brickwork
serves as part of a building there are additional complications in the pre-
diction of its performance.
1 Senior research staff member, United States Gypsum Co., Des Plaines, Ill. 60016.
81
R. Gillard 1 and H. N. Lee s
Testing of Building Mortars Using the

New British Standard Methods
REFERENCE: Gillard, R. and Lee, H. N., "Testing of Building Mortars

Using the New British Standard Methods," The Reaction Parameters o[
Lime, ASTM STP 472, American Society for Testing and Materials, 1970,
pp. 82-116.
ABSTRACT: The proposal of the British Standard for mortars is that all
ingredients of mortars should be specified by weight proportions of the total
dry weight of the mortar. In the case of lime:sand mortars it also is sug-
gested that the "available lime content," as specified by ASTM Method C
25-65, is used to determine the active lime in the mortar.
In the first part of this investigation the effects of varying the available
lime content on the physical properties of mortars have been studied. It
has been shown that using one sand and one hydrated lime the physical
properties of the plastic mortars are related to the available lime content,
and that when hydrated lime mortars are aged for 24 h as a mortar the test
methods are more reproducible.
In the second part of this investigation a number of different types of limes
have been tested in the form of lime:sand mortars and gaged with portland
cement. From the results of the second series of tests it was shown that
controlling the amount of lime in a mortar by its available lime content
is a useful form of standardization, but that the physical properties of
different types of lime do affect the final properties of the mortar.
The proposed British Standard methods of testing mortars were found to
give reasonably satisfactory results and capable of classifying types of
building mortars.
KEY WORDS: construction materials, calcium oxides, portland cements,

standards, sands, moisture content, air entrainment, consistency, field
strength, evaluation, tests, mortars (materials), mechanical properties
Traditionally, site b a t c h i n g of materials f o r building m o r t a r s has b e e n b y

v o l u m e , as buckets and shovels are c o m m o n p l a c e site e q u i p m e n t . W i t h the
i n t r o d u c t i o n of f a c t o r y - m a d e mortars, it was f o u n d that v o l u m e p r o p o r t i o n -
1 Lecturer on building materials, Harrow College of Further Education, Pinner,

Middx, England.
z Deputy director of research, Welwyn Hall Research Association, Welwyn, Herts,
England.
82
Copyright
Copyright by9 ASTM
1970 Int'l
by ASTM International
Aug 1 12:04:31 EDT 2012
GILLARD AND LEE ON TESTING OF BUILDING MORTARS 83
ing, even under controlled conditions, produced mortars of widely differ-

ing composition. Bessey and Lee [1] 3 investigated this problem and
showed, by calculation, that with extreme ranges of bulk densities of lime
and sand, a 1:6 lime:sand mortar could contain between 4 and 14 percent
of dry hydrated lime, when related to dry weight of materials. In the paper
[1] it was proposed that the "available lime content," expressed as a per-
centage on the dry weight, should be used as a standard for specifying
lime:sand for mortars. Such a method of specifying has been used in the
draft British Standard for lime: sand mix for mortars [2].
Volume proportioning always gives an advantage to the purer types of
lime, as it is the available lime content, as specified by the ASTM Standard
Methods of Chemical Analysis of Limestone, Quicklime, and Hydrated
Lime (C 25-65) of a lime which contributes mainly to the physical prop-
erties (other than strength) of mortars. To obtain a standard available
lime content of a mortar, a greater quantity of chemically impure lime must
be added, and then the wet physical properties of the mortar should be
nearer the same as those obtained with a purer type of lime. The type of
stone and its burning does, however, affect the physical properties of the
lime and hence the properties of the mortar made from it.
In the present work the effect of the available lime content of a lime
mortar on its physical properties, when tested by the methods proposed in
the draft British Standard [3], has been studied. This investigation was
undertaken to determine systematically the effect of proportioning ready-
mixed lime:sand mixes for mortars by their available lime contents and to
examine the test methods of the Standard [3]. For this work a commercial
sand and one hydrated lime were used. The investigation was then ex-
tended to study the effects of different types of lime when used to prepare
mortars with equivalent available lime contents. For these tests the sand
was prepared from closely graded, washed natural quartz sands as speci-
fied in the Standard [3].
Experimental
Using One Sand and Varying the Lime Content
Materials--A commercial white chalk hydrated lime (coded L359), prop-
erties of which are given in Table 1, and a commercial sand (coded D46),
details of which are given in Table 2, were used for all the tests in this sec-
tion. Tap water was used for mixing instead of distilled water, a departure
from normal practice at these laboratories, but it was considered in this
case that it would be more equivalent to site practice.
The italic numbers in brackets refer to the list of references appended to this
paper.
Enrique Maldonado (MInorte+S.A.+de+C.V) pursuant to License Agreement. No further reproductions authorized
T A B L E 1--The properties of the limes.
Source . . . . . . . . . . . . . . . . . . . . . white chalk carbide waste white chalk gray chalk limestone limestone white chalk white chalk
Type o f lime . . . . . . . . . . . . . . . hydrated putty hydrated hydrated quick hydrated quick hydrated
L359 LP29 L277 L381 L391 L397 L399 L403

W H R A code . . . . . . . . . . . . . . .
Physical tests (BS 890:1940):
Residue on 72 mesh BS
.. 0.1 1.1 0.0 0.1
sieve, 7o . . . . . . . . . . . . . . . . . 0.1
t
Passing 72, retained on 170
.. 0.5 3.6 1.3 0.9
mesh, 7o . . . . . . . . . . . . . . . . . . . 0.9
9. 0.0 2.2 0.0 0.0
Soundness Le Chatelier, r a m . . 0.8
Density at flow table con-
1.40 1.40 1.44 1.30 1.39 1.38 1.37
sistence, g / c m 3 . . . . . . . . . . . . . 1.39
Workability as bumps:
... 13 14 19 13
To 19 c m - - i m m e d i a t e . . . . . 14
39 13 15 43 21 18 13
24 h soaking . . . . . . . . . . . . . 15
Bulk density:
9 0.51 0.56 0.46
g/cm a................... 0.51
... 32 35 29
l b / f t a. . . . . . . . . . . . . . . . . . . . 32
Chemical analyses:
47.9 2.2 1.8
Free water, as 7o H20 . . . . . 1.0
39.8 70.4 65.7 96.6 72.0 95.0 71.4
Neutralizing value, as ~o C a O . 72.4
33.6 65.2 52.0 94.8 70.1 93.2 67.2
Available lime, as ~o CaO . . . . 67.8
GILLARD AND tEE ON TESTING OF BUILDING MORTARS 85
T A B L E 2--The properties of the sands.
BS Sieve Mesh No. Metric Equivalent, mm

D46, Standard,
Passing Retained Passing Retained 70 by weight 70 by weight
... 3/16 in . . . . 4.77 0.0 0.0

3/16 in. 7 4.77 2.40 6.6 0.0
7 14 2.40 1.20 10.3 25.0
14 25 1.20 0.60 16.7 25.0
25 52 0.60 0.30 36.9 25.0
52 100 0.30 0.15 25.8 15.0
100 170 0.15 0.09 2.0 10.0
170 ... 0.09 ... 1.7 0.0
Dry bulk density (g/cm3). . . . . . . . . . . . . . . . . 1.57

Dry bulk density (lb/ft 3). . . . . . . . . . . . . . . . . . 98
Organic content . . . . . . . . . . . . . . . . . . . . . . . . . nil nil
Clay . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . trace nil
Methods of Test--Twelve mixes, each with a different amount of lime,

were prepared so that the available lime contents were within the normal
range for ready-mixed lime:sand for mortars as sold in the United King-
dom. The nominal properties of lime:sand were standardized at the follow-
ing values:
Volume Proportions, Available Lime Content,

lime: sand % Ca(OH)2 on dry weight
1:2 . . . . . . . . . . . . . . . . . . . . . . . 15
1:3 . . . . . . . . . . . . . . . . . . . . . . . 11
1:4V2 . . . . . . . . . . . . . . . . . . . . . . 8
1:6 . . . . . . . . . . . . . . . . . . . . . . . . 6
1:9 . . . . . . . . . . . . . . . . . . . . . . . . 4
1:12 . . . . . . . . . . . . . . . . . . . . . . . 2
The methods used to test the mortars were in accordance with the re-
quirements of the draft British Standard [3], the available lime content by a
method similar to the one given in the ASTM Methods of Analysis for
Lime (C 25-65). Two identical mixes were prepared, one tested imme-
diately after preparation and the other after standing, covered, in the
laboratory for 24 h. At least two batches of each mix were prepared and
the results given are averages.
TABLE 3--The properties of the portland cement.
Setting Times Strength of BS 12:1958 Concrete
Water, % . . . . . . . 28.0 3 days (psi) 1 995

Initial, min . . . . . . 260 7 days (psi) 2 990
Final, min . . . . . . 340 28 days (psi) 4 750
Surface Area Strength of Vibrated Mortar Cubes

(BS 12: 1958)
(cm~/g) . . . . . . . . . 3 100 3 days (psi) 4 545

7 days (psi) 6 590
Expansion
mm . . . . . . . . . . . . . 2
The water content of the mortars was adjusted to bring them to a

standard consistence, as determined by the dropping ball test, and then the
following tests made:
water content;
available lime content;
water retentivity (both as weight lost and percent of total water retained);
consistence retentivity;
air content (both pressure and density methods) ;
plasticity by flow table; and
density of plastic mortar.
Results--The results obtained from all these tests are given in Tables 4
and 5 and shown graphically in Figs. 1-9.
Dropping ball consistence----The water content of the mortar was ad-
justed wherever possible to a dropping ball penetration of 10.0 --- 0.5 mm
so that all the mortars were tested in a similar consistence. By this means a
constant factor is provided for the comparison of all other properties of the
mortars. In most cases it was found possible to obtain the penetration
within the limits of 10.0 • 0.2 mm as can be seen from Tables 4 and 5.
This standard consistence was chosen to correspond with a typical mix
used by a bricklayer or plasterer. Recent work has suggested that for
adhesion tests the consistence is lower than normally encountered on site.
T A B L E 4--Properties of plastic mortars tested immediately.
Theoretical available lime, as 7o Ca(OH)2

on dry weight . . . . . . . . . . . . . . . . . . . . . . . . . . 2 4 5 6 7 8 9 10 11 12 13 15
D e t e r m i n e d available lime, as ~o Ca(OH)~ 0
o n dry weight . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8 3.8 4.8 5.6 6.6 7.4 8.5 9.4 10.2 11.2 12.2 13.5 ~.
D r o p p i n g ball penetration, m m . . . . . . . . . . . 10.1 10.2 10.0 9.9 10.2 10.2 10.1 10.0 10.0 10.1 10.5 9.9 o
W a t e r content, ~o o n dry weight . . . . . . . . . . 22.3 20.9 21,3 20.4 18.6 19.8 19.1 19.6 18.7 18.8 19.2 19.2 z
Water retentivity.. ~m
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12.5 10.5 7.5 9.0 9.0 7.5 4.5 4.5 4.5 5.5 4.5 2.0
0
~o retained . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 85 89 87 88 88 92 93 93 91 93 97 z
Consistence retentivity, ~o . . . . . . . . . . . . . . . . 50 50 55 45 50 45 75 65 60 55 50 80
Density, g/cm~ . . . . . . . . . . . . . . . . . . . . . . . . . 1.89 1.93 1.96 1.99 1.99 2.00 2.00 1.99 2.00 2.01 2.01 2.00
Air content: 0
Pressure m e t h o d . . . . . . . . . . . . . . . . . . . . . . 9.4 7.7 5.4 4.5 5.3 4.6 4.6 4.6 3.8 4.0 3.2 4.2
Density m e t h o d . . . . . . . . . . . . . . . . . . . . . . . 7.0 6.1 2.9 3.4 5.3 3.5 3.5 3.0 3.3 2.8 2.2 2.6
o_
Plasticity, ~o spread . . . . . . . . . . . . . . . . . . . . . 135 135 140 130 140 135 115 125 125 120 115 105 z
O
o
-4
),.
oo
.,q
Oa
Oa
T A B L E 5--Properties of plastic mortars tested after 24 h soaking. o

7,
Theoretical available lime, as % Ca(OH)2

on dry weight . . . . . . . . . . . . . . . . . . . . . . . . . . 2 4 5 6 7 8 9 10 11 12 13 15
Determined available lime, as 7o Ca(OH)2

on dry weight . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8 3.8 4.8 5.6 6.6 7.4 8.5 9.4 10.2 11.2 12.2 13.5
o
'-I1
Dropping ball penetration, m m . . . . . . . . . . . 10.2 10.2 10.1 10.2 10.0 9.9 9.9 10.0 10.1 10.2 10.3 10.2 t-
Water content, ~o on dry weight . . . . . . . . . . 22.0 21.8 21.8 21.6 19.5 20.7 20.3 19.5 20.5 19.5 21.5 20.6
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.5 8.0 6.0 6.0 7.0 4.0 5.0 3.0 3.5 3.0 2.5 2.0
7o retained . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 89 92 92 91 93 93 96 95 95 96 97
Consistence retentivity, 7o . . . . . . . . . . . . . . . . 55 50 65 60 55 65 65 75 65 70 75 75
Density, g / c m s . . . . . . . . . . . . . . . . . . . . . . . . . 1.91 1.94 1.95 1.95 1.97 1.96 1.97 1.96 1.97 1.96 1.96 1.94
Air content:
Pressure method . . . . . . . . . . . . . . . . . . . . . . 7.8 7.2 5.7 5.2 5.0 5.7 4.5 5.8 4.2 5.0 4.5 4.8
Density method . . . . . . . . . . . . . . . . . . . . . . . 6.4 4.8 4.0 3.9 3.4 4.1 3.8 4.2 3.6 4.3 4.8 4.4
Plasticity, 7o spread . . . . . . . . . . . . . . . . . . . . . 135 130 125 120 130 110 110 100 110 100 105 95
Available lime content The amount of lime used in each mortar was
calculated from the following formula:
W --
(-~- ,~)
where:
w ---~ weight of hydrated lime (or putty) required (g),
ot ~-- required available lime content of mortar ( % ) ,
/3 ~ weight of dry sand to be used ( g ) , and
y ~ available lime content of hydrated lime (or lime putty) on wet
basis as Ca(OH)2 (percent).
As a check on the amount of lime added, an available lime determination
was made on each mix. The values were found to be lower than the theo-
retical (Fig. 1 ) being approximately 0.93 of the theoretical content. As the
sand contained only a trace of clay it is assumed that some reaction must
have occurred between the sand and lime.
Water content at standard consistence The results obtained are given
in Tables 3 and 4 and shown graphically in Fig. 2. As the lime content of
15
LJ
n~ 12 Ideal /
...r
o
>.
a
.<
9
6
/
FIG.
s
o //I
0 3 6 9 12
Nominal Lime Content, Ca(C)H) 2 per cent
15
1--Relationship between available lime content determined by calculation and

by experimental methods.
23
o.. 21 o "~
g .
~) 19
o Tested immediately o
~" 17 9 Tested after 24h

0 3 6 9 12 15
Available Lime Content, Ca(OH) 2 per cent

FIG. 2--Effect of available lime content on water content o[ the mortars.
the mix is increased, the water content decreases until maximum packing
occurs, after which the water increases. For mortars under investigation the
minimum water content was obtained at 9.7 percent lime content. The re-
sults of tests on mortars soaked for 24 h exhibit a similar degree of scatter,
but the range between maximum and minimum moisture contents is
smaller.
Water retentivity~This test gives an estimation of the workability of a
mortar after suction by a high suction background. The results are quoted
as grams lost (that is, volume lost from the volume of mortar used in the
test) or as the percentage of the water in the original mortar retained. The
two results are related and the relationship, shown in Fig. 5, is 100 -
1.42 • weight of water removed. This, of course, applies only to lime:sand
mixes. In view of this relationship only the percentage retained has been
plotted against the available lime content (Fig. 3). The spread of results
is greatest for the mixes tested immediately, and the range from maximum
to minimum is smallest for the material soaked over a period of 24 h.
e-
100
Cl. 9 0
"O
a)
e.*
O
,v, 80
o Tested immediately
9 Tested after 24h
~ 70
0 9 12 "--~5
Available Lime C o n t e n t , Ca(OH) per cent

2
FIG. 3--Effect of available lime content on water retentivity of the mortars.
GILLARD AND LEE O N TESTING OF BUILDING MORTARS 91
Consistence retentivity--This test is used to indicate the ability of a

mortar to retain its plastic properties after application to a background
with a high suction. The results obtained are shown graphically in Fig. 4.
Mortars tested immediately after mixing show no correlation at all and cast
doubts on the usefulness of this test for unsoaked lime:sand mortars. The
results obtained after the mortars had been soaked for 24 h show better
correlation, but, even so, they too cast some doubts on the test.
Air content--The air content o f a mortar affects its workability, and two
test methods are recommended in the Standard.
Air content by pressure m e t h o d - - T h e results are shown graphically in
Fig. 6. In this test the air content is measured using a pressure cup of
known volume. For both immediate and 24-h mortars the curves are sim-
ilar, and the air content falls with an increase in lime content.
Air content by density m e t h o d - - T h e results are shown graphically in
Fig. 7. In this test the air content is calculated from the wet density of the
mix and the specific gravities of the components. The determinations on
the mortars tested immediately are a little erratic, and the curve obtained
from the soaked mortars, although better, has a minimum at approximately
the point of maximum packing.
Plasticity by flow table The numerical value obtained from this test is
intended as an assessment of the craftsman's judgement of the workability
of the mortar. The result is expressed as a percentage, and a lower figure
indicates a more plastic mortar. The test is based on the ASTM flow table
and workability test, and the diameter of the pat is measured after the table
90 . . . . . .
t-
|
u o Tested immediately
80
|
o. 9 Tested after 24 h 9 9
>. _x~
~ 70
P j-
60 '" o
50 $ o e
g o o
t.) 40
3 6 12 15
Available Lime C o n t e n t , Ca(OH) 2 per cent
FIG. 4--Effect oJ available lime content on consistence retentivity o/the mortars.
100
9 Tested after 24h
95 N.
u
-~ o ',,,,,.
-
c 90
~ oe
~ 85
80
0 3 6 9
\
12 15
Water Lost, g
FIG. 5--Relationship between amount of water removed and percentage lost.
10! . r
I
~ ~ I o Tested immediately
8d *~o 9 Tested after 2~. h
o ~ 9 ~ I
0 o j oh i
U I0
ol 0 6 12
I
15
Available Lime C o n t e n t , Ca(OH) 2 per cent

FIG. 6--Relationship between air and available lime content of mortars.
10
9 Tested after 24 h
c~
o)
c 4
O
U O o
I O oh
< 2i
?
I
0
J
9 12 15
Available Lime Content, Ca(OH) 2 per cent
FIG. 7--Relationship b e t w e e n air and available l i m e c o n t e n t o ] m o r t a r s .
has been "bumped" 25 times. The results given in Tables 4 and 5 are
shown graphically in Fig. 8.
When the mortars are tested immediately there is no improvement in
plasticity until the mortar contains 7~/2 percent lime. For the soaked mor-
tars as the lime content increases the plasticity improves.
Density ol plastic mortar--The densities of the soaked mortars are
lower, due to the higher water contents. For both conditions of the mortar
there was little scatter of results about the density against lime contents.
Discussion--The available lime analysis does not normally include any
magnesia present in the lime. Therefore, the method would not be generally
160
C
u
9 140 ~ -Io o
~u v~ v
.~ 12o
10o o Tested immediately

9 Tested after 24 h
8ol 0 3 6 12 15
Available Lime C o n t e n t , C a ( O H ) per cent
FIG. 8--Relationship between spread and available lime c o n t e n t o [ m o r t a r s .
applicable for mortars made with dolomitic lime. A neutralizing value

could be used, but experience has shown that inaccuracies caused by the
presence of carbonates in the lime or the aggregate or both are greater
than those due to the presence of magnesia in the lime. In the United King-
dom there is only a very limited production of dolomitic lime, and hence
the use of the available lime content for specifying the amount of lime in
mortars is practicable.
There is a reasonable relationship between the available lime content
and most of the physical tests examined. The consistence retentivity test
when used with unsoaked mortar does not appear to be related to the
available lime content. The amount of lime present in a soaked lime mortar
has a pronounced effect on its plasticity.
As might be expected more consistent and reproducible results were ob-
tained when hydrated lime:sand mortars were soaked for 24 h before
testing.
Using One Standard Sand and Various Limes
Materials Seven different limes were used in these tests and included high
calcium limestone limes, high calcium chalk limes, gray chalk limes, and
carbide waste putty. Details of these limes are given in Table 1. The sand
was prepared by blending weight portions of standard washed silica sands,
as given in Table 2. An ordinary portland cement (coded F29) was used,
and its properties are given in Table 3.
Methods o[ Test--Four types of mortar were prepared from each of
seven different limes as follows:
Volume Proportions, Available Lime Content,

lime: sand % Ca(OH)2 on dry weight
1:3 . . . . . . . . . . . . . . . . . . . . . . . 11
1:41/i . . . . . . . . . . . . . . . . . . . . . . 8
1:6 . . . . . . . . . . . . . . . . . . . . . . . . 6
1:9 . . . . . . . . . . . . . . . . . . . . . . . . 4
Quicklimes were run to putties and allowed to stand for seven days before
use.
After testing, these mortars were gaged with portland cement to produce
the following mixes equivalent to traditional volume mixes of 1:2:9; 1 : 1:6;
2:1:9; and a 1:3 cement:sand mortar was prepared for comparison.
2100
oh ,
~ 2000
o v 24h
"~
a
19oo
/J o Tested immediately
9 Tested after 24 h
1800
0 3 6 9 12 15
Available Lime C o n t e n t , C a ( O H ) p e r cent
FIG. 9--Relationship between density and available lime content o] mortars.
The formula used to calculate the amount of cement to add to the ready-
mixed lime:sand for mortar was as follows:
c= w x-d n
where:
C ~ the weight of cement required (g),
W ~ the weight of ready-mixed mortar (g),
D ~ the density of ready-mixed mortar (g/cm3),
n ~ the number of parts of ready-mixed mortar to each part of
cement (by volume), and
d ~ the density of the cement (1.44 g/cm3).
This method is not the one given by the British Standard [2] which was
issued after the completion of this work.
The water contents of the mortars were adjusted to bring them to a
standard consistence, as in Part 1, and the following tests made:
water content;
available lime content (on some of the lime:sand mixes only);
water retentivity (both as weight lost and percent of total water retained);
consistence retentivity;
air content (pressure method) ; and
plasticity (by flow table).
The cement mortars were cast into six prisms 100 by 25 by 25 ram,
demoulded without suction after 24 h, and cured in limewater for seven
days and tested for transverse and compressive strengths.
R e s u l t s - - T h e results obtained from all these tests are given in Tables
6-21 and shown graphically in Figs. 10-17.
~o
o~
T A B L E 6---Properties o f mortars made with carbide waste putty (LP 29). Ill
Type of mortar . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lime: sand P o r t l a n d c e m e n t : lime: s a n d
7
Nominal volume proportions ................ 1:9 1:6 1:4~ 1: 3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
A v a i l a b l e lime co nt e nt , as % Ca(OH)~ on dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11
D r o p p i n g ball p e n e t r a t i o n , m m . . . . . . . . . . . . . . 10.1 9.9 9.8 I0.1 9.9 9.8 9.8 9.8 I0.1 tn
O
W a t e r co nt ent , % on dry weight . . . . . . . . . . . . . 17.7 17.2 17.6 19.4 14.4 15.1 16.3 17.4 19.4 "1
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8.0 4.6 2.8 2.0 10.0 2.9 3.4 3.2 2.0
7o r e t a i n e d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 93 95 97 83 95 94 95 97
C o n s i s t e n c e retentivity, 7o . . . . . . . . . . . . . . . . . . . 50 60 70 75 30 55 55 55 75
A ir c on ten t, pressure m e t h o d . . . . . . . . . . . . . . . . 4.5 5.0 4.5 4.0 4.5 3.5 4.0 4.0 4.0
Plasticity, ~o s p re ad . . . . . . . . . . . . . . . . . . . . . . . . 125 115 100 100 145 110 105 100 100
T r a n s v e r s e s t r e n g t h at 7 days, psi . . . . . . . . . . . . . . . ... 530 270 140 40 ...
S t a n d a r d dev iat ion , psi . . . . . . . . . . . . . . . . . . . . . . . . ... 35 20 15 0 ...
Coefficient o f v a r i a t i o n , % . . . . . . . . . . . . . . . . . . . . . ... 6 7 13 4 ...
C o m p r e s s i v e s tr en gt h at 7 days, psi . . . . . . . . . . . ... 2 350 940 450 130 ...
S t a n d a r d d evi atio n, psi . . . . . . . . . . . . . . . . . . . . . ... 205 45 50 15 ...
Coefficient o f v a r i a t i o n , 7o . . . . . . . . . . . . . . . . . . ... 9 5 11 10 ...
T A B L E 7--The properties of mortars made with white chalk hydrated lime (L277).
Type o f m o r t a r . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lime: sand Portland cement: lime: sand
N o m i n a l volume p r o p o r t i o n s . . . . . . . . . . . . . . . . 1 :9 1 :6 1 :4~ 1 :3 1 : 0: 3 2:1 :9 1 : 1 :6 1 : 2: 9 0: 1 : 3
Available lime content, as 70 Ca(OH)2 on dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11
o
D r o p p i n g ball penetration, m m . . . . . . . . . . . . . . 10.1 10.2 10.2 10.2 9.9 10.1 9.9 10.2 10.2
Water content, 70 on dry weight . . . . . . . . . . . . . 17.3 15.1 14.6 15.0 14.4 15.0 13.9 14.3 15.0
z
Water retentivity: ~7
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.7 7.4 4.7 3.2 10.0 5.5 4.1 3.9 3.2
70 retained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 87 82 95 83 90 93 93 95 M
O
50 60 60 30 50 60 55 60 Z
Consistence retentivity, 70 . . . . . . . . . . . . . . . . . . . 50
Air content, pressure method . . . . . . . . . . . . . . . . 4.5 4.5 4.5 4.0 4.5 4.0 3.5 4.0 4.0
Plasticity, 70 spread . . . . . . . . . . . . . . . . . . . . . . . . 135 135 120 120 145 125 120 115 120 O
Transverse strength at 7 days, psi . . . . . . . . . . . . . . ... 530 360 220 60 O
Standard deviation, psi . . . . . . . . . . . . . . . . . . . . . . . ... 35 50 25 30
Coefficient of variation, 70 . . . . . . . . . . . . . . . . . . . . ... 6 14 11 48 _6

z
O
Compressive strength at 7 days, psi . . . . . . . . . . . . . ... 2 350 1 360 780 240
Standard deviation, psi . . . . . . . . . . . . . . . . . . . . . . . ... 205 195 110 60 O
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . . . ... 9 15 14 26
~O
~0
T A B L E 8--The properties o f mortars made with gray chalk hydrated lime (L381).
Type of mortar ............................ Lime: sand P o r t l a n d c e m e n t : lime: s a n d
Nominal vo|ume proportions ................ 1:9 1:6 1:4~ 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3 Z
Available lime content, as 70 Ca(OH)2 on dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 1l . . . . . . 11
o
W a t e r content, 70 on dry weight . . . . . . . . . . . . . 16.5 16.0 15.7 16.0 14.4 15.3 15.2 15.4 16.0
r-,
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10.0 6.0 3.5 3.2 10.0 5.5 5.2 3.5 3.2
7o retained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 90 94 95 83 90 91 94 95
C o n s i s t e n c e retentivity, 70 . . . . . . . . . . . . . . . . . . . 45 50 65 60 30 50 55 55 60
Air content, pressure m e t h o d . . . . . . . . . . . . . . . . 5.0 5.0 4.5 4.5 4.5 4.0 4.0 4.0 4.5
Plasticity, 70 spread . . . . . . . . . . . . . . . . . . . . . . . . 135 125 120 120 145 125 115 115 120
T r a n s v e r s e strength at 7 days, psi . . . . . . . . . . . . . . . 530 370 220 120
S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . . . . 35 30 15 25
Coefficient o f variation, ~ . . . . . . . . . . . . . . . . . . . . . 6 8 7 21
C o m p r e s s i v e strength at 7 days, psi . . . . . . . . . . . . . . 2 350 1 240 720 380
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . . . . 9 11 9 7
T A B L E 9--The properties of mortars made with limestone quicklime (L391).
Type o f m o r t a r . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lime: sand P o r t l a n d c e m e n t : lime: s a n d
Nominal volume proportions ................ 1:9 1:6 1:4~ 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
Available lime content, as ~o C a ( O H h on dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11
O
D r o p p i n g ball penetration, m m . . . . . . . . . . . . . . f-
10.1 10.2 10.1 10.1 9.9 10.3 10.0 10.0 10.1
T"
W a t e r content, 7o on dry weight . . . . . . . . . . . . . 17.4 17.5 17.8 20.0 14.4 15.5 16.2 17.2 20.0
>.
Water retentivity: z
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.8 3.7 2.5 1.6 10.0 5.2 3.5 2.5 1.6
~o retained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 94 96 97 83 91 94 96 97
0
Consistence retentivity, 7o . . . . . . . . . . . . . . . . . . 60 65 75 75 30 50 55 65 75 z
Plasticity, ~o spread . . . . . . . . . . . . . . . . . . . . . . . . 130 115 105 100 145 125 115 105 100 z
0
T r a n s v e r s e strength at 7 days, psi . . . . . . . . . . . . . . . 530 250 160 60 0
Coefficient o f variation, ~o . . . . . . . . . . . . . . . . . . . . . 6 18 6 8
z
S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . . . . 205 210 40 10 0

Coefficient o f variation, 7o . . . . . . . . . . . . . . . . . . . . . 9 23 8 5
~O
~O
o
T A B L E lO--The properties of mortars made with limestone hydrated lime (L397).
T y pe o f m o r t a r . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lime: sand P o r t l a n d c e m e n t : lime: s a n d
Nominal volume proportions ................ 1:9 1: 6 1:4~ 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
A v a i l a b l e lime c on ten t, as 70 Ca(OH)~ on dr y

w eig h t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11
D r o p p i n g ball p e n e t r a t i o n , m m . . . . . . . . . . . . . . 10.0 9.7 9.9 9.9 9.9 10.1 9.9 10.2 9.9
W a t e r content, 70 on dry weight . . . . . . . . . . . . . 16.4 16.4 18.1 20.2 14.4 15.5 15.5 17.9 20.2
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.8 3.8 2.9 1.5 10.0 4.9 3.7 3.0 1.5
70 r e t a i n e d . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 93 95 98 83 92 94 95 98
C o n s i s t e n c e retentivity, 70 . . . . . . . . . . . . . . . . . . 60 65 7O 80 30 55 55 60 80
A ir co n ten t, pressure m e t h o d . . . . . . . . . . . . . . . . 4.5 4.5 4.5 3.5 4.5 3.5 4.0 3.5 3.5
Plasticity, 70 s pr ead . . . . . . . . . . . . . . . . . . . . . . . . 125 110 110 100 145 120 110 110 100
T r a n s v e r s e s t r e n g t h at 7 days, psi . . . . . . . . . . . . . . ... 530 280 180 50 ...
S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . . . ... 6 4 16 6 ...
Coefficient o f v a r i a t i o n , 70 . . . . . . . . . . . . . . . . . . ... 35 10 30 5 ...
C o m p r e s s i v e s t r e n g t h at 7 days, psi . . . . . . . . . . . ... 2350 970 620 140 ...
S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . ... 205 70 105 5 ...
Coefficient o f v a r i a t i o n , 70 . . . . . . . . . . . . . . . . . . ... 9 7 17 5 ...
T A B L E 11--The properties of mortars made with white chalk quicklime (L399).
Type o f m o r t a r . . . . . . . . . . . . . . . . . . . . . . . . . . . . Lime: sand P o r t l a n d cement :lime: sand
N o m i n a l volume p r o p o r t i o n s . . . . . . . . . . . . . . . . 1:9 1:6 1:4~ 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
Available lime content, as 70 Ca(OH)~ on dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11 O
D
Water content, 70 on dry weight . . . . . . . . . . . . . 16.6 17.4 16.9 17.4 14.4 15.3 15.6 16.6 17.4 >
Z
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5 4.6 2.8 1.3 10.0 5.2 4.2 3.2 1.3
70 retained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 93 95 98 83 91 93 95 98 O
Z
Consistence retentivity, 70 . . . . . . . . . . . . . . . . . . . 65 70 80 85 30 50 55 60 85
Plasticity, 70 spread . . . . . . . . . . . . . . . . . . . . . . . . 130 120 115 105 145 125 110 110 105 O
... 530 300 160 70 ...
?
Transverse strength at 7 days, psi . . . . . . . . . . . . . .
Standard deviation, psi . . . . . . . . . . . . . . . . . . . . . . . ., . 35 15 5 5
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . . . ... 6 6 4 4 ...
Compressive strength at 7 days, psi . . . . . . . . . . ... 2 350 1 070 510 190 ...
O
Standard deviation, psi . . . . . . . . . . . . . . . . . . . . . ... 205 60 50 10 ...
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . ... 9 6 10 4 ...
bo
T A B L E 12--The properties o f mortars made with white chalk hydrated lime (L403).
Type of mortar ............................ Lime: sand P o r t l a n d c e m e n t : lime: s a n d

-4
Nominal volume proportions ................ 1:9 1:6 1:4~ 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3 O
z
Available lime content, as 70 Ca(OH)~ o n dry

weight . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 6 8 11 . . . . . . . . . . . . 11
-4
W a t e r content, 70 on dry weight . . . . . . . . . . . . . 16.4 17.8 18.2 15.7 14.4 15.1 14.5 15.1 15.7 o" 1 1
Water retentivity:
g lost . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9.8 6.0 2.2 2.9 10.0 5.8 2.7 2.4 2.9
70 retained . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 90 97 95 83 90 95 96 95
C o n s i s t e n c e retentivity, 70 . . . . . . . . . . . . . . . . . . . 45 55 80 70 30 50 65 65 70
Plasticity, 70 spread . . . . . . . . . . . . . . . . . . . . . . . . 140 135 110 120 145 125 115 100 120
T r a n s v e r s e strength at 7 days, psi . . . . . . . . . . . . 530 370 200 70
S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . .. 35 15 5 5
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . .~ 6 4 2 10

S t a n d a r d deviation, psi . . . . . . . . . . . . . . . . . . . . . . . . .. 205 140 55 10
Coefficient o f variation, 70 . . . . . . . . . . . . . . . . . . . . . .o 9 12 8 4
TABLE 13--The comparison of the available lime contents of selected ready-mixed

lime-sand for mortars.
Lime
number LP29 L277 L391 L397 L403
Required
Content
White Limestone White
Carbide chalk lime Limestone chalk Ca(OH)2
Type putty hydrate putty hydrate hydrate
1:9 . . . . 4.0 3.9 3.9 3.9 4.3 4.0

1:6 . . . . 6.1 5.7 5.7 5.9 5.9 6.0
1:4~. 7.4 7.6 7.7 7.8 ... 8.0
1:3 . . . . 10.0 10.4 10.6 ... 10.4 11.0
D r o p p i n g ball c o n s i s t e n c e - - A s s t a t e d i n P a r t 1 all m o r t a r s w h e r e p o s -
s i b l e w e r e b r o u g h t t o a s t a n d a r d d r o p p i n g b a l l c o n s i s t e n c e of 1 0 . 0 - 0 . 2
mm.
Ava i l a b l e lime content Limited checks were made on the lime:sand
mortars to ensure that the correct amount of lime had been used. It can be
s e e n f r o m T a b l e 13 t h a t all t h e m i x e s a n a l y s e d d i d c o n t a i n t h e c o r r e c t
available lime content.
W a t e r content at standard consistence It can be seen from Table 14
that the lime: sand mortar mixes with the higher water contents are those
TABLE 14---The comparison of the moisture contents of all the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403
White Gray Lime- Lime- White White

Carbide chalk chalk stone stone chalk chalk Av
Type putty hydrate hydrate quicklime hydrate quicklime hydrate
Ready-mixed mortar
1:9 . . . . . 17.7 17.3 16.5 17.4 16.4 16.6 16.4 16.9
1:6 . . . . . 17.2 15.1 16.0 17.5 16.4 17.4 17.8 16.8
1:4~... 17.6 14.6 15.7 17.8 18.1 16.9 18.2 17.0
1:3 . . . . . 19.4 15.0 16.0 20.0 20.2 17.4 15.7 17.7
Cement: lime: sand
1:0:3... 14.4 14.4 14.4 14.4 14.4 14.4 14.4 14.4
2:1:9... 15.1 15.0 15.3 15.5 15.5 15.3 15.1 15.3
1:1:6... 16.3 13.9 15.2 16.2 15.5 15.6 14.5 15.3
1:2:9... 17.4 14.3 15.4 17.2 17.9 16.6 15.1 16.3
0:1:3... 19.4 15.0 16.0 20.0 20.2 17.4 15.7 17.7
LIME :SAND MORTARS CEMENT :LIME :SAND MORTARS

23
231 1
u
21 211 !
Q.
~
C 19
..... ~:,::i:ii::iii;ili:~i., 19 ] .....
U0 17
~i~~:::::::::::::::::::::::::
. 111i '
~ 15
13 13t -.-~ J
1:9 1:6 1:4"5 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
Nominal Mix Proportions by Volume
L__~L___.I~ ..J ..~ . 9 j

0 2 4 6 8 10
Available Lime Content
Ca(OH) 2 per cent
FIG. lO--Relationships between nominal mix proportions and water content.
containing the limestone hydrated lime (L397), limestone quicklime

(L391), and carbide lime putty (LP29). Generally, there is an increase in
water content with the increase in the amount of lime, as can be seen from
Fig. 10. When cement is added to the lime:sand mortar similar water
trends persist, as can also be seen from Fig. 10.
Water retentivity--Tables 15 and 16 show the comparison of the water
retentivity of all the mortars in grams lost and percentage retained respec-
tively, from which it can be seen that the best water retentivity is obtained
when mortars are made with the limestone hydrated lime (L397), lime-
stone quicklime (L391), and white chalk quicklime (L399). The results
for the lime:sand mortars are shown graphically in Figs. 11 and 12. When
cement is added to the mortars there is less difference (Figs. 11 and 12)
between mortars made with different types of limes.
Consistence retentivity This test is similar to that for water retentivity
and the higher the results, as a percentage, the better the mortar.
As in the first investigation, the results obtained have a considerable
spread. The mortars made with white chalk quicklime (L399), limestone
quicklime (L391), and limestone hydrated lime (L397) give the best con-
sistence retentivity. Only one lime, (L277, a poor grade white chalk
hydrated lime), does not follow this trend as is shown by the difference of
only 10 percent in consistence retentivities of the 1:9 and 1:3 lime:sand
mortars. These results imply that any improvement by increasing the lime
content for the lime L277 is small. It can be seen from Fig. 13 that the
GILLARD AND LEE ON TESTING OF BUILDING MORTARS 10,5
TABLE 15--The comparison of the water retentivity (in grams lost) of a l l the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Ready-mixed mortar
1:9 . . . . . 8.0 9.7 10.0 5.8 4.8 5.5 9.8 7.7
1:6 . . . . . 4.6 7.4 6.0 3.7 3.8 4.6 6.0 5.2
1:4~... 2.8 4.7 3.5 2.5 2.9 2.8 2.2 3.1
1:3 . . . . . 2.0 3.2 3.2 1.6 1.5 1.3 2.9 2.2
Cement: lime: sand

1:0:3. 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0
2:1:9. 2.9 5.5 5.5 5.2 4.9 5.2 5.8 5.0
1:1:6. 3.4 4.1 5.2 3.5 3.7 4.2 2.7 3.8
1:2:9. 3.2 3.9 3.5 2.5 3.0 3.2 2.4 3.1
0:1:3... 2.0 3.2 3.2 1.6 1.5 1.3 2.9 2.2
TABLE 16---The comparison of water retentivity (as percent retained) of all the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Ready-mixedmortar
1:9 . . . . . 87 85 84 90 92 90 84 87
1:6 . . . . . 93 87 90 94 93 93 90 91
1:4~... 95 92 94 96 95 95 97 95
1:3 . . . . . 97 95 95 97 98 98 95 96
Cement:lime:sand
1:0:3... 83 83 83 83 83 83 83 83
2:1:9... 95 90 90 91 92 91 90 91
1:1:6... 94 93 91 94 94 93 95 93
1:2:9... 95 93 94 96 95 95 96 95
0:1:3~.. 97 95 95 97 98 98 95 96
106 THE REACTION PARAMETERS O F LIME
LIME :SAND M O R T A R S CEMENT:LIME:SAND MORTARS

10
8
O)
4
f::!!iiiiiiiii::i::i~i:: ~
1:9 1:6 1:4".5 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
L I 1 I I L~J
0 2 4 6 8 10
Ca(OH) 2 per cent
FIG. ll--Relationships between nominal mix proportions and water lost.
LIME :SAND M O R T A R S CEMENT:LIME:SAND MORTARS

100
e-
u
95
c 90
a
85
7
80
1:9 1:6 1:4'5 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
9 I l I I I ]
0 2 4 6 8 10
A v a i l a b l e Lime C o n t e n t
Ca(OH) 2 per cent
FIG. 12--Relationships between nominal mix proportions and water retentivity.
TABLE 17--The comparison of the consistence retentivity of a l l the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Ready-mixed mortar
1:9 . . . . . 50 50 45 60 60 65 45 55
1:6 . . . . . 60 50 50 65 65 70 55 60
1:41/~... 70 60 65 75 70 80 80 70
1:3 . . . . . 75 60 60 75 80 85 70 70
Cement:lime:sand
1:0:3... 30 30 30 30 30 30 30 30
2:1:9... 55 50 50 50 55 50 50 50
1:1:6... 55 60 55 55 55 55 65 55
1:2:9... 55 55 55 65 60 60 65 60
0:1:3... 75 60 60 75 80 85 70 70
LIME:SAND MORTARS CEMENT: L I M E : S A N D MORTARS

c 100 1
u
t L
~0.80 - -
i~i~i~;i~;!~!i!~!;!.....................
i .::.:::::............................... ~ ~:.::.:::.:.:.:.::.::
::::::::::::::::::::::::::::::::::::::::::::::::
> 6 0 - -
~ ~ ~ ~ ~ ~:~!:!i!!i
!!!~!~!~!~!
c.
o)
r
"~ 40
o
~ 2o 20 i
o
._~
g o 0
1:9 1:6 1:4"5 1:3 1: 0: 3 2:1:9 1:1:6 1:2:9 0:1:3
U
I I I I I I ./
0 2 4 6 8 10
Ca(OH) 2 per cent
FIG. 13--Relationships between nominal mix proportions and consistence reten-
tivity.
TABLE 18--The comparison of plasticity (percent flow table spread) ofall the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403
White Gray L i m e - L i m e - W h i t e White

Carbide c h a l k chalk stone stone chalk chalk Av
Ready-mixed mortar
1:9 ..... 125 135 135 130 125 130 140 130
1:6 ..... 115 135 125 115 110 120 135 120
1:4~... 100 120 120 105 110 115 110 110
1:3 ..... 100 120 120 100 100 105 105 110
Cemolt:lime:sand
1:0:3... 145 145 145 145 145 145 145 145
2:1:9... 110 125 125 125 120 125 125 120
1:1:6... 105 120 115 115 110 110 115 115
1:2:9... 100 115 115 105 110 110 110 110
0:1:3... 100 120 120 100 100 105 105 105
mortars improve with an increase in lime content. A n examination of Fig.

13 for cement:lime:sand mortars shows that although there is a consider-
able difference in consistence retentivity between the 1:0:3 cement:sand
mortar and 0 : 1 : 3 lime:sand mortar, the difference between the three types
of mortar in general use, that is, 2 : 1 : 9 ; 1 : 1 : 6 ; and 1:2:9, is only 10
percentage points.
Plasticity by flow t a b l e - - T h e results of this test are given in Table 18
and illustrated by the graphs in Fig. 14, from which it can be seen that
there is a large difference in the flow table spreads. The best mortars were
those made with the carbide lime putty ( L P 2 9 ) , soaked limestone putty
(L391), and the limestone hydrated lime ( L 3 9 7 ) . The workability of a
lime mortar improves as the lime content increases.
The large span of results in flow table spreads is reduced considerably
when the mortars are gaged with cement. The results show that generally
the plasticity of a cement mortar is improved as the amount of lime present
increases.
Air c o n t e n t - - T h e results obtained for air content tests of all the mortars
show that this remains almost constant, as can be seen from Table 19 and
Fig. 15.
Transverse strength--The seven-day transverse strengths of the cement:
lime:sand mortars are given in Table 20 and Fig. 16. The mortar bars were
demoulded after 24 h and then cured in limewater for seven days before
GILLARD A N D LEE O N TESTING O F BUILDING MORTARS 109
LIME:SAND MORTARS CEMEN1: LIME:SAND MORTARS

150 150
c 140 140 %
a)
u
L. 130 130
iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii
"o
o
120
~. 11o
9
,2o
I10
~1
100 10o
90 9o
1:9 1:6 1:4"5 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
t l t I I [ I
0 2 4 6 8 10
Ca(OH) 2 per cent
FIG. 14---Relationships between nominal mix proportions and plasticity.
TABLE 19--The comparison of the air content (by the pressure method) of all the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Ready-mixed mortar
1:9 . . . . . 4.5 4.5 5.0 5.0 4.5 6.0 6.5 5.0
1:6 . . . . . 5.0 4.5 5.0 5.0 4.5 5.5 5.5 5.0
1:4~... 4.5 4.5 4.5 4.5 4.5 5.0 5.5 4.5
1:3 . . . . . 4.0 4.0 4.5 4.0 3.5 4.5 4.5 4.0
Cement: lime: sand
1:0:3... 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5
2:1:9... 3.5 4.0 4.0 4.0 3.5 4.0 4.5 4.0
1:1:6... 4.0 3.5 4.0 3.5 4.0 4.5 4.0 4.0
1:2:9... 4.0 4.0 4.0 3.5 3.5 4.0 5.0 4.0
0:1:3... 4.0 4.0 4.5 4.0 3.5 4.5 4.5 4.0
I 10 THE REACTION PARAMETERS OF LIME
LIME:SAND MORTARS CEMENI: LIME:SAND MORTARS

7
~6
Q.
e-
5 i)iii'iii!
i i i !i)i i i i i !ii i!!i!i)i !i i li :.: :.:.:.:.: . . . . . .
4 iiii)iiiiii!iiiiiiiiiiiii)
....':"
O
U 7! iiiii!iiii!iiiilj
JiiiiiiJi!iii!iiiii!i
."
,< 3
2
1:9 1:6 1:4"5 1:3 1:0:3 2:1:9 1:1:6 1:2:9 0:1:3
9 f I I I I [
0 2 4 6 8 10
C,a(OH) 2 per cent
FIG. 1S--Relationships between nominal mix proportions and air content.
testing. By this means carbonation of the lime mortars is reduced to a

minimum. The straight 1:0:3 cement: sand mortar had a transverse
strength of 530 psi and a 1:2:9 cement:lime:sand mortar 65 psi. As ex-
pected the pozzolanic material present in the less pure lime made a con-
tribution to the initial strength of the mortars. The highest strengths are
those containing the gray chalk hydrated lime (L381) and the two white
chalk hydrated limes (L277 and L403). These it will be noted (Table 14)
are the limes which tend to require less water to bring the mortars to a
(3)
O
I-- 0
1:0:3 2:1:9 1:1:6 1:2:9 0:1:3

FIG. 16--Relationships between nominal mix proportions and mortar transverse
strength at seven days.
GILLARD AND LEE ON TESTING OF BUILDING MORTARS I 11
TABLE 20---The comparison of the transverse strength (psi) of all the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Cement:Hme:sand
1:0:3... 530 530 530 530 530 530 530 530
2:1:9... 270 360 370 250 280 300 370 315
1:1:6... 140 220 220 160 180 160 200 180
1:2:9... 40 60 120 60 50 70 70 65
0:1:3 . . . . . . . . . . . . . . . . . . . . . . . . . . .
s t a n d a r d consistence, a n d h e n c e the w a t e r / c e m e n t r a t i o is r e d u c e d also.

C o m p r e s s i v e s t r e n g t h - - I t c a n b e seen b y c o m p a r i n g T a b l e 20 with
T a b l e 21 a n d Fig. 16 with Fig. 17 t h a t the results o b t a i n e d in these tests
are higher, b u t of the s a m e r a t i o as those o b t a i n e d in the t r a n s v e r s e
strength. T o d a t e t h e r e is insufficient evidence to relate the results of the
strength tests to the strength of b r i c k w o r k .
D i s c u s s i o n - - T h e w o r k in this section of the r e p o r t shows t h a t although
for c o n t r o l p u r p o s e s the a v a i l a b l e lime c o n t e n t of l i m e : s a n d m o r t a r s is a
useful m e t h o d of specifying, the p h y s i c a l p r o p e r t i e s of the l i m e u s e d d o
h a v e a p r o n o u n c e d effect on the p h y s i c a l p r o p e r t i e s of the m o r t a r s . W h e n ,
however, p o r t l a n d c e m e n t is a d d e d the m o r t a r s h a v e m o r e u n i f o r m p h y s i c a l
p r o p e r t i e s , a n d in all tests the s p a n of results is reduced.
TABLE 21--The comparison of the compressive strength (psi) of all the mortars.
Lime
number LP29 L277 L381 L391 L397 L399 L403

Cement:~me:sand
1:0:3... 2 350 2 350 2 350 2 350 2 350 2 350 2 350 2 350
2:1:9... 940 1 360 1 240 880 970 1 070 1 210 1 095
1:1:6... 450 780 720 500 620 510 710 615
1:2:9... 130 240 380 180 140 190 240 215
0:1:3 . . . . . . . . . . . . . . . . . . . . . . . . . . .
C o p y r i g h t b y A S T M I n t ' l ( a l l r i g h t s r e s
D o w n l o a d e d / p r i n t e d b y
E n r i q u e M a l d o n a d o ( M I n o r t e + S . A . + d e + C .
I 12 THE REACTION PARAMETERS OF LIME
2O
O~
c 12
~ 8
>
.~,
~ 4
E
0
U 0
1:0:3 2:1:9 1:1:6 1:2:9 0:1:3

FIG. 17--Relationships between nominal mix proportions and mortar compressive
strength at seven days.
It also is apparent from the results that an increase in lime content im-
proves the wet properties of mortars and thus confirms the work Minnick
[4], Ritchie and Davison [5], Johnson [6], Wells et al [7], and Boynton and
Gutschick [8]. The results also confirm that all the proposed Standard tests
[3] are sensitive to a change in the available lime content thus confirming
the results found for one lime in the first section.
Sand also has a considerable effect on the properties of building mortars
as discussed elsewhere [9].
Conclusions
The properties of building mortars, as determined by the methods pro-
posed in the draft British Standard for testing mortars, are dependent upon
the available lime content. More reproducible results are obtained from
hydrated lime after it has been soaked for 24 h.
The proportioning of mortars by weight is recommended. Lime:sand
mortars proportioned by the available lime contents, calculated on the total
dry weight of mortar, have less differences in physical properties when dif-
ferent types of lime are used than when mortars are proportioned by
volume.
As the lime content of a mortar is increased and the cement content de-
creased the wet plastic properties improve and the seven-day strength
decreases.
The draft British Standard tests for mortars generally give reproducible
results for lime:sand ready-mix for mortars and for portland cement:lime:
sand mortars. The exception is the consistence retentivity test. This is re-
grettable as this property is extremely important, and a satisfactory test is
necessary.
GILLARD AND LI~E ON TESTING OF BUILDING MORTARS I 13
Acknowledgment
The authors wish to thank E. W. Ball for his help with the practical
work and the Council of Welwyn Hall Research Association for permission
to publish this work.
References
[1] Bessey, G. E. and Lee, H. N., "Proportioning of Materials for Building Mortars,"
Cement Lime and Gravel, 1965, pp. 273-276.
[2] 3rd Draft British Standard Ref 68/24173, "Ready-Mixed Lime:Sand for Mortars,"
British Standards Institution.
[3] 8th Draft British Standard Ref 68/3502, "Methods of Testing Mortars," British
Standards Institution.
[4l Minnick, L. J., "Effect of Lime on Characteristics of Mortar in Masonry Con-
struction," American Ceramic Society Bulletin, Vol. 38, No. 5, 1959, pp. 239-245.
[5] Ritchie, T. and Davison, J. I., "Cement-Lime Mortars," Building Research,
Ottawa, 1964, pp. 10-15.
[6] Johnson, H. V., "Cement-Lime Mortars," Technical Papers of the Bureau of
Standards, No. 308 (Part of Vol. 20), U.S. Department of Commerce, 1926,
Washington, D. C.
[7] Wells, L. S., Bishop, D. L., and Watstein, D., "Differences in Limes as Reflected
in Certain Properties of Masonry Mortars," Journal of Research of the National
Bureau of Standards, Vol. 17, 1936, pp. 895-907.
[8] Boynton, R. S. and Gutschick, K. A., "Strength Considerations in Mortar and
Masonry," Masonry Mortar Technical Notes, National Lime Association, Sept.
1964.
[9] Lee, H. N. and Pyle, M. A., "The Design of Mortars for Calculated Load-bearing
Brickwork," Proceedings of the British Ceramic Society, Vol. 11, 1968, pp.
143-161.
DISCUSSION
1. I. Davison a (written discussion)--Gillard and Lee have introduced us

to some new and interesting tests for masonry mortars. A statement in the
Foreword of one of the early drafts of the British Standard "Methods for
Testing Mortars" explains that it resulted from a greater concern for the
quality of site mixed mortar in more critical conditions such as calculated
brickwork. Improvement in quality control in the conventional masonry
process will be welcomed by all those interested in the future of the
industry.
The use of a system of specifying sand:lime mortars on the basis of
"available lime content," thus ensuring that a particular mortar type will
contain equal amounts of "active lime," regardless of the source of the
material, is a notable advance. Unfortunately, the method used is applicable
only for high calcium limes, and would be of limited use in North America
where dolomitie limes commonly are used in masonry mortars.
Widespread use of factory-made lime mortars in England has facilitated
another of the basic practices in the available lime content philosophy--
namely, batching by weight, thus eliminating slap-dash on-site volume
batching with shovels, buckets, etc., and other problems such as bulking in
damp sands.
One of the most intriguing aspects of the British testing philosophy in-
volves the use of standard consistence, as measured by a dropping ball
penetration test, rather than standard plasticity used by ASTM and meas-
ured by the flow table, as a constant factor for comparing other mortar
properties. This reflects earlier work 2 at the Building Research Station in
England, which indicated that the consistence test gave a better agreement
with the bricklayers' judgment of workability than a number of other tests
including the flow table. A comparison of flow values for mortars having
the same consistence gives a good measure of workability. This is illus-
trated by the average results in Table 18 of the paper, where decreasing
flow values with increasing amounts of lime in ready-mixed sand:lime and
in cement:lime mortars at the same consistence indicate improved work-
ability.
Two new methods for determining the water retentivity of mortars are
discussed. In the first method the amount of water extracted by blotting
~Research officer, Atlantic Regional Station, Division of Building Research,
National Research Council of Canada, Halifax, N. S., Canada.
2 Ryder, J. F., "Testing the Working Properties of Mortars," Ch'emistry and
Industry, 21 May 1960.
114
DISCUSSION ON TESTING OF BUILDING MORTARS ] 15
paper from the top surface of 10 cm (4 in.) of mortar in a circular metal

mold is measured. Results, expressed either as gram of water absorbed by
the paper or by comparing the final and original water contents of the
mortar are quite consistent. The second method compares dropping ball
penetration before and after the blotting paper suction, and the results are
considered too erratic to be reliable. These tests have a very desirable fea-
ture in that they are performed on an undisturbed sample, thus eliminating
the handling involved in the ASTM test. The only reservations with the first
method concern the reproducibility of the blotting paper.
ASTM Committee C-12 members will note with interest the use of two
air content tests, the gravity method and the pressure pot method. Use of
only the latter method in the second part of the paper, after obtaining
erratic results from the gravity method in the first part, suggests a prefer-
ence for it. Results in Figs. 6 and 7 of the paper indicate higher values
for the pressure method. Since air-entraining agents were not used in the
mortars, a comparison of the two methods has some limitations.
Another procedure foreign to North American practice is the use of
mortar bars (100 by 25 by 25 m m - - 4 by 1 by 1 in.) for transverse and
compressive strength tests. Quite apart from the use of bars rather than
cubes is the curing for seven days in limewater, which, the authors note,
reduces the carbonation of the lime to a minimum. This will be of interest
to ASTM Committee C-7 members who are currently questioning labo-
ratory curing procedures which ensure an accelerated curing for the cement
content while retarding carbonation of the lime content in cement-lime
mortars.
R. Gillard and H. N. Lee (authors' closure)---The authors would like to
thank Mr. Davidson for his comments on their paper.
With the introduction of new building techniques the future use of
bricks will depend to some extent on the predictable properties of the
mortar used for jointing. The British Standard Institution test methods for
mortars is the first step in the United Kingdom to produce an official col-
lection of test methods. Members of the various committees responsible
for the standard will agree that improvements and modification in these
methods will be necessary. Some of the ideas incorporated in the tests are
the result of new approaches to the science of building mortars and only
extensive investigations will prove the validity of these assumptions.
The importance attached to the design and use of mortars in the United
Kingdom is illustrated by the fact that a special British Standards Institu-
tion Committee is now producing a document; "Guidance on specifying
building mortars."
With the greater universal awareness for scientific control in the build-
ing industry, it is becoming more important that test methods for materials
] 16 THE REACTION PARAMETERS OF LIME
such as mortars should be internationalized as far as possible. As Mr.

Davidson points out the use of "available lime content" reported here as a
control for the lime content of lime-sand mixes for mortars is not appli-
cable to dolomitic lime mortars, but doubtless a similar technique could be
developed. The use of the pressure method for air content in the second
part of the paper was not solely due to the erratic results obtained in the
first part when using the density method, but in order to reduce the quan-
tity of work required. The authors preferred the pressure method as it
takes less time and is at least as accurate as the gravity method.
R . C. M u l l i n s 1 a n d J. D. H a t f i e l d 1
Effects of Calcination Conditions on the

Properties of Lime*
REFERENCE: Mullins, R. C. and Hatfield, J. D., "Effects of Calcina-

tion C o n d i t i o n s o n the P r o p e r t i e s of L i m e , " The Reaction Parameters or
Lime, A S T M STP 472, American Society for Testing and Materials, 1970,
pp. 117-131.
ABSTRACT: Experiments were made to d e f n e quantitatively the effects

and interactions of the time of calcination, the temperature of calcination,
and the particle size of a pure limestone upon the properties of the calcine
that may affect the absorption of sulfur dioxide from flue gases. Response
surfaces were derived for the degree of calcination, pore volume, density,
crystallite size, and capacity to absorb sulfur dioxide as functions of the
calcination conditions. It is predicted that wide variation in the degree of
utilization will occur over relatively narrow ranges of retention time and
injection temperature likely to be encountered in attempts to control sulfur
dioxide emissions by injecting limestone in power plant furnaces.
KEY W O R D S : limestone, roasting, particle size, sulfur dioxide, absorbers

(materials), calcines, porosity, calcium oxides, crystallites, evaluation, tests,
time dependence, temperature control
The problem of atmospheric pollution by sulfur oxides emitted from

power plants using fossil fuel is rapidly becoming a serious one. Among the
number of removal methods that have been proposed [1,2] ~ the limestone
injection process, where ground limestone is brought into contact with the
hot flue gases, is especially attractive because of its simplicity and low
investment cost. Although the large amount of research currently being
done has not defined the interrelated physical and chemical factors that
control the process, it seems to be agreed generally that conversion of the
limestone to the oxide is the first step, and the conditions under which the
* Work performed under contract TV-29232A with the National Air Pollution
Control Administration of the U.S. Public Health Service.
1 Research chemists, Division of Chemical Development, Tennessee Valley Author-
ity, Muscle Shoals, Ala. 35660.
-~The italic numbers in brackets refer to the list of references appended to this
paper.
117
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
1 18 THE REACTION PARAMETERS OF LIME
calcination takes place has a major influence on the subsequent reaction of

the calcine with the sulfur oxides.
Studies of calcination have been made by many investigators
under the conditions used in the lime industry where relatively large par-
ticles are heated in kilns for considerable lengths of time; however, no in-
formation was found on the shock calcination of micron-size particles in
time intervals of seconds or less as it would occur in an injection process.
This investigation was made to obtain information on calcination under
conditions applicable to the injection process.
Experimental
Design of Experiments
The experimental design of the tests was that of the rotatable central
composite method by Box and Wilson [3]. The three variables tested were
time of calcination, temperature of calcination, and particle size of the
limestone. A full factorial of the three variables, each at two levels, was
made, and additional tests were made at the extremities of each variable
and at the center of the design. Thus, each variable was tested at five
levels in a manner to determine its effect and interactions with the other
variables; in addition, the curvature of the various responses was de-
termined for each variable at fixed conditions of the other variables. This
type of design is very efficient for response surface treatment, and it re-
suits in a rather uniform variance of prediction throughout the experi-
mental region.
The levels of the variables are shown in Table 1. The time of calcina-
tion was varied from 89 to 8 min in geometric units; the temperature was
varied from 1018 to 1272 C with the increments between levels becoming
progressively smaller as the temperature increased; the average particle
size (see preparation of materials) was varied from 645 to 81 /xm in
closely sized fractions. Each variable was coded, xi (i = 1, 2, 3), and the
relationships between the experimental variables and their respective coded
form are given by the equations at the bottom of Table 1, in which t
time, minutes; T = temperature, deg C; and/xm ~ the average particle
diameter, microns, of the limestone charged. The coded levels varied from
--2 to +2, corresponding to the levels of time, temperature, and particle
size in Table 1.
The ranges of the variables were limited by equipment and measuring
techniques and are thus not entirely ideal for application to injection tests.
They represent a compromise on values where quantitative measurements
could be made readily without elaborate equipment and without introduc-
ing complicating factors that might affect the results. From these measure-
MULLINS AND HATFIELD ON CALCINATION CONDITIONS 1 19
T A B L E 1--Coded values of variables affecting limestone calcination.
V a l u e o f V a r i a b l e w h e n Its C o d e d V a l u e is
Variable Code - 2 - 1 0 1 2
Time, min, t ................. x, 0.5 1 2 4 8

T e m p e r a t u r e , d e g C, T . . . . . . . . x~ 1 018 1 100 I 168 1 225 1 272
P a r t i c l e size, u m . . . . . . . . . . . . . x3 645 384 227 135.5 81
Tyler screen equivalent, mesh.. (-24 ( - 35 ( - 60 ( - 100 ( - 170
-{-28) +42) -I-65) + 115) -t-200)
NOTE--
t = 2 X 2 x~
L o g (1500 - T) = 2.5207 - 0.081365x2
um= 227 X 0.6xa
ments it was hoped that reliable extrapolations could be made over the
range of conditions useful in studying the process.
Selection and Preparation of Material

To avoid the possible complicating effects of impurities, a calcitic lime-
stone analyzing very near theoretical was selected for the tests. The per-
centage composition from wet analysis was: calcium oxide (CaO) 55.2
(theory 56.0), magnesium oxide (MgO) 0.3, carbon dioxide (CO2) 43.7
(theory 44.0), and silicon dioxide (SIO2) 0.2 percent. Petrographic ex-
amination identified the small amount of accessory mineral impurities as
predominantly quartz with a minor quantity of illite clay. The well-formed
grains were larger than 250/zm in diameter. X-ray examinations of the cell
parameters showed that there was essentially no isomorphous substitution.
Samples for testing were initially sized by dry screening of the hand-
ground material on closely sized screens with the appropriate mesh open-
ings (Table 1 ). These fractions were further sized by dispersing and wet
screening. The wet-screen fractions after acetone washing and air drying
were dry screened again. The final product was examined microscopically
for uniformity of size and freedom from aggregates. The diameter of the
particles was assumed to be the arithmetic average of the size of the open-
ings of the two screens which just passed and retained each fraction.
Calcinations
Shock calcinations were made in an environment somewhat similar to
that to be expected if limestone were injected into the hot gas stream of a
power plant. Heating was provided by a 4.5 cm inside diameter, vertical
] 20 THE REACTION PARAMETERSOF LIME
tube furnace mounted so that it could be quickly raised around a sample

holder suspended above the furnace. A 15 percent CO2, 85 percent air
mixture flowed through the furnace at 1400 cm3/min providing a change
of atmosphere approximately 2.5 times per minute. The 3.5 by 3.5-cm
cylindrical sample holder, made of 100-mesh platinum gauze with a per-
forated foil lid, permitted free escape of CO2 during heating of the samples.
By limiting heatings to 0.5 g of stone spread on the foil sample holder floor
in essentially a monoparticle layer the calcination approached that occur-
ring with particles dispersed in a gas stream. Products from five to eight
heatings at each factorial level were blended to obtain sufficient quantities
for response tests.
Temperatures were monitored with a potentiometer connected to a cali-
brated platinum-platinum 10 percent rhodium thermocouple placed in the
center of the furnace tube so that the bead just cleared the bottom of the
sample holder when it was in the heating position. Furnace temperatures
were adjusted to the required level before each heating. When the furnace
was raised into position around a sample the temperature always dropped
20 to 30 C during the first 8 to l0 s of heating. Recovery was dependent
on starting temperature. About 52 s were required at 1018 C and 22 s at
1272 C. Particle size did not appear to affect this temperature change.
Changes of about one half this magnitude with a rapid recovery occurred
with the empty sample holder. The difference was, presumably, caused
largely by heat absorption of the endothermic decomposition reaction,
although some heat would be required to raise the particles to decomposi-
tion temperature. Temperature for the remainder of each heating period
was held within - 4 C by adjusting the furnace current. The total time the
sample was in the heating zone of the furnace was recorded as the heating
time. Obviously, for a part of this time the sample was not at furnace tem-
perature, and the percentage of total time the sample was below tempera-
ture is much greater for those heated for shorter times. No attempt to
closely follow these changes, or compensate for them, was made because
there would be similar delay in the particles coming to temperature in any
injection process.
Thermal shock produced some spalling, particularly with the larger par-
ticle sizes and at higher temperatures. Again, this was considered a
normal event of shock calcination, and the calcines were used as produced
without regard to change in particle size.
Calcines were held in evacuated desiccators containing a layer of dehy-
drite to protect them from atmospheric hydration and carbonation. Expo-
sure to air during weighings and other preparations for tests was held to a
minimum.
MULLINS AND HATFIELD ON CALCINATION CONDITIONS 121
Response Tests
Response to the treatment at each factorial level was determined by
measuring the SO2 absorption of the calcines. The pore volume, density,
percentage calcination, and crystallite size also were measured because of
the possible relation of these properties to SOe absorption under conditions
differing from those used in the absorption tests.
SO2 absorption tests were made in a thermogravimetric analytical appa-
ratus (TGA). Fifty milligram samples of the calcines were spread in a thin
layer, to minimize effects of bed depth on absorption, on a porous alundum
plate before it was suspended in the reaction tube and lowered into the
heated TGA furnace. During the 10 to 13 min required to bring the
sample to reaction temperature, 920 to 940 C, it was swept with dry
nitrogen (N2). A gas mixture containing 4 percent SO._,, 4 percent 02, and
92 percent N~ was then admitted, and a flow rate of 500 cm3/min of this
mixture was maintained for the 30-rain absorption time. Calcium sulfate
(CaSO4) was the only absorption product under these oxidizing condi-
tions; therefore, the weight increase monitored by the TGA was equivalent
to SOa absorbed even though the gas mixture contained only SO.,. The
small weight increases, in some cases, approached the lower sensitivity
limits of the TGA and were somewhat erratic; therefore, all increases were
verified by weighing the product after cooling the furnace while sweeping
with N2 and then analyzing it for sulfate by conventional wet methods.
Averages of these results on replicate absorptions were used.
The pore volume, which had been shown by earlier investigations to have
a high correlation with fixed-bed absorption of SO,, (unpublished Ten-
nessee Valley Authority and National Air Pollution Control Administration
data), were measured with a mercury porosimeter that had an upper pres-
sure limit of 5000 psia which limited penetration to pores 0.035 /zm in
diameter. Use of the volume of pores with diameters between 17.5 and
0.035/zm minimized the effect of the difference in particle size on the pore
volume.
Densities were calculated from weights of the porosimeter penetrometer
containing the sample and mercury. At the point calculated, with pores
larger than 17.5 #m in diameter filled, the values are comparable to bulk
density determined by mercury displacement.
Loss of weight in these tests was used as a measure of calcination. Per-
centage calcination was calculated from the loss in weight of the calcines on
further heating to constant weight and the ignition loss of the original
material.
CaO crystallite size was measured by the X-ray line-broadening tech-
nique described by Rau [4] using the value of/3 as defined by Azaroff [5].
The experimental design and the results of the tests are listed in Table 2.
Each response was fitted to a quadratic in the coded variables, xl, x2,
and x3, as follows:
y = bo + b,xl + bex2 ~- b3x3 + b, lxl 2 + b22x22 Av b33xa2 +

bt2xlx2 + bl~xlx3 + b2~x2x~ . . . . (1)
In Eq 1, y is a function of one of the responses listed in Table 2, yl
through y~. The function y was limited to the response or its logarithm
(base 10), and Table 3 shows the coefficients of Eq 1 for the function that
was considered superior in reproducing the data and extrapolating to other
levels of the variables. The standard deviation of the fit, s, and the correla-
tion coeff• R, are also given in Table 3. It should be noted that the
standard deviation is expressed in units of the response when the response
itself was used for y (the case for Y4); when the logarithm of the response
was used for y (as for yl, y2, y3, and ys), the standard deviation becomes
TABLE 2--1nfluence of time, temperature, and particle size on the properties of calcines.
Response Measured as
Level of SO2 Absorp-

Variables tion, Mg Pore Volume, Density,
(coded) a weight gain pores 17.5 to pores >17.5 CaO Crystal-
(SOD/100 Mg 0.035 um dia, um dia filled, Calcination, lite Size,
x, x2 xa calcine, yl cc/g, y2 g/cc, ya percent, y4 ,~, y5
--I -1 -1 36 0.160 1.82 96.3 1 800

+1 -1 --1 23 0.150 2.04 97.5 2 300
--1 +1 --1 13 0.093 2.45 98.6 1 900
d-1 --kl -1 11 0.087 2.57 99.7 5200
--1 -1 +1 31 0.132 1.88 95.9 1 300
+i -1 +1 17 0.126 2.24 98.0 2700
--1 -bl +1 11 0.097 2.51 99.1 4800
-1-1 --kl +1 11 0.082 2.63 99.3 3 750
--2 0 0 34 0.126 2.01 96.6 1 900
-+-2 0 0 13 0.083 2.61 99.5 8 750
0 -2 0 49 0.217 1.76 96.3 1 950
0 +2 0 13 0.080 2.67 99.5 4 800
0 0 --2 17 0.116 2.31 98.3 5 200
0 0 +2 15 0.156 2.35 99.1 4 800
0 0 0 18 0.093 2.47 98.5 4 150
0 0 0 20 0.114 2.38 98.6 3 600
Notation as in Table 1.
MULLINS AND HATFIELD ON CALCINATION CONDITIONS ]23
T A B L E 3--Coefficients of Eq 1.
Coefficients when y is in Indicated Units
L o g SOs L o g Pore
Absorption, Volume, pores Log Density,
M g weight gain 17.5 to 0.035 pores > 17.5 ~ m
(SO3)/100 M g ~ m dia, cc/g, filled, g/cc, Calcination, Log Crystallite
Coefficient calcine, log y~ log y2 log y3 percent, y4 Size, A, log y~
bo. . . . . . 1.2448 -0.99557 0.37945 98.425 3.4982

bl . . . . . . -0.085194 -0.032046 0.024599 0.65000 0.13051
b2 . . . . . . -0.15964 -0.10371 0.049164 0.96250 0.11661
ba . . . . . . - 0.023593 0.0056656 0.0056342 0.11250 0.0076306
bll . . . . . . 0.011140 0.00074240 -0.0061797 -0.12500 0.0070863
b2~. . . . . . 0.030980 0.026770 -0.012156 -0.16250 -0.023836
b3~. . . . . . -0.018720 0.029024 -0.0043243 0.037500 0.028869
b12 . . . . . . 0.047867 -0.0067112 -0.010575 -0.25000 -0.012006
blz . . . . . . 0.00077657 --0.0045211 0.0032558 --0.000000014900 --0.042485
b2~. . . . . . 0.015459 0.0189813 -0.0042718 -0.~14900 0.041952
s, ~ . . . . 18.5 14.2 3.5 0.46 54.6
R ...... 0.974 0.958 0.987 0.973 0.852
the percent of the response measured. With the exception of crystallite

size, the expressions reproduce the experimental data satisfactorily; how-
ever, it is likely that some other transformation of the responses, or combi-
nations of them, would prove more useful in interpreting the results. This
is beyond the scope of this paper.
Figures 1, 2, and 3 show calcination isochrones of the different responses
as functions of calcination temperature with limestone particle size con-
stant. They were obtained by fixing the time and particle size, xl and x3,
which reduces Eq 1 to
y = bo' + b._,'x2 + b~x.,9 . . . . . . . . . . . . . . . . . . . . . (2)

The magnitude of the constants bo' and b=,' vary with the fixed conditions
of xl and x~, thereby affecting the shape of the curve. Similar curves for
time and particle size could be constructed also at fixed conditions of the
other variables. Extrapolations beyond the experimental range were made
by substituting appropriate values of xa and x3 using the relations in Table
1. Extrapolations in either time or limestone particle size or both are shown
in the figures. Such extrapolations, although useful, are always subject to
verification. They were developed here for their possible value in predict-
ing the effect of variables in a region not conveniently studied. They are
presented, except for some examination for reasonableness, without at-
z~ I 0 0
hi z-~ s~ '
0
~ 90
Z
o /1/i ~ /
~ 80
Z
_1
70 I I
I000 I100 1200 I I00 1200 I100 1200 1300
TEMPERATURE, DEG C
FIG. 1--Effect of initial particle size and time and temperature o/ calcination on
degree o/ calcination.
I I
645 F
2.4
-7//-
r
f 2.0
1.6
///:.c _/, __/,os.c/_
(.9
k 645//. _ 227//. 81/J. _
Io
'5
0.3
tJ
/
o
hi
0.2
_ %'~EC
~ SEC
Ir _ 6 0 " 2 4 0 ~
0 0.1
0 I I 1227F _
_ 645/./.
,3 8 0 0 0
Ix.
o 5000
<-
2000
I,r
._1
.-I
,,:z I 0 0 0 - I0 SEC _
I--
(/)
>-
u I I
50,
1000 I I00 1200 I tO0 1200 I100 1200 1300
TEMPERATURE, DEG C
FIG. 2--Effect o/ initial particle size and time and temperature of calcination on
physical properties o] calcines.
tempting to explain the mechanisms involved, which will require further

study.
Plots of the isochrones of percent calcination at extrapolated calcination
times down to 0.1 s at the two extremes of limestone particle size studied,
and at l0/zm are shown in Fig. 1. In this figure, as well as in Figs. 2 and 3,
the spread between the isochrones at a given temperature shows the effect
of time upon the response; thus, the time of heating affects percent calcina-
tion more at low temperatures than at high temperatures. Particle size
seems to have little effect on calcination. This could be due, in part, to the
spalling of the larger particles when subjected to thermal shock; however,
there was no indication that particle size was reduced eightfold by spalling.
The prediction that a 10-/zm particle of limestone heated for 0.1 s at 1300
C would be less than 90 percent calcined is of interest because of the
relation of calcination to SO~ absorption. The extrapolated values for the
other two particle sizes, 81 and 645 /zm, are not significantly different,
and these predictions should be more reliable because only time was ex-
trapolated. Clearly, if these predictions are true, fine grinding of limestone
would not increase significantly the percent calcination at short time
intervals.
Density, pore volume, and crystallite size are interrelated properties. The
I.l.I
,o- T
effect of the variables on each of them can be compared in Fig. 2 at the - 2 ,
645//.
T r
50F
~ r ~
lop.
z 60
q i / IsEC
0
o 50-
m
o I0
_.9_
~ 40
o
~ 60
~ 3C
ID
~ zo - I0
II1
ffl
60-
240
I000 I I00 1200 I I00 1200 I I00 1200 1300
CALCINATION TEMPERATURE, DEG C
F I G . 3--EfJect o[ initial particle size and time and temperatztre oJ calcination on
absorption of sal[ar dioxide by calcines. Calcines sul]ated 30 rain at 920 to 940 C.
0, and + 2 factorial levels of limestone particle size. The isochrones for dens-
ity and crystallite size show, in general, increases with increasing temperature
while those of pore volume decrease. This is consistent, because denser cal-
cines with larger crystallites are less porous. The tendency of density to reach
a maximum at about 1250 C with longer heating times was unexpected. A
corresponding minimum in pore volume at essentially the same temperature
is in agreement. It is further substantiated by a maximum in crystallite size
shown particularly with 645-/~m limestone particles. Even though both time
and particle size have some effect on the location and magnitude of these
maxima or minima there is a suggestion of a common cause. The failure of
density to increase continuously with temperature was observed in an
earlier investigation of shock calcination on minus 10, plus 20-mesh parti-
cles at retention times of 1 to 4 h [6], where it was found that the bulk
density of calcines increased with calcination temperature to a maximum at
1200 C, then decreased until the temperature passed 1300 C before in-
creasing again. At shorter time intervals the proiected curves indicate that
the maxima in density and crystallite size disappear within the temperature
range shown, but the pore-volume minima are still apparent. The iso-
chrones for density, pore volume, and crystallite size appear to be in general
agreement and thus lend support to the validity of the curves, despite the
poor fit of the crystallite size data shown in Table 3. The very marked
effect of time on crystallite size when large limestone particles are calcined
is understandable, but the disappearance of this effect in the small particle
size needs further study. The extrapolations of the crystallite size to high
temperatures and short times gave a "saddle-point" surface which is most
difficult to understand and explain.
The SO:: absorption curves of Fig. 3, in effect, can be considered a sum-
mation of Figs. 1 and 2 because the result of each of the other responses
has a possible effect on SO., absorption. Here again time has a greater effect
at lower than at higher temperatures. This effect is smaller as the particle
size becomes smaller. The tendency toward a minimum of SO,_, absorption
at about 1200 C in the longer time isochrones agrees with the maximum in
density and minimum in pore volume occurring at approximately the same
temperature if the concept that a highly porous, less dense calcine is more
absorbent is accepted. This minimum is not so readily apparent in the
projections at short time intervals and small particle size, but it probably
occurs outside the temperature range shown. The effect of limestone par-
ticle size shown by the extrapolations is particularly interesting. At a pro-
jected calcination time of 1 s and a calcination temperature of 1300 C
50-/xm particles absorb no better than 645-/xm particles, and 10-/xm par-
tides only about one third as well. This suggests that fine grinding of lime-
stone is of doubtful advantage, particularly if the calcination temperature is

high.
When only one variable is fixed, say x~, Eq 1 becomes
y = bo" + bl"xt + b('x2 + bl~xl~ + b.,.,,.x22 + ba~xlx~ . . . . . . . . (3)

The magnitudes of b0", bl", and b2" vary with the fixed particle size, and
the response surface likewise is altered. This is illustrated in Figs. 4 and 5
in which lines of constant SO2 absorption are shown as functions of both
time and temperature of calcination. Figure 4 shows the results using minus
170- plus 200-mesh limestone with the experimental region inside the
IO00 IIO0 1200 1300

CALCINATION TEM~ DEG C
FIG. 4--Extrapolation oJ effects o/ calcination conditions on capacity o] calcines
to absorb sul[ur dioxide. Initial particle size, 81 tzm: calcines sulfated 30 min at 920
to 940 C; experimental data in area enclosed by broken lines.
6O I I 1 I I
I . . . . . . . . . . [ I
u)
o
z
o
o
w
(/)
u2
I--
z
o
i.-
z
.J
,<
u
C
0.._
I000 I100 1200 1300
CALCINATION TEMP, DEG C
F I G . 5--Extrapolation o / e f f e c t s o/calcination conditions on capacity of calcines to
absorb slllfur dioxide. Initial particle size, 10 ~m; calcines sul]ated 30 min at 920 to
940 C; experimental data in area enclosed by broken lines.
dashed lines. The results show that the isopleths of reaction converge to a
very narrow temperature region at short times; that is, the response surface
is very steep in this region. This indicates that temperature is extremely
important in obtaining good reaction with SO,, when the retention time is
short. For example, at 1250 C for 0.15 s it is predicted that the calcine will
react to 90 percent of its capacity with SO3; the capacity of the lime to
react is decreased to 30 percent by (1) changing the temperature of calci-
nation from 1250 to 1300 C, or (2) changing the time of calcination from
0.15 to 1.0 s, or (3) changing the temperature to 1275 C and changing
the time to 0.35 s. Figure 5 shows the same trend for 10-Fm limestone,
but the temperature for a given degree of reaction is lowered for a given
time of calcination. For example, the predicted capacity to react decreased
from 90 percent at 1160 C and 0.15 s to 14 percent at 1240 C and 0.60 s.
The significance to injection conditions is quite obvious in view of the
present lack of knowledge of retention times and temperature profiles
within the furnace.
MULLINS AND HATFIELD ON CALCINATION CONDITIONS ] 29
While these predictions represent considerable extrapolation from the

experimental range in both time and particle size, the results appear rea-
sonable. They do not include consideration of the degree of calcination,
pore volume, density, crystallite size, or any other property of the calcine
which might limit the extent of the reaction. Such considerations could be
made by overlaying response surfaces on each other, providing the limi-
tation mechanism is understood. For example, an overlay of the percent
calcination on Figs. 4 and 5 for the same fixed conditions might show that
the degree of reaction at short times would be limited by the degree of
calcination. Similar considerations for the pore volume, density, and crys-
stallite size could be made, although our present knowledge of the mech-
anisms involved preclude any reasonable present-day applications. How-
ever, the quantitative relations that have been developed permit a multitude
of comparisons not previously available and should be most helpful in both
understanding the mechanisms of the sulfation reaction and optimizing
conditions for the decrease of SO2 emissions in flue gases.
Conclusions
The response surfaces for various properties of calcines from a pure
limestone have been described quantitatively, and predictions in regions
difficult to investigate have been made. The results, while somewhat specu-
lative, show that the temperature of injecting limestone into a furnace and
its retention time significantly affect its capacity to absorb SO2 and other
properties of the calcine. The particle size of the limestone affects the cal-
cination rate only slightly, and the results show that fine grinding of the
limestone is of doubtful value for SO2 absorption particularly if the calcina-
tion temperature is high.
References
[1] Squires, A. M., "Air Pollution: The Control of SO,, from Power Stacks. Part
I I - - T h e Removal of SO2 from Stack Gases," Chemical Engineering, Vol. 74,
No. 24, 20 Nov. 1967, pp. 123-140.
[2] Slack, A. V., "Air Pollution: The Control of SO2 from Power Stacks. Part I l I - -
Processes for Recovering SO-,," Chemical Engineering, Vol. 74, No. 25, 4 Dec.
1967, pp. 188-196.
[3] Box, G. E. P. and Wilson, K. B., "On the Experimental Attainment of Optimum
Conditions," Journal o] the Royal Statistical Society, Vol. 13, No. 1, 1951, pp.
1-45.
[4] Rau, R. C., Advances in X-Ray Analysis, Vol. 5, University of Denver, Plenum
Press, New York, 1962, pp. 104-116.
[5l Azaroff, L. V., "X-Ray Diffraction Methods," 56th Norelco X-Ray Analytical
School, Philips Electronics Instruments, Mt. Vernon, N. Y., 1967.
[6] Fischer, H. C., "Calcination of Calcite. I. Effect of Heating Rate and Temperature
on Bulk Density of Calcium Oxide," Journal o] the American Ceramic Society,
Vol. 38, No. 7, 1955, p. 245.
DISCUSSION
A. E. Potter 1 (written discussion)--Battelle Memorial Institute, working

under National Air Pollution Control Administration contracts PH 86-67-
115 and PH 86-68-84, has reported the degree of calcination for limestone
particles injected at room temperature into a moving, high-temperature
isothermal flue gas. With Battelle's equipment, localized conditions found
in power boilers can be closely simulated. Shock calcination rates reported
by Battelle for the short contact times expected in power boilers are sub-
stantially higher than those predicted by the mathematical model proposed
by Mullins and Hatfield. For example, at a flue gas temperature of 1100 C,
Battelle reported that three high calcium stones (average CaO = 95 per-
cent) sized between 20 and 40/~m reached 95 percent calcination in 0.61
s. For the same average particle size at the same calcination temperature,
the Tennessee Valley Authority (TVA) model predicts that a contact time
of 10 s would be required to reach the same degree of calcination.
The differences between the calcination rate in Battelle's injection en-
vironment and the rate predicted by the authors' mathematical model may
be due to differences in the experimental conditions employed. Convection
is considered to be the limiting heat transfer mechanism in the Battelle
study; conduction is probably the limiting heat transfer mechanism in the
test procedure used by TVA. Also residence times differ substantially in
injection environments and in fixed beds. In the Battelle reactor the resi-
dence time is approximately 1 s; Mullins and Hatfield had to extrapolate a
residence time in the 1-s region from data collected at exposure times of
30 s and longer. Since the form of the TVA model of necessity is empirical
and is not based on a fundamental mechanism, such large extrapolations
may not be reliable.
The model predicts the existence of maxima or minima in physical prop-
erties. It would seem that experimental work is needed to verify this in-
teresting result. Also, the model indicates that the degree of calcination is
practically independent of particle size. Perhaps the authors will have an
opportunity to conduct further research and to make heat transfer calcula-
tions that will explain the reaction mechanism responsible for this result.
R. C. Mullins and .1. D. Hatfield (authors' closure)--The lack of agree-
ment between the Battelle data on calcination and the projections in this
paper is recognized. All the reasons listed by Mr. Potter, including the
1 Division of Process Control Engineering, National Air Pollution Control Adminis-
tration, Cincinnati, Ohio.
1:30
DISCUSSION ON CALCINATION CONDITIONS 131
admittedly extensive extrapolations, could contribute to the differences.

The well-known wide variation in the reactivity of limestones also could
contribute, and the Battelle data support this. Because of the empirical
nature of the model and the magnitude of the extrapolations, the present
data are perhaps best used to indicate generalizations on the interaction
effects of the variables and overall trends in response, rather than to make
specific predictions at selected points.
The maxima and minima in physical properties are substantiated by re-
cent electron microscopy studies ("X-Ray and Electron Microscope Stud-
ies of Calcined and Sulfated Limestones" by G. H. McClellan, S. R. Hun-
ter, and R. M. Scheib) in which the mechanisms are discussed.
The effect of particle size of the stone on the properties of the calcine
may have been influenced by the spalling that occurred during the shock
calcination. The important point in these studies is the interaction effect of
particle size with both time and temperature of calcination in determining
the capacity of the lime to absorb sulfur dioxide.
Gerhard Derge' and J. R. Shegog a
Observations on the Solution of

Calcium Oxide in Slag Systems
REFERENCE: Derge, Gerhard and Shegog, J. R., "Observations on the

Solution o f Calcium O x i d e in Slag Systems," The Reaction Parameters
o] Lime, ASTM STP 472, American Society for Testing and Materials, I970,
pp. 132-142.
ABSTRACT: A modified hot-filament microscope is used for direct

observation of the solution of calcium oxide (CaO) in synthetic melts
simulating slags of metallurgical interest.
In the CaO-SiO2 system the process is uncomplicated in acid slags.
However, in basic slags, when the composition approaches the liquidus in
equilibrium with 2CaO-SiO2, a protective film develops which has many
of the characteristics of a glassy phase. The crystallized film has the
composition of 2CaO-SiOe, and crystallization results in more rapid solu-
tion of the CaO, apparently on account of the associated decrease in
specific volume.
This mechanism operates with or without imposed temperature gradients
and convection. It is not changed significantly by small additions of other
common slag components. It appears to be general and has been observed
in all other binary systems studied, including MgO-SiOe and CaO with A1,_,Oz,
P._,Os, B.,O3, and V205. Related experiments have demonstrated the release
of oxygen gas as a result of the combined influence of temperature and
composition gradients during CaO solution. This is due to the change in the
ferrous/ferric ion ratio and associated changes in slag structure.
Presentation based on high-temperature micrographs.
KEY W O R D S : hot-filament microscope, calcium oxide, slags, crystalli-

zation, temperature gradients, evaluation
The general and rapid adoption of basic oxygen steelmaking processes

has led to a renewed interest in the reactions of slag formation which are
important for process control. Other papers on this program present infor-
mation on the limiting equilibria and thermodynamics of slag formation.
This one presents studies of the mechanism of calcium oxide (CaO) solu-
i Professor and research metallurgical engineer, respectively, Carnegie-Mellon

University, Schenley Park, Pittsburgh, Pa. 15213.
132
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
DERGE AND SHEGOG ON SLAG SYSTEMS 133
FIG. 1---Sketch o/ chamber /or hot filament specimens.
tion in slag, which in turn influences the rate at which the desired refining
equilibria can be achieved.
Knowledge of the equilibria gives us some intuitive understanding of the
mechanism of C a O solution in slags. Some of the difficulties expected from
the formation of refractory 2CaO 9 SiO2 have been confirmed by general
steelmaking experience and by petrographic studies of quenched samples.
However, direct observation of the process at temperature has given new
insight. This has been accomplished by adoption of the hot-filament micro-
scope used by ceramists" for phase diagram studies, Plate I a. The essential
features have been described, 3 but modifications were required for some of
the experiments reported now, Fig. 1.4 An important feature of the equip-
'-'Ordway, F. "Techniques for Growing and Mounting Small Single Crystals of
Refractory Compounds," Journal of Research, National Bureau of Standards, Vol.
48, 1952, pp. 152-158.
~9Derge, G., "Heterogeneity and Interface Reactions in Iron and Steelmaking,"
(The 1967 Howe Memorial Lecture) Transactions of the Metallurgical Society, Ameri-
can Institute of Mining, Metallurgical, and Petroleum Engineers, Vol. 239, 1967, pp.
1480-1488.
4 Stoehr, R. A., "Intermediate Phases in the Solution of Oxides in Basic Slags,"
Ph.D. thesis, Department of Metallurgy and Materials Science, Carnegie-Mellon
University, Pittsburgh, Pa., 1969.
ment is its simplicity. The specimen is a single droplet of molten slag

weighing about 1.0 mg, adhering by its own surface tension to a small loop
of 0.025-cm platinum alloy wire which serves as the heating element and
crucible. The ability to observe this entire melt stereoscopically at magnifi-
cations from • 10 to • is considered more important than higher mag-
nification. The gas composition is controlled readily, and small crystals,
microthermocouples, and auxiliary heaters can be manipulated with the
sliding probes. It is estimated that when the heating power is cut off the
entire specimen is quenched to room temperature in less than 2 s.
Lime Solution
The typical features of lime solution in molten slag will now be observed.
The crystalline sample has been cleaved from electrically fused C a t and is
about 0.025 cm at the maximum dimension of the cross section. When in-
serted in a relatively acid 30 C a t - 7 0 Site slag at 1600 C the C a t is wet
readily by the melt, and solution proceeds without formation of inter-
mediate layers, or other complications, Plate I b. The crystal must be fed
into the slag at about one minute intervals to maintain continuous reaction,
but this period decreases as the slag becomes more basic, and finally a new
phase appears at the interface, at which time the system essentially is
stabilized. Presumably the slag has reached the liquidus composition in
equilibrium with 2 C a t 9 SIO2. This is confirmed by repeating the experi-
ment with an initial slag composition of 55 CAO-45 SIO2, when the film
forms almost immediately at the C a t interface, and solution is immeasur-
ably slow until the film appears to crystallize, Plate I c. Then definite in-
crease in rate of the overall solution process requires continuous feeding of
the C a t , Plate I d.
Although the analogy may not be completely rigorous, since the metas-
table film has not been characterized completely, the qualitative observa-
tions can be explained by reference to the "fictive temperature" concept,
Fig. 2. The initially formed intermediate film has the high viscosity of a
supercooled liquid or glass, but is highly protective toward the C a t sub-
strate since there is no discontinuity in density (specific volume) between
it and the slag. The change in volume associated with crystallization leads
to imperfections or capillarity which result in spalling and provide renewed
access of bulk liquid to the CaO. After the crystalline 2CaO" SiO2 has
been nucleated, protection is no longer provided, and solution proceeds at
an accelerated pace. Diffusion rates through such viscous phases are known
to be several orders of magnitude lower than in the corresponding liquids,
and the typical data in Table 1 show that mass transport through a film of
the observed thickness must be extremely slow.
(a) Photograph of microscope assembly. (b) Solution of calcium oxide in slag
See Howe Lecture, Fig. 5. (37CaO--63SiO2), about 1600 C, no
intermediate phase formed.
(c) Solution of calcium oxide crystal in (d) Same as (c), 56 min after contact,
slag (55Ca0-45Si02), 1580 C, 16 min complete crystallization, renewed wet-
after contact (• ting of calcium oxide.
(e) Pair of calcium oxide crystals dis- (D Solution of magnesium oxide in slag
solving in slag (55Ca0-45Si02), 45- (35Mg0-65Si09), about 1570 C.
deg temperature gradient at about
1500 C, left cooler.
PLATE I
(a) Solution of calcium oxide in slag (b) Quenched sample after solution of
(55CaO-45PeOs), about 1620 C. calcium oxide in slag (initial 55CaO-
45SiOe, with 2 percent FeO added).
Transmitted light shows FeaO4 crys-
tals rejected at slag-film interface.
(c) Homogeneous slag during calcium (d) Escape of oxygen bubbles at surface
oxide solution, showing temperature removed from calcium oxide solution
gradient. area. Oxygen evolution at hot, low
calcium oxide surface.
(e) Escape of oxygen bubbles at surface

removed from calcium oxide solution
area. Eruption caused by violent
oxygen evolution.
PLATE II
DERGE AND SHEGOG ON SLAG SYSTEMS 137
~ quid
i .,oy
1
I
Tfictive Tmelt
TEMPERATURE
F I G . 2--Characteristic changes o/ volume o/ glass-/orming materials in the region
o/ the fictive temperature.
This solution mechanism has been described in considerable detail be-

cause it appears to have general significance. Experiments have failed to
establish a situation when a basic melt of liquidus composition in equi-
librium with a high melting crystalline phase does not produce such a
protective film.
In the binary CaO-SiO2 system the film thickness and solution rate are
related to the temperature gradient, Plate I e. If two CaO rods are main-
tained at different temperatures, it is observed that the hotter one has the
thinner film, but this intermediate layer is always present, even in the
absence of a measurable temperature gradient.
Extension to More Complex Systems

Similarly, films are observed during the solution of magnesium oxide
(MgO) in MgO-SiO2 (Plate I 1) and during the solution of CaO in non-
silicate melts with A1203, P205, B2Os, and V205 (Plate II a) as the acid
components. Thus the relevance of the protective film formation should be
considered in other processes involving solution of basic oxides, such as
glassmaking and ceramics.
TABLE 1--Typical high-temperature diffusion velocities.
Process D, cm2/s a, cm D/a, cm/s
S o l i d Z n in m o l t e n Bi . . . . . . . . . . . . 1 X 10 5 0.001 4 X 10 - s
Ox in m o l t e n F e . . . . . . . . . . . . . . . . 5 X 10 ~ 0.003 1.7 X 10 -2
Si +4 in C a O - A 1 2 O r S i O ~ . . . . . . . . . . 1 X 10 7 0.000004 2.5 ~< 10 2
S o l i d C a O in b a s i c C a O - S i O 2 . . . . . 1 • 10 is 0.025 glass 5 X 10 12
Returning to the basic calcium silicate slags, surveys were made to de-
termine if other components in steelmaking slags influenced the formation
or character of the film. Additions of P._,O.~up to the large amounts found
in Thomas slags had no important influence on the CaO solution process.
However, as hoped, 1~ percent P._,O~ was enough to stabilize the 2CaO.
SiO._, transformation so that quenched samples could be mounted, sec-
tioned, and examined by microscopy, X-ray diffraction, and the electron
probe. Within the limitations of the techniques involved, all such tests were
consistent with the interpretation offered, and it is considered certain that
the protective film has the composition of 2CaO. SiO2, although its
amorphous character remains speculative.
An alternate mechanism4 which avoids the assumption of a noncrystalline
phase is that the film is like a brush with many fibers or bristles of 2CaO 9
SiO., entrapping melt in the capillaries. The silica-rich slag cannot reach
the CaO interface by convection, and the reaction is slow until complete
crystallization causes spalling.
One percent of B~O:~ was required to stabilize the 2CaO ~SiO.,, and this
increased the rate of CaO solution, apparently due to increased spalling
and sloughing at the slag-film interface. The slag remained transparent
enough for direct observation with additions of 2 percent of ferrous oxide
(FeO) and manganese oxide (MnO), and these amounts had no observable
influence on the solution mechanism, although they were apparently re-
jected from the protective film, which remained completely clear. When the
argon atmosphere was replaced by oxygen there was an immediate increase
in wetting of the CaO crystal and an apparent development of idiomorphic
Fe:~O4 crystals at the slag-film interface, Plate II b.
Related Processes--Slag Eruptions

Although not a part of the CaO solution mechanism, some related phe-
nomena were observed which are of interest to steelmaking. These have to
do with the shift of the ferrous-ferric equilibrium with composition and
temperature, the lower valence being favored by low oxygen activity, high
SiO._,, and high temperature.
Fe ++ ~ Fe +++ + e.
All of these gradients exist in varying degrees during oxygen steelmak-

ing. In the early stages the exothermic oxidation of silicon at the hot-
metal interface must result in considerable deviation from bulk slag com-
position and temperature while the opposite extreme will result from the
endothermic solution of CaO. Thus, as shown by the equilibrium studies
DERGE AND 5HEGOG ON SLAG SYSTEMS 1 39
TABLE 2--Relation o f ferric oxide to oxygen pressure 1550 C (weight percent).
Slag Condition CaO FeO Fe~O3
(a) CaO saturated, equilibrium liquid Fe . . . . . . . 38 45 17

(b) Equilibrium, 1 atm. oxygen . . . . . . . . . . . . . . . 38 nil ~62
of Timucin and Morris 5 the slag in contact with undissolved CaO will have
the maximum amount of Fe+++ and that in contact with hot metal will
have the minimum. The significance of this shift is strikingly indicated by
using Timucin's data. Table 2 shows the composition of two slags at 1550
C, (a)CaO saturated and in equilibrium with liquid iron and (b) the same
CaO content but in equilibrium with oxygen at 1 atm. Stoichiometry shows
that if 100 lb of slag from the iron interface could be isolated and brought
to equilibrium at 1 atm of oxygen, the initial 45 percent of FeO would be
oxidized to Fe,,O,~ by 5 lb of oxygen gas. Conversely, if the oxidized slag
could reach the iron interface intact, it would provide 5 lb of oxygen for
refining the hot metal. However, as realized by furnace operators and
shown by the microscope, thermal and composition gradients make it pos-
sible to reach the critical pressure for nucleation of gas bubbles before
reaching the metal, and violent eruptions can occur. Dennison6 considers
these eruptions as a major hazard. The potential for this hazard is more
evident if volumes are used. Iron rich slags have a specific gravity of about
four, and a cubic foot would weigh about 250 lb; this would evolve about
1000 ft3 of gas for the gradient described. It is realized that these exact
conditions never exist in an operating furnace where convection and mix-
ing of all components is violent and rapid, but the gradients described can-
not be avoided completely. It is clear that they should not be allowed to
become large enough to nucleate oxygen bubbles.
This is seen in a sequence of pictures showing CaO solution in an iron-
silicate slag melted under argon to produce a homogeneous melt of about
20 SiO.,-80 FeO, Plate II c. When some oxygen is bled into the system gas
evolution begins at the hot side of the slag which is also furthest removed
from CaO, Plate II d. As more CaO dissolves, this proceeds with increas-
ing violence until the experiment goes out of control, Plate II e.
Conclusion
The solution of CaO and other basic oxides in highly basic slags is in-
hibited by the formation of a glass-like film which is highly protective. The
5 See p. 25.
'~ Dennison, T., "Progress and Change in the Iron and Steel Industry," Journal o/
the Iron and Steel Institute, Vol. 206, 1968, p. 647.
changes of volume associated with the crystallization of this film lead to

spalling and more rapid solution.
Gas evolution associated with a decrease in ferric ions due to composi-
tion and temperature gradients can account for the eruptions which occur
in oxygen steelmaking.
Acknowledgment
The research program which provided the basis for this paper was spon-
sored by Charles Pfizer and Company, Inc., Minerals, Pigments, and
Metals Division.
DISCUSSION
R. J. Leonard 1 (written discussion)---On behalf of the participants in this

ASTM symposium on lime, we wish to thank Dr. Derge and Mr. Shegog
for an interesting paper. Although the results reported in their work are
primarily qualitative, a basis for future quantitative work on the rate and
mechanism of calcium oxide dissolution in steelmaking slags is established.
However, there is some doubt that either of the models tentatively ad-
vanced by the authors to explain the mechanics of lime dissolution in steel-
making slags applies to dissolution under truly isothermal conditions.
In their discussion of the intermediate layer observed during the dissolu-
tion of lime in the CaO-SiO2 binary system, the authors make the statement
that " . . . this intermediate layer is always present, even in the absence of
a measurable thermal gradient." This statement is not supported by the
series of photographs presented by the authors. Furthermore, careful
analysis of the equilibrium phase diagram s and surface tension, density 3
and viscosity4 data for lime-silica liquids leads one to the conclusion that
the observed intermediate layer is primarily the result of a thermal gradient
existing between a cooler crystal and a hotter slag. This type of thermal
gradient in very small melts is discussed by Ordway. 5 In fact, the relative
emissivities between the partially dissolved cylinders and the liquid as re-
corded in the color photographs clearly indicate that in every case, includ-
ing Plate I e, the crystal is cooler than the slag. Unfortunately, the authors
have not reported on any experiments in which the crystal is deliberately
heated to a temperature above that of the slag, and this type of experiment
is required as a test of the models they have attempted to apply.
An extensive critical analysis of the models proposed cannot be made
until the question of an undefined thermal gradient is resolved. There is
one point which should be discussed in the event that an apparently
amorphous intermediate layer is still observed when the entire system is
1 Engineer, Refractories Development, Reduction and Refining Research, Homer
Research Laboratories, Bethlehem Steel Corp., Bethlehem, Pa.
"-Muan, A. and Osborn, E. F., Phase Equilibria Among Oxides in Steelmaking,
Addison-Wesley, Reading, Mass., 1965, p. 37.
'~Barret, L. R. and Thomas, A. G., "Surface Tension and Density Measurements in
Molten Glasses in the CaO--AI20:~--SiOe System," Journal o] tile Society of Glass
Technology, Vol. 43, 1959, p. 179,
' Bockris and Lowe, Proceedings o[ the Royal Society, London, A226, 1954, p. 423.
5 Ordway, F.. "Techniques for Growing and Mounting Small Single Crystals of
Refractory Compounds," Journal of Research, National Bureau of Standards, Vol. 48,
1952, pp. 152-158.
141
isothermal or the crystal is superheated. The authors are certain that the
film has the composition 2CaO 9 SiO,, and they assume that the slag has
the liquidus composition in equilibrium with 2CaO 9 SiO.,; yet, they con-
tend that there is no discontinuity in density between the film and the slag.
This contention is not consistent with their own photographic evidence.
If, as is the case, the photographs clearly show a film and a film-slag inter-
face, then there is indeed a discontinuity in properties. This discontinuity--
which is a direct reflex of the difference in the index of refraction between
the film and the slag--means a difference in density between the two
phases. This conclusion is a simple consequence of the well-known Lorenz-
Lorentz equation which, for this case, states that any discontinuity in re-
fractive index must be accompanied by a discontinuity in density.
Interpretive difficulties aside, the positive value of the work is that the
photographs provide visual evidence of dissolution phenomena occurring in
a thermal gradient and is similar to lime dissolution during steelmaking
which is not an isothermal process. In practice, the lime is charged cold to
the vessel, and reactions occur at the surface of the lime before the entire
particle reaches the ambient temperature of the vessel. Thus, the experi-
mental design employed in this work is quite analogous to the thermal con-
ditions during slag formation. Similarly, the experiment on oxygen evolu-
tion has considerable value in analyzing the causes of slopping in the basic
oxygen furnace. If, through violent agitation caused by the lance, the pro-
tective film on the surface of lime particles is disrupted, droplets of slag
can dissolve more CaO. This will result in an increase in the oxygen con-
tent of the droplet. When such an oxygen-enriched droplet comes into
contact with metal, the reaction can release oxygen with explosive force.
Gerhard Derge and J. R. Shegog (authors' closure)--The authors wish
to thank Dr. Leonard for his constructive discussion of our observations.
We appreciate that many uncertainties remain regarding the mechanism of
lime solution in slag, and it is hoped that they will be removed by further
study. It is believed that exploratory, qualitative studies of this type are
important for the effective planning of definitive, quantitative research.
W . J. Schlitt t a n d G. W. H e a l y 2
Characterization of Lime: A Comparison and

Scaling Down of the Coarse Grain Titration
Test and the ASTM Slaking Rate Test*
REFERENCE: Schlitt, W. J. and Healy, G. W., " C h a r a c t e r i z a t i o n of

L i m e : A C o m p a r i s o n a n d Scaling Down of t h e Coarse G r a i n Titration
Test a n d t h e ASTM S l a k i n g Rate Test," The Reaction Parameters o[
Lime, A S T M STP 472, American Society for Testing and Materials, 1970,
pp. 143-160.
ABSTRACT: A comparison of the ASTM slaking rate test and the

G e r m a n coarse grain titration test was made using results obtained from
trials on hard-, medium-, and soft-burned lime. Included in the comparison
were such factors as the relative slaking rate, the thermal behavior, and
the effect of variations in the prescribed test procedures. Both methods
proved to be reproducible and were generally suitable for industrial use.
However, the G e r m a n test required less time for hard-burned lime and
covered a wider range of properties within its specifications. From the
comparison a correlation was worked out which allowed the results of one
test to be translated into those of the other test. A scaled-down version of
the titration test also was developed which duplicated the results of the
full-scale test.
KEY W O R D S : characteristics, testing, burning, slaking, volumetric an-

alysis, reactivity, evaluation, tests, calcium oxide, water, density ( m a s s /
volume), thermal stability
Tests to determine the degree of lime burning have become quite im-
portant to kiln operators since many other industries use a burning criterion
as an indication of overall lime quality. Usually the degree of burning is
* This paper is based on a portion of a thesis submitted by W. J. Schlitt in partial
fulfillment of the requirements for the degree of Doctor of Philosophy in metallurgy
at the Pennsylvania State University, College of Earth and Mineral Sciences Con-
tribution No. 68-38.
1 Formerly graduate student, Metallurgy Section, Department of Materials Science,
The Pennsylvania State University. Now scientist, Kenecott Copper Corp., Salt Lake
City, Utah 84111.
'-'Associate professor of metallurgy, Department of Materials Science, The
Pennsylvania State University, University Park, Pa. 16802.
143
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
TABLE 1--Natural lime properties.
Soft-Burned Medium-Burned Hard-Burned
Physical properties:
Size as received, cm . . . . . . . . . . . . . . 1 by 5 1 by 5 5 by 13
Porosity, 70 . . . . . . . . . . . . . . . . . . . . . 49.4 43.5 46.2
Bulk density, g/cm 3 . . . . . . . . . . . . . . 1.62 1.83 1.75
Apparent specific gravity . . . . . . . . . . 3.21 3.24 3.25
Size fractions on crushing for CGT tests, 70:
9.51 by 6.30 mm . . . . . . . . . . . . . . . . . 49.5 54.8 38.5
6.30 by 3.36 mm . . . . . . . . . . . . . . . . . 23.4 20.0 23.8
3.36 by 1.00 mm . . . . . . . . . . . . . . . . . 16.2 15.9 13.0
- 1.00 mm . . . . . . . . . . . . . . . . . . . . . . 10.9 9.3 24.6
Size fractions on crushing for A S T M tests, 70:
6 by 10 mesh . . . . . . . . . . . . . . . . . . . . 44.6 43.9 34.2
10 by 20 mesh . . . . . . . . . . . . . . . . . . . 23.4 27.5 22.5
20 by 50 mesh . . . . . . . . . . . . . . . . . . . 18.1 16.7 24.3
50 by 100 mesh . . . . . . . . . . . . . . . . . . 7.0 5.1 9.2
- 100 mesh . . . . . . . . . . . . . . . . . . . . . . 7.0 6.7 9.8
Chemical analysis, 70:
Loss on ignitions. . . . . . . . . . . . . . . . . 2.3 1.8 0.4
Fe203 . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.2 0.2 0.2
AI~O3. . . . . . . . . . . . . . . . . . . . . . . . . . . 0.6 0.6 0.05
SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 0.9 1.0 0.1
MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.0 1.0 0.5
S ............................... 0.02 0.02 0.08
CaO . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96.8 96.8 98.7
, Includes any moisture.
found through correlation with measurements made on the water reactivity

of lime. This means that in some way the tests follow the kinetics of the
reaction
CaO + H20 --~ C a (OH)2 + 15.3 k c a l / g - m o l e [1] 3
O b v i o u s l y , t h e v e l o c i t y of t h e h y d r a t i o n r e a c t i o n c a n b e d e t e r m i n e d e i t h e r
calorimetrically by noting the rate and amount of heat being evolved, or
c h e m i c a l l y b y m o n i t o r i n g t h e q u a n t i t y o f h y d r o x i d e f o r m e d as a f u n c t i o n
o f t i m e . B o t h m e t h o d s a r e i n use, t h e c a l o r i m e t r i c t e c h n i q u e i n t h e A S T M
s l a k i n g r a t e test, as d e s c r i b e d i n A S T M M e t h o d s f o r P h y s i c a l T e s t i n g o f
Quicklime and Hydrated Lime (C 110-58), and the chemical approach in
t h e G e r m a n c o a r s e g r a i n t i t r a t i o n ( C G T ) t e s t [2]. B e c a u s e e a c h t e s t is
:~The italic numbers in brackets refer to the list of references appended to this
paper.
SCHLITT AND HEALY ON CHARACTERIZATION OF LIME 145
used widely, work has been done to compare and evaluate the two methods
quantitatively. Furthermore, a scaled-down version of the titration test has
been developed which permits the determination of the degree of burning
of small samples, as might be produced in the laboratory under closely
controlled conditions.
Materials
Four types of lime were used in comparing and scaling down the water
reactivity tests. Three were high-calcium material produced from lime-
stone; the fourth was prepared by compacting and sintering high-purity cal-
cium oxide (CaO) powder under controlled conditions. Various physical
and chemical properties of the natural lime are shown in Table 1. Table 2
gives similar information for the synthetic CaO samples and shows the
wide variation in the properties which can be developed by controlled
fabrication. The physical properties were determined by using a modified
version of the ASTM Test for Apparent Porosity, Water Absorption,
Apparent Specific Gravity, and Bulk Density of Burned Refractory Brick
(C 20-46). In the test the lime was saturated with USP olive oil rather
than water. The modification of this test and the fabrication of the pressed
and sintered samples have been described in greater detail elsewhere [3].
TABLE 2--Physical properties of synthetic lime produced under various conditions.
Compacting Sintering Sinter- Bulk Apparent Specific

Pressure, Temperature, ing Density, Specific Surface
psi deg C Time, h Porosity, ~o g/cm 3 Gravity Area, m2/g
5 400 900 12 58.7 1.36 3.31

9 100 900 3 54.3 1.51 3.31
9 100 900 12 54.8 1.49 3.30 2.05
9 I00 900 48 54.3 1.52 3.32
9 100 1 250 3 53.7 1.53 3.31
9 100 1 250 12 53.0 1.56 3.33
9 100 1 250 48 52.1 1.60 3.32
18 100 900 12 46.9 1.71 3.27 1.60
27 200 900 12 45.0 1.83 3.32
36 200 900 12 42.6 1.90 3.31
45 300 900 12 40.8 1.96 3.31 1.30
63 400 900 3 35.5 2.14 3.31
63 400 900 12 36.1 2.11 3.31
63 400 900 48 36.0 2.13 3.32
63 400 1 250 3 35.0 2.16 3.32
63 400 1 250 12 34.2 2.18 3.32
63 400 1 250 48 33.0 2.22 3.32 0.85
The three natural limes proved to hard-, medium-, and soft-burned, ac-
cording to the G e r m a n criteria. The latter two types were quite normal, but
the hard-burned material was not. It was extremely resistant to crushing,
yet was of unusually low density and high porosity. Since microscopic ex-
amination showed that the material was composed of many dense granules
held together by a rather porous matrix, this material may have been com-
pletely calcined oolitic limestone. Unfortunately, the manufacturer retained
no record of this lime.
Both water reactivity tests were run on each grade of natural lime. To
ensure that identical material was used in all tests on a particular type of
lime, the large lumps in each lot were broken, and the entire sample was
remixed before removing material for crushing and sizing.
A S T M Slaking Rate Test

The slaking rate test was run as specified in the A S T M standard. How-
ever, a mercury thermometer was used in place of the dial type called for
in the standard. Briefly, the test was conducted by adding 76 g of freshly
crushed - 6 mesh lime to a l/2-qt Dewar flask containing 380 ml of water
at 24 C - ~/~. The lime-water mixture was stirred at 300 rpm -+ 50, a
speed which was adjusted during the test with the aid of a variable-speed
strobe light. Based on the temperature rise of the water during the first 30 s
of the test, temperatures were recorded every half minute for soft-burned
lime, every minute for medium-burned material, and every five minutes for
a hard-burned product. The test was continued until the temperature rise
during three consecutive readings was less than 1A C. According to the
ASTM criteria, lime was categorized as soft-burned if the test was com-
pleted in 10 rain or less, medium-burned if 10 to 20 min were required,
and hard-burned if more than 20 min were needed.
To check the effect of particle size, which did vary to some extent as
shown in Table 1, tests were run on the soft- and medium-burned lime
using a 6 by 20 and a - 2 0 mesh fraction. Initially, the coarse material
s!aked more slowly than normal, while the fine product slaked more
rapidly. However, the maximum difference in the rates was only about five
percent, and decreased with time so that the rates became indistinguishable
before the tests were 50 percent complete. These results indicated that lime
properties have a much greater effect on the slaking rate than do small
variations in the feed size.
Coarse Grain Titration Test

The German coarse grain titration test was described originally by
Wuhrer [2], but has undergone some modification since industrial accept-
SCHLITT AND HEALY ON CHARACTERIZATION OF LIME "147
ance [4,5]. Now 50 g of 1.0 by 10.0-mm lime are added to 2000 g of

water at 40 C. The mixture is agitated and titrated to a clear end point
every minute for 10 or 20 min using 4 N hydrochloric acid (HC1) and
phenolphthalein indicator. The amount of acid added each minute shows
how much hydroxide has formed, that is, how much lime has slaked in the
preceding minute. The results are plotted as acid consumption versus titra-
tion time and the degree of burning is specified by comparison with stand-
ard curves for hard-, medium-, and soft-burned lime. These curves are
shown in Fig. l, with acid consumption given as percent rather than vol-
ume. The percent consumption is, of course, the percent of the acid vol-
ume needed to neutralize the entire 50 g of lime. The increase in the water
temperature is recorded also.
Only one change was made in the procedure outlined above. A U.S.
standard 3/8 sieve (9.5-mm openings) was used in place of the screen with
10.0-mm openings. This substitution should have had little effect on the
results since Eckhard [4] showed that the coarse grain test, like the ASTM
one, is quite insensitive to minor variations in feed size.
None of the references to coarse grain titration specified the stirring con-
ditions, although the stirring rate was found to exert a considerable in-
fluence on the results. Curves obtained using soft-burned lime and stirring
speeds of 125 to 225 rpm are shown in Fig. 2. At 125 rpm much of the
hydroxide which formed settled on the remaining lime and practically
I00
Soft
~, 80
/
o-
/
0 I
~- 6o
/
I /
/ f
I
/
Medium i . I
n~
~ 4o i I
J
%
U
!
i /
/ f
f
J
4~
~ 2o / f
/
Hard J
i ///
/
4 8 12 16 20
Titration Time, rain

FIG. 1--Standard coarse grain titration curves [or so/t-, medium-, and hard-
burned lime.
Ioo I
225 rpm ~-41~-_~_. I ---~
o .~17
0 5 r 0''~', " 1:~.-~--Cr-
~ 80 pm
"5
~ 60
125 rpm
~5
~ 2o
I-.-
0
0 4 8 12 16 20
T i t r a t i o n Time, min
F I G . 2--Effect of stirring rate on the measured slaking rate in titration tests on
so/t-burned lime9
stopped the slaking reaction. The apparent slaking rate increased with the
stirring rate until a speed of 225 rpm was reached. Here the lime was
swirling about freely, and greater agitation had little effect on the observed
slaking rate. When stirring was slow, the rate at which fresh water reached
the unreacted lime appeared to be rate controlling. Above 225 rpm, the rate
at which water reacted with the lime seemed to be the controlling factor.
Hence, the properties of the lime became more important at higher rpm's.
Stirring speed affected the observed slaking rate of the harder burned lime
in a similar manner 9 However, here the slaking rate became independent of
stirring conditions at slightly lower rpm's.
Two other variations were made in the CGT procedure without detect-
able variation in the results9 One of these was to compare slaking curves
resulting from continuous titration and intermittent titration carried out
every minute. The other variation was to use acid of different strengths
(4-N versus 6-N HC1). The failure of these variations to affect the meas-
ured slaking rate is shown in Fig. 3.
Scaled-Down Titration Test

The development of a scaled-down water reactivity test was based on
the German test, since the ASTM method proved to be difficult to scale
down. The resulting scaled-down titration (SDT) test was conducted by
SCHLITT AND HEALY ON CHARACTERIZATION OF LIME 149
100
80
0 J
0 Intermittent titration,
6.0 N HCI
o
I-I Continuous t i t r a t i o n , _ _
4O
4.0 N HCl
% V Intermittent titration,
u
4.0 N HCl
i=
0
0 4 8 12 16 20
FIG. 3--Effect of acid strength and titration method on the measured slaking rate
o/ so/t-burned lime.
adding 0.6 to 0.7 g of carefully weighed 1.0 by 9.5-mm lime to exactly 40

times this weight of water at 40 C. A magnetic stirrer was used to keep the
lime swirling about, and the mixture was titrated to a clear end point every
minute using phenolphthalein as an indicator. Since acid strength had
proved to be unimportant, 0.6-N HC1 was used because a 50-ml burette
would conveniently deliver sufficient acid to neutralize the entire sample.
As before, the results were plotted as percent acid consumption versus
time. Thus, the titration curves for the C G T and SDT tests could be shown
on the same scale.
Results
The results of the three water reactivity tests on each grade of natural
lime are shown in Figs. 4, 5, 6, and 7. Wide differences in the slaking be-
havior of the different limes are evident, but, in all cases, there was excel-
lent agreement between the SDT results and those obtained at 175 and
225 rpm in the full-scale titration tests. All the titration curves represent
average values for a particular set of conditions. Only three trials were
used to determine the coarse grain results since these were quite repro-
ducible. At a given stirring speed, the variation was one percent when slak-
ing was slow and as much as three percent when the reaction was quite
rapid and stirring could not maintain a constant pH throughout the system.
8O
Medium ~ ~ ~
~,, 60
~ 40
4.J
:3:
20
0 0 20 40 60 80
FIG. 4 - - R e s u l t s of the A S T M slaking rate tests on lime defined as so]t- (left),

medium-, and hard-burned (right) by German standards.
100
# 6O Standard t i t r a t i o n
o curve, soft-burned lime
.... Results of this study
~ 4o
% /k Average results, 225
and 260 rpm
2o 0 Average results, 175 rpm

I---
I 9 Average results, SDT test
r I r
4 8 12 16 20
F I G . 5--Results o] the coarse grain titration tests run at diOerent stirring rates
and o] the scaled-down titration (SDT) tests on so[t-burned lime.
SCHLITT AND HEALY O N CHARACTERIZATION OF LIME 15]
I00 i I I I
Standard t i t r a t i o n curve, medium

burned lime
80
0 Average results, 225 and 260 rpm
z,
0 Average results, 175 rpm
j +0 _ 9 Average results, SDT ~ s t ~

^
40
~ 20
0;Z 0 16 20
FIG. 6----Results o[ the coarse grain titration tests run at different stirring rates
and o] the scaled-down titration (SDT) tests on medium-burned lime.
I00 - - I i l +
Standard t i t r a t i o n curve, hard-
burned lime
u
8O
A Averageresults, 225 rpm
0
,tJ
0 Average results, 175 rpm
~- 6o
o
c~
9 Averageresults, SDT test •//r-t
o
"5
6.1
~ 20
d 12 16 20
Titration Time, min

FIG. 7--Results o[ the coarse grain titration tests run at different stirring rates and
o[ the scaled-down titration (SDT) tests on hard-burned lime.
The ASTM test was even more reproducible. For three trials the maximum
scatter about the average was one percent, regardless of conditions.
Reproducibility was not as good in the scaled-down tests, where results
for a single trial sometimes differed from the average by as much as 15
percent. Thus, ten trials were run on each grade of lime. The scatter was
attributed to variations in the density of the lime which occurred within a
simple lump of lime and between different pieces of material within the
same lot. These variations were smoothed out in the full-scale tests since
50 g of well mixed lime were used. However, the differences would be
emphasized in the SDT tests because the few specimens of lime used in a
single trial might be quite different from the average. Evidence for this was
found in the good agreement of the average results of the two titration tests,
but the poor agreement of the individual trials. Further evidence was found
in the improved reproducibility of the SDT tests run on the pressed and
sintered samples with closely controlled properties.
Comparison of the ASTM and C G T results showed that there was not an
exact correlation between the two. The shape of the curves was roughly
the same, but the degree of completion as a function of time was not. For
example, the ASTM test on the soft-burned lime was complete after 4.5 to
5.0 rain. However, according to the German test, slaking was only 78 per-
cent complete after 4.75 rain. Likewise, the slaking rate of the medium-
burned material was more rapid in the ASTM than in the titration test.
On the other hand, the situation appeared to be reversed for the hard-
burned lime. Here titration was 65 percent complete after 20 min, but only
25 percent of the total temperature rise had occurred during this interval.
This reversal was caused by an unusual sudden increase in the apparent
slaking rate which occurred after 8 to 10 rain. When the degree of comple-
tion was compared before the upturn, slaking was again seen to be more
rapid in the ASTM test.
The curves obtained during the normal portion of each test and the rela-
tive slaking rates found for tbe three grades of lime provided sufficient in-
formation to translate the ASTM criteria for the degree of burning into
titration curves. These are shown in Fig. 8. The translation was then used
to estimate the ASTM degree of burning of the pressed and sintered
samples. To do this scaled-down titration tests were run on eight different
grades of synthetically prepared lime. Since the pellets were 3/8 in. in
diameter, they were within the 1.0 by 9.5-mm size range and were tested
without being broken. Two pellets provided sufficient lime for each trial.
Four trials were conducted on each grade of CaO, with the average titra-
tion curves shown in Fig. 9. In these trials, reproducibility was five to ten
percent during rapid slaking, and only one percent when slaking was slow.
SCHLITT AND MEALY ON CHARACTERIZATION OF LIME 153
I00
I
f Soft
f
f
i
J
J
f
~, 8o
/ J
/ Medium f
g / f
/ 7 Hard
~ 60 / f
/ J /
g /
/// 2 j
~ 40,
l
/
/
/
/
5 ~
g2~ / / 3
/ J
J
J
0 12 16 20
Titration Time, min

The regions marked soft, medium, and hard (divided by the broken lines) refer to
the ASTM degrees of burning. The solid lines numbered 1, 2, and 3 are, respectively,
the German standard curves for soft-, medium-, and hard-burned lime.
FIG. 8--Titration curves defining the A S T M and tile German criteria /or the
degree of burning.
Discussion
The lack of any significant effect caused by small variations in feed size
and the excellent reproducibility of the ASTM and CGT tests shows that
both methods should be suitable for industrial use. However, each method
did have its disadvantages. As pointed out earlier, the CGT results could
be influenced by the test procedure if stirring was too slow to provide good
agitation of the lime. On the other hand, the ASTM test on hard-burned
material took over an hour to complete, while the CGT test would require
only 10 or 20 rain. Furthermore, a wider range of properties was covered
by the German specifications for the three degrees of burning. The cri-
teria for soft-burned lime was about the same in each test, but the German
concept of medium-burning was closer to the ASTM hard-burned specifi-
cation. Thus, any material which slakes very slowly could be classed more
precisely by the titration method. Of course, the problems associated with
the ASTM test do not arise if only fairly reactive lime is being produced.
In addition to these practical differences, there were fundamental dif-
ferences between the two tests. These were the thermal conditions estab-
lO0
Ill
Soft ~/! ,
~_ 80
0
~s
~ 60 : Hard
m
o
N 40 .. I"t/S~I//1~1/11
%
T,
~
g
I.--
2O /i //
0 4 8 12 16 20
Titration Time, min
T h e regions m a r k e d soft, m e d i u m , and h a r d (divided by the heavy, solid lines) refer
to the A S T M degrees of b u r n i n g .
Line N o . Compacting Sintering Sintering

Pressure, psi T e m p e r a t u r e , deg C Time, h
1 ................ 27 200 900 12

2 ................ 9 100 900 12
3 ................ 45 300 900 12
4 ................ 9 100 1250 12
5 ................ 63 400 900 12
6 ................ 63 400 1250 48
F I G . 9--Scaled-down titration curves for lime produced under different conditions.
lished by each procedure. In the ASTM test conditions were adiabatic,

while in the C G T version, they were nearly isothermal. When the heat of
hydration is conserved, it would be sufficient to raise the temperature to
75 C, if slaking were complete and no heat escaped or was needed to heat
the apparatus. Although the final temperature is usually closer to 70 C, the
effect on the slaking rate is significant since the rate of hydration almost
doubles for each 10 C increase in temperature [6]. Thus the results of the
ASTM test reflect a constantly accelerating reaction rate. On the other
hand, almost no acceleration effects will be included in the C G T results
since the temperature rise here is less than 10 C. The high temperatures
and accelerated slaking rates encountered in the ASTM test provide a
SCHLITT AND HEALY ON CHARACTERIZATION OF LIME ] 55
partial explanation of the higher slaking rates normally observed with this
procedure. Since the feed size was also finer in the ASTM test, there would
be a higher surface-to-volume ratio here. Thus, there would be more slak-
ing per gram of lime in a given time, a fact which also helps explain why a
particular lime usually slaked more rapidly in the ASTM test.
Because the hard-burned material did not always slake more rapidly in
the ASTM test, this lime appears to be abnormal. The hard-burned prod-
uct also displayed the unusual behavior in which the measured slaking rate
increased with time. Both these phenomena resulted from the rather
porous matrix of the lime which was attacked rapidly and soon reached
the point where the dense particles could no longer be held together. These
particles then began spalling off the larger specimens and caused a sudden
increase in the exposed surface area. This in turn led to the abrupt increase
in the observed slaking rate. The point at which break up took place
depended on the test conditions and apparently occurred sooner in the CGT
test. Thus, hydration appeared to be more rapid here. The finer feed in
the ASTM test meant that there was less material that would undergo
extensive spalling and prevented any abrupt rise in the observed slaking
rate in this procedure.
Although the titration curves obtained in the scaled-down tests on the com-
pacted and sintered pellets also showed an increase in the observed slaking
rate, the explanation is quite different. Here the initial segments of all the
titration curves were nearly horizontal and were parallel, regardless of the
lime properties. Since two pellets with very smooth surfaces of nearly equal
area were used in each trial, the initial portion of each curve appeared to be a
function of the surface, not the bulk properties. Evidence of this was found
by testing pellets which had been quartered. Here, the initial region was
reduced, but the accelerated portion remained parallel to that of the un-
quartered trials. This indicated that the properties of the bulk lime de-
termine the shape of the titration curve after its upturn. Thus, to translate
the scaled-down results into ASTM degrees of burning, the origin of the
curves should be taken at the point where the upturn occurred. When this
is done, all grades of synthetically prepared lime, except that pressed at
63,400 psi and sintered 48 h at 1250 C, would be considered as soft
burned. The latter sample would be classed as hard burned.
The scaled-down titration tests also showed that the porosity and firing
temperature have a combined effect on the observed slaking rates. Figure 9
shows that for a single firing temperature the slaking rate dropped as the
bulk density increased. However, the sintering temperature is also im-
portant, since pellets fired at 1250 C slaked more slowly than denser
pellets fired at 900 C.
Conclusions
The ASTM slaking rate test and the German coarse grain titration test
proved to be suitable for the determination of the degree of lime burning.
Both were quite reproducible and were unaffected by small variations in
the feed size. Acid strength and method of titration also proved to be
unimportant. However, the stirring rate affected the results of the German
test when agitation was insufficient to keep the lime swirling about freely.
On the other hand, the ASTM test required considerable time when used
on hard-burned lime and covered a narrower range of properties within its
specified degrees of burning. The criteria for soft-burned lime were the
same in each case, but German concept of medium-burned lime is similar
to that of hard-burned lime in the ASTM test.
Except under unusual circumstances, lime actually slaked faster in the
ASTM test. This was due mainly to the relatively large surface-to-volume
ratio of the feed and the high temperature occurring toward the end of this
test. The adiabatic nature of the ASTM method meant that the temperature
of the system would increase and cause the slaking rate to accelerate
throughout the test. Being nearly isothermal, CGT measurements would
not reflect such an acceleration.
The scaled-down titration test was not as reproducible as the full-scale
tests, since the former emphasized rather than smoothed out differences
between individual pieces of lime. The SDT tests would be suitable for
testing lime produced under closely controlled conditions. Even when
there were variations in the lime the average results of the two titration
tests agreed closely. The scaled-down tests on the synthetically prepared
pellets did show that feed with an excessively low surface area would lead
to an initially low slaking rate characteristic of the surface rather than the
bulk properties. Results on this material also showed that the firing tem-
perature and percent porosity both affected the slaking rate.
References
[I] Hutton, W. E. et al, "The Chemical Thermodynamic Properties of Calcium
Hydroxide," Journal of the American Chemical Society, Vol. 81, 1959, pp.
5028-5030.
[2] Wuhrer, J., "Report," Schriltenreihe des Bundesverbandes der Kalkindustries,
Vol. 2, 1956, pp. 101-106.
[3] Schlitt, W. J. and Healy, G. W. "Preparation of Lime Specimens with Closely
Controlled Properties," American Ceramic Society Bulletin, Vol. 49, 1970, pp.
212-215.
[4] Eckhard, S., "The Relation Between Specific Volume, Coarse Grain Titration
and Chemical Analysis in the Case of Quicklime," Zeitschri[t [iir Analytische
Chemie, Vol. 209, 1965, pp. 156-162.
[5] Behrens, K. F., Koenitzer, J., and Kootz, T., "The Effects of Lime Properties on
Basic Oxygen Steelmaking," Journal oJ Metals, Vol. 17, 1965, pp. 776-781.
[6] Boynton, R. S., Chemistry and Technology oJ Lime and Limestone, Interscience,
New York, 1966, pp. 296-297.
DISCUSSION
R. H. Lepley a (written discussion)---The author has shown in Fig. 2 of

the paper, the critical nature of the stirring rate on measured slaking rate
in titration tests on soft-burned lime. If this is true of the chemical ap-
proach, is it not also true for the calorimetric technique?
Two calorimetric methods are in wide use today by both consumers and
producers of lime, and these methods cover a broad range of stirring rates.
The ASTM slaking rate test permits a range of from 250 to 350 rpm. The
American Water Works Association slaking rate test, which was adapted
from the ASTM test, permits a range of from 350 to 450 rpm.
We have conducted several series of stirring rate tests on samples of
soft burned high calcium lime. The results of one series are shown in Fig.
10. Within the 250 to 450 rpm range, the values lie within the shaded area.
FIG. lO--Calorimetric slaking rate tests.
Minerals Pigments and Metals Div., Charles Pfizer and Co., Easton, Pa. 18042.
157
This area also coincides with the range of precision of the test when repli-
cate samples were tested at 250, 350, and 450 rpm. From this data we can
conclude that the specified ranges of mixing speeds are satisfactory for
uniform results. However, we would recommend adhering to the stirring
rate limits specified in the method of test which is standard for the given
laboratory.
A second area of interest which we would like to discuss is the measur-
ing and recording of the thermal history of the sample in the ASTM slak-
ing rate test. ASTM specifies the use of a dial thermometer while the
author modified the test to use a glass thermometer.
When the slaking rate test is employed routinely for kiln control, it is
advantageous to continuously record this thermal history. Such a modifica-
tion is shown in Fig. 11. For our use, we have selected a single pen, six
inch chart electronic laboratory recorder. It is a continuous balance poten-
tiometer having high accuracy and fast response. By adding a battery-
operated thermocouple reference ]unction, temperature rise can be meas-
ured and recorded directly for either dolomitic or high calcium lime. A
Type T or copper/constantan megapak thermocouple assembly is used
FIG. 1 I--Eqtdpment used/or recording thernml history.
DISCUSSION ON CHARACTERIZATION OF LIME 159
FIG. 12--Graphic display [rom A S T M slaking rate test.
with the recorder. An integral junction and 1/16-in.-diameter stainless

steel sheath gives the response and ruggedness desired.
As Fig. 12 shows, the standard chart is graduated in percent from - 2
to 102. By simply changing the span adjustment within the instrument, a
50 C spread is obtained between 0 and 100 percent on the chart. Each
chart division is then 1A C. Linearity of the thermocouple over this range
is within the precision range of the test, the thermocouple, and the measur-
ing and recording equipment.
There are several other advantages in the use of this recorder. The chart
and scale configuration has a right-hand zero to enable the final record to
have time increasing from left to right along the abscissa, and the tem-
perature variable increasing from bottom to top along the ordinate as in a
conventional graph. Further, the "live zero" has great advantage in adjust-
ing the initial water temperature.
The author is to be commended on the work described in this paper,
particularly the scaled-down version of the titration test. This test should
find application in research efforts where available samples are small or
where measurements of suspected differences of reactivity are desired as
within large lumps of lime.
W. I. Schlitt and G. W. HeaIy (authors' closure)~The authors agree

that the stirring rate employed in the ASTM test should be kept within
the specified limits. Mr. Lepley's application of automatic temperature
recording to the ASTM slaking rate test seems quite worthwhile. A con-
tinuous, permanent temperature profile should aid in quality control and
process automation.
R. W. Limes ~ and R. O. R u s s e l l ~
Crucible Test for Lime Reactivity in Slags
REFERENCE: Limes, R. W. and Russell, R. O., "Crucible Test for

Lime Reactivity in Slags," The Reaction Parameters oJ Lime, ASTM STP
472, American Society for Testing and Materials, 1970, pp. 161-172.
ABSTRACT: The rapid acceptance of basic oxygen furnace (BOF) steel-
making has caused a veritable revolution within the steel industry and also
the lime industry as a major supplier of a raw material. The speed of the
process requires a lime product which goes into solution rapidly to form a
slag. Field observations of the BOF steelmaking process showed major
differences in the rate of slag formation with various commercial lime
products. Operating practices could be adjusted to take poor lime into
solution but would have a detrimental effect on the furnace refractories and
metallurgical processing. The slagmaking reactions are discussed.
The ASTM water reactivity test for lime would differentiate between the
lime products observed to react differently in BOF slagmaking. However,
arguments were made that this test did not simulate slagmaking or lime
solution rate in a slag. A crucible test was devised in which minus 5 plus 6
mesh lime sample is mixed with a lime deficient slag and heated for various
lengths of time. The free lime is determined in the fired samples and plotted
against time. This gives an indication of solution rate. A correlation was
found between this crucible test and the ASTM water reactivity test for
commercial lime products of interest. There are ways to lower water
reactivity without decreasing slag solution rate, notably through prereaction
with other slagmaking ingredients. The crucible test has been used to
evaluate these experimental products.
The water reactivity test is adapted more easily to plant quality control
than is the crucible test. Since the correlation existed between the two for
products of interest, the water reactivity test was selected for control of
incoming lime product. Specifications were established for reactivity, loss
on ignition, sulfur, and calcium oxide content. The specifications are realistic
and can be met by commericial suppliers of lime.
KEY WORDS: calcium oxide, metallurgical furnaces, reactivity, tests,
roasting, slags, specifications, reaction, kinetics, evaluation, steelmaking
Steelmaking
S t e e l m a k i n g p r a c t i c e s h a v e u n d e r g o n e a v e r i t a b l e r e v o l u t i o n since t o n -
n a g e o x y g e n of h i g h p u r i t y has b e c o m e c o m m e r c i a l l y a v a i l a b l e at a n e c o -
n o m i c price. B a s i c o x y g e n f u r n a c e ( B O F ) s t e e l m a k i n g is r a p i d l y r e p l a c i n g
x Division head and technologist, respectively, Ceramic Division, Republic Steel

Corp., Cleveland, Ohio 44131.
161
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
open hearth steelmaking, and soon over half of the steel made in this coun-
try will be by the former method. The main advantage of the process is the
speed with which iron can be refined. Heat times are well under 1 h,
whereas the open hearth requires 4 to 6 h in heat time even with the use
of oxygen. The process requires the effective use of heat from all exo-
thermic reactions involved and a minimum use of any material which
extracts heat from the process. This requires the use of burned lime in-
stead of limestone, and the rapid acceptance of BOF steelmaking has
created a parallel revolution within the lime industry.
Although one usually thinks of the metal aspects of steelmaking, another
most important factor is the development of slag. Slag is the reservoir for
the impurities that must be extracted from iron to produce steel. Since
these impurities are acidic in nature, silica, sulfur, and phosphorus, it is
natural to react them with a basic material for their effective removal, and
lime or limestone has been the traditional material used for this. This lime
is most effective in the removal of impurities when it is in solution in the
slag. With the short time cycle in BOF steelmaking and the need for rapid
slag development, the solution rate of lime in slag takes on major im-
portance.
Early in our experience with BOF steelmaking, the burned lime obtained
from two commercial sources were observed to be markedly different in
their rate of slag development. One lime was observed to produce a lumpy
slag obviously containing undissolved lime, whereas the other lime con-
sistently produced fluid slags. This was traced to the degree of burn of the
lime, the one having a slow solution rate being a hard burned product
while the other was soft burned. The National Lime Association has
adopted the terms LoR and HiR, respectively, for this difference in lime
product, and these terms will be used hereafter. It would have been pos-
sine to develop an operating practice to take the LoR lime into solution,
but these practices would have been detrimental to other aspects of the
process, notably lining life and yield of product. Our Division within Re-
public's research effort is concerned primarily with refractories, and our
interest was naturally the refractory aspects of the process. Since the re-
fractory lining for the BOF is also a basic material, magnesite or dolomite,
the acid slags developed would satisfy themselves by dissolving the lining
if the lime put in for this purpose did not go into solution fast enough. The
processing steps that might be taken to increase the solution of the lime
into the slag also would accelerate the rate of wear on the refractory lin-
ing. Obviously the most satisfactory solution was to insist on a HiR lime
with a rapid solution rate for our BOF operations, and our work was aimed
at proving the importance of this approach and the tolerances in lime
quality we could stand without adversely affecting the process.
LIMES AND RUSSELL ON LiME REACTIVITY IN SLAGS ] 63
Slags
It might be well to describe how BOF slags are made. The major in-
gredient to form this slag is lime. To a ceramist, lime is a refractory hav-
ing a melting point in excess of 4500 F. The major impurity which the lime
must remove from the iron is silica from oxidized silicon in the hot metal.
The first reaction product between lime and silica is dicalcium silicate
which still has a melting point above 3800 F and forms a refractory coating
on the lime lumps. Obviously some fluxing ingredient is still required to
remove this coating. This flux is primarily iron oxide although there are
other components in the slag which help to lower the temperature of
liquid formation. Figure 1 indicates the high temperature liquid formation
of slags involving calcium oxide-silicon dioxide-RO, the latter primarily
iron oxide. Note the nonliquid ridge which extends into the diagram which
is caused by the formation of dicalcium silicate. In order for the slag to
effectively remove phosphorus and sulfur, it must be below the tie line
dicalcium silicate-RO. This means the slag development must go around,
or fight its way over, the ridge to arrive at its final composition. The easy
road to travel would be to produce high iron oxide slags and go around the
ridge staying well out in the liquid area. This has metallurgical disad-
vantages as well as being extremely erosive to the refractory lining. Using
a HiR lime has two main advantages, (1) it has a faster solubility rate
without the need for excessive iron oxide, and (2) the formation of
dicalcium silicate rims on the surface of lime lumps is minimized. Figure 2
is a photomicrograph of a LoR lime particle in a BOF slag. Note the
F I G . l--Diagramatic triaxial o/ slag making ingredients in BOF slag. Final slag

must be below C,,S-RO line. Note ridge o)' nonliquid extending into diagram.
FIG. 2--Photomicrograph of LoR lime in BOF slag. Note dicalcium silicate rim
around lime particle which slows solution in slag.
dicalcium silicate rim sealing the lime and slowing the rate of slag develop-
ment. Figure 3 is a similar photomicrograph of a HiR lime showing the
breaking off of small dicalcium silicate rims and an obviously improved rate
of slag formation.
Lime Testing
Returning to our early experience with lime quality, the water reactivity
tests described in ASTM adequately showed the difference between the
HiR and LoR lime on which the slag development observations were made.
However, there was a great deal of argument that this type of test did not
simulate the solution of lime into a slag. Efforts were then made to de-
velop such a test to simulate slag development which resulted in our so-
LIMES AND RUSSELL ON LIME REACTIVITY IN SLAGS 165
FIG. 3--Photomicrograph of HiR lime in BOF slag. Note absence of dicalcium

silicate rim and small particles breaking off to enter into slag.
called crucible test for lime reactivity. Burned lime is crushed to produce
monosized screened fraction of minus 5 plus 6 mesh material. This is done
to have a nearly uniform outside surface area for all lime products as they
are tested. By reacting this grain with a lime deficient slag, its rate of solu-
tion into the slag would be an indication of its slag reactivity. Figure 4
shows the slag composition which is a synthetic one made with fine chem-
ical oxides. It is mixed with the lime grain, three parts lime to one part syn-
thetic slag, to produce a surface coating on each lime particle. A problem
developed in a container for the reaction products at temperature. Some
of the more refractory crucibles were too porous, and the liquids drained
away into the crucible before complete reaction with the lime grains. The
best solution was found in the highly silicious Leco crucibles used for
SYNTHETIC
SLAG COMPOSITION
SiO2 56.0%
AI203 3.8
TiO 2 3.7
Fe203 19.0
MgO 8.5
MnO 9.0
FIG. 4--Synthetic slag added to minus 5 plus 6 mesh lime. Fine chemical oxides
used. Simulates an early BOF slag without lime.
sulfur determinations. Although not as refractory and tending to melt and

deform if held at temperature for long periods, this type of crucible did
retain the developed slag with minimum penetration. In order to aid in
minimizing slag penetration, a coating of colloidal graphite is painted on
the interior surface of the crucible. This also tends to produce some degree
of reducing conditions within the crucible in order to more closely simulate
BOF atmospheres. A series of these crucibles containing the lime grain-slag
mixture are placed in a gas fired furnace running at 2700 F. A crucible is
withdrawn at 2 min intervals up to 12 min. The crucible and slag are
crushed and ground for chemical analyses and the free lime determined by
the sugar method. A plot of free lime against time in the furnace gives an
indication of lime solubility in the slag. Many times it is possible to visually
observe the rate of slag formation. Figure 5 shows such a test where the
lime grains can be still seen at up to 10 min of test time for the LoR
lime, whereas they have disappeared completely in 6 min with a HiR
FIG. 5--Crucible test /or HiR and LoR lime. Lime grains ean be seen up to 10
min with LoR lime but are dissolved by 6 min with HiR lime.
5o
u~,,O
0 I R LIME
9 o 30
.=== - ,
~ 2o
X
I '~
4 8 I0
TIME-MIN.
F I G . 6 - - F r e e lime in samples from crucible test shown in Fig. 5.
lime sample. Figure 6 shows the plot of free lime versus time for the series
of samples in Fig. 5.
In the development of this slag crucible test, a number of lime samples
were investigated, all being from commercial sources available to our BOF
operations. ASTM water reactivity values also were obtained as well as the
values by the hydrochloric acid titration method. Surface area determina-
tions also were made on some of the lime samples. We found that all tests
were running parallel paths to that observed by the crucible test. In other
words, there was a correlation between all these tests and the rate of lime
solution in the slag. Figure 7 shows the ASTM water reactivity curves for
the two lime products used in the crucible tests shown in Figs. 5 and 6.
Since the water reactivity test was the easiest one to adapt to plant quality
control, it was used to develop specifications for incoming lime products.
Specifications were developed on reactivity, loss on ignition, sulfur, and
total CaO. These are a minimum water reactivity of eight, a maximum
LO! of two, a maximum sulfur of 0.035, and a minimum CaO of 95 per-
cent. Figure 8 shows the frequency charts for 1968 on incoming lime from
several suppliers. It can be seen that the specifications are reasonable and
can be easily met. In fact, the b O I can be reduced to under 1 percent and
still make a reactive lime.
Effect o n O p e r a t i o n s
It is felt the crucible slag test is a more realistic evaluation of lime
solubility, but it does not lend itself to plant quality control. There are
ways to produce a lime with good slag solubility but with poor water reac-
'~6 8 THE REACTION PARAMETERS O~ LIME
FIG. 7 - - W a t e r reactivity o] two lime samples used in crucible test shown in

Fig. 5.
tivity. None of the lime products we have tested from our commercial
sources fall into this category, however. Some experience has been gained
with prereacted products which would reduce the water reactivity values.
Here the crucible test has been used for screening and evaluation o[ these
FIG. 8--Freqaency charts o[ lime quality delivered to a BOF shop. Lime A is

borderline on sul]ur. Otherwise, specifications generally are maintained.
products. Anything which can be done to speed the rate of slag formation
in BOF operations consistent with metallurgical and refractory practices
should be advantageous to the process. Prereaction to partially produce a
slag before addition to the BOF should be beneficial and is felt to have a
bright future.
Our BOF operators have developed rather strong feelings in regard to
lime reactivity and its effect on their steelmaking practice. One plant hav-
ing a relatively high phosphorus in their hot metal was able to trace diffi-
culties in phosphorus removal back to the use of LoR lime. Another of
our operators has estimated his lining life would decrease by 25 percent if
he were forced to use LoR lime over his present use of a HiR product.
The importance of slagmaking practice is becoming more and more appar-
ent in our operations, and the slag crucible test is one which gives us num-
bers to support opinion. Since lime is the principal slagmaking ingredient,
control of its quality will come under greater and greater scrutiny. The
desired highly reactive product can be made by the industry, and we are
hopeful of seeing additional improvements in the years to come.
DISCUSSION
W. J. Schlitt 1 (written discussion)--The authors are to be commended

for the development of their crucible test for lime reactivity in slags. When
commercially pure calcium oxide is considered, Limes and Russell show
that the results of their test correlate well with those of the accepted water
reactivity tests. However, there is growing evidence that only the crucible
test will predict adequately the dissolution rate of different types of lime in
slag. On the one hand, Timucin and Morris" show that even small addi-
tions of iron oxide drastically reduce the rate of hydrolysis in air. On the
other hand, Obst et al z show conclusively that prefluxed lime containing
iron oxide or other additives such as aluminum oxide (AleO:~) or fluorspar
(CaF.,) greatly increases the rate at which the lime dissolves in the steel-
making slags. Thus, the necessity for using the crucible test, at least under
certain circumstances, seems obvious.
Some recent observations made on lime dissolution in calcium oxide--
iron oxide--silicon dioxide (CaO-FeO-SiO._,) slags (in contact with metal-
lic iron) help explain the importance of iron oxide in basic slag formation.
When a pellet of lime is immersed in the initially acid furnace slag, iron
oxide immediately begins to penetrate into the calcium oxide and leads to
the development of an iron-rich region around a core of unreacted CaO.
Chemical analysis shows that the region usually contains 10 to 12 percent
ferrous oxide, 4 to 7 percent ferric oxide (Fe~O:~) and less than I percent
silica. Some of the iron actually is dissolved in the lime since diffraction
patterns for CaO in this region show a significant shift in peak position
toward that obtained for CaO + 10 percent FeO in solid solution. Micro-
scopic examination also shows that there is a calcium-iron oxide liquid
phase present in the pores in the iron-rich region of the lime. Apparently,
the iron in the slag diffuses into the lime and forms a low melting CaO-
FeO-FezO:~ liquid phase.4,5, 6 Since the viscosity of this liquid is relatively
low compared to that of the silicatious slag, 7 the liquid begins filling the
pores and dissolving lime with which it comes in contact. Calcium ions
' Scientist, Kenecott Copper Corp., Salt Lake City, Utah 84111.
2 See p. 25.
3See p. 173.
' Although the entire liquidus surface has not been determined for the system
CaO-FeO-Fe.,O:~, a melting point as low as 1100 to 1200 C has been observed.
Phillips, B. and Maun, A., "Stability Relations of Calcium Ferrite," Transactions,
Metallurgical Society, American Institute of Mining, Metallurgical, and Petroleum
Engineers, Vol. 218, 1960 pp. 1112-1118.
Levin, E. M.. Robbins, C. R., and McMurdie, H. F., Phase Diagrams ]or Ceram-
ists, The American Ceramic Society, Columbus, Ohio, 1964, p 48.
McGannon, H. E., The Making, Shaping, and Treating o[ Steel, United States
Steel, Pittsburgh, Pa., 1964, p. 316.
170
DISCUSSION ON LIME REACTIVITY IN SLAGS 171
then diffuse out into the slag while iron diffuses into the liquid. Lime will
continue to dissolve, and some unreacted pieces may be actually dislodged
from the remaining pellet. Only when the iron oxide content of the slag is
low and the silica content is high will the lime-iron oxide reaction be sup-
pressed by the lime-silica reaction. When this occurs a dicalcium silicate
layer will build up on the lime and retard dissolution.
The observations make possible at least a partial explanation of the role
which fluxes play in the behavior of lime in the water reactivity and crucible
tests. When lime-iron oxide mixtures are sintered, some iron will go into
solution in the lime. However, much of the iron oxide will be tied up as
calcium ferrites. Since these calcium-iron oxide phases have rather low
melting points, the prefluxed lime simply may melt when added to the
basic oxygen furnace. Even if the material does not melt, the local concen-
tration of iron will be so high around the solid lime that calcium silicate
formation is avoided. However, the same compounds which hasten the
dissolution of lime in the slag should retard hydrolysis. Since water reac-
tivity tests showed that ferrites do not react rapidly with water, they should
stabilize lime in these tests by setting up barriers to slaking. The protective
mechanisms need further clarification, however, since Timucin and Morris
have shown that even small amounts of iron oxide in solid solution slow
the rate of hydrolysis significantly.
E. B. Snyder 8 (written discussion)--I wish to commend Mr. Limes and
Mr. Russell for their interesting, revealing, and rather complete laboratory
study on lime dissolution in BOF slags.
The authors refer to the replacement of most of the open hearths by the
BOF. It begins to appear that the electric furnace will replace most of the
rest of them. The e!ectric furnace consumes sizeable tonnages of burned
lime, also. Electric furnace heat time is decreasing to the point that rapid
lime solution is becoming almost as important a factor in the electric as in
the BOF.
Although many researchers have theorized and drawn conclusions from
slag studies, operating data, and opinions, Republic's work was the first to
visually, chemically, and mineralogically show the difference between high
(HiR) reactive and low (LoR) reactive lime. While many of us were certain
that HiR lime would increase the rate of slag development, we had no
reliable way of measuring the slag development rate prior to this crucible
test.
It is interesting to note that the same dica/cium silicate protective cover
is found on BOF burned lime particles as was found 30 or more years ago
on limestone lumps fished out of open hearth slags. Either spar or iron
oxide must be used to wash away this dicalcium silicate layer. For several
years after the development of the BOF, we almost forgot that slag was
Marblehead Lime Co., Division of General Dynamics Corp., Chicago, 111.
important in steelmaking. As the BOF operation became more refined, we

are led back to slag studies to find answers to many of the remaining
unsolved problems.
The paper points out that with HiR lime, there is less need of high
oxide slags (or high fluorspar) to wash off the dicalcium layer on the lime
lump. As we get more information on the early slags, we may find that the
iron oxide level of the early slags, using LoR lime, may be higher than
when HiR lime is used. Since the oxide level of the slag is the major fac-
tor in rate of lining wear, we may be fooled by a low oxide final slag,
whereas the early slags may have been high enough in iron oxide to cause
severe lining wear.
With this excellent work to guide us, we need further work to define
limits for HiR and LoR lime. The crucible method, along with studies of
early slag, should give us enough data from which we can draw rather
definite conclusions regarding the overall effect of lime quality on BOF
operation and lining life.
These same slag studies should contribute data that will help find the
answers to sulfur and phosphorus removal efficiencies.
R. W. Limes and R. O. Russell (authors' closure)--The comments made
by Mr. Schlitt and Mr. Snyder are very much in order and we generally
agree with them. Metallurgical lime available to Republic's BOF operators
always has been from high purity limestone, and the water reactivity test,
a test suitable to plant quality control, adequately characterizes this type of
product. We agree that less pure lime products or ones altered by addi-
tives would not be characterized by water reactivity. As mentioned, we
have used the crucible test to evaluate these in the laboratory.
Although Mr. Schlitt points out that lime immersed in an acid furnace
slag shows iron oxide penetration, we have evidence from actual furnace
slags which indicates the dicalcium silicate layer can form first and this then
effectively inhibits the penetration of iron oxide into the lime. This can
happen even with relatively high iron oxide slags. In our experience, this
silicate rim generally is associated with a LoR lime. We believe the silica
derived from hot metal silicon reacts more readily with lime than does the
silica contained in a premelted slag. In any event, this only strengthens the
role of prereacted materials where additives inside the lime lump would
flux off the dicalcium silicate layer from within.
The early BOF slags mentioned by Mr. Snyder are presently under in-
vestigation, but the work has not progressed enough for comment. From
our standpoint, we plan only to work with HiR lime so this will not answer
one of the questions raised by Mr. Snyder. Work to date has indicated that
lime solution in BOF slags is still relatively slow, even with HiR lime, and
many areas for investigation remain.
Karl-Heinz Obst,' Ji~rgen Stradtmann, ~ Wolfgang Ullrich/ and
Gert K6nig 4
Present Status and Technical Advances

of Steelworks Lime for Basic Oxygen
Furnaces in Germany
REFERENCE: Obst, Karl-Heinz, Stradtmann, Jiirgen, Ullrich, Wolfgang,

and K6nig, Gert, "Present Status and Technical Advances of Steelworks
Lime for Basic Oxygen Furnaces in Germany," The Reaction Parameters
o] Lime, A S T M STP 472, American Society for Testing and Materials,
1970, pp. 173-192.
ABSTRACT: The effect of chemical analysis, grain composition, and
reactivity of lime on slag formation and metallurgy of steelmaking is dis-
cussed. Test showed that reburning of soft burn lime may occur in the BOF.
By using special lime, which is manufactured from lime and fluxes, it is
possible to work against reburning and C2S-formation. The acceleration of
lime dissolution and the resulting improvement of the metallurgical reac-
tions lead to a reduction of the blowing time.
KEY W O R D S : steelmaking, calcium oxide, combustion, reactivity, mag-
nesium oxide, sulfur oxides, slags, metallurgical furnace, dissolving, grain
size, fluxes, phosphorus inorganic compounds, evaluation, tests
Concerning economical and metallurgical aspects, the quality of the lime

is very effective on the optimal conduct of basic oxygen heats. Therefore
the introduction of the basic oxygen steelmaking process helped decisively
to draw more attention to lime properties.
Importance of Lime Quality in Steel

In Germany, one was able to refer to many papers dealing with the effect
of chemical analysis, grain composition, and reactivity of lime on the
1 Prokurist der Abteilung, Kalk/Dolomit fiir die Stahlindustrie, Kalksteinwerke
GmbH u. Dolomitwerke GmbH, Wilhelmstr., Wiilfrath, West Germany.
2 Gruppenleiter der Abteilurlg, Kalk/Dolomit fiJr die Stahlindustrie, Kalksteinwerke
GmbH u. Dolomitwerke GmbH, Wilhelmstr., Wiilfrath, West Germany.
Letter der Abteilung, Stahlwerksmetallurgie, August Thyssen-HiJtte AG, Posffach,
Duisburg, West Germany.
4 Letter der Abteilung, Feuerfeststoffe und Mineralogie, August Thyssen-Htitte
AG, Postfach, Duisburg, West Germany.
173
Copyright
Copyright by9 ASTM
1970Int'l
by ASTM International
Aug 1 12:04:31 EDT 2012
metallurgy of open hearth and basic Bessemer process. This research was
started in 1943 and was intensified in the fifties [l-18]. 5 For the basic
oxygen furnaces ( B O F ) the demands for chemical analysis and grain com-
position were taken over from the former steelmaking processes, and the
correctness was confirmed in comparative tests.
Effect oJ Chemical Analysis

With regard to chemical analysis, the calcium oxide (CaO) content had
to be as high as possible. Nowadays, in general, it runs from 87 to 95 per-
cent. The carbon dioxide (CO~) content should be rather low as it is im-
portant for the thermal balance and for a smooth heat conduct. Lime from
shaft kilns has about 2 to 5 percent. Depending on the burning or calcining
degree, soft-burnt lime from rotary kiln has less than 1.5 percent.
In addition, the magnesium oxide (MgO) content [19] of the lime and,
with regard to the increasing demands for better steel quality, the sulfur
content is of interest to a high degree. In the bibliography the favorable
effect on lining life when adding dolomitic lime is sometimes reported
[20-22], but this practice is not usual in Germany. Fundamental research in
the laboratory has shown the advantages of such a measure for lining life
[23-25], but indicated at the same time that the MgO content of the lime
should be so low that the saturation on magnesium oxide with its detri-
mental effect on the metallurgy is not exceeded [26-29]. The steelworks
lime which is used for the basic oxygen process in Germany and which has
about 1 to 2 percent MgO, to a greater extent, reaches this requirement.
The sulfur content of the lime is of interest for steelmaking as the desul-
furization may be limited [30]. Generally, the sulphur content of the scrap
varies and is mostly unknown. Therefore, the steelmaker tries to get a
good metallurgical result by using a lime of low sulfur content though the
amount of sulfur inserted into the melt by the lime is low compared to that
of scrap and pig iron. The sulfur content of the lime depends on the kind
of fuel and the time of exposure when calcining. In Germany it is 0.06 to
0.09 percent in coke fired shaft kilns and less than 0.02 percent in rotary
kilns fired by natural gas.
Effect o/ Grain Size

Concerning the grain composition of steelworks lime the demands are
different according to the type of top blowing process. When blowing low
phosphorus pig iron particles of lime from 8 to 40 mm are used. Some
plants are even operating in smaller ranges of the mentioned measurements.
The italic n u m b e r s in brackets refer to the list of references appended 1o this

paper.
OBST ET AL ON BASIC OXYGEN FURNACES IN GERMANY 17 5
Most people pay attention that the amount of undersize grains is not more
than 10 to 20 percent and that in particular this does not contain powdered
lime as clogging may be produced. For blowing high phosphorus pig iron
some people use pulverized lime. For the reasons already mentioned the
lime powder should be coarse.
Effect o] Reactivity
While there is agreement concerning the chemical analysis and the grain
size, the results differ with regard to the effect of the reactivity of the lime
on the slag formation. In this connection particular interest was taken in
soft-burnt lime which has a large specific surface and is said to be of high
reactivity. Hammerschmid et al [31] did not find any advantage when using
soft-burnt lime in the top blowing process. Through working together the
LD-plants of Koninklijke Nederlandsche Hoogovens- en Staalfabrieken in
Ijmuiden and Rheinische Kalksteinwerke in Wfilfrath achieved the result
[32] that, compared to normal lime for steelmaking, both soft-burnt and
hard-burnt lime have advantages. Schleicher et al [33] came to the conclu-
sion that LD-steelworkers should prefer a lime, which is burnt as soft as
possible and which is of small grain size. Behrens et al [34] concluded that
soft-burnt lime leads to a more rapid dephosphorization and better de-
sulfurization as well as to an easier conduct of heat with reduced slopping.
However, as already mentioned, the conclusion that the soft-burnt lime
is advantageous in LD-steelmaking is only partly confirmed in bibliography
and is not recognized in general [31-39]. In the case of lime powder this
may be explained by the fact that the difference between types of lime of
various burning degrees is decreased by grinding and pulverizing [40,41]
and in theory will disappear when the crystal size is reached. Experimental
work in the plant has proved this [38]. But the discrepancy with regard to
the effect of the reactivity of particles of lime could not be explained till
now.
In Fig. 1 some types of lime are shown together with their charac-
teristics. They have been burnt intentionally at different temperatures in a
laboratory muffle furnace in order to get various burning degrees. Their
reactivity against water is quite different both in the coarse grain titration
and in the slaking test [19]. The reason for this is the difference in the
specific surface which can be made visible by the stereoscan method. In
order to demonstrate the possibilities of this research technique by which
many of our new results have been obtained, Limes A and E of Fig. I are
shown separately in Figs. 2 and 3. Looking at these figures it becomes clear
that some other interrelations not yet sufficiently known are affecting the
dissolution of the lime; otherwise, all plants using high reactive soft-burnt
lime should have a more rapid dissolution in the primary slag.
FIG. l--Data of laboratory lime with 0.08 percent residue carbon dioxide.
Reburning of Lime
Recent investigations gave the explanation for the different results with
regard to the use of soft-burnt lime. In the laboratory it was tested
[42,43] whether it is possible to change the reactivity of lime within the
short time which is characteristic for the top blowing process. It was found
that after passing a critical value of temperature and time, the soft-burnt
lime is reburned. Because of the crystal growth the reactivity is decreased
(Fig. 4). At 1400 C this reduction is only small, whereas at 1600 C with 3
to 5 min reburning former soft-burned lime is of medium reactivity and
after 10 min is a hard-burnt lime of low reactivity. The changes in the
crystallite size at 1600 C reburning tests can be seen in Fig. 5. The crystal-
lite size increased from 1 to 10/zm.
These results were checked under operational conditions in two BOF-
plants. In Plant A where low-carbon steel is produced, the rate of decar-
burizing is high, but the temperature is relatively low. Plant B manufac-
tures high-carbon steels by caught heats; for this reason the decarburization
must be retained for the temperature rises quickly. In Fig. 6 the tempera-
tures during heats in Plants A and B, which are affected by the different
OBST ET At ON BASIC OXYGEN FURNACES IN GERMANY ] 77
FIG. 2--Stereoscan o[ Lime A.
quality of the produced steel, can be compared. A selection of stereoscan

photographs of slag samples containing lime is attached. It can be seen
that at a heat conduct, keeping the temperature low for a long period, the
lime is not reburnt. Through this the advantages of soft-burnt lime are
utilized. But a heat conduct with rapid rise of temperature in metal and
slag results in the reburning of soft-burnt lime which, in this case, has no
advantage. The practice, based on operating experience--Plant A used
FIG. 3--Stereoscan o / L i m e E.
FIG. 4--Effect o[ reburning time on reactivity o[ lime.
FIG. 5--Coarse grain titration and morphology when reburning lime.
OBST ET AL ON BASIC OXYGEN FURNACES IN GERMANY ]79
FIG. 6--Effect o[ heat conduct on morphology o[ lime.
soft-burnt lime successfully, Plant B, which does not normally use this
lime, had very different results--now can be explained. When adding
soft-burnt lime into the converter there is a competition between reburn-
ing and dissolution of the lime. If dissolution is quicker than reburning the
use of soft-burnt lime is advantageous; but if reburning is quicker than
dissolution, its behavior is similar to a less reactive lime.
Effect of Dica|cium-Silicate Formation on the Dissolution of Lime

Working against the dissolution is another phenomenon which is already
reported in some papers [45-52]. In the LD-process the manganese iron
silicates formed in the early period react with the lime. The result is the
formation of high melting dicalcium silicate which may coat the lime and
therefore interfere in its dissolution. In Fig. 7 an example of such a phe-
nomenon is shown. Mostly, the dicalcium silicate shell is accompanied by
a metal(II)-oxide one. Investigation of these shells by X-ray micro-
analyzer showed that the dicalcium silicate is a complex solid solution
dicalcium silicate/tricalcium phosphate (C~S-C3P). Calcium is substituted
partly by iron and manganese, silicon dioxide by phosphorus pentoxide.
When blowing high phosphorus pig iron, silico phosphates are formed.
The metal(II)-oxide shell is a calcium-iron-manganese-oxide solid solu-
tion. The lime in dissolution was measured quantitatively by the micro-
analyzer [54,55]. Corresponding to the fundamental research on dissolu-
tion of lime in the system CaO-FeO,, [54,56], lime picks up iron(II)-oxide
into solid solution till saturation is reached, then it melts. As the dicalcium
FIG. 7--Shell of dicalcium silicate.
silicate shell works against the dissolution of the lime, it promotes reburn-
ing and therefore has a double disadvantageous effect. Investigators of
equilibrium diagrams showed that in the 4-component system FeOn-CaO-
SiO._,-P.,O5 there is a barrier of silico phosphates at low P~.O5 contents which
already should be taken into consideration in slags of the LD-process [57].
Therefore, one has to consider the question whether soft-burnt lime which
in many cases has proved to have advantages compared to normal steel-
works lime, is the optimum or whether further measures with regard to
lime can be taken to obtain the optimal conduct of basic oxygen heats [19].
Lime with Admixtures

Concerning the facts reported above, such a step should be characterized
by an increase of the rate of dissolution as a result of effecting the formation
of dicalcium silicate and anticipating the solid solution, both causing a de-
crease of the reburning phenomenon. For effecting the formation of
dicalcium silicate shells it is necessary to force back the saturation area of
the C_oS, to bring it to lower temperatures or to change the kind of C2S
from dense shells to small islands under the microscope.
From the investigation of equilibrium diagrams it is already known that,
contrary to the P205 mentioned above, an addition of manganese oxide
[46,58] or magnesium oxide [23,29] forces back the saturation area of the
dicalcium silicate in the system CaO-FeOn-SiO2. In Fig. 8 is shown the re-
duction of the melting point of C,S by some additions as can be seen from
OBST ET At ON BASIC OXYGEN FURNACES IN GERMANY 181
,. 2000 l-Y~'~-~--~T-
~1400~
, oo
admixture [wt." %2
F I G . 8--Effect oJ admixtures on the melting point of 2CaO-Si02.
the ternary diagrams CaO-SiO2-X in the "Phase Diagrams for Ceramists"

[59]. Pure iron oxides are of a stronger effect than dicalcium ferrite. A
much better performance is achieved using alumina, fluorspar, and borates.
For the special lime required, the additions to the lime should be the
oxides of the first to the third group of the periodic system or their com-
binations. They may diminish the saturation area of the CeS, reduce the
melting point of CaO, and delay or prevent the reburning.
These considerations were checked by laboratory tests [60]. The dissolu-
tion of special lime, pressed from lime powder and fluxes, was observed as
a function of time. The lower dashed line in Fig. 9 is characteristic for the
dissolution of soft-burnt lime. A considerable acceleration is effected by
adding BOF dust or mud, which is further increased by the addition of
alumina bearers.
Use o[ Special Lime in BOH

This effect of alumina bearers was even found in the slowly operated
open hearth furnace, when particles of lime and flux were added [61].
Without changing the mode of operation and the batch of lime, the charg-
ing of calcined bauxite into the open hearth furnace results in a better
utilization of the lime than normal due to the formation of more basic slags
without increased slagging of iron (Fig. 10). The CaO/SiO.~ ratio of the
melt down slag is changed to higher values, indicating that already at this
time larger amounts of dissolved lime are available in the slag. This means
] 82 THE REACTION PARAMETERS OF LIME
2 e ~ 50% BO~Fmud l
~.1 L : " 30% AIpO3 I
I N. " 50% red mud ' ~ I

~20H:withou' ~ - ~ ~ ~
0 14 21 28 35 42 49
l i m e f min3
FIG. 9--Slagging o/so/t-burnt lime with admixtures.
that even during the melt down period the dissolution of lime is accelerated
by the charging of bauxite.
Due to the homogeneous dispersion when using special lime which is a
briquetted or pelletized mixture of lime powder and fluxes, one should have
an effect similar to the premelted slag of Lellep [62]. Besides these fluxes
may be already in the limestone or be added when calcining. The use of
special lime has been considered and described mainly for the open hearth
and electric arc furnace [46,47,62-85], particularly in Russia.
50^ . . . . 440 .,
~ o ~ ~ . ~ ~eo_' \20 §
p soA :~ :\ :, ~ o : \
I0 20 30 40 50 6O
--(FeOtot)'in wt.-% ~
FIG. l O--E[]ect o/bauxite addition on slag composition in BOH-process.
OBST ET AL ON BASIC OXYGEN FURNACES IN GERMANY ] 83
Use of Special Lime in BOF

In order to compare the use of special lime with the normal practice and
to answer the question whether soft-burnt lime is the optimum, test heats
were carried out in a 6-ton basic oxygen furnace [82], The investigations
were performed with soft-burnt lime of 10 to 30 mm grain size and with
pelletized special lime which contained equally dispersed iron oxides com-
ing from the dust collectors of the LD-plants or from residues of the
aluminum production out of bauxite (red mud).
With regard to the heat conduct, in particular lance distance, oxygen
flow, and interruption of the blowing process for sampling and measuring
of temperature, conditions were the same for all heats. The charging of the
additions was variable. In the first series of experiments two thirds of the
necessary lime was charged as soft-burnt lime before the blowing, the rest
as special lime or soft-burnt lime after a blowing time of 12 rain. In the
second series of experiments lime was charged in such a way that one third
as special lime or soft-burnt lime was added before blowing, the rest as
soft-burnt lime after 6 min.
By balancing the slag analysis the ratio of the dissolved amount CaO to
the charged quantity CaO was calculated (Fig. 11 ). Compared to soft-
burnt lime the charging of special lime results in a considerable accelera-
tion of the dissolution rate. The early formation of a slag with a high
Ioo
,A lB 1,--~
8 o - - - - /"
60
t,o _ /J io. I
. I ~ 2/gcoObys,,ft-b,,.,t I)~~
i
..~ B I I 3 CoO b y
a) J s o f t - b u r n t lime
20 4k- - - lira@ ~ O F m u d - p c / l e t s -
II-.-- lime-red mud-l~//ets
I 1 1
9~ ~= I00
60
20~ b) - I t
O~ 5 I0 15 20 25 30
blowing time [ m i n i
FIG. l l---Dissolution o/ c(//cit/m oxide in BOF whelt cl/arging special lime.
CaO/SiO2 ratio and with a high iron content is an important condition for
a good dephosphorization to which particular attention must be paid in
Germany on account of the analysis of the pig iron. The effect of the spe-
cial limes used on the dephosphorization related to decarburization is
shown in Fig. 12. There is a similar dephosphorization in all heats of the
first series (Fig. 12a) till the time when the different limes are charged.
At 2.5 percent carbon in the metal there is still 0.11 percent phosphorus.
Compared with heats where only soft-burnt lime was used the charging of
special lime containing converter dust results in a considerable acceleration
of dephosphorization which is even exceeded by feeding special lime with
red mud.
A more rapid dephosphorization with regard to decarburization was ob-
served also when the special lime is charged before blowing starts (Fig.
12b). After a blowing time of 6 min, that is, before the general aftercharge
of soft-burnt lime and at carbon contents of 3.6 to 3.9 percent the phos-
phorus was still 0.125 percent when using soft-bumt lime, whereas it was
reduced already to 0.080 percent when feeding special lime with red mud.
As a result of this it is proved that the expected effect of a good mixture
of lime and fluxes is existing in the converter.
Using a large BOF vessel it was found also that the charging of lime-
fluorspar briquets resulted in a quick slag formation. This was indicated by
the curve of the sound level meter. The heat conduct was extraordinarily
smooth without any tendency to slopping in spite of increasing the intake
of oxygen by 20 percent and diminishing the blowing time. Moreover in
comparison to the normal practice the amount of CaF~ charged to the con-
verter by briquets could be reduced considerably as further tests proved.
o,200
o)
S.j A
o,15o
,-~ o, too
~ Bo1/3Co0 by:I ,o,-I~r.t~ k _lime
" o,050 .soft-burnt lime l
lip. /" 9 -- - hme-BOF mud-pellets
B.-.-- lime-red mud-pellets
o i i
o 0,200
&
o, 150
Cl. /
0,I00
O,O50
00 I,o 2,O 3,O 4,O 5.o

corbon [wt.-%3
FIG. 1 2 - - D e p h o s p h o r i z a t i o n by charging special lime.
OBST ET AI ON BASIC OXYGEN FURNACES IN GERMANY ] 85
Conclusions
Generally speaking it may be said that in the future interest in the use
of special lime will increase in Germany. The improvement of the metal-
lurgical reactions resulting in lower phosphorus and sulfur contents and in
a reducing of the scatter ranges allows for a more defined heat conduct.
Due to the early slag formation the blowing behavior is smooth. By in-
creasing the input of oxygen, a reduction of the blowing time is possible.
By the use of special lime the lance is relieved of slag reactions and there-
fore can be used for decarburization in particular. From this point of view
a blowing time of 5 rain is not impossible. The resulting increase of output
can compensate the higher manufacturing costs of special lime compared
with soft-burnt lime. In addition, the precise refining to low phosphorus
contents allows the production of high-carbon steel by caught heats or even
of alloyed steel.
Finally it should be mentioned that by use of special lime the final slags
may have no free lime. This should improve the possibilities of selling the
slag as the application of the LD-slag for road building and other purposes
is hindered, among other things, by the disintegration due to the slaking of
the lime. It may be possible in the future when charging special limes with
suitable composition that the slag would be used for purposes which
nobody has considered yet.
Summary
Concerning economical and metallurgical aspects, the quality of the lime
is very effective on the optimal conduct of basic oxygen heats. Therefore
chemical and grain composition as well as reactivity have been subject of
many investigations in which one was able to refer to former research in the
basic Bessemer and open hearth process. While there is agreement con-
cerning the effect of the analysis (besides CaO particularly MgO and
sulfur) and of grain size (small range, little powder), the results differ
with regard to the effect of reactivity (burning degree) on the slag forma-
tion.
The reason for the fact that the use of soft-burnt lime was not always
advantageous is the possible reburning in the LD-vessel if a critical value
(temperature, time) is passed. There is a competition between reburning
and dissolution of the lime. Reburning is as bad for a quick dissolution of
the lime as is the formation of dicalcium-silicate shells. Therefore one has
to consider the question whether the soft-burnt lime of today is the
optimum.
By using special lime it is possible to work against reburning and CeS
formation. This special lime contains lime and additions for better dissolu-
tion and is a step towards preformed slag. Experiments in the laboratory
and in the steelplant proved the acceleration of lime dissolution by use of

b r i q u e t t e d or pelletized mixtures being c e m p o s e d of lime and flux. By the
resulting i m p r o v e m e n t of the metallurgical reactions a better heat c o n d u c t
and a reduction of the blowing time is possible. T h e lance can be relieved
of slag reactions and therefore can be used for d e c a r b u r i z a t i o n in partic-
ular. I n addition, one is able to get final slags without free lime.
References
[1] RiSchling, H., private communication, 1943.

[2] Senfter, E., Schnfirch, G., and Guthmann, H., Stahl und Eisen, Vol. 72, 1961,
pp. 334-343 (Stahlwerksausschuss 477).
[3l Tr6mel, G., unpublished paper given to the Stahlwerksausschuss, 13 Oct. 1953
in Diisseldorf.
[41 Gruschka, J., unpublished paper given to the Stahlwerksausschuss, 13 Oct. 1953
in Dfisseldorf.
[5] Leroy, P., Gombert, M., and Trentini, B., Revue de Mgtallurgie, Vol. 50, 1953,
pp. 642-664.
[6] Gruschka, J., unpublished paper given to the Parit~itischer Kalkausschuss, 5 Feb.
1954.
[7] Latour, A. and Heinen, L., Stahl und Eisen, Vol. 77, 1957, pp. 426-428.
[8l Mayer, K. E., Diirrnann, H. J., Tr~3mel, G., and Obst, K.-H., Stahl und Eisen,
Vol. 77, 1957, pp. 1614-1618 (Stahlwerksausschuss 631).
[9] Weber, F., Kootz, Th., and Obst, K.-H., Stahl und Eisen, Vol. 78, 1958, pp.
1734-1745 (Stahlwerksausschuss 659).
[10] Eickworth, E.. Tr6mel, G., Obst, K.-H., and Peter, O., unpublished paper, 1968.
[11] K6hler, W., Schoop, J., Tr6mel, G., and Obst, K.-H., Stahl und Eisen, Vol. 80,
1960, pp. 1689-1695 (Stahlwerksausschuss 699).
[12] H6fges, H., Willems, J., Aschendorff, K. K., K/ihler, E., and Obst, K.-H.,
unpublished paper given to the Arbeitsausschuss Thomasstahlbetrieb, 17 May
1960 in Wiilfrath.
[13] Rellermeyer, H., unpublished paper given to the Arbeitsausschuss Thomasstahl-
betrieb, 17 May 1960 in Wiilfrath.
[14] Gruschka, J., unpublished paper given to the Arbeitsausschuss Thomasstahl-
betrieb, 17 May 1960 in Wiilfrath.
[15] Obst, K.-H., unpublished paper given to the Arbeitsausschuss Thomasstahl-
betrieb, 17 May 1960 in Wfilfrath.
[16] Obst, K.-H., K6hler, W., Meier-CortEs, E., and G6rl, E., Stahl und Eisen, Vol.
81, 1961, pp. 1503-1510 (Stahlwerksausschuss 727).
[17] Eickworth, E., unpublished paper given to the Windfrischgemeinschaft, 11 Dec.
1961.
[18] Eickworth, E., unpublished paper given to the Parit~itischer Kalkausscbuss, 22
Oct. 1962 in Diisseldorf.
[19] Obst, K.-H. and Stradtmann, J., Stahl trod Eisen, Vol. 87, 1967, pp. 1543-1546.
[20] Circulaire d'Informations techniques.
[21] MacNamara, J., Journal o[ Metals, Vol. 17, 1965, pp. 781-784.
[22] U.S. Patent No. 3,288,592, 29 Nov. 1966.
[23] Tr6mel, G., Obst, K.-H., G6rl, E., and Stradtmann, J., Tonindustrie-Zeittmo und
kerarnische Rundschau, Vol. 90, 1966, pp. 193-209.
[24] Tiickhardt, K. W,, unpublished Diplom-Arbeit, Technische Hochschule Clausthal,
1966.
OBST ET AL ON BASIC OXYGEN FURNACES IN GERMANY 187
[25] Schenk, H. H., unpublished Diplom-Arbeit, Technische Universit~it Clausthal,

1968.
[26] Fischer, W. A. and Spitzer, H., Archiv/fir das Eisenhiittenwesen, Vol. 29, 1958,
pp. 611-617.
[27] Margot-Marette, G. and Riboud, P. V., Revue de M6tallurgie, Vol. 61, 1964,
pp. 709-713.
[28] Tr6mel, G., Fix, W., and Kaup, K., Archly [iir das Eisenhiittenwesen, Vol. 38,
1967, pp. 595-605.
[29] Grosskurth, N., Dr.-Ing.-Dissertation, Technische Universit~it Clausthal, 1969.
[30] Schleicher, W., Lutz, H., and Gravenhorst, H., Stahl und Eisen, Vol. 81, 1961,
pp. 13, 88-92.
[31] Hammerschmid, P., Lamge, K., and Schiel, V., unpublished paper given to the
Parit~itischer Kalkausschuss, 22 Oct. 1962 in DiJsseldorf.
[32] Unpublished paper of Hoogovens- en Staalfabrieken, ljmuiden and Rheinische
Kalksteinwerke GmbH., Wfilfratb.
[33] Schleicher, W., Lutz, H., and Graf, H., Technische Mitteilungen Krupp,
Forschungs-Berichte, Vol. 21, 1963, pp. 139-146.
[34] Behrens, K. F., Koenitzer, J., and Kootz, Th., Journal of Metals, Vol. 17, 1965,
pp. 776-781.
[35] MacNamara, J., Petrilli, E., Pehlke, R. D., and Ehrlich, R., Proceedings o[ the
National Open Hearth and Basic Oxygen Steelmaking Con[erence, Iron and
Steel Division of the American Institute of Mining, Metallurgical. and Petroleum
Engineers, Vol. 47, 1964, pp. 73-86.
[36] Gregory, J. A., Schrader, A., Bashford, R., and Hubbard, F. G., Jottrnal of the
Iron and Steel Institute, Vol. 203, 1965, pp. 886-891.
[37] Meschi, P. and Ceraldi, C. S., Metallurgia ltaliana, Vol. 59, t967, pp. 748-752.
[38] Schoop, J., Aschendorff, K. K., Fleige, H. G., and Radke, D., Stahl und Eisen,
Vol. 88, 1968, pp. 756-766 (Stahlwerksausschuss 865).
[39] Reinders, F., Fried|, E., and Kauder, G., Stahl und Eisen, Vol. 89, 1969, pp.
57-63 (Stahlwerksausschuss 879).
[40] Obst, K.-H., Stradtmann, J., and Ullrich, W., in preparation.
[41] Behmenburg, K., unpublished Diplom-Arbeit, Technische Universit~it Clausthal,
1968.
[42] Obst, K.-H., Stradtmann, J., and MiJnchberg, W., Tonindustrie-Zeitung und
keramische R,ndscha,], Vol. 92, 1968, pp. 389-392.
[43] Obst, K.-H., Stradtmann, J., and Miinchberg, W., Tonindustrie-Zeitung und
kerarnische Rundschau, Vol. 93, 1969, pp. 328-331.
[44] Obst, K.-H., Stradtmann, J., Miinchberg, W., and Ullrich, W., Stahl und Eisen,
in preparation.
[45] Fetters, K. L. and Mahany, E. W., Iron Age, Vol. 159, 1947, No. 10, pp. 62-66;
No. II, pp. 64-68; see Stahl und Eisen, Vol. 68, 1948, pp. 162-163.
[46] TrOmel, G. and G/Srl, E., Stahl und Eisen, Vol. 83, 1963, pp. 1035-1051.
[47] Tr6mel, G., Ullrich, W., Willems, J., and Rudack, W., Stahl und Eisen, Vol. 83,
1963, pp. 1226-1234
[48] Tr6mel, G. and G/Srl, E., Archly ]iir das Eisenhiittenwesen, Vol. 35, 1964, pp.
287-298.
[49] Husson, G., Revue de M6tallurgie, Vol. 61, 1964, pp. 715-731.
[50] Fischer, W. A. and Fleischer, H. J., Smhl nnd Eisen, Vol. 84, pp. 117-135.
[51] K6nig, G.~ Rellermeyer, H., and Obst, K.-H., Stahl ,nd Eisen, Vol. 87, 1967,
pp. 1071-1077.
[52] Schfirmann, E., NiJrnberg, K., UIIrich, W., and Overkott, E., Archly [iir das
Eisenhiittenwesen, Vol. 39, 1968, pp. 815-821.
[53] Obst, K.-H., Stradtmann, J., and Horn, H.Chr.. Mikrochimica Acta (Wien),
Supplementum II1, t968, pp. 140-146.
[54] Obst, K.-H. and Stradtmann, J., Archiv fiir das Eisenhiittenwesen, Vol. 40, 1969,
pp. 615-617.
[55] Nfirnberg, K., Dr.-Ing.-Dissertation, Technische Universit~t Clausthal, 1968.
[56] Obst, K.-H., Horn, H.Chr., and Stradtmann, J., Mikrochimica Acta (Wien),
Supplementum III, 1968, pp. 147-154.
[57] Tr6mel, G., Fix, W., and Koch, K., Archiv ]iir das Eisenhiittenwesen, Vol. 38,
1967, pp. 177-184.
[58] Klages, R., Dr.-Ing.-Dissertation, Technische Universitiit Clausthal, 1968.
[59] Phase Diagrams for Ceramists, The American Ceramic Society, Columbus, Ohio,
1964.
[60] Piepenbrock, R., unpublished Diplom-Arbeit, Technische Universit~it Clausthal,
1967.
[61] Ullrich, W., Meichsner, W., Niirnberg, K., and Rudack, W., Stahl und Eisen,
Vol. 89, 1969, pp. 918-927.
[62] Lellep, O., Bericht fiber die Versuche zur Stahlherstellung im Herdofen und
Konverter unter Benutzung von konzentriertem Sauerstoff, Diisseldorf, 1951.
[63] Henke, G., comment given to the Parit~itischer Kalkausschuss, 6 June 1958 in
Wfilfrath.
[64] Wakabayashi, K., Takeda, M., Tsubakihara, O., and Sasaki, S., Tetsu to Hagane,
Vol. 51, 1965, pp. 734-740.
[65] Tamamoto, S., Iwase, K., and Yoshida, K., Tetsu to Hagane, Vol. 51, 1965,
pp. 740-742.
[66] Fiedler, W., Freiberger Forschungshefle, Vol. B 43, 1960, pp. 9-64.
[67] Chovlov, D. J. and Frivalov, S. J., Stal in Deutsch, Vol. 4, 1964, pp. 119-124.
[68] Klejn, A. L. and Danilov, A. A., Stal in Deutsch, Vol. 4, 1964, pp. 422-425.
[69] Moiseenko, A. J. and Loscev, V. J., Stal in Deutsch, Vol. 5, 1965, pp. 133.
[70] Utkov, V. A. and Kudinow, B. A., Stal in Deutseh, Vol. 6, 1966, pp. 637-638.
[71] Huysmanns, J., Circulaire d'ln[ormations t~chniques, Vol. 21, 1964, pp. 2055-
2070.
[72] Voronov, F. D., Brigrev, A. M., Kotov, V. N. et al, Stal in Deutsch, Vol. 4,
1964, pp. 607-609.
[73] Chater, W. J. B. and Cook, L., Steel Times, Vol. 188, 1964, pp. 718-72l.
[74] Allard, F,, Pasche, F., Terrat, S., and Gohin, M., Circulaire d'ln]ormations
t~chniques, Vol. 23, 1966, pp. 1739-1751.
[75] Tr6mel, G., comment given to the Parit~itischer Kalkausschuss, 6 June 1958 in
Wiilfrath.
[76] Kalinnikov, E. S., Izvestija Vys~ich U~ebnych Zavedenij, Cerna]a Metallurgiia,
Vol. 6, 1963, pp. 65-69.
[77] PIechanov, P. S., Stal in Deutsch, Vol. 4, 1964, pp. 565-567.
[78] Lubenic, I. A., Zukov, D. G., Vojnov, S. G. et al, Stal in Deutseh, Vol. 5, 1965,
pp. 649-653
[79] Fischer, W. A., Fleischer, H. J., Leihener, O., and Hffer, F., Stahl und Eisen,
Vol. 84, 1964, pp. 117-137.
[80] Utkov, V. A., Ravikovic, I. M., Tretjakov, M. A. et al, Stal in Deutsch, Vol. 8,
1968, pp. 416-419.
[81] Zigulin, V. I., Rubinskig, P. S., Kulagin, G. F. et al, Stal in Deutsch, Vol. 6,
1966, pp. 244-245.
[82] Obst, K.-H., Stradtmann, J., Rellermeyer, H., and Ullrich, W., Tonindustrie-
Zeitung und keramische Rundschau, Vol. 92, 1968, pp. 348-352.
[83] Fischer, W. A. and Wahlster, M., Archly ]iir das Eisenhiittenwesen, Vol. 27,
1956, pp. 77-84.
[84] Arzamascev, E. I., Umrichin, P. V., Gudov, V. I. and Fadew, I. G., Stal in
Deutsch, Vol. 6, 1966, pp. 232-235.
[85] Berens, L., Hoppe, H. J., and Masuhr, M., paper given to the Parit~itischer
Kalkausschuss, 6 June 1968 in Dornap.
OBST ET AL ON BASIC OXYGEN FURNACES IN GERMANY 189
Bibliography
Bauer, G., Koenitzer, J. and Zimmermann, K. A., paper given to the 5th LD-Working
Meeting Committee of Brassert Oxygen Technik A. G. in Diisseldorf, 1969.
Obst, K.-H., Stradtmann, J., and Tr/Smel, G., paper given to the 5th LD-Working
Meeting Committee of Brassert Oxygen Technik A. G. in Diisseldorf, 1969.
Deneen, C. M,, paper given to the 5th LD-Working Meeting Committee of Brassert
Oxygen Technik A. G. in Diisseldorf, 1969.
Russell, R. O., Journal o[ Metals, 1967, pp. 104-106.
Obst, K.-H., paper given to the 4th LD-Working Meeting Committee of Brassert
Oxygen Technik A. G. in Sydney, 1966.
Obst, K.-H., Lime (Japan), No. 10, 1966, pp. 3-17.
Obst, K.-H., Stradtmann, J., Rellermeyer, H., and Ullrich, W., Lime (Japan), No.
158, 1969, pp. 17-26
Obst, K.-H. and Stradtmann, J., Lime (Japan), No. 160, 1969, pp. 6--tl.
Bardenheuer, F., yore Ende, H., and Oberh~iuser, P. G., Stahl und Eisen, Vol. 88,
1968, pp. 1285-1290.
vom Ende, H, Bardenheuer, F. Oberh/iuser, P. G., and Hofmann, E. E., Archiv [iir
das Eisenhiittenwesen, Vol. 39, 1968, pp. 571-576.
Obst, K.-H., Stradtmann, J. and Tr6mel, G., Journal of the Iron and Steel Institute,
in preparation.
DISCUSSION
R. O. RusselP (written discussion)--It is interesting to note, the parallel

philosophies of the authors and ourselves at Republic Steel Corporation. As
has been stated elsewhere, the present BOF steelmaking process is now
being retarded in heat time by slagmaking. The key to steelmaking is a
rapid solution of the lime charge. To decrease slagmaking time, rapid
lime solution must be attained. The lime solution factor is important be-
cause desulfurization and dephosphorization is much faster with lime in
solution than when solid pieces of lime are present in a liquid slag. A step
toward achieving better lime solution is to provide the most reactive lime
possible. If properly calcined a lime will have a high reactivity (as de-
termined by water or hydrochloric acid), a low LOI, and low sulfur. This
type of lime is specified by Republic and corresponds to the lime Type A
of the paper. The upper part of the range stated in the paper, 95 percent
calcium oxide (CaO), is our minimum specification. The microstructures
as shown by the electron scanning microscope in the paper present very
dramatic support of the surface area determinations which have been used
in the past.
The reburning of lime in the BOF at various temperature is a new and
interesting concept. It is open to question whether or not the affect of the
reburning of lime is a major factor to lime solution. In Republic's vessels
most heats will have a temperature rise of 200 F in the last few minutes to
a final tap temperature of 2910 F (1600 C). The reburning affect for the
lime under these conditions would be somewhere between the two reburn
curves (2550 and 2910 F) shown by the author for approximately 4/5ths
of the heat. Lime pieces (1.5 cm) have been obtained at various times
during the blow surrounded by liquid slag from a 175 ton vessel. These
limes still appeared soft burned even late into the heat.
In Republic Steel's Southern District where we experience the highest
phosphorus bearing hot metal, a study was made relating phosphorus re-
moval to type of lime used. This district had up to five or six lime suppliers
at the time of the study ranging from soft to hard burned lime. Under
essentially the same type of practice, poor dephosphorization was related
directly to hard-burned lime. In this particular instance the poor dephos-
phorization was not due to reburning of the lime in the vessel.
1 Ceramic technologist, Research Center, Republic Steel Corp., Cleveland, Ohio

44131.
190
DISCUSSION ON BASIC OXYGEN FURNACES IN GERMANY 1 91
It is somewhat surprising to see the temperature profiles as reported in

the paper for the high- and low-carbon heats. In Republic temperature pro-
files have not been determined, but the tap temperature of "caught" high-
carbon heats are lower than those of low-carbon heats. The profiles, how-
ever, could be explained by a higher hot metal/scrap ratio for the works
producing the high-carbon heats.
It was indicated also in the paper that in the production of high-carbon
heats a higher blowing position was used to increase temperature. If this is
so, then, it is at the probable expense of yield in the form of iron burning
to iron oxide (FeO). The formation of FeO is a known fluxing agent which
in turn should take lime into solution faster, therefore, allowing little re-
burning of the lime to occur. These types of variations in steelmaking
practices can quite often completely overshadow the reactions involved in
slagmaking. An affect of this type was seen in one of Republic's districts
using lining life as the criteria. It was decided to increase lance height
early in the oxygen blow for a campaign compared to the normal practice.
As a result there was a decrease of more than 200 heats from a normal
lining life of over 400 heats.
Another step in rapid lime solution is achieved by the combining of
fluxing materials. This step is a different approach--a chemical condition-
ing--instead of the previously mentioned physical conditioning. As pointed
out in the paper these materials form low eutectics with lime. The increased
dephosphorization by the use of red mud (iron bearing bauxite) or
fluorspar (CaF2) with lime is support of rapid lime solution by this
method.
Republic has been working in the area of prefluxing lime by additions of
iron oxide and other fluxing materials. Our work in the laboratory and
some field experience again supports a faster lime solution with these spe-
cial prefluxed limes. In this country generally dephosphorization is less a
problem than desulfurization. Desulfurization, however, should parallel de-
phosphorization, in a general trend, with increased lime solution rate.
Desulfurization trends are much harder to establish, thus are much harder
to prove unless they are quite marked and statistically supported. We are in
the midst of an evaluation as to the rate and effectiveness of desulfuriza-
tion with these prefluxed limes. In light of the dephosphorization results
reported by the authors we expect to see a parallel effect on desulfurization.
Our experience has shown reactive lime is a benefit in rapid slag forma-
tion. In general, the trend is to overcharge lime to attain low sulfurs, etc.
This practice not only wastes fluxes but the improvement in metallurgical
reactions is questionable. The prefluxed limes can attain complete lime
solution before or at least at tap, that is, no free CaO. The prefluxed lime
will not only save on flux costs in amount of CaO, CaF,,, or A120a but
will decrease slagmaking time.
A question I have is, how are these fluxes to be combined on a commer-
cial basis? It is stated in the paper that these products were calcined, re-
duced in size, blended with the other flux, and bricquetted. This could
prove to be a costly method, particularly in the United States.
Republic's experiences agree with those of the authors that increased lime
solution is best attained by combining fluxes to decrease heat time and to
increase metallurgical benefits.
(Authors' closure)--We are glad to see that Mr. Russell confirms most
of our results. In our opinion the operating conditions in Republic's vessels
are more like the lower curve in our Fig. 6, and therefore no considerable
reburning occurs. Besides the addition of fluxes is important for this effect.
We should clarify Fig. 6: The temperature profiles of the metal are not
plotted to the tap temperature. The higher blowing position in the produc-
tion of high-carbon heats is necessary for a quick slag formation by iron
oxide flux which results in the increased rate of dephosphorization. Iron
oxide flux should take lime into solution faster, but simultaneously burn-
ing iron to iron oxide increases temperatures. Now there is a competition
between reburning and dissolution of lime, further interfered by hot metal/
scrap ratio and the kind of scrap (cooling agent).
It is too early to give a definite answer on Mr. Russell's question con-
cerning the commercial basis of special lime. Anyhow, in test heats with an
oxygen input of 13 Nm3/t" rain a blowing time of about 7 rain was ob-
tained which could not be reduced due to the limited dissolution rate of the
lime. Therefore, the commercial basis for the more expensive special
lime may be balanced by reduced blowing time, higher yield because of
smooth blowing behavior and changed analysis of final slags without free
lime.
J. 1. D a v i s o n ~
Curing of Cement-Lime Mortars*
REFERENCE: Davison, J. I., " C u r i n g of Cement-Lime Mortars," The

Reaction Parameters of Lime, ASTM STP 472, American Society for Test-
ing and Materials, 1970, pp. 193-208.
ABSTRACT: Masonry mortars are assessed on the basis of tests on

specimens prepared and cured in the laboratory. Curing procedures differ
depending on the relative amounts of cement and lime in the mortar, and
the relation between the end result and that attained in the field, where no
concession is made for the composition of the mortar, is often questioned.
Laboratory and outdoor curing of a series of cement-lime mortars were
compared on the basis of compressive strength values. Outdoor curing
reflects a variety of weather conditions typical of six geographical areas of
the continent. Results indicate increasing discrepancies in values as the
amount of cement in the mortars was decreased and the lime increased.
Drying laboratory cured cubes before testing substantially reduced these
discrepancies for cement and cement-lime mortars, but values for laboratory
cured lime mortars remained well below those cured outdoors.
KEY WORDS: curing, environments, weather, laboratories, carbonation,

moisture, mortars (material), cements, calcium oxide, compressive strength,
assessments, evaluation, tests
The first recorded use of lime in masonry mortar was in the building of
the Egyptian pyramids between 4000 and 2000 B.C. 2 From that time until
the beginning of the present century lime remained the basic cementitious
material in mortar.
Soon after the introduction of portland cement during the early part of
the twentieth century, it was found that the addition of cement accelerated
the curing process and provided the high early strength now required by
* This paper is a contribution from the Division of Building Research, National

Research Council of Canada, and is presented with the approval of the director of
the division.
1Research officer, Atlantic Regional Station, Division of Building Research,
National Research Council of Canada, Halifax, N. S., Canada.
2 Boynton, R. D., Chemistry and Technology o[ Lime and Limestone, Interscience,
New York, 1966, p. 3.
193
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
the construction industry. The trend to replace lime with cement continued
until, in the early 1930's, serious moisture penetration problems were en-
countered in masonry walls in which predominantly cement mortars had
been used.
Since that time mortars containing lime and cement in varying propor-
tions have been used extensively. These mortars combine two materials,
each with desirable properties to contribute to the end product. Cement
adds strength, particularly early strength, to the slow-setting lime mortars.
Lime adds workability and good water retentivity to the harsh cement
mortars, properties essential in ensuring maximum bond with the masonry
units. Cement-lime mortars give the architect maximum versatility. He can
adjust the cement and lime contents to meet his requirements: high
strength on the one hand and the ultimate in workability and extent of
bond on the other.
For an assessment of the relative merits of the various cement-lime
mortars, the architect relies on laboratory tests described in mortar specifi-
cations, such as ASTM Specification for Mortar for Unit Masonry (C
270). Many students of masonry have observed that current laboratory
curing procedures do not reflect adequately the end result attained in
the field with mortars containing high percentages of lime. The excellent
durability of lime mortars, as evidenced by the performance of many old
buildings (for example, Independence Hall in Philadelphia) along the
northeast coast of the Continent, would not be predicted on the basis of
laboratory test results. Staley3 noted an increasing discrepancy in the ratio
of compressive strength values for cylinders, cured 6 months and 28 days,
as the percentage of lime increased in cement-lime mortars. Others have 4
noted the lack of a satisfactory method for curing cement-lime mortars and
suggested an accelerated curing in a carbon dioxide (CO,_,) atmosphere.
Interest in improving curing procedures for mortars containing lime, in
ASTM Committee C-7, resulted in a preliminary study to compare current
laboratory procedures with outdoor curing. The program, which was de-
veloped in the Research Subcommittee of Committee C-7 and coordinated
in the DBR Atlantic Regional Laboratory of the National Research Coun-
cil of Canada, compares the two methods of curing on the basis of com-
pressive strength values for 2-in. mortar cubes. There were five partic-
ipants, and they provided outdoor curing environments typical of six widely
separated locations on the North American continent.
3 Staley, H. R., "Volume Changes in Mortars and Strength Characteristics of Brick

Masonry," Proceedings, National Lime Association, Washington, D. C., 1939, pp.
37-65.
4 Private communication.
DAVISON ON CURING OF CEMENT-LIME MORTARS 195
TABLE l--Mortar proportions by volume.
Parts by Volume
Mortar Portland Hydrated Volume

Type Cement Type 1 Lime Aggregate
C ........... 1 ... 3
M ........... 3 I 12
S ............ 2 1 9
N ........... 1 1 6
O ........... 1 2 9
K ........... 1 3 12
L .............. 1 3
The Mortars
The mortars included in the study are listed in Table 1. In addition to
the five mortars listed in ASTM Specification C 270, two others, a 1:3
cement:sand, and a 1:3 lime:sand mortar are included. All participants
used cement and lime available in their respective areas. All used hydrated
lime; one participant also included a lime putty. The hydrated limes were
all dolomitic; the lime putty was high calcium. The aggregate was a combi-
nation of equal parts graded and 20:30 Ottawa sand. The mixing of the
mortars and the molding of the cubes followed procedures outlined in
ASTM Specification C 270-64 T, with the following exceptions: (1) the
weight of hydrated lime used in calculations to determine the amount to be
used was taken as 50 lb/ft 3 (a recommendation from ASTM Committee
C-7); and (2) the waiting period as stated in Section 6. Subsection 5, was
increased from 1V2 to 3 min. Thirty-six cubes were molded for each mor-
tar. As the cubes were removed from the molds they were numbered; one-
third (12 cubes) were designated for laboratory curing and the remaining
two-thirds (24 cubes) for outdoor curing. The numbering and selection of
the cubes was done according to a predetermined pattern carefully set out
in the instructions.
Curing Procedures
Laboratory
Laboratory curing was of 28 days' duration and followed the procedures
designated in ASTM Specification C 270-64 T.
Types C, M, and S--The "cement" mortars. After molding, these cubes
were kept in molds in a moist cabinet maintained at a relative humidity of
90 percent or more for 48 to 52 h. After their removal from the molds,
196 THE REACTIONPARAMETERSOF LIME
those cubes designated for laboratory curing were returned to the moist
cabinet. At the end of seven days they were immersed in clean water where
they remained for the duration of the curing period.
Types N and O - - T h e "cement-lime" mortars. After being molded these
cubes also were placed in the moist cabinet for 48 to 52 h. Upon removal
from the molds the cubes designated for laboratory curing were returned
to the moist cabinet for the duration of the curing period.
Types K and L - - T h e "lime" mortars. After being molded these cubes
were left in molds in laboratory air at a temperature of 70 • F for 48 to
52 h, and after their removal from the molds they were stored in the
laboratory air for the entire curing period.
Outdoor
All cubes designated for outdoor curing were placed on an exposure site
in wooden shelters facing toward the south immediately after their removal
from the molds. The shelters (Figs. 1 and 2) were designed in such a
way that five sides of the cubes were protected, while the sixth side was
exposed to the weather. The design also permitted free circulation of air
around the cubes. The shelters were supported on frames 18 in. above
ground level to prevent their being buried in snow. Outdoor curing periods
were three months, six months, and one year.
PLYWOOD
=•Ii; END DETAILOF

/
. ~
/ ~ /
j / ~ - - " ~
~
~ 2
__
SHELTERSON
EACHRACK
F ~~/- ~SUPPORTING RACK
"J...,,~F~"fL ~ 3/4PLYWOOD
l ~ 3 ~ X77"LG.PLYWOOD
SPR,,C,
- I_ 15/l~~25t~ SPRUCEAPPROX.36'LG.
FIG. l--Shelter and rack ]or mortar cubes.
DAVISON ON CURING OF CEMENT-tIME MORTARS 197
FIG. 2--Cubes curing on exposure site: (a) close-up of shelter and rack; (b)
general view.
Compressive Strength Tests

ASTM Specification C 270-64 T directs that compressive strength tests
be conducted on cubes in the condition in which they were cured. Thus
the cement mortars (Types C, M, and S) are tested wet, the cement-lime
mortars (Types N and O) are tested damp, and the lime mortars (Types
K and L ) are tested air dry. This procedure was questioned on the grounds
that results would not be comparable. It was noted also that the moisture
content of cubes removed from the outdoor curing site for testing would
vary with weather conditions at the end of the respective curing periods.
Therefore, it was decided to test all cubes in an oven-dry condition and to
compare the results with those for laboratory-cured cubes tested, as
directed, in their as-cured condition. Thus, half the laboratory-cured cubes
were tested in the normal manner, while the remainder and all the outdoor
cured cubes were dried upon completion of the curing period and prior to
compressive strength tests.
The procedure outlined in ASTM Test for Drying Shrinkage of Concrete
Block (C 426-66T) was selected for drying the cubes. Although this pro-
cedure applies specifically to concrete blocks, it was selected because it
was adequate for the study, and it seemed more logical to use a recognized
ASTM test rather than draw up a new one. Under its provisions, the cubes
were dried in an oven for 48 h at a temperature of 122 ---2 F and a rela-
tive humidity of 17 ---2 percent. The cubes were then cooled to room tem-
perature (70 ---5 F) and compressive strength tests carried out. The cubes
tested in the dry condition were thus two days older than the indicated
curing period, that is, laboratory-cured cubes tested dry were tested at 28
+ 2 days and compared with as-cured cubes tested at 28 days.
Variables
There were a number of major variables in the program that should be
recognized before considering the results:
1. The use of different cement and lime by each participant. This was
not considered important as the object of the study was a comparison of
curing procedures and not absolute values.
2. An unexpected variable, as a result of variable No. 1, appeared in
the form of a range in the water requirements for each mortar in the dif-
ferent laboratories. The differences can be seen in Fig. 3 where the amounts
of water required to produce a flow of 110 to 115 percent are shown. It
will be noted that results from Laboratory 6 were quite different than
those from the other laboratories. This appears to relate to the lime since
the water requirement for the cement mortar was similar to the other
laboratories, and the discrepancy widened as the percentage of lime in the
mortar was increased.
3. A third major variable was the weather conditions which governed
the outdoor curing, and reflected typical conditions in various parts of the
continent: Henderson, Nev.; Chicago, Ill.; Gibsonburg, Ohio; New Or-
leans, La.; Philadelphia, Pa.; and Halifax, Canada (Fig. 4). Records of
800 I I I I I
9 LAB I
"E 700 - o LAB 3
I-,- 9 LAB 4 /
Z Q LAB 6 /
u.I 9 LAB 7 / _
n,..
600 - o7
~400 -- o/ * --J
/
300 l l I l I l
MS N OK L
MORTAR TYPE
FIG. 3 - - l Y a t e r required to produce mortars in [tow range 110 to 115 percent.
monthly average temperature, relative humidity, and rainfall were compiled

from weather summaries published by meteorological stations nearest the
exposure sites and are plotted in Fig. 5. The data indicate that: (a) highest
relative humidity occurred at Halifax and by far the lowest at Henderson;
(b) Highest temperatures occurred at Henderson and New Orleans. In New
Orleans the high temperatures were associated with the second highest
relative humidity. Lowest temperatures were recorded at Halifax; (c)
Lowest rainfall totals were at Henderson. The most distinctive features of
the weather data are the low rainfall and humidity recorded at Henderson.
I Glfl$ONBUFG- ~PHILADELPHIA
__ HENDERSON --ANS
FIG. 4 - - L o c a t i o n s o] curing sites.
PHILADELPHIA
I
NEW ORLEANS I
CHICAGO
I
HALIFAX ,,]
GIBSONBURG ]
HENDERSON
I I I I I I
0 I0 20 50 40 50
RAINFALL, INCHES
(a)
9^/1;'ll''l'''ll~Z 90
u ~-" ./l~ HALIFAX......,~'-1
80
70
" q
~ so
~ 3o
20 ~ m~'~'HENDERSO
2o
I0 - ~ 10
I I I I I 1 I I I I I I I 1 0 It Itillll lilt
JASO.OJF.A-J J JASO.OJF.A"J
1966 I ~ssr ~sss I ~9s7
(b) (c)
9 Philadelphia --5 miles from Corson Laboratory
A New Orleans --International Airport
[] Chicago --Midway Airport, 25 miles from U.S. Gypsum
[] Halifax --Shearwater Naval Air Station, 5 miles from NRC
9 Henderson --McCarran Field, Las Vegas
O Gibsonburg --Toledo Express Airport
FIG. 5--Weather data for the six curing environments.
Results
Average values obtained by each laboratory for the different mortars
are shown in Table 2. The overall averages, listed in Table 3 and shown
graphically in Fig. 6, reveal large differences in values for the different
laboratories. Contributing to these differences are the major variables listed
above plus the inevitable variations in laboratory techniques despite the use
of uniform procedures.
TABLE 2--Compressive strength values (psi) individual laboratory averages.
Mortar Type
Curing
No. C M S N O K L Information
1,,. 6736 3 020 1 801 627 430 92 28-day labora-

2,., 6 563 . . . . . . . . . . . . . . . tory curing
3,,. 7 233 4 715 2 324 1 002 563 93
4... 6 389 4 358 4 186 2 499 1 150 299 88
5 . . . . . . 4 225 3 756 2 275 940 469 125
6... 5 883 4 220 3 244 1 458 408 448 151
7... 4 604 2 029 1 219 638 522 ...
1... 7 732 3 710 2 288 1 120 517 94 28-day labora-
2... 9 247 . . . . . . . . . . . . . . . tory curing
3.., 9 025 6 104 2 971 1 650 701 126 plus 48 h dry-
4... 7 105 5 506 5095 3 210 1 561 374 104 ing at 122 F
5 . . . . . . 5 455 4973 3 323 1 625 537 139 and 177o R H
6... 7 500+ 5217 4 454 2 052 592 464 155
7... 5000-t- 2 850 1 477 754 438 ...
1... 7 629 4 118 2 495 1 004 477 97 3 months' ex-
2.,. 7 273 4 255 2 896 1 531 958 289 posure curing
3.,. 7 653 4 724 2 998 1 498 899 257 plus 48 h dry-
4... 7 854 5 796 5 125 3036 1 375 990 276 ing at 122 F
5 . . . . . . 5 318 4 735 2 965 1 148 932 418 and 17% R H
6... 5 166 4 118 3 425 1 808 700 426 199
7... 7 215 2 461 1 801 833 694 ...
1... 8 632 4 396 2 900 1 207 637 147 6 months' ex-
2.., 7 934 4 636 3 493 1 684 1 250 400 posure curing
3... 8 247 5 224 3 467 2 009 1 324 400 plus 48 h dry-
4... 8 075 6 025 5 790 3 750 1 779 1 203 527 ing at 122 F
5 . . . . . . 5 670 5015 3 280 1 245 1 015 376 and 17~o R H
6... 5 419 4213 3 549 1 825 817 524 253
7... 7 202 2 855 1 714 1 303 1 045 ,,.
1... 9 046 4 389 2 907 1 343 698 163 12 months' ex-
2... 8 416 5 103 3 223 1 701 1 244 430 posure curing
3... 9017 6016 4016 2402 1 574 730 plus 48 h dry-
4.., 8 350 6 220 6118 3898 1890 1555 465 ing at 122 F
5 . . . . . . 5 608 5 238 3 103 1 130 1 044 354 and 17~o R H
6... 6511 4 604 3 420 2 000 801 515 223
7,.. 8 084 3 025 2 517 1 551 1 272 ,..
NoTEs--Laboratory 3 prepared two sets of cubes for curing on two different outdoor
sites; these values are listed as Nos. 2 and 3. Laboratory-cured values are listed
under No. 3.
Laboratory 4 prepared two sets of cubes, one set of mortars containing hydrated
lime (No. 4), the other set containing lime putty (No. 5).
Only Nos. 4, 5, and 6 included Type M mortar in their program. No. 7 did not
test a Type L mortar.
I,,o
o
T A B L E 3--Summary of average compressive strength values (psi).
O
Improve- Improve- Improve- Improve- Z
ment ment ment ment

Type of Mortar A B B over A, ~o C C over A, 7o D D over A, % E E over A, ~o
C 1:3 cement:sand . . . . 6 235 7 601 q- 21.9 7 132 14.4 7 585 21.6 8 237 32.1
M 1:1/3:4 C:L:S . . . . . 4268 5393 26.4 5077 18.9 5303 24.2 5477 28.3 O
r-.
S 1 : ~ : 4 1 ~ C: L:S . . . . 3 492 4 531 29.7 4 120 18.0 4 495 28.7 4 758 36.2
N I:I:6C:L:S ....... 1929 2553 32.3 2571 33.3 2918 51.2 3095 60.4
O 1:2:9 C : L : S . . . . . . . 794 1 217 53.3 l 155 45.5 1 435 80.7 1 545 94.6
K 1:3:12C:L:S ...... 455 505 11.0 768 68.8 1000 119.8 1 129 148.l
L 1:3 lime:sand . . . . . . . . 112 124 10.7 256 128.6 350 212.5 394 251.8
NOTE--A. 28-day laboratory curing.

B. 28-day laboratory curing plus 48 h drying at 122 F and 17~o RH.
C. 3 m o n t h s ' exposure curing plus 48 h drying at 122 F and 177o R H .
D. 6 months' exposure curing plus 48 h drying at 122 F and 177o R H .
E. 12 m o n t h s ' exposure curing plus 48 h drying at 122 F and 17~o RH.
DAVISON O N CURING OF CEMENT-LIME MORTARS 203
9000 I I I I I I I
9 28-DAY LAB CURING I
8OOOP t, 28-DAY LAD CURING PLUS DRYING ]
9 3 MONTHS EXPOSURECURING PLUS DRYING
7000
n
9
6 MONTHS EXPOSURE CURING PLUS DRYING
12 MONTHS EXPOSURE CURING PLUS DRYING I
6000
5ooo
4000
Z
=0 3000 \
2000
1000
0 ~
C M S N 0 K k
MORTAR TYPE
FIG. 6--Compressive strength values a]ter different curing periods.
Laboratory Curing
There were great differences between the compressive strength values
for the as cured and the dry cubes. Drying the wet cement mortars (Types
C, M, and S) resulted in increases of 21.9, 26.4, and 29.7 percent of the
as cured values. The biggest increases--32.3 and 53.3 percent--occurred
with the cement-lime mortars (Types N and O), while the effect of dry-
ing was much less for the air-cured lime mortars (Types K and L)
(Fig. 7).
Weight losses were checked in the control laboratory and results (Table
4) show that the moist cement-lime mortars contained more water than the
wet cement mortars. Increasing weight losses in mortars Types C through
O suggests an increasing capacity to hold water as the pore volume in-
creases with increasing lime content. In addition, apparently the conditions
of moist curing, at least in the control laboratory, were sufficient to main-
tain a high level of saturation in the pores of the cement-lime cubes. The
140 I I I I I I
.
ae I20 - 3-MONTH VALUES / /~
,100 -- / --
z__ zuj 3-MONTH EXPOSURE.,,, /
F 80- CURING DRY CUBES / ' -
~ 60-- 28-DAY LAB 9149

--~ ~ 40 CURINGDRY CUBES , , ~ o ~
w 2_L-- \
o 20 ~_ . . . . . . . o " 'o- ''
oJ I J a i i
C M S N 0 K L
I_CEMENT--I CEMENT-LIME I _ LIME _ l
I-- -[- r -1
MORTAR TYPE
(a)
220 I I I I I
=* 200 - .~
i IBO - 6"MONTH VALUES / -
/
,~ - / -
/ _
~_ i,m - S-MONTH EXPOSURE /
120 - C U R I N G DRY CURES "'~L oS -
LLI
i I@ --
7I
o 2R-DAY LAB /
80 - CURING DRY CUBESs ~ -
60
40
cJ
=- 20
o I I I I [
M S N U K
I _ CEMENT_ I C E M E N T - L I M E I _ LIME _ l
I-- Vl MORTAR TYPE"-I I
(b)
FIG. 7--Comparison oJ compressive strength values Jor different curing periods.
pattern of increasing weight losses on drying was broken by air curing for
the lime mortars. Figures indicate that they contained very small amounts
of moisture.
Outdoor Curing--Three Months

Increases in the values for dry cubes after three months of outdoor cur-
ing over 28-day laboratory-cured cubes tested in the as cured condition are
shown in Figs. 6 and 7. The data indicate an increasing improvement as
the amount of lime in the mortars is increased. The pattern changes if the
comparison is made against the values for cubes dried before testing after
DAVISON
ONCURING
OFCEMENT-LIM
MORTARS
E 205
220 - IZ-MONTH VALUES /

"200
~180 - ,2-MONTH EXPOSURE ,

~160- CURIN6 DRY CUBES "-"~' --
,,o - o/ -
Q. izo - /
/
z 80 ~' *DAY LAB
260~__
4020 ~~~DRY CUB~_~
0 I I I i |
M S N 0 K
I-- CEMENT _1 CEMENT-LIME i_ LIME _
I- - I~MORTAR TYPE--I -
(c)
FIG. 7--(continued).
28 days' laboratory curing. In this case the values for the three-month
cubes are below the 28-day cubes for mortar Types C to O, with the ex-
ception of Type N, where they are about equal. There is a sharp increase
in values for the lime mortars (Types K and L) over the 28-day dry values.
Thus the results suggest that laboratory curing is superior to three
months of exposure curing for cement and cement-lime mortars, but that
it is inferior for lime mortars.
T A B L E 4 - - Weight losses in mortar cubes ( ~o dry weight) after drying

for 48 h at 122 -4- 2 F and 17 -4- 2~o R H determined in control
laboratory.
Laboratory O u t d o o r Curing
Mortar Curing,
Type 28 Days 3 Months 6 Months 1 Year
C ............ 2.8 2.1 1.8 0.!

M ............ 4.7 1.9 1.5 2.0
S ............. 5.2 1.6 1.9 0.9
N ............ 7.4 2.9 2.7 1.1
O ............ 10.6 0.8 6.9 1.1
K ............ 0.5 1.7 1.3 1.0
L ............ 0.2 0.2 0.6 0.6
Outdoor Curing--Six Months

Increases in the values for mortars after six months of outdoor curing
over values for as cured mortars at 28 days are shown also in Figs. 6 and
7. There is a continuing and growing improvement over the original values
as the percentage of lime in the mortars increases, as was noted in values
for the three-month cubes. The increases range from 22 percent for Type
C (cement) mortar to 212 percent for Type L (lime) mortar. When the
comparison is made against values for dry cubes at 28 days, the values for
cement mortars are about equal, but outdoor curing resulted in an 18 to 35
percent improvement for the cement-lime mortars and 110 to 200 percent
for the lime mortars.
Outdoor Curing--Twelve Months
The trends noted above continue as the values of mortars cured outdoors
for twelve months are compared with mortars cured in the laboratory and
tested in the as cured condition (Figs. 6 and 7). There are increasing im-
provements as the amount of lime in the mortars is increased. If the com-
parison is made with the values for dry cubes at 28 days, all the mortars
have improved beyond their original values. The cement mortars show an
increase of 2 to 10 percent, the cement-lime mortars have increased 28 to
41 percent, and the lime mortars 137 to 141 percent.
Results for the twelve-month outdoor-cured mortars indicate a reduc-
tion in the curing rate for cement-lime and lime mortars in the six to
twelve-month period as compared with the rate during the three to six-
month period. This was not as evident for the cement mortars (except
Type M where there were only three values). It should be noted that the
six-month to one-year period included the winter months, and the slow-
down in the curing rate during this period may reflect, in part, the adverse
effect of winter weather conditions on the curing of the lime portion of the
mortar.
Discussion
It is important to be realistic when considering the extent to which
laboratory curing of masonry mortars should reflect the end result achieved
in the field. Certainly laboratory curing of lime mortars cannot be expected
to approach the condition of the mortar in buildings like Independence
Hall. Lime cures very slowly by reacting with the CO,, in the air, and its
ultimate strength is not attained for many years. But the architect must
specify a mortar that will acquire the strength required when the building
is ready to assume its full load. In discussing this aspect, Voss ~ suggests
Voss, W. C., "Exterior Masonry Construction," Bulletin 324, National Lime
Association, Washington, D. C., p. 41.
that "occupancy involving the full loads of design is usually delayed by at

least six months from the time of laying." It was probably on this basis
that Staley compared compressive strength values for mortars cured six
months with those cured 28 days. A comparison of his results with those
obtained in the present study is as follows:
6 Month/28 Day Ratio

Staley ASTM Committee C-7
Laboratory Cubes Laboratory Cubes
Mortar Mortar As Cured Dried
1:0:2.5 C:L:S...1.76 1:C:3 C:L:S ..... 1.22 0.99

1:1:5 C:L:S 1.82
. . . . . 1:1:6 C:L:S ..... 1.51 1.14
1:2:7.5 C:L:S...2.42 1:2:9 C:L:S ..... 1.81 1.18
1:3:12 C:L:S .... 2.20 1.98
The same pattern of increasing discrepanices, in the six-month/28-day

ratio, as the lime content of the mortars is increased, occurs in results of
this study as observed by Staley, although the differences are not as great.
Most significant, however, are the figures in the column comparing the six-
month values with those for dry cubes at 28 days: the 28-day laboratory
results equal those for the six-month cement mortar, but the increases in
the 1:1:6 and 1:2:9 cement-lime mortars have been reduced sharply. The
big increases remain with the lime mortars where, as noted previously,
drying has no appreciable effect.
The weight loss data in Table 4 indicate that cement and cement-lime
mortars cured on outdoor exposure had much lower moisture contents
than those cured in the laboratory, while lime mortars were slightly higher.
It is noted also that moisture contents generally became smaller as the
curing period was lengthened. A notable exception to this is the value 6.9
percent for Type O mortar after six months' outdoor curing. It was raining
on the day these cubes were removed from the exposure site, and had the
cubes been tested in their as cured condition the resulting value would not
have been representative. Drying the cubes eliminated the possibility of in-
consistencies of this type. Weight loss data, as previously noted, indicate
that cement-lime mortars remain near saturation during moist cabinet cur-
ing. The result of curing at lower relative humidities that would allow some
air to enter the pore spaces and facilitate a more extensive carbonation of
the lime might be studied.
Conclusions
Compressive strength values for mortars cured outdoors show increasing
discrepancies, when compared with values for mortars cured and tested by
conventional laboratory methods, as the percentage of cement in the mortar
is decreased and the percentage of lime is increased.
These discrepancies are reduced greatly if laboratory-cured cement and
cement-lime mortar cubes are dried before testing.
Big differences remain between values for outdoor- and laboratory-cured
lime mortars even when they are compared on the basis of values for cubes
that have been dried before testing.
G. H. M c C l e l l a n 1 a n d J. L . E a d e s ~
The Textural Evolution of Limestone Calcines*
REFERENCE: McClellan, G. H. and Eades, J. L,, " T h e T e x t u r a l Evolu-

t i o n of L i m e s t o n e Calcines,"The Reaction Parameters of Lime, ASTM
STP 472, American Society for Testing and Materials, 1970, pp. 209-227.
ABSTRACT: A pure limestone and Iceland spar were shock calcined at
several constant temperatures in the range 750 to 1300 C in a study of the
pore structure of the calcines. The calcines were examined with a scanning
electron microscope to follow the development of the pore structure and to
correlate changes in the pores and in the related surface area with the
properties of the lime and the temperature of calcination.
Limestone calcines prepared at temperatures below 1000 C had larger
pores and lower surface areas than Iceland spar calcines prepared at the
same temperature. Raising the temperature of calcination caused a decrease
in surface area and an increase in pore size of both materials. The decrease
in surface area on calcination at 1000 C resulted from the growth of large
pores at the expense of smaller pores, but the physical characteristics of
the lime were largely unchanged. A t temperatures above 1000 C the calcium
oxide crystals sintered and grew in size as the pore size continued to increase
and the surface area decreased.
The larger initial crystallite size of the Iceland spar resulted in an
unfavorable pore size distribution in its calcined products prepared below
1000 C. The limestone calcines prepared at the same temperatures had
larger pores and smaller surface areas. Literature reports confirm that there
is an optimum temperature of calcination for each stone for producing the
proper surface area, pore distribution, and lime condition for maximum
solid-fluid reactivity.
KEY WORDS: calcite, limestone, roasting, calcium carbonate, calcium
oxide, electric power plants, flue gases, sulfur dioxide, air pollution, injec-
tion, scanning electron microscope, density (mass/volume), porosity, poroism-
eters, evaluation, tests
The injection of dry limestone into power plant furnaces is the most
economical means of decreasing sulfur dioxide concentrations in the
effluent stack gas. The calcium oxide produced from the stone reacts with
* Part of this work was performed under contract T V - 2 9 2 3 2 A with the National
Air Pollution Control Administration of the U.S. Public Health Service.
1 Research chemist, Division of Chemical Development, Tennessee Valley Authority,
Muscle Shoals, Ala. 35660.
2 Research assistant professor, Department of Geology, University of Illinois,
Urbana, Ill. 61801. Personal member ASTM.
209
Copyright
Copyright by9ASTM
1970Int'l
by (all
1 12:04:31 EDT 2012
sulfur dioxide and oxygen to form calcium sulfate that can be removed by
conventional dust-collecting systems. The results reported here are a part
of a continuing laboratory study of the properties of calcines prepared by
shock heating (calcinations carried out in an environment preheated to a
selected temperature in contrast to calcining at rising temperatures). The
materials examined were portions of the samples used by McClellan et al ~
in reactivity tests, and the physical properties of the calcines were corre-
lated with their reactivities. The previous results showed that the nature of
the original stone influences the properties of its calcines, including their
reactivity with sulfur dioxide.
Limestones and their calcines have been evaluated for industrial use
largely on the basis of their chemical purity. Advances in industrial tech-
nology [1] 4 have shown, however, that physical properties such as surface
area, porosity, pore size distribution, and crystallite size are important fac-
tors in determining the rate and degree of the chemical reactions of the
calcines.
In this study, two high-calcium limestones were shock calcined at tem-
peratures between 750 and 1300 C. These two materials differ only in
texture, so that the effects of composition can be ignored. The calcines of
these stones were studied by scanning electron microscopy and by mercury
porosimetry, and the results were used to interpret the changes in texture
with rising temperature of calcination.
The two limestones were a high-purity calcitic limestone (USDA Refer-
ence Sample 89) and Iceland spar (Ward's Scientific Company) in the
form of clear crystals. Both stones were crushed and screened to produce
a minus 20- plus 24-mesh fraction from which samples were hand picked
to minimize the content of accessory minerals.
X-ray and petrographic examinations showed the samples to be free of
accessory minerals. Their cell constants showed that both materials were
pure calcites as defined by Goldsmith and Graf [2] and were without
significant isomorphism.
A 3-g sample of each calcite was calcined in a platinum boat for 16 h
at constant temperatures in the range 750 to 1300 C. The samples were
placed abruptly in a preheated furnace to effect initial shock calcination;
the long retention time was sufficient for complete calcination at each
temperature.
a See p. 32.
4The italic numbers in brackets refer to the list of references appended to this
paper.
McCLELLAN AND EADES ON LIMESTONE CALCINES 211
Several particles of each calcine were stored under vacuum until they
were examined in the scanning electron microscope. Immediately prior to
the examination, each sample was coated in a vacuum evaporator with a
2:1 mixture of gold and palladium that was deposited from several direc-
tions to minimize charging of the rough, porous surfaces of the calcines
during examination.
The pore volumes and pore size distributions were measured with a mer-
cury porosimeter that had an upper pressure limit of 5,000 psia which
limited penetration to pores 0.035 /zm in diameter or larger. Apparent
densities of the calcines were calculated from weights of the porosimeter
penetrometer containing the sample and mercury. Densities calculated from
measurements with only the pores larger than 17.5/zm in diameter filled
with mercury are comparable to bulk densities determined by mercury
displacement.
Results
Raising the temperature os calcination decreased the total pore volume
and shifted the distribution toward larger pores in all calcines of sample 89
except that made at 1100 C (Fig. 1). This calcine showed a higher pore
volume and a more even distribution of pores in the range 17.5 to 0.175
/xm than the 1000 C calcine. Each Iceland spar calcine (Fig. 2) had less
than half the total pore volume of the corresponding limestone calcine,
and almost all the pores in the 750 and 850 C spar calcines were smaller
0.6
r
950
r
0.4
~E
--I
o
0.2
/,~" NUMBERS ON CURVES DENOTE
0~
I00 50 20 I0 5 2 I 0.5 0.2 0.I 0.05
FIG. l - - P o r e volumes o/ 16-h limestone calcines.
I I I I I I I L I t
NUMBERS ON CURVES DENOTE / ,

0.3 TEMPERATURE, DEG C, OF CALCINATION rso~.~
=E
(..)
//
0
hi
.0.2
=E
:3
-J
O
>
hi
(~ O. 1
a.
1300
0 ~1 I I t I ~ I I I I
I00 50 20 IO 5 2 I 0.5 0,2 0.1 0.05
FIG. 2--Pore volumes o[ 16-h Iceland spar calcines.
than 0.2/zm. The total pore volume of the spar calcines decreased, and the
pore distribution shifted toward larger pores with rising calcination tem-
perature except for the 1200 C calcine. The total pore volume of this cal-
cine was larger than that of the 1100 C spar calcine and may have re-
suited from the mechanism that caused the larger pore volume in the
1100 C calcine of sample 89.
Murray et al [3] showed that the reactivity of a lime is related directly
to its surface area. Rootare and Prenzlow [4] derived a method for cal-
culating surface areas from mercury porosimeter measurements that gives
results in good agreement with those of gas-absorption measurements, and
surface areas calculated by this technique may be more applicable to solid-
fluid reactivities than those measured by some other techniques. This con-
clusion is based on the assumption that diffusion times for fluids in pores
smaller than 0.30/zm are longer than the contact times used in measuring
reactivity [5]. The surface areas calculated from the porosimeter data are
shown in Table 1.
The surface areas and pore sizes of the calcines determined from mer-
cury porosimetry data and from measurements of the scanning electron
micrographs are shown in Table 2. The individual surface areas and equiv-
alent mean spherical pore diameters were calculated by the method de-
scribed by Mayer and Stowe [1]. Surface areas and mean pore diameters
were calculated only for calcines prepared at 1100 C or below because the
number of pores decreases rapidly at the higher temperatures as sintering

becomes pronounced.
There is good agreement between the surface areas calculated from the
porosimeter and from the electron microscopic data. The distribution of the
surface area within a sample also is important. The data in Table 1 show
that most of the surface area of samples calcined below 1000 C is asso-
ciated with small pores, those smaller than 0.2/zm. If Potter's data [5] on
the sulfur dioxide capacity of limestones are correct, diffusion into pores
this small and smaller is too slow to be effective in short-time reactivity
tests. The formation of films of calcium sulfate on the surface could block
areas containing many of these pores, further decreasing their availability
for reaction. The pores provide the fluids access to the surface area of the
solids, and materials with mean pore diameters larger than 0.2 /~m are
more responsive in short-term reactivity tests because of the shorter times
required for diffusion of sulfur dioxide into these larger pores. As shown in
Table 2, calcines of sample 89 had mean pore diameters larger than those
of Iceland spar calcines prepared at the same temperature, and the pore
diameters of both materials increased with rising temperature of calcination.
Raising the temperature of calcination changes the nature of the solid
lime as well as its pore size distribution. McClellan et aV showed that the
crystallite size of the limes of both materials slowly increases with rising
temperature of calcination below 950 C and decreases slightly at 1000 C.
At temperatures above 1000 C, the rate of crystallite growth increases with
rising temperature. These changes in the physical properties of the lime
decrease the potential reactivity of the lime surface as crystal perfection
increases and crystal growth influences the texture of the surface itself.
Scanning electron microscopy has previously been used to study the sur-
face of limes prepared in commercial kilns. '~ The work reported here is the
first laboratory study of shock-trea'~ed limestone calcines prepared under
laboratory control at several different temperatures.
The main advantage of scanning electron microscopy over optical and
transmission electron microscopy is its greater depth of focus, which is as
much as 100 times that of the other techniques. This advantage, combined
with the simple sample preparation, allows the investigator to examine the
unaltered surface of materials and to obtain information that was pre-
viously unavailable, or only to be guessed at, on surface texture and pore
size, shape, and distribution. In the study of limes, scanning electron
microscopy presents clear evidence on surface areas and the properties of
pores.
See p. 3.
T A B L E 1--Surface areas o f calcines calculated from porosimeter measurements.
Surface Area a Surface A r e a a Surface A r e a a
Po re Size, ~m M~/g 70 o f T o t a l M~/g 7o of T o t a l M~ / g 7oofTotal
LIMESTONE 89
750 C calcine 850 C calcine 950 C calcine
17.5 . . . . . . . . . . . 0.12 0.3 0.08 0.04 0.07 1.5

5.0 . . . . . . . . . . . 0.17 0.5 0.12 0.6 0.11 2.4
1.75 . . . . . . . . . . 0.22 0.6 0.16 0.8 0.19 4.0
1.0 . . . . . . . . . . . 0.36 1.0 0.26 1.3 0.28 5.9
0.5 . . . . . . . . . . . 0.54 1.5 0.43 2.1 1.15 24.5
0.4 . . . . . . . . . . . 0.71 2.0 0.84 4.1 1.87 39.8
0.2 . . . . . . . . . . . 3.72 10.3 8.62 42.4 3.76 80.0
0.1 . . . . . . . . . . . 26.26 72.9 20.17 99.3 4.70 100.0
0.05 . . . . . . . . . . 35.68 99.0 20.31 100.0 4.70 100.0
0.035 . . . . . . . . . 36.03 100.0 20.31 100.0 4.70 1000.
17.5 . . . . . . . . . . . 0.04 0.6 0.06 5.2 0.03 5.9

5.0 . . . . . . . . . . . 0.08 1.I 0.09 7.3 0.05 9.7
1.75 . . . . . . . . . . 0.15 2.2 0.17 13.7 0.09 16.1
1.0 . . . . . . . . . . . 0.32 4.7 0.37 29.2 0.31 57.6
0.5 . . . . . . . . . . . 0.67 9.9 0.82 65.4 0.50 92.3
0.4 . . . . . . . . . . . 0.96 14.1 0.92 73.2 0.54 100.0
0.2 . . . . . . . . . . . 4.88 71.8 1.06 84.5 0.54 100.0
0.1 . . . . . . . . . . . 6.79 100.0 1.12 89.6 0.54 100.0
0.05 . . . . . . . . . . 6.79 100.0 1.25 100.0 0.54 100.0
0.035 . . . . . . . . . 6.79 100.0 1.25 100.0 0.54 100.0
ICELAND SPAR
17.5 . . . . . . . . . . . 0.01 0.0 0.01 0.0 0.01 0.1

5.0 . . . . . . . . . . . 0.03 0.0 0.01 0.0 0.01 0.1
1.75 . . . . . . . . . . 0.09 0.1 0.04 0.1 0.02 0.3
1.0 . . . . . . . . . . . 0.19 0.3 0.06 0.2 0.05 0.7
0.5 . . . . . . . . . . . 0.25 0.4 0.06 0.2 0.05 0.7
0.4 . . . . . . . . . . . 0.28 0.4 0.06 0.2 0.05 0.7
0.2 . . . . . . . . . . . 0.38 0.6 0.06 0.2 0.08 1.2
0.1 . . . . . . . . . . . 0.38 0.6 4.26 13.2 1.02 14.5
0.05 . . . . . . . . . . 47.38 75.3 29.86 92.7 5.95 84.3
0.035 . . . . . . . . . 62.93 100.0 32.20 100.0 7.06 100.0
TABLE 1 (conthtued).
Surface Area a Surface Area a Surface Area a
Pore Size, u m M~/g ~o o f Total M~/g ~ o f Total M2/g ~oofTotal
17.5 . . . . . . . . . . . 0.00 0.0 0.00 0.1 0.00 2.0

5.0 . . . . . . . . . . . 0.01 0.7 0.01 0.4 0.01 5.0
1.75 . . . . . . . . . . 0.01 0.7 0.01 0.6 0.02 11.6
1.0 . . . . . . . . . . . 0.03 2.5 0.02 1.0 0.03 15.6
0.5 . . . . . . . . . . . 0.04 3.4 0.02 1.0 0.06 29.1
0.4 . . . . . . . . . . . 0.05 5.0 0.04 1.9 0.10 50.8
0.2 . . . . . . . . . . . 0.08 7.6 1.14 56.6 0.20 100.0
0.1 . . . . . . . . . . . 0.40 37.9 1.89 93.8 0.20 100.0
0.05 . . . . . . . . . . 0.69 65.2 2.02 100.0 0.20 100.0
0.035 . . . . . . . . . 1.06 100.0 2.02 100.0 0.20 100.0
Area contributed by pores o f indicated and all larger sizes.
T A B L E 2--Correlation of porosimeter and scanning electron microscope measurements.
Porosimeter Scanning Electron Microsocpe
Calcination Surface Pore Surface Pore No. o f

Temperature, deg C Area, M2/g Size, um ~ Area, M2/g Size, um Pores b
LIMESTONE 89
750 . . . . . . . . . . 36.0 0.05 27.4 0.06 482

850 . . . . . . . . . . 20.3 0.09 14.6 0.12 514
950 . . . . . . . . . . 4.7 0.37 4.2 0.42 471
1 000 . . . . . . . . . . 6.8 0.26 6.7 0.26 502
1 100 . . . . . . . . . . 1.2 1.44 1.4 1.27 188
ICELAND SPAR
750 . . . . . . . . . . 62.9 0.03 66.5 0.03 477

850 . . . . . . . . . . 32.2 0.05 46.4 0.04 470
950 . . . . . . . . . . . . . . . . 46.0 0.04 348
1 000 . . . . . . . . . . 7.0 0.25 10.8 0.16 368
1 100 . . . . . . . . . . 1.1 1.58 0.9 1.92 75
Calculated from the relation A = 6/Dp, where A = surface area, M2/g; D = mean
diameter, ~m, of pores assumed to be spherical; p = absolute density, g / c m 3.
b N u m b e r of pores measured for calculation of pore size.
In calcines prepared at temperatures below 1000 C, the most diagnostic

features are the pores and their growth by coalescing. A representative
area of the 750 C limestone (sample 89) calcine is shown in Fig. 3 in
which the evolving pore structure of the lime is superimposed on a residual
rhombohedral cleavage fragment of the stone. There is a wide range of
pore sizes, even in this soft-burned stone. The solid lime is generally fea-
tureless, and no significant points of contact have developed between the
individual lime units within each particle. Electron micrographs of 750 C
Iceland spar calcine show essentially the same evolution of pores, but the
pores are smaller and there are more per unit area.
The 850 C calcines (Fig. 4) show continuing coalescing of the pores,
although residual rhombohedral features of the original stone persist. This
figure shows that the larger pores grow at the expense of the smaller ones,
as observed in the porosimeter data. There is no evidence of individual
calcium oxide units within the larger particles.
The 950 C calcines (Fig. 5) show additional coalescing of pores super-
imposed on detectable cleavage features of the original stone. The pores
FIG. 3--Limestone calcined at 750 C showing pore evolution superimposed on

cleavage /ragments (X6300).
FIG. 4---Limestone calcined at 850 C showing coalescing o[ pores (•
seem to be oriented randomly, and there was no detectable crystallographic

control of pore evolution in any of the calcines studied. Discrete subunits
of calcium oxide, which appear for the first time in calcines prepared at
950 C, can be seen throughout Fig. 5.
The 1000 C calcines show final pore growth by coalescing, and the cal-
cine of sample 89 (Fig. 6) is representative of this stage. Pores 0.5/zm or
larger are abundant, and the subunits of lime appear relatively unchanged
from those in the 950 C calcines. The open textural appearance and an
essentially unchanged lime appear to indicate optimum surface availability
for solid-fluid reaction.
The Iceland spar 1000 C calcine (Fig. 7) shows only a few pores as
large as 0.05/xm, and most of the pores are much smaller. The distinguish-
able lime subunits seem smaller (about 0.1 /,~m) than the lime in the
limestone calcine (about 0.5 /zm) and seem to have proportionally larger
points of contact.
Calcines prepared at 1100 C or above show sintering and shrinking of
the oxide that is not seen in the lower-temperature calcines. The limestone
calcine, shown in Fig. 8, has a more compact texture with extensive con-
tacts developed between the lime units, and a pronounced decrease in
porosity over that shown in Fig. 6. Growth loops or spirals are present on
the individual lime units in the right half of the figure, indicating that
crystal growth and development of single-crystal morphology has begun,
even though residual rock cleavage features are still present.
FIG. 5---Limestone calcined at 950 C showing continuing coalescence o[ pores

and the development o[ individual lime units (X 2665).
The 1100 C Iceland spar calcine in Fig. 9 also shows the increased com-
pactness of the lime and the resultant decrease in porosity. Although
growth spirals are not well developed, many of the lime units are develop-
ing flat faces and straight edges between crystal faces. The pores in the
1100 C calcines of both materials are beginning to show straight sides as
crystal growth begins.
FIG. 6---Limestone calcined at 1000 C showing completion o] pore growth by

coalescence (•
FIG. 7--Iceland spar calcined at 1000 C showing the pores and individual lime
traits (•
As shown in Fig. 10, the 1200 C limestone calcine is quite compact,

and the porosity is confined to a few large pores. The figure contains a
good example of a residual cleavage fragment on which typical features of
the calcine are clearly apparent. Epitaxial growth of a potential crystal face
is noticeable on six or seven oxide units, and the few remaining pores are
large and contribute little to the surface area of the lime. The 1200 C Ice-
land spar calcine in Fig. 11 also shows well-developed and developing
crystal faces and has the compact, nearly pore-free appearance of extended
points of contact.
The 1300 C Iceland spar calcine (Fig. 12) has a very compact and
practically pore-free surface texture with abundant growth loops. A very
well-developed oxide crystal appears at the right of the figure. This photo-
graph shows why the calculated surface area of this sample is only 0.2
m2/g and why the surface would be considered unreactive in a solid-fluid
system.
FIG. 8--Limestone calcined at 1100 C showing sintering texture and growth

spiral (X 1350).
The application of scanning electron microscopy to the study of lime-
stone calcines demonstrates the meaning of pore volume, pore distribution,
and surface area more clearly than other techniques. The evolution of both
solids and pores as the temperature of calcination is raised can be observed
directly rather than imagined by conceptual models as required in the past.
These studies illustrate the access that pores provide reactant gases to the
surface area of the calcines.
The calculation of surface areas from porosimeter measurements pro-
vides an insight into the physical characteristics of the calcines that is not
provided by inspection of the pore-volume data alone. The calculated areas
were essentially the surface areas generated by the pores observed in the
scanning electron microscope studies. The surface area calculated for the
750 C Iceland spar calcine should be considered a low approximation
because the data were calculated only for pores approximately 0.035 ~m
222 THE REACTION PARAMETERS OF tIME
FIG. 9--Iceland spar calcined at I100 C showing developing crystal [aces and
geometric pores ()<9720).
or larger. Because of this restriction there was no plateau in porosimeter

pore volume as in the other calcines, indicating that this calcine had pores
smaller than 0.035/~m and would have a surface area larger than 63 m2/g.
Potter [5] concluded from his studies of calcines sulfated in fixed-bed
tests that pores in the range 17.5 to 0.3/~m are most important in the sulfa-
tion reaction and that smaller pores require diffusion times too long to be
effective when dry limestone is injected into a power plant furnace. The
porosimeter data show that 4 m'-'/g of the 36 m'-'/g of the surface area of
the 750 C calcine and 9 m2/g of the 20 m2/g of the surface area of the
850 C calcine of sample 89 are accounted for by pores in the effective
range, and that rising temperature increases the fraction of pores in this
size range. In contrast, the Iceland spar calcines have only 0.1 m-~ of the
1.1 m2/g surface area contributed by pores in this size range at 1100 C
and 1.1 m2/g of the 2.0 m~/g surface area at 1200 C. This study has
shown that both the porosity and the physical condition of the lime in the
calcines prepared at temperatures up to 1000 C were influenced strongly
by the nature of the starting materials. The Iceland spar calcines had
FIG. 10 Limestone calcined at 1200 C showing epitaxial growth o[ crystal faces

on cleavage .fragment ( X 2183).
smaller mean pore diameters and larger surface areas than the correspond-
ing calcines of sample 89. Calcination at higher temperatures decreases
the porosity and sinters the oxide of both materials so that the reactivity is
decreased.
The Iceland spar calcines have a distribution of pores that is unfavorable
for sulfation reactions, and sintering has occurred at temperatures at which
suitable pores begin to develop, with a resultant decrease of surface area
and potential reactivity.
This interpretation is consistent with the observations of McClellan
et al 3 on the relative reactivities of limestone and Iceland spar calcines
with sulfur dioxide in fixed-bed tests. They found that the limestone cal-
cines were superior reactants under all the experimental conditions tested
and concluded that unfavorable pore distribution and poor properties of
the lime accounted for the relative inactivity of the Iceland spar calcines.
Eades and Sandburg5 drew similar conclusions from a series of limes on
which they measured hydration reactivity. Their data showed that a de-
veloped pore structure of the limes was necessary for satisfactory hydra-
FIG. l l - - I c e l a n d spar calcined at 1200 C showing well-developed crystal growth

(X9315).
tion of the surface, and that softer burned stones without suitable pore
structure but with larger surface areas were less reactive.
Murray et al [3] have shown that the time required for a coarsely crystal-
line limestone to reach 920 C during its calcination has a significant effect
on the porosity and activity of the lime produced. If the time is too short,
the porosity and activity are quite low. If the time is too long, porosity
develops satisfactorily, but the activity decreases slowly with prolonged
exposure. Fischer [6] found similar results for the densities of a stone he
shock calcined at different temperatures. McClellan et aP measured bulk
densities of shock-heated limestone and Iceland spar calcines prepared in
the temperature range studied by Fischer. The bulk densities of sample 89
shock-heated calcines were consistently lower than those of the correspond-
ing Iceland spar calcines. The nature of the starting material again appears
to influence the physical properties of the calcine, even though the rate of
heating prior to and during calcination, as well as the maximum tempera-
tures, were the same within experimental error for corresponding samples
of both materials.
The differences in physical properties of equivalent calcines of Iceland

spar and limestone 89 may reflect differences in the difficulty of removing
carbon dioxide from the calcite structure of the materials [7]. The crystal-
lite size of the Iceland spar measured by X-ray line broadening was 0.71
/zm, whereas the crystallite size of sample 89 was 0.39 /zm. This is the
only difference in physical properties measured on the starting materials.
FIG. 12--Iceland spar calcined at 1300 C showing a sintered surface with growth
loops and a well-developed single crystal (arrow) (X4042).
Perhaps the larger crystallite size of the Iceland spar inhibits the migration
of carbon dioxide from the crystal structure.
The results of this study show that the texture of limestone calcines
evolves in two distinct steps. Pores form initially as carbon dioxide is re-
leased during calcination. Raising the calcination temperature causes the
pores to grow by coalescing (that is, big pores grow at the expense of small
pores). This textural feature predominates in materials calcined below
1 ! 00 C. At about 1100 C, the change in the physical characteristics of the
calcium oxide predominates as the limes become compact as a result of
sintering and crystal growth of the calcium oxide. These changes are
accompanied by a marked decrease in porosity as the calcination tempera-
ture is raised. Both stages of textural development may be present in a
single particle if the external surface and edges are calcined before the
center, as reported in the literature [6,7].
Summary and Conclusions

Results of scanning electron microscope and mercury porosimeter studies
of the calcines confirm several general observations, among which is the
fact that the nature of the uncalcined carbonates influences the properties
of their calcines. The larger crystallite size of the Iceland spar confers
undesirable physical characteristics on its calcines.
Raising the temperature of calcination causes a systematic evolution of
texture in the calcines that is characterized by stages dominated by pore
growth and later by sintering and calcium oxide crystal growth. The rate
and nature of these changes also are influenced by the characteristics of
the starting material. The undesirable pore size distribution of the Iceland
spar calcines indicated that its properties were similar to those of some
shock-calcined, coarsely crystalline materials that are described in the
literature. Properties of calcines prepared from limestone 89 compare
favorably with those of some of the reactive limes described [6] "~.
It can be inferred from these results that solid-fluid reactivity is corre-
lated with pore distribution and surface area. :*,~ The pores provide the
reactant fluid with access to the surface area. If diffusion of the gas in small
pores is slow [5], then each stone has some optimum time and temperature
of calcination for development of a favorable pore size distribution and
surface area that results in a reactive lime.
Acknowledgment
R. C. Mullins contributed to this paper through discussions of the pore
sizes and pore volumes, all of which were measured under his supervision.
McCLELLAN AND LADES ON LIMESTONE CALCINES 227
References
Lime," Azbe Award No. 4, National Lime Association, Washington, D. C., 1964.
[2] Goldsmith, J. R. and Graf, D. I., "Relation Between Lattice Constants and
Composition of the Ca-Mg Carbonates," American Mineralogist, Vol. 43, 1958,
pp. 84-101.
[3] Murray, J. A., Fischer, H. C., and Sabean, D. W., "The Effect of Time and
Temperature on the Properties of Quicklime Prepared from Calcite," Proceedings,
American Society for Testing and Materials, Vol. 50, 1950, pp. 1263-1277.
[4] Rootare, H. M. and Prentzlow, C. F., "Surface Areas from Mercury Porosimeter
Measurements," Journal of Physical Chemistry, Vol. 71, No. 8, 1967, pp 2733-
2736.
[5] Potter, A. E., "Sulfur Oxide Capacity of Limestones," U. S. Public Health
Service Symposium on Limestone-Sul[ur Dioxide Reaction Kinetics and Mecha-
nisms, National Air Pollution Control Authority, Cincinnati, Ohio, 1969 (abstract).
[6] Fischer, H. C., "Calcination of Calcite: I. Effect of Heating Rate and Temperature
on Bulk Density of Calcium Oxide," Journal of the American Ceramic Society,
Vol. 38, 1955, pp. 245-251.
[7] Hyatt, E. P., Cutler, I. B., and Wadsworth, M. E., "Calcium Carbonate Decompo-
sition in Carbon Dioxide Atmosphere," Journal of the American Ceramic Society,
Vol. 41, 1958, pp. 70-74.

The Reactions Parameters of Lime PDF

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

The Reactions Parameters of Lime PDF

Caricato da

Copyright:

Formati disponibili

Copyright by ASTM Int'l (all rights reserved); Wed Aug 1 12:04:31 EDT 2012

ASTM SPECIAL TECHNICAL PUBLICATION 472

List price $15.25

AMERICAN SOCIETY FOR TESTING AND MATERIALS

Printed in Lutherville-Timonium, Md.

Very early in man's development of permanent structures lime was em-

Characterization of the Properties of

REFERENCE: Eades, I. L. and Sandberg, P. A., "Characterization o f

ABSTRACT: Reactivity of lime (CaO, CaO-MgO) is a function of surface

KEY W O R D S : roasting, calcium oxides, porosity, time dependence, tem-

Research assistant professor and associate professor, respectively, Department of

"~T h e italic n u m b e r s in b r a c k e t s refer to the list o f r e f e r e n c e s a p p e n d e d to this

standard, but conceptually abstract notation of total surface area as M~/g

Materials and Methods of Calcination

Because of the greater uniformity and degree of control of temperature

SEM Observations Correlated with Surface Area

FIG. 2--Detail view o[ micritic pellet in center oJ Fig. 1 (X5165).

lites of CaO develop as pseudocarbonate "open" structure (produced by

FIG. 5--Outer margin o] same partially burned specimen (X1836).

FIG. 6--Normal burned vertical kiln lime, Sample 400A (X4590).

FIG. 8----Normal rotary kiln lime, Sample 400R (>(4590).

worm-like crystallites and elaborate tunneled voids in comparably treated

FIG. 9--Normal rotary kiln lime, Sample 500A (•

FIG. lO--Hard burned rotary kiln lime, Sample 500B (•

TABLE 1--Reactivity and surface areas.

Figure Sample Sample ~ Reactivity, b Surface

1......... 400 stone . . . . . .

FIG. ll--Metamorphosed limestone, Sample 700 (X 1400).

FIG. 12--Normal burned rotary kiln lime, Sample 700A (X2592).

FIG. 13--Fluid solids calcined marble, Sample 800A (>(6800).

FIG. 14--Fluid solids calcined marble, Sample 800B (•

FIG. 15--Vertical kiln calcined dolomitic lime, Sample 600A (>(5865).

FIG. 16--Calcimatic calcined dolomitic lime, Sample 600B (X6162).

FIG, 17--Dolomite calcined at 1000 C in laboratory furnace, Sample 900 (>(22,525),

Discussion and Conclusions

[10] Eades, J. L. and Sandberg, P. A., "Scanning Electron Microscope Study of

G. H. McClellan 1 (written discussion)--The most important contribution

1 Fundamental Research Branch, Division of Chemical Development, Tennessee

Phase Equilibria and Thermodynamic

REFERENCE: Timucin, M. and Morris, A. E., "Phase Equilibria and

ABSTRACT: This paper is a brief presentation of research work on the

KEY WORDS: fluxes, slags, steelmaking, evaluation, tests, calcium

In order to provide a basis for understanding the fluxing behavior of

Formerly, graduate student, Department of Metallurgical and Nuclear Engineer-

--'o/, 'o~ o.I o.~ o.~ o.~ o.#

1450 *C LIME SATURATION

s;o~0.6 / / / / / ~,,,Z.,.-- 20%Si 0~

FIG. 2 - - T h e effect o] silica~lime ratio o f lime-saturated slags on the ]errous/]erric

601" 'FeO' ACTIVITIES ALONG~

0,1 0"2 0.3 SinG4 0.5 0.6 0.7 0.8

12DO /~t--~:--'~_-- : ? = ~ WUSTITE

Y' XI= SOLUBILITY Of WUSTITE IN LI~

In addition to a study of completely liquid solutions, we also have in-

o.51- /// ,~,;5o~

FeO and CaO ACTIVITIES

' o.dz o.~, o.~6 o68 o.to

I0o_ TEMP: II00*C

90- Pn_RH : 55*/.~lO_B.5~tm

10 TIME,hr5 . 100 1000

phase equilibrium calculations made from 1450 and 1550 C diagrams.

G. Derge ~ (written discussion)--It has been my privilege to have visited

1 Professor, Metals Research Laboratory, Carnegie-Mellon University, Pittsburgh,

X-Ray and Electron Microscope Studies