INTRODUCTION

Standard staining methods have been developed for carbonate rocks that are specific
for calcite (Friedman, 1959), ferroan calcite (Dickson, 1965) and magnesium-calcite
(Choquette and Trusell, 1977). These techniques are applicable to many types of
carbonate rocks, but except for a combined calcite and ferroan calcite stain, are not
normally used in any combination because they are incompatible alkaline and acidic
stains. Except for preparing and alternately staining serial thin sections, there would
be little way to examine the relationship of intergrown calcite, ferroan calcite,
magnesium-calcite and dolomite.
During a study of the mineralogy of coal balls, it became evident that standard
staining techniques were inadequate to study the relationship of the carbonate
minerals present in the coal balls. A combined calcite and ferroan calcite stain
overpowered the thin section and made observation of the intergrowths of mineral
grains difficult. Separate staining using a modified potassium ferricyanide stain and a
titan yellow stain for ferroan calcite and magnesium calcite, respectively, revealed
many details about the coal ball mineralogy, but could not be easily combined to yield
textural information.
Experimentation with staining techniques led to the realization that separate sides of a
thin section could be stained with otherwise incompatible stains and, when viewed in
transmitted light, the stains would superimpose in such a way that information about
the relationship of the minerals could be recovered.
METHOD
Step 1:
The thin section black must be smoothed to at least a semi-polish. Sanding to 6001200 mesh grit is acceptable and depends on the grain size. Fine grained
microdolomites require 1200 mesh or a 3 micron pre-polish. After sanding, the blank
should be lightly etched (15 to 30 seconds) and 1% acetic acid or 1% hydrochloric
acid are recommended.
Step 2:

The thin section blank is stained in the first stain. For this research the initial stain was
a Titan yellow stain specific for magnesium calcite:
1.0 g Titan yellow
8.0 g sodium hydroxide
4.0 g EDTA
1.0 l water
The blanks were stained at room temperature for approximately 30 minutes, rinsed
with distilled water and fixed with a 30 second immersion in:
200 g sodium hydroxide
1.0 l water
After fixing the blank was allowed to air dry.
Step 3:
The stained blank was then attached to the glass slide with epoxy mounting medium.
Tests showed that mounting of the blank using a vacuum degassing processing
resulted in less parting of the blank and also infilled porous areas that might "bleedthrough" when the second stain was applied to the thin section.
Step 4:
The mounted blank was then reduced to a thin section using standard techniques. The
surface was additionally smoothed using 600-1200 grit and lightly etched.
Step 5:
The thin section was immersed in a potassium ferricyanide (PFS) stain specific for
ferroan calcite (combined PFS and Alizarin red S can also be used but represented
"overkill" on the coal ball samples):

2.0 g potassium ferricyanide

100 cc 1.0% hydrochloric (or acetic) acid
If hydrochloric acid is used the staining time is very short (30-45 seconds) and care
must be exercised to prevent complete etching away of the thin section. Acetic acid is
more easily monitored and staining times range up to 5 minutes, but acetic acid may
be ineffectual in some cases (on coarse dolomite intergrown with the calcite, for
example).
After staining the thin section is rinsed with distilled water, air dried and mounted
using permount or any similar acid mounting medium.
USE OF THE DOUBLE SIDED STAIN TECHNIQUE ON COAL BALLS
Many coal balls have a relatively unique mineralogy and consist of intergrown calcite,
ferroan calcite and a "microdolomite" that is actually a metastable product from
magnesium-calcite (Barwood, 1995). Unique features such as "bushes" of
"microdolomite", botryoids and spherules have been observed using separate staining
techniques. The superimposition of some of these features was inferred, but could not
be observed directly.
Figures 1-5 illustrate how this staining technique can be used to see the relationship of
the initial magnesium-calcite infillings of cells and plant stems to later ferroan calcite
that is a diagenetic overprint.
The areas of these thin sections that were stained as magnesium-calcite were in reality
a metastable, fine grained breakdown product from magnesium-calcite. Microprobe
analysis of this material shows that it is compositionally:
CaO 50.59%
MgO 8.30%
FeO 0.13%
MnO 0.08%

X-ray diffraction analysis showed that this mineral was "kutnahorite", but kutnahorite
is a manganese-magnesium member of the dolomite group (figure 6). Apparently this
mineral represents a metastable product intermediate between magnesium-calcite and
dolomite and probably has a formula of Ca(Ca,Mg)(CO 3)2. Work is proceeding on
characterizing this mineral.
REFERENCES
Barwood, H.L. 1995. Mineralogy and origin of coal balls. Geol. Soc. Am. Abst. with
Programs, North-Central and South-Central Sections 27(3):37
Choquette, P.W. and F.C. Trusell. 1978. A procedure for making the titan-yellow stain
for Mg-calcite permanent. J. Sed. Petrology 48:639-641
Dickson, J.A.D. 1965. A modified staining technique for carbonates in thin section.
Nature 205:587
Friedman, G.M. 1959 Identification of carbonate minerals by staining techniques. J.
Sed. Petrology 29:87-97
BACK
2.

*Shannon Shaw, M.Sc. is a Geochemist with Robertson Geoconsultants Inc. in Vancouver

Introduction

Basic Chemistry of ARD Generation

Methods and Techniques

Examples

References

Introduction

Acid Rock Drainage (ARD), as described in the Introduction Page, is the product formed by the
atmospheric oxidation (i.e. by water, oxygen and carbon dioxide) of the relatively common iron sulfide
minerals pyrite (FeS2) and pyrrhotite (FeS) in the presence of (catalyzed by) bacteria (Thiobacillus
ferrooxidans), and any other products generated as a consequence of these oxidation reactions (i.e.
heavy metals solubilized by acidic solutions). To understand this more fully the basic chemistry must be
examined.
Basic Chemistry of ARD Generation
The following chemical reactions describe the oxidation of pyrite (FeS 2) to the products that constitute the
contaminants generically termed Acid Rock Drainage (ARD), although similar equations may be written
for the oxidation of pyrrhotite (FeS).
FeS2 + 7Fe2(SO4)3 + 8H2O = 15FeSO4 + 8H2SO4

(1)

FeS2 + Fe2(SO4)3 = 3FeSO4 + 2S

(2)

4FeSO4 + O2 + 2H2SO4 bacteria = 2Fe2(SO4)3 + 2H2O

(3)

2S + 3O2 + 2H2O bacteria = 2H2SO4

(4)

4FeS2 + 15O2 + 2H2O = 2Fe2(SO4)3 + 2H2SO4

(5)

S0 + 3Fe2(SO4)3 + 4H2O = 6FeSO4 + 4H2SO4

(6)

Neutralization of the acidic metal-rich solutions that can be generated by the above chemical reactions
may also occur as a result of dissolution of neutralizing minerals (most importantly carbonates) that come
in contact with the acidic solutions. These chemical reactions must also be examined to fully understand
the processes occurring and to be able to predict the chemistry of solutions resulting from the
combination of oxidation and neutralization processes. Examples of these reactions include:
Calcite dissolution by sulfuric acid
CaCO3 + H2SO4 -> CaSO4 + H2O + CO2

(7)

Dolomite dissolution by sulfuric acid

CaMg(CO3)2 + 2H2SO4 -> CaSO4 + MgSO4 + 2H2O + CO2

(8)

Reactions of other gangue minerals may also contribute to the neutralization potential of the system
under specific pH conditions (Ritchie, 1994), for example:

Muscovite dissolution
KAl2[AlSi3O10](OH)2(s) + H+ + 3/2H2O -> K+ + 3/2Al2Si2O5(OH)4(S)

(9)

Biotite dissolution
KMg1.5Fe1.5AlSi3O10(OH)2(s) + 7H+ + 1/2H2O -> K+ + 1.5 Mg2+ + 1.5 Fe2+ +
H4SiO04 + 1/2Al2Si2O5(OH)4(s)

(10)

Albite dissolution
NaAlSi3O8(s) + H+ + 9/2H2O -> Na+ + 2H4SiO04 + 1/2Al2Si2O5(OH)4(s)

(11)

Anorthite dissolution
CaAl2Si2O8(s) + 2H+ + H2O -> Ca2+ + Al2Si2O5(OH)4(s)

(12)

K-feldspar dissolution
KAlSi3O8(s) + H+ + 9/2H2O -> K+ + 2H4SiO04 + 1/2Al2Si2O5(OH)4(s)

(13)

Iron oxy-hydroxide dissolution

Fe(OH)3(s) + 3H+ -> Fe3+ + 3H2O

(14)

When studying these reactions and the resulting systems it should be clear that mineralogy is the key
factor. However, in many instances where ARD systems are studied in order to assess or predict water
quality, it is the mineralogy that is largely ignored. The primary excuse for excluding or doing only minimal
mineralogical characterization is that detailed mineralogy is often time consuming, expensive and
specialized. In recent years, more and more people in the industry have acknowledged that mineralogical
characterization is necessary, however there remains a lack of detailed work and/or interpretation of it.
Methods and Techniques
Petrographic or mineralogic examination of samples in ARD predictive work is usually conducted by
transmitted and reflected light microscopy, and by various X-ray diffraction (XRD) techniques. Although
electron probe microanalysis (EPMA), scanning electron microscopy (SEM) and other more specialized
techniques are employed, their use is generally confined to sulphide minerals where compositional
abnormalities affect ARD testwork interpretation. Such techniques are particularly useful in the
determination of the chemical composition of sulphide oxidation products such as rims, inclusions and
amorphous (non-crystalline) species.
Transmitted light microscopy utilizes thin (30 m) sections of samples and reflected light microscopy
utilizes polished mounted samples. Current practice combines the two sample preparation procedures to
produce polished thin sections, so that the two techniques can be used on the same sample. McCrone et
al. (1979) describe in detail the techniques of thin and polished section microscopy. Samples may be
prepared from whole rock in the form of drill core, or from fragmented material such as humidity cell feed
and residue samples, or from tailings.
Transmitted light microscopy is used to examine those minerals that transmit light in thin section, and
these include most of the gangue or non-metallic minerals that may have neutralizing capability. Reflected

light microscopy is used to examine those minerals that do not transmit light in thin section, but reflect
light to varying degrees when polished. Such minerals include metallic sulphides that may oxidize to
generate acid.
Both types of microscopy are used (often with supplementary techniques such as selective
staining or etching) to identify individual mineral grains, to determine mineral grain size and size
distribution, and to identify mineral grain spatial interrelationships.
Reaction products of sulphide oxidation (rimming of grains) are readily observed, as are many
other characteristics of mineral grains (such as inclusions) not readily seen by other investigative
techniques. These capabilities of microscopic examination are extremely useful in ARD studies of
both tailings and waste rock.
The ultimate size limitation of these methods is the wavelength of the light used, and the optical
arrangement of the microscope, but it is typically about 1 m grain size. Consequently, samples
containing significant quantities of clay minerals (< 2 m) present identification problems to the
microscopist.
It is usually possible to determine the frequency of occurrence of individual minerals within a sample by
the examination of a number of fields of view. Quantitative mineralogical analysis by this method is
termed modal analysis.
For some well-defined, unaltered, rock types it has been possible to calculate a modal analysis (or
quantitative mineralogical analysis) from elemental oxide analyses of whole rock samples using
mathematical techniques. Such calculations, known as CIPW from the initials of their original developers
(Cross et al., 1902), can be undertaken by computer programs such as NewPet for DOS (Clarke, D.,
1993). However, for the rock types typically associated with significant sulphide mineralization, CIPW
calculations have not yet been shown to have general applicability (Lawrence and Sheske, 1997,
Paktunc, 1998c) because they were developed for unaltered magmas, and cannot be applied to
sedimentary or metamorphic rocks or to altered igneous rocks. This is most unfortunate, since whole rock
elemental oxide analysis is generally less expensive than microscopic analysis and does not require the
considerable skill of an mineral microscopist. Paktunc (1998b) has developed a computer program called
MODAN that may be used to determine modal mineralogy from whole rock elemental oxide analysis and
a knowledge of the mineral species present in a sample. Paktunc (1998a) has also discussed the use of
MODAN in conjunction of mineral reactivity data to estimate the Neutralizing Potential (NP) of samples
containing neutralizing silicates in addition to carbonates.
Low-power stereoscopic microscopy is also a useful tool, particularly in the examination of tailings and
other relatively fine, fragmented samples. This technique is valuable in the determination of degree of
sulphide mineral liberation and may also be used as an aid in sulphide mineral identification. The
identification of mineral grains is well covered by Jones and Fleming (1965). It is usually preferable to
examine screen-size fractions when using low-power stereoscopic microscopy, and it is helpful also to
remove the bulk of the gangue mineral particles using one or more heavy liquid procedures at a Relative
Density of 2.8 to 2.9 (Mills, 1978,1985).
Some workers (Jambor and Blowes, 1998) obtain an X-ray diffractogram for each sample examined by
transmitted and reflected light microscopy and compare the mineral identification data obtained from the
two procedures for corroboration. This is a highly recommended approach.
Individual mineral grains greater than about 100 m may be positively identified by XRD using the X-ray
film method with Debye-Scherrer or Gandolfi cameras, or with modern microdiffractometry instruments
(Jambor and Blowes, 1998). These XRD methods all give qualitative data on mineral identity.
Examples

It is the intention of this site to act as an introduction to the mineralogical and petrological basics
associated with ARD in an effort to emphasize the importance of mineralogical characterization in ARD
studies and prediction. One of the major criticisms of petrological characterization of minerals is that it is
largely non-quantitative or semi-quantitative. In an effort to quantify sulfide oxidation, Blowes and Jambor
(1990) have developed a Sulfide Alteration Index tailored to the oxidation of mine wastes. Although it is
objective it serves to put into relative terms the degree of oxidation occurring or having occurred at one
site and give an indication of the progression and remaining oxidation of a particular waste as it is easily
adapted to specific site mineralogy. The index (developed initially for the Waite Amulet Tailings, Quebec)
is reproduced below.

Numerical
Scale

10

Degree of Alteration of Sulfides

Pyrrhotite and pyrite obliterated; only traces of sulfide, typically

chalcopyrite are present.

Similar to 10, but with a few scattered remnant grains of pyrite.

9

8-7

First appearance of trace amounts of pyrrhotite (at scale 8); at

scale 7 the vestiges of strongly altered pyrrhotite increases in
abundance or degree of preservation.

6-2

At scale 6 the pyrrhotite grains have broad alteration rims, but

the cores of numerous grains are preserved; gradation to scale
2 is marked by the appearance of narrower alteration rims and
a predominance of unaltered grains.

1-0

Only a few grains of pyrrhotite are weakly altered along rims

and fractures; >95% of the grains have sharp, fresh margins.

A second criticism of petrological characterization of minerals is that it is relatively abstruse to the majority
of people studying in this field. The following photomicrographs (1-9) and their corresponding descriptions
and interpretations have been included as examples of sulfide oxidation and dissolution of neutralizing
minerals from various sites throughout North America.

Photomicrograph 1: Reflected light photomicrograph of altered pyrrhotite grain.

Alteration is proceeding as preferential replacement along the {0001} crystallographic parting plane. The
alteration (secondary) mineral phase is predominantly an iron-oxyhydroxide.

Photomicrograph 2: Reflected light photomicrograph of altered pyrrhotite and unaltered pyrite

grains.
This photomicrograph demonstrates the different alteration rates between pyrrhotite and pyrite. Alteration
of pyrrhotite in this case is occurring both around the grain periphery and along the parting plane.

Photomicrograph 3: Reflected light photomicrograph of altered pyrrhotite and pentlandite grains.

Both the pyrrhotite and pentlandite exhibit alteration to iron-oxyhydroxides at approximately equal rates of
oxidation, however, the alteration textures are significantly different. Pyrrhotite shows predominant
alteration along the grain's parting plane, whereas pentlandite alteration is seemingly non-preferential,
primarily along fractures in the grain.

Photomicrograph 4: Photomicrograph of altering pyrrhotite grains and associated primary

minerals 'cemented' by secondary gypsum and iron-oxyhydroxides (a) in reflected light, (b) under
crossed Nicols.
This photomicrograph suggests that significant sulfide alteration has occurred producing iron and sulfates
that have re-precipitated out of solution as iron-oxyhydroxides (orangey-red) and gypsum (white). These
'cementing' phases likely serve to slow further oxygen penetration and therefore sulfide oxidation.

Photomicrograph 5: Photomicrograph of pyrrhotite pseudomorph (a) in reflected light, (b) under

crossed Nicols.
Complete pseudomorphic replacement of pyrrhotite. In reflected light the alteration product looks
relatively homogeneous, under crossed Nicols however it is clear that it is a multi-phased and progressive
replacement. This grain was examined in further detail as described below.
Many of the mineralogical processes of interest and importance that control the acid generation/metal
leaching character of mine waste occur on a small scale (micron level), in particular for tailings. For this
reason, the use of the Scanning Electron Microscope (SEM) can greatly aid in the understanding and
therefore interpretation of these mineralogical controls. For instance the pyrrhotite pseudomorph shown in
Figure 5 above (turned 90 degrees) was examined under the SEM using both back-scattered electron
imagery (BSE) and elemental x-ray maps as shown below.

Photomicrograph 6: Back Scattered Electron image of pyrrhotite pseudomorph (field of view=300

microns).
The BSE image allows for detailed examination of the texture of this grain. The pseudomorphic
replacement occurred along a preferred orientation, most likely along the {0001} crystallographic parting
plane. It also appears that portions of the pseudomorph are more crystalline than others.

Photomicrograph 7: Element x-ray maps of the same pseudomorph (field of view=300 microns).
The x-ray maps allow for non-destructive, semi-quantitative analysis of the chemistry of alteration
products.

These mineralogical "tools" , although documenting a snapshot in time, illustrate clearly that alteration of
sulfides is a progressive process with complex mineralogical changes occurring throughout and various
intermediate phases dominating different stages. The above grain would be classified on the S.A.I. given
above as a 9 or 10, depending on the alteration of other sulfides in the sample. If this grain was typical of
an entire site, it may suggest that the rate of oxidation, and therefore acid generation, would be slowing.
This conclusion could affect the selection of particular control technologies or closure requirements. For
example, the selection of a complex tailings cover to prevent oxygen infiltration as a means of controlling
sulfide oxidation at a site where the sulfides were typical of the above example may not be appropriate.
Other predictive tools that are commonly used include the acid-base-accounting (ABA) tests and other
static and kinetic laboratory procedures. Interpretation of these results is critical and as proven more than
once, very site specific. One of the issues most difficult to interpret is the neutralization potential (NP) of
the ABA test. Carbonates play a dominant role in acid neutralization, but other minerals, depending on pH
conditions, can contribute to NP. Plagioclase feldspar and biotite are two such minerals as seen in the two
photomicrographs (8 and 9) presented below.

Photomicrograph 8: Transmitted light photomicrograph of weakly altered plagioclase feldspar.

Weak alteration of the plagioclase feldspar known as saussuritization is seen in this photomicrograph, the
grain is also rimmed by fine grained iron-oxyhydroxide precipitating from solution.

Photomicrograph 9: Transmitted light photomicrograph of altered biotite grain.

Significant alteration has occurred in this biotite grain as evidenced by the loss in colour and pleochroism.
Electron probe microanalyses of similar altered biotite grains showed a depletion in K, Fe and Mg

indicating alteration to vermiculite. Similar results were reported by Jambor (1994). This grain, as was
seen with the plagioclase in Fig. 8. is also coated with a secondary phase, likely an iron-oxyhydroxide.
The identification of secondary alteration products also plays an important role in the prediction of pore
water quality. Geochemical equilibrium speciation models, such as MINTEQA2 (Allison et al., 1991), are
frequently used for these predictions. Pore water chemistry is dependent on the solubility constraints of
the minerals through which the pore water migrates. Therefore, minerals identified during mineralogical
characterization, in particular the secondary alteration products and carbonates, can be used in
geochemical models as constraints and controls on the predicted pore water chemistry.

The contents of this web page are protected by copyright law. Please contact
the authors for permission to re-use the contained information.

REFERENCES
Allison, J.D., Brown, D.S., and Novo-Grada, K.J. (1991), MINTEQA2/PRODEFA2, A Geochemical
Assessment Model for Environmental Systems, version 3.0, EPA/600/3-91/021, 1991, Office of Research
and Development, U.S. Environmental Protection Agency, Athens, GA.
Blowes, D.W. and Jambor, J.L. (1990), The Pore-water Geochemistry and the Mineralogy of the Vadose
Zone of Sulfide Tailings, Waite Amulet, Quebec, Canada., Applied Geochemistry, vol. 5, pp. 327-346.
Clarke, D. (1993), NewPet for DOS, Dept. of Earth Sciences, Memorial University of Newfoundland, St.
John's, NF.
Cross, W., Iddings, J.P., Pirsson, L.V. and Washington, H.S. (1902), A Quantitative Chemicomineralogical
Classification and Nomenclature of Igneous Rocks, Journal of Geology, v10, p555-690.
Jambor, J.L. (1994), Mineralogy of Sulfide-rich Tailings and Their Oxidation Products., in Environmental
Geochemistry of Sulfide Mine-wastes, Mineralogical Association of Canada Short Course Vol. 22., pp. 59102.
Jambor, J.L. and Blowes, D.W. (1998), Theory and Application of Mineralogy in Environmental Studies of
Sulfide-Bearing Mine Wastes, in Modern Approaches to Ore and Environmental Mineralogy (Cabri, L.J.
and Vaughan, D.J., Eds.), Mineralogical Association of Canada Short Course Vol. 27, p367-402..
Jones, M.P. and Fleming, M.G. (1965), Identification of Mineral Grains, Elsevier, London, 102p.
Kwong, Y.T.J. and Ferguson, K.D. (1997), Mineralogical Changes during NP Determinations and their
Implications, Proc. 4th International Conference on Acid Rock Drainage, Vancouver, BC, p435-447.
Lawrence, R.W. and Sheske, M. (1997), A Method to Calculate the Neutralization Potential of Mining
Wastes, Environmental Geology, v32, p100-106.
McCrone, W.C., McCrone, L.B. and Delly, J.G. (1979), Polarized Light Microscopy, Ann Arbor Science
Publishers, Ann Arbor, Michigan, 251p.

Mills, C. (1985), Specific Gravity Fractionation and Testing with Heavy Liquids, in SME Mineral
Processing Handbook, American Institute of Mining, Metallurgical and Petroleum Engineers, New York,
30:44-52.
Mills, C. (1978), Mineralogy and Heavy Liquid Analysis in Gravity Separation, Short Course on Gravity
Concentration Technology, University of Nevada, Reno, October, 25p.
Paktunc, A.D. (1998a), Characterization of Mine Wastes for the Prediction of Acid Mine Drainage, in
Environmental Impacts of Mining Activities - Emphasis on Mitigation and Remedial Measures (Azcue,
J.M., Ed.), Springer-Verlag, Berlin (in print).
Paktunc, A.D. (1998b), MODAN: An Interactive Computer Program for Estimating Mineral Quantities
based on Bulk Composition, Computers & Geosciences, v24, n5, p425-431.
Paktunc, A.D. (1998c), Discussion of A Method to Calculate the Neutralization Potential of Mining Wastes,
Lawrence, R.W. and Sheske, M., Environmental Geology (in print)
Ritchie, A.I.M. (1994), The Waste-rock Environment, in Environmental Geochemistry of Sulfide Minewastes, Mineralogical Association of Canada Shortcourse Handbook (J.L. Jambor and D.W. Blowes,
eds.), vol. 22, pp. 133-161.

Most recent update: 07/17/2010 18:49:55

Return to ARD at Enviromine

3. CHEMICAL STAINING METHODS USED IN THE

IDENTIFICATION OF CARBONATE MINERALS
Tamer AYAN
Mineral Research and Exploration Institute of Turkey

INTRODUCTION

Carbonate minerals are the major constituents of sedimentary rocks; however,

they are also found in igneous and metamorphic rocks, either as primary or as secondary
minerals. In carbonate rocks formed either by chemical or mechanical deposition, these
minerals constitute the main rock-forming components. Sometimes they are also found
in great abundance in pelitic, psammitic and psephitic rocks.
According to their crystallographic characteristics, carbonate minerals may be
subdivided into two main groups :
1) Calcite group : Hexagonal-rhombohedral system.
2) Aragonite group : Orthorhombic system pseudohexagonal.
Of the calcite group of minerals, calcite (CaCO3) and dolomite [CaMg (CO3)2]
are the two minerals which are dominantly found in sediments. Depending on its
purity, or iron and magnesium content, calcite may be found in states of pure calcite,
ferro-calcite, or slightly to abundantly magnesian calcite. Similarly, according to the iron
content percentage, dolomite may also be regarded as having been composed of two end
members, pure dolomite and ferrous dolomite, in varying proportions. The other calcite
group minerals are ankerite ferroferric dolomite [CaFe(CO3)2], magnesite (MgCO3),
siderite (FeCO3), smithsonite (ZnCO3), rhodochrosite (MnCO3) and spherocobaltite
(CoC03).
The most important mineral of the aragonite group is aragonite (CaCO3); the
others, in decreasing order of importance, are witherite (BaCO3), strontianite (SrCO3),
cerussite (PbCO3) and alstonite [(Ba, Ca)CO3]. Apart from their refractive indexes
(R.I.), the optical and crystallographic characteristics of carbonate minerals are very

similar to each other. Therefore identification of carbonates on hand specimens or even

in thin sections, is rather difficult. The determination of the R.I.'s, on the other hand,
can only be carried out by oil-immersion methods.
The identification and discrimination of carbonate minerals in hand specimens
or thin sections, are made easier by the use of simple chemical staining methods, without
losing a great 4 amount of time in chemical analyses or optical investigations.
Studies in this field have begun towards the end of the 19 th century and are continuing
at the present time. The production of dependable results in a short time by using
simple techniques, has made this method faisly popular. Numerous workers have contributed
a wealth of knowledge to this field, In purely scientific or economic studies, it
134 Tamer AYAN

proves to be useful and successful to sturdy sedimentary, especially carbonate, rock

specimens by staining methods, before engaging other microscope techniques.
It is hoped that the following list of descriptions of staining methods will be
useful to those who intend to carry out some more research in this field.
PROCEDURES BEFORE STAINING

It is recommended that the thin section or the cut and polished surface of the
hand specimen be etched with diluted HC1 acid before staining. Diluted acetic acid or
formic acid may also be used in place of HC1 acid (Williams, Turner, Gilbert, 1954).
Different carbonate minerals in a rock specimen, immersed in an appropriate HC1
solution for an appropriate period of time, wili show -different reactions. When this
specimen, after being thoroughly washed with distilled water, is inspected under a
binocular or polarizing microscope, the textural and mineralogic features of carbonate
minerals may be observed in detail. In Table 1, acid densities and the periods of
time for each test employed by various workers are indicated. However, it will be
more appropriate to determine the exact acid density and the duration of test, according
to the lithological characteristics of each specimen to be tested. All acid solutions shown
in Table 1 have been used cold (at room temperature). However, Warne (1962) points
out that in tests carried out with cold acid solutions, calcite, aragonite and witherite
fizzes quickly, rhodochrosite, ankerite, cerussite, smithsonite and strontianite show a
weak fizzing, whereas siderite, dolomite and magnesite do not react at all. He suggests
that minerals that show a weak reaction should be treated with warm HC1 acid for
about 30 seconds to 1 minute.
STAINING METHODS

For the identification of various carbonate minerals, the following available

tests may be listed:
I - Discrimination between aragonite and calcite :
(1) Meigen test; (2) Feigl test; (3) Rhodizonic acid test.
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 135

II - Discrimination between calcite and dolomite :

(1) Lemberg hydroxide test; (2) Lemberg test; (3) Fairbanks test; (4) Lemberg
silver chromate test; (5) Copper nitrate test; (6) Trypan blue test; (7) Harris
hematoxilin test; (8) Alizarin red test; (9) Friedman test; (10) Potassium
ferricyanide test; (11) Alizarin red and potassium ferricyanide composite test;
(12) Mann test; (13) Ramsden test.
III - Discrimination between magnesite and smithsonite :
(1) Friedman test; (2) Magneson test; (3) Tropaeolin 00 test.
IV - Discrimination between ankerite and siderite :
(1) Kirchberg test; (2) Hydrogen peroxide-potassium hydroxide test.
V - Discrimination of rhodochrosite :
(1) Benzidine test.
The outlines of each test are given below :
I. 1 - Meigen test
This test was first described by Meigen (1901). The rock specimen is boiled in

cobalt nitrate solution (Holmes, 1921; Twenhofel and Tyler, 1941).

Solution. Cobalt nitrate [Co(NO3)2. 6H2O].
Test. Specimen is boiled in cobalt nitrate solution for 20 minutes (Twenhofel
and Tyler, 1941; Williams, Turner and Gilbert, 1954). Togari has carried out this test
(1955) by boiling 0.2 gr rock specimen in 2 cc 0.1 N cobalt nitrate solution and
filtering the specimen off.
Result. During the test aragonite first takes a lilac color, which slowly turns
into purple. On the other hand, in calcite such coloring is either not present or slow
developing. In the latter case, this color disappears within a few hours after the test
(Twenhofel and Tyler, 1941; Le Roy, 1950; Williams, Turner and Gilbert, 1954;
Friedman, 1959).
The disadvantages of this test are illustrated by the following :
Jirova (1956) carried out a Meigen test on three foraminifera species which
indicated aragonite; yet later an X-ray analysis showed calcite. Another difficulty arises
in the investigation of fine-grained specimens: since cobalt nitrate solution spreads over
both minerals to the same degree, discrimination becomes difficult. However, sensitivity
of the method can be increased by the application of ammonium sulphide to the stained
surface. In this case aragonite appears as black spots (cobalt sulphide=Co2S3), while
the color of calcite remains greyish.
I2- Feigl test
This test has been arranged by Feigl (1937) and is based on the slightly different
dissolution rates of calcite and aragonite in water.
Solution. To prepare the solution, 1 gr Ag2SO4 is added to a mixture of
11.8 gr MnSO4. 7H2O and 100 cc distilled water. The whole mixture is boiled, cooled
and filtered, before adding one or two drops' of diluted NaOH. After letting it settle
for two hours the solution is re-filtered and kept in a dark-colored bottle (Feigl, 1946).
136 Tamer AYAN

Test.The rock specimen is soaked in the solution for 10 minutes.

Result- Aragonite becomes black, while no change of color is observed in
calcite, dolomite and witherite (Warne, 1962).
I. 3 - Rhodizonic acid test
Feigl (1946, 1954) used this test for the detection of the presence of barium
and strontium in solutions.
Solution. It is prepared by dissolving 2 gr disodium rhodizonate in 100 ml
distilled water. Sodium potassium rhodizonate may also be used for the same purpose.
Test. Previously etched specimen, after having been washed with distilled
water is placed in this solution for 5 minutes.
Result. Witherite takes a color between orange and red, while no change is
observed in calcite (Warne, 1962).
II. 1 - Lemberg hydroxide test
This test has been devised by Lemberg (1887) for discrimination between calcite
and dolomite (Rodgers, 1940).
Solution. 1 part of FeCl3.6H2O is mixed with 10 parts of distilled water.
Test. The specimen is kept in th solution for about 1 minute (fine-grained
specimens for a shorter period), washed with distilled water and then immersed in
(NH4)2SX solution (the strength of the solution and the length of time are not important).
Result. Prior to immersing in (NH4)2S solution, the color of calcitedue to
Fe (OH)3would be pale brown; after immersion, it will turn black. If the specimen
is kept in the second solution for a long time, dolomite assumes a light green color.
The disadvantages of this test are: the color is not stable, it is easily scratched
off and, in time, locally cracks and flakes off.
With a slight modification this test has been adapted by Keller and Moore
(1937) in the following way, for using on bore-hole samples and fragmentary specimens:
Freshly broken or cut face of the specimen, after being wetted with water, is placed
in FeCl3 solution (2.5 %) for about 5-10 seconds. After being washed thoroughly in
distilled water, the specimen is immersed in (NH4)2S solution for the same period of

time. Once again it is rinsed and dried. While calcite becomes black, no color change
will be observed in dolomite.
II. 2 - Lemberg test
This test was first described by Lemberg (1887) and slightly modified later by
Steidtmann (1917) (Rodgers, 1940).
Solution. 4 gr AlC13 and 6 gr logwood chips are boiled in 60 cc distilled
water for 20-25 minutes. The amount of loss due to evaporation is replaced by the
addition of some more distilled water. After cooling the solution is filtered and kept
in a bottle.
Steidtmann, slightly modifying the formula, has used 6 gr of logwood spirit
(hematoxilin) instead of logwood chips and has diluted the solution with 1200 cc
distilled water before making the tests (Rodgers, 1940).
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 137

Test.The specimen is kept immersed in the solution for about 5-10 minutes.
Result. During this time calcite acquires a purple color as opposed to
dolomite, which does not change color within the first 20 minutes. However, after 20
minutes, dolomite turns into pale blue (Rodgers, 1940; Twenhofel and Tyler, 1941).
The outstanding disadvantages of this test are the instability of the solution and the
ease of scratching and flaking of the acquired color.
II. 3 - Fairbanks test

This is essentially a Lemberg test, improved by Fairbanks (1925).

Solution. 0.24 gr of hematoxilin and 1.6 gr of A1C13 are boiled in 24 cc
of distilled water. After cooling, a little amount of hydrogen peroxide is added to the
solution after which it is filtered and kept in a dark-colored bottle.
Test. Specimen is immersed in the solution for about 30 seconds, then
washed carefully.
Result. Calcite acquires a dark purple color, while there appears to be no
change in the color of dolomite. As far as the stability of the solution and the results
are concerned, this test in general is considered to be quite satisfactory.
II. 4 - Silver chromate test

This test was first described by Lemberg. (1892) for the discrimination between
calcium minerals and magnesium minerals. Some details of this test have been given
later by Rodgers (1940) (Friedman, 1959).
Solution. 10 % silver nitrate (AgNO3) and potassium chromate (K2CrO4).
Test. Specimen is soaked in silver nitrate solution at a temperature of
60-70 C for about 2-5 minutes (Rodgers, 1940; Twenhofen and Tyler, 1941;
Friedman, 1959). After washing with distilled water, the specimen is immersed in
potassium chromate solution for about 1 minute.
Result. Calcite and aragonite acquire a chocolate or red-brown color, while
dolomite and magnesite do not show any change in color.
II. 5 - Copper nitrate test
This test was first described by Hinden (1903) as a means of identification of
calcite by the use of FeCl3. Mahler (1906) and Spangenberg (1913), who also worked
on this subject, have considered it more suitable to use copper salts [CuSO 4 or Cu (NO3)2],
instead of FeCl3. Lately, Rodgers (1940) has further developed this test and has given
some more details, which have bearing on the results of the test, such as duration of
test, density of the solution, degree of acidity, temperature and the calcite percentage
of the specimen tested.
Solution- Copper nitrate molar solution. Prepared by mixing 188 gr of
Cu (NO3)2, 225 gr of Cu(NO3)2 . 3H2O or, 332 gr Cu (NO3)2 . 6H2O and 1000
gr distilled water. In addition there should be a sufficient amount of NH4OH
available.
Test. Specimen is soaked in copper nitrate molar solution for about 5-6
hours. Care must be taken that the particular surface of the specimen to be stained

138 Tamer AYAN

should not be in contact with the walls of the vessel containing the solution, and also
that no bubbles should accumulate on this surface. After the treatment, the specimen
is washed. dried and immersed in NH4OH solution for a few seconds. Once again the
specimen is washed carefully.
Result. Calcite acquires a green or bluish-green color, while dolomite does
not show any change in color (Rodgers, 1940).
II. 6 - Trypan blue test
Solution- There are two different sets of formula available (Friedman, 1959).
a) 10 gr of potassium aluminium sulphate [KA1 (SO4)2 . 12H2O] is dissolved in
100 cc of warm water and this solution is mixed with the solution obtained by dissolving
0.25 gr trypan blue in 5-8 cc methanol. Also 8 cc of 10 % HC1 is added.
b) Preparation of the other solution is much easier : 6 cc of 10 % HC1 is added
to the solution obtained by dissolving 0.1-0.2 gr of trypan blue.
Test- Specimen is soaked in the solution for an unspecified period of time.
Result. As a result of this test, both calcite and dolomite acquire colors.
Color of calcite becomes dark blue, while dolomite becomes pale blue
II. 7 - Harris hematoxilin test
Solution. Harris hematoxilin may be either obtained commercially in a
ready-made form or prepared in the following way as described by Gurr (1956): 5 cc
of hematoxilin (C16H14O6) solution (10 % hematoxilin in pure alcohol) and 100 ml of
potassium aluminium sulphate solution are mixed and heated. When the mixture reaches
boiling point, 0,25 gr of mercury oxide (HgO) is added. Heating is stopped when the
color of the solution becomes dark lilac. After cooling, 4 ml of acetic acid (CH 3.COOH)
is added to the solution.
For the test, a mixture of 50 cc Harris hematoxilin solution and 3 cc 10 %
HC1 is used. Hematoxilin bottle must be well shaken before use.
Test. Specimen to be inspected is soaked in the solution for 3-10 minutes.
With freshly prepared solutions the results are obtained in 9-10 minutes. When the
solution is re-used, the test duration must not exceed 3 minutes.
Result. Color of calcite changes to lilac, while there is no corresponding
color change in dolomite (Friedman, 1959).
II. 8 - Alizarin red test
Alizarin red was first used by Huegi (1945) to discriminate between ankerite
and siderite. Later, Friedman (1959) has succesfully applied this technique to other
caibonate minerals Warne (1962), Evamy (1963) and Dickson (1965) have all contributed
to the development of this test.
Solution. According to Friedman, the solution is obtained by dissolving
0.1 gr of alizarin red [sodium alizarin sulphonate = CO.C6H4.CO.C6H (OH)2.SO3 Na
+ H2O] in 100 ml of 0.2% cold HG1. 0.2 % HC1 can be prepared by adding 2ml
conc. HC1 to 998 ml distilled water.
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 139

The same formula has also been used by Warne.

Evamy has obtained the solution by mixing 0.2 % HC1 with 0.2 % alizarin

red.
Dickson has slightly altered formula by dissolving 0.2 gr of alizarin red in
100 cc of 1.5 % cold HCl.
Tests carried out by the author were made with a solution obtained by dissolving
0.1 gr of alizarin red in 100 cc 2 % cold HC1.
Test. Previously etched and washed specimen is soaked in the solution for
a certain period. This period has been determined as 5 minutes by Warne, 2-3 minutes
by Friedman, 1 minute by Evamy, 10-15 seconds by Dickson and as 3 minutes by
the author. Care should be taken that no accumulation of air bubbles occurs on the
surface of the specimen. After the test, specimen is washed lightly with distilled water.
If tap water has to be used, damage due to the pressure of water can be prevented
by holding the opposite side of the specimen of thin section against the water.

Result. Color of calcite will turn into red-brown, whereas dolomite will not
be affected (Friedman).
Evamy states that calcite and ferrocalcite will be colored red, while no change
will take place in the color of dolomite, ferrodolomite and ankerice.
Dickson states that calcite and ferrocalcite will acquire a color between pink
and red, whereas dolomite and ferrodolomite will acquire no color.
According to the observations made by the author, calcite and ferrocalcite acquire
a color between light and dark-pinkish red, as opposed to dolomite and ferrodolomite
which do not acquire any color at all.
According to Warne, as a result of this test calcite, abundant magnesium-bearing
calcite, aragonite and witherite acquire a dark red color, while ankerite, ferrodolomite,
strontianite and cerussite acquire a lilac color. On the other hand, the colors of siderite,
dolomite, rhodochrosite, magnesite and smithsonite are not affected at all.
II. 9 - Friedman test
This test has been described by Friedman (1959).
Solution. 0.2 gr of an organic dye (titan yellow, eosin Y, Congo red, alizarin
red, etc. may be used) is boiled in 25 cc methanol, while 15 cc of 30 % sodium
hyroxide (30 gr NaOH + 70 cc distilled water) are added.
Test- Specimen is soaked in boiling solution for about 5-10 minutes.
Result. Dolomite acquires a color depending on the organic dye used. Thus,
with :
Titan yellow dark orange-red
Eosin Y - dark pink
Congo red red
Alizarin red lilac
Faded colors may be restored back by reheating the specimen with diluted
NaOH.
140 Tamer AY AN
II. 10 - Potassium ferricyanide test

Lemberg has first used potassium ferricyanide [K 3Fe (CN)6] in determining FeS
in the hydroxide test. The same compound was used by Krech (1909) for the staining
of Fe++ in dolomite. Later it was used by Heegel (1913) for discriminating between
dolomite and calcite, according to their iron content. Also Rodgers (1940), Twenhofel
and-Tyler (1941), Friedman (1959), Warne (1962) and Evamy (1963) have all contributed
to the development of this test.
Solution It can be prepared in different ways according to different
workers:
Krech has obtained his solution by acidizing freshly prepared potassium ferricyanide
solution by the addition of one or two drops of HC1.
Heeger has mixed a couple of drops of potassium ferricyanide with diluted HC1.
Henbest (1913) has added 10 parts of K3Fe(CN)6 to 2 parts of concentrated
HC1 and 88 parts of distilled water.
Twenhofel and Tyler have added one or two drops of potassium ferricyanide
to diluted hydrochloric acid (1 part conc. HCl+100 parts of distilled water).
Friedman recommends that the solution - be prepared by adding one or two
drops of potassium ferricyanide to diluted HG1 (1:50 - 100).
Warne has considered it best to use a solution obtained by mixing equal parts
of 2 % HC1 acid and potassium ferricyanide (0.01 gr K3Fe(CN)6 + 100 ml distilled
water).
Evamy has used a mixture of 0.2 % HC1 and 0.5-1.0 % potassium ferricyanide.
In tests made by the author this mixture was prepared by adding 2 cc of
concentrated HCl and 98 cc distilled water into the solution of 2 gr of potassium
ferricyanide in 100 cc of water. However, since the solution is not stable, it should be
used up within one or two days. Otherwise it changes into HCN and acquires a dark
color.

Test- Specimen is immersed in cold potassium ferricyanide solution, for a

certain period of time. The author has found 3 minutes to be sufficient for this.
Evamy recommends 1 minute. After the test, specimen is carefully washed with distilled
water.
Result- According to Twenhofel and Tyler, at the end of this treatment
dolomite will acquire a blue color, while calcite will remain unaffected. This reaction
is due to Turnbull blue [Fe3 (FeC6N6)2J formed by the combination of the ferrous iron
in dolomite with potassium ferricyanide. Although from the test results it may be
concluded that the ferrous iron component is more abundant in dolomite and less
abundant in calcite, this of course, may not always be true; because in some cases
dolomites may have very little or no ferrous components; on the other hand this
component may be quite abundant in some types of calcite.
According to Friedman, while dolomite with ferrous iron acquires a blue color,
no coloring is observed in calcite.
Warne points out that after tests carried out with cold solution, ankerite and
ferrodolomite acquire a dark blue color; whereas dolomite and siderite may acquire
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 141

color only after treatment with a warm solution. During heating tests change of color
occurs in siderite earlier than in dolomite.
Evamy reports that ferrocalcite, ferrodolomite and ankerite acquire a light or
dark blue color (depending on the amount of Fe++ component), while neither pure
calcite nor pure dolomite will show any change of color.
In tests carried out by the author, ferrodolomite and ferrocalcite have acquired
a blue color, while no change appeared in pure calcite and pure dolomite. The degree
of darkness of blue is proportional to the iron content of the minerals.
II. 11 - Alizarin red and potassium ferricyanide composite test

This test is used for discriminating between four different types of carbonates
(calcite, ferrocalcite, dolomite and ferrodolomite) in a single series of operation. The
test and results were described by Evamy (1963) and Dickson (1965).
Solution. Evamy has obtained the solution by mixing 0.2 % HC1, 0.2 %
alizarin red, and 0.5-1.0 % potassium ferricyanide.
According to Dickson, two solutions are prepared separately :
a) Alizarin red solution: This solution is obtained by dissolving 0.2 gr of
alizarin red in 100 cc of 1.5% hydrochloric acid (98.5 cc distilled water + 1.5 cc
concentrated HC1).
b) Potassium ferricyanide solution : 2 gr of potassium ferricyanide is dissolved
in 100 cc 1.5 % HC1.
The mixed solution, to be used in the test, is prepared by mixing 3 parts of
alizarin red solution and 2 parts of potassium ferricyanide solution.
Solutions for the tests carried out by the author have been prepared in the
following way :
a) 0.1 gr of alizarin red is dissolved in 100 cc of 2 % HC1.
b) To the mixture of 2 gr of potassium ferricyanide and 100 cc distilled
water, 100 cc of 2 % HCl is added.
These two solutions are mixed in equal parts for obtaining the mixed solution
to be used in the test.
Test Specimen is soaked in cold solution for 3 minutes (according to the
author). Evamy considers 1 minute as sufficient, while according to Dickson a period
of 30-45 seconds is adequate. After the test, specimen is carefully washed and dried.
Kesults- According to Evamy, the results of the test are as follows :
Calcite : Red.
Ferrocalcite, (low ferrous iron content) : lilac red dominant.
Ferrocalcite (high ferrous iron content) : scarlet blue dominat.

Dolomite: no coloring.
Ferrodolomite: pale blue.
Ankerite: dark blue.
142 Tamer AYAN

Dickson lists the following results :

Calcite : between very pale pink and red. (The tone of the color depends on
the optical orientation of the crystal. Stained surfaces parellel to c-axis are
darker than those which are at right angles to the axis.)
Ferrocalcite: between lilac (pinkish purple)-scarlet and royal blue, derived from
the mixture of very light pink-red group and pale blue-dark blue group.
Dolomite: shows no coloring.
Ferrodolomite: Light to dark turquoise. Tone of the color depends on the ferrous
iron content.
The following results were observed in tests carried out by the author:
Galcite: pinkish red.
Ferrocalcite: lilac-mauve or light scarlet.
Forrodolomite: blue-green.
Dolomite: No change of color observed.
With staining on thin sections, a mixture of Durofix and amilacetate (1:3)
should be applied to the stained surface, before the cover glass is placed. In this way
the colors will be protected during heating operation.
II. 12 - Mann test
Mann (1955) has used alkali p-nitrobenzene-azoresourcenol solution to differentiate
between pure and MgO-bearing limestones. This solution was first described by
Feigl (1946) and used by him to determine the Mg content in solution.
Solution- 10 % HC1 and solution of 0.002 gr p-nitrobenzene-azoresourcenol
in 100 cc 2N NaOH.
Test- First one drop of 10 % HCI is placed on the specimen's surface.
When the fizzing stops, one drop of p-nitrobenzene-azoresodrcenol is placed on the
same spot.
Result If within 30 seconds the color changes to blue, there is a high
concentration of MgO in the specimen. Purple or scarlet color is indicative of no MgO
present. The tone of the blue color is proportional to the percentage of MgO present.
This method can be used successfully by the field geologist in places where
the lithological boundaries are not visible or difficult to detect. Boundaries between
limestones and dolomitic limestones may easily be determined in the field by the geologist.
II. 13 - Ramsden test

This test was described by Ramsden (1954) for the discrimination between
calcite and dolomite.
Solution It is prepared by dissolving 2.5-3.0 gr of A1C13 and 1 gr methyl
red in 1000 cc of warm water. This is a stable solution.
Test In a small beaker, 2 parts of solution are mixed with one part of
powdered specimen.
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 143

Result. In less than 30 seconds, pure calcite is observed to acquire a color

between pink and pale yellow. Dolomitic limestone shows very little coloring. No change
is observed in dolomite.
III. 1 - Friedman test
This test has been described by Friedman (1959). 0.2 gr of one of the organic
dyes shown in II.9 is boiled in methanol and in the meantime 15 cc of 5 % NaOH
is added. The test and results are similar to those explained in II.9.
III. 2 - Magneson test
This test is based on the determination of Mg content in solutions (Feigl, 1946
and 1954; B. D. H., 1946 and 1963).
Solution. 0.5 gr of magneson [p-nitrobenzene-azoresourcenol
is dissolved in 100 ml of 0.25 N (1.0 %) NaOH (B. D. H., 1946).
For the same purpose magneson I [4-p-nitrophenyl-azoresourcenol = NO 2. C6H4.

N: N. C6H3 (OH)2] or magneson II [4-p-nitrophenyl-azo-l-naphtol = C 6 H4 . NO2. N:

N. C10 H6OH] may also be used (B. D. H., 1963).
Test and result. Equal parts of 30 % NaOH and magneson solution,
prepared as described above, are mixed. The specimen is soaked in this solution for a
certain period. Magnesite, after 1 minute becomes blue; after 2-3 minutes, dark blue.
Smithsonite, on the other hand, becomes slightly bluish only after 5 minutes. After
this treatment, if the specimen is thoroughly washed and heated in 30 % NaOH
solution (without attaining boiling point), it will be observed that only the blue color
on magnesite will remain stable, while -the color on smithsonite will disappear (Warne,
1962).
For this test Feigl (1946) has used a mixture of 0.001 gr p-nitrobenzeneazoresourcenol
or p-nitrobenzeneazo-a-naphtol and 100 ml of alkali.
III. 3-Tropaeolin 00 test
This test was first described by Vogel (1945) for the determination of zinc in
solutions. It was later used by Warne (1962) to discriminate between smithsonite and
magnesite.
Solution. This is a mixture of 1 part tropaeolin solution [0.01 gr tropaeolin
00(4-p-sulphophenyl-azo-dyphenylamin) dissolved in 100ml of distilled water], 1 part N
sulphuric acid (H2SO4) and 3-5 parts freshly prepared 2 % potassium ferricyanide
solution [2 gr of K3Fe (CN)6 + 100 cc of distilled water].
Test. Specimen is soaked in the solution for 5 minutes.
Result. While no change is observed in magnesite, smithsonite acquires a
yellow color.
IV. 1 - Kirchberg test
This test was first used by Kirchberg (1940,41) for the determination of
ankerite (ferroferric dolomite) (Friedman, 1959; Warne, 1962).
144 Tamer AYAN

Solution- 10 % copper sulphate (CuSO4) solution, and also ammonium

sulphide [(NH4)2S] solution.
Test- The polished face of the specimen is kept in 10 % hydrofluoric acid
[80 cc distilled water + 48 % HF) for 2 minutes, after which it is washed and dried.
This- time specimen is immersed in ammonium sulphide solution for about 1 minute,
washed and then soaked in copper sulphate solution for about 5 minutes. After being
washed thoroughly the specimen is once again immersed in ammonium sulphide solution,
for a time. If necessary, this procedure may be repeated several times.
Result. Ankerite acquires a gray-black color
In the preparation of the solution, sodium sulphide may be used instead of
ammonium sulphide. In this case, while ankerite and ferrodolomite become almost
black after a few repetitions, siderite presents very little coloring (Warne, 1962).
IV. 2 - Hydrogen peroxide - potassium hydroxide test
This test was used by Hallimond (1925) for the determination of ankerite and
siderite by staining (Warne, 1962).
Solution. Concentrated potassium hydroxide (KOH) and hydrogen peroxide
(H2O2).
Test.Specimen is immersed in warm KOH solution, for about 5-10 minutes,
during which time drops of H2O2 are added to the solution. After removing the
specimen, it is washed with distilled water and dried.
Result. After the test ankerite acquires an orange color, while no coloration
is observed in dolomite (Friedman, 1959). Siderite, on the other hand, is stained
brown (Warne, 1962). According to Taylor (1948), the tone of darkness of the color
depends on the amount of ferrous iron.
V. 1 - Benzidine test
This is based on the determination of Mn in solutions (B.D.H., 1946; Warne,
1962).
Solution. It is obtained by adding and mixing 2 gr of pure benzidine
(NH2.C6H4.C6 H4.NH2) into 100 ml of distilled water containing 1 ml 10N of HCl.
Test. Specimen is immersed in diluted sodium hydroxide solution (1-3 %
NaOH) for about 1.5 minutes. After airing for approximately 1,5 minutes, it is colored
with benzidine solution.

Result. Rhodochrosite acquires a blue color, while no color change is

observed in dolomite.
CONCLUSIONS
The identifications of some of the carbonate minerals becomes fairly easy timesaving,
when the simple chemical staining tests described above are used. Some of
these tests can be carried out in a small laboratory set up near a drilling operation,
which would facilitate the study of core specimens and small fragmentary chips of
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 145

boreholes. Also, some of the more easily preparable and relatively stable solutions can
be easily carried by the field geologist in strong bottles. Simple tests carried out in the
field may enable the field geologist to recognize his lithological boundaries or important
marker horizons in sedimentaryespecially carbonateareas. Thus, the geologist may
have some idea about the lithological and mineralogical details on his maps and
sections, even before final chemical analyses and sedimentary petrographic determinations
are concluded.
ACKNOWLEDGEMENTS

I would like to express my deep gratitute to Dr.J.E. Hemingway of the

Geology Department, University of Newcastle upon Tyne, and to post-graduate
students T.M. Chowns, B. Waugh and to Mr. Tuncay Kine of the Geology Department,
University of Durham, for their help and valuable suggestions in the preparation
of this paper. I would also like to thank Dr. Sadrettin Alpan, General Director of the
Mineral Research and Exploration Institute of Turkey, and Dr. Cahit Erentz, Director
of the Geology Department of the same Institute, for providing me with grant to carry
out a post-graduate study in Great Britain and for allowing this paper to be printed.
Manuscript received April 1, 1965

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(1955) : Geological Abstracts, v. 3, no. 2, pp. 126-127.
HOGBERG, E. (1950) : Staining methods for examination of carbonate rocks in the field. Geol. Foren.i.
Stockholm Forh., v. 72, pp. 348-358.
HOLMES, A. (1921) : Petrographic methods and calculations. Thomas Murby Comp., London.
HUEGI, Th (1945) : Gesteinbildend wichtige Karbonate und deren Nachweis mittels Farbmethoden.
Schweizerische Mineralog. und Petrographische Mitteilungen, v. 25, pp. 114-140.

IVES (1955) : Evaluation of acid etching of limestone. Kansas Geol. Sur. Bull. 114, pt. 1.
JIROVA, D. (1956) : Modifications of CaCO3 in the shells of Foraminifera. Casopis mineral, geol, v.l,
pp. 101-104.
KELLER, W. D. & MOORE, G.E. (1937) : Staining drill cuttings for calcite-dolomite differentiation.
Am. Assoc. Pet Geol. Bull., v. 21, pp. 949, 951.
KIRCHBERG, H. (1940) : Die Bestimmung des Ankerites in Spateisenerzen. Berg- und Huettenmannische
Monatshefte, v. 88, pp. 73-77.
(1941) : ber Feinbauuntersuchungen an Eisenerzen. Metal und Erz, v. 38, pp. 361-365.
KRAUS, HUNT & RAMSDELL (1951) : Mineralogy. McGraw-Hill Book Comp., pp. 225-226.
KRECH (1909) ; Jahrbuch der kniglichen preussischen geologischen Landesanstalt, I, p. 68.
LEMBERG. J. (1887) : Zur mikrochemischen Untersuchung von Calcit, Dolomit und Predazzit. Zeitschrift
der deutschen geologischen Gesellschaft, v. 39, pp. 489-492.
(1888) : Zur mikrochemischen Untersuchung von Calcit, Dolomit und Predazzit. Zeitschrift der
deutschen geologischen Gesellschaft, v. 40, pp. 357-359.
(1892) : Zur microchemischen Untersuchung einiger Minerale. Zeitschrift der deutschen geologisihen
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LEITMEIER, H. & FEIGL, F. (1930) : Der Nachweis von Magnesium in Mineralien. Tscherm. Min.
Petr. Mitt., v. 40, pp 325-334.
LEROY, L.W. (1950) : Stain analysis : Subsurface geologic methods. Colorado School of Mines, Golden,
Colo., pp. 193-199.
MAHLER, O. (1906) : ber das chemische Verhalten von Dolomit und Kalkspath. Freiburg.
MANN, V.I. (1955) : A spot test for dolomitic limestones. Journal of Sedimentary Petrology, v. 25, pp.
58-59.
MEIGEN, W. (1901) : Eine einfach Rraktion zur Unterscheidung von Aragonit und Kalkspath. Centralb.
fur Min. Geol. und Paldont., pp. 577-578.
RAMSDEN, R.M. (1954) : A colour test for distinguishing limestone and dolomite. Journal of Sedimentary
Petrology, v. 24, p. 282.
RODGERS, J. (1940) : Distinction between calcite and dolomite on polished surfaces. American Journal
of Science, v. 238, pp. 788-798.
RUDI, D. I. (1954) : Method for investigating (research) the composition of carbonate rocks by means
of stains. Miner. Sbornik Lvov Geol. Soc., no. 8, pp, 295-296.
SPANGENBERG, K. (1913) : Die kunstliche Darstellung des Dolomites. Zeitschrift fr Krystall. u. Min.,
v. 52, pp. 529-567.
STEIDTMANN, E. (1917) : Origin of dolomite as disclosed by stains and other methods. Geol. Soc. Am.
Bull, v. 28, pp. 431-450.
TAYLOR, J. H. (1949; : Petrology of the Sand Ironstone formation. Mem. Geol. Survey Great Britain,
VI, p. III.
CHEMICAL STAINING METHODS OF CARBONATE MINERALS 147
TOGARI, K. & TOGARI, S. (1955) : Conditions controlling the crystal form of calcium carbonate
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TWENHOFEL, W.H. & TYLER, S.A. (1941) : Methods of study of sediments. McGraw-Hill Book
Comp., London, pp. 128-131.
VOGEL, A.I. (1945) : A textbook of qualitative analysis including semimicro qualitative analysis: III.
Edition. Longmans-Green and Comp., London, p. 578.
WARNE, S. St.J. (1962) : A quick field or laboratory staining scheme for the differentiation of the major
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WELCHER, F. J. (1948) : Organic analytical reagents. D. Van Nostrand Comp., v. 4, p. 624.
WILLIAMS, TURNER & GILBERT (1954) : Petrography. Freeman Comp., pp. 335-337.
WOLF, K.H. & WARNE, S. St.J. (1960) : Remarks on the application of Friedman's staining methods.
Journal of Sedimentary Petrology, v. 30, pp. 496-497.

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Some of them are restricted difficult to obtain. (A good relationship with a high
school or college chemistry instructor helps there.) They really need to be lab grade.
Industrial grade hydrochloric acid (aka mureatic acid) might be fine for cleaning
specimens. But it is not a testing lab chemical. Ditto the sulfuric acid that is used in
car batteries. And other industrial chemicals that arent lab grade. You substitute such
inferior chemicals at the risk of screwing up tests. If you stick to lab grade chemicals,
youll be able to trust the results with a much higher degree of confidence. Honest!
Most of what you will need is available from chemical supply houses. If you do not
live in an urban area where one of these is handy, some pharmacies will order things
for you though not restricted chemicals. Again, a local chemistry instructor is your
best bet for those. Get to know one, gain their respect - and their understanding of
what you are doing. They can help you in a lot of ways safety, chemicals and
labware, protocols and procedures, and tests that might not get mentioned here. (I
cant think of a good reason NOT to strike up a relationship with a chemistry
instructor if you want to get into the chemical testing of minerals Even if the
nearest school is an hour away.)
A BASIC APPROACH TO TESTING
Think small! It doesnt take a beaker full of HCl to dissolve a tiny pinch of powdered
mineral. And you dont need a pound or two of powdered mineral to do the testing.
Work in small batches pinches of powders and drops of liquids. Work in the flat
glass dish under your microscope, placing the powders and liquids on a glass
microscope slide (those with depressions ground in them work best keeping the
drops where you put them) for ease of cleanup and positioning, and use the scope to
observe reactions. While not all tests require this, most can be done this way. Even

when you dont work under the scope, thinking small is still a good idea minimal
amounts in the bottom of a test tube. Its cheaper, it should be safer, and it should be
easier to mix the solutions youll need get the strengths youll need. Besides, with a
lot of mineral testing you probably wont have much pure mystery mineral to work
with. Maybe just a tiny crystal or two tweezed off its matrix. If you start out learning
to work in small amounts, you wont get caught short when you run into this situation
which will be quite often.
Be methodical. And take notes. Working helter-skelter gets helter-skelter results. And
often a miss instead of a hit. And if you dont take notes you may not remember
exactly what you did to get the results you got good or bad. Its nice to be able to
repeat the good tests avoid the bad ones. Notes help guide you in that direction.
Keep them to refer back to the next time you test something. It might be a year
between doing certain tests for certain things and those notes will be worth their
weight in gold as reminders.
There are basically two broad categories into which tests fall: Qualitative and
quantitative. Qualitative tests tell you whether or not a certain element, radical, or
compound is present in your mystery mineral. Quantitative tests tell you how much of
that constituent is present weight percents or mole percents of various elements or
oxides of elements, etc. Quantitative tests are rather tricky or at least reliable ones
are. They are advanced mineral chemistry. Well stick to qualitative tests for this
basic introduction to home lab work, with maybe some hints on rough quantitative
measurements now and then. Youre interested in seeing what the mystery mineral
contains, not how much of it or how pure the sample is. At least that should be the
focus when you start out. Any quantitative hints that get discussed will serve to point
out that there is that next level of chemistry available when you feel up to moving
on.
In qualitative testing the goal is to find out whether or not certain constituents are in the mystery
mineral. If you suspect a calcium-bearing mineral, you test to see if there really is calcium present.
And so on. Most of the tests well discuss here are of that type. Is it or isnt it present? Negative
results are as important as positive ones. They tell you what isnt present. So you can move on to find
out what is.
METHODOLOGY & THOROUGHNESS
You dont need a home lab to identify minerals that can be identified from gross
physical features such as quartz, kyanite, and muscovite (usually) Save the lab
work for stuff that is defying identification by simpler means. Except its not a bad
idea to experiment on knowns see if you can prove a pyrite sample is pyrite by
chemical testing. Same with other species you are familiar with. The practice will
familiarize you with testing procedures, give you experience working with the

chemicals, and give you some confidence once you get things worked out and are
proving the samples are what you know they are. But, by-and-large, save the lab
work for the tough ones.
As stated in the previous post, lab tests are all about finding out whats in your
mystery mineral(s). You narrow down the possibilities to two or a few species, and
then you say Okay now what are the chemical differences between these species
that I can test for to figure out which I have? Lets take a simple example: You have
a sample that youve narrowed down to being one of the following species: calcite,
magnesite, siderite, or smithsonite. Normally, figuring out the specific gravity of the
mineral would tell you which you have but your sample is small crystals, nothing
big enough for you to work with on the triple beam balance (or whatever you use to
do S.G. tests.) So you look these species up and find that calcite is CaCO3, magnesite
is MgCO3, siderite is FeCO3, and smithsonite is ZnCO3. The only difference between
these species is their metallic ion: Ca, Mg, Fe and Zn. So the way to find out which
species you have is to test for those ions find out which is present. You therefore
need a chemical test that will identify Ca, another that will identify Mg, and so on
A simple chemical test for Ca is to dissolve a pinch of the powdered sample in a drop
or two of hydrochloric acid (HCl) and then add sodium sulfate (Na2SO4) to the
solution. If you get a white precipitate (its CaSO4) there is Ca in the sample. Its
probably calcite. BUT a single test is not conclusive. Any of these minerals may
have Ca in them in small amounts as a substitution for the principal metallic ion.
(We get the ideal formulas fed to us in books not actual formulas.) So you
would still need to test further. You can test for Mg by dissolving a pinch of the
powdered mineral in HCl and adding several drops of a strong solution of ammonia to
it. Then add a bit of Na2HPO4.12H2O to the solution. If you get a white precipitate
(its NH4MgPO4) then there is Mg in the sample. To test for Fe you could use any of
several test. One simple one is to dissolve a pinch of the powdered sample in a drop or
two of HCl and then add several drops of ammonia hydroxide (NH4OH) solution to it
to make it alkaline. If you get a tannish to white precipitate (its Fe(OH)3 ) then there
is Fe in the sample. Then, for Zn, dissolve a pinch of powdered sample in HCl and
add sodium disulfide (Na2S) solution if you get a white precipitate (its ZnS) theres
Zn in the sample.
As you do each test, observe the volume of precipitate formed keep adding the
reagent to the solution (in tiny amounts) until no more reaction is taking place, no
more precipitate forming. (If you keep the slides (or test tubes) of each solution lined
up on the table, when all the tests are done you can compare the solutions with one
another directly if necessary.) Note any negative results such as no Mg found. Those
eliminate species from your list of likely suspects. Lets say you got negatives for
Ca and Mg, positives for Fe and Zn. But the Zn test barely showed a trace, while the
Fe test showed the sample is loaded with Fe. Youre mystery mineral is no longer a

mystery its siderite with a little bit of Zn substituting for the Fe. Actual formula:
(Fe,Zn)CO3. Ideal formula: FeCO3. [And here weve looked at rough quantitative
testing: How much? As opposed to Is it there?]
Aha! Someone says. But how do you know it is an iron *carbonate*? not a
sulfate or something else? Well I said youd already decided it had to be on of the
carbonates named. And you probably did that be testing a sample or two with HCl to
see if it fizzed. And it did Which is another chemical test a simple test for CO2
(which is what comes bubbling out of a solution of carbonate mineral and acid.) See
you already knew one chemical test and didnt even realize it! If you didnt do that
test, and decided it must be one of those carbonates by other means, then that test
needs to be done to prove your guess is correct. Because without knowing for sure
that the mineral is a carbonate, it may well be something else, like a sulfate. (Actually,
if you think about it, you proved the mineral to be a carbonate as you dissolved the
powder in acid because it bubbled as it dissolved PS: The sulfates of Fe, Mg and
Zn are readily soluble in acids and likely to stay dissolved not precipitate out of
solution. Another reason youd know the mineral was a carbonate not a sulfate - in
the above scenario.)
You have to test for EACH of the suspected constituents in a mineral not just one.
Which can be tricky if you only have a little bit of powdered mineral to work with and
need to do a bunch of tests. Here the minimalist approach I recommend becomes
critical else you may not be able to do all the tests needed. It is always a good idea
to figure out how many tests you are going to need to do and then divide up the
available mineral powder solution into that many batches. In some cases this may
mean that all you have to work with are a drop or two of solution for each test. A
micro-eyedropper is handy for working with tiny amounts of solutions and youll
probably need to work under the microscope in order to see the reactions in the tiny
drops of solutions you have. But it can be done. You can also divide up the mineral
powder into tiny piles ahead of time and then make the solutions you need from
them. This is handy if you need different powder solutions for different tests. But it
can be tough to do with tiny quantities of powder possibly ending up with just a few
grains of powder to make solutions from.
Of course not all tests are as simple as the series described above. Or all results as
certain as our hypothetical case. I picked an easy one to illustrate the methodology.
And to point out that you cant just test for one thing and if its positive say
Voila! You cant. You have to take other possibilities besides your prime suspect
into consideration. In the above case, if youd just tested for Zn you would have
falsely concluded the mineral was smithsonite Chemical testing is about proving
your case beyond a reasonable doubt. Any single test is more than likely to leave
plenty of room for doubt. Conclusive results come from being thorough testing for

all possible culprits and finding out which you have, and which is the most likely
prime candidate based on comparisons.
LAB PROCEDURES & TIPS
MAKING SOLUTIONS
Nearly all of the tests require that you first dissolve some of the powdered mystery
mineral to make a solution that is then used for testing. This can be a problem in itself:
What do you use to dissolve the powder? (And here we are talking about *dissolving*
the powder not just mixing it in liquid. In a mixture, the powder is not dissolved,
just stirred in and floating around. In a solution the powder has been dissolved
broken up into its constituent ions.)
Only a few minerals are soluble in water mostly halides and iodides. (Which can be
a quick test to see if you have one of those species.) But the odds are that your powder
wont dissolve in water youll have to try something else. Try hydrochloric acid
(HCl) first. A great many minerals will dissolve in HCl. If that doesnt work, try nitric
acid (HNO3). If that doesnt work, try sulfuric acid (H2SO4) last. If that doesnt work
the odds are your mystery mineral is a silicate, few of which will dissolve in acids.
Zeolites do, and a few others, but by-and-large silicates are insoluble in anything short
of hydrofluoric acid (HF) and thats one acid you cant play with at home. (Its
extremely dangerous and requires special lab equipment including a negative
pressure ventilation hood to work with safely.) If you run through the list of acids
you can use at home and still cant get the powder to dissolve, youve pretty much
determined the mineral is a silicate and probably not a Zeolite. Important
information in itself.
A few other acids are also used in making solutions, such as acetic and oxalic. But
these are rather weak acids, comparatively speaking (they can still be strong, for
them, and are dangerous.) They are usually not used unless a specific test calls for
them. And if a test does call for one and you cant get the powdered mineral to
dissolve in it, the odds are the mineral is not what you think it is and are testing for:
You can scratch that possibility and move on to other tests.
ACIDITY vs ALKALINITY
Quite a few of the tests require you to start with an acid solution and then make it alkaline by adding
a base, such as ammonium hydroxide (NH4OH). In some cases you simply overload the solution
with the base to get it there. In others you need to work carefully to make the solution just slightly
alkaline.
You use litmus paper for checking the pH of solutions. But since you are working
with such small quantities of liquids, you dont want to just stick the tip of the test

strip in the solution it might wick up your entire batch of liquid! Instead, dip a small
diameter (approx. 2.5 mm) glass rod in the solution and then touch the wetted end of it
to a fresh spot on the litmus paper. The wetted spot on the paper will then tell you
where things stand alkalinity wise.
Also, sometimes (though rarely) you need a neutral solution pH of 7. Which can be tricky to
achieve. You pretty much need to use a micro-eyedropper to slowly add the base and drop by drop
neutralize the acid, testing your solution with a glass rod and litmus paper after each drop has been
added and stopping the first time the litmus paper doesnt turn color.
MAKING A MICRO-EYEDROPPER
You can buy eyedroppers with small diameter ends if you have a good chemical
supply house in your area. But otherwise they can be hard to come by and they
arent really micro eyedroppers. So you might want to try and make your own. Take
an 8 inch length of glass tubing about the same diameter as a typical medicine
eyedropper. Heat the center of it over a propane torch flame until its soft. Then
remove it from the flame and pull on both ends so the middle stretches out. Snap the
middle so there is a roughly 3 inch long thin capillary tube coming off the end of the
unstretched part of the tube. Once the glass has cooled, then heat the wide end of the
tube until its soft and flare it slightly with the tang of a file so it looks roughly like
the top end of a regular medicine dropper. After it cools again, fit the flared end with a
medicine dropper bulb.
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5. PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

23

SAMPLE PREPARATION TECHNIQUES IN

PETROGRAPHIC
EXAMINATIONS OF CONSTRUCTION MATERIALS:
A STATE-OF-THE-ART REVIEW1
Dipayan Jana
President, Petrographer, Construction Materials Consultants, Inc. Greensburg,
PA, USA.
ABSTRACT
Appropriate preparation of a sample is an important step in petrographic
examination.
Over-preparation, inadequate preparation, or inappropriate preparation can
reduce or destroy
important information, or may provide wrong information. A state-of-the-art
review of various
sample preparation techniques for light and electron microscopy is provided.
Techniques described
are: cleaning, fresh fracturing, oil-immersion mount preparation,
encapsulation, vacuum
impregnation, sectioning, lapping, grinding, polishing, etching, staining, thin
sectioning,
fluorescent thin section preparation, half section preparation, staining
techniques for rapid
identification of alkali-silica reaction gel, sample preparation for air-void
analysis of hardened
concrete by conventional and image analyses methods, conductive coating
for examination in
SEM, ultra-thin-sectioning, sample preparation for x-ray diffraction, and a few
modern techniques
such as cryo-SEM, ESEM, and x-ray microscopy.
KEYWORDS: Petrography, Sample Preparation, Sectioning, Grinding,
Polishing, and
Microscopy.
INTRODUCTION
Petrography (Greek petra - rock, graphic - picture) is the 150-year-old
discipline of
geology that deals with the description and classification of terrestrial
(igneous, sedimentary, and
metamorphic) and extraterrestrial (e.g., lunar, meteoritic) rocks including the
made-made rock
(concrete), and various construction materials manufactured by using natural
materials.
Petrography encompasses microscopical examinations at the nucleus and
various supplementary

chemical and physical testing needed for detailed description (type,

composition, texture,
mineralogy, and microstructure) and classification of rocks. Since the midnineteenth century,
petrography has been applied in the analyses of various construction
materials for their
characterization, quality assurance, and failure investigation.
This article provides a concise and yet comprehensive review of various
sample
preparation techniques practiced in petrographic examinations of
construction materials. Detailed
descriptions of individual techniques, however, are beyond of scope of this
article and can be
Dedicated to late Wase U. Ahmed for his significant contributions in sample preparation techniques
for almost four decades.
1

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found elsewhere e.g., Hutchinson [1], St. John et al. [2], Ahmed [3-6], ASTM
standards C 295, C
457, C 856, and C 1324 [7-10], French [11], Mielenz [12, 13], Walker [14],
Campbell [15],
Detwiler et al. [16], and Buehler Sum-Met [17]. The present review is mainly
adapted from these
above references, along with the authors own experience on various sample
preparation tips, and
several manufacturers product literature.
MATERIALS AND SAMPLING
Petrography, as the name implies, is a pictorial-based descriptive science
that follows the
principle that a picture is worth a thousand words. Petrography: (a) provides
detailed
compositional, textural, mineralogical, and microstructural properties of a
material including its
detailed characterization and quality assurance, and (b) diagnoses evidences
and causes of
improper behavior, poor performance, or failure to provide satisfactory
performance. Since
photographs provide an excellent documentation of the appearance and
condition of a material,
samples received for petrographic examinations should first be adequately
photographed,
described in detail, and properly documented prior to the subsequent
destructive sample
preparations steps for microscopical examinations. Samples, as received,
should be adequately
representative of the material in question and for the purpose of the
examination. Locations of

the samples in the field should be adequately photographed (or recorded

with a video camera)
and provided with the samples.
The sampling strategy should depend on the type of the material and the
purpose of the
examination. If is it for quality assurance, or simply for materials
characterization, any suitable
size, number, or amount representative of the material is appropriate. If it is
for failure
investigation of a structure, sampling should be done after thorough
documentation of the
location and extent of deterioration. Depending on the circumstances,
samples could come from
the deteriorated areas alone (e.g., during investigation of chemical, fire, or
frost attacks in
concrete), or from both deteriorated and relatively sound areas for
comparative examinations
(e.g., during investigation of scaling, cracking, and other surface distress). A
thorough field
investigation is helpful not only to visualize the overall condition in place, but
also to locate the
deteriorated areas, mark the locations for sampling from the sound and
deteriorated areas,
document the environmental conditions, and observe the extent and severity
of the deterioration.
Construction materials amenable to petrographic examinations include: (a)
whole or
crushed clinker samples and raw feeds; (b) pozzolanic and cementitious
materials including lime,
gypsum, portland cement, blended cement, high alumina cement, expansive
cement, masonry
cement, fly ash, slag, silica fume, metakaolin, natural pozzolan, dry prepackaged cementitious
materials; (c) natural sand, gravel, crushed stone, lightweight, heavyweight,
and other synthetic
or manufactured aggregates; (d) portland cement based hardened concrete,
mortar, grout, and
plaster; (e) high alumina cement based products; (f) carbon, steel, glass, and
organic fibers used
in concrete; (g) clay, stone, or concrete masonry units and various masonry
mortars (lime mortar,
portland cement lime mortar, and masonry cement mortar); (h) lime and
gypsum based products;
(i) natural stone, dimension stone, and cast stone; (j) ceramic or vinyl tiles
and various other

resilient floor coverings and gypsum or portland cement based floor

underlayments, and (k)
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regolith, soils, and other subbase materials. Due to the opaque, nontransparent nature, asphaltic
materials (except aggregates in asphaltic concrete) have limited applications
in petrography.
A subset of the laboratory sample selected for a specific sample preparation
(e.g.,
grinding, polishing, or thin sectioning) must be representative of the entire
sample to be
examined. Following is a brief description of field sampling strategies for
various materials.
Clinker - In clinker microscopy, various authors practice different sampling
preferences
(e.g., see Campbell [15] for details). Usually, a representative amount is
collected at regular
intervals from the kiln during clinker production, mixed, quartered down to
smaller size,
sometimes crushed, and used for sample preparation. A grab sample is
preferable to composite
samples. Various sample preparation steps including sectioning, grinding,
polishing, staining,
etching, thin sectioning, and half sectioning described in this article are
common in the
microscopy of clinkers and raw feeds.
Cement - For lime, gypsum, portland cement, blended cement, high alumina
cement,
pozzolans, and other special cementitious materials, a representative
amount is selected from the
lot to be analyzed, which upon further quartering is reduced down to a
manageable amount for
appropriate sample preparation. Various modes of petrographic examinations
of cements and
pozzolans include: (a) immersion of a small amount transferred by a needle
to a refractive index
oil on a clean glass slide for examination of individual grains in a
petrographic microscope (oilimmersion
mounts), (b) a small amount of grains sprayed on an epoxy-coated frosted
glass slide
for grain thin section examination in a petrographic microscope, (c)
approximately 10 grams of
the representative sample is encapsulated with epoxy as a binder in a
castable mold to be used

for thin sectioning and examination in a petrographic microscope, (d)

polished sectioning for
scanning electron microscopical work, and (e) a small amount of bulk sample
(~10 grams)
selected by quartering for x-ray diffraction or chemical analysis.
Aggregate - ASTM C 295 recommends various methods of field sampling of
aggregates,
such as: (a) drilled cores from undeveloped quarries, (b) 100 pounds or 300
pieces (whichever is
larger) of each size of crushed stone from operating quarries and operating
sand and gravel
deposits with stock piles of materials produced, (c) at least 4 pounds of
material (each piece is
greater than 1 pound) from each stratum or bed or a drilled core from the
exposed faces of nonproducing
quarries where stock piles are not available; and (d) at least 50 to 400
pounds (amount
should increase with sieve size) of material from test pits dug in undeveloped
gravel and sand
deposits. During petrographic examinations of crushed stone, natural gravel,
and sand, at least
150 particles of each sieve fraction should be examined microscopically.
Various modes of
aggregate examination are: (a) sieve analysis of a representative portion
selected by coning and
quartering of the total amount received (the amount selected should provide
at least 150 particles
in each sieve); (b) examinations of hand specimen, fresh fracture, and
lapped sections of grains
in core samples or in each sieve fraction of aggregates in a low-power
stereomicroscope; (c)
examinations of oil-immersion mount, ground section, thin sections, and
grain thin sections in a
petrographic microscope; and (d) x-ray diffraction.
Concrete - For hardened concrete, either drilled cores or sawn sections are
commonly
collected. Detailed coring techniques are described in the US Department of
Interior Concrete
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Manual [18]. Strategies of condition survey and sampling concrete in the
field are described in
ACI Committee 201[19], ASTM C 823 [20], and C 856 [9]. Water-cooled
diamond-bit coring
using a 1-in. to as large as 12-in. diameter drill bit is common for
petrographic sampling in the

field; a larger diameter drill is preferable for obtaining a cracked, fragmented

or disintegrated
concrete. Dry cut diamond or tungsten carbide bits, though generate
considerable heat during
drilling due to the lack of cooling, is sometimes preferred where leaching of
concrete by cooling
water is unacceptable (e.g., for chloride analysis). The diameter of the core
should be at least
three times the nominal maximum size of the aggregate. The length or depth
should be adequate
to include all the layers of interest including the crucial exposed (sometimes
altered) layer, the
near-surface transitional zone, and the interior bulk concrete. A 3-in. (75
mm), or preferably 4in. (100 mm) diameter core is most common. For deteriorated concrete or
mass concrete
containing larger aggregates, larger diameter cores are preferred for better
recovery and
representation (possible damage to reinforcing steels during drilling,
however, may restrict the
core diameter). Sometimes, a rebar-location (pachometer) survey is done in
a heavily reinforced
concrete to detect the locations of steel in concrete and avoid them during
drilling. Rigid
clamping of the drilling machine to the concrete surface provides a good core
with minimum
damage. Wet drilling, use of a good drill bit, less vibration of the bit during
drilling, the in-situ
condition of the sample that is being drilled - all these factors control the
ultimate condition of
the core recovered.
The number of samples should be adequate and representative of the field
conditions.
ASTM C 856 states, the minimum number of samples should amount to at
least one core for
each mixture or condition or category of concrete. If a particular type of
deterioration is
observed in the field (e.g., cracking, scaling, surface delamination,
efflorescence, alkali-silica
reaction gel exudation, corrosion, staining, chemical attack, etc.), at least
one to three cores
should be taken from each of the severely deteriorated, moderately
deteriorated, and sound areas
for a comparative study. Loose, broken, spalled samples from around the
structure, which is

exposed to prolonged and considerable atmospheric weathering to mask or

complicate the
original in-situ deterioration of concrete should be avoided unless they
provide any specific
information (e.g., loose scales on a scaled concrete slab, or efflorescence
deposits on the old
concrete surface). Concrete debris, collected in a coring locale may retain
deposits washed away
by the drilling and could be used for microcopy, x-ray diffraction, or chemical
analysis.
Masonry - For masonry units, at least one full size unit or multiple units
encompassing all
the features of interest should be collected. For mortar sampling, multiple
pieces are needed
from the exposed face and the interior of the masonry joints from several
locations. Mortar
samples from bed and head joints should be carefully collected by: (a) using
a hammer and chisel
(without breaking the adjacent masonry units), (b) carefully sectioning along
the interface
between the mortar and masonry units with a hand-held dry or wet masonry
saw, or (c) drilling a
1 to 3 in. diameter core including the head and/or bed joint mortar and
adjacent masonry units
through the wall. Sometimes an entire panel (e.g., of 1 ft2 size) is saw cut
from the wall for
investigation of masonry units, jointing mortars, and mortar-masonry unit
interfacial bonds. Dry
drilling of mortar joints using a tungsten carbide tipped masonry drill collects
dry powders useful
for chemical analysis and x-ray diffraction. Efflorescence deposits on a
masonry wall are
carefully brushed or scraped off to a piece of paper and then transferred to a
sealed ziploc bag.
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Plaster and Gypsum products - For plaster, stone, tile, and floor
underlayments, single or
more preferably, multiple representative samples should be collected and
the petrographer should
choose appropriate pieces for sample preparation and subsequent laboratory
examinations.
Gypsum based plaster or floor underlayments should be collected in dry
conditions and handled
carefully. Portland cement plaster products (stucco), shotcrete, and
swimming pool plasters are

examined by the conventional methods of sample preparation described

here.
Stone and Tile Products Natural or dimension stones and samples from
stone cladding
are prepared by conventional petrographic techniques of thin sectioning and
other methods
practiced in geology. Efflorescence deposits on stone surface are examined
by oil immersion
mount, x-ray diffraction, and SEM. Stone, ceramic, quarry, or vinyl tile
products and the
associated underlying setting bed mortar, adhesive, and adjacent jointing
mortars or grouts are
examined in as received condition in a stereomicroscope, and in lapped
section and thin section
for detailed microscopical study.
The amount and selection of samples is a matter of judgment, which is based
on the scale
of the examination, the nature of the sample, field conditions, the depth and
extent of
deterioration or of the concerned area, experience, and the project budget.
Surface Area to be Examined - The sample surface area of examination
required for
adequate characterization of a constituent increases significantly with the
size of the constituent
of interest. For example, a representative section necessary for adequate
characterization of
aggregates in a concrete is significantly larger than the usual area required
for air void
characterization (e.g., at least 77 cm.2 for characterizing < 1mm size air
voids in a concrete
containing 25 mm size aggregate). The area of examination in a scanning
electron microscope is
significantly less than that covered in a light optical microscope; therefore,
information obtained
from electron microscopy should be carefully interpreted to assure proper
representation of the
entire area of study. For example, a set of 10 usual SEM micrographs taken in
various places on
a 1 sq. cm. area of a cement paste sample surface at a 10,000X provides a
sampling of only
0.001% of the surface of that specimen; in a heterogeneous sample as
concrete, such a limited
sampling may question proper representation of the overall microstructure
(Diamond [21]). A
small 27 47 mm thin section may be adequate for characterization of
cement, ground clinker,

sand, or plaster of homogeneous composition but multiple large area thin

sections (each at least
50 75 mm in size) are sometime necessary for better characterization of a
heterogeneous
material such as a deteriorated concrete. The size of the component of
interest and the degree of
homogeneity of the material both determine the area of examination.
Samples collected in the field should be properly located, labeled, its field
orientation
should be marked, and the sample should be wrapped in plastic bags or
carefully protected to
preserve the on site moisture and other conditions. Information about the
location of the sample
in the structure and photographs of the field condition should also be
supplied. Spalled,
weathered, or broken chunks, scales, or small pieces of concrete laying
around the structure
should either be avoided or should be carefully considered as they may
provide only limited
information; after dislodgement from the structure loose pieces may have
been subjected to
weathering and mechanical disintegration, which can erase or alter any insitu evidence of actual
deterioration in the structure. In many cases, a thorough field investigation
directly by the
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petrographer provides many valuable information about the condition of
concrete in the field,
structural integrity, locations, severity and extent of deterioration, and may
even the cause(s) of
failure or poor performance.
A detailed communication between the petrographer and the
engineer/architect about the
project background and service history is necessary. A field survey,
examinations of field
photographs, review of the results of previous testing, and information about
the original mix
design(s) are helpful to determine the total number and locations of
representative samples to be
taken for examination. Adequate communications between client and
petrographer should
ensure that: (a) the samples selected for petrographic examinations are
representative of the
structural unit and field conditions, (b) sample locations were carefully
selected considering the

variations in structural units, environmental conditions, extent and intensity

of damage, and any
variation in the type of concretes, and (c) adequate samples are provided for
obtaining sufficient
data for a reasonable interpretation. Without these preliminary requirements,
and without
adequate and proper sampling, the data obtained, the interpretation, and
conclusion drawn from
petrographic examination can be inadequate, and even highly misleading.
PRELIMINARY EXAMINATIONS
Since any sample preparation is essentially a destructive procedure,
information
susceptible to damage or alteration during sample preparation should be
recorded prior to any
such step. The sample should be adequately photographed in as-received
condition, logged-in,
and detailed preliminary investigation should be made including:
Background information of the project (client name and address; project
name, number, and
location; date of sampling; geographic location of the structure; sample
location in the
structure; detailed photographs of field condition including the sample
location; sampling
procedure; drawing showing sample locations, field and environmental
conditions at the
sample locations, mix design, weather conditions during concrete or masonry
placement and
subsequent periods, age of the structure; service history, results of other
tests performed on
the sample or on other samples from the project; nature and extent of
deterioration, when
was it first noticed, and any other information that may seem relevant).
Dimensions, integrity, appearance, condition (a broken piece or total
number of pieces, core,
saw-cut section, powdery, dusty, fragile, hard, intact, etc.) of the material
including any
unusual features.
Nature of the exposed surfaces and any surface deposits on the samples
from the field.
Nature of the fresh fractured interior surface of solid material.
Size, location, and condition of embedding materials (steel or fiber
reinforcement).
Size, location, and distribution of voids, cracks, joints, sealants, etc.
Properties of basic ingredients (such as aggregate, paste, and air in
concrete)
Signs of chemical and physical deterioration.

 Variations in materials or properties in the sample.

Nature of interfaces between multiple layers in a composite sample.
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Petrographer should observe the sample as thoroughly as possible and
gather sufficient
information regarding the condition of sample in terms of its integrity,
composition, fabric, and
imprints of any external or internal deterioration processes in the field.
Preliminary laboratory
examinations should be made visually, with the help of a hand (magnifying)
lens, and with a low
power stereomicroscope.
During the visual and low-power stereomicroscopical examinations, multiple
sample
photographs should be taken by using a 35-mm color camera, or a digital
camera with at least 3mega pixel resolutions, and a flatbed scanner. Preliminary examinations
should determine the
areas of interest in the samples and mark locations for subsequent sample
preparation steps.
SAMPLE PREPARATION TECHNIQUES
The primary purpose of sample preparation is to reveal the in-situ
microstructure and
composition of the sample. Care must be exercised in all preparation stages
to avoid any loss or
alteration of the original composition and microstructure. Appropriate sample
preparation
techniques are, therefore, crucial for obtaining maximum and accurate
information. Ability to
observe various minute details in the microstructure depends strongly upon
the sample
preparation procedures. Inadequate preparation may not reveal the details
clearly whereas overpreparation
may lose much of the in-situ information, which is almost always crucial for
interpretation; both can introduce preparation-artifacts that are not related
to the original material
or problem. Depending on the nature and condition of a sample, various
preparation methods
such as epoxy impregnation, sectioning, grinding, polishing, staining,
etching, thin sectioning,
coating, pulverizing, etc. are followed. Brief descriptions of these procedures,
mainly from the
references mentioned in the introduction, are given below.
(1) Cleaning

Cleaning of a hardened concrete core in running tap water removes the dust,
dirt, and
muddy coating of drilling dust that are sometimes present on the cylindrical
surface due to wet
drilling. Such cleaning can highlight: (a) the pristine condition of the sample
after removing the
artifacts from coring; (b) the type of aggregates and their grading and
distribution; (b) large
voids, cracks, joints, and reinforcements; (c) variation in color, density, water
absorption, and
other properties through depth or in a single location in the sample, which
can indicate variation
in the concrete composition; and (d) different layers in a composite core.
Wetting is sometimes
helpful to highlight many fine or wide cracks in a concrete core; cracks
become prominent
during differential drying of concrete between the cracked and uncracked
portions. Exudations
of white alkali-silica reaction gel through the cracks are sometimes distinct
when a core dries out
from its moist condition and contains alkali-silica reactive aggregates. Drying
after cleaning of
concrete and masonry units sometimes reveals soft, white, powdery
efflorescence deposits on the
air-dried surface, which can be characterized by examinations of oilimmersion mounts.
Thorough cleaning of a sample is essential within and between various
sample preparations steps
to wash the debris generate in each step (e.g., cleaning in running water or
in ultrasonic cleaner
in between the steps of sectioning, grinding, polishing, thin sectioning). Soft,
fragile, and watersensitive
materials (e.g., clinker, cement, gypsum based materials), however, should
not be
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cleaned in water, for which non-aqueous isopropyl alcohol, acetone (Ahmed,
[3]), 1,1,1,
trichloroethane (Walker [14]), or other non-aqueous media can be used.
Cleaning, however,
should be done carefully, after knowing its effect on the material being
examined, subsequent
possible alterations, and its effects on the interpretation of the
microstructure.
(2) Fresh Fracturing

Obtaining a fresh fracture surface of a small piece of hardened concrete,

mortar, masonry
unit or other solid material by hammering from a larger piece and examining
that fresh exposed
surface at progressively higher magnifications using a hand lens, low-power
reflected-light
microscope stereomicroscope, and scanning electron microscope can reveal
a wealth of
information including: (a) physical, compositional, mineralogical, and textural
properties of
paste; (b) types of aggregates from mineralogy and texture; (c) bond
between aggregates and
paste; (c) corrosion of reinforcing steel and extension of corrosion products
into the paste; (d)
coatings, reaction rims, and weathering rims around aggregates; (e)
secondary deposits in voids
and cracks; (f) depth of carbonation; (g) signs and depth of chemical
alterations in concrete by
atmospheric alterations and weathering; (h) signs and depths of chemical
attacks in a concrete by
migration of deleterious chemicals; (i) air content and air-void system in
concrete, mortar, grout,
and plaster; (j) thickness of different layers in a multi-layered composite
system; (k) selection of
areas of interest to be further examined for compositional analysis by oilimmersion mounts;
etc.
Examination of fresh fracture surfaces of concrete in a stereomicroscope is
an important
mode of examination in concrete petrography, which, with increasing
experience, can provide a
great deal of information. Fresh fracture surfaces provide information about
the condition and
composition of pristine, unaltered interior of a sample, which should be
examined immediately
after fracturing before any extended atmospheric exposure. Fresh fracturing
of an already
cracked concrete, however, may open up the preexisting cracks and may not
provide information
of unaltered interior; many times secondary deposits precipitate in cracks in
an old concrete and
become exposed by fresh fracturing, which, then, could be examined by oilimmersion mount or
SEM.
(3) Immersion Mounts Preparation

Oil-Immersion Mount - Preparation of an oil-immersion mount involves: (a)

observation
of a fresh fracture surface of a sample or of the original sample as received
in a low-power
stereomicroscope; (b) selection of an area of interest (e.g., in hardened
concrete an area of bulk
paste apart from the aggregates, air voids, and carbonated or altered areas;
or a secondary deposit
in an air void in a concrete); (c) collection of a tiny amount of sample from
the area by
scratching the area with a sharp-pointed needle and carefully transferring
that powder onto a
clean glass slide; (d) placing a small cover glass on top of the powder to
prevent loss; (e)
immersing the powder in an oil of known refractive index by applying the oil
along the edges of
the cover glass (oil is drawn under cover glass by capillary action); (f)
spreading the powder
uniformly in the oil and breaking thick, agglomerated portions with a rubber
such as the eraser in
a pencil; (g) observing individual grains in the powder in a petrographic
microscope and
characterizing the composition and mineralogy of the grains from their
relevant optical
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properties including size, shape, relief, color, interference color,
birefringence, refractive index,
extinction angle, pleochroism, and dispersion staining.
Particle mounts on removable resins or on permanent thin epoxy films
Campbell [15]
mentioned examination of fine clinker grains and cement by immersing small
powders on a
molten Hyrax or Meltmount resin (refractive index 1.70) on a glass slide and
placing a cover
glass before the hardening of the resin. Fine particles (74 to 149-m1)
sprinkled on a glass slide
coated with a thin film of epoxy (where only the bases of the particles are
permanently mounted
in the epoxy) can be examined in a series of refractive index oils with
intermediate washings of
the oils and cover glasses by gentle streams of acetone or xylene, and rinse
with isopropyl
alcohol.
Applications - Oil-immersion mounts are helpful for rapid identifications of:
(a) cement

and clinker phases including their relative abundances and various optical
properties; (b) clinker
raw feeds; (c) secondary deposits in concrete; (d) cement hydration
products, residual cement
particles, degree of cement hydration in the paste, and the type of cement
used; (e) fly ash,
ground granulated blast-furnace slag, other pozzolanic and cementitious
materials, and
microfillers in paste; (f) the presence of hydrated lime, portland cement, and
limestone fines in
mortars and from that the types of mortars (i.e., lime mortar, portland
cement-lime mortar,
masonry cement mortar); (g) efflorescence deposits on masonry walls
(calcium and alkali
sulfates, carbonates, and hydrates); (h) lime and gypsum based products,
and various forms of
gypsum (gypsum, alpha hemihydrate, beta hemihydrate, soluble anhydrite,
and insoluble
anhydrite) and lime (calcitic, dolomitic, hydraulic); (i) various potentially
expansive materials
including alkali-silica reaction gel (e.g., ettringite and gypsum in a concrete
exposed to surface
attack; epezite or epizet and brucite in concrete cracked by delayed
hydration of free lime and
magnesia, respectively); (j) types and mineralogy of aggregates; and (k)
depending on the
situation and the depth of the examination, the overall type, composition,
and characterization of
the material, and the cause of deterioration, if any.
(4) Encapsulation and Vacuum Impregnation
Purpose - Encapsulation and/or impregnation of a sample with a resin,
especially if it is
soft, powdery, cracked, brittle, friable, or broken is helpful to: (a) fill the
voids, pores and cracks;
(b) improve the overall integrity and ease of handling; (c) preserve the
original microstructure
and distribution of components and edges in the sample; (d) keep the
detached, de-bonded,
fragmented portions adhered to the rest of the sample; and (e) prepare a
solid mass of the original
fragmented or powdery sample for sectioning, grinding, thin-sectioning, or
polishing.
Encapsulation indicates immersion of the sample within a resin in a mold to
improve the external
integrity of brittle, friable materials and for better handling for subsequent
sampling steps,

whereas impregnation indicates injecting or penetrating a liquid resin into a

porous sample to
improve its internal as well as external integrity. Epoxy-based resins are best
for both
encapsulation and impregnation.
Encapsulation Methods and Resins - Unlike the common compression
mounting method
for encapsulating metallurgical samples at high temperature and pressure in
a press (which uses
1

m = micron = 0.001 millimeter.

PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

32
phenolic or epoxy-based thermosetting resins, or methyl methacrylate-based
thermoplastic
resin), castable mounting method is more common for encapsulating both
metallurgical and
construction materials, where the material is mounted without using a press
in a plastic or metal
mold by using an acrylic or epoxy-based resin and is cured at relatively low
temperatures (except
for the acrylic and some fast-cured epoxy resins, which can generate heat by
exothermic
polymerization reactions as high as the heat generated in the compression
mounting). The term
cold mounting is sometimes used for the castable mounting method due to
the absence of
external heat and pressure for mounting, however, the term cold can be a
misnomer for
mounting heat-sensitive materials in an acrylic resin, or in a fast-curing
epoxy resin, or in a
large-volume epoxy medium, or in an insulating mounting mold - all of which
can generate high
exotherms during resin polymerization.
Acrylic resins: (a) cure quickly, (b) have low cost, (c) are too viscous for
impregnation,
(d) can generate heat in excess of 100C by polymerization, (e) usually do
not bond to the
sample, (f) have classic problems with high shrinkage during cuing, which
creates shrinkage
gaps between the resin and sample, and (g) have poor edge retentions.
Epoxy resins, although more expensive than acrylics, are more commonly
used because:
(a) epoxy will physically adhere to the sample with good bond and eliminate
shrinkage gap, (b)
epoxy will not react with the sample and with other solvents, etchants,
chemicals, and oil

lubricants used in sample preparation, (c) epoxy can be used at room

temperature or at a
temperature of up to 60C and can be cured within 9 hours (the lower the
viscosity of epoxy at
room temperature, the longer its curing time; lowering the viscosity by slight
warming, however,
fastens curing), (d) epoxy is hard enough to produce flat surface during
grinding and polishing,
(e) sets relatively quickly and more so by slight warming, (f) it has a very low
setting shrinkage,
(g) it provides excellent edge retention of samples (especially for
metallurgical samples and thin
sections of concrete including surface features) due to better adherence to
sample and low
shrinkage, and (h) due to low viscosity, epoxy can be drawn into pores and
cracks by vacuum
impregnation. The curing time of epoxy varies from a few minutes to several
hours, depending
on the type of epoxy used and the ambient temperature. A slight warming
can accelerate the
polymeric reactions and shorten the curing time (however, any fast-cure
epoxy will have higher
polymerization exotherms). Castable resins are sensitive to shelf life, which
can be extended by
keeping them in a refrigerator.
Dyes - Different types of dyes or colorants are sometimes mixed with epoxy
to highlight
the cracks, voids, and pore spaces in sample while observing in the planepolarized light or in
ultraviolet-light mode in a petrographic microscope. Various types of dyes
are: (a) a dry pigment
thoroughly mixed with epoxy (heating epoxy at 100C with the dye helps
thorough mixing), (b)
pre-mixed red, green, or blue coloring paste thoroughly dissolved in epoxy at
100C, (c) dyes
soluble in epoxy resin, which are superior to pigments and impart a uniform
color to the epoxy,
and (d) fluorescent dye mixed in epoxy, which sometime fades with time in
exposure to light. A
fluorescent dye mixed alcohol applied to a lapped surface of concrete can
highlight the micro
and macro cracks (by greater absorption of dye in the cracks) during
exposure in a short
wavelength ultraviolet light. Table 1 provides a list of various castable resins
and dyes. The

amount of the colorant or fluorescent dye powder commonly added to the

epoxy resin is 1 to 2
percent by mass of the resin, depending on the desired intensity of color.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

33
Encapsulation Procedure - For encapsulation, a small sample (with a small
paper of
sample identification) is placed in a 1 to 1.25-in. diameter plastic
(polyethylene, reusable PVC
pipe sections), flexible (silicon mold, or Buehlers reusable EPDM cup mold),
or metal (brass,
copper pipe sections) ring form, cup, or other (square or rectangular-shaped)
cold mounting
container coated with a thin film of mold release agent (such as petroleum
jelly, or Buehlers
release agent). The sample should be dry as moisture in the sample can
interfere with
polymerization of epoxy and affects adhesion. Freshly mixed, clear, or dyed
epoxy (at correct
resin-to-hardener ratio) is poured on and around the sample to immerse it
completely in the
epoxy, the epoxy is allowed to cure, and eventually the sample in hardened
epoxy is removed
from the mold, properly identified, and sectioned. For larger samples such as
a severely cracked
or fragmented concrete sample, it is wrapped in an aluminum foil to form a
bowl or placed in a
disposable plastic or aluminum bowl, oven-dried at ~ 30-40C to remove its
free moisture; then
encapsulated in epoxy. Sample should be re-identified immediately after
removing it from the
mounting mold.
Vacuum Impregnation - The lower the viscosity of the epoxy, the deeper its
depth of
penetration into the sample during impregnation, and the better its
mechanical bond to the
constituents.
For effective epoxy penetration, the following procedure is helpful. A thin
slice of
sample, approximately 5-10 mm thick, is first thoroughly dried either in an
oven at 30 to 40C
for 12-16 hours to a constant mass, or, by immersing it in alcohol for
removing free internal
moisture by the solvent replacement method, or, by rapid freeze-drying by
immersing the sample

in liquid nitrogen followed by sublimating water directly to gas in a cooled

chamber under
vacuum (Detwiler et al. [16]). A very low-viscosity epoxy (viscosity in the
order of 100 to 250
centi-poise at room temperature) should be used for impregnation (e.g.,
EpoThin, Epo-Tek 301,
Epoxy Pack 301, see Table 1). A slight warming of resin in a slide warmer or
hot plate
immediately before mixing with the hardener further reduces the viscosity
and provides deeper
penetration into the sample). Epoxy should be poured in the sample in the
vacuum; alternately, a
container having the dry sample already immersed in an epoxy medium
could be placed in a bell
jar and slowly evacuate with a vacuum pump until bubbling in the epoxy coat
of sample due to
air withdrawal ceases completely. Drawing a vacuum on epoxy causes it first
to evolve its
entrapped air, then eventually to boil forming additional air. Breaking and
restoring the
vacuum several times will help to expel all trapped air from inside the
sample and to allow the
air pressure to force the epoxy into all voids, cracks and open spaces in the
sample. Curing time
generally increases with decreasing epoxy viscosity (e.g., Epo-Thin cures in 9
hours at room
temperature), which can be accelerated by slightly warming the epoxy and
sample in an oven or
a hot plate at 40-45C. Table 1 lists various epoxy resins and their mix
proportions, curing
temperature, and curing time.
Beside viscosity, the depth of epoxy penetration also depends on: (a) the
porosity and
connectivity of pores in the sample, (b) the vacuum pressure applied during
impregnation
(should be at 0.05 bar maximum pressure for 10-20 minutes), and (c) the
degree of drying of the
sample. The purpose of impregnation in vacuum is to remove air out of the
voids, pores, and
cracks so that the epoxy can easily flow into these open spaces. Also,
vacuum impregnation
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

34
removes air bubbles within the epoxy, which usually prevent good bonding.
In the absence of

such sealing with epoxy, pores and margins of cracks or air voids may be
enlarged during
sectioning, grinding, or polishing operations and may entrap various foreign
materials like
grinding and polishing abrasives, solvents and stain-producing etchants.
Impregnation with a
colored or fluorescent dye mixed low-viscosity epoxy can highlight pores,
voids, and cracks. The
effective epoxy-impregnation procedure depends on thorough pre-drying of
the sample to a
constant mass so that all free water in the pores, cracks, and voids are
removed to make room for
the epoxy. Drying should be restricted to a temperature of around 30-40C to
prevent excessive
shrinkage and cracking of the concrete or mortar by dehydration of cement
hydration products.
Sample is commonly dried overnight in an oven or on a slide warmer or hot
plate at 30-40C.
To check the tendency of paste to crack during drying, the oven-dried sample
could be compared
with the room-temperature-dried sample. High curing temperatures can
induce strain
birefringence in the epoxy. Drying a field concrete at > 60C can cause
dehydration of ettringite
and microcracking due to temperature gradients. For fragmented and
powdered samples like
mortar fragments, cement, aggregate, and ground clinker successive stages
of oven drying,
vacuum impregnation and encapsulation into blocks of epoxy resin and
hardening the resin under
heat (~50C) are not uncommon before sectioning, grinding, polishing, and
thin sectioning
operations.
Stutzman and Clifton [22] described a three-stage procedure for
impregnation of very low
viscosity epoxy in cement paste, mortar, and concrete without drying (to
avoid drying shrinkage
cracking), by solvent replacement, first by replacing the pore solution with
ethanol, and then by
replacing ethanol with a low-viscosity epoxy, which is then cured at room
temperature.
Removable Mounting Medium - If the bonding medium needs to be removed
after the
examinations, instead of epoxy, which permanently hardens in the sample,
other types of

temporary mounting media can be used. Roberts and Scali [23] suggested a
1:5 solution of
commercially available colorless nylon fingernail hardener in methanol,
which can be later
removed by soaking in an appropriate solvent. ASTM C 457 mentions use of
Carnauba wax that
must be used with safety precautions to prevent accidental explosion during
the heating over the
flash point to remove the excess wax. Alternately, some mounting epoxy can
be dissolved in
methylene chloride (carcinogenic), or softened by dipping it in boiling
glycerin for 1 to 2 hours
(Ahmed [6]).
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

35
(5) Sectioning
Purposes Sectioning helps to: (a) obtain a smaller, manageable sized
specimen from
the parent material, which helps to keep the rest of the sample for other
analysis; (b) expose the
internal surface of interest for grinding; and (c) reduce the thickness of the
sample to minimize
time for subsequent grinding as in thin sectioning. Concrete samples should
be sectioned at
longitudinal and transverse directions relative to their orientations in the field
(i.e., direction of
placement) to reveal the microstructural details in all orientations including
the most crucial
near-surface zone. Sectioning can be the most damage-producing step
(especially for a brittle or
poorly consolidated material) in the entire process of sample preparation.
Proper selections of
saw and blade are, therefore, crucial to minimize the surface damage. More
damage will
increase the grinding time, which, in turn, can increase the relief. Minimizing
surface damage
during sectioning is, therefore, beneficial for subsequent grinding.
Large Saws Various abrasive-wheel or diamond-bonded sectioning
machines
containing blades from 8-10 in. to 18-24 in. in diameter and using water or
oil as coolant are
used for sectioning large samples. Wet cutting produces a smooth, sectioned
surface and
prevents excessive surface damage from overheating. An oil-cooled saw
usually produces

smoother sections than do the surfaces produced with a water-cooled saw

(Walker [14]). Various
abrasive wheels (i.e., abrasive cut-off blades, ~ 9-in. to 14-in. diameter)
consisting of alumina,
silicon carbide, or cubic boron nitride abrasive filler in a resin, rubber, or
resin/rubbed mixed
binder are common for sectioning ferrous and non-ferrous metals and
minerals in abrasive
cutters. Resin-bonded or metal-bonded diamond blades are most common
for sectioning rocks
and concrete (Buehler [17]). In order to reduce any potential damage to the
sectioned surface
during sectioning (especially for the brittle materials that are susceptible to
grain plucking), thin
abrasive or diamond blades are used for sectioning large samples. A 10-in.
diameter (5/8 in.
diameter arbor), good quality thin (blade thickness 0.032 to 0.045-in.),
continuous rim diamond
blade in a table top tile saw is suitable to cut many construction materials
including concrete
cores up to 3 in. in diameter. The type and thickness of the blade used,
grain-size of diamond or
other abrasives in the blade, the pressure applied during sectioning, blade
speed and feed rate,
and the coolant supply rate are the important factors, which control the
ultimate smoothness of
the sectioned surface. As a general rule, the quality of the surface finish is
proportional to the
blade thickness and abrasive size on the blade.
Precision Saws - Precision saws, as the name implies for very precise cuts,
are used to
section materials that are small, delicate, friable, extremely hard, or where a
cut must be made as
close as possible to a feature of interest, or where the cut width and material
lost must be kept
minimal. Precision saws house 3 to 8-in. diameter diamond wafering (ultrathin) blades and are
recommended for sectioning small samples and for thin sectioning (Ahmed
[3-6]). Table 5 lists
various manufacturers of precision saws. Wafering blades in precision saws
are much thinner
(from 0.006-in. thick for the 3-in. size to 0.035-in. thick for the 8-in. size
blade) and load applied
during cutting are much lesser than the abrasive cut-off blades in abrasive
cutters. Consequently,

less heat generates during sectioning and the sectioned surfaces have
minimal deformations.
Although cubic boron nitrade (CBN), aluminum oxide, and SiC are used for
abrasives in
precision blades for metallurgical applications, diamond blades are most
common for both
metallurgical and petrographic sample preparations. Selection of a thin,
proper diamond blade is
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

36
crucial to reduce the surface deformation. Various types of wafering blades
are: bonded blades
composed of inner metal core and an outer rim of metal or resin bonded
abrasive; plated blades
consisting of a solid metal core with diamonds nickel-coated to the rim; and
diamond segmented
rim or continuous rim blades. Table 5 lists various manufacturers of abrasive
cutters, precision
saws, and blades.
Coolant Water is the most common coolant, which should be mixed with a
corrosion
resistant chemical to prevent rusting of the blade. Water-sensitive materials
should be sectioned
with a cutting fluid, propylene glycol, isopropyl alcohol, or more economically
with a low
viscosity cutting oil, or a hydraulic food-line mineral oil (e.g., baby oil or Mobil
DTE FM 32,
Campbell [15]). Cutting fluids should not be flammable and should not
impose any health
hazards in the form of vapor or aerosol, in which case proper safety
precautions and ventilations
should be taken in handling and disposing the fluid. Use of gloves is
recommended.
The sectioned sample should be thoroughly cleaned with water, acetone, or
isopropyl
alcohol to remove the debris formed by sectioning, and any cutting fluid, and
then air- or ovendried
prior to subsequent grinding and other preparation steps. Small samples
should be cleaned
in a sonic cleaner with the appropriate cleaning solution.
(6) Lapping and Grinding
Purpose - Grinding1 and lapping remove deformations, surface irregularities,
and saw
marks induced during sectioning and provide a smooth, perfectly flat, and
matt-finished surface.

A finely ground surface is essential for examination of clinker, aggregate,

concrete, and mortar
in a low power reflected light microscope (stereomicroscope) and air-void
analysis in hardened
concrete at a magnification up to 100X.
Procedure - Grinding is usually done by using successively finer-grained
abrasives in
water, solvent, or oil-based carrier on a horizontal rotary grinding/lapping
wheel. In transition
from a coarse to the next fine grit size, the ground surface is thoroughly
cleaned to remove the
loose abrasives and fine particles of sample produced during coarse grinding.
In the traditional
approach to lapping and grinding, progressively smoother and finer ground
surface with lesser
sample removal is achieved by grinding with successively finer abrasives.
Abrasive used for
each grinding step is one or two grit sizes smaller than that used in the
preceding step, which
removes the surface deformation induced by the former coarser grit. The
depth of surface
damage decreases with the abrasive size and so does the sample removal
rate. For a given size,
the damage is greater for a soft material than for a hard material.
Grinding Machines - Three types of grinding machines are common:
(a) A large, bench top or stand alone unit containing a motor-driven, 18-24in. diameter
horizontal rotary iron lapping wheel (plain, or with radial or concentric
grooves), with or
without condition rings as sample holding fixtures, which can receive either
loose
SiC/alumina abrasive powder, or fixed abrasive papers with pressure
sensitive adhesive
(PSA) backing, or resin and metal-bonded diamond discs with magnetic
backings. Large
concrete samples up to 6 12-in. in cross section can be lapped by this unit;
The term grinding here should not be confused with pulverizing or making a powder of the
material.
1

PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

37
(b) A single or dual-deck bench top or stand alone grinding/polishing unit
housing horizontal
rotary wheel(s) (usually 8 to 12 in. diameter) to accept clean, or PSA-backed
grinding papers,
or magnetic discs with or without single/multiple sample holding fixtures
(head); a wide

variety of samples can be both ground and polished by using various

interchangeable
magnetic plates with grinding abrasive papers or polishing cloths on the
same single or dual
grinding/polishing wheels; and
(c) Micrometer-attached vertical, diamond cup wheel or plate to traverse the
sample for
controlled and precision grinding; this is used for grinding thin sections in
thin-sectioning
equipments (diamond particles embedded in cup wheels are usually 60-m
in size).
Grinding Abrasives - Abrasives used for grinding are:
(a) Either applied as loose grains or powdered form in a premixed slurry or
suspension in water,
oil, or solvent, or as powders charged concurrently with water spray and
applied on a solid
iron lapping/grinding wheel where the abrasive particles are free to roll
around as they abrade
the sample surface, or
(b) Fixed or bonded to a paper, polymeric, or cloth backing materials of
various weights in the
form of sheets or discs of various sizes which are attached to a horizontal
rotary grinding
wheel or as belts in a stationary roll (or belt) grinder, or
(c) A series of small (8 to 12-in.) or large (18 to 24-in.) diameter, fixed, metalbonded or resinbonded
diamond discs of various grit sizes that magnetically adhere to the grinding
wheels
(for the same abrasive size, a metal-bonded diamond disc removes more
material faster and
produces a rougher or coarser surface finish than a resin-bonded disc).
Fixed abrasives (diamond discs or abrasive papers) are generally more
aggressive and
remove much more material per unit time for the same abrasive size than
loose abrasives and
tend to produce somewhat more deformation at the surface than that noted
when abrasives roll
over the plate during lapping (Buehler [17]). For both types, the size of the
abrasives determines
the cutting rate and surface damage depth. The coarser the abrasive, the
faster the sample
removal rate but the greater the damage depth at the surface, and vice
versa. Soft and brittle
materials should grind with as fine abrasive as possible, which, though takes
a longer time to

remove the sectioning damage, produces less damage from grinding than a
coarser abrasive.
Diamond discs have a long service life but can be far more aggressive for
grinding soft and
sensitive materials than the SiC abrasive papers, which have relatively short
service life but are
better for grinding soft materials.
Common abrasive grains are: (a) silicon carbide (SiC) or aluminum oxide
(Al2O3) with
the following various ANSI/CAMI (USA) grit numbers (the corresponding
median micron size
of the particle size distribution is in parenthesis, Buehler [17]): 60 (268-m),
80 (188-m), 100
(148-m), 120 (116-m), 180 (78-m), 220 (66-m), 240 (51.8-m), 280
(42.3-m), 320 (34.3m), 360 (27.3-m), 400 (22.1-m), 500 (18.2-m), 600 (14.5-m), 800
(12.2-m), 1000 (9.2m), 1200 (6.5-m), and 3000 (3.5-m); and (b) diamond paste or
suspension applied on a
grinding paper, disc, or cloth attached to a horizontal rotary wheel (10 to15m size diamond
paste and 9.5-m alumina powder slurry are commonly used for the
intermediate to final fine
grinding operations). The Mohs hardness of alumina and SiC are 9, and
diamond is 10
(corresponding Knoop hardnesses are 2100, 2300, and 8000, respectively).
Due to its high
hardness, diamond is the abrasive of choice for grinding hard materials such
as rocks, concrete,
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

38
ceramics, and glass. Diamond abrades faster, removes more material per
unit time, and produces
a more consistent surface finish (usually with less relief) than alumina or SiC.
SiC and alumina
both occur either as loose powders or as fixed abrasive paper. Aluminum
oxide crystals are
more blocky than SiC crystals - the former breaks down into uniformly
shaped particles.
Alumina is a better choice for a scratch-free surface and for grinding a soft
material than SiC.
Alumina is available in hexagonal and cubic crystal forms and produced by
calcination (tends to
have agglomerated forms) or by sol-gel process (agglomerate-free).
Deagglomerated alumina

produces a better surface finish than agglomerated form of the same particle
size. Methods for
sizing the SiC/Al2O3 abrasives in the abrasive papers are by sieving for the
coarsest grits,
sedimentation grading for the intermediate grits (240-600), and electrical
resistance method for
the very fine grits. Hack-sawed, bandsawed, and other rough sections
produced on a rough or
thick diamond blade or abrasive cut-off wheel require coarse grinding to
remove surface
irregularities by using grit sizes of 60 to 100; whereas samples sectioned by
using a thin,
precision blade (which produces minimum surface deformation) should start
grinding with grit
sizes of 320 or 400.
A grinding disc of fine stainless steel mesh attached to a substrate (e.g.,
Buehlers UltraPlan disc charged with diamond slurries or sprays) is promising to produce a
surface finish
between grinding and coarse polishing, for rapid sample removal without
producing large
amounts of deformation in the sample, and to minimize surface relief,
especially during the final
thinning of a thin section on a glass slide from 30 to 40-m down to 15 to 20m (Campbell
[personal communication]).
Clinker, Cement, and Concrete Grinding Sectioned whole or crushed clinker
samples
and encapsulated cement samples are commonly ground on a horizontal
rotary wheel with
successively finer sized fixed abrasive papers charged with SiC, Al2O3, or
diamond and
lubricated with a solvent (propylene glycol), or oil. Concrete samples are
lapped on a larger
diameter (18 to 24-in.) horizontal rotary cast iron lapping wheel charged with
SiC or Al2O3
powder abrasives, or, more efficiently, with a series of diamond magnetic
discs. Samples are
either lapped by holding in hand (for larger samples) or placed inside a
lapping ring on the
lapping plate with weights on the samples (for samples up to 4 6-in.
dimension). Single or
dual-wheeled 8 to10-in. diameter horizontal rotary grinding/polishing
machines are also used for
grinding concrete samples prior to thin sectioning, and for polishing.

Carrier Water-sensitive and anhydrous materials are ground with a suitable

lowviscosity
lapping oil or other organic solvents such as ethanol, glycol, or alcohol. Good
nonwaterbased carriers are propylene glycol, 1:1 mixture of propylene or ethylene
glycol and
alcohol, or a low-viscosity water-free lapping oil such as denatured kerosene
mixed with 1/10th
part motor oil (Walker [14]) or a hydraulic food-line mineral oil (e.g., such as
the one used in
commercial baby oil or Mobils DTE FM-32, Campbell [15]). The diamond saw
manufacturers
sell a variety of light lapping oils. The flatness of the finely ground surface
can be checked by
viewing it at a low angle of incidence in a strong light or in a
stereomicroscope. In an airentrained
concrete, the margins of air voids should be sharply defined after the
grinding
operations.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

39
Lapping Although in many literatures the term lapping is used
synonymously with
grinding, lapping is the type of grinding where the abrasive particles are
applied as loose grains
and roll freely on the surface of a cast iron or plastic lapping wheel or disc.
The wheel is usually
charged with slurries of small amounts of SiC, alumina, or diamond.
(7) Polishing
Purpose - Polishing produces a smooth, flat, deformation-free, and scratchfree surface,
which is bright, shiny, and mirror-like in appearance with sharp edges and
good differentiation
between the constituents. Polishing minimizes all fine surface irregularities
left over during the
grinding operation. A polished surface is essential for observations of stained
and etched
surfaces in a high-power reflected-light (metallurgical) microscope and for
detailed
microstructural evaluations including secondary and backscatter electron
imaging and x-ray
microanalysis in a scanning electron microscope. Polishing operations should
not introduce
extraneous structures such as damage on the surface, pitting, scratches,
dragging out of

inclusions, comet tailing, staining, or relief. Grain mounts, small finely ground
sections of
concrete, mortar, and other building materials, and uncovered thin sections
of materials can be
polished by using various polishing abrasives and lubricants on polishing
cloths attached to a
horizontal rotary wheel. Prolonged polishing can introduce relief or height
difference due to
differential rates of abrasion of soft and hard components.
Polishing Abrasives Unlike grinding abrasives, the smallest of which are
around 5-m
in size, polishing abrasives are usually from 5-m to submicron in size.
Traditional polishing
abrasives are: (a) diamond paste or suspension in distilled water, oil, or in an
appropriate carrier,
(b) deagglomerated aluminum oxide in powder form or in suspension in
distilled water, or in an
organic solvent (ethylene glycol, alcohol, kerosene, glycerol), or in polishing
oil, and (c)
amorphous silicon dioxide in colloidal suspension. Water-based carrier is
avoided in polishing
water-sensitive materials. Cerium oxide, chromium oxide, magnesium oxide,
or iron oxide are
sometimes used for polishing specific materials (e.g., glass). Diamond pastes
or suspensions
containing either virgin natural diamond, or, synthetic monocrystalline, or
more effective
polycrystalline forms of diamonds are excellent polishing abrasives and have
been used for
metallurgical polishing since the late 1920s (Buehler [17]). Aqueous fine
alumina powders and
slurries, such as Buehlers MicroPolish deagglomerated alumina powders and
suspensions of
alpha alumina (0.3-m size) and gamma alumina (0.05-m size) slurries (or
suspensions) are
good for final polishing (either in sequence or singularly) with medium nap
polishing cloths. As
mentioned in grinding, deagglomerated alumina produced by the sol-gel
process produces a
better surface polish than fine alumina abrasives of the same size produced
by the traditional
calcination process (which always includes some agglomeration). Colloidal
amorphous silica
suspension is common in metallurgical applications and produces a good
surface polish in

concrete (Ahmed [5]); crystallization of amorphous silica on evaporation and

its precipitation on
the surface, however, can introduce scratches, which can be avoided by a
10-15 second spray of
water on the polishing cloth at the end of a cycle. Diamond abrasives usually
produce less
surface relief than other abrasives.
Polishing Cloths - A good polishing cloth should: (a) hold the abrasive media,
(b) have a
long life, (c) not contain any foreign material, which may cause scratches, (d)
have appropriate
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

40
hardness/softness and low, medium, or high nap (fiber) depending on the
polishing abrasive
used, and (e) be clean of any processing chemicals (such as dye), which may
react with the
sample. Many cloths of different fabrics, weaves, or naps are available.
Napless or low nap
cloths are good for coarse polishing with diamond abrasives. Napless, low,
medium, and
occasionally high nap cloths are good for final polishing. A hard polishing
cloth that does not
have a nap is good for minimizing surface relief. A soft cloth that has a nap
controls
scratching and produces a better quality surface finish. Usually, successively
finer sized
diamond or alumina abrasives on moderately hard to hard napless or lownap polishing cloths
(e.g., Buehlers TexMet) are used for coarse to fine polishing, and softer,
submicron-sized
deagglomerated alumina or colloidal silica abrasives on a soft, napped cloth
(e.g., Buehlers
MicroCloth) is used for the final polishing.
Polishing Methods - Coarse polishing involves the use of successively finer
(from 6 or 5m to 1-m) diamond or alumina abrasives charged onto napless or low-nap
polishing cloths.
Intermediate and fine polishing involve the use of successively finer submicron-sized (0.3-m
and 0.05-m) deagglomerated alumina or diamond abrasives on napless or
low nap to medium
nap polishing cloths. Mechanical polishing indicates procedures involving the
use of polishing
abrasives on cloths; the cloths may be attached to a rotating wheel or a
vibratory polisher bowl;

the samples may be held by hand, held mechanically in a fixture such as a

conditioning ring in a
roller arm, or merely confined within the polishing area [Buehler, 17].
Electrolytic polishing,
common in metallurgical applications, involves a slow sample removal rate
(1-m per minute)
and creates a slightly wavy surface, which increases the difficulty of focusing
at high
magnifications; the method is not common in cement and concrete polishing
[17]. Manual hand
polishing involves holding sample by hand with controlled pressure onto the
polishing wheel,
rotating it opposite to the rotational direction of the wheel, and back and
forth rotation from
center towards the edge of the wheel to ensure even distribution of abrasive
and uniform wear of
polishing cloth [17]. Automated polishing involves the use of a mechanical
polishing device,
either a simple one or a rather sophisticated, minicomputer, or
microprocessor controlled unit,
which can grind and polish a single or multiple (up to half a dozen or more)
samples
simultaneously with a higher degree of quality than hand polishing and at a
reduced consumable
cost [17]. Samples in an automated device are either held in place rigidly
and pressed onto the
cloth by a central force on the sample holder (produces best surface flatness
and edge retention),
or, held in place loosely and force is applied to each sample by a piston and
planarity is achieved
individually rather than collectively. Polishing time depends on abrasive size,
cloth type, force
applied, and wheel speed, which usually varies from 2 to 5 minutes for each
step of polishing.
An unnecessary long time spent in polishing is not only wasteful but can also
produce
undesirable surface relief (Ahmed [6]).
Cleaning and Drying after Polishing - A polished surface should be cleaned
ultrasonically
for 30-40 seconds with a solvent having a high flash point or no flash point.
Excessive ultrasonic
cleaning, however, can damage the surface. Sample can also be washed by
swabbing with a
liquid detergent solution, rinsed in running water, or with forcefully sprayed
alcohol or ethanol,

and then dried. Thorough cleaning of the surface after grinding and polishing
are important to
remove the abrasive residues and their interference during x-ray
microanalysis in SEM. Rapid
drying of the ground/polished surface can be done by applying a stream of
forced warm air or
compressed air to the surface.
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Table 2 provides various grinding and polishing methods. Table 5 provides a
list of
various manufacturers of polishing abrasives, cloths, and equipments.
(8) Etching and Staining
Etching Etching a polished section of a clinker, cement, slag, or concrete
with a
chemical reagent (etchant) highlights various components (e.g., individual
clinker phases,
residual clinker particles in concrete, slag, etc.) by selective absorption of the
etchant with
removal of surface layers of the components of interest in solution. The
etched surface is
observed in a high-power reflected-light (metallurgical) microscope. Etching
of carbonate
aggregates by dilute hydrochloric acid produces CO2-effervescence.
Limestone aggregates
show higher effervescence than dolomitic aggregates. Etching can be
performed on a smooth,
dry, highly polished section, which is free of any surface irregularities and
lubricants from the
previous grinding or polishing operations. Usually the polished surface is
immersed into a thin
layer of etchant in a shallow petri dish (or held above in case of diluted HF
acid vapor etchant;
HF acid is placed in a platinum crucible and the inverted polished surface is
held above it) and is
then washed with alcohol to stop the reaction and quickly dried in an air
current. Nital, HF
vapor, potassium hydroxide in alcohol, and salicylic acid in alcohol are the
most common
etchants used in clinker microscopy (see Campbell [15]). Borax and sodium
hydroxide solutions
are the etchants for examinations of high alumina cement. Table 3 provides
twenty different
staining and etching procedures for examination of polished sections of
clinker, cement, raw

feeds, slag, concrete, and aggregates (see Campbell [15], St. John et al. [2],
Walker [14], and
Hutchinson [1] for comprehensive reviews).
Crack Identification Various authors suggested a dye impregnation method
for
highlighting cracks in concrete by solvent replacement procedure, which
involves immersing a
wet, cleaned, finely ground, and polished section of concrete (polished with
6-m diamond
paste) in a red or fluorescent dye-mixed alcoholic solution, followed by
careful re-polishing in
water with 1 to 3-m diamond to remove any excess dye from the surface
(Hornain et al. [24];
Gran [25). Dye-impregnated micro and macro cracks are easily highlighted in
reflected-light
examination. A fluorescent dye mixed alcohol treated ground or polished
surface can highlight
many fine cracks when examined in ultraviolet light. Dye-mixed epoxy
impregnated thin
sections are also excellent for highlighting cracks (described later).
Staining Selective staining of finely ground, polished or thin sections of
clinker,
cement, or concrete with a chemical reagent highlights various components
with a reaction
product remaining on the surface which is either colored or can develop
characteristic colors by
further treatment. Tables 3 and 4 describe various staining techniques for
identification of
different phases in clinker, cement, aggregate, and concrete. Hutchinson [1]
and Campbell [15]
described various staining techniques applied on uncovered or polished thin
sections to highlight
various silicates (feldspar, quartz, mica) and carbonates (calcite versus
dolomite) in rocks,
aggregates, and raw feeds.
(9) Thin Sectioning (Including Fluorescent Thin Section Preparation)
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Thin sectioning indicates reducing a sample thickness down to approximately
20-m
(0.020 mm), through which light can transmit. Thin sectioning is an
important step in sample
preparation, which provides the detailed anatomy of a materials
microstructure, and a wealth of
information about the overall texture, condition, mineralogy, composition,
and the depth of

deterioration or alteration in the sample.

The first petrographic thin section (of a calcareous rock) was prepared by an
English
Scientist, Sir Henry Clifton Sorby in 1849 (published his procedure in 1868),
who has led the
foundation of modern sample preparation techniques in petrography. Sorbys
work on metallic
meteorites made him interested in preparing metallic samples. Because of
his pioneering work,
Sorby is considered the father of both petrographic and metallographic
sample preparations.
Thin sectioning: (a) can still be done entirely manually, by hand as Sorby did,
or, (b) more
rapidly, consistently, and precisely with excellent edge retention by using
various modern semiautomated
thin-sectioning machines for preparing one sample at a time (e.g., Hillquests
thinsectioning
machine, Buehlers Petro-Thin unit, and Ingram-Wards thin-sectioning
machine all
three units have a separate precision diamond wafering blade for sectioning
and a diamond cup
wheel for precision grinding), or (c) by using completely automated thinsectioning equipments for
preparing multiple samples simultaneously (e.g., Microteks Micro-Trim thinsectioning machine,
or, Logitechs horizontal rotary grinding/polishing units with precision
grinding jigs, see Table 5).
Irrespective of the equipment used, following is a series of steps generally
followed in any
thin section preparation; many of these steps are already described in detail
in the preceding
paragraphs. The exact procedure depends on the type and condition of the
sample and is a matter
of convenience or preference of the individual.
(a) Encapsulation and/or Epoxy Impregnation If the sample is a loose, small,
powdered,
cracked, porous, disintegrated, or deteriorated material, it must be
encapsulated and vacuum
impregnated with a low-viscosity epoxy. Clinker and cement samples must be
encapsulated in
epoxy before thin sectioning. A hardened concrete or mortar is usually
encapsulated (if
fragmented or cracked) and vacuum impregnated with a colored epoxy. A
concrete sample is
first oven-dried to a constant mass at 30-40C for several hours to remove
its internal moisture

and then vacuum impregnated at room temperature with a low-viscosity,

easy-flowing epoxy.
Fluorescent or other colored epoxy can be used, which highlights cracks,
pores, and voids in the
final thin section. A slight warming of epoxy on a hot plate or in an oven
lowers its viscosity,
promotes thorough mixing of powdered dye, and later, during impregnation
at room temperature,
helps deeper penetration in the sample. A slight warming of the impregnated
sample in an oven
at 45-50C accelerates epoxy curing (curing temperature should be
restricted to a lower value for
the materials containing thermally sensitive phases).
(b) Trimming In case of a hardened concrete, mortar, or other relatively
hard material, the
sample is first trimmed down from a large size to a small, manageable,
rectangular block
approximately 5-10 mm in thickness that will fit in a frosted glass slide
(commonly 27 46 mm
or 50 75 mm size), where it will be mounted. The trimmed, rectangular
block is then epoxy
impregnated as described above. The thinner the sample, the faster it dries
during the ovendrying.
The hardened, epoxy-impregnated sample prepared in the previous step is
also sectioned
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

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down to a small slice, slightly smaller than the glass slide of the final thinsection and around 510 mm in thickness. Trimming is usually done in a wet tile saw or in a
precision saw having a
thin diamond-bonded blade, which produces a very smooth cut with
minimum surface
deformation. For water-sensitive materials, a cutting fluid or oil is used. For
soft and brittle
materials, a second epoxy impregnation is sometimes required after
trimming of the epoxyimpregnated
sample if the trimmed surface (which will be the final thin-section) does not
achieve
the desired hardness and integrity by vacuum impregnation.
(c) Fine Grinding Fine grinding of the saw-cut surface of trimmed sample is
necessary for
good bonding of that surface to the glass slide. Fine grinding at 320 or 600
grit abrasive paper is
necessary to remove the minimum surface irregularities created during
sectioning and to achieve

a perfectly smooth and flat surface that will bond intimately to the glass
slide. After grinding,
the surface should be thoroughly cleaned, freed of oil, dirt, grease or
lubricant from previous
actions, and oven-dried to a constant mass at 30-40C.
(d) Bonding the Ground Sample to a Glass Slide The oven-dried, smooth,
flat, clean,
ground surface of the sample is glued with an adhesive to a clean, dry, and
ground (frosted) glass
slide of known thickness. A low-viscosity, fast-setting liquid adhesive is used
for bonding (e.g.,
see Table 1, Canada balsam resin, having a refractive index of 1.54, is
commonly used, other
choices are Buehlers Epothin, Logitechs Epoxy Pack 301, or Loctite
manufactured by Loctite
Corporation, which cures in 15 minutes in a 385nm UV light having an
intensity of 300
microwatt at 6 in.). Various spring-loaded thin-section bonding fixtures (e.g.,
Buehlers
PetroBond) are helpful for applying uniform pressures over the slide during
the hardening of the
thin film of epoxy at the sample-slide interface. Glass slides up to 50 75
mm in size are
usually 1-1.5 mm in thickness; larger slides up to 100 150 mm should be 3
to 4 mm thick and
all slides should be frosted or ground in one side for uniform thickness of the
slide, better
adhesion, and flat, continuous contact of the ground sample to the slide.
Usually, a few drops or
a thin film of epoxy is spread on the ground surface and the frosted side of
the glass slide is
placed onto the surface from a 45 angle. Pressing and rubbing the back of
the slide against the
sample surface remove all trapped air bubbles.
(e) First-stage Thinning by Precision Sectioning The excess portion of the
glass-mounted
sample block is removed by using a micrometer-controlled diamond wafering
blade in a
precision saw, leaving a thickness of about 0.5 mm attached to the glass
slide (or about 1 mm
thick slice if done by hand on a regular tile saw with a thin diamond blade).
Table 2 lists various
precision sectioning machines that can be used for this purpose.
(f) Second-stage Thinning by Precision Grinding After the first sectioning,
the sample is

further thinned by grinding in an automated thin-sectioning machine by a

micrometer-controlled,
precision grinding wheel or cup down to a thickness of about 25 to 30-m, a
thickness through
which light can transmit. Precision grinding can be done on a horizontal
rotary wheel with loose
5 to 15-m sized SiC/Al2O3 abrasives (e.g., in Logitechs machines), or in a
vertical diamondbonded
cup wheel (where about 60-m size diamond is embedded to a brown cup
wheel, e.g., in
Buehlers Petro-Thin), or in a vertical diamond-bonded grinding plate (e.g., in
Micro-Trim).
Both horizontal and vertical precision grinding methods have some
advantages and
disadvantages. A precision micrometer (calibrated in microns) controls the
final thickness. The
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

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first order gray interference color of quartz indicates 25 to 30-m thickness
of the sample (in
thicker samples, quartz grains are usually yellow or purple). In the absence
of a thin-sectioning
equipment, precision grinding can be done by holding the glass slide with a
suitable sample
holder (with the sample side down) on a horizontal rotary grinding wheel
covered with a fine
steel mesh or a metal- or resin-bonded diamond disc or Buehlers Ultra-Pad
and charged with
fine (5 to 15-m) diamond or alumina abrasive slurries.
(g) Final Thinning by Hand Grinding - Some authors (Ahmed [5], Campbell
[15]) and thin
sectioning equipment manufacturers (Buehler, Logitech) suggest thinning of
the sample down to
40 to 50-m by using the precision sectioning/grinding machine and then
final thinning down to
20-m by careful hand grinding of the sample on a glass plate charged with
5 to 10-m sized
alumina or SiC abrasive slurry in water, light oil, or glycol, or, more
efficiently, on a fine woven
steel-mesh pad (e.g., Buehlers UltraPlan) charged with 15 to 25-m size
diamond suspension or
paste. Thinning of the paste of portland cement concrete (relative to much
harder aggregates) can
be accomplished with the Buehlers Ultra-Pad on a rotary wheel with a slurry
of silicon carbide

or diamond powder, bringing the paste to a thickness of approximately 20

microns (judged by
the bright gray interference color of the calcium hydroxide component of
portland cement
hydration; Campbell, personal communication).
(h) Polishing or Protecting Thin Section with a Cover Slip- A thin section can
be further
polished to a shiny surface for various benefits such as: staining tests and
reflected-light
observations on thin sections, observation in SEM, x-ray microanalysis,
opaque mineral study,
mineral hardness/microhardness determination, and examinations at high
magnification and high
resolution in a petrographic microscope by using a 100X oil-immersion
objective. A doublepolished
thin section is sometimes prepared in high-resolution works by polishing both
sides of
the sample. Polishing should be done first on a hard and then on a soft
polishing cloth by using
successively finer sub-micron sized diamond or alumina polishing abrasives
in water, light oil, or
glycol-based lubricant. In the absence of polishing, thin section should be
protected from
atmospheric oxidation, carbonation, and other alterations by using a 0.17
mm thick glass cover
mounted on a clean, dry, freshly ground thin section of the sample either
temporarily by an
immersion oil, or a temporary mounting media, or permanently by a fastsetting medium (e.g.,
Canada Balsam, Epothin, Loctite), which is uniformly distributed throughout
the sectioned
surface in the slide without enclosing any trapped air.
(i) Cautionary notes on fluorescent thin section preparation for determination
of watercement
ratio by image analysis (Jakobsen et al., Roy and Idorn [26]) Several
scientists have
described the procedures for determination of water-cement ratio in a
hardened concrete from
image analysis of photomicrographs taken from fluorescent-dye mixed epoxy
impregnated thin
sections [26]. In this determination, it is important to mix a fixed
concentration of dye in the
epoxy and use a fixed thickness of thin-section in both the standard and the
unknown samples
because both these factors have strong influences on the degree of
fluorescence of the paste. Too

much dye in the epoxy, or too thick section will increase the total amount of
fluorescence (show
brighter image) and gives an apparent water-cement ratio, which is higher
than the actual value.
If the epoxy appears too pale or too yellow in large voids this would indicate
a wrong dosage of
fluorescent dye during the preparation of epoxy. Usually, the amount of dye
to add is 1 percent
by mass of the epoxy resin. Inhomogeneity in color distribution may indicate
insufficient mixing
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

45
of dye in epoxy. The thickness of thin-section should provide first order gray
interference color
of quartz (i.e., 20-m or 0.02-mm thick). The thin section should be located
in the fully epoxyimpregnated
part of the sample. Due to the very small depth of impregnation of epoxy
into
concrete, thin section should be prepared from the top impregnated surface
with as little grinding
after impregnation as possible. Depending on the water-cement ratio (i.e.,
density or porosity) of
a concrete and the viscosity of epoxy, this depth of epoxy penetration can
vary from as little as
0.05 mm to 1.5 mm. Insufficient impregnation is indeed a common problem,
therefore, check
the small voids in thin-section in plane-polarized light to make sure that they
are completely
filled with the fluorescent or colored epoxy. Also, since the intensity of
fluorescent dye
decreases with time and exposure to light, new standards should be
prepared relatively often and
fluorescent thin-section should be kept in dark cupboard. The intensity of
light source in the
microscope should also be constant. Areas of carbonated or leached paste
should be avoided as
these processes change the porosity of paste and hence the degree of
fluorescence. Avoid the
areas of the paste that are too close to a large void or crack or at the edges
of thin-section because
the bright light flares from the epoxies may increase the brightness of the
paste and, hence, the
apparent water-cement ratio. Depending on the inhomogeneities of the
paste, approximately 10
to 30 randomly selected areas in each thin-section are selected for ratio
determination (avoiding

the effects of any inhomogeneous mixing or dispersion of cement) from

which the average
water-cement ratio is measured.
A thick section does not resolve the microstructural details; an ultrathin
section may
induce cracking, grain plucking, edge loss and other damages, blurred
images, and very little
microstructural details; variable thickness across the surface (wedged
section) complicates the
examination and provides poor images. Detailed descriptions of thin section
preparation are
available in Hutchinson [1], ASTM C 856 [9], Nordtest Method NT Build 3611991 [27], St.
John et al. [2], Walker [14], Campbell [15], and Ahmed [3-6]. Rapidity and
reproducibility of
thin sections depend on the sample type and size, thorough drying and
epoxy impregnation
procedures, type of epoxy used, quality of the ground surface bonded to the
glass slide, frosty
nature and cleanliness of the glass slide, sample thickness left after precision
sectioning, quality
and condition of the sectioning blade, hardness of the sample to be used for
precision sectioning
and grinding, and use of diamond paste for final hand grinding on a steel
woven disc.
Consistencies in thin sectioning procedures and in the final thickness of the
sample are important
when thin sections are used for quantitative petrography (as described
above in the section of
determination of water-cement ratios by fluorescent microscopy).
(10) Grain Thin Sections
Unlike the above discussion of thin section preparation of concrete, mortar,
aggregate,
stone, and other solid samples, thin sections of powered and fragmented
materials such as fine
sand, pea gravel, cement, whole or crushed clinker, raw feeds, ground
pozzolan, etc. are usually
prepared in a different manner. The procedures are simple and require less
time than a usual thin
section of concrete. Three methods are common.
The first method involves usual encapsulation of powder or crushed material
in castable
epoxy in a mold as a thick, viscous, paste-like consistency, followed by
curing, sectioning,
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46

grinding, bonding the ground surface to a frosted glass slide, precision

sectioning, precision
grinding to the final thickness, and optional polishing.
The second method involves applying a thin film of epoxy to a clean, dry,
frosted glass
slide and sprinkling the fine power (of cement, fine sand, clinker, raw feed,
etc.) over the epoxy
(or placing the powder first and then applying a few drops of epoxy), or
applying a thin film of a
paste of already mixed epoxy and fine powder on a frosted glass slide,
letting it to cure either
in air or in an oven, grinding the surface down to a smooth plane to expose
majority of the
grains, and slow, continuous grinding, and occasional coarse polishing to the
final thickness.
The thin section can be further fine polished or covered.
For relatively coarser grains such as pea-sized whole clinkers, crushed
clinkers (1 to 2
mm), sieved fine aggregate particles (having uniform grain size of most of
the particles), and
finer fractions of coarse aggregates, the grains are either sprinkled over a
clean, dry, and frosted
working glass slide coated with a thin film of epoxy, or, the grains are first
soaked in an epoxy
medium and then removed from the epoxy with forceps and placed on the
working glass slide
(epoxy from the wetted grain surfaces will provide the necessary bond to the
frosted surface of
the glass, Campbell [15]). The grain mounted glass slide is cured either in
air, or in an oven, or
on a hot plate at 40-50C and then either thin-sectioned in a precision saw
and/or ground down to
expose full cross sections of majority of the grains. The sectioned and ground
surface is then
bonded to a clean, dry, frosted glass slide, which will be the final sample
slide. The sample
sandwiched between the two slides is then further processed by second
precision sectioning and
grinding of the sample slide down to the final thickness of 30 to 40-m. The
companion side of
the thin section left over on the working glass slide from precision sectioning
can be further
polished on a horizontal rotary wheel with a suitable slide holder for
reflected-light or SEM
examination.

(11) Polished Grain Mounts (Half Sections, This section is provided

by Dr. Donald H.
Campbell1)
Examination of polished tops of grains encapsulated in epoxy is common in
SEM studies,
particularly in ore microscopy. The method has been modified for use in
routine concrete and
cement microscopy in which the polished surface passes roughly through the
middle of particles.
The grains are polished on only one surface instead of two (as in a doubly
polished thin section).
Hence, the grain mount may be termed a half section. With a one-particlethick layer, grains can
be examined in reflected- or transmitted-light, or both simultaneously with
some microscopes.
Transmitted light through a transparent mounting medium allows particle
observations in three
dimensions, but reflected light gives only a planar (two dimensional) view.
Both have their
phase-identification advantages. The section can easily be etched or stained.
In this method, non-stick paper (for example, the backing from an adhesivebacked
polishing cloth) is placed on a slide warmer at 45 degrees C, a drop of epoxy
is put on the paper,
and the particles are added to the liquid. A clean, labeled, glass microscope
slide placed on the
mixture and with a light finger pressure and movement the excess epoxy is
squeezed out. A
Modified from Campbell, D. H., 2004, "Microscopical Quality Control of Clinker and Cement," in
Innovations in Portland
Cement Manufacturing, Chapter 8, Portland Cement Association, Skokie, Illinois, USA, CD (1387 pages).
1

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weight is placed on the slide and the epoxy is allowed to harden. After
hardening, the
encapsulation easily separates from the non-stick paper, the excess epoxy is
trimmed from the
edges of the slide with a single-edge razor blade, and the sample is ready for
coarse and fine
polishing with diamond pastes or slurries on Buehler's TexMet or equivalent
cloth. The particles
can be seen at the base of the epoxy.
Grain mounts normally require no lapping with silicon-carbide papers. No. 2
rubber
stopper, or a cabinet door "bumper" is affixed with Super-Glue to the back of
the microscope
slide, facilitating holding the slide to the horizontal polishing wheel.

The first polishing step is primarily for thinning the grain mount until broad
cross
sections of individual particles can be seen under the microscope. The entire
preparation of the
specimen surface can be done on a horizontal polisher-grinder. In the final
stages of polishing,
seeing the particles with the naked eye is normally difficult if the particles
are, say, cement-grain
size. Therefore frequent checking with the microscope is necessary until the
desired thickness
(usually 20 to 40 microns) and degree of polish is attained. The stopper is
removed with a singleedged
razor blade after final polishing or etching. If no transmitted-light
observations are
planned for the section, then a ceramic tile and Super-Glue can be used
instead of a glass
microscope slide and epoxy. The method normally requires roughly 15 to 30
minutes, depending
on temperature and embedding liquid characteristics. Gridded microscope
slides are helpful for
returning to a particular grain.
(12) Thin-Sections for Aggregate Petrography (ASTM C 295)
For aggregate petrography (ASTM C 295), the author uses several 50 75
mm thinsections
for preparation of coarse and fine aggregates. Following careful washing,
oven drying,
and sieve analysis of the aggregates, a representative size fraction retained
in each sieve is
collected by coning and quartering. At least 150 particles are examined in
each sieve. For the
size fractions coarser than 3/8 in., the author uses one or multiple 50 70
mm-thin sections, or a
large-area (up to 100 150 mm. size) thin section per size fraction to
include adequate number
of grains. For sizes finer than 3/8 in., one frosted, 50 75 mm glass slide is
first covered at four
sides and partitioned inside into multiple compartments by gluing several
small glass or plastic
partitions on the glass slide with a rapid setting commercial resin (e.g.,
superglue). Alternately, a
plastic, compartmented, disposable sample mold with 4 to 6 compartments
placed on a silicone
grease-coated glass plate (or glued to a frosted glass slide by superglue) can
also be used (e.g.,
plastic fluorescent-light diffuser panels with multiple square chambers
described for preparation

of clinker and raw feed thin sections by Campbell [15]). Each selected sieve
fraction is mixed
with enough epoxy to create a thick paste-like consistency and poured into
each labeled
compartment on the glass slide and then vacuum impregnated. For fine
aggregate, one 50 70
mm glass slide can hold up to 5 or 6 different sieve sizes with more than
enough grains to
examine. A few minutes in a vacuum chamber removes most air bubbles.
The epoxyencapsulated
grains are cured either in air, or in an oven, or on a hot plate at 40-50C. The
hardened sample is then thin-sectioned according to the steps described in
thin sectioning. The
hardened sample is first sectioned down to 300 to 500-m in a precision saw
and then reduced to
the final thickness by precision grinding. The frosted glass slide on which the
epoxy-mixed
grains were poured can be used to make the final thin-section. The method is
similar to grain
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48
thin section preparation, which is also recommended by ASTM C 295 for
examining particles
finer than No. 50 (300-m) sieve.
(13) Phenolphthalein and Rainbow Indicators for Determining the
Depth of Carbonation
The above-two solutions are used for determining the depth of carbonation in
a portland
cement concrete. A fresh fracture surface or a fresh saw-cut section of a
concrete is treated with
a 1 percent phenolphthalein alcoholic solution - the non-carbonated concrete
turns to pink color
due to its inherent high alkalinity (pH > 9) whereas the carbonated portion
does not change to
pink due to a drop in alkalinity by carbonation (pH < 9). Carbonation of paste
along a crack can
be distinctly observed by application of phenolphthalein. Upward migration
of soluble alkalis
through a concrete slab by moisture and accumulation of those ions near the
carbonated surface
can give a false pink coloration, which should be corrected for the true
depth of carbonation
(usually by further examinations of the true depth of carbonation in a thinsection). Another less
common method is the similar treatment of a fresh fracture surface with a
solution called

rainbow indicator1, which provides a range of pH-correlative colors from

orange (for a pH of 5)
through yellow (pH=7), green (pH=9), purple (pH=11) to dark blue or black
(pH=13).
(14) Staining Techniques for Rapid Identification of Alkali-Silica Gel
in Concrete
Uranyl Acetate Treatment2 - In this procedure, a damp, fresh fracture surface
of a
concrete is treated with a spray of uranyl acetate solution (prepared by
thorough mixing 5 grams
of powdered uranyl-acetate in an warm 100 ml acetic acid solution). After
absorption of the
solution to the surface for a minute and rinsing the excess solution from the
surface with distilled
or deionized water, the treated surface is exposed to a short wavelength
ultraviolet light (254 nm)
in a viewing cabinet or in a dark room. Alkali-silica gel fluoresces bright
greenish-yellow,
especially in and around the reactive aggregate particles, in cracks, and in
voids. Ettringite,
carbonated areas, agglomerated particles of fly ash, silica fume, slag, and
some chert particles in
aggregate may also fluoresce; however, these fluorescence can be
distinguished from the bright
greenish-yellow fluorescence of gel at the specific locations. Alkali-silica gel
identified this way
should be confirmed by other petrographic techniques such as oil-immersion
mounts and/or thinsection
microscopy. The procedure is described in detail in Natesaiyer and Hover [28]
and
ASTM C 856 [9]. Uranyl acetate is a hazardous material and should be
handled, stored, and
disposed following the environmental regulations; eyes and skins should be
protected from the
UV light.
Cuprammonium sulfate staining In this method a broken surface, ground
surface, or
thin section of concrete is absorbed in a 4M cuprammonium sulfate solution
for 7 hours and then
washed in water. Alkali silicate gel exudations in voids and cracks stain blue.
The method is
described in detail in Poole et al. [29].
Both phenolphthalein and rainbow indicators are available from Germann Instruments, Inc.
8845 Forest View
Road, Evanston, IL, 60203, USA 847-329-9999 (Tel).
1

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49

Sodium Cobaltinitrite Staining2 Guthrie and Carey [30, 31] proposed

staining of a fresh
fracture or aged, exposed, pre-rinsed surface of concrete with a saturated
aqueous solution of
sodium cobaltinitrite solution, which reacts with exchangeable potassium in
the ASR-gel to form
a bright yellow precipitate on the gel surface. The intensity of yellow staining
provides a rough
indication of the variation of potassium content in the gel. A counter stain
with a rhodamine B
base compound highlights calcium-rich ASR gel (and can also stain
carbonated zones or other
deteriorated and porous pastes) in pink and provide a high contrast to the
yellow stained gels,
making them easier to observe. Yellow staining of high alkali ASR-gel by
sodium cobaltinitrite
is more consistent and diagnostic than pink staining by rhodamine, which
highlights both Ca-rich
ASR gel and other deteriorated concretes. Unlike uranyl acetate, the
chemicals pose minimal
health risks and are environmentally benign. Since ettringite deposits in
voids or cracks remain
unstained, this method helps to distinguish secondary ettringite from ASR-gel
[30, 31].
It is important to remember that detailed petrographic examinations of
concrete,
including examinations of: (a) fresh fracture surface of concrete in
stereomicroscope for
detection of clear, shiny, or white, matt-finished alkali-silica gel in cracks and
voids, (b) oil
immersion mounts of alkali-silica gel in petrographic microscope, (c) gel in
cracks, voids, around
the reacted aggregate particles, and in other places in thin section, and (d)
sawn, fractured, or
polished surface in SEM provide more unquestionable evidences of such a
reaction in the
concrete than the staining methods, which are not necessarily unequivocal.
Therefore,
conclusions from staining methods must be confirmed by detailed
petrographic examinations.
(15) Sample Preparation for Air-Void Analysis in Hardened Concrete
by ASTM C 457
The conventional method of sample preparation for determining air-void
parameters in
hardened concrete is described in ASTM C 457 [8]. In this method, a sample
is first sectioned

by using a conventional water or oil-cooled diamond saw at a direction

perpendicular to the
direction of placement or finished surface, and then lapped/ground to a
smooth, flat ground
surface. Grinding is done either by using successively finer loose SiC
abrasives on an iron
lapped plate, or, more efficiently, with metal-bonded magnetic diamond discs
of 80 (used for
initial grinding of very rough, sectioned surface), 240, 320 grits and then
resin-bonded diamond
discs of 400, 600, 1200, and 3000 grit sizes. The ground surface should be
thoroughly cleaned in
moving from one to the next finer abrasive size. In case of a soft, friable
material, a concrete
with weak aggregate-paste bond, or a concrete with excessive air, an epoxy
or a carnauba waximpregnation
stage is recommended after sectioning and oven-drying, and prior to
grinding,
which strengthens the sectioned surface and preserves the air void margins
during grinding.
The quality of the final ground surface is very important for good results.
Poor quality of
the lapped surface can give an erroneously high air content, especially when
the concrete has a
high amount of air. The finished surface should be free of scratches, it should
have excellent
reflection of a distant light source when viewed at a low incident angle, there
shall not be any
noticeable relief between the aggregates and paste, and the air void margins
should be sharp and
not eroded or crumbled.
Uranyl acetate is available from Fisher Scientific International, Inc. (800-766-7000); Sodium
cobaltinitrite stain is
available from Fisher Scientific Instruments, Inc. and James Instruments, Inc. (800-4266500).
2

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Though not common, dye-mixed epoxy impregnated large-area (50 75
mm) thin
sections prepared from the top, middle, and bottom portions of a concrete
core, or, an ultra-large
100 150 mm thin section prepared from a 4-in. (100 mm) diameter
concrete core can be used
to study air voids in a stereomicroscope or petrographic microscope
equipped with an automated
air void analyzer (Buckingham and Spaw [36]). An area of at least 12 in.2 (77
cm2) is needed for

examining a concrete containing .-in. or 1-in. nominal maximum sized

aggregate. Inadequate
filling of the air voids by the dyed epoxy, however, can reduce the air
content.
ASTM C 457 provides the minimum area to be covered for concrete
containing various
aggregate sizes, which increases with increasing the maximum size of
aggregate. The area to be
covered also depends on the overall homogeneity of the sample. If the
concrete is heterogeneous
in distribution of aggregates, or has large voids (e.g., poorly compacted), the
total area of
examination should be increased proportionately. For small size samples
(e.g., concrete core less
than 3-in. in diameter and length), two parallel sections are prepared and are
oriented
perpendicular to the finished or exposed surface and studied either side by
side or one after
another in a stereomicroscope; the distance between the parallel sections
should exceed the
maximum size of the aggregates to ensure that each section intersects new
concrete material.
(16) Sample Preparation for Air-Void Analysis in Hardened Concrete
by Image Analysis
During the past two decades, a number of techniques have been developed
for rapid
measurements of air-void parameters in concrete by automated binary
image analysis techniques,
where the air voids are highlighted on a lapped section. The lapped section is
treated with a
black ink to darken all phases except the air voids, which are then filled with
a white paste of
alumina, zinc oxide, wollastonite, or cornstarch; voids in aggregates are then
darkened by a
marker pen. The prepared section is photographed by an image-grabbing
device (e.g. digital
camera, video camera, or a flat bed scanner). Either the whole lapped
section or a series of
adjacent lapped areas are captured at regular intervals. The captured images
are processed for
measuring the amount, size distribution, and air void spacing by various
softwares [see
references 3, 4, 32-38].
In order to increase the contrast between the air voids and the surrounding
matrix in an

image, one method suggests treatment of a finely ground, clean, and oven
dried concrete section
to black ink (by slightly wetting a surface of a stamp pad with black ink and
gently pressing that
surface against the ground surface without filling the voids with ink),
followed by oven drying
the ink and filling all the voids with white zinc oxide paste (smeared over the
warm, dry, black
ink-treated surface). The surface is then cooled and re-dried to harden the
paste, carefully
scrapped with a plastic scraper or putty knife to remove the excess paste,
and slightly re-ground
to highlight the white paste-filled air voids and pore spaces against the black
background
(Ahmed [4]). Void spaces within the aggregate particles should be manually
darkened with a
black marker pen to reduce errors in air void calculations.
Another method suggests vacuum impregnating the sample with a lowviscosity epoxy,
which is thoroughly mixed with a white titanium dioxide pigment (where the
voids will be filled
and thus highlighted by the white epoxy), treating the epoxy impregnated,
lapped and oven dried
clean surface with black ink, drying the ink in an oven, followed by slightly
re-grinding the
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51
surface just to remove the ink stain from the white epoxy filled voids so that
the white voids can
stand out against the black background (Ahmed [3]).
Several other authors have proposed determination of air void parameters by
semiautomated
image analysis techniques where similar white filling materials were used to
highlight
the air voids against the dark background of surrounding matrix in the finely
ground or polished
section and to enhance their contrasts in the image (Chatterji and
Gudmundsson [32]; Cahill et
al. [33]; Roberts and Scali [23]; Peterson et al. [34]; Laurencot et al. [35],
Buckingham and Spaw
[36], Pade et al. [37], and Zhang et al. [38]).
Any surface defects resulting from sample preparation (e.g., grain plucking)
may increase
the void content in an automated image analysis procedure. Coalescence
and clustering of

excessive voids resulting in irregularly shaped coarse void clusters can

complicate the results,
which could be avoided by the manual (i.e., ASTM C 457) method.
Refinements in software
programs and sample preparation techniques are, therefore, attempted to
overcome these
difficulties [34, 35, 37, 38].
(17) Conductive Coating of Sample for Scanning Electron Microscopy
During observation in a scanning electron microscope under high voltage,
high vacuum,
and high magnification, a thin coating of an electrically conductive material
(carbon, gold, or
gold-palladium alloy) is necessary to prevent accumulation of electrical
charge on the surface.
Coating is applied on dry, as received, fresh fracture, polished, powdered, or
thin section of a
nonconducting material (such as concrete) to prevent direct charging by the
incident electrons.
Metals, on the other hand, do not require a conductive coating. Detailed
procedures for
preparation of polished surfaces of metals, ceramics, and geological
materials, including various
conductive coating techniques (e.g., thermal evaporation of C, Au, Au-Pd, or
Pt-C at high or low
vacuum; sputter coating by direct-current, plasma-magnetron, ion-beam, or
penning sputtering of
Au, Pt, Au-Pd or other noble metal alloy targets), are given in Goldstein et al.
[39]. In the
absence of conductive coating, a sample directly exposed to incident
electron at high vacuum
will be charged resulting in distortion and blurring of image and thermal and
radiation damage,
which can lead to a significant loss of mass from the sample. Carbon coating
minimizes the
absorption and attenuation of the incident electron and outgoing x-rays. Gold
coating has
interference with elemental sulfur in the sample. The coated sample must be
electrically
grounded by providing an electrical connection between the coated surface
and the metal
specimen holder by using an electrically conductive silver or carbon paint. A
small amount of a
sample of interest (e.g., power mount), however, can be transferred by a
needle to a conductive
carbon tape (which is attached to a sample holder) for rapid examination and
characterization in

some SEM (e.g., low-vacuum or variable pressure SEM) without necessarily

providing a
conductive coating.
(18) Ultra-thinning
Ultra thinning can be of two types. The first type involves ultra thinning a
usual 20 to 25m thick thin section down to 6 to10-m to reveal many ultra-fine grains
that are smaller than
the usual 20 to 25-m thickness of thin sections and can stack one on top of
the other. Due to the
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52
very fine grain size of many cement clinkers and portland cement hydration
products in a
concrete (finer than 25-m), ultra-thin sections are necessary. They are
usually prepared by a
vibratory polisher (e.g., Buehlers Vibromet, Ahmed [3, 5, 6], Ray [40]) which
slowly and very
gently polishes a conventionally prepared thin section to carefully grind it
down to the desired
thickness and provide microstructural details by removing the grain stacking.
The vibratory
polisher uses a polishing cloth attached to a polishing bowl and receives a
micron to submicron
size abrasive. Generally, a steel mesh cloth (e.g., Buehlers Ultra-Plan)
charged with 5 to 6-m
diamond slurry is used for first stage ultra-thinning down to 12 to15-m and
then a hard, napless
cloth (TexMet pad) charged with 1-m diamond slurry, or a soft napped cloth
(MicroCloth)
charged with submicron sized alumina is used for final delicate thinning
down to 6 to 10-m
(Ahmed [5, 6]). Due to the very slow sample removal, the entire process can
take 12 to16 hours
depending on the sample hardness.
The second type, i.e., ultra thinning a slice of concrete down to less than 0.1m, is in fact
a very delicate procedure, which is needed for observation in a transmission
electron microscope.
This is done first by mechanical abrasion and then by careful slicing,
polishing, and finally
bombarding the doubly polished disc of sample with argon ion or atom beam
until perforation.
Differential rates of thinning by different constituents, and heat and radiation
damage during

beam-milling make sample preparation a crucial part of examination.

Operating at low ion/atom
beam current and the presence of a cooling stage reduce the heating
damage whereas decreasing
the operating voltage and the angle of incidence of the ion/atom beam at the
end of the thinning
process can reduce the radiation damage. At present, this technique is used
only in research
(e.g., observation of hydration products around clinker or silica fume
particles at ultrahigh
magnification) and is not essential for regular petrographic examination.
(19) Sample Preparation for X-Ray Diffraction in Powder
Diffractometer
For x-ray diffraction, a small amount of a previously crushed bulk sample
should be
pulverized in a bench top laboratory mill to a very fine power (less than 45m, preferably in 1 to
10-m size) of talc-like consistency. Fine particle size produces strong
intensity diffraction
peaks and reduces the problems of microabsorption, extinction, preferred
orientation, and sample
homogeneity, all of which can result in peak intensity errors. Pulverization
should not generate
heat high enough to dehydrate any hydrous phases in the sample. Sample
should, therefore, be
mixed with acetone, alcohol, ethanol, or other solvent to minimize the
frictional heat. During
pulverization, the sample should not be contaminated with any foreign or
mill material.
Depending on initial fineness and softness, the sample can also be
pulverized by hand in a small
agate pestle and mortar with an acetone or alcohol lubricant. Excessive
grinding or dry grinding
may deform or decompose the crystalline phases, or may produce an
amorphous component,
which is indicated by a decrease in peak intensity and an increase in peak
width. Bulk samples
are used for examination of cement, lime, gypsum, crushed/ground clinker,
efflorescence
deposits, mortar and concrete. In concrete, however, selective collection and
pulverization of
paste and mortar fraction from a crushed bulk concrete can enhance
detection of secondary
deposits and cement hydration products in the x-ray diffraction pattern by
reducing the influence

of aggregates. Besides pulverized fine powder, polished and thin sections of

concrete and other
materials can also be examined by placing them in suitable sample holders
in the x-ray
diffractometer. Very small amount of sample can be analyzed by smearing on
a sample holder
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53
containing a single-crystal quartz glass plate, or by using a thin-film sample
holder. Other
methods for analyzing fine samples are smearing the fine mineral powder on
a normal
petrographic slide and slurry it with acetone (can led to preferred orientation
of platy minerals),
or, sprinkling powder onto a tacky adhesive coat on a glass slide (will provide
less preferred
orientation than the slurry with acetone). Hutchinson [1] described various
other preparation
techniques for clay minerals such as powder pressing, smearing clay paste
on a glass slide,
suction on ceramic tile, and centrifugation on ceramic tile.
Various selective extraction techniques of portland cement and clinker1, such
as
potassium hydroxide/sugar extraction, salicylic acid/methanol extraction, and
nitric
acid/methanol extraction selectively dissolve the interstitial (aluminate,
ferrite) phases, calcium
silicate phases, and silicate/aluminate phases in the cement, respectively,
which, thereby, reduce
the peak interference problem, and highlight the selectively un-dissolved
phases in the
diffraction pattern. Cement and other moisture-sensitive materials should be
handled carefully
during the preparation steps, and stored in a vacuum desiccator to eliminate
hydration.
(20) Sample preparation for environmental and cryo-SEM and other
new x-ray
microscopical techniques
Cryo-SEM and environmental SEM (ESEM) offer examination of early
hydration of
cement and associated microstructural development without any possible
alteration induced by
drying of sample in a conventional SEM. In cryo-SEM, sample is freeze rapidly
in liquid
nitrogen at 195C to stop any ongoing hydration (e.g., of freshly mixed
cement paste) where the

water in sample freezes to an amorphous solid or sublimates; the frozen

sample is examined in
the SEM with the possibilities for x-ray microanalyses of selected phases
(including frozen pore
solution at any given time). Unlike examination of a static frozen hydration,
in ESEM sample
can be examined in a moist or wet condition, which provides an excellent
opportunity to examine
progressive microstructural development during cement hydration. Unlike
normal SEM,
samples do not have to be coated and elemental analysis can be done on a
moist sample.
Examination in ESEM, however, cannot be done in the presence of any
excess water film on the
sample. Soft x-ray transmission microscopy and x-ray computed tomography
provide
microstructural examination of cement hydration and three-dimensional
imaging at high
resolution in wet or dry conditions (Juenger [41]). All these relatively new
techniques require
minimum sample preparation for examination of cement hydration in wet
condition. X-ray
microscopy is a promising technique to examine hardened concrete in an
ambient condition for
imaging, quantitative microanalysis (similar to EDS and x-ray mapping in
SEM), and phase
identification by x-ray diffraction (Sutter et al. [42]).
CONCLUDING REMARKS
Various sample preparation techniques described in this article are the
essential parts of
detailed petrographic examinations, which should preferably be done by the
petrographer rather
than by a commercial sample preparation laboratory. Information obtained
during sample
For different extraction techniques, see Stutzman, P.E., Guide for X-ray Powder Diffraction Analysis of
Portland Cement and
Clinker, NISTIR 5755, US Department of Commerce, 1996.
1

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54
preparations (e.g., ease of sectioning and grinding, depth of epoxy
penetration, etc.) can provide
clues about the nature of the sample or even the cause of deterioration.
Table 6 provides various
common sample preparation steps for clinker, cement, aggregate, concrete,
mortar, and plaster
materials. The basic methods of preparation remain the same with some
necessary and minor

modifications depending on the type of materials to be examined. Table 7

provides sample
preparation methods for specific modes of microscopical examinations. After
sectioning,
grinding, and polishing: (a) surface deformations induced by these processes
should be removed
or be at minimal; (b) scratches from grinding or polishing abrasives should
be removed; (c)
pullout, pitting, cracking or hard particles, smear, and other preparation
artifacts should be
avoided; (d) relief or excessive surface height variations between
components of various
hardness should be minimized to obtain uniform focus of the surface at high
magnifications; and
(e) the surface must be flat with edges properly retained. Sample must be
cleaned adequately
between preparation steps, after preparation, and after etching. The
preparation methods should
be as simple as possible, should yield consistent high quality results in a
minimum time and cost,
and must be reproducible. Sample preparation itself should not destroy or
alter the composition
of the material and its microstructure. Table 8 provides examples of various
artifacts of sample
preparation and the consequent misinterpretations of materials and
microstructures.
The number of sample preparation techniques to be followed for a particular
sample in a
specific investigation should be minimal and yet adequate enough to provide
all the information
possible to extract for the purpose of the investigation. Applying multiple
sample preparation
techniques on a sample and obtaining similar information from each is not a
cost effective
approach. For example, to detect the presence of fly ash in a powder or in a
hardened concrete
requires only oil-immersion mount examination; a thin section, though can
provide the same
information, is more time consuming and may not be a cost effective
approach for simple fly ash
detection. Many times, examination of oil-immersion mounts is the best
technique for rapid
identification of an unknown material, which can be further explored with
other techniques of
sample preparation. Examinations of as received samples, oil-immersion
mounts, fresh fracture

surfaces, ground surfaces, thin sections, and polished surfaces are the
common modes of
observations of concrete and masonry in optical microscopes. Powder
mounts on a conductive
carbon tape, carbon or gold coated fresh fracture surfaces, polished sections,
and polished thin
sections are the common modes of examinations in scanning electron
microscopy. A pulverized
sample is used for x-ray diffraction and chemical analysis.
There are some specific claims of minimum sample preparation and
examination of as
received, fresh fractured, or saw-cut (unlapped, carbon-coated) section for
concrete materials
characterization and failure investigation in SEM (Marusin [43, 44]). Minimum
sample
preparation may be preferable at some specific cases, such as examination
of water-soluble salts,
efflorescence deposits, or specific areas of interest in a sample, which could
be lost by
subsequent sample preparation. Despite such specific cases, careful and
appropriate sample
preparation, often adequate and satisfactory enough to show the necessary
microstructural details
are very crucial for detailed examination and correct interpretation of
materials and
microstructures.
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55
ACKNOWLEDGMENTS
The author acknowledges help from Prof. David Walker of Columbia
University, George
Vander Voort and late Wase U. Ahmed of Buehler Ltd., and Dr. Donald H.
Campbell of
Campbell Petrographic Services on various issues of sample preparation. A
thorough review of
the manuscript by Dr. Campbell is highly appreciated. Dr. Campbell has
contributed the section
on polished grain mounts. This article is dedicated to late Wase U. Ahmed for
his significant
contributions in sample preparation techniques for more than three decades.
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56
REFERENCES
[1] Hutchinson, C. S., Laboratory Handbook of Petrographic Techniques, John
Wiley and
Sons, New York, 1974, pp. 527.

[2] St. John, D.A., Poole, A. W., and Sims, I., Concrete Petrography: A
Handbook of
Investigative Techniques, John Wiley & Sons, New York, 1998, 474 pp..
[3] Ahmed, W.U., "Petrographic Methods for Analysis of Cement Clinker and
Concrete
Microstructure", Petrography of cementitious materials, S. DeHays, and D.
Stark eds,
ASTM STP 1215, American Society for Testing and Materials, Philadelphia, PA,
1994, pp.
1-12.
[4] Ahmed, W.U., Advances in sample preparation for clinker and concrete
microscopy,
Proceedings of the 13th International Conference on Cement Microscopy,
1991, pp.1729.
[5] Ahmed, W.U., New equipment & methods for preparing concrete &
concrete making
materials for petrographic examination, Proceedings of the 19th
International
Conference on Cement Microscopy, 1997, pp. 130-139.
[6] Ahmed, W.U., Petrographic Examination Methods, Buehler, Ltd. TechNotes, Vol. 3,
Issue 5, 2000.
[7] ASTM C 295 (1998): Standard Guide for Petrographic Examination of
Aggregates for
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American
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[8] ASTM C 457 (1998): Standard Test Method for Microscopical
Determination of
Parameters of the Air-Void System in Hardened Concrete, In: ASTM Vol. 4.02
(Concrete
and Aggregates), Philadelphia, USA, American Society for Testing and
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[9] ASTM C 856 (2004): Standard Practice for Petrographic Examination of
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Concrete, In: ASTM Vol. 4.02 (Concrete and Aggregates), Philadelphia, USA,
American
Society for Testing and Materials.
[10] ASTM C 1324 (2004): Standard Test Method for Examination and
Analysis of Hardened
Masonry Mortar, In: ASTM Internationals Masonry Standards for the Building
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Fifth Edition, Philadelphia, USA, American Society for Testing and Materials.
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Geology, 24 (1), 1991, pp. 17-48.

[12] Mielenz, R. C., Petrography Applied to Portland-Cement Concrete,
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[13] Mielenz, R. C., "Petrographic Evaluation of Concrete Aggregates",
Significance of Tests
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Lamond
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Philadelphia, PA,
1994, pp. 341-364.
[14] Walker, H. N., Petrographic Methods of Examining Hardened Concrete: A
Petrographic
Manual, Virginia Transportation Research Council, VTRC 92-R14, 1992.
[15] Campbell, D. H. Microscopical Examination and Interpretation of
Portland Cement and
Clinker, Portland Cement Association, 1999.
[16] Detwiler, R. J., Powers, L. J., Jakobsen U. H., Ahmed, W. U., Scrivener,
K.L., and
Kjellsen, K. O., Preparing Specimens for Microscopy, Concrete International,
November, 2001, pp. 51-58.
[17] Buehler Sum-Met The Science Behind Materials Preparation, Buehler,
Ltd. 135 pp.,
2004.
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57
[18] US Department of the Interior Concrete Manual, Water Resources
Technical Publication,
8th Ed., Revised, Denver, US Department of the Interior, 1981.
[19] ACI 201.1R-92, Guide for Making a Condition Survey of Concrete in
Service, American
Concrete Institute, 2004.
[20] ASTM C 823 (2000): Standard Practice for Examination and Sampling of
Hardened
Concrete in Constructions In: ASTM Vol. 4.02 (Concrete and Aggregates),
Philadelphia,
USA, American Society for Testing and Materials.
[21] Diamond, S. Cement Paste Microstructure, Proceedings of 8th
International
Conference on Chemistry of Cement, 1986.
[22] Stutzman, P.E. and Clifton J.R. Sample preparation for scanning electron
microscopy,
Proceedings of 21st ICMA Conference, Las Vegas, Nevada, 1999.
[23] Roberts, L. R., and Scali, M. J., Factors affecting image analysis for
measurements of air

content in hardened concrete, Proceedings of International Conference on

Cement
Microscopy, Duncanville, Texas, 1987, pp. 402-419.
[24] Hornain, H., Marchand, J., Ammouche, A., Commene, J.P., and Moranville,
M.,
Microscopic observation of cracks in concrete A new sample preparation
technique
using dye impregnation, Proceedings of 17th ICMA Conference, 1995, pp.
271-282.
[25] Gran, H. Chr. Fluorescent liquid replacement technique: A means of
crack detection and
water-binder ratio determination in high-strength concrete, Cement and
Concrete
Research, 1995.
[26] Jakobsen, H. J., Laugesen, P., and Thaulow, N., Determination of water
to cement ratio in
hardened concrete by optical fluorescence microscopy, Water-Cement Ratio
and Other
Durability Parameters: Techniques for Determination, Khan, M. (ed), SP-191,
American
Concrete Institute, Farmington Hills, Michigan, 1999. Roy, D.M., and Idorn,
G.M.,
Concrete Microstructure, TRB SHRP-C-340, 1993.
[27] Nordtest Method NT Build 361, Concrete Hardened: Water-Cement
Ratio, Approved
1991-02.
[28] Natesaiyer, K., and Hover, K. C. In-situ Identification of ASR Products in
Concrete,
Cement and Concrete Research, Vol. 18, 1988, pp. 455-463.
[29] Poole, A.B., McLachlan, A., and Ellis, D. J., A simple staining technique
for the
identification of alkali-silica gel in concrete and aggregate, Cement and
Concrete
Research, Vol. 18, 1988, pp. 116-120.
[30] Guthrie, G. D., and Carey, J. W., A simple environmentally friendly, and
chemically
specific method for the identification and evaluation of the alkali-silica
reaction, Cement
and Concrete Research, Vol 27, No. 9, 1997, pp. 1407-1417.
[31] Guthrie, G. D., and Carey, J. W., A Geochemical method for the
identification of ASR
gel, TRB Paper No. 991261, 1998.
[32] Chatterjii, S., and Gudmundsson, H., Characterization of entrained air
bubble systems in
concretes by means of an image analyzing microscope, Cement and
Concrete Research,

7, 1977, pp. 423-428.

[33] Cahill, J., Dolan, J.C., and Inward, P.W., The identification and
measurement of
entrained air in concrete using image analysis, In DeHays, S.M., and Stark,
D., (eds),
Petrography of cementitious materials, ASTM STP 1215, American Society for
Testing
and Materials, Philadelphia, 1994.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

58
[34] Peterson, K. W., Swartz, R. A., Sutter, L. L., Van Dam, T. J., Air void
analysis of
hardened concrete with a flatbed scanner, Proceedings of the 24th
International conference
on cement microscopy, San Diego, California, 2002, pp. 304-316.
[35] Laurencot, J. L., Pleau, R., and Pigeon, M., The microscopical
determination of air voids
characteristics in hardened concrete: Development of an automatic system
using image
analysis techniques applied to micro-computers, Proceedings of 14th
International
Conference on Cement Microscopy, 1992.
[36] Buckingham and Spaw, Direct measure of spacing factor in air
entrained concrete,
Proceedings of 10th International Conference on Cement Microscopy, 1988,
pp. 82-92.
[37] Pade, C., Jakobsen, U. H., Elsen, J. A new automatic analysis system for
analyzing the air
void system in hardened concrete, Proceedings of the 24th International
Conference on
Cement Microscopy, San Diego, California, 2002, pp. 204-213.
[38] Zhang, Z., Ansari, F., and Vitillo, N., Automated determination of
entrained air-void
parameters in hardened concrete, ACI Materials Journal, V 102, No. 1,
January-February,
2005.
[39] Goldstein, J. I., Newbury, D. E., Echlin, P., Joy, D. C., Roming, A. D.,
Lyman, C. E., Fiori,
C., and Lifshin, E., Scanning Electron Microscopy and X-Ray Microanalysis A
Text for
Biologists, Materials Scientists, and Geologists, 2nd Edition, Plenum Press,
1992, pp. 819.
[40] Ray, James A., Preparation of concrete samples for petrographic
studies, Proceedings
of 6th International Cement Microscopy Association, 1984, pp. 294-308.

[41] Juenger, M. C. G., X-ray vision for cement-based materials, Concrete

International,
December , 2004, pp. 38-41.
[42] Sutter, L. L., Peterson, K. R., and Van Dam T. J., The X-ray Microscope: A
New Tool
for Concrete Analysis, Proceedings of 25th ICMA Conference, Richmond,
Virginia,
2003.
[43] Marusin, S. L. Preparations of samples for SEM investigation The less
the better!,
Proceeding of 25th ICMA Conference, Richmond, Virginia, 2003.
[44] Marusin, S.L., Sample Preparation the key to SEM studies of failed
concrete, Cement
and Concrete Composites, V 17, 1995, pp. 311-318.
[45] Dolar-Mantuani, L., Handbook of Concrete Aggregates: A Petrographic
and Technological
Evaluation, Noyes Publications, 1983.
[46] Higgs, N. B., Methylene blue testing of smectite as related to concrete
failure, In
Petrography Applied to Concrete and Concrete Aggregates, ASTM STP 1061,
B. Erlin
and D. Stark (eds), American Society for Testing and Materials, Philadelphia,
1990.
[47] Mayfield, B., The quantitative evaluation of the water/cement ratio
using fluorescence
microscopy, Magazine of Concrete Research Vol. 42(150), 1990, pp. 45-49.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

59

Table 1: List of various encapsulating and impregnating castable resins and dyes 1
Epoxy and
Acrylic
Resins
Reference, Manufacturer Resin-to-hardener
mix ratio
Peak
temperature
(C)
Curing time
at room
temperature
Comments
Epoxide resin
and hardener
Buehler Ltd. 5:1, by weight 29 6-8 hours Medium viscosity; best
for encapsulation,
refractive index is 1.565.
EpoKwick Buehler Ltd. 5:1, by weight 85 90 minutes Fast cure, some
shrinkage, high heat,
transparent
EpoThin Buehler Ltd. 5:1.95, by weight 27 9 hours Low viscosity (250 cps at

25C), low shrinkage,

transparent, best for
vacuum impregnation
EpoColor Buehler Ltd. - 79 90 minutes Red dyed epoxy
SamplKwick Buehler Ltd. - 79 5-8 minutes Very fast cure,
translucent, high heat,
some shrinkage
CIBA GEIGY
BY 158 resin
and CIBA
GEIGY HY
2996 hardener
Nordtest Method NT
Build 361; Jakobsen et al.
[26]
28 grams of hardener to
100 grams of fluorescent
resin
27 15 hours DAYGLO HUDSON
YELLOW or equivalent
fluorescent dye (such as
Epo-dye from Struers)
added at 1 percent level
by weight of the epoxy
Araldite AY
105 epoxy and
hardener 935F
Chemical and Engineering
Co., Inc. 221 Brook Street,
Media, PA 19063, USA
Equal proportions of
epoxy and hardener, 1
part mixture is dissolved
thoroughly in 3 volumes
of toluene
100 1 hour Mentioned for rock
sectioning by Hutchinson
1974. Refractive index of
epoxy medium is 1.55.
Araldite 506
Resin with
Hardener HY2964
Ciba-Giegy Corp. Mktg.
Resins Division, Brewster,
NY, 10509, 800-222-1906
(Tel)
2 parts resin to 1 part
curing agent
- - Low viscosity resin good
for impregnation,
refractive index 1.56,
Epon 828 plus
Curing agent
Z heated to

60C in a oven
and so does
the sample
Shell Chemical Co. Suitable amount of epoxy
is mixed with 10-15 ml
of curing agent
60 Overnight Recommended method
for impregnating highly
friable or porous rocks
(Hutchinson 1974).
Refractive index of Epon
epoxy is 1.59.
EpoFix resin
and hardener
Struers Inc. 810 Sharon
Drive, Westlake, OH,
44145,
800-321-5834 (Tel)
9:1, by weight (8:1, by
volume)
43 8 hours Low viscosity resin good
for impregnation,
refractive index 1.57
Epo-Tek 301 Epoxy Technology, Inc.,
14 Fortune Drive,
Billerica, MA 01821, 978667-3805 (Tel)
4:1, by weight - - Low viscosity resin,
refractive index 1.56.
Permanent
mounting
media
Various petrographic
supply houses
Canada Balsam Resin or
Lakeside 70 synthetic
resin
- - Refractive indices 1.537
for Canada Balsam and
1.54 for Lakeside 70 used
for attaching sample to
glass slide
Meltmount for
grain mounts
Cargille Laboratories, Inc.
Cedar Grove, NJ 07009,
- - - Refractive indices 1.539
to 1.704 for grain mounts

PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

60
973-239-6633 (Tel)
Quickmount Fulton Metallurgical
Products Corp., PO Box
118A, Saxonburg Blvd.,
Saxonburg, PA 16056,

724-265-1575 (Tel)
2 parts powder to 1 part
liquid, by volume
- - Used for grain mount and
encapsulation, a medium
viscosity resin
LR White Ernest F. Fullam, Inc.
900 Alabny Shaker Road,
Latham, NY 12110,
518-785-5533 (Tel)
Premixed resin - - Low viscosity good for
encapsulation and
especially impregnation
Loctite 363 Henkel Loctite Corp.
Rocky Hill, CT 06067
- - - 365 nm wavelength UVlight
cure rapid setting
glue for bonding samples
to frosted glass slide for
thin sectioning
Epoxy EPON
Resin 815C,
HELOXY
Modifier 61,
and
EPI-CURE
Curing Agent
3223 (DETA)
Miller-Stephenson
Chemical Company, Inc.,
George Washington
Highway, Danbury, CT
06810,
203-743-4447 (Tel)
E. V. Roberts,
8500 Steller Drive,
Culver City, CA 90232,
800-374-3872 (Tel);
70% epoxy+25%Heloxy
modifier+15% Curing
agent by weight
- 6-8 hours Low viscosity epoxy
good for impregnation
Epoxy Resin
GCR 324
mixed with
EPI-CURE
3234 (TETA)
Gulf Coast S & S, 6322 E.
Hwy 332, P. O. Box. E,
Freeport, TX, 77541, 408233-7277; EPI-CURE
3234 is from MillerStephenson
12 mL Epi-Cure in 100

mL GCR 324 Epoxy

- 6-8 hours Good for encapsulation
and impregnation
Epoxy Pack
Type 301 twopart
epoxy
resin
Logitech Inc. 810 Sharon
Drive, Westlake, OH,
44145,
800-321-5834
4:1, by weight (3:1, by
volume)
- Overnight;
(1 hour at
65C)
Very low viscosity (100
cps at 25C) resin best for
impregnation; refractive
index 1.538 to 1.540;
shelf life 1 year at room
temperature, do not
refrigerate
1The above list of various consumables are for information purposes only. In no case does
this imply that these
products are the best, nor the only materials available. Colored dyes (usually mixed in resin
at high temperature by
thorough mixing and kept prior to adding the hardener): (1) Orasol BR Blue BN by CibaGeigy Corp., Ardsley, NY,
USA 0.25 gram dye per 100 mL epoxy; (2) Blue Supra Conc. PDR (O5D17) dye from
Specialty Coatings &
Chemicals, Inc. 7360 Varna Avenue, North Hollywood, CA 91605, 323-875-0233 (Tel); (3)
Fluorol Yellow 088
Fluorescent dye from BASF Wyandotte Corp., Holland, Michigan; (4) Epoxy-Dye (fluorescent
dye) from Electron
Microscopy Sciences.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

61

Table 2: Various grinding and polishing techniques used in petrographic

examinations of construction materials
Abrasives Lubricant Grinding Papers, Discs, and
Polishing Cloths
Purpose
Coarse Grinding
SiC powders from 60 to
240 grit (268 to 51.8-m)
Water, Propylene
Glycol, or Light
Lapping Oil
Abrasive slurry spread on a
fixed or variable speed rotating
iron lapping wheel.
Used for removing saw marks on
the material.

Fixed SiC abrasives (60

to 240 grits) bonded to
paper discs with clear or
pressure sensitive
adhesive backings
Water, Propylene
Glycol, or Light
Lapping Oil
Abrasive papers attached to
fixed or variable speed rotating
iron lapping wheel.
Used for removing saw marks on
the material.
Fixed diamond grits from
60 to 240 sizes (268 to
51.8-m)
Water, Propylene
Glycol, or
Lapping Oil
Metal- or resin-bonded
diamond discs attached to a
rotary iron lapped wheel.
Used for removing saw marks on
the material.
Intermediate Grinding
SiC powders from 320 to
1200 grits (34.3 to 6.5m)
Water, Propylene
Glycol, or Light
Lapping Oil
Abrasive slurry spread on fixed
or variable speed rotating iron
wheel.
For successively smooth, flat, fine,
matt-finish of the surface.
Fixed SiC abrasives 320
to1200 grits bonded to
paper discs with clear or
pressure sensitive
adhesive backing
Water, Propylene
Glycol, or Light
Lapping Oil
Abrasive papers attached to
fixed or variable speed rotating
iron wheel.
For successively smooth, flat, fine,
matt-finish of the surface.
Fixed diamond grits from

400 to 1200 (22 to 6.5m)

Water, Propylene
Glycol, or
Lapping Oil
Resin-bonded diamond discs
attached to a rotary iron lapped
wheel.
For successively smooth, flat, fine,
matt-finish of the surface.
Fine Grinding
Loose alumina abrasive
powders from coarser to
finer grain sizes (the
finest size is about 5-m)
Water, Propylene
Glycol, or
Lapping Oil
Abrasive slurry spread on fixed
or variable speed rotating iron
wheel.
For successively smooth, flat, fine,
matt-finish of the surface.
Diamond paste or
suspension from 5 to 20m in size
Water, Propylene
Glycol, or
Lapping Oil
(when applied as
paste)
Paste or suspension applied to a
diamond disc adhered to
horizontal rotary
grinding/polishing wheel in a
single or dual deck tabletop
machine.
For successively smooth, flat, fine,
matt-finish of the surface.
Diamond size
approximately 60-m
Water or Glycol
or Grinding oil
Diamond bonded grinding cup
wheel in a thin sectioning
machine.
For precision grinding of a sample
down to 35-45 m thickness.
Coarse Polishing
5 to 1-micron sized

diamond, deagglomerated
alumina, or colloidal
silica abrasive
Distilled water
for alumina
abrasive, water or
propylene or
ethylene glycol
for diamond
abrasive
Diamond paste or suspension
and alumina or colloidal silica
suspension on a hard, napless
or low-nap polishing cloth
(e.g., Buehlers TexMet).
For polishing a thin section or a
small piece of sample for SEM or
metallurgical microscope study; to
produce a low relief surface.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

62

Intermediate Polishing
Sub-micron sized
diamond, 0.3-m
deagglomerated alumina,
or colloidal silica
abrasive
Distilled water
for alumina
abrasive, water or
propylene or
ethylene glycol
for diamond
abrasive
Diamond paste or suspension
and alumina or colloidal silica
suspension on a moderately
hard to hard, napless or lownap
polishing cloth (e.g.,
Buehlers TexMet).
For polishing a thin section or a
small piece of sample for SEM or
metallurgical microscope study; to
produce a low relief surface.
Final Polishing
0.05-m deagglomerated
alumina powder or
colloidal silica
Water or
Propylene Glycol

or Ethylene
Glycol
Soft, napped polishing cloth
(e.g., Buehlers MicroCloth).
For fine polishing with a high
quality surface finish. MicroCloth
produces relief, which helps to
identify periclase in clinker,
cement, and concrete polished
sections.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

63

Table 3: Various etching and staining techniques on polished surfaces of clinker,

slag, and cement (adapted from
St. John et al. [2] and Campbell [15])
Outline of the Staining or Etching Method
and Exposure Time
Observation
10% Potassium hydroxide (KOH) Alite - Does not etch; Belite-Does not etch; C3A - Bluish
gray;
Ferrite-Bright white
KOH + 5% Ethyl Alcohol, immersed for 20 secs, followed by
washing in 1:1 ethyl alcohol plus water solution and then in
isopropyl alcohol solution, buff for 15 sec on MicroCloth wetted
with isopropyl alcohol
C3A turns blue
NaOH (2.5 g) + ethyl alcohol (10 mL) + water (40 mL) solution,
immersed for 10 sec, followed by washing in 1:1 ethyl alcohol plus
water solution and then in isopropyl alcohol solution, no buffing
Darkens alkali sulfates
10% boiling NaOH 20 sec immersion, wash with alcohol CA in high alumina cement turns
blue or brown
KOH (0.1 molar aqueous) immersed for 30 sec, followed by rinse
with isopropyl alcohol spray and dry with forced warm air
C3A and alkali aluminate turn blue-brown, alkali-sulfate darkens,
free lime turns brown
Dilute salicylic acid stain (0.2 g salicylic acid + 25 mL ethyl alcohol
+ 25 mL water), immersed for 20-30 sec., followed by alcohol spray
wash
Alite and belite are blue green; a solution with isopropyl alcohol
(instead of ethyl alcohol) will provide a faster stain on alite than
belite and hence distinguishes two phases
Salicylic acid etchant (0.5 g salicylic acid in 50 mL methyl alcohol)
45 sec. etch.
Alite and belite are clear, alite more strongly etched than belite,
belite shows lamellar structure
Nital (1.5 mL nitric acid in 100 mL ethyl, methyl, isopropyl, or amyl
alcohol) etched for 6-10 sec.
Alite and belite react quickly; alite turns blue to green, belite turns
brown to blue both show detail internal structure. Nital
superimposed on a 20-sec KOH etch turns C3A light brown and
colors the silicates.
HNO3 in alcohol immersed for 2-15 sec. Alite - Grayish brown; Belite-Blue; C3A - Light gray;
Ferrite-

Bright white
Hydrofluoric acid (HF) vapor (kept at 20-22C) exposure for 5-10
sec.
Alite - Buff brown; Belite-Blue; C3A - Light gray; Ferrite-Bright
white; C2AS (melilite) in a high alumina cement is colored in HF
vapor
10% Isopropyl Alcohol (10mL isopropyl alcohol plus 90 mL water),
immersed for 30 sec.
Reacts strongly with alite and weakly with belite; C 3A shows a
weak reaction
Ammonium chloride (saturated, aqueous), 10 sec. Hexagonal section of alite perpendicular
to the three-fold axis
stains light yellow; prismatic section parallel to the c-axis turns
blue; zoned alite shows light-blue core and dark-blue rim
Ammonium chloride stain = 1g NH4Cl + 20 mL H2O + 20 mL ethyl
alcohol + 10 mL acetone + 150 mL isopropyl alcohol, 10-20 sec.
Alite turns brown, belite is unaffected. After 30-45 sec., Alite turns
yellow to yellowish green, belite to brown
Ammonium nitrate solution (1g NH4NO3 + 20 mL H2O + 20 mL
ethyl alcohol + 10 mL acetone + 150 mL isopropyl alcohol), 20-30
sec. etch.
Alite turns yellow-green; belite turns brown
Ammonium nitrate solution after the salicylic acid stain, 30 sec. Shows internal structure of
alite and belite.
Distilled water, 3-5 sec. Free lime (CaO) shows rapid etching from dark to iridescent green
and blue. C3A turns dark blue. Alite becomes brown, belite is
distinguished morphologically. Alkali sulfates are dark.
Water pH 6.8-7 on a saturated microlap cloth, 3 secs. Isopropyl
alcohol wash, warm air dry
MgO hard high physical relief, CaO turns dark to green/blue, C 3A
turns dark blue, C3S turns brown, C2S shows lamellar structure
10% MgSO4 solution, etch for 60 secs at 50C C2S in slag shows striation.
1% borax solution, etch for 30 sec., wash with alcohol C12A7 in high alumina cement turns
gray
Borax solution (1%, boiling) immersed for 10 sec. Etches blade-like pleochroite crystals in
high alumina cement
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

64

Table 4: Various staining techniques in concrete, aggregate, and clinker raw feeds
Specimen Method Observation Reference
Sulfates
Lapped, polished or
thin sections
Immerse in 2:1 mixture of BaCl2 : KMnO4
6% solution for 2 minutes, wash first with
water then with saturated oxalic acid.
Ettringite, gypsum,
anhydrite, plaster stain pink
to purple.
St. John et al. [2]
Feldspar, Quartz, and
Calcite for staining
raw feeds, aggregates,
and thin sections

Two minute exposure to concentrated HF

vapor (52%), two minute immersion in sodium
cobaltinitrite solution, washing in distilled
water, 15 sec. exposure to 10 mL of barium
chloride solution, washing in distilled water,
two minute immersion in amaranth solution
(28 grams of F.D. and C. Red No. 2 pure coal
tar dye in 2 liters of water), quick washing is
distilled water, and drying.
Plagioclase feldspar (other
than albite) stains red,
potash feldspar stains
yellow, quartz and glassy
slags are unstained, calcite
stains to various shades of
pink, dolomite to deep red.
Hutchinson [1]
Campbell [15]
Carbonates
Lapped surface
Thin sections
10 sec etching in 15% HCl;
30 sec immersion in 1:1 g Alizarin Red S + 0.9
g Potassium.
Ferricyanide in 100ml 1.5% HCl.
10 sec immersion in 0.2g Alizarin Red S in
100 ml 1.5% HCl, wash in water.
Calcite stains pink
Ferroan calcite stains
purple-blue.
Ferroan dolomite stains
turquoise.
Dolomite is unaffected.
Dickson in
Hutchison [1]
Evamy stain for
calcite, ferroan
dolomite, and ankerite
applicable to
aggregates, raw feeds
and thin sections
Immersion in 1% solution of HCL for 2-3
minutes (for thin section 0.2% solution for 30
sec), rinse with distilled water, flood with
evamy solution and keep there for 2 minutes,
wash with distilled water, dry with warm air.
Evamy solution is prepared by mixing 1 gram
of alizarin red S with 5 grams of potassium
ferricyanide in distilled water, adding 2 ml of
concentrated HCl and brining the final solution

to 1 liter with distilled water, solution is stored

in dark container.
Iron-free calcite stains red,
iron-poor calcite stains
mauve, iron-rich calcite
stains purple, iron-free
dolomite not stained,
ferroan dolomite stained
light blue, ankerite stains
dark blue.
Campbell [15],
Hutchinson [1]
Copper nitrate
staining test for
carbonate rock
identification,
classification
(limestone versus
dolomite) and
detection of impurities
including clay or shale
inclusions or seams in
limestone and
dolomite
Immerse aggregates in 0.5M copper nitrate
solution (prepared by dissolving 250 grams of
copper nitrate trihydrate in 1 liter distilled
water and filtering) for 16 hours; to convert
stained calcite to the deep blue color,
aggregates can be immersed in a strong
ammonia solution for a few minutes. Finally
aggregates are thoroughly washed in water and
air dried.
Splits in clay or shale
seams; calcite or dense
pure limestone stained deep
blue, or greenish if
limestone has iron
impurities. Dolomite stains
very light blue. Noncarbonate
or silicate
impurities are not colored.
Argillaceous limestone or
dolomite may show
splitting or cracking.
Dolar-Mantuani
[45]
Methylene blue
staining for detection
of smectite in

aggregates
Prepare a methylene blue solution containing
4.5 grams of trihydrate methylene blue dye or
4.283 grams of dihydrate dye per liter of
distilled water; a uncovered grain thin section
Smectite particles turns
blue, muscovite, biotite and
other rock forming
minerals do not stain,
Higgs [46]
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

65

containing different sieve fractions of

aggregate is immersed in the dye solution in a
petri dish for 5 minutes, rinse, and then dry.
Another method is dye adsorption by finer
than No. 200 sieve (75-m) fraction of sand
grains in a titration process and spot testing of
grains on a filter paper until a light blue ring
forms around the central dark blue spot of the
adsorbed grain.
amount of blue-stained
smectite grains can be
determined by point
counting.
Alkali-silica gel
Fractured, grounded
or thin section
Fractured, grounded
or thin sections
Fractured, or aged
surface
15 min immersion in 10% uranyl acetate 1.5%
acetic acid solution, wash in water.
72 hour absorption in 4M cuprammonium
sulfate, wash in water.
Aqueous saturated solution of sodium
cobaltinitrite followed by a counter stain with
rhodamine B base solution.
UV light at 240 nm
wavelength gives yellowgreen
fluorescence of ASR
gel.
Gel exudations in voids
and cracks stain blue.
Bright yellow stain of
alkali-rich ASR-gel; pink
rhodamine stain of
calcium-rich gel.
Natesaiyer and

Hover [28]
Poole, McLachlan
and Ellis [29]
Guthrie and Carey
[30, 31]
Highlighting
microcracks
by fluorescent dye
mixed alcoholic
solution
Treatment of a ground section of moist
concrete with a fluorescent dye mixed
alcoholic solution followed by rinsing excess
solution, drying, and observation in a UV
light.
UV light at 240 nm
wavelength gives yellow
green fluorescence of
microcracks.
Gran [25], Mayfield
[47]
[Note: Consult the original reference before using a particular procedure for the first time]
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

66

Table 5: Lists of various equipment and consumables used in petrographic sample

preparation1
Equipments Manufacturers, Brands, and Models
Wet diamond drilling machine for core extraction Various manufacturers (can be
found in an internet search engine)
Large diamond-edged rotary saws housing 12 to
24 in. diamond blades and small tile or trim saws
with 4 to 10 in. diamond blades
Various manufacturers (can be found in an internet search engine,
e.g., Covington Engineering, Raytech, Diamond Pacific, Lortone),
Buehler (SamplMet 2, Delta AbrasiMet, Abrasimatic 2,
OscillaMet, Delta PetroCut, Lapro Slab Saw, IsoMet series),
Struers (Exotom, Unitom, Discotom-5, Labotom), Logitech (GTS1
Trim Saw), SBT (Model 650 and 660), Pace Technologies
Abrasive Cutters (Metalcut, Servocut), Allied (TechCut 10), Extec
Corp (Labcut).
Encapsulation and Vacuum-impregnation Units Struers (Epovac), Logitech (IU-20, IU30), Buehler (Cast N Vac
system and 1000).
Large horizontal rotary grinding/lapping machine
stand alone or tabletop unit with or without
sample holding fixtures (circular conditioning
rings and weights)
Covington Engineering (16-in. horizontal single and two-speed
lapping units), Diamond Pacific (12 and 18 in. rotting disc flat
laps), ASW Diamond Trust (SW Series Lapping Machines),
Lapmaster International

Tabletop, single or dual-wheel, single or variable

speed grinding and polishing machines with or
without automated sample holding fixtures (heads)
Buehler (MiniMet, Polimet, MotoPol, MiniMet 1000, MetaServ
2000, Alpha and Beta Units, EcoMet series, AutoMet, Petro-Pol,
PowerPro Family, Phoenix 4000 System); Leco (Spectrum System
1000 and 2000); Struers (RotoPol, RotoForce, LaboPol,
LaboForce, Abramin, Abraplan, Abrapol, Planopol); Logitech (PS
2000, WG2, PM5, and LP 50 precision lapping/polishing
machines); SBT (Model 900, 910, 920, TL-MC1); Pace
Technologies Manual and Automatic Polishing Machines (Gripo,
Digiset, Gripomat, Digimat, Forcimat), Lapmaster International,
Allied (DualPrep, OptiPrep, MultiPrep, M-Prep, and TwinPrep
units with AP-3 power head and AD-4 fluid dispenser), Extec Corp
(Labpol).
Automatic Abrasive Dispensing System Buehler (PriMet, MetLap), Leco, Pace
Technologies (Lubomat,
Dispomat), Struers (Multidoser).
Vibratory lapping machine for grinding, polishing,
and ultrathinning
Buehler (VibroMet), Other Units from Covington Engineering,
Diamond Pacific, etc.
Automated thin sectioning (precision-sectioning
and/or grinding) machine housing precision blade
and/or diamond grinding cup wheel or plate
Buehler, Ltd. (Isomet low speed saw, Isomet Plus, Isomet 1000,
Isomet 5000, Petro-Thin thin-sectioning system); Struers
(Accutom, Minitom, and Discoplan-TS units); Logitech (PS 2000,
WG2, PM5, and LP 50 precision lapping/polishing machines with
PLJ2 and PLJ7 precision lapping jigs); SBT (Model 650 and 660);
Wards Natural Sciences (Ingram-Ward Thin Section Equipment
Ingram Model 103 saw and model 303 grinder); Hillquists thinsectioning
machine; Microtec Engineering Lab (Micro-Trim
Automatic Thin Sectioning Machine); Pace Technologies Diamond
Wafering Saws (Finocut, Micracut), Allied (TechCut 4 and 5, Trim
Saw). Germann Instruments thin-sectioning machine has roller
grinding components. Buehlers Petrol-thin, Hillquists unit, and
Ingram-Wards unit have separate, parallel 8-in. diamond wafering
blade and diamond cup wheel on the same compact tabletop unit
for precision sectioning and grinding.
Thin-section Bonding Fixture Buehler (PetroBond), Logitech (BJ2, BJ6, BJ9, and BJ12
thin
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67

section bonding jigs)

Miscellaneous equipments - Ultrasonic Cleaner,
Oven, Hot plate, Vacuum Impregnator, Sieve
Shaker, rock trimmer, hood with exhaust system,
sink and drain, water supply and drain lines for
sectioning, grinding, polishing equipments, recirculating

systems for sectioning or lapping units,

tabletop hot air blower or hand held hair drier
Various manufacturers (e.g., internet search engines, Fisher
Scientific, Gilson, etc.).
Consumables Manufacturers
Loose grinding and polishing abrasives Buehler, Leco, SBT, Extec, Allied, Pace
Technologies, various
manufacturers in the internet
Fixed Grinding Abrasives as PSA backing discs or
paper for belt grinder
Buehler, Leco, SBT, Struers, Logitech, Extec, Allied, Pace
Technologies,
Polishing cloths and diamond polishing pastes and
suspensions
Buehler, Leco, SBT, Pacific Diamond, Extec, Allied, Pace
Technologies, various manufacturers in the internet
Thin section slides (2746 mm, 5075 mm) Wards Natural Sciences, Fisher
Scientific, Erie Scientific,
Logitech, Buehler, Electron Microscopy Sciences
Magnetic diamond discs for lapping (18-in. to 24in.)
Pacific Diamond, ASW, Extec, Allied, Pace Technologies, various
manufacturers in the internet
Magnetic 8-in. to 12-in. resin-bonded and metalbonded
diamond discs for grinding
Buehler, Leco, Extec, Allied, Pace Technologies, various
manufacturers in the internet
Low-viscosity Sectioning and Lapping Oil Buehler, Leco, Diamond Pacific, Extec,
Allied, Mobil Oil Corp,
Fisher Scientific
Solvents for Polishing Fisher, Buehler, Leco, Extec, Allied, various manufacturers in
the
internet
Deagglomerated alumina (0.3 and 0.05-m) fine
polishing powders
Buehler, Leco, Extec, Allied
Various castable epoxy resins and dyes See Table 1
Miscellaneous equipments - Disposable petri dish,
aluminum foil, wax paper, disposable aluminum
containers, plastic and metal cylindrical molds or
cups, metal trays, fine and coarse permanent
markers, carpet tape, dropper bottles, paper towels
Miscellaneous (Fisher Scientific, Electron Microscopy Sciences,
etc.).
Consumables for electron microscopy Electron Microscopy Sciences
1The

above list of various equipments and consumables are for information purposes only. In
no case does this imply that these
products are the best, nor the only materials available. Manufacturers addresses and phone
numbers: (1) Buehler Ltd.; 41 Waukegan
Road, Lake Bluff, IL 60044; 847-295-6500; (2) Struers, Inc., 810 Sharon Drive, Westlake, OH
44145, 440-871-0071; (3) SBT - South

Bay Technology, Inc., 1120 Via Callejon, San Clemente, CA 92673, 800-SBT-2233; (4)
Microtec Engineering Laboratories, Inc., PO
Box. 636; Clifton, CO 81520; 970-434-8883; (5) Wards Natural Science Establishment, Inc.
PO Box 1712, Rochester, NY, 14603, 800962-2660; (6) Mobil Oil Corp. Products and Technology Dept., 3225 Gallows Rd., Fairfax,
Virginia, USA 22037, 703-849-3265; (7)
McCrone Associates and Companies, 850 Pasquinelli Drive, Westmont, IL 60559-5531 800622-8122; (8) Diamond Pacific Tool
Corporation, P. O. Box 1180, Barstow, CA 92312, 800-253-2954; (9) Covington Engineering
Corp., P. O. Box 35, Redlands, CA
92373, 877-793-6636; (10) ASW Diamond Trust, P.O. Box 116, Gorman, CA 93243, 800-8252792; (11) Electron Microscopy
Sciences, 321 Morris Rd. Box 251, Fort Washington, PA 19034, 800-523-5874; (12) Leco
Corporation, 3000 Lakeview Avenue, St.
Joseph, MI, 49085-2396, 269-983-5531; (13) Pace Technologies, 1802 W. Grant Rd. Suite
102, Tucson, AZ 85745, 888-PACE-654,
(14) Lapmaster International, 6400 West Oakton Street, Morton Grove, IL 60053, 877-3528637; (15) Hillquist Inc, 1144 S. Bannock
Street, Denver, CO 80223, 303-722-9766 (Tel), (16) Allied High Tech Products, Inc. 2376 East
Pacific Place, Rancho Dominguez, CA
90220, 800-675-1118; (17) Extec Corp. 99 Phoenix Avenue, P.O. Box 1258, Enfield, CT
06083-1258, 800-54-EXTEC.
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Table 6: Some common petrographic sample preparation steps for clinker, cement,
concrete, aggregate,
mortar, and other construction materials1
Sample Preparation Clinker Cement Aggregate
(after sieve
analysis)
Concrete and
Masonry
Units
Mortar Plaster and
Gypsum
Products
Washing and drying - - Optional Optional Drying Optional
Encapsulation 1A, B 1A, B 1A 1A, B
If fragile
1A
If fragile
1A If fragile
Vacuum Impregnation 2A, B 2A, B 2A 2A, B Of
trimmed or
impregnated
section
2A Of
trimmed or
impregnated
section
2A Of
trimmed or

impregnated
section
Sectioning/Trimming 3A, B 3A, B 3A 1A, B 3A 3A
Coarse Grinding (with
SiC/diamond grit)
4A, B 4A, B 4A 3A, B 4A 4A
Fine grinding (320 and
600 SiC/diamond grits)
5A, B 5A, B 5A 4A, B 5A 5A
Coarse Polishing (with
5-m Al2O3/diamond
abrasive on hard cloth)
6A 6A - 5A Optional Optional
Fine Polishing (with
0.3 and 0.05-m
Al2O3/diamond
abrasives on cloth)
7A 7A - 6A Optional Optional
Bonding to glass slide 6B 6B 6A 5B 6A 6A
Precision sectioning 7B 7B 7A 6B 7A 7A
Precision grinding
down to m-size
thickness
8B 8B 8A 7B 8A 8A
Coarse and fine
polishing of thin
sections
9B 9B - 8B Optional
Oil-immersion mounts 1C 1C Fine size, 1B 1C 1B 1B
Grain thin sections 1D 1D Fine size, 1C 1D 1C Grain mounts in epoxy 1E 1E Fine size, 1D 1E 1D Pulverization for XRD 1F Use as is 1E 1F 1E 1C
1A,

B, C, etc. indicate separate modes of sample preparation with separate subsets of a

sample. For each subset,
successive steps of a sample preparation technique are shown numerically.
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Table 7: Various modes of petrographic examinations of construction materials

Sample
Preparation Stereomicroscope Metallurgical
Microscope
Petrographic
Microscope SEM XRD Image
Analysis
As received 1 - - 2 - 1
Fresh fracture
section 1 - - 2 - 1
Oil-immersion
mounts - - 1 - 1
Powdered sample 1 - 1 1 1 1
Saw-cut sections 1 - - 2 - 1

Ground sections 1 - - 2 2 1
Polished sections 2 1 - 1 - 1
Thin sections 2 - 1 - - 1
Grain thin sections - - 1 - - 1
Polished thin
sections - 1 1 1 - 1
Fluorescent
alcohol treated
ground sections
22---1
Fluorescent thin
sections - - 1 - - 1
1 = Primary method of examination, 2 = Secondary method of examination, Image analysis
system includes image
capture device (scanner, camera, digital camera, micro video camera) and an image
analysis software.
PROCEEDINGS OF THE TWENTY-EIGHTH CONFERENCE ON CEMENT MICROSCOPY, DENVER, COLORADO, U.S.A., APRIL 30 MAY 4, 2006

70

Table 8: Examples of misinterpretation of microstructure due to the artifacts from

sample preparation
Observation Preparation artifact Misinterpretation
In Thin Sections
Microcracks in paste Oven-drying Drying shrinkage cracks
Grain cracking Ultra-thinning Alkali-silica reaction
A gap or separation between a
floor covering and concrete
Drying, Thin sectioning Moisture condensation on floor
Fly ash in concrete Air bubbles not impregnated with
epoxy due to preparing thin section
from beyond the zone of impregnation
Excessive abundance of fly ash
Voids and cracks in a thin section
that are free of any reaction
products
Washing of alkali-silica reaction gel
during excessive cleaning of sample
No ASR in concrete
No salt deposits at the surface Washing of water-soluble salts Absence of
efflorescence or salt
hydration distress in masonry or
concrete
Deep carbonation Prolonged exposure to atmospheric
CO2 during sample preparation
Poor quality concrete
Patchy appearance of paste in dyemixed
epoxy impregnated thin
section
Incomplete epoxy impregnation or
deep grinding of impregnated surface
Inadequate mixing of batch or
tempering water in the concrete;

error in water-cement ratio

determination
Bright yellow fluorescence of thin
section in a petrographic
microscope
Too much dye in epoxy, too thick
section
Provide erroneously high watercement
ratio in image analysis
(Jakobsen et al. [26])
In Polished Sections
Cracks, scratches, holes, pits,
effects of interference from
residual grinding, polishing,
etching, and cleaning liquids
Artifacts of polished and thin section
preparations of clinkers
Misinterpretation in clinker phase
identification, distribution,
reactivity, and chemical attack
from exudation of cleaning or
polishing solutions, etch halo (see
Campbell [15])
Carbon, aluminum peaks in x-ray
microanalysis in SEM
Inadequately cleaned polished surface
on which remains of alumina or
diamond polishing abrasives are
present
Misinterpreted as elemental
composition of the material being
examined
In Lapped Sections
Excess irregularly-shaped or very
fine voids during determination of
air void parameters by automated
image analysis
Voids from grain plucking, voids in
aggregates that are filled with the
void-filling white paste in the binary
image, or surface defects [Cahill et al.
[33]
Erroneously high air content and
errors in air void parameters
Indistinct (eroded or crumpled)
margins of air voids; poor surface
finish
Inadequate grinding of the surface Erroneously high or low air
contents and errors in air void
measurements