Cement Compatibility

T E S T I N G FOR
CEMENT-ADMIXTURE INCOMPATIBILITY
EDGAR FURTADO
A Thesis Submitted in Conformity With the Requirements
For the Degree o f Master o f Applied Science in Civil Engineering

Concrete Materials Group
Graduate Department of Civil Engineering
University o f Toronto
O Copyright by Edgar Furtado 1999
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TESTING FOR CEMENT-ADMIXI'URE INCOMPATIBILITY
Edgar Furtado
(MA&.- 1999)
Department of C i d Engineering
Universic). of Toronto
Although chefnicd admi~turesare not an essentiai component in the production
of concrete they do prove to be induable ingredients whm produckg a h g h qualirg

concrete. Chernical admixtures are incorporated into concrete to yield both economic
and physiral hece5rr.
However, it is important that an understandmg of their
compatibility with certain cernents, or \\ith other adxnisunrres, be established before they
are used in practical applications.
The aLn of this project is to determine the cornpatibility of commerady

availabie \vz ter reducers, superpiasacizers, and air entraining agents. The compatibility of
admktures is determined by the loss of workability of cernent pastes and concretes with
respect to t h e . This project utilises small scaie laboratory tests, inducimg Kantro's
miniature Slump test and the Foam Index test as proposed by V H . Dodson.
1w-ould E e to express my gratitude to Professor R. D. Hooton, P.Eng., of the

Departxnent o f Cilil Engineering at the University o f Toronto for his assistance and
guidance during the course o f this thesis.
I would also like to thank Don Lamb and Cam Monroe o f mast ter Builders
Technologies Ltd., Jim Peel and Gerta Campbel of W-R Grace & Co. and Vito
Debendictis and BPan Salazr Gom The Eudid C h e r n i d Company; each for conmbuting
their t h e , the product information that \vas needed, as well as for the products that they
donated for use in this thesis.

For their help in the laboratories and in the technical aspects o f this project 1
would iike to acknotv1edge the assisrance of U d a Nyd;o, Dr. Amr El-Dieb and Kyle
Stanish.
iii
Absttact
..
u
.
-..
Acknowledgements ........................................................................................................................ rrr
List Of Tables ....................

.
.
................................................................................................
...List
..............O.....f....Illustrations
.......................................
.-*
vru
iu
List of Abbreviations and Symbois............................................................................................
--
,uu
CHAPTER 1. INTRODUCTION
Background .......................................................................................................................1
Objective .............................e.............................................................................................
Plan of Organisation .......................................................................................................
CHAPTER 2. LITERATURE REVIEW

2-1. O r d i n q Portland Cernent.............................................................................................
2.2. Eady Reaaion Chemistry and Stiffening.............................................~~......................

6
2.3. Wockability .........

,
...........................................................................................................
2.4. Chernical Admiunires and Their Use in Coacrete ...............................-................... 10

2.4.1. Air Entraining Agents .......................................................................................
24.1-1.
Factors Influenciag Air Entrainment.................-..-.--..---.--.-........

13
3-42. Water-reducing Admtvtures.............................................................................

2.4.2.1.
Lignosulfonates....................................................................................
3.4.3. Superplasticizers ...............................................................................................

2.4.3.1.
II
H o w Superphsticizers Work In Concrete...................................
15
17
18
19
TABLE OF CONTENTS
2.5. Slump Loss and S t i f f k g of Coacrete .....................................................................

21
Incornpatibility.......................
.
.
.
.................................................................
25.1.
22
...*........
2.6. Factors That Lnfluence SIump Loss................ ,
.
.
.
2 3
Cernent Properes...........................................................................................
26.1.
2 4
26.1.1.
T h e Effect of C3A o n Early Stiffening.......................................2
2.6.1 .S.
Effect of Sulphate Content ................................................................26
2.6.l.2,l.
26.1.2.2.
36.2 3 .
Influence o f Water reducers & Superpkticzer on the
Rok of Sulphates ..........................................................................
28
Suiphate Form ...............................................................................
30
Fineness of the Cement and Excessive Fines.....................
31
ALkali Content ................................................................................. 3 2

..
2.6.2. Superplaseiuzer Propemes...............................................................................
34
2.6.1.4.
2.6.2.1.
Degree of Suifonation......................................................................... 35
2.6.2.2
Effect o f Molecular Weight ...............................................................
35
2.6.3.
DelayedAddition ...............................................................................................
36
2.6.4.
Temperature .......................................................................................................
37
26.5.
Reduced Cernent Paste and Water Content............................................ 38
36.6. Initial SIump ......................................................................................................

. .
Proloaged ~Mtxmg
........................................................................................
2.6.7.
38
3
2.7. Influmces of Admixtures on the Hydration and SetMg Properties o f
........................................................................................... 3
Cements ....................
.
2.7.1.
Set Retardation...................................................................................................
39
2.7.2.
Ettringite Formation .........................................................................................
40
CHAPTER 3 EXPERIMENTAL PROCEEDURES
3.2 Introduction ................... .-.......................................................................................
4 2
3.2 M a t e d s .....................................................................................................................
4 . 3
Cments ......................
3.2.1
3.2.1.1
3.2.2
.
.
..........................................................................
Cement Propedes ..........................................................................
44
Air Entraining Admi.xtures ......................... ..,

.................................. 4 6
ISSUES IN ADMIXTURE COMPATIBIL1TV
TABLE OF CONTENTS
vi
3.23
WaterReducers ..............................................................................................46
3.2.4
Superplasticizers......................................................................................... 41
3-3 Aggregate ...................

....
...........................................................................................
48
3.4 Foam Index Test ....................................................................................................

4
8
.
............................................................ 50
3.5 Mini-Slump Cone Test .............................. .
3-51 Inadequaties of the hIini-slump cone test .................................................52
3.52
hLini-Slump Test Program ...........................................................................
53
3.6 MeasuDng Heat Rise of Hydrating Cernent Pastes..............................................55

3-61 Cali'bration of the Thennocouple Apparatus ........................... .
57
3.1 Coacrete Trial Mixes....................................................................................................
58
3.8 ~MeauringSoluble Alk ali. Contents .....................

.
.
............................................ 61
..
3.9 Determining Air Content.............................................................................................
61
CHAPTER 4 OBSERVATIONS & RESULTS
4.1 TesMg.............................................................................................................................
63
3.2 Foam index Tests.......................................................................................................
63
3.3 LLIUll-Slump Resuin ....................................................................................................
6 5
..
Superplasttazer-Cemenr interactions............
.................................. 65
4.32 Influence of Air Entraining Agents ............................................................ 68
4.4 Optimum SP Dosage ....................................................................................................
63
43.1
4.5 Slump Loss In Concrete...............................................................................................
75
4.6 hfid-slurnp w .Concrete Slump ..............................................................................
79
4.7 Heat Rise Li Cement Pastes ....................... .

.
.
.
......................................................8 3
4.7.1
The Influences of the Water Reducer ........................................................ 83
4.7.2
The Influences of Superplasticizers.........................................................
4.7.3
Influence of Air-Entrainiog Agents ...................................................... 8
84
6
4.8 Soluble Alkali Contents of Cernent........................................................................91
ISSUES IN AOMUCTURE COMPATIB1LITV
vii
TABLE OF CONTENTS
CHAPTER 5. DISCUSSION
.
.
93
5.1 Product Protection .........................................
5 2 Change of Cements In Concrete Tests......................................................................93
5.3 Cement Properties......................................................................................................... 94
.
.
.
...........................9
5.4 rI-Entmimnent ..........................................
5.5 High-rUkali Cernent & Melamine Sulfonate SP Incompatibility........................... 95

5.6 Low-alkali Cement/SP Interactions-,..
..,.......-- --..-.-. ......--. -.96
5.7 hfodifications for the Mini-Slump Test.....................................................................
96
5.8 TreaMg Eady StiffeaiLlg Problems ............................................................................
97
CHAPTER 6. CONCLUSIONS & RECOMMENDATIONS

6.1 Conclusions ................................................................................................................
Evaluation of the Mini-Slump Cone Test .....................
6.1.2
...................... 98
Influence of Akalis.....................................................................................
99
6.1-3
The Influence of Admixtures .................................................................
6.1.1
6.2 Recommendations......................................................................................................
REFERENCES
100
101
.........................................................
.
.....
.
......................................103
APPENDICIES
Appeadi,~A
bLi~Designs: mi ni-Slump & Heat Developmwt Tests............. 109
Appendiv B
Mid-Slump Results: Loss of workability aith Time.................. 1 14
Appendiv C
Heat Dew.lopment: Temperature vs.T h e Plots ....................... 136
Appendiv D
Grain Size Distributions for Fine and Coarse Aggregates .........157
&SUES IN ADMIXTURE COMPATiBlLlTY
Physical and chernical properties of cemena .................................................35
Table 3.2 .
Active agents and physicd and properties of air entraining agents ............46
.
Table 3.4 .
Active agents and physical propertes O E water-reducers............................
Active agents and physicd and propertks of superplastizea...................47
Table 3-5
iblLving regiment for cement pastes prepared in a kitchen blender..........-54
Table 3-6
Concrete mi.??
design and composition ......................................................
Table 3-7
Miving regime for coacrete teal mixes ............................................................
Table 4-1
Foam Indes results on plain cements....................................................... 64
Table 4-2
Foam Indes results on cements with calcium lignosulfonate WR. .............64
Table 4-3
Soluble alkali contents of cements ................... .

.
........................................... 91
Table 3.1
Table 3.3
47
9
60
.
.
.
.
Figure 2-1.
Rate of heat evolution of orciinary podand cerneut....................................... G
Figure 3-1.
hn illustration of the foam index test ...............................
Figure 3-2.
..
The muir-slump cone.......................................................................................... 51
Figure 3-3.
Thermocouple apparatus....................................................................................
55
Figure 3-4
Typical temperature profde of hydrating cernent pas te ............................... 5G
Figure 3-5
Calibrated temperature cuve for insulated themiocouple........................... 57
Figure 4-1
MiPi-slump vs. time for low-allrali TlO/melamine SP combination
(No AEA) .............................................................................................................

Figure 4-2
66
Adhi-slump rs. time for low-alkali TlO/naphthalene SP combination

(No A U ) ............................................................................................................66
Figure 4-3
hfni-sl~~~~p
n. rime for high-akali TlO/melamine SP combination
(No AEA) .............................................................................................................
Figure 4-4
67
Mini-slump r s - time for hi&-alliali TlO/naphthalene SP combinaaoa
(No AEA) .....................................

Figures 4-5 to 4-8
.
.
.
......................... 67
5 & 60 min mini-slump vs. SP dose for LAPC, melamine SP

and various AEA agents ........................
.
. .
.
.............
Figures 4-9 to 4-12
71
5 & 60 min mini-slump 1%- SP dose for LAPC, naphthalene

SP and Fanous AEA agents ......................................................
UST OF ILLUSTRATIONS
Figures 4-W to 4-16
5 & 60 min mini-shmp vs. SP dose for HAPC melamine SP

and d o u s riEA agents .......................................................................
73
Figures 4-17 to 4-20 5 & 60 min mini-slump vs. SP dose for HAPC, naphthalene
SP and ratious M2.A agents ...-.-.................................................-.--....74

Figure 4-21
Estimated slump as a functioa of water content for various sizes of
Figure 4-22
Slump loss in concrete over time using high-alkali Tl0 cernent and
.
.
.
. . . . . . . . . . . .78
varied SP type and dose...........................

..-.......
Figure 4-23
Slump loss in c o n a e t e orer time using low-alkali Tl0 cement and

varied SP tvpe ................... .
.
..-*-..-..........-.....................-......-.-.-..--..-.---.--.--.-----.-..
78
Figure 4-24
Figure 4-25
Cernent paste mini-slump area vs. concrete slump high-dld Tl0

cement ..*.................................-......*....-....*-*.*.....*...-.......*-...---..--..-..
-*--...--...---..-.--81
Figure 4-26
Cernent paste mini-slump area vs. conuete slump for the l o w - W
TI0 cement.........,.... .
.
..-.-....-.-..
.
. . .82
Figure 4-27
Cernent paste mini-slump area vs. concrete slump for the low-akaL
Tl0 cement ...-..........-.....................-.....

--..........................................................-.-..82
Figure 4-28
Time to peak temperature vs- SP dose fol: the low-alM Type 10

cernent with melamine SP & Ca LignosuKonate W R .....................................
87
Figure 4-29
Time to peak temperature vs. SP dose for the low-alkali Type 10

cement with naphthalene SP & Ca iignosuifoaate W R ........................-..-m.--87
Figure 4-30
Time to peak temperanue vs. SP dose for the high-alkali Tl0 with
melamine SP & Ca iignosulfonate WR ,..............-...-.--.....--......-...-.-.-.........--....
88
Figure 4-3 1 Time to peak temperature vs. SP dose for the high-alkali Tl0 with
naphthalene SP & Ca lignosulfonate WR .................................................. 88
ISSUES IN ADMIXTURE COMPATlBlLlTY
xi
LIST OF ILLUSTRATlONS
Figure 4-32
Peak temperature vs- SP dose for the low-alkali Type 10 cement with
melamine SP & Ca iignosulfonate WR ............................................................89
Figure 4-33
Peak temperature vs. SP dose for the low-alkaii Type 10 cernent with
naphthalene SP & Ca lignosulfonate W R ....................................................... 89
Figure 4-34
Peak temperature 1s.SP dose for the hi&-ahb Tl0 with meLunine
.............................. 9
SP & Ca lignosdfonate W R .................-.-.--....---..--.-.-.Figure 4-35
Peak temperature m. SP dose for the hi&-&di
Tl0 mith
naphthaiene SP & Ca lignosulfonate WR ....................................................... W
ISSUES IN ADMIXIURE COMPATlBlLlTY
AND SYMBOLS
AEA
CA
CA
Ar En training Agent
Coarse Aggregate
Tricalcium Nwninate - 3Ca0.A1203
CJAF Tetracalcium A l i o f e r t e - 4CaOai-0,aFq03
C2s
c3s
CLS
Dicalaum Silicate - 2CaOmSi0,

TficalUurn Silicate - 3CaO*SiOl
Calcium Lignosulfonate
Wh-Alkali Poaland Cemerit
W C
L o w - L WPortland Cement
OPC
MW
Ordinaq Portland Cernent
Molecular Weight
M-Type
Melamine Type Superplasticizer
N-Type
Naphthalene Type Superplasticizer
PNS
PoIynaphthalene Sulfonate
PMS Polymelamuie Sulfonate

SCM Supplementary Cernenting Materials
SP
Superplasticizer
w/c
Water Cernent Ratio
WR
Water Reducer
xii
Irnprowxnent to the durability and mechanicd behaviour of concrete can be

achieved by reduung the interstitial void space, this requLes that the individual cernent
must be moved doser to one another v o v e r , 1998). The production of these high-
strength or durable concretes can cypically be achieved implemenog a low

water/cementitious materials (\-/cm) ratio. Unfortunately, the use of a low %-/cm ratio
requires thar either workability be compromised, or h g h canent content be used to
maintain a workable concrete, however, neither is a desirable option (Hover, 1998).

Fortunately, the development of commercial chemicai admi~tureshas made it possible to
increase concrete w-orkability Li low- w-/cm concretes, thus making high- per forniance
concretes a reaiiv.
The use o f chemicai admixtures has become cornmon place Li the production of
concrete; concretes absent of admi~turestend to be the exception today. i\dmiunires are
used
to
impart some benefiual influence ont0 concrete whether it is to be in its fresh o r
hardened state. Typicdy, ad-tues
are used in combination with others so as to
achieve a combined benefig and are generally successfd when used together.
Each
INTRODUCTION
interacts nith the various constituents of cements, and influences the hydration reactions
in differing wztys.
Under c
d circumstances compatibility between admisures, or admixtures
and cernent, may be of concern.
Predicthg the compatibility of admixtures in
combination wiith cement is an almost impossible kat to perform by chemical analyses

alone. Admiunires and cements are both complex in their nature. Portland cements and
chemical adrnktures are multi-component m a t d s , m-hich undergo cornplex chernical
reactions during the hydration of ponkad cernent paste.
Cases have been reported o admi~trrre-cernent incompatibiliry, sometimes

resulting in estreme cases of set retardauon or flash set (Dodson and Haydeo, 1989;
Johnston, 1987; Aitn et ai., 1994; TuthiU et al., 1961). In either ciccumstance, cementadmiunire incornpatibility is a major problem in the concrete industry that affects the
efficiency of concrete piacng, the quality of conccete, and may resuit in changes made to
the scheduled consmction. The resultlig costs incuned may be esueme. Fortunately
when the one of the components of the concrete is replaced, most typicdy to a different
type or source of superpiastizer or cernent, the problem disappears (Dodson, 1990;
Helmuth et al., t 995).
Compatibility tests have traditionaily been performed using small t i a l &es
of
concrete. Howerer, these &al mixes remain to be both costly and materiai intensive.
Recent advancements have led to the daelopment of smd-scale tests on cernent pastes
and mortan.
Typicaliy retardes, wxter reducers, accelerators, and air-entraining agents (AEA)

and superplasticizers (SP) are compatible when used in concert with cernent, and ofieten
rcsults in an enhanceci combined e f f e a The induceci high w-orhbility of lou- w/m

concrete contaking a superplasticizer is maintained generally for about 30-bOmLiutes,
and this rapid decrease in slump is terrned slump loss. However, in some cases sernay be sigdcantiy reduced or offset by the incorporation of these admiunires. It is
INTRODUCTION
essential that each admiunire combination be evaluated before it can be practicdy

udised .
The general scope of this smdy is to investigate the eects that chemical
admisme incompatibility has on the siump loss of superpiaticized high-perfomiaace
(low W/C) conuete. This investigation emphasises the use of s
d scale laboratory tests
ro measure the rheological behaviour of cernent pastes, O f ciiffixent alkali contents, under
the influence of chemical a c h k s ~ ~ e as
s ; weU as th&
admixnire enhanced concrete.
ability to predict the behaviour of
The tests used in ~ h econtesx of this study include
Kantro's Miniature-Slump Test, Dodson's Foam Indei Test and the measurement of the
heat of hydration of the cernent pastes; a bief investigation
also caMed out to
characterise the efiect of the soluble alkali content on the eady hydration properties of
three cornmerciaiiy aniiable cements. The &dmgs of these tests are discussed hereafier
in this paper.
1.3 PLAN OF ORGANIZATION

The remaliiry: sections of this thesis can be divided into nvo portions: the kt
being a literature rex-iea- of the cruciai concepts that are at the heart of chemical
adrnkx~esand the compatibility issues assoaated uith them, and the second portion
consisting of the elxperimenta.i work performed in this paper. The literature review is
contained in Chapter Two, and i provided to give the reader the understanding and
knowledge necessary to oliow the w o d c perfomied in the following chapters. Issues
covered indude the influence of tricalaum duminate ( C d ) content, content and form of
sulphate and alkali content on early hydraaoa reactions of portland cernent paste with
and without the influence of admistufes.
The experhental portion of this work commences in Chapter Three with a

description of the mateeah used and the experimentai procedures used in the resting
program. Chapter Four presents the results and hndings obtained in the Iaborato.
These results are then discussed Li the Efth chapter of this uiritten work.
ISSUES IN ADMIXTURE COMQATlBlCrrY
Chapter SLY completes this report and draws conclusions kom the enaie body of
this work, and goes as far as to discuss several recommendations on how- this work could
be improved if amended.
ISSUES IN ADMUCTURE COMPATIBILITY
Before continung on into the topic OF chemical admi~niresand th& interactions

with ordliary portland cements (OPC) it is needed to reriew some of the processes
assouated with the hydration, and early age behaviour, of plain cernent paste. P o d m d
cement paste is the most actire component of any mortar or concrete; and is a complez
misme of mulaple inorganic components such as the aluminate phases (CA, GiW)and
silicates phases (C,S, CzS), and to a lesser degree gypsum and other sulphate orms
( C ~ S O ~ ~ S Hallralis
~ O ) ,(NazO, &O), etc (Jolicoeurand Simard, 1998). Naturally, more
components can be found in blended cemenu. When xater is introduced
cernent a series of chemical ceactions are teggered that lead
to
to
portland
the formation of
hydration products and inter-partide bondkg which results in a.dense stable ma&.
REACTION CHEMISTRYAND STIFFENING
2.2 -Y
Upon initiai contact w+th water, the multiple phases and components of the
cernent undergo a variecy of chemicai reactions, as weil as peciods of varieci reactivirates. The hydration of cernent undergoes three distinct phases; the h n t is an initiai
period of rapid chemical reaction. This is then followed by what is ofien termed as a
'dormant' or 'induction' phase where the rates of reactioo are slowed. The induction
phase then leads =a\- to a second heightened rate of reacrion which, readies a peak and
then subsides once
again, this second raised rate of reaction denotes the chemical
processes associated with the se*
of the cemen& while the hardening process occun
during the h a 1 sequence of the reactions.
These changing rates of reactions are
reflected in the derelopment of heat due to a s&es of exothennic reactions. A typical

representation of this heat production is illustrateci in Figure 2-1.
c
rn
a
- I
II
';' so-
O
-t40
Cu
IV
111
12
76
20
24
28
Tirne - hrs
Figure 2-1,
Rate of heat evolution of o r d i n q portland cernentWith the (i)

initial reactions, (II) induction, (III)
acceIerated or setting, and 0hardeaiag phases.
Cernent hydrahon begins Lnmediately upon contact with water. Within several
minutes, the easily solubilized components (Nac, KC, Ca*, S 0 4 , OH-) of the cernent
are dissolved into the aqueous phase, and initiai hydration reaaions commence (Jolicoeur
ISSUES IN ADMIXTURE COMPAflBlLlTY
LITERATURE REWON
and Simard, 1998). The hydration process of cernent inoolres the series of compler
chernical readons presented in Equations 2-1 to 2-8. iMuch of these iaitiat reactions
involve the rapidly hydrating tricalaum aluminate ( C d ) phase and its interactions aith
the sulphates present in the cemenb and results in a rapid production of heat, depicted as
the hrst peak in Figure 2-1. A thin layer of hydration products (in the fomi of caiciurn
sulphoaluminates consiscing of ettringite 3CaOeAL~0+3CaSO~.3W20)is fomied as

the surface hydration O cement particles, inrolving reactions \cith the sulphates present,
continues. Eventually the cernent parcides become fulty coated with a protectke layer of
hydration products that hinders the diffusion of reacting species in and out of the
reaction interphase, thus sharply reduciq the rate of the various reactions (Hehuth et
al., 1995; Jolicoeur and Simard, 1998; Stein, 1961). This perod of high initial reactions
O ften
has a duration of only minutes.
The initial phase of high reactiiitg is followed by a p&od of ktency n o d y

referred to as the 'domiant' or 'induction' p e r d u n d the onset of s e t h g (Helmuth et
al., 1995;Jolicoeur and Sirnard, 1998). Although the reactions initiateci in the tirst phase
c o n ~ u de u ~ the
g induction p e n d , iictie emingite is produced duxing this latent period
ailowing the cernent paste to maintain most of i plastiaty. Solidification (semng) starts
after about ca-Oto t h e hours, due to the formation of calcium silicate hydrate (Meyer
and Perenchio, 1979). The only no table event at this stage is a progressive thid-
of
the surface gel layer. Any loss in the consistency at this stage is m d y attributable to the
physicai coagulation of the cernent particles rather than to any chernical process
(Ramachanran, 1995).
The induction pePod may be shorrened in durauoa if there is an insuffiuent
sulphate content in the cernent as excessive nudeation and growth of C-A-H products
rnay occur (flash set); if, on the other hand this concentration is too high (hemihydrate,
alkali sulphates), massire nudeaion and g r 0 6 of g y p s u . a p a k may be obsemed.

(false set) (Jolicoeurand S i d , 1998).
The end of the induction p e r d is m k e d by a sharp increase Li the reaction rate
of cernent, in general, indicated by the second pronounced temperature rise (Stein, 196 1).
The number and energy of the interactions bemeen the growing particles of the system
also increase, rapidlv convertkg the system into a stiff maais (Jolicoeur and Sirnard,
1998). The ormation of an internal structure results when the deposition of hydration
products on the surfaces of cernent grains are allowed to the corne Lit0 contact with
neighbouing gains (Guo, 1994).
Cernent grains bond to one anocher by the
intenvea~ingof the C S hydration products, this graduaily orms an internal structure

that as it c o n ~ u e sto grow
~~~ bring about the stiffening, and e v e n d y the set of
concrete. Ultimately, producing a strong durable matris of cement hydrates.

Thc accelerated acti~tyin the cernent paste has been acknowledged to be die
result of tncalcium silicate (CS)hydration (Jolicoeur and Simard, 1998; Stein, 1961).
Several effects have been considered to explain the onset of the acceleration period
(Jolicoeurand Simard, 1998):
Disruption of the hydrate protective layer by physico-chernical
transformations of the hydrates;
Breakdown of the protective laye by osrnotic efects;
Nudeation and growth of C-SH products, and;
CH nudeation and grow-th.
ISSUES IN ADMIXTURE COMPAflBlLllY
The second peak of heat evolution in Figure 2-1 often denotes the hydraaon of
the C S phase. In some cements there may be a thLd less pronounced peak in this curve,
the result of renewed Cs4 hpdraaon once all the SO, is reacted, the gypsum is depleted
and ettarigite formation has conduded, and cypically occurs w i t h k a several days Lom
the tint contact wth water (Stein, 1961). This renewed C d hydration may occur
simultaneously sith CjS h$ration and the two wiu appear as one peak temperature rise.
When desaibing the qualities of Gesh concrete the term \vorkability7 is ofien
applied, yet it laclis an =act definirion. Workability' can be described in terms of i a

qu;ilitative components, such as flow, compaction, stability, ease of fnishing, and i o
abiliv to be pumped.
Each of these components is a rheological quality of some
complesiy, how-ever, each of these characteristics is determined by the ease with which
an applied stress results in some f o m of plastic deformation (Kantro, 1980; hIantegazza
and hlberti, 1994). The ability of a cernent paste to resist a gii-en shear suain is
amibuted to the intemai Giction of the solid particies, the Fiscosity of the liquid medium
and forces of electrostaac attraction or repulsion benveen the partides (Guo, 1994). The
term workability can chus be described as a hnction of both yield stress and plastic
vkcosity (Kantro, 1980).
Workability has traditionaUy been rneasured in terms of slump, although the
slump test is more a rneasure of consistency than of worlrability. Studies have pointed
out that slump is dkectly related to the yield value of the conuete, o r cement paste
(Kantro, 1980).
Hence, slump can be used as an indirect methoci for rneasuing
consistency. D u e to the formation of hydration products when cement is reacted Mth

water, the workability of the concrete is progressively reduced, resulting in the loss of
slump with tirne (LMantegazza and Alberti, 1994).
ISSUES IN ADMUCTURE COMPATlBlLlTV
LITERATURE REVlEW
10
CHEMICALADMIXTURES AND THELR USE IN CONCRETE
2.4
Production of high-swngth concrete or durable concrete resistant to severe

environmental conditions can not be reaked by the use of plain portland cernent
concrete, chernicai admi~turesmust be incorporated into the
N e d e defines an
admiunire as a ccchemicalproduct which, except in speual cases, is added to the concrete

mis
in quanaties no larger than 5% by mass of cernent dung mixing or dueiig an
additional mi*
operation pdor to the placing of concrete, for the purpose of achieving
a certain modification, or moditications to the n o d properties of concrete" ( N e d e ,

1997).
The most p i c d reasons for which admixtures are used in practice are:
To reduce the cost ofconstruction;
To achieve the properties in concrete more effectively than by
other means;
To ensure the quality of concrete dung the stages of
misin&
transporting, plang and cuPng in adrerse w-eather conditions;

To improve the durability of concrete esposed to adverse weather
conditions.
Most of the commeral chemicai admixtures are composed of orgaaic
compounds, and perfonn rarous hnctions through a variety o f both phpical and
chernicai interactions with the hydrating cernent phases- The addition of chernical
admi~nires further cornplicates the already elaborate behaviour of hydrating cement
paste. Ir is important to understand the specific effects and consequences of acLmk~ecernent interactions prior to incorporation into concrete. To optimise the hnctional
properties of admixtures in a given cernent appropciate understandkg of their mode of
action must be reached.
The majority of chemicai admixtures can be dassified, according to L I S T ~C

494-92, as:
TYPe A
Water-reducing
Type B
Type C
Retarding
Type D
Water-reducing and retard@
Type E
High-range mater-reducing o r superplastizing, and
AcceIefaeing
T F G High-range w-ater-reducing and retarding or

superplasticizing and retarding
Howeever7this p a p a s h d o d y investigate the influences of Air En-
Agents
(.-WA), water reducers (WR), and or superplasticizers (SP) when used in concert in the
production of concrete.
As k i r name impiies, an AEA is used to purposely entrain microscopic air

bubbles in to concrete. It has been proven rime and h e again that air-entrainment has
the effect of drasticallv improving the durability of concrete elrposed to moistue d u k g
cycles of freezing and thawing (Kosmath et al.,
1995). The mechanics of how the
entrained au void svstern works w d not be discussed here since it is not relevant to the
issues at hand. However, ifs influence on early aged concrete and its interaction with
admistures ltili be covered.
The majority of traditionai air entraining admisnues
are created Gom the by-
products of the pulp and paper industy, refnernent of petroleum or the processing of
animal fats and hides (Dodson, 1990)- The main forms of air entraining agents can be
classified as (a) saits of fatty acids derived Erom animal and vegetable fats and oiIs @)
alkali salts of wood resins (c) allrali salts of sulphated and sulfonated organic compounds
(Neville, 1997). It is important to noie that AEA's d o not generate air, rather they simply
stabilise the bubbles that are formed during the miviog- AEA are comprised of long
ISSUES IN ADMIXTURE COMQATlBlUlY
LITERATURE REVIEW
12
chained soluble molecules that hnction as surfa-ts
and act to d u c e the surface
tension of the \iater. The hEA adsorbs onto the cernent partides, causing them to
become hydrophobie, so chat the bubbles that are generated during the mixing process
become adhered to the cernent (Ramachandran, 1995).
This process stabilises the
entrained air and prevents th& coalescence.

Once incorporated into the mixture the e n t r a i d air becomes c o ~ e r e dby a
sheath of LE
molecules that repel one another, resulthg in the u d o r m dispersion of the
m u a l i e d air
(Neville, 1997). The film that encapnilates the ai.void must be able to resist
intemal and =temal pressures, deterioration and resist coalescence while the concrete
remains in its green state (Dodson, 1 9 0 ) , it must also not impair the physical properties
of the concrete. Howerer, even if they were to possess some deomentai propertes they
are used in such s
d amounts that the effects would be negligible.
The incorporation of an air-enrraining agent into a concrete m k not O+
exhibits
beneficid qualities in concrete's hardened state, but also &parts some beneficial traits
while in its plastic state. Air-enrraining agents have been found to have the ability to
improve workabiliy of fresh concrete, the presence of the microscopie air void .stem
has the effect of acting as 'bdbearings' that help to tluidise the concrete to a Limited
estent. The enaainment of e v q I0/o air d o w s for a water reduction of 1h, up to 16%
of entrained air (Dodson, 1990).
Enuained air dso benefits kesh conaete by
eliminating or mliimising segregation and subsequent bleeding by at least nvo

mechanisms (Dodson, IWO):
1. It provides a certain degree of buoyancy to the aggregates, reducing
their rate of sedimenta tion; and

2. It reduces the effective volume through which the difierential
movement of water may occur.
ISSUES IN ADMMTURE COMPATlBlLlTY
When air-entrainkg agents are used with other admiunires, the interaction
between the admixtures and th& interaction with cernent become important for
compatibiliy purposes (&machandran, 1995). When used with a wxter-reducer, there is

the chance that less AEA wili be required to achiere a desired air content in concrete,
even if the \WR has no air enrrainlig propertes. Water reducers alter the physicd o r
chemical environment so as to permit the AEA to operate effisiendy (Neville, 1997). It
should be noted that some water-redung admixtures have air-entrahing characte&ics,
most noted wodd be those tbat are based upon Lignosulfonates (Ramachandtan, 1995).
Unfortunately, some combinaaons of chemical adrnixtures are capable of

producing detemental results. The incorporation of some superplasticizers into airentralied concrete may produce an unstable roid system.
Typically, the irnpro~ed
compaction and fluidity achieved with a superplasticizer can faciltate the escape of some
air or coalesce the air bubbles to sorne estent ( N e d e , 1997; Okkenhaug and Gjom,
1992; Rarnachandran, 1995). The entrained air is thus more easily .1--rked out of the
concrete d u k g compaction, vibration and h i s h m g , causing a decrease in the air content

and to ta1 air void surface areas, resulting in an inuease in the spacing factor. The extent
of die superplasticizer's effect on the air void system depends on the dosage used (Dhir
and Yap, 1983). In g e n d the addition of an SP to concrete inmeases the bubble
spacing, and sornetimes to unacceptable lemls. Research has shown that the freeze-thaw
durability of air-encralied superplasticked conaete, in spite of increased bubble spa*

factor, not to be adversely affected when compared with that of the air-entrained
reference concrete (MacInnis and Racic, 1986; IMalhotra, 1981).
The type of
superplasticizer used also has an influence on the air void system. It has been noted that
by using a melamine-based admixture, as opposed to a naphthalene-based agent, a better

and more stable air void system can be produced (Okkenhaug and Gjorr, 1992). This
illustrates the importance of using a compatible combination of materials in the

production of concrete.
ISSUES IN ADMlXTlJRE COMPATlBlLlN
Aside kom the influences of other admi~hireson the entrainment of au, other
factors that influence the ML4 requkmeot are (Dodson, 1990; N e d e , 1997;
Ramachandran, 1935):
1. Fineness of portiand cernent
- As the heness of a cernent increases, the
ability for an air-enelitrainiog agent to act becomes inhibited.
It has been
specdated that the presence of the ultra-fine Lacnon has a tendency to dismpt
the proteciive 61m around the entrained air void, reducing the effdveness of
an hEA to protect the air voids Gom codescing.
This has the effect of raishg
the required amount of AEA to produce the desired air void sysrem.
2. Alkali content of concrete - aUialis tend to depress the solubility of calcium
ions in the aqueous phase of concrete. The calcium-anioaic A E X 61ms that

surround the air voids in the keshly mived concrete are probably thinner (or
possibly more soluble) than those which would develop in concretes of low
alkali content. This reduces the stability of the air void system.
3. The amount of coarse and fine aggregate - as the mauimum size of coarse
aggregate (CA) inueases
the air requirement deueases; the hnc aggregate
portion of the rnkture that serves as a screen to trap the air during mishg. The
fine aggregate provides interstices that contain paste and air bubbles, so it
generates the air elfiuendy. Thus, as the portion of sand in the total aggregate
is increased, so is the air content of the concrete.
4. A high proportion of ultra-fine material in the aggregate - The presence of
finely divided materiais causes a reduction Li the air content of concrete and an
increase in the required dosage of air-entrainingagent,
5. Temperature - a higher temperature of the conaete resula in a lower air

content, and vice versa.
ISSUES IN ADMIXTURE COMPATIBILITY
6. Mixes with high cernent contents and v e y low w/c ratios (0.30 co 032)
require extremely high admi,xture dosages.
7. Contamination by oil or grease (even in very s
4 amounts) contributes to
poor entrainment of air.
8. Use of fly ashes with high carbon content - The hW may be adsorbed
ont0
the surfaces of carbon partides thus increasing the content of agent
required.
2.4.2
WATER-REDUCINGADMILCTURES
As implied by th& m e , the function of these admivtures is to reduce the
amount of water needed in concrete, usualiv in the range of 5 to lQO/o,

to achieve a aven
wvorkability (Kosmatka et ai.,
1995; N e d e , 1997; Ramachandran, 1995). G e n e d y
s-ater-reduog admixtures are water-soluble macromolecular substances which, when
present in the cement paste, may be adsorbed at the surfaces of cernent grains to form an
inten-ening iiquid layer benveen adjacent grains thicker than what could be maintruneci in
the case of pure water. This lowers the intemal fricaon and reduces the yield stress of
the paste, thus a 'lubricating' effect can be wimessed dispersing the cement particles, and
they remain dispersed &ter mising (Guo,1994; Helmuth et al., 1995). Some researchers
have suggested that the plasticking eect may be due to a retardation of enriogite
formation, and a decrease in the interlocklig effect of ettrngite panides, thus produang
decreased miter dernand (Ramachandran, 1995); o r by irnposing a net n e e e electic
charge to the cernent partides produchg an electrostatic repulsion beween partides.
What ever the mechanism may be, the liberated w-ater that is fked Gom the flocculated
system now becomes available for lubrication ( N e d e , 1997).
Water reducers can be employai to obtain diffrrnt physical effects on the plas tic
state of concrete; they c m be used to reduce the quantity of mixing \%merrequired to
produce concrete of a given slump, reduce w-ater-cementhg materiais ratio, d u c e

cernent and .riater content, or increase slump (Kosmatka et al., 1995). Due to slow
ISSUES IN ADMWTURE COMPATlBlUTV
LITERATURE REVlEW
16
hydration dwng the induction phase, the effects of a water-reducer dimliish with time
as the admixture is slow-ly removed Gom solution by sorpaon on the hydratai products
(Helmuth, 1995). The efficiency of a witer-reducer tends to be greatest when used in

concretes made Gom cements of low aLkali and/or low- C d contents (Docison, 19W)However, the effects of alkalis and C d content are topics that wiU be discussed later.
It shouid be expected that that the interacon of a chernical admivture that is
physicdy adsorbed o n to the reactive components of a cernent, may significantly alter
the hydration sequence of cernent pastes and concretes dwing the induction p&od
(Jolicoeurand Sirnard, 1998; Meyer and Perenchio, 1979). The use of a water-reducer
must \t-airrant some cauaon since that most are capable of retarding the hydration of the
cernent. This ability of a w-ater reducer tends to be the result of the presence of a sugar
or carbohydrate in the water-reducer- The retardation of the time of set may be e-xtreme
if the recomrnended addition rate is esceeded (Kosrnada et ai., 1995).
The dispersing capaaty of these admkniies can contribute to accelerated

hydration of the cernent and lead to an increased rate of slurnp loss. Under non-waterreduced conditions, the mixing of portland cernent and -ter
causes tiny bubbles of
warer to be encapsulated by cernent partides, rendering a Gacaon of the mishg a m e r

unai-ailable for workabiiity, placing and hishing (Dodson, 1990). By dispersing the
cernent
particles some of this entrapped water becomes liberated and d e s additional
surfaces OF cernent partides anilable for hydration (Dodsoa, 199; N e d e , 1997). A

second resdt of the increased dispersal oE the cement partides is that the surfaces of
cernent particies formerly abutting each other are now- arailable for eady hydraton. This
liberates approximately 12-20% of the cernent surface for direct contact Mth a-ater
(Dodson, 1930).
The problems of accelerated set can be overcome by incread dosage, or redosing, howexr, this may result in unacceptable set retardation, if at all possible, a slight
delay to the addition of the adrniuture in the m
-i
process c m enhance performance
( N e d e , 1997).
ISSUES IN ADMUC~URECOM~A~~~L~TY
Most water-reducers in production today are based on lignosulfonates, the hrst

polyrneric wvater-reducer that n;as used by the coacrete industry. They are manufacwed
Gom one of the wastes produced by the pulp and paper industry, maste Liquor whose
composition indudes about 20-309'0 of Iignin (Ramachandran, 1995). This liquor is
primarily a solution/suspmsion of sulfonation products of LignLi, decomposition

products of ceilulose and lignin, various sugars, and sulphates (Ramachandran, 1995).
When hrst introduced to the industry, lignodonates were reiatively inexpensive and
could be esploited wvthout much cost Unfortunately, due to the non-udormity of the
raw materials used variances in sugaz content and lignin decomposition products
produced problems associated aith excessive set retardaaon and air entrainment (Aitan
et al. 1994; Ward et al., 1980). The reliability of the performance of these admixtures
has become more predictable as the producers of these products have drastically
irnproved th& quality control (Ward et al., 1980).
hlthough the probiems assoated with excessive retardation in the eariy
generations of iignosdfonates have been minimise4 they stiu rnay occur when used at
hqgh dosages.
The presence of sugars and other contaminants in commercial
Lignosulfonates can be biamed for this, since that these compounds are difficuit to
remove completely (Atciu, et al., 1994). Under certain circumstances, a high enough
dose of a iignosulfonate admixture may pemianently suppress hydration of C S and

inhibit strength developmenk pYticularly in cements with rery low C d content and lowv
alkalis (Johnston, 1987).
The use of lignosulfonates should be avoided for the
production of high slump loa- w/c concrete; the problern is so serere that the Cernent
and Concrete Association in Bntain have categorked lignosulfonates as a category TV
retarder, indicating that they act as cernent destroyers when used at faidy high doses
(Johnston, 1987).
Lignosulfonate-based acimisaes s d maintain some air-entraining characteristics
(Nedle, 1997; Okkenhaug and Gjorv, 1992; Ramachaadran, 1995), therefore, the dose
of any riEA should be reduced to avoid excessive air entrainment.
ISSUES IN ADMIXTURE COMPATlBlUTY
LITERATURE REWEW
18
Superplasticizers, are additives that are water-soluble dispering agents. When

incorporated into concrete these admixtures act rnuch in the same way as ordioary water
reducers, oniy nith far p a t e r efficiency. In compacison to o r d i n q uater-reducing
admktures, SP's can be used in considerably larger dosages without such a significant
delay of cernent hydration and setting. In facq they are capable of reducing the mater
requirements of concretes by 15-30% (Kosmatka et al., 1995; Singh et ai., 1992), and can
be used to produce flouable concrete or concretes of very low w/c ratio.
Superplasticizers are either synthetic products, produced dLectiy from pure components;
or obtained as industrial by-products from 0th-
indusmes (Atcin et ai., 1994;
Ramachandran, 1995). The most common agents that are used as SP's are m d y
sulfonated melamine-formaidehyde (ShIF) condensate salts and su1fonated nap hthalene-
f o d d e h y d e (SNF) condensate salts, both of these agents are synthetic products that
have been f o d a t e d from pure components
et al., 1991). However, due to their
comparaticely low costs, research c o n ~ u e sin the dedopment of a superplasticizer

based on m&ed
lignosulfonates, Gom which sugars have been completely rernored
(Ramachandran, 1995). Due to the benefits they provide in improving the hancikg,
placing, compaction and xkg of cernent dong with other technicd economic
advantages the use of superplasticizers are increasing in commercial use (Singh et al.,
1992).
The e-xact mechanism with which superplasticizers act has been the centre of
much debate, however, it is agreed that superplasticizing admixtures act by causing the
cement agglommtes to disperse (Maihoua, 1981; Singh et al., 1992). This dispersion of
the cernent agglomerates iiberates water that is typicdy bound and inaccessible for the
fluidification of the concrete. The e f k of the superplasticizer is exhibited by large

increases in slump for the respective w/c ratio. As long as suffiuent superplasticizer
moledes are present in the solution thek influence wiu persist; as the p o l p e r s are
c o n ~ u a i l ybeing entrapped in the hydration products the effects of the superplasackr
dimliish (A-tcin et al., 1994). The increase in fluidity can be s h o a lived, and may
ISSUES IN ADMlXtCIRE COMPATlBlLlTY
dissipate within as little as 30 to GO minutes from the time of the addition of the SP and
the concrete rererts back to its original consistency (Malhotm., 1981). This can be even
shorter at high tempefames.
The newer generation superplasticizers that have been
developed are less sensitive to these effects. This rapid loss of workability is terrned as
'slump loss'. The rate of slump loss can be ambuted to the type of superpiasticizer
used, its dose rate, the chernical composition of the cemen& chernical and physical
changes in the cement paste of Eresh concrete, and other extemai factors 6.e.
iemperaueJ mi*
the,
etc.).
This rapid dump loss c m be overcome mith an
increased dose of the superplasticizer, although doing so may result in undesirable side
effects such as excessive set retardauon, which may prove to be estremely costly. In
such a case it is said that the cernent and the superplasticizer are incompatible in terms of
rheology (Jianget al., 1998).
Although superplasackers are far more effective than ordinary \vater reducers
are, they remain quite e-cpensive Li cornparison to them. For h i s reason the nvo are
tvpically used in combination together (Kosrnatka et al.,
1995). The superplastiQzer
addition is typicaily delayeci u n d several minutes after the addition of the wxter reducer.
This way the benefits of the WR can be achieved without the rapid consumption of the
superplasticker in the early hydrauon reactions of the cernent.
2.4.3.1 How SUPERPLASTICIZERS

W O R ~rn CONCRETE
When &ed
with water, portland cernent has a strong tendency to form flocs.
This tendency is the result of several types of interactions induding van der Waals
in teractions berneen particles, electrostatic attraction, and snong interactions involving
water molecules and hydrates (xtcin et al., 1994). The flocculation of cement particles
l a d s to the formation of an open nemork that cffectively traps part of the misingwater,
and renders it unavailabk for surface hydration of the cernent particles and for the
fluidification of the mi\-. Hence, to achieve a workable mk larger volumes of water are
used than is necessary for complete hydration of the cement Unfortunately when tqing
to develop hgh-strength concrete the w/c ratio musc be reduced, which would mean a
LITERATURE REVlEW
- -
- --
20
-
- -
--
--- -
- --
reduction in the workability of the concrete. In order
CO produce
a low w/c coaaete
with sufficient workability would require that the cernent partides are (A-tan, 1998)
propedy deflocculated and (A-tcin
et al., 1994) kept in a state of hi& dispersion.
This is where superplasticizers corne into effect. SuperplastiaZers are d a c e
active agents, meaning that they act on the surfaces of cement partides and influence the
reacuons that d e place at the cernent-water surface interface. The exact method with
which they work is of debate.
FIoweoer, most researchers offer esplanations that
incorporate one or more of the following mechanisms (A~cin

et al., 1994):
1.
Lnduced electrostatic repulsion berneen parrides;
Induced steric hindrance preventing partide-to-particle contas
3.
Dispersion o f cernent grains, reieasiag wiater trapped w i h

cernent Qocs;
4-
Inhibition of the surface hydration reactions of the cernent

particies, lea-
more -ter
to fluidify the mts; and
5. Change in the morphology of the hydraaon products.

The f k t nvo mechanisms are the most s ~ c a n int t e m s of fluidification of cement
pas te and concrete, the others listed tend to be side effecrs o f the hrst nvo mechanisms.
When contacted aith uater, cernent partides acquire electrostatic charges of
different magnitudes and charge.
As a resdt of rhese electrostatic forces, cernent
particles w4.i either be repeiled by others of like charge, or d

lbe attracted to particles
eshibiting opposite surface charges. The combined influences of these forces \iucause
the coalescence of cernent particles and form stable floc structures, which is then Further
et al., 1994).
stabilised by soluble electrolytes (e-g.allrzlis) ( J o i i c o e ~
The most agreed to method of action for superpksticizers is that the dispersion
of cernent partides is accomplished by the adsorption of the long chained polymeric
molecules of the superplasacizer onto the surface of the cement grains (Andersen and
Roy, 1988). Each SP molecule possesses a hydrophobie group that becomes adsorbed
onto the surfaces of the cernent and hydrate particies; while an opposite hydrophilic
group becomes aiigned with the water side of cement-viater interface (Uchikawa et al,
ISSUES IN ADMUCTURE COMPAflBlLlN
1792). The net resdt is that the adsorbed ~ ~ t u imparts

r e a e h negati~~e
elecmical
charge on to the cernent pariicles. As a resulq an electrostauc repulsion is developed

benieen particles and causes the dispersion of the flocs that are n o d y f o m d ,
produchg the water-reducing effect (&tcin et al., 199+ Jolicoeur and Sirnard, 1998;
Neville, 1997; Uchikawa et al., 1992).
Others have pointed out that in addition to the electrostatic forces induced by the
WR and SP admiunires, a series o f stecic repuisive forces are also developed.
The
physical interference (steric hindrance) of adsorbed m o l d e s onto the cement grains

w i l l lead to additional shon-range repulske forces (Jolicoeurand Simard, 1998;Jolicoeur
et al., 1994; Uchikawa et al., 1997). Since the average molecular size of?an admixture is
sereral hundred times the size of a -ter
molecule the adsorbed molecules prevent
particle-partide contact (Guo, 1994). Stenc hindrance is a result of the osmotic pressure
that is generated due to the tendency of admis~es
to concenuate at
the cernent g&s,
this increase in osmoac pressure reliet-es the local increase of density caused by
orerlapping of the adsorption layers of admixture (Uchiliawa et al., 1997).
The
magnitude of these forces is closely related to the moiecular structure and size (molecuiar
wveight) of the admixture.
(Uchkawa et al., 1997).
In addition to the physical mechanisms that produce fluidifiing effects,

superplasticizers also possess chernical properties that are capable of inhibiting surface
hydration reactions of the cernent partides, leaoing more wxter to fluidify the
SP
molecules can bind ont0 h h l y reactive surface sites (cg. C3A or CAF) and reduce the
rate of subsequent hydration reactions. Jolicoeur et al stated that "the eady hydration
reaction behaklour shows that the SP effect is not merely that of a physical barrier to
water and ion diffusion at the interface; it seems best described as a partial b l o c b g of
speafic surface sites which play a key role in hydration reactions" (Jolicoeur et ai., 1994).
2.5
SLUMP ~
s AND
S STIFFENING
OF CONCRETE
It can be e\~ected that a4 concretes u d undergo a process of stiffeolig and

hardening brought about mainly by the hydraaon of cernent Rheological properties of
ISSUES IN ADMIXTURE COMPATiBILIlY
22
LITERATURE REVlEW
nonnal concrete are determined by the amount of mkkg water, calcium sulphate, and
the reactirity of the cernent, such chat slump loss problems are rare and accidental (Jiang
et al.,
1998)- This l o s of workability may be accelerated by the influences o f
evaporation of the mi~.i.g water and adsorption of =ter
by the aggregates.
The
reduction of the free water of the fresh concrete causes an increase in the inter-partide
contact and bondng of the cernent particles, thus reducing the fluidity of the mix
(Ravina and Soroka, 1994). Slurnp loss, as usuaUy evpehenced in practice posses no real
problems because slurnp can cgpicallp be maineined long enough so that the concrete
can be worked and manipulated to its desired h s h (Ratina and Soroka, 1994).
Even though slurnp loss is espected in aii concretes, the rate at wvhch slump is
lost c m be drastically increased with the incorporaaon of chernical admixtures into
concrete (Jiang et d,1998; Meyer and Perenchio, 1979)). It is essencial that the Gesh
concrete cemains workable so that the trauspomtion, placng, consolidation and
tinishing can be done without excessive effort and in reasonable tirne.
Concrete
suffenng Erom hadequate workability will be either re-tempered with water in the field,
to irnprove workability, or wil( not be sufficiently consoiidated or poorly finished; neither
a desirable outcome (Hover, 1998).
In low
W/C
ratio concrete where the use of a superplasticizer is a musG the
rheological properties become largeIy a hnction of the superplasticizer dosage and its
interaction with other reactive components of the concrete. The influences of water
reducers and superplasticizers have ~ . p i c d ybeen as e-xpected. However, as w r e n t
practices are reducng the \kater-cementitious mat*
ratio to extremes, une-xpected
behaviouc occasionaliy arises in particuiar cernent-niperpiasticker cornbinations, despite

the fact that both components have satisfied th&
respective acceptance requirements.
Such phenornena are usually deemed as cases of cernent-superplasacizer incompatibility

(Atcin et al., 1994).
ISSUES IN ADMIXTURE COMPAflBlUTY
It shouldn't be assumed chat any indiscriminate combinaaon of admiunises and

cernent \dlbehave satisfactory- An admixture rnay have a proren performance record
when used separately; however, it mav produce compatibility problems a-hen used in
combination with others (Neville, 1977).
Furthermore, assurnptions should not be
drawn on the performance of an admixture if another admixture that belongs to the

same genenc type has perfomed accepmbly. Admivtures of the same genePc type may
still bebave differently in concrete due to variations in molecular weight, the different
cations associateci with them, chah length, erc. The s a m e condusions caa be drawn
regardmg the behaviour of cements of the same type; differences in mineral, alkali,
sulphate contents and h e n e s s can vary cirastically (Ramachandran, 1995).
The reasoos for the seasitiviry of some cements to these issues are poorly
understood, but typicdy can be
or of the adrm-tue.
easily remedied by the replacement of either the cernent
Howeier, an understanding musc be dwdoped so that the
occurrences of such events can be minimised, if not elimio;ited. The research p e r f o d

in this field has evpanded drasticdy in the past few deades and many mechanisms of
incompatibiiity have been discussed.

Since cernent consists of multiple compooents and phases, the chemistry
involveci in i a hydration is lairv complicated and becomes Lrther agpvated by the
addition of chernical admi~tures.The comple'rity of these interactions is compiicated by
chernical admiutmes due to the great varkty of components, both organic and inorganic,
in their formulations (Heimuth et al., 1995).
Hence, one shouid e-xpect that any
esplmation on the causes that ma produce c o m p a a i t y problems would involve many

mechanisms, both phpical and chemical. The cernent-superplasticizer interaction c m be
affected by nurnerous parameters of either the cemen& such as its chernical and phase
composition, its h e n e s s and its content of sulphares and allialis; or of the
superplasticizer itselc svch as its chemical nature (or molecular structure), its molecular
weight, its degree of sulfonation and its counter ion (Jianget al., 1998; Ramachandran,
ISSUES IN ADMlXTURE COMPATBlLlTY
1995). Unfortunately, knowing the chemical compositions of the cernent or c h a n i d

admixturesc m dratv no dehnite condusions, ody generai trends have been discovered.
There have been reported fieid cases where concretes have experienced an
unexplained rapid slurnp loss soon after mi+
(Hersey, 1975; Meyer and Perenchio,
1979; Dodson and Hayden, 1989). These occurrences usu*
arise in the presence of
chemical admixtures in a Iimited aumber of cernents, even though when used alone these
cements exhibit no tendency to produce abnomal se*
(Hersey, 1975). The factors
respousible for the slurnp loss of admixture enhanced concrete, although complicated,
may be attnbuted to an amay of influences induding initial slurnp value, type and arnount
of SP used, type and arnount of cernent, time of addition of SP, humidity, temperature,
miuing, the presence of other ad&inires
in the miu, and the accelerated formation of
ettringite (Ramachandran, 1981; Ramachandran, 1995). Extensive research has been
conducted in this field ooer the years, and the key principies are:
1. The C
A content of the cernent;
2. The effect of the sulphate content and its form in cernent;
3. Aikalis and their influence

4. Average molecular weight of the superpiasticizer used;
5. Delayed addition of the superplasticizer;

6 . Temperame of the concrete;
7. The fmeness of the cernent and the presence of excessive &es; and
8. reduced paste and water content; and

9. Superplasticizer degree of sulfonation and nature of the counter-ion,
Each of these factors =dl be discussed in the foiiowing sections.
ce men^ being
the most reacuve cornponent in concrete, h a , received much
attention in terms of research to determine the effects of its composition on the

rheological behaviour of fiesh conccete. The foiioaing sections desabe some of the
ISSUES IN ADMIXTURE COMPAfl6lLlN
relex-ant issues, as determined by previous works, regardkg the composition of the

cernent and th& influences on slump and slump loss in superplasticized concrete.
Comprising only a s m d percemage of a portland cernent's composiaoo, the C A

present can s g n i i c a n *
affect setting and eady hydraoa. For this reason much of the
previous work regarding the influences of amer reducers and superplasticizers has been
devoted to studying theif role in C d hydraaon (Ramachandran, 1995). It has long been
accepted that due to their high reactivicy Mth water and rapid hydraton, relative to the
other phases of the cemeoh the aluminate phases and th&.hydratioa producn are key to
the early hydration processes and slump loss. The behavour of hydrating cements and
structural formation during the &t tsvo to three hours is governed by reactions of the
aluminate phases, partidady tncalcium aluminate. The processes of se+
sue+
and early
development, on the other hand, is mostly developed by the hydration of the
silicate phases, particdady CjS aolicwur and S k d , 1998).

C d sen-es as a base for the development of a loosely coagulateci structure. In
tirne, it protides a rapidly det-eloping crystalhe stmcnrre of ettrkigite, which et-entually
permeates the entire volume of the systern. This structure may be destroyed, and usudy
is destroyed through the mechanicd action of mixing. This results in the fomiation of
small free crystals of etmngite, which determines the water requirements related to
workability. The comparatively slow silicate reactioas that determine the strength of
cernent paste in hardened mortars and concrete develop against the background of the
aluminate reactions (Khaiil and Ward, 1980).
In portland cement the dumina containing phases, especially the ticalcium

aluminate, are the phases that react rapidly euough to gire rise to the undesirable
quickset (Lerch, 1946). As oon as contact is initiated benk-een the cernent and miter, the
rate at which heat is evoloed inaeases rapidly and reaches a s h q peak. This peak has
been a&buted to the rapid reaction of C d compounds. In comparson with silicates,
ISSUES IN ADMIXTURE COMPATIB1LilY
26
LITERATURE REVIEW
aluminates are g e n d y tugh in reactiviy and react very rapidly owing to the high
solubility ofboth the unhydrated and hydrated states (Khalil and Ward, 1980).
Invesgators have ofien related the problem of rapid slump loss to the C d
content of superpksticized concrete due to its high reactivity, g i k b i g it the greatest
potential influence upon slump loss. The results of these investigations are cootroversd
because CJA reactions are highly dependent upon the amount of gypsurn added to the
cernent to control its se*
(Khalil and Wrd, 1980). However, its influence cannot be
complerelr dismissed. Research bas indicated that the tricaluum alumliare phase, and to
a lesser degree te+ncalcium durninoferrite, and their hydration pro duc^ exhibit
preferenual adsorption of water reducers and superplastickrs, thereby rend-
them
inactive and allowing the main cementing compounds (CS and CzS) to control the
reaction (Blank et al., 1963). D u e to its rapid adsorption of dispersants, the C d phase
may act as a sink for water-redung and superplastiaMg adxriistures,
rend-
them
u n a ~ d a b l efor fluidifcatiou of the mis (Ramachandran, 1995). Accordlig to Malhotra,

cernents having moderate to high C d contents ( C d > 9.0h) when used in
superplasucized concrete -hibit
increased slurnp loss, @Ialliotra, 1981), while the
opposite eeffet c m be witnessed in concretes made with cements h a ~ ag low C A

content ( C a < 5.0/o) (LMalhotra, 1981).
It is important to realise that the duminous compourtds of portland cernent

hydrates very rapidly, and if dowed to proceed unchecked w d form a structure built of
stout crysds of calcium hydroaluminates, resulting in a fias h set (Guo, 1994;Helmuth et
al., 1995). Thus it is elident that the rate at which C3A hydrates musc be regukted. For
this purpose some fomi of calcium sulphate (CaSOr) is inter-ground with cernent clinker
to moderate this reaction.
The sulphate ions that go into solution control the reaction
rate by reactlig with the tricalcium to f o m miseci aluminate sulphate products namely
ettPngite and
monosulfoaluminate (Dodson and Farkas, 1964; Feldman and
Ramachandran, 1966;Guo, 1994;Jolicoeur and Sirnard, 1998; Lerch, 1946; Meyer and
ISSUES IN ADMIXTURE COMPATlBlLllY
27
LITERATURE REVfEW
Perenchio, 1979)). Due ro th& mtical role in the h y d d o n processes of cemenk any
change to the suiphates and their d u e n c e s on cement due to the use of chernical
admixtures may be expected to be sigdcant-
To produce normal set portland cement paste, mortar or concrete, Cas04 must
be sufficiendy soluble in the uater/cement aqueous phase to provide the calcium and
sulphate ions necessary for the formation of an etuhgite
on the cernent parlicies-
This protecuve film reduces the rate at w-hich M e r C d can enter solution. In cernent,
SOS also serves a second purpose, in addition to retardlig the hydration of the
aluminates; it is also responsible for acceleracing the hydration of the silicates, if present
in the proper amounts (Haque et al., 1987; Khalil and Ward, 1978; Khalil and Ward,
1 980).
In a paste made Gom a commercial cernent an optimum concentration o f Cas04

is soon estabiished in the iiquid medium so that the hydroaluminates produced are
immediately m e d Lito calcium sulfoalumliate or etmngite by reacclig with Cas04 and

Lune. The etmiigite, when deposited on the surfaces of cernent
proiides an
effective barsier to W e r reactions. This hLn of ettngite, which snrrdily retards the
hydration, lasts as long as the Cas04 concentration of the iiquid medium remains at a
certain htgh level. M e r this, hydration resumes its inpetus and a normal se-
begins
(Guo, 1994). For the initiai reactions that are n e c e s s q to form these dense coatings the
solution must become rapidly saturated u,ith respect to both calcium hydroside and
gypsum. Should this saturation not be achia-ed, or is delayed, there is considerable risk
of early stiffening, o r in extrerne cases, flash se5 associated with rapid reaction of the
aluminates and heat liberation
(Helmuth et al., 1995). In the absence of an effective
retarder, such as h e l y ground gypsum, the release of siiica and dumina into soluaon
l a d s to the rapid precipimtion of alumina-silica gel that causes both early stiffening and
retards hydration of C3S and strength de\-elopment (Helrnuth et al., 1995).

At this point it becomes necessary to distinguish the aferences between 'flash'
and 'fdse' set.
Flash set resuits Gom rapid hydration of C d in the absence of calcium
sulphate and is often distinguished by its considerable heat evolution and the resultbg
stiffening of fksh set which cannot be easily dispelled by mechanicd disturbance
ISSUES IN ADMIXTURE COMPATlBlLlTV
(Dodson and Hayden, 1989)- Talse' o r 'plaster' set rnay develop if the gypsurn in the
cernent has been dehydratecl to hemihydrate during intergkdmg with a c h k e r that is
too hor
If the cement contains more hemihydrate than is required for immediate
combination with the aluminate phases, it aiu rehydrate and produce a rigid skdeton of
gypsum when contacted with w-ater (Heknuth et al., 1995; lMeyer and Perenchio, 1979).
If 'alse' set occurs afier miviag is completed, a brie re-mixing of the concrete aithout
req*
any additionai amer can d
p elLniaare it
The rate at whch C a hydrates is slowed as long as gypsm is present The

process of C d hydration may e v e n d y deplete the sulphate concentration in the
aqueous solution. Shouid ali the gypsum be consurned before ali the C d has been
reacted to orm calcium sulfoaluminate a rapid reactioo ad occur mith the remairing
C d (Lerch, 1946; Meyer and Perenchio, 1979). Thus, the length of rime that C d
persists is a hnction of the sulphate content of the cernent (Meyer and Perenchio, 1979).
The required gypsum content ro produce a propedy rerarded cernent is af6ected
b - the composition and fineness of the cemen&dosage and type of admixture used, as
weil as other iduences such as increased temperatures (Haque et al., 1987; Khalil and
Ward, 1980; Lerch, 1946). D u e to its effects on strength developmenb shrinkage, and
n v e h g , there esists an optimum range of SOScontents (Haque et al., 1987; Ward et al.,
1980), howvver, due to its impact on durability a masimum iimit has been instituted by
certain organisations induding the ASIM.
Due to its key role in the early hydration
reactions of tricalcium aluminate it is obvious that should there be an alteration to the
S o l content some f o m of abnormal setting may occur (Guo, 1994).
2.6.1.2.1
INFXUENCE OF WATER REDUCERS & SUPERPLAST~CIZER

ON THE
ROLE OF SIJLPHATES
As already noted, if the action of Cas04 in a paste is disturbed, abnomial setting

take place. The incorporation o f a water-reducing or superplasticking admknue can
cause the disturbance necessary to initiate such a case of abnonnal setring- Even though
a cernent may behave normally nithout the addition of a chernical admixture, it rnay
LITERATURE REVlON
29
behare as if under-suiphated when one is presmt (Khalil and Ward, 1978). Si.rnddy, the
S03 content of cernent
oui
have a pronounced influence on the slump loss of
superplasacized concrete- Researchers have conduded that the S03 content of concretes
should be optimised for use with such c h e m i d admi~nrre(Kaque et al., 1987; Khalil and
Ward, 1980; Ward et al., 1980). Optimisation of the S 0 3 content can result in improved
retention of the increased workability bene& obtained by the use of the admixture
(Khaiii and Ward, 1980). HoWever,optimisation of the sulphate coatent of a cooaete is
not viable.
It would be exrremely dimcult for a manufacturer to opcimise the
SO3
coatent of his cernent for a particular admixture, since this wodd have to be doue at the
time of production.
Cernent sery low in C d eidier does not require or requices v q iittle gypsum to
provide set-control and to optimise the strength potentiai of the cemenc. In the presence
of admistures, howeser, the gypsum requirements are rnodified to the =tent that
\vithout the additionai gypsum such cements can e-&bit excessive retardation (Ward et
ai., 1980). The presence of calaum Lignosulfonate (
0
increases the optimum gypsum
content for a given cernentAs suggested by Tagnit-Hamou et. al. and Tuthill e t al. problems of
cement/fluidiser incompatibility cari result from inadquate calcium sulphate in the
cernent of ION- w/c ratio pasres with superplasacizer or water reducers (Jianget ai., 1999;
Tuthill et al., 1961). The presence of chernical admisues can exert an influence on the
availability of sulphate ions raising the required SO, content for nomial hardening, and
may lead to the loss of concrete fluidity and belated harde*
of the concrete (Aitcin et
al., 1994). A pronounced flse setting of cernent pas te and, hmce, a rapid slump loss of
concrete
is usuaiiy brought about by the use of a superplasacizer o r water reducer, which
is probably amibuteci to delayed retardmg effect of CaSOr while the solution status of
the latter is distubeci (Guo, 1994).
The strongest arguments against adjusMg the S o i content of cements
commerciaily are (Xtcin, 1998) the as yet uannwered question of potential durability of
concretes containiog greater than normal arnounts of SO3 and (A-tcin et al., 1994) the
problem of quaiity control (Ward et ai., 1980).
ISSUES IN ADMUCTURE COMPATlBlUTY
LITERATURE REVlEW
30
Having gone through the effects of sulphate and its concenmtion in ponland
cemen&it is important to note tbat the form of sulphate used has a s w c a n t impact on
its ability to regulate the setting of superplasticized concretes.
Key to the issue of
sulphate's ability to produce cernent that cari perfomi as desired is that it must be readily
available in the solution- Thus the rate at wfiich the SO4> ions c m dissolve into solution
musc be chemicaily baianced with the chernical r e a c t i ~ qof the C a (A-tcin et al., 1994).
Hence any changes to the solubilitg rate of the sdphates c m s ~ c a n d influence
y
the
early setting properties of the concrete.
~Uthoughgypsum (CaSO.&HrO)
is more suitable for this task than other
sulphate orms, the use of naturai anhydrite (CaSO4) is growing in popularity due to the
reduced cost associateci Mth its use. N a d anhydrite, even when used in large amounts
\dlperforrn normally in portiand cernent. Howerer, cases of early stiffening have been
detected in concretes where mniral afihydrite (used to replace one-third or more of the
gypsum) m s employed when water-reducing and superplasticizing admixtures u-ere
utilised (Docison, 199; Dodson and Hayden, 1989; Helmuth et ai., 1995).
The problem of rapid set and impaired uater-reduction that results d e n
anhy&te is used in superplasticized concrete is a consequence of its rate of solurion.
The rate at which anhydrire goes into solution is slower (a few hours) when compared to
dcin that of gypsum or calcium d p h a t e hemihydrate; diis inabiliq to rapidly solubilize

produces a ccsulphate-sraned" system in the concrete, in which the superplasticizer acts
as if it has been added to an under-sulphated q s t e m (Dodson and Hayden, 1989).
Dodson and Hayden also detected that in the presence of a calcium lignosulfonate WR
that the rare of solution of the naturai anhydete can be further reduced, and the amount
of soluble sulphate becornes insuffiuent to keep up with the demand of the C d
(Dodson and Hayden, 1989).
Other problems regarding the sulphate content of the cernent are a result of the
rnanufacniring processes. The recent use of hgh-sulphur fbels, air-pollution control
systems, and recyding of cement kiln dust has led to significmtly higher dliker sulphate
LITERATURE REVIEW
31
contents (Heimuth et al., 1995). An excess of sulphate in the dinlrer will cause the alkalis
present to be in the form of highly soluble aikali sulphates, which in this fomi can
accelerate the hydration of both alite and C A or the escess sulphate miIl form as
insoluble Gactions in the silicate or aluminate phases, or as anhydrite (Helmuth et al.,
1395). Unfominateli; it has becorne more diffidt to propedy regulate the tirne of set by
M e r addition of sulphates due to the presence of strict indusq limitations with a

masirnum sulphate content. Also, indusrrial by-products are being used in some cases as
a source of calcium sulphate, as a partial replacement for gypsum. The incorporation of

these m a t d s may lead to further i-aciabilityin cernent performance.
2.6.1.3 FINENESSOF THE CEMENTAND EXCESSIVE

FINES
A bnef ovemiew of the effects of the cernent fkeness is necessary. It is well
known that a cement of high heness \dlhydrate at a higher rate than a cernent of the
same composition aith a lower specific surface. The inaeased surface area associated
with a hgh fineness increases dramatically the amount of cernent physically contacted
with water and afi-ailable for immediate hpdration. Aitcin et al ha\-e demonstrated that
cernent particles hydrate at diEferent speeds according to the heness (Xtcn et al., 1987).
As a result, the superpiascizer dosage wwdI have to be increased with cements of
increased 6neness to cornpensate for the rapid hydration of the fine cernent grains
(Mtcin
et al., 1994).
Accorduig to th& work, superpiasticizers are most effective in retarding the
hydration of the medium size hction of the cernent (4-30~).The superplasticizer is

unable to affect the hydration of the h e s t hction (c4 pm) due to th& high reactivity
and the fact that the S 0 3 and alkalis tend to concentrate in the fine fraction of the
cernent; and the coarse fraction of the cernent (30-72p) is not influenced b y the
presence of a superpiasticizer since it is not very active in the hydraaon process
et
al., 1987).
The presence of ultra fine materiai, indudlig cernent and 6ne aggregate
particdate inaeases the superpiasticizer demand of a conaete. "The h e part of a
ISSUES IN ADMIXTURE COMPAflBlClTV
conaete concentrates all of the swface area of the grains likely to adsorb molecules of
superplasticizer" (De Larrard et al., 1997). Concretes possessing an excess amount of
fine materials require a more substantial coating of aggregate surtace areas br the cernent
paste. This additional surface a r a can hold some of the superplasticizer solution and
prevent it kom fluidi-ing the miu (Dhir and Yap, 1983).
n e hneness and C d content of cernent govern the initiai flow characteristics of

cemenL while floa- loss is dictateci mosdy by the ionic s ~ e n g t hof the pore solutions
(Bonen and S a r h , 1995). Thc rheological behaviour usvailp eahibited by high-allrali
cements is considerably poorer compared to other cements containing low-er leveis of
alkalis. The increased Bow- loss of hgh ionic strength pore soluaon cm be attributed to a
greater electrostatic attraction (Bonen and S a r k , 1995). Increases to the concentration
of alkalis n a d y alter the pH of a conaete and conoibute to a change in the ionic
strength of the pore solution and thus influences the rheology of the cement paste
(Jolicoeur et al., 1991). The presence of alkdis in portland cernent clinker promotes the
dissolution of Cu\, thus increasing its rate of reaction and accelerates early hydration.
Alkali-rich solutions, provded that the ggpsum content is low, encourages the formation
of aluminate hydrate and produce a quick set in concrete(Jaweedand Skalny, 1978).
The liquid phase of a cernent paste is s s f i c a n t l y affected by the presence of
alkalis. When alkaii-containing cement is mtxed aith water, the allrali metai ions readily
go into the tiquid phase of the hydrating system and influence the rate of hydration and
the rnorphology of the hydration products vaw-ed and Skalny, 1978). The presence of
alkalis in cernent causes a decrease in the initial ettxingite formation, but has the effect of
accelerating the C3S and C2S hydration (Jawedand Skalny, 1978).
Increases to the a W content have the effect of dramatically increasing the
solubility of the sdphate ion (Dodson and Hayden, 1989). For cements of the same C d
content, those high in alkalis react with gypsum more rapidly and require larger additions
of gypsum than those low in a k a h (Lerch, 1946). The presence of alkalis in the cements
ISSUES IN ADMIXTURE COMPAliBltlTY
-- -
- ---
- -
causes a higher coasumption rate ofgppsum (Odler and Wonnemann, 1983). It appears
that at least part of the &dis of the cernent are present in the aluminate phases, and that
aluminate phases containiog allialis react uith =ter more rapidly than d o similar phases
which are W - k e e or of Io=-er alliali content- Thus the cements of higher alkali content
require a lacger addiaon of gypsum for proper retardation than do similar cements of
l o w r alkali content (Lerch, 1946). Thus the possibility of flash set is naeased if
insuffiaent levels of SOSare present in htgh alliali cements.
When the aUralis are present in sulphate Fonns ( N a 2 S 0 ~or GSO4) the adsorption
of superplasticizer on C d and CAF is inhibited, thus p 6 m q inaeased adsorption
on C S and CzS, resulting in reduced viscosity of cernent paste (Nana et al., 1989).
Unfortunately, increased adsorption of the superplasticizer onto the siiicate phases d
result in retarded set-
of the cernent
However, the presence of eucessire allrali
sulphates compresses the electric double layer, providing an increase in ~ s c o s i t yof

cernent paste. Hence, with regards to the fluidity of the cernent paste, cbere ests an
optimum alliali sulphate levei of cernent paste containing SP (Nawa et al., 1989)). It must
be noted that the presence of aikali sulphates does not alter the progess of C S and C d
hydration. When alkalis are present in sulphate forms (NazSO4 or =O&), the tirne of
set is accelerated due to the formation of syngenite that may result from reactions with
the gypsum (Oder and Womemann, 1983). The formation of a ngid syngenite structure
not only Ieads to quick set-
but also decreases the sulphate content in the liqud phase
of the kydrating cernent to the estent that it cannot adequatelv retard the hydration of
C d ; this in turn d s o leads to e d y stiffening (Jawed and S U y , 1978).
There is some evidence that cements contaliing Na20 require larger amounts of
gypsum than do similar cements containhg an quivalent quantitg of &O (Lerch, 1946;
Jawed and Skalny, 1978). However, when relatively large amounts of S 0 3 are present in
clinker a substanaal h c t i o n of the total allialis passes into the solution Mthin a few
minutes (Jawed and Skalny, 1978).
In addition to th&
influence on the hydration of 0rd.ina.q portland canenk
alkalis also influence the pedormance of admktures.
With increased concentrations of
ISSUES IN ADMUCTURE COMPA'IIBILIW
LITERATURE REVlEW
34
alkatis the adsorption of admixtures onto the cement phases are deaeased considerably
(Ramachandran, 1995).
The ratio of d p h u r to total alliali detemiines the quantity of ahdi sulphates in a
ciinker. When a dinker contains relatidy large amounts of SO3, a substantial fiaction of
the alkalis goes into solution within a fav minutes. In ION- S03 dinker, Na20 and E(20
are incorporateci preferentidy into the C A phase, but also into the CtS phase of
portland cernent cIinker- Therefore, although the cerneats may have s d a r SO3 and
total alkali contents, the amount of a l k & that are r d y soluble in them cian vazp niddy
aimg et al., 1999).

Jianget al argue that the amount of soluble aikalis that go into the solution durkg
-i
the hrst few minutes after m
rather than the total a M content as specified by the
manufacturer, is critical in ensuring superplasticker compatibility with a cernent.

hccording to their work uiith a PNS superplasticker, there evists an o p & m n soluble
alkali content at which utial Buidity is maxiaiseci and slump loss is minimised. They
indicate this o p h u m soluble alkali content to be 0.4-0.59'0 N a 2 0 soluble equivalenb and
claim that this optimum range is independent of the superpiastizer dosage and cernent
type used (Jiang et al., 1999). The CG% content has practicailp no effect on fluidity loss in
a cernent Mth an optimal soluble a k a h content (Jianget al., 1999).
The consequence of e'rtremely hi& la-els of soluble alkalis C>-l.OO/o N a t 0

equivaient) in a cernent is that higher additions of gypsum is required due to the
accelerating effect of the alkalis on C d hydration Fang, 1992).
The nature of the admiunire bears a signikant influence o n the issues of slump
loss and set retardation. It has been noted that the Lntical characteristics of a
superplasticker are the percentage o f sulfonation, average molecular w-eighk distribution
of molecular weights and polymer configuration (Altcin et al., 1994).
The average
molecukc weight and the distribution of molecular weights are particulaily important
LITERATURE REWEW
35
with respect to the fluidificatioo of cemenatious systems and rheological behaviour *th
tirne (Atcin et al., 1994).
As already mention& the pre-=ce of sdphates in the cement reacts rapidly \xi&
the CS+ to control the early age behaviour as it hydrates. The presence of sulfonates in
chernical admiunires can interfere with the hnction of other sulphates; spedicaiiy those
incorporated into the cernent (Le. gypsum, anhydrite, etc).
Sdfoaated WR and
superplasacizers have also been shoan to interact more speuficdy Mth aluminate
phases, via th&
SO3- groups, cornpeting with the sulphates (SO4>) in the cernent
~oiicoeurand Sixnard, 1998). When added to the
water these sdfonate admkxtures
wiU rapidly bind to the cernent grains, when the gypsum should have done so.
Unfortunately, the adsorption of the admivtures onto the most reactioe sites of
the cernent partides, the C d phase, causes rapid consumption of the admixture and thus
results Ln rapid sIurnp loss. Due to these effects of sulfonated admi.-tures, th& addition
should be delayed to aliow- the sulphates incorporated into the cement to perform their
desired function. A delay o f o d y a minute in most cases is sufficient.
2.6.2.2 EFFECT
OF MOLECULA.
WEIGHT
The retention of slump of kesh coocrete depends to some =tent
on the
characteristics of the superplasticizer used. The retarding ability of superplastizers has
been weii documented and has been atuibuted to the ability of the superplastizer to
adsorb to die surface of the cernent particles and their hydrates.
Ho\k-aer, the
effectiveness, or sereriry, w i t t h which a superplasticizer c m retard the rate of hydration

varies Mth the nature of the superplasticker. Andersen has shown that superplasticizers
with longer polymer chains have a hgher dispersing capabiity, but that the shorter chain
polymers have a more pronounced influence on retardation (Andersen and Roy, 1988;
Andersen et al., 1987).
ISSUES IN ADMCTRE COMPATlBlLlTY
LITERATURE REVlEW
36
Changes in the molefular weight @fW) of the polymer S u e n c e s the dispersion

properties and the morphology of the C d hydration products (lltcin et al., 1994).
Independent of the superplasticizer qpe or cation, the higher the molecular rnass of the
SP, the higher the effiuency OC the superplastiUzer. Jolicoeur et al (1994) suggest that
the relationship of the mole&
weight of an SP and its water-reducing capaciy may
originate in elecaostatic effects. A d m x ~ e of

s high molecuiar weight are compked of
larger rnoiecuies, which are capable of conveying a higher number of oegative charges to
the particle, diereby increasing the forces of electrostatic repulsion (Mersen and Roy,
1988; Jolicoeur et al., 1994). It should also be noted that as the molecular weight of an
admixture is increased, so is its ability to adsorb onto cernent partides (Ramachandran,
1 995).
Although higher mole&
weight nater reducers may provide higher initial
slump increases and are more readily adsorbai, th&
innuences are short lired as
compared to the influence of low iMW admkunires. It appears that high molecdar weight
polymers are ineffectire at bringing about a banier to water (and ion) vanspoa ac the
mlieral/solution interface (Jolicoeur et al., 1994), thus ailowng hydration to progress at
a rate high enough to cause detrimental slump loss.
admistue the
By decreasing the M W of the
EluidiSing effect is reduced, as would be expected, howerer, the potental
of low molecular weight superplasticizers to retain slump and pronounced set retardauon
are markedly higher than its high LWcounterpam (Jolicoeur et al., 1994).
Low
molecular weight polymers can be more effective at b l o c h g hydration at specifc

reaction sites (a larger number of srnder molecules c m yield a more complete coverage
of individual surface sites, and a more compact surface packing, than a s m d nurnber of
larger molecules) (Jolicoeur et al., 1994).
The timing of admixture additions can be critical, when added dong with the
mixing water the superplasticizer is coasumed mpidy. Fluidising agents show an afhnity
for the aluminate phases and attach Li substantial arnounts to the tricalaurn aluminate
ISSUES IN ADMIXTURE COMPAlBILtTY
phase before it reacts M y with calaum sulphate, thus very Little of the admixture is lefi
to attach to the silicate phases (Dodson, 1990; Ramachandran, 1995)- Due to the rapid
hydration that C A undergoes when contacted *th wtter, the bound superplasticizer
becomes contained by the hydrated aluminates and caanot contibute itself to the \vater
reduction \i-hich creates a mpid loss in slump (Dodson, 1990, Helmuth et al., 19%).
The early cernent SP surface reactions apparently result in a high initiai
cc
consumption" of the superplasticizer molecules, thus it should introduced as the Iast
component in the mi*
process (Jolicoe~ret ai., 1994).
By delayed addition the
effectiveness of the chemical admixture c m be drasticdy increased. By ailowiug the

cernent to react nith the water the C d can undergo its normal reaction with the
sulphates to form the calcium alumino sulphate compounds. These compounds are less
prone to adsorb the admi,xture and the cernent's afhity for the admixture is deaeased
(Uchihva et al., 1992; Whiting, 1980). As a result the admiunire is adsorbed to a lesser
estent, there wilI be sufficient admixture left iu the solution to promote dispersion of the
silicate phases and to lower the viscosity of the system (Ramachandran, 1981;
Ramachandran, 1995). The e f k t of delayed addition is sgnificant eoen if only delayed
for several minutes.
To begin aith, elevations in the arnbient temperature that Eresh concrete is

exposed to incrases the rates of hydration and evaporation, consequentiy, decreasing the
free \ w e r content in the mk, thereby, accelerating slump loss and t h e of set (Bonen
and Sarkar, 1995)- The reduction in the kee water content increases the inter-partide
friction benveen the cernent and aggregate +cles
and brings about a corresponding
stiffening of the fiesh mkx (Ravina and Soroka, 1994)-
It has J s o been shown that temperame influences the effectiveness of chemical

admiunires. The amount of SP necessq to obtain an initial Gued slurnp and a-atmcernent ratio ws found to increase aith a decrease belon- 2 3 O C and to remairx faidy
constant betsveen 23 and 32OC. Slump loss, on the other hand, showed a signil3.cant
ISSUES IN ADMUCrURE COMPATIBILI'TY
increase with an uicrease in temperatures across the entire range studied.
h45vtcrres
containing melamine-based SP evhibited sornewhat higher rates of slump loss chan did
those containing naphthalene-based SP when a cernent containkg a modecately high
C d content was used. No consistent dirferences in slump loss were ound berneen the
nvo admixtures w h e n a cernent with a somewhat lowver C d content =;as tesred (Whitiog,
1980).
There is a need, however, for more detailed data on the effects of temperature on
these properes, so diat the
designer and user may know in advance what
adjustments to make and ho=- these adjustments w i l i affect behaviour of concretes

containhg these mate&
over the raage of temperature commody encountered on the
job (Wh~ting,l98O).
2.6.5
REDUCEDCEMENT PASTE AND WATER CONTENT

The process of slump loss can be rnarkedly different in superplasticized concretes
than in 0rdku-y mkes. The arailable m k water, not already used for the hydration of
cernent, contributes to the fluidity of a concrete m k , and is often present in loa-er
volumes in superplasacized concretes.
The formation of eren minute amounts of
hydration products o r the loss of any f3ee wxer d result in an e~aggeratedloss of

slump due to the low volume of water in the paste fraction.
Part of
diis increased rate of slump loss may be because conaetes
prepared at
htgher initial slumps exhibit highe rates of slump loss (Dodson, 1990; Whiting, 1980).
SLight changes to the intemal structure of the h y d r a ~ gpastes rnay simply be more
visible as larger changes in slump, as compared to conuetes with lower initial slump
values.
ISSUES IN ADMIXTURE COMPATlBlLrrY
Escended duration of oi.riag as rnay occur in transport have also been shown to
aggravate the problem OF rapid stiffening. The constant abrasion OC aggregates and
cernent particles that occurs d&g
m
e
i can effectirely remove the coating of
hydration products that Fomis on the aluminates and silicates (Docison, 1990). This
allows the hydration of these phases to occur at higher rates than normaily occur in the
dormant period. The removd of these protective coangs exposes unreacted cernent
surfaces, making them availabie for hydration vcith m k wxter.
2.7
INFLUENCES OF ADMIXTURES O N THE

AND SETTINGPROPERTIES
OF CEMENTS
Since most organic admi~turesdemonstrate an d&ty
HYDRATION
t o w d s the s d a c e of
cernent parrides, and their hydration products, an absorbed Iayer is formed on the
cernent partides. The presence of this adsorbed layer on the &hly reactive mineral
phases of cernents ( C d ) c m participate in, or interfere with n o d hydration reactions;

potentially inhibitkg crystal nudeaaon (Jolicoeur and Simard, 1998; Khalil and Ward,
1980).
Ignoring the possibility of poreutid chernical reactions, these adsorbed
compounds alter the surface properties of the cement partide and thus its interactions
with the solution phase, as well as with other cernent parades ~ o i i c o eand
~ . Simard,
1998; Singh et al., 1992).
Under normal circumstances, most wmter-reducing and superpkstiaPng

admi~niresalso act to a Limited estent as retarders, in that they increase the time of set
(or the onset of hardening). It must be undentood that a case of set retardation does
not necessdy mean improved slump, or better retention of slump (Khalil and Ward,
1980). It is broadly acknowledged rhat the presmce of a superplasticizer in a hesh
concrete delays the cernent hydration and fiequently l a d s to a retaration of the paste
setting Oohnston, 1987).
Although set rerardation of several hours is p i c a l , fluiidising
agents can produce cases of severe set retardation lashg upwxrds to and greater than 24
hours; e s p e d y when large doses of water reducers o r superplastizers are used
(Fielmuth et ai., 1995). The effect appears to be quite general, although it is dependent
on the nature of the SP and markedly influenced by the composition of the cernent;
usuaily, retardation is inverseiy related to C d content (Jolicoeur et al., 1994).

Results h m both Iaboratory and field results indicate that low sdphate content
is the major
cause of ooenetardatioa in conaete,
espeaally when combined with che
effects of a low C d content (Netde, 1997). Under such circumstances, escessive set
i
retardation is produced since large portions of any admiynire, e s p e d y if deiayed, d
be adsorbed onto the silicate phases (Khalil and Ward, 1980). With the hydration of the
C S phase as the conuoiling factor for the time of se5 any interference with its naturai
hydraaon by the adsorbent wd cause a delav to the time of set (Dodson, 1990)Set retardation has also been attributed to other factors inciuding gross overdosage of severai cimes the normal amount of admiunire, cnidity and variability of the
product, the presence of sugars, an extremely Io=- s p e d c s d a c e and temperature
(Atcin et al., 1994; Tuthiil et al., 1961).
Adding to the number of compiicated factors involved with the process of slump
loss, cesearchers have amibuted cases of abnormal set, r e s u i ~ gform the presence of
certain organic ndmi.xnues, to altered processes of etmngite formation (Helmuth et al.,
1995; Ramachandran, 1981).
The presence of a superplastizer not only influences the rates of reacbon of the
hydrating phases but dso has an abilicy to change the rnorphology of some of the
reaction products. The morphology of the ettringite that is produced in the presence of
a superplasucizer has been altered to f o m uystals that are very small and cubic, as
apposed to its n a t d needle like formations. This new cubic fomi is considered to be
much less detrimental to the slurnp loss of the hydrating paste and should have a marked
ISSUES IN ADMWIURE COMPATlBlLlTY
influence on the rheological properties of cementitious systems at v q eady ages (&-tcin

et al., 1994;Jolicoeur et aL, 1994).
The growth of emkgite may even be halted depending on the concentration of
the s u p e r p l a s t i ~or vater-reducng admixture used; the formation of other
compounds may replace the ex~ecteden9ngite growth (Legrand and Wirquin, 1994).
Fadure to f o m an ectnngite protective Iayer dows there to be continued \vater-cernent
interfaces, thus dowing cernent to hydrate. This may be responsible for the premature
stiffening (slump loss) u s d p encountered =ben a fluidisinp agent is used in cernent

pastes or concretes (Guo, 1994).
The continuous formation of the fine eccangite structure is capable of rapidly

Mthdrawing =ter Gom the
&Y,
Helmuth et al report that a reduction of 5 to 10/o of
die Gee water content in conuete (Helmuth et aL, 1995). The formation of ettringite,
and its \vater bindlig capabilities results in a ioss of workability. The amount and size of
crystaliine ettringite formed, under different conditions are dependent upon the amount
of gypsum and C d present in the system (Khalit and Ward, 1980).
ISSUES IN ADMUCTRE COMPATIBILITY
In the field, an inadence of admixture-cernent incompatibility can result in
placement problems and lead to litigation. Problems of rapid slump loss could lead to
the rejection of conuete deliveries, or the redirecrioo of labour to manage the excessive
work required to place, consolidate, and &sh
the concrete before the concrete becomes
dl
incur
unworkable. In the case of excessive set retardation, upsets to the schedule \
men larger costs as weil as lost tirne.
It would be best if the occurrences of these
compatibility probiems could be elimliated in construction.
The goal is to k d combinations of cernents and admixtures that can mainain

th& fluidity (even at a low- w/c ratio) and can remain workable long enough so that the
concrete may be placed and finished (De L
both admistures
d et al., 1997). A pre-selection process of
and cernent couid prooe an econornical means to avoid these issues in
practice (Helmuth et al., 1995). Unfortunately, as already mentioaed, the compatibility of
EXPERIMENTAL PROCEDURES
-
---
43
- -
the components cannot be detemiined simply by looliiilg at the chernical compositions

or the materials data sheets for the cements and admimxres. AIthough o d y gneral
patterns can be detemned Lom the composition of the cernent and admixture, the
determination of cornpatibility must be done by experimentai means on the prospetxke
cementladmiuture cornbinaaons.
Typically the measurement of admisme-cernent
interactions are canied out Mth
actual concrete mx triais. Unfortunatdy, to do so requires large arnounts of m a t e d s ,

cost, time,
and physical labour. This does not seem to be the most efficient use of
resources. Recent snidies have Ied to the derelopment of severai srnall scaie methods;
not only do these tests require much srnaller arnounts of material they are also far easier
to implement and repeat, and c m be k e d out by a single operator Mthin a s m d
period of time. These s d - s c a i e tests can be used to rapidly screen for efficient and
non-efuent combinations; however, it is inadvisable to use these as the only methods
for evaluaMg of cernent-admixture compatibili.

portion of rhis project. It
This chapter of this report deah aith the es-~erirnental
frst begins with a description of the different cements and admi~niresused in the
escerimental program.
Followiq, is a desnption of the acmal experimental n-ork
conducted, induding the procedures and apparati that were used.
Ali the materials that were selected for
t h i s work are cornmerally aiailable
producn that represent the typical qpes of cements and admktures a~ailablein the
southern Ontario area. ,Ail m a t d s were donated for this projecb and
au be discussed
in the followng sections.
Three commerdy available portland Cements were used in the course of this
investigation. W brands are CSA Type 10 Normal portland Cements, one manufactured
by Lafarge at their W d s t o c k plan5 the second by St Mary's Cernent in Bowmanviiie,

ISSUES IN ADMUCTURE COMPATlBlLlTY
41
and a third produced by SL Lawrence Cernent Gom ~MississaugaThe two cements from
S t M a r f s and Lafarge are used extensively in the testkg program of this thesis. The
third cement was used in a limiteci testhg regime.
For each of the cements c
physical and chemical properties were
determineci so that th& influences on the rate of reaction could be considered. Of d

the physical properties it aas important to determine both the fineness and density of
the cernent The heness of the cements were determineci by the Blaine a u penneability
apparatus according to ASTiM C 20494a, while the densities wvere determineci by the use
of a Quantachrom& Stereoppcnometer. The rele\-ant physical and chernical data, as

w-das the computed Bogue compositions, for the cements can be found in Table 3-1.
The htgh-alkali SL Laa~enceType 10 cernent used for part of the evpePmental
program Kvas used due to preiious expmence that indicated it mas incompatible aith the
combination of PNS SP and WR utilised in this study. However, preliminary t e s ~ g
with the mini-slump test indicated that this was not the case, and that it behal-ed much
like the St. ~Mary'shigh-alkali Type 10 cernent.
ISSUES IN ADMIXTURE COMPATlBlLlN
45
TABLE
3-1
Physicai and chemical properties of cemens.
Chernical and Bogue compositions are expressai as mass percentages.
SiO,
%O3
TiO,
20.90
4.92
0.26
19.82
5.13
026
19.54
3-97
0.21
1 BOGUE COMPOSITION
ISSUES IN ADMIXTURE COMPAllBlLlN
46
3.2.2 AIR ENTRAINING ADMIX~URES

Withn the scope of chis project three c o m m e r d y andable au entraking
admktures were used. The three MM's were selected to represent the most common
types of used in constniction. The three selected admixtures indude &&ter Builders'
iLLB VR@ and iMicro A~I@hEA, a s weii as Darex II@ AEA manufactured by the Grace
Chernical Company. The active components of these agents as weU as their relative
densities and solids contents are provided in Table 3-2.
TABLE
3-2
Active agents and physical and properties oEair eatraliing agents.
MB V R CONCENTR~TEQThis product is composed of vinsol resins aith a solids
content of Z O S - Z S ? % by mass O t:the admLunice
M~CROAIR@ Micro air is a multi-composent spthec agent composed
pr;manty of ta11 oils and other proprietary surfactants; and
has a solids content 11.7-13.5%
DAREXII@ This AEA is comprised of an allraline solution of fatty acids
When selecting the water-reducing admiunires it wu found thar there was only
one main type used by all the local manufactures. iMost commercidy avdable =ter
reducers are based on Ligaosulfonic acids (Iignosulfonate). For this reason, only one
brand of water reducer \vas eutensiveiy used throughout the testing program, namely
Eucon WR@, marketed by the Eudid Chernical Company- T o detemine if the results
thar were obtained are characteristic of the rheological behaviour of lignosulfonates, and
not just the result of one manufacturer's product, a second =ter
limited tes-.
reducer was used in
The iMaster Builders Company Ltd are the producers of the second water
reducer used, ConchemB 25XL. According to the manufacturers' spe&cations both of

the WR's meet ASTM C 494 requirernents for Type A -ter-redung
adaii,xtures when
used at appropriate dose rates. The relevant information pertaining to these products are
presented in Table 3-3.
ISSUES IN ADMUCTURE COMPATlBlLrrY
47
XPERlMENTAL PROCEDURES
Table 3-3
Active agents and phJTid propertes of wvater reducers.
.Ali d u e s obtained through personal communication with the manufamers.
i\CTn/'E -4GFIST
C,.\~OS
R E L ~ ~D~u'srrs
E
O
'
S o w ~BY
s L ~ ~ S S
AVG. LMOLECLUR WT-
EUCONW R @
Lqposulfonate
Sodium Sait
1.207
COXCHEM25 Xi.
l3gnosdfonate
Calcium salt
1.17-1.21
45.0/o
3843%
NA
NA
The superplasticizers used in this investigation were selected using the same
critena as used for the a;iter reducer and air enaaining agents; the SP7swere selected due
to th& Wde use in concrete. The two most dominant W e s of superplasticizers are
either
melamlie
sulfonates
PI-cype) or
naphthalene
suKonic acids (N-type)
superpiasticizers. The mo SP's selected for use in the experimental portion of diis
in\-estigition are iMaster Builder's Rheobuild 2000B, a melamine sulfonate solution, and
Eudid7s Eucon 37, an aqueous solution of Naphthalene sulfonic acids. The physical
properties of these two chernical a d m i m e s can be found in Table 3-4.
Table 3-4
Active agents and p hysical and properties O superpiasticizers.
M values obtained through personal communication with the manufacturers.
Naphthalene Sulfonic Acids

Sodium Salt
Melamine ~ulfo&e
Sodium Salt
ISSUES IN ADMIXTURE COMPATllUTY
48
The testing o f slump in concrete required the use of quamieci Limestone from
Duferin Aggregate as the coarse aggregate and Dunlop sand for the fine aggregate. The
coarse aggregate used in the initial
had a 20 mm nominal aggregate size, but had to
be substinited with a 10 mm nominal aggregate size to improve the consistency of the

mis
to remedy problems of segregation. The coarse aggregate used had a density of
2600 6-g/m3 and an adsorption of
1.8O/0,
\\-hile the 6ne aggregate had a density of 2650
k g / d and an adsorption of 0.896. Plots of the g a i n size distribution for the w o coarse
aggregates and sand can be found in Appendk D. The two sizes of coarse aggregate, as
weil as the sand used, meet the specifcation Limia set out in ASTM C 33-93
The foam indes test, as proposed by Dodson (1990) is a simple means for
determining the hEA requkemenr of a gken cement.
Although the procedure w a s
oegindv developed to evaluate the influence of cementitious, as \id as pozzolanic,

materials on the entrainment of air in concrete, it has since been used to detect the
source of air envainment problems. The procedure involves hlling a 125ml-glass jar
with 20grarns of cernent and 50rnl of distilled water. The contents are the iigorously
shaken for a 15-second period to thoroughiy wet the cement. Then a diiuted amount of
AEA (1 part AEA to 20 parts distilled water by volume) is dosed in srnall aliquots and
then agitated for a hrther 15 seconds. The jar is thea set to stand on a stable surface
and obseri-ed for to see if the added AEA is capable of produting stable foam in which
n o visible bubbles coilapse for a 15-second period. If the foam is deerned not to be
stable, an additional aliquot of
is added and the procedure is repeated und a stable
layer of oam is developed.

The foam index s h o w promise as an evaluator of the air entrainment
requLements of cements. Haigh et al. (1984) have assessed the reiiability of the foam
index tesr and found an excellent correlation between the foam index and the admixture
ISSUES IN ADMIXTURE COMPATlBlUTV
49
requirement in a standard mortar. Furthemore, accorchg to thek assessment, the test is

exuemely practical; th& investigations reveaied that the test is not eunemeiy sensiave to
the influences of water type, temperature, minor ~arationsin the cernent content, or
variations to the speed and duration of agitation (so long as a minimum agitation of 3
shakes per second for approxnately 5 seconds is achieved). Due to the fact that no
stringent controls are required on the aforementioned factors, the test can be peiformed
repeatedly \vithout the worry ii f operator error. Some researchers have uiticised the
foam index tests for using an evaemely high w/cm ratio (w/an= 2S), however,
attempts to perfomi this test at more practicai w/c ratios has proven to be unrealistic
(I-Iaigh et al., 1984).
Figure 3-1.
Au illustration of
the foam index test. The layer of
foam that is produced should nse
h i ~ hand remain srahle-
In the contert of this thesis the foam indes test was used to test the compatibility
of a given AEA alone, and in combination with the chosen WR, with the svo different
cements. The foam index test was chosen due to the fact that it has been proven to be a
reliable method for evaluating the air enuaLiLig capauty of an AEA in cements and in
SCM blended cernents. The foam index test was also perfocmed as a preliminary test so
that an "adequate" AEA dose, as determined by the
oaai
index test, couid be applied to
the subsequent tests.
When detemiining the foam indm of an AEA combined not o d y with cernent
but aiso uiith a uater reducer some modifications were necessary. The wxter reducer
used \vas added to the rniu water at the recornmended manufacturer's dosage of
ZSOmi/lOOkg of cernent However, shce that the required amount of water reducer for
ISSUES IN ADMIXTURE C O M P A ~ B I ~
50
the samples is miauscule it is necessary to dilute the WR 120 wkh distilled water so that
accurate dosing wu possible. To achieve the manufacturds suggested dosage, 1 ml of
the diiured water reducer =as added to the sarnple after 1 minute of agitation o f the p
cernent and wxter, the jar was subsequently agitated for 30 seconds to ensure proper
dispersal of the witer reducer in the cement-mater miunire. Aftenvards the test was
conducted as per the usual foam index test
3.5
THE IMLNI-SLUMPCONE TEST

The non- properties of a concrete are largely dependent upon the cernent
component of the m k and some invesrigators have deuded to iovestigate the rheologicai
properties of neat cenent pastes (Kantro, 1980). Rheology is the science devoted to
studying the flow and defomiaaon of matter, that result hom the influences of shear
stresses and shear strains, and the time involved in such deformation Fang and
Bhattacharja, 1997). As a result, a series of oew test methods has been produced for the
determination of the rheological properties of cernent pastes; the ta-Omost popular
methods beiag discussed at present are the Marsh cone and the iMin-Slump test The
Marsh flow cone is used as a measure of the fluidity of different grouts and slunies. The
test involves the measurement of the time taken for appro-simately 1 L of prepared sluny
to pass through a hinnel ha+
an orifice of 12m.m diameter. The superplasticizing
effect is represented as a decrease in the flow time.
The mlii-slurnp test merhod is a
scaled down version of the slump cone used in ASTM C 143 for the measuruig o f slump
of concrete, however the miai-slump is used on neat cernent pastes
O*.
The deusion
to use either of these methods is enarely subjective; the decision to use the mini-slump
test for the purpose of this work was based upon previous work perfomied at the
Unkersi~
of Toronto (Lee, 1998).
The miniature slump test was designed by Kantro (1980) to evaluate the
performance of water-reducing admixtures on the workabilig of cernent pastes. The
mini-slump test is simple, inexpensive and can be perfomied rapidy aiith a small sarnple.
Consuucted ?om Luute, the mini-slump cone is a scaled down (1:5) version of the
51
ASmf C 143 siump cone, the design details are illustrated in Figure 3-2. Due to action
ofgravitv cernent pastes slump, much like concretes do, to a point where its yield value is
no longer erceeded (Kaotro, 1980). Aithough cernent pastes and concretes may be very
cliffereut in terms of th&
rheology, there should be a good correiation betw-een the
slump of a concrete (&th
a given aggregate) and that of a cernent paste; since that the
flow characteristics of a concrete are detemiued iargely by the yield value of the cernent
paste coatained aithli it (Kmtro, 1980). D u e to the rektively s m d size of the pat
produced by the mini-slump test it is impracticd to masure changes in heighq rather the
resultant pat area is measured. Both tests, howet-er, remain to be masures of the
deformation irnposed by gravitationai force. Application of the mini-slump test has
proven prornising in that the test show a good condation with the regular slump values
of concrete (Ramachandran, 1995) and has prooen
to
have e d e n t reproducibilicg with
a single operator Fang and Bhamcharja, 199'7).
Figure 3-2 The mini-slump cone. (a) A

general view of the cone, (b) top view, and
(c) side view
Note: units are in millimerres
ISSUES IN ADMIXTURE COMPATIBILIN
52
Evea though the mini-slump test is not an exact representation of concrete

behaviour it does have its adraneges over conventiod concrete slump tests. Due to
the greater concenuation of paste in the specimen, the test is more sensitive to changes
in the paste that are not readily diffmtiated aith conaete miu data (Kantro, 1980)Due to its increased sensitivity to changes in the rheologicd behaviour of cernent pastes,
the test bas been adapted for use in numerous studies testing rhe affects of admixture
y stiffening problems (Heimuth er al.,
1995;
Kantm, 1980; Meyer and Perenchio, 1979; Tang and Bhanacharja, 1997).
'The
combinations on workability, and d
rheological behaviour of cernent pastes as a Function of time and superplasticizer dosage

provides reievant information on key properties, such as slump and slump loss, w-hich
can be tram ened to fiesh concrete"
3.5.1
(Jiaoget al., 1999)).
INADEQUACIES OF THE MINI-SLUMPCONE TEST
Since Kanuo (1980) introduced the miniature slump test for cernent pastes it bas
been suggested that some modifications be made to the tesk so that it could produce
more realistic results. One disadvantage of the o + d y
the rnethod of mi*
proposed test method is that
did not realisticallv simulate the shear brces that occur in cernent
paste during concrete misng ( H e h u t h et al., 1995). The low intensity nJ,Ingas used by
Kantro
.kas
inadequate in that the pastes produced e'diibited low workability,
represented by small pat areas, and any subsequent loss in worliability \vas ciifficuit to
observe (Tang and Bhattacharja, 1997). For this reason much of the pralous work
performed on early sffening problems is of linle d u e .
The workabiliq of a cernent paste is profoundiy influenced by the intensity of

rnising. When Li concrete, a cernent paste is subjected to high shear rates, that are nor
simulated in the work of Kantro, and can o d y be achieved bg a high intensity mixer
when dealing with neat cernent pastes. Modification o f the mising procedures to use a
high intensity
produced more workable cernent pastes mith higher mlii-slurnp pat
areas, dowing for more perceptible slump loss Fang and Bhattacharja, 1997)-
To
achieve the hgh shear rate n e c e s s q in the laboratory portion of this work, a Sunbeam
ISSUES IN ADMIXTURE COMPATlBlLllY
53
Osterizer 8 8 kitchen blender Wth a capauty 1 2 5 L \vas used to prepare the cernent
pas tes.
The flow loss can be regardeci as a more sensitive indicator than the total Eiow since it
records intemal changes; in particular those that take place afier rapid precipitation of
errringite that foilows initial hydration (Bonen and S a r h , 1995).
Since that the goal of this portion of the research is to detect problems of rapid
slump loss a single batch required suffiuent material to yield si\- slump cones. A suitable
batch size using 50Og of cernent, and a water content of 175 g (produ+
035) w a s unlised. in the admixture enhanced &es
a w/c ratio of
air entraining agents were applied in
doses as determined by the foam index tests, and wwe applied according to whether a
miu did oc did not incorporate a water-reducing admisture. The actual doses used can be
found in Tables 4-1 and 4-2.

When the water-reducing admixtures were used, either alone or in concert with a
superplasocizer, they were dosed using the minimum dosage as specified by the
manufacturer. The minimum dose was used so that the effects of severe retardation
produced by the ligaosulfonate mi.s~tureswouid not influence the resuits. It was decided
that the addition of the superplasticizer wouid be delayed u n d after the
1 minute of
miuing and 2 minutes of standLig to avoid the rapid consumption of the achixmre onto
the C u l phase of the cernent- To investigate the effect of superplasticizer dosage on

slump loss, superplasticizer additions were made in the range of 0.1 to 1.0 percent on
separate batches. Note that the superplasticizer concenmtions Listed abooe, and those
espresseci hereafter for al1 the procedures and results are evpressed relative to the mass
of the portland cernent A listing of the exact
designs ulised in the e-xperimental
phase can be found in t\ppendk A.
ISSUES IN ADMIXTURE COMPATiBlUTY
54
The mking o f the cernent pastes conformed to the foliowing schedule, and was
doue using a Sunbeam Osterizer 8 8 variable speed kitchen blender nith a fluid capauty
of 1-25L. The blender has eight speed senugs (3 pulse settings and 5 continuous speed
settings) that operate between speeds o f 4 000 and 11 000 rpm. The speeds used in the
mixing regime were the lowest (s tir), middle (miu), and highest @ce crus h/lique+)
conkmous speed set*
that operate at 7000,!W and 11O rpm respectively.
Table 3-5
iMiUing regiment for cernent pastes prepared in a kitchen blender
-on.
/TIME
T=O
I
T=3
- -
- -
--
IM~Y
together water, cement and AEn cf required), and m k at lowest
continuous setting (7 000 rpm) for 15 sec, add WR and continue miuing for an
T=6
additional 45 seconds at medium (9 000 rpm) continuous speed setting,

Let stand for 2 minutes, scrape the sides and bottom of blender with a spanila;
Add superplasticizer, to slurry and miu at lowest continuous setting (7 000 rpm)
for 15 sec, then 45 seconds a t medium (9 000 rpm) continuous speed setting,
Let Stand for two minutes, scrape the sides and bottom of blender with spatula
T=4
T=1
1
1
if necessary
hLx at lowest conthuous setting (7 000 rpm) for 15 sec, then 45 seconds at
hfter completing the mi+
-1
highest (11 000 qxn) continuous speed seaing
process, mini-slump tests were perfomied with the
paste at t=5,15,30 45,6O and 75 minutes afier m i - -this was ro reflect the rime Game
during which a high degree of w-orkabihty is required for transportarion, placement, and
vibration. Prior to each masurement the paste was re-mked
at the lowest continuous
speed senhg on the blender for a duration o f 10 seconds to eliminate the possibility of
fdse set, as weU as to ensure a unit-orm consistencv of the mk. Bem-een each test, the
EXPERIMENTM PROCEDURES
55
blender jar was seaied to minimise any loss of water due to evaporation, and once a test
w-as completed the cernent paste used was discarded.
Wthin previous works the rate at which heat is iiberated mm hydrating cernent
is a useful means of measurlig the rate at which hydration progresses at and its enent o f
completion ( S M et al., 1993). The heac of hydration, Q, has been assumed to be
directiy related to quanay of hydrates formed; thus the evolutioa of heac h m a cernent
paste c m be used as a measure of the total reaction. The iduences of an admiyftlze on
normal c e m a t hydration can be detected in studies of the heat developrnent produced
by cernent hydration, such that high initial temperames are indicative of high losses in
\vorkabiliv (Khalil and Ward, 1980), whiie a delay to the second temperature peak
illusvates delayed set of the paste (Meyer and Perenchio, 1979)Thermocoupk wire
Figure 3-3.
Themiocouple apparatus. Right, a cross-seccional illustrarion of a

single thermocouple c d ; lefi, a schematic drawing of the insulated
box used.
ISSUES IN ADMIXTURE COMPAllBlLlTY
Ha+
56
no available conduction calorimeter on hand to masure the rate of h a t
evolution from cernent pastes an adhoc, semi-adiabatic calorimeter \vas de\-eloped. For
the salie of this investigation a quantitative methoci was developed to simply measure the
temperame changes produced by a lOOmm x 200mm cyhder of hydrating cernent
To do this a simple insulated box \vas constmcted from 1" Celfort 2U@
paste.
estruded polystyrene insulation with an R value of 5. The insulated bos was constmcted
\%<th the
qhders.
dimensions as illusaated in Figure 3-3 and made to accommodate four
The temperature
eses of the cernent pastes are m e a s d using Type
thermocoupIe \ires and recorded by a Campbele Sentifc 21 X@ data logger. The

thermocouple w+es are Liserted into the centre Lue of each of the qlinders at mid
depth. The entire apparatus =-as maintaineci at a laboratory temperature of 21 f 1C. The
temperature of each pas te was monitored from immediately after the mixing process was
complete to the point a-here the temperature retumed to ambient temperature d e r

havng obtained its peak temperature- The characteristics of the temperature protile can
be best illustrated in a Temperature vs. T e plot as shown in Figure 3-4.
Figure 3-4 Typical temperature profile

of hydfating c e m mt paste.
(Note that temperames and
time units aze arbitrary)
As a result of the mising procedure and thermocoupie set up the hrst
temperature measurements were obtained appro-simately 2 minutes d e r mbsing (or 5)
minutes afier initial contact of the =ter and cement); as a result, only a portion of the
k
heat p d could be recorded-
ISSUES IN ADMIXTURE COMPAlBlLlTY
57
For this series o f tests, cernent pastes were mixed both aith and without the
addition o f the chernical admk~tures.
The m k desigus and mixhg procedures
conforrned to those used in the mini-slurnp evaluation o f diese systems, the only
made wxs a reduced batch size due to the fact tbat these tests required Iess
m&cation
paste volume. The batch size =-as reduced to use 350g of cement-
3.6.1
CALIBRATION OF THE THERMOCOUPLE

APPARATUS
To "cc&brate" the set-up describecl above a simple test was perforxned using
heated wxter (appro-simately 7 2 O C) in ail four of the diermocouple ceiis in place of
cernent paste. This was done to obtain a profe of the heat retaining capaaty of the
insulated box, with respect to tirne, and is provideci graphicaliy in Figure C-1. Note that
the plot is that of the average temperame of the four cells.
10
1O
15
25
20
30
35
40
nme (hm)
Figure 3-5
Calibrated temperature cuve for insuiated themiocouple cells GUed with

a-ater heated to approx. 72 OC
ISSUES IN ADMIXTURE COUPATIBILITV
3.7
58
CONCRETETRIAL MIXES
Regardiess of the perfomaoce of die d - s l u m p tests it is necessary that some
trnals be performed on conaete mi~hires. Even &ou& they may be difficult to cany
our, the data that caa be obtained kom these e~rperimentsare indispensable, since results
obtained romtests on neat cernent pastes cannot be assumed to be directly applicable to
concrete.
(1988) found that there are some combinaaoas that work fine with a
grout and which do aot perfonn as a-ell in a concrete,
and some that give a fair
performance Mth a paste o r grout may perform much better in a concrete. This is due
mosdy to the fact that the mi+
conditions under the two &-tances
are not the
same. This is why in spite of the meet of these simplified methods; it is always necessary
to do a fa$- triai batcbes. By doing so the compatibility of die admixtures aith cements
and other job m a t e d s can be better obsemed. To obtain the best results possible, triai
&es
should be conducted according to the antiapated enriro<iment (temperature,
hurniditv, etc.) and procedures (miIngsequence, mixer speed, etc) e-xpected to occur on
the job (Kosmacka et al., 1995).
Trial batches u-ere conducted using the standard ASTiM C 143 slump cone.
rUthough the slump cone is not a tme measure of c\vorliabilicy", but rather a masure of
the consistency of concrete, the test is continudv used as an indirect measure of
concrete's w-orkabili. As already mentioned ccworkability"is a defbed as the ease with

which a concrete defocms due to an applied stress. The slump test is primady a measure
of the jeld stress of a concrete; when the cone is lifted the concrete deforms under the
force of gravity u n d the slumping concrete reaches an equilibrium point where the yield
stress of the conmete is not overcome by the action of gratity (Hehuch et al., 1995).
Caution should be taken when attfmpang to produce flowable conaete, since that the
slump test reaches it practical lLnit at about 220-250mm (Ramachandran, 1995).
ISSUES IN AOMlXTURE COMPATiBlLlTY
59
Table 3-6
Coacrete miu design and composition
WA~R
REDUCER
(mL/lOOkg of cernent)
SUPERPLASTICIZER
( r n ~ lookg
/
of
One basic
250
MEI-CC~-E
0.4'/0
800
250
250
0.8%
1600
N m - 1 ~
0.2%
408
0.40h
816
250
MEL..L~~'E N
0.400
800
0.8'/0
1600
0.2?/0
408
0.4?h
816
design was used throughout the concrete testkg program, with
\-ariarions made only to the SP dose (as seea in Table 3-6). The miu proportions were
designed according to the guideluies provideci in CSA A23.1 (Kosmacka et al., 1995).
Each batch of conaete =-as prepared in 10 litre volumes (23 kg), and was made using a
Lancaster pan miver witb a nomliai 20-litre capauty. The compositions of the different
concrete mkes are given in Table 3 4 . Note that the mass o f actual mi+
water was
adjusted to compensate for the water available in the superpiasticizers and water reducers
and to compensate for the moisme content of the aggregates.
EXPERlMENTAL PROCEDURES
60
MIXING REGIME
The mk.ting of the concretes conformed to the foliowing schedule:
Table 3-7
hLiving regime for concrete trial &es
TraaE
. T=O
-Action.
.. .
-iMi.x together water, cement, aggregate and water reducer (added to

water)
~~
for 1 minute
~ = l
Add %ofrequired SP and
T=2
Let stand for 3 minutes
T=5
lhfk for 1 minute
T=6
for 1 minute
Add remainng SP and miu for an additional minute
SIump =as measured at t = 5, 15, 30, 45, 60, 75 minutes d t e r mising. Whese
shmp was s t i l l measurable a k r the initial 75 minutes additionai measurements were

made at 90, 105 and 120 minutes.
Prior to each slump rneasucemenG the mixer was
tumed on for a p e r d of 10 seconds to eliminate any erconeous measurernents that

could result Gom fdse set A k each test the concrete was retumed to the pan mixer
immediately for use in subsequent slump measurements. T o prevent any slump loss that
could occur due to the evaporation of mixing water the rniuing pan sas covered with a
sheet of polyethylene.
ISSUES IN ADMIXTURE COMPATlBlLll'Y
3.8
61
MEASURING SOLUBLE AIXAH CONTENTS

In response to the daims made by Jiang et aL (1999) a bcief investigation \vas
conducteci ro see the need For adequate soluble alkali contents to ensure
cement/superplasticizer compatibility. As noted in 0th- works the concentration of
W
s that
go k t o solution in the very early stages of hydration cannot be determined
from the total alkali content found when analysing the cernent
As a resdt the
concentrations must be detemiined by experimentai examination of the cement pastes.

hlthough the =act procedure as used by Jiang could not be reproduced aith the fadties
available, however, a suitable altemate procedure was developed.
Like Jiang, the cemmt and -ter

mised for an additional 2.5 min in a
u-ere h t mked
by hand for 1 5 min and then
high shear kitchen blender. Two vials were then
Ued with appro'rlnately 20g of cernent paste and then placed into a centrifuge at t=
7min. The paste \vas subjected to an acceleration of 10G for a pePod of 5 min so that
some of the miu water could be evtracted
trom the paste for analysis.
The solution was then diluted 1:3 with disalled wxter so that it could be analysed
by lame photomeq. The flame photometer is capable of detecting sodium (Na) and
potassium, (K) in i n o l / L of the solution. Kno\*&g the concentraaon of both sodium
aod potassium the concentration of the equiraient alkalis 9'0 (P4a-O
+ 0.658K.0)
can
easily be calculated.
Attempts were made to detennuie the influence of the SP's and WR on the ability
of the three r\Er\'s to provide an adequate enuained air i-oid system. The compatibility
issues were to be tested using smd-sale laboratory tests on cernent pastes and mortars.
The &t methoci attempted utilised the 400d brass cup fiom A S l U C 185 and a
modified testing procedure. The 400 ml masure is 6ed with cernent paste and the
mass is rneasured. Knolting the theoreticai air fcee density of the cemeat and the actual
62
mass of the paste it is possible to calculate the actual air content of the paste u s k g the
follo=ing equation, a modified fomi of the equation in ASTM C 185.
AirContenl,vol%=IW-W(
X 7 +P
400 + 4 P
Where,
W = mass of-KM mi of cernent paste, g,and
P = percemage of mking wxter, based on
cnass of cerneat used.
However, when conducng the q e r i m e n t it
wa
found that the test
WT~S
incapable of produchg meaaiagful results. AL contents were computed in the ranges of

O ro 2 percenh eren when overosed with AG\. For analyDcal purposes this test was
abandoned since the results produced would not provide any disceinibte condusions. It
is this thought that the paste lacked the consistency to retain the envained air during
mising or in the process of filhg the W m l measure.
Another method was adopted to try to test the compatibility of the rhree AEA's
Mth the SP's and WR. This second approach confomied to A!YM C 185 in that the
approach used a cement mortar
and not a cernent paste. ~Uthough,to conform to
other testhg in this project the w/c ratio w-as pre-set to 035. Air content determination
\ a s to be calculateci accordkg to the following equation.
Air Content ,vol % = 100 - W
'X
= mass of44M
. ml of cement paste, g, and
P = percenmge of mixing
water,
based on
mas of cernent used.
Unfortunately s e t h g the a-/c ratio to 0.35 made this test impraCacai, espeaaliy at
low- SP doses. Tfs procedure \vas also abandoned.
No other method =-as used to
determine the influence the SP's and WR have on the effectiveness of the three S-'.
The aihole of this chapter is the presentation of the observations of the

cement/admknire interactions and the results of the tests that they were subjected to, as
described in the previous chapter. W tests were performed by a single operator, and
carried out under controfled laboratory conditions with a constant temperature of 21
ZC and a RH. of SOTO. As akeady rneotioned, ail superplasticizer dosages are evpressed
on a dry basis (mas of
the solids of the superplasticizer relati~eto the m a s of cernent).
The results of the foam index tests on the cements are s h o w in Tables 4-1 and
4-2.
Note that the diluted
was dosed in 0.1-ml aiiquots, and not in the 02-ml
aliquots as suggested by Dodson (199), so that a more accurate detennination of the

required S A doses could be achieved.
As e.spected the addition of the lignosulfonate wxter reducer resulted in a
decrease of the foam indices for both of the cements. This reduction in the M A
requirement necessay to produce a stable au roid system in concrete is a result of the air
entraking characteristics of lignosulfonates ( N e d e , 1997; Okkenhaug and Gjorv, 1992;
Ramachandran, 1995). This trait of lignosulfonate water reducers has been recognised
by the ndusuy to reduce the AEr\ dosage used to produce air-enuained concrete. This
section of work is not ertensively deeiled since it was perfomied oniv as prelLnLiary
work necessacy to derennine the relatke quanaties of each
w-ork.
required for further
To aroid complicating issues foam indices w-ere not detemned for
cement/AEA/superp~ticiz~
combinations; since in iater work the SP doses appiied are
v&ed in the range of 0.1 to 1.O% soiids by mass of cernent
Table 4-1
Foam index results on plain cements.
CEMENT
TYPE
AEA
TYPE
MASSOF
CEMENT
WATER
(ml)
FoAM
ADDITIONS INDEX
NO.O F
(mL,20g)
Actuai
Dose
<m/lk
of cernent)
Table 4-2
Foam index results on cemwts with sodium lignosulfonate \XrR.
CEMENT
TYPE
AEA
TYPE
MASS OF
WATER
CEMENT
(ml)
FOAM
ADDITIONS INDEX
NO.O F
(mL/ZOg)
Actual
Dose
(d/lOO@
of cernent)
ISSUES IN ADMIXTU RE COMPATlBlLlTY
OBSERVAliONS & RESULTS
65
Observations of the rheological behaviour of the cernent pastes mere conducted
using the mini-slump test The measurements of mini-slump pat areas w - s e recorded as
a fnction o f time and superplasticizer dosage to study the effects of admiuttire
incompatibility and rapid slump loss. The resuits preswted in Figures 4-1 to 4-4 are the
results of the miai-slump tests conducted o n the low- and hgh-alkali cements combined
mith the sodium lignosaonate water roducer and either the melamine or naphthalene
superplasticizers. These four sets of data represent the typicai 6ndings for the different
air entrainment conditions; results for the air-entrained mixes c a . be found in the
hppendix B.
4.3.1 SUPERPLASTTCIZER-CEMENT
INTERACTIONS
The results dearly illustrate the effects of superplasticizers on the rheological
behaviour of cernent pastes. The results illustrated in Figures 4-1 and 4-2 indicate that
the low-alkali cement is easily influenced by the addition of a supeiplas6cizer. the
polynaphthalene sulfonate is much more effective than the melamine sulfonate. The
e ffect of the m;o SP's are minimal at the low-er doses (mini-slump pat area is usuaily less
than 5MH) mm' at doses less than 0.4'/0), smaii increases to the SP dose in the range of
0.5Oio to 0.8
pat area.
*/O
under most circumstances result Li sigiificant increases to the resultant
Unfortunately problems were encountered with the Iow-nlkaii cernent when
a t t e m p ~ gto use high SP doses. It mas found that when mlii-slump pat areas began to
esceed an area above 21,000
mm2
thar tLie test began to reach its practical limin for
measurement, e s p e d y c o n s i d a that the cernent-water miunire lost consistency and

the cernent solids began to segregate from die solution. It shodd be expected that this
would pose severe problems in a concrete mixture if the same SP dose =as to be used,
caution shouid also be taken at moderate doses of 0.6 to 0.8%.
ISSUES IN ADMIXTURE COMPAllBlLllY
OBSERVATIONS & RESULTS
66
30
50
40
fime (min)
Figure 4- 1
Mini-slump vs. bme for low-allrali Tl O/sodium lignosulfonate/melamine SP

combination (No A I X )
30
50
40
lime (min)
Figure 4-2
Mini-slump vs. Mie for low-akali T10/ sodium lignosulfonate/PNS

combination (NoAEA)
ISSUES IN ADMIXTURE CdMPAflBlClTY
67
Time (min)
Figure 4-3
&-slump vs. thne br high-alld TlO/sodium ligoosulfoaate/melamifie SP

combination (No - S A )
30
50
40
Time (min)
Figure44
irai-slurnp W. time for tilgh-alkali TlO/sodium

combination (No AEA)
Lignosulfonate/PNS
ISSUES IN AMOCrURE COMPATIBILITY
68
For the melamine SP large losses in workability were wimessed within 75 minutes
fkom the me of miving for doses in the range 0.6 r o 0.80/.. This type of loss in
workability should be expecred to result due to the fact that the non-superplasticized m k
possesses such low workability, and is expected ro reoert to that workabiliy as the
superplasticizer is consumed in the eady hydration reactions of the cement
By r e r h i n g Figures 4-2 to 4-4 one can dearly see that the high-alliali cernent is
less responsve to the influences of the PNS superpiasticizer and does not achieve the
fluidity as the Iowv-aW cement This observation con6rms preRous
same lerel of
rcsearch (Jianget al., 1999)). How-ever, a combination of high-alliali cernent and SP does
prove to be compatible, since much of the BuidiSing effect of the SP is retaked even at
-/ 5 minutes after mixing.
This cernent is also not ooerly sensitive to variations in the SP
dosage as the low-ahii cernent proved to be, such that s m d increases to the
superplastizer dosage do not yield dramatic iucreases in the resulting pat area
A m e case of admknire incompatibility arose when cornbining the hgh-allrali
cernent with the melamine sulfonate superplasticizer. This case of admixture-cement

incompatibility proved to be so severe that the mini-slump area measured at 5 minutes
afier mising for a

than 8,000 mm'
using as much as I.O?/oSP rarely achieved a par area greater

The PNS admkture at a dose of 0.4?/0
soiids by mass of the cernent
c a s e esceeds such a result.

a d m i ~ t u r cdid
Et-en an excessive dosage of 1.5% of the meiamine
not show-much improrernent.
Under the cicumsances when an air-enuainlig agent was employed in the

cernent pastes, no compatibiiity probiems were wimessed to result Erom th&
incorporation. However, to report that they had no influence would be inaccurate.
When tested mith the mini-slurnp test, each of the three air entraining agents had a
tendency to improve the iow characteristics of the pastes with SP doses in the range of
0.5 to 1.0%0. As already menuoned in previous sections, the euttainment of air inro
cernent paste or coacrete, aside fiom improving fkeeze-thaw resistance, also acts to
ISSUES IN ADMIXNRE COMPATlBlLITY
OBSERVAIIONS 6 RESULTS
69
-
lubricate the
The microscopie air bubbles act Like '%ad bearings" and d
partides to p a s one another uith reduced friction. These improved flow characteristics
are represented as an inaease in the mini-slurnp pat a r a
Unfominately these irnprovements were not found with the high-aliiali cernent
when used with the meiamine-based superplasticizer. Under most circumsrances, the
incorporation of an air-entralung admimice into this cernent-SP combination yielded
lower mini-slump areas. These resdts do not agree with the hdings of Okkenhaug and
Gjorv (1992) who found that in superplasticized
a melamine-based admixture,
as opposed to a naphhalene-based agent, produced a better and more stable air void.
No evplanation is offred for these results. The level of aikaiis may &t be suspected,
hou-ever, no problem was detected with the other SP, and other researchas have fomd
that cements with high-allrali contents tend to entrain air more easily than cements of
lower alM contents (Dodson, 1990; Ramachandran, 1995).
The optimal superplasticizer dosage c m be d e h e d as the dosage rate that
provides the maximum fluidity for the least dose of SP. Once the optimum is reached
any additional superplasticizer
have limited effect on the fluidiq of the concrete o r
cernent paste. Any SP dosage greater than the optimum results in increased costs for
minimal r e m , and nuis the risk of retardation of set and segregation problems. To
detemrlie the optimal superplasticizer dosage rates for both the
high- and low-alkali
cemens, the results from the loss of workability tests (mini-slurnp
\-S.
time) were re-
plotted in Figures 4-5 to 4-20 on a mini-slump area rs. SP dose axis for the
rneasurements made at 5 and 60 minutes afier mixing. The m o t h e s were selected as
r e p r e s e n ~ gthe ideal time Game when a concrete is required to be most workable for
the purposes of placing, compacting/~ibratingand bishing. The resulting plots for the
m-Ocements are contained in Figures 4-5 to 4-20. The optimum superplasticizer dosage
c m be wirnessed as an Liflection point on these cun7es
ISSUES IN ADMIXTURE COMPATiBlLlrY
70
As can be seen in Figures 4-5 ro 443 the effect of the melamine sulfonate
superplasticizer on the low-alkali Tl0 cernent does not begin to become prominent u n d
doses larger than O.QOh are used @ &es
with a w/c ratio of 035). The low-alliali
cement is highly sensitive to minor inaeases in the SP dose in the range of 0.4'/0 to
0.8?/0. For this @zen combination of cernent and SP there appears to be an optimum SP
dose of approxknately 0.8% (0.696 when used \vith the ~McroaidBhEA) at a t h e of 5

minutes after mi--
T h e plot of mini-slump areas obtained at 60 minutes &er
the
completion of mi+
pmides some indication of the cernent's ability to re&
in
workability. As e-xpected the 60-minute plots are lower than their correspondkg 5minute plots. The f i e r apart these m-Oplots, the greater the loss in a-orkability.
Howewx, at SP doses of 1.0% the nvo niiai-slump areas obtained at 5 minutes and 60
minutes are neady equd. This is an indication that there may problems assouated with
set retardation instigated by an escessive dosage of the superplasticizer.
Figures 4-9 to 4-12 represent the optimum SP dose determinauon for the low-
alkali csment when used with the naphthalme based SP, As can be seen the cernent is
much more sensitix-e to the influences of this paaicuiar SP. Pronouaceci fluidification
ody begins to occur at doses of O.2?,'0 and greater. For the 5 minute plot the optimal
dose for this superplasticizer is approximateIy 0 5 to 0.696, considerably lower than the
melvnine product. By quickly obsening F i e s 4-9 to 4-13 it can be seen that the 5 and
GO-minute plots closely appro-simate one another for each of the graphs. This is an
indication that there is Little loss in worlrability over the tirne Gdme in question, one c m
conclude diat the naphthalene product is more effective in delaylig the early C3A
hydration reactions typically responsible for rapid slump loss.
71
ISSUES IN ADMIXTURE COMPATlBlLlrV
25000
...........
. .
- . - ........ - -........... -
. . . -. - . . . . . . . -
-.~-
..................
3
.-
0,0040
0,20%
0,40%
0.60%
SP D o n
0,80%
0.00%
'
" "
0,40%
0.60%
SP Dow
. . . . . . . . .-
-,
-.
... -....
....
0.80%
--
1,00%
Figure 8-11: 5 min (Ir 60 iiiin Mini-slump vs. SP dosc
Figure 4-9: 5 min & 60 min Mini-slump W. S1' dosc
+5
0.20%
'
min
.
......
0.00%
Figure 8-10:
0.20?'0
0.40%
0.60%
SP Dore
0.80%
1.00%
5 min & 60 min Mini-slump vs. SI' dosc

(l
.Al>C/NaplithdilencSI>/ Nri 1.iposulfoiiatc
WK/Vinsol Rcsin A IIA)
Figure 4-12: 5 min & (>O min Mini-slump vs. SI' dose
(1.AlY~/NaphthnlcncSI3/Na 1 ,iporiilfonatc
Wlt/Synthctic A 1!A)
,
l
0.00Yo
0.20%
0.40%
0.60%
O,W%
1.00%
...-
...........
+5
+60
0.00%
- ...
mln
.....
min
O.MO/o
SP Dow
Figure 4-13: 5 min & 60 min Mini-slump vs. SI) dosc

(i-IAl~C/MclamincSI)/Na liposulfonate
WK/No A I N )
0.80%
1.00%
Figure 4-15: 5 min & 60 miii blini-slump vs. SI) dose
..
-1
Acids Al'.A)
.............
--
+5
+60
0.00%
5 min & 60 min Mini-slump vs. SI)dosc

(1 1Al3(:/ Melaminc SI1/Na 1.i~moriilfon~tc
WK/Vinsol Kesin A fSA)
0.60%
SP Dow
. . .
Figure 4-14:
0.40%
--
....
min
min
O.M%
0.40%
0.60%
SP D o n
0.80%
1.00%
Figure 4-16: 5 min & 60 min Mini-slump vs. SI' dose

(1-IAl3C/MclamincSI3/ Na I.ignosullonatc
WK/ Syntlwtic A M )
25000
.-
- -
-~ -
- .
i2 0 ~ ) 0.
. .
.-.
. . . . .
...
......
,--0.00%
0.20%
-.
-,..
I r - '
0.40%
0.60%
SP Dow
.'1
0.80%
1.00%
Figure 4-17: 5 min & 60 min Mini-slump vs. SI' dose
0,00016
0.20%
0.40%
0.60%
SP Dom
0.80%
1.00%
Figure 4-19: 5 min & 60 min Mini-slump W. SI' dosc
. . . . . . .
-. ......
.... ..--.
+5 min
- -
+0O
min
.-....... -.........
...- -.. . . . . .
Figure 4-18: 5 min & 60 min Mini-slump vs. SI)dosc

(IIAI'C/Naphth;ilene SI>/ Na 1,iposulfonatc
WK/Vinsol Rcsin A l!A)
Figure 4-20: 5 min (Ir 60 min Mini-slump W. Sl>dosc

(I-IAlY:/Naphtlialcnc SI>/Na1,iposulfonatc
WK/ Synthctic AI?A)
75
-
The htgh-akdi Type 10 cement a-heu used wth the melamlie based
superplasticizer, as already noted, exhibits a problem of a d m i m e incompatibiiity. As
seen in Figures 4-1 3 to 4-16 che mini-slump areas remali relativeIy srnaIl, even at doses
of 1.00/0. The optimal SP dose is not as pronounced as the other cement-admiunire
combinations, the plot of the mini-slump area rs. SP dose produces a near Iineac plot in
the range of O to 1.0% o f the superplasucizer.
The optimal SP dosage can be
a p p r o s k t e d as O.GO/o solids by rnass of cernent. Approlshatdy haif of the workability

gained by the use of the superplasticizer is lost within 60 minutes h m the completion of
mising.
When used with the naphthalene-based admixme the cernent produces more
desirable resuits. The fluidifkation eftect is more prominent and the optimal SP dose is
f i r more obvious.
As
can
be seen in Figures 4-17 to 4-20 the optimum dose is
appro'cimately 0.6 to 0.8?'0 solids by mass of cement. The plot of the mini-slutnp areas at
60 minutes produces a w
e that is a dose appro-rimation of the 5-minute cuve
indicating good retention of the improred w-orliability.

Note that the air enuaining agents had linle effect upon the oprimal
superplasticker dose.
The 6rst slump test performed used a conaete mis with a 20 mm nominal sized
coarse aggregate, low-alkali Type 10 cemenb and a PNS superplastcizer dosage of 0.8%
soiids by mass of cernent. The dose of 0.8% soiids by the mass of the cernent was
considerab- higher than the optimum SP dose detemiined for the low-alkali and PNS
SP combination in section 4.4. Uader these ciccumscances this superplasacizer dosage
proved to be excessive, the cement paste becarne too fluid and was unable to maintain
the coarse aggregate in suspension producing seoere segregation and bleedlig. The
slump w-as not measuiable since that the loss of large amounts of bleed water resulted in
shear fdure of the concrete sample duPng the h
two measurements.
ISSUES IN AOMlXrCIRE COMPATlBlLlTY
OBSERVAflONS & RESULTS
As a result the
76
design was modified to produce concrete of better
consistency at these SP doses. The soluaon \asto use a concrete rnisture
a IO-mm
nominal aggregate size, thereby increaslig the requked volume of sand in the mis, which
stabilised the mi'r. These changes to the basic concrete miu design improred the ability
for measurement of the concrete slump and its loss with time when subjected to the
different admi~turesand dosage rates.
The slump measurements wth respect to tirne are presemed for both the hghalkali Type 10 and the low-alkali Type 10 cements in Figures 4-22 and 4 2 3 respecti~elp.
Due to th&. diffezcing l e d s of reacu~itywith the superplasticking admiswes, the mal
&es were performed mith ciiffereut SP doses. As predicted by- the mini-slump tests, the
melamine sulfonate admistue with the high-alkali cernent would perform poorly when
compared to the naphthaiene sulfooate.
The PNS superplasticizer
W
SI
capable of
producing s i d a r or better levels of fluidifcation at half the dosage required of the

melamine SP. At a dose of 0.89'0 solids by mass of cernent the melamine sd6onate SP
fded to produce concrete that flowed to die sarne extent as the PNS admisture could at
a dose of only 0.4?/0. lMore noticeable is the rapid slump loss experienced by the
concrete produced using the melamine SP. As c m be seen in F i e 4-22 the m i ~ t u r e

using 0.8% of the melamine sulfonate SP lost nearly half of the slurnp increase nithin the
k s t hour and almost ail ofits workability by the second hour after mi+
The results obtained for the Iow-alkali Type 10 cernent w-ere not as expected.
According to the mini-slump test results, the superplasticbers should have been Far more
effective viith respect to fluic(lfylng the concrete. As c m be seen in Figure 4-3 the
cernent esperiences considerable losses in slump aithin the k t hour after mi.iUig- The
measured slump of the concretes mith 0.8% of the melamine based SP and 0.4?'0 of the
naph thalene based SP rererted to slumps near that of their lower dose counterparrs. In
cornpackon to the high-ailah Type 10 cernent the low-alkali cernent e ~ ~ e r i e n c eFar
d
greater slump loss. This nconsistency with the results of the mini-slump is e'rpkined in
the followirig section.

.Mthough "admi_xture kee" batches were not produced for the concrete teal
mixes it can be deduced that for the given
design such concretes a-ould have zero

ISSUES IN ADMIXTURE COMPAllBlLllY
77
slump as illustrated by Figure 4-21. The conaete mix design utilised in this portion of
the lab work consists of a 10 mm nominal aggregate size and a water content of 140
kg/m3, by Figure 4-5 it can be seen that such a mx would possess no slump.
150
160
170
180
190
200
210
220
230 2 4 0
250
Water Content (kg/ cubic rneter)
Figure 4-21
Estimated slump as a funaion of water content

for various sizes of coarse aggregate.
(Hover, 1998).
ISSUES IN ADMIXTURE COMPA~~BILITY
OBSERVATiONS & RESULTS
78
lime (minutes)
Figure 4-22 Slump loss in concrete over h e using high-aikali Tl0 cernent, sodium
lignosulfonate, and t-arious SP type and dose.
'
\
I
'
200
: +0.4%
1
naphthalene L,
-0.4%
melarnine
-0.8%
melamine
lime (minutes)
Figure 4-23 Slump loss in concrete over rime using low-alkali Tl0 cernent, sodium
lignosulfonate, and vatied SP type and dose
ISSUES IN ADMUCTURE COMPATlBlLlTY
In an attempt to determine the accuracy with which the mini-slump test c m

predict the slump loss characteristics of concrete mkes, the results o f the concrete slump
tests were plotted against their equivalent mini-slurnp tests (equivalent in
temis
of SP
dosage used and the Mie after mkxing that the measurement w-as taken). These plots can
be seen in Figures 4-24 ro 4-27. These plots indicate tbar there is a h e a r correlation
benveen the miai-slump values and those obtained wvich the slump cone on the conaete
trial &es.
As can be seen by the trend lines in Figures 4-24 and 4-26 there esists a
h e a r relatiooship between the workability measured by the slump of a concrete and in
corresponding mini-slump pat areas. This suon& supports the hnciings stated in the
investigations of Tang and Bhatrachaja (1999) that "there e-sis6 a Linear relationship
bens-een the rate of loss of workability measured by the reduction in slurnp in the
concrete slump cone test and reduction in pat area in the mini-slurnp cone test".
Linear regression analysis of the results for the nvo separate cements indicate that
the Rz values for the linear trend lines to be very accurate for Figure 4-24 (R- = 0.8045)
and there esists some correlation in Figure 4-26 (R' = 0.5831). Hoaiever, by perfocming
a more specific analysis of the resdts a stronger relationship is indicated benveen mini-
slurnp and slump values when the nvo cemmts are malyseci accordhg to th&
interactions with the specifc superplasticizer. With the exception of the results relating
to the melamine SP when used in combination with the low-aikali cernent, the F values
for the plotted trend lines esceed 0.8.
The high variance (R? = 0.6379) of the mini-slump measurements in relation to

the slump values for the results presented in F i e 4-26 can be accounted for. D u h g
testing for the influences of the SP's on the slump loss characteristics of concrete mixes
the original stock of the low-alkali Tl0 cernent had ran out before the final test could be
completed. As a result the concrete batches that used a 0.8% dose of melamine based
SP and a 0.4% dose of the naphthalene based SP were conducted on a different supply
of the low-alliali cernent Although this suppiy *-as of the same type and manutacwed
at the same plant, it is assumed that minor variations in the mill run could account for
the une-xpected results.

cernent to
%d
Unforcunately no chernid analysis =-as conducteci on this
idenafy the esact cause o f the inueased reactiviy and accelerated loss of
workability in the second supply of the low-alkali cernent
ISSUES IN ADMIXTURE COMPA~BILITY
OBSERVATlONS & RESULTS
81
25000 ,
'
+naphthalene
50
100
150
250
200
Concrete Slump (mm)
Figure 4-24
Cement paste mini-slump area FS. concrete slump for hi&-alkali
Tl0 cemeot
25000
+naphthalene
s'20000 - mmelamine
E
E
2 15000
naphthalene
y = 28.529~
+ 2945.7
10000
2
*
C
al
g
O
'
5000
y = l8.392X + 2737.8
R 2 = 0.8174
50
100
150
206
250
Concrete Slump (mm)
Figure 4-25
Cernent paste mini-slump a r a vs. concrete slump for hgh-alkali Tl 0 cernent
ISSUES IN ADMIXTURE COMPATiBltlTY
OBSERVATIONS a RESULTS
82
O '
50
100
150
200
250
C o n c m Slump (mm)
Figure 4-26
Cement paste mini-slump area vs. concrete slump for the low-aikali Tl0
cement
+naphthaiene
mdamine
y = 91.Si& + 231-27
R2 = 0.8204
O
50
100
150
200
250
Contrats Slump (mm)
Figure 4-27
Cernent paste
cement
mini-slump area vs. concrete slump for the low-alkali Tl0
ISSUES IN ADMIXTURE COMPAliBlLlTY
83
As already indicated the rate at which heat is developed by hydrating cernent
paste is an excellent indicator of the reaction rate of the cement phases.
nius
measurernents of temperature rise in cernent pastes were conducted on numerous WRLEA-SP-cernent combinarions. The resuits of n-hich c m be found in Appendiv C,
however for anaiytical purposes the results of al1 these tests were eraluated according to
the peak temperature obtained r s . SP dose and the M i e taken to obtain the peak ms.
the
SP dose. The plots of these values are giren in Figures 4-28 to 4-31 and 4-32 to 4-35.
When compared to each other on an admixture
Gee basis, the temperature Bse
proales For the NO cements are very much alike. The low-alkali and high-allrali cements
had peak temperatures of 75.6 and 77.2 OC, and the time d e n to achieve those p&
temperatures were 6.32 and 6.17 hrs respdvely (as can be seen in Figures C-2 and C1l). Unfortunately, as already diswsed nor ail cements behave the same when subjected
to the effects of
chemicai admstures.
The results reveal, through th& effects o n the kuietics of heat evolution, that the
addition of chernical admistues
produces pronounced effects on the semng
characteristics of both cements used. Th& effects on ettringite formation Lom C d and
SOI c m be posnilated kom the heat erolx-ed diipng the 6+st nvo hours (Wuhl and
Ward, 1980). Unfortunately due to the techniques used, the development of heat in the
1-ery
early stages (the production of heat Ecom the time of &t contact with water) could
aot be rneasured. Therefore an accurate analysis is not possible. While their influences
on the subsequent C S hydraton can be detected by changes Li the dormant phase and
second peak of heat development.
Tt can htst be noted that the addition of the m-ater reducer alone has a notable
effect on the high-alkai Type 10 cernent The addition of this admiunire alone causes an
acceleratioa of the s e t h g characteristics of the cernent When cornparhg the admistue

ISSUES IN ADMIXTURE COMPATtBlUTV
free blend to those incorporating the water reducer it can be noted that the me to the
second temperature peak is reduced from 6.17 hrs d o m to 458 hrs wMe the
correspondmg peak temperatures rose Gom approi\imately 77 OC to 1 0 0 OC. Only minor
variations kom these values occur when the AEA admisaures
were added to the picture.
In the case of rhe low-alliali Tl0 cemeng the water reducer delayed the setting process of
the cernent by incrashg the duraaon OF the dormant pe9od. When comparing the peak
remperanire benveen the
NO
conditions there is a rninor increase in temperature of less
than 1 OC, however, a pronounced extension in the t h e taken to achieve chat pealr
temperature is noted as a delay of almost 2 hours (from 632 to 8.13 hrs). W h e n
incorporated, AEA's caused some variabihty in the peak temperature (Qnging from 77.3
to 78.9 O C ) while the t h e to peak temperature ranged from 7.46 co as high as 11.6 hours
when used with the ME3 VR concentrate.
These results illustrate that the high-&aIi cernent displays a high amnity for the
water reducer and consumes it rapidly. It should be evpected that the accelerated setting
of this cernent paste due to the WR is a result of a variety of factors. The inueased
reacti~lrc m be easily e'rplained to result Lom the dispersion of the Qocculated cernent
partides, eqosing additional surface area of the cernent to be mposed ro water for
hydraaon. The fact that the WR delays the setting time of the lower alliali cernent and
not the hgh-alkali cernent iodicates that the Iignosulfonate \KrR is rapidly consurned by
the hydration products of the high-alkali cemen t. The inability of the WR to e f f e h e l y

coat the cernent partides and delay the hydraaon of the C S c m be attributed to the high
alkali content of the cement.
When a superplasticizer was added in addition to the water reducer other effects
were obsen-ed. A n orerail increase in the duration of the induction phase was wtnessed
in a!l the batches, though the severity of this retardation and its influences on the peak
temperature depends on the s p e d c cernent and a d m i m e used.
However, the
retardation of setting is proportional to the superplasticizer dose used. By observation of

ISSUES IN ADMIXTURE COMPAllBlLlTY
OBSERVATlONS & RESULTS
85
the results it c m clearly be shoan that the 10%--alkaLi Tl0 cernent to be subject to the
influences of the SP's to a greater extent than the high-alkati cernent
When used in the presence of a superpiasucizer the low--aikali cernent
esperimced pronounced retardation of set, espeuay at the higher doses, as weii as a

reduction in the peak temperature reached.
The melamine sulFonate SP is a more
effective retarder of the low-alkali cernent At doses of 0.6O/o soiids by mass of cement
and above, remdation became excessive. At a 0.6% dose, the peak temperature \vas
achieved at approskately 30-34 hrs, whde at a dose of 1.00.0, peak temperature aas
delayed to u p w d s of 62 hrs.
The naphthalene sulfonate SP proved to be less
detrimental than the melamine based SP, however it too produced results of excessive
set retadation. At a dose of 1.05'0, tme to temperature peabi =-as in the order of 41-49
hrs, with the exception of the resdts attained when used \sith the Mcro Air @ where a
time of 63.5 hrs \*-as recorded.
The high-alkali T l 0 cernent prooed to be less influenced by the effects of a
superplasticizer. Although there is evidence of some retardation of the setting time, the
incorporation of the superplasticker does not hare any detrimentai effects in ternis of
excessive set retardation as c m be seen in Figures 4-30 and 4 3 1 - When used with the
melamine sulfonate, even at high doses of
l.OO/o
solids by mass of the cernent, the &ne
required to achiet-e the peak temperature never esceeded more than 29 hrs. That is a
retardaam of the C3S and C2S hydration of a p p r o h t e l y 25 hrs compared to the delay
of 56 hours required for the Io\--alkaii cernent to achieve its peak temperature at the
same dose.
When the same high-ailrali cernent is used in combination wth the
naphthalene sulfonate SP there is an even s m d e r influence on set retardation. For aii

combinations incorporatkg this combination of cernent and SP the peali temperature
was achieved within 18hrs, a delay of Iess than 14 hrs.
These delays to the se*
o v e d p d temperature.
time are g e n d y also accompanied by changes in the
With both cements chere are cases of increased peak
temperature. With the low-alkali cernent these increased temperatures w e r e obsen-ed to

occur up to a dose of approximately 0.4O/0 solids of SP,regardless of the SP used; while
86
for the high-alM cernent this occuned up to a SP dose of 0.6%. Abooe these values,
peak temperatures are reduced as the SP doses are increased. This reduction of the peak
temperature c o h s that some levei of reactivity of the cernent phases continues duriag
the "dormant" period, just at very minimal rate. These c o n ~ u e dreactions consume
part of the silicate phases before the onset of the second p e n d of high reactirity, thus
reducing the total volume of silicate phases that can contribure to the development of
heat.
To view- the temperame
trends caused by individual
S P s or SP and AEA
combinations consult Figures 4-28 to 4-35 or for more d e d e d data Appeadix C.
The effects of air-entraining agents, in terms of their influence on the heat

developrnent of the hydrating cernent pastes, are disputable. Since that they make up
only a minusnile Gaction of the proportions OC the cernent paste or concrete it is
accepted that chemicdy they should have litde or no influence at al1 on the hydration
products or on the rates at d i c h they are formed or reacted. No dehnite trend can be
distinguished Gom the results presented in Figures 4-28 to 4-29 or in Appendiv C.
OBSERVATlONS a RESULTS
O
0.00%
0.10%
020%
0.30%
87
0.40%
0.50%
0.60%
0.70%
0.80%
0.90%
1.00%
SP Dosage
Figure 4-28
Tiie to pealr temperature vs. SP dose for the low-alkali Type 10 cernent with
melamiue SP & sodium lignosulfonate W R
-+
Micro Air
+Darex
- +ME
AEA
VR
J(t None
Figure 4-29
T m e to peak temperature i-S.SP dose for the low-alkali Type 10 cernent with
PNS & sodium lignosulfonate W R
ISSUES IN ADMIXTURE COMPATlBlLrrV
C5
60
88
- +Micro Air
-m- Darex AA
1
1
Sp Dose
Figure 4-30
60
Figure 4-31
T h e to peak temperature vs. SP dose for the high-ak& Type 10 cernent

with meiamine SP & sodium lignosulfonate WR
+-Micro
Air
+-Darex AEA
Time to pe& temperature vs. SP Dose for the high-alkali Type 10 cement
with PNS & sodium iignosuifoaate WR
ISSUES IN ADMIXlRE COMPATlBlLlTY
110
-, +Micro
89
Air
I
l
' +Darex
AEA
2 100
+ME
50
0.00%
VR
0.10%
020%
030%
0.40%
0.50%
0.60%
0.70/6
0.80%
0.90%
1.00%
SP Dosage
Figure4032
110
--
Peak temperature vs. SP dose for the low-akdi Type 10 cement with
melamine SP & sodium lignosulfoaate WR
+-Micro Air
-C Darex AEA
50
0.00%
O-10%
020%
0.30%
0.40%
0.50%
0.60%
0.70%
0.80%
0.90%
1.00%
SP Dose
Figure 4-33
Peak temperanire vs. SP dose for the low-alkali Type 10 cement with PNS &
sodium LgnosuXonate W R
ISSUES IN ADMIXTURE COMPATIBIUTV
90
SP Dosage
Figwe4-34
Peak temperature vs. SP dose for the hgh-akdi Type 10 cernent with
mdamine SP & sodium iignosulfonate WR
+Micm
70
Air
+Darex AEA
+ME
VR
SP Dosage
Figure 4-35
Peak temperature vs. SP dose for the high-alkaii Type 10 cernent with PNS &
sodium lignosulfonate, WR
4.8
81
SOLUBLEALKAU CONTENTSOF CEMENT

The alkali contents from the PC andysis for each of the cements dong with the
corresponding soluble alkali contents, as detennined using lame
photomeuyy are
reported in the followi.9 table.
TABLE
43
PC alkati contents & soluble alkali contents of cements espressed as
O r b w/w of the dry cement.
PC Anaiysis Akaii
Cernent
Content (%)
Na0
IL0
N-O,
Low-alkali Lafarge Tl 0
Kgh-alk'li St Mary's Tl0
High-alkali St Lawrence Tl0
0.22
0.27
0.32
0.46
1 .O8
1.13
0.52
0.98
1.O6
Soluble Aikaiis (Yo)
Na0
0.033
0.073
0.156
0.259
0.785
0.816
NaO,
0.203
0.5W
0.693
As claimeci by Jiang et al. (1999) the concentration of soluble alkaiis in a cernent
paste during the &t
few minutes, after being combined with water, cannot be
determined from the numbers provided in the cernent analysis. W
e the concentration
of die soluble alkalis cannot be d e t d e d by some equation or the application of a
constant, the relative order of the cements accordlig to the soluble akali content
remains the same as in the cernent andysis. Jiang et al. daimed that at an optimum
solubk alkali content of 0.4-0.5~~

N a 2 0 soluble equivalent the efficiency of a
polynaphthalene su1foaate superplasticizer shodd be ma'rimised regardess of the C3A
content or SP dosage. They make further daims that "imdequate soluble allialis in
solution in the hrst few minutes OC hydration is more likely to render a cernent-admiunire
combination incompatible than excessive soluble allialis" @ang et al., 1999. p. 76). The
results reported in previous sections when compared to the data in Table 4-3 does not
entely support Jiang's daims. The St iMaryysTl0 cernent, with a soluble alkali content
near their claimeci optimum, has been found to be compatible with a PNS. How-mer,
the cernent prores to be incompatible with a melamine sulfonate admiuture-
ISSUES IN ADMIXTURE COMPAllBIL!w

-
92
---
On the other hand, the Lafzge Tl0 cernent ha\%
a soluble
alkali content
considerably belou- Jiang's optimum of 0.4-0500 Na20 soluble quit-dent e-shibits no

problems of incompatibility (in terms of rapid slump Loss) with either superpiasacizer.
The performance of these nvo admiunires must be eA.uplainedin terms of thek a W

content skce there is no major difference betsveen the C d contents of the iwo cements
@oth cemens have a C d content of9 to 10 9'0).
ISSUES IN ADMIXWRE COMPA~BIU*
Unfortunately, due to the product information protection poliaes of one of' the
manufactures, infomiation regarduig the average molecular weight and the degree of
sulfonation for the melamine sulfonate SP codd not be obtained.
As a result an
extensive discussion on the role that these factors ha\-e is not possible.
5.2
CHANGEOF CEMENT IN CONCRETE TESTS

As already mentioued there was a change in the supply of the low-alM cernent
in the latter stages of the eypetimental wvork, narnely the conuete via1 tests. Although,
this \.as ongindy not suspected to pose a problem, it is responsible for the flawed
results obtained. Khalil and Ward (1978) mention that slight variations in SO3 content
during difkrent millruns may result in excessive changes in the workability of a cernent
when used in the presence of admiunires. Although it hasn't been determineci, changes
in the SOJ content, alkali content or C3.4 content may be responsible for the clifferkg
behak-iour betsveen the tsvo supplies.
DISCUSSION
94
The tsvo cemeats that have beea used evtensively in this work are very similu in
both th&
physical and chernical traits. Both cements have finenesses in the range of 39
to 400 m'/kg and densities of 3130 and 3140kg/m3. Chemicdy the two cements are
neady indisanguishable from each other, aside from the differences in allialis (most
notably in the concentration of &O) and sulphate contents. As a r e d t the trvo cements
behave very much &e
when used in the absence of chernical admktures. F M y there
are no sgn5cant differences in the Bogue compositions that can account for the
differences in compztibility with admiunires. The C d contents d i f k by only IOh.

Therefore the analysis of the results c m therefore concentrate on the influences of alkalis
on cernent-admkture interactions-
Unfortunately neither of the methods utilisng the b r a s cup specified in ASTLI C
185 for the determination of the air content of the cernent pastes (desccibed in section
3.9 of the erperimental proceduces chapter) proved to be practical in measuiing the
effccts of air entrainment. rUthough the effects of the air entraining agents in question
@lB VR II 8, Darep II @ and iL[crohL 09) could not be detemiined in this work,
findings by others have pointed out some interesting obsem-auons. WMe there is no
agreemenr on the behaviour of air entraining agents in the presence of superplasti&ers

there is a consensus that low --/cm,
superplasticized concrete has a superior
performance with regard to keeze-&aw durability- Its resistance is so good thac the need
for any air-entrainment for concretes of very Iow- w/cm raao has been questioned
(Cohen et ai., 1992).
ISSUES IN ADMIXTURE COMPATIBtLIlY
DISCUSSION
95
The mini-slump data obrained for the htgh-akah cernent aas very simikr to those
of the low-alkali cernent, except when used with the mekmine sulfonate superplasticizer.
This combination of cernent and SP failed to produce highly workable mixes as were
obtained with other combinations.
This failure to produce high slump pastes can
probably be e-tplained in tenns of inadequate suiphare contenb and rapid gypsum and
syngenite crystallisation (Jawed and S k y , 1978; O d e r and Womemnon, 1983; Tang,
1992). The behaviour evhbited by the combination of the high-allah cement aud
melamine sulfonate SP are similar to that which w-ould be espected of an under
sulphated cernent. The cernent when used without admi~mresbehat-es similat to that of
the low-aikali cernent, as if properly sulphated.
For rasons aLready discussed in the
iiterature review, the presence of allialis in portiand cernent promotes the dissolution of
C A This increased rate of dissolution in tum intensifies its rate of reaction and
accelerates d
y hydratioq provided that the gypsum content is low and produces qui&
set (Jaa-edand Skalny, 1978). Further aggravating the situation is the act that h g h - a W
cements have the effect of dramaticaily increasing the solubility of the sulphate ion
(Dodson and Hayden, 1989). Unfortunately, these soluble sulphate ions in the cements
rnay become consumed in the foxmation of syngenite that may result from reactions of
allrali sulphates with the gypsum (Oder and Wonnemann, 1983). Syngwite fornation
produces a agid structure that lends itself to qui& semng- Syngenite formaaon
decreases the sulphate content of a hydraliog cernent to the ertent that it cannot
and
adequately retard the hydration of Cd; h d e r promoting early stiffening ( J a ~ d
Skalny, 1978).
This increased consumption of the gypsum and accelerated C d
hydration demands that larger additions of gypsum be made for high-alkali cements.
While the high-akaii cernent behaves normay in absence of chernical admixtures,the
addition of a WR or SP may upset the sulphate content to a sufficieut estent that the
aforementioned processes occur.
ISSUES IN ADMIXTURE C O M P A ~ ~ ~
96
DISCUSSION
AccordLig to Ramachandran (1995) the presence of a large concentration of

al&
in a cernent also influences the perforniance of admi~tures. With inueased
concentrations of alkalis the adsorption of admixtures on to the cernent phases are

decreased considerably- This statement may hold tme for the melamine superplasticizer.
Perhaps the aikalis prevented the adsorption of suffiaent admjsture ont0 the cernent
partides necessary to protide the desired piasticinng e f f ~ t ,or the deiay in C d
hydration.
When combined with either SP, the low-alid cernent in the concrete slump tests
yield a greater rate of slump loss than the high-all<ati. The results of the mini-slump test
had predicted a far greater level of fluidification in the concrete tests than was obtained.
This appears to be an indication of a cernent-admkmre incompatibiliry and reflects

poorly upon the mlu-slump test as an evaluator of cement paste behasour.
esplained in previous sections, diis is not the case.
As
The unescpected behaviour in
concrete slump has been attributed to a change in the stock of the low-allrali cernent
The cernent used during the concrete test program, although the cernent \vas of the same
manufacturer and type, was obtained almost a year a f k the initial supply was obtained.
It is espected that vaPaoons in the mil1 production can account for the erratic behaviour.
5.7
MODIFICATIONS FORTHE MINI-SLUMPTEST

Unfortunately the work produced by Tang and Bhattachq-a (1997) was not
obtained before the mini-slump test program was \veli under way.
The paper cites
several suggestions made by H e h u t h regarding modifications that should be made to

improve the mini-slump test H e h u t h advised that a coollig T t e m be used during the
mixing processes to offset the heat produced by the high intensity mixing produced by
the blender. Unfortunately no such cooling system wu available at the tirne, however if
future work is to be conducted this issue should be addressed.
Furthermore Helmuth
ISSUES IN ADMIXTURE COMPATiBlLlTY
DISCUSSION
97
proposes that the mkag schedde for the mini-slump cone be shortened so that the test
becomes more sensitive to eady saffening resdting from false set F
a
n
g and
Bhattacharja,1997).
The problems associated w-ith rapid slump loss may be remedied by several
methods. Often used in the field is the practice of delayed or multiple additions of the
superplasticking admktures.
The delayed addition of a superplasticizer minimises die
consumption of the admixture by the hydrating C d phase in the \-eV eady stages of
crment hydration, this allowvs the admiunire to adhere to hydrates and other phases and
disperse them more efficientiy. The adding of a retarding admi?unire has also been used
to slow the rate of slump loss, aithough this may be effective the addition of yet another
chernical may produce other complications.
Cauaon shodd be taken under these
crcumstances since that the addiaon of a chefnical retarder might r s u l t in ertreme ser
retardauon.
Researchers have suggested that vaPations in the sulphate content of cernent
should be made to resolve slump loss problems of superplasticized concrete @mg et ai.,
1998). This can be done at the me of manufacture at the cernent plan&or later on by
the possible addition of sodium sulphate. Combinations of superplasticizer and retarders

are cornmonly used in the field to resolve these issues, aithough effective, this rnay
hrther complicate cement-admixture interactions and lead to other problems. However,

the most effective means to eliminatng rapid slump loss is the replacement of either the
cernent or problern admixture with another (Ramachandran, 1995).
ISSUES IN ADMUnURE COMPATlBlLlTY
6.1.1 EVALUATION
OF THE MINI-SLUMP CONETEST
The issues related to admisnire interactions and the problems associated \.+th
admiunire-cement incompaability are ememely cornplicated due to the nature of the
multi-component and rnulti-phasic coostituents that comprise concrete.
Problems of
admixtureincompacibility cannot be amibuted entirely to one single cause; rather there

are several key issues vith respect to cement and admixture compositions that may be
responsibie for the poor workabilio/ of fresh concrete. Such being the case, it quickly
becomes impossible to determine which combinaaon o f cernent and admi.~turesare
suitable for use together simply by an inspection of chernical analyses and manufacturer
specification sheets. The solution is then to develop a method for the pre-qualification
of cemenatious materials and admixtures
to elimliate the use o f an incompatible
CONCLUSIONS & RECOMMENOAIIONS
99
combination in the field. By conventional test methods research into these problems can
become expensive and cime consuming. What is required is a reliable rapid method that
can predict the performance of a concrete while using a minimal amount of material and
which can be manageci by a single- operator.
The miai-slump cone tes&as initially developed by Kantro, appears to be useful

in this respect. In this work as u d i as works by others, the mini-slump test is provng to
be a reliable evaluator of canent-admivture interactions. The finduigs Gom this work
show that the miniature-slurnp test may have promise in accuratelv predicting the
performance of workabilitg enhancing admixtures in concrete as a hnction of the
cernent and aggregate combination. There e-xkts a strong linear relationship beneen the
mini-slump and the slump cone for the hgh-alkali canent tested; the relationship that
easts
benveen the nvo for the low-alkali cernent did not prove to be as good, for reasons
aiready- explained. In addition the mini-slump test proved to have sufficieut sensitivity to
changes in the consstency of a mLx whether it be due to the loss of slump due to
hydration of the cernent, incorporation of AEA, or changes in the SP dose (except when
doses are sufficiently high, i-e.:greater than 1940 in most circumstaaces, such that the test
reaches i a practical Limitations for the measurement o f mini-slump pat ara).
It is
concluded that Kantro's rnini-slump test is an escellent e d u a t o r of an admixture's

performance and suitable for the assessment of cernent-admixture Licompatibility with
regards to the issues of ~ p i slump
d
loss.
When not in the presence of a WR or superplasacizing admknues, the low- and

high-alkali cements behave much in the same way. Once admixtures are incorporated
into the mixture, the differences in behaviour of the two cements can become quite
pronounced.
The wxter reduced and superplasticized
ualising the high-alkali
cernent possessed lower workability's than the low-akdi cernent at the same admisure
dose rates, and produced a case of cernent-admixture incompatibility when used with the
iignosuifonate water reducer and melamine sulfonate superplasticizer. This occurrence
CONCLUSIONS & RECOMMENDAllONS
100
of cernent-admixture incompatibility persisted even d e n excessive doses of the

melamine sulfonate SP w-ere used, a dosage of lSO/o still produced a mini-slump Bo\.equivalelit to compatible mixes with approximately half the amount of the PNS
superplasricizer.
By analysing the temperature changes in cernent pastes

ro th&
h problems relating
senhg diaracteristics were detected with certain admixture and cement
combinations. The addition of the sodium ligiosuifonate water reducer to the high-
alkali Tl0 cernent resulted ed a k g e increase in the peak temperature of the hydratiag
cement of more than 20CI WhiIe the water reducer causes a mild retardation of set in
the low-alkali cernent it produced an accelerating e f k t on the high-alkali cernent. Aside
fiom its effects on the hydration of the hgh-alkali cernent, the indusion of the
lignosulfonate water reducer has the effect of depressing the foam index (ie. reducing
the i\E\dosage required) of both cements regardless of the air-entrainingagent used.
When incorporated into the cernent pastes, the superplasticizing agents had the
ability to suppress the hydration reactions. As noted by Boaen and S a r h (1995) the
irnprovement in fluidity caused by a superplasticizer is accompanied by the retardation of
the main peak of heat evolution and hydration of C3S. With increasing concentrations of
either SP an increasing retardation effect \vas witnessed. In the case of the low-alkali
cernent a delay of the peak temperature of as much as 50 hrs uas witnessed in cases
where a 1% dose of SP \ a s used. A delay in this peal; temperature is an indication that
the C S phase of the cernent is severely retarded, as is the setting of the concrete For
which the C3S is responsible.
Un fortunately the Lirestigaaon into the infiuences of'air entraining agents on the
rheological behaviour of cernent pastes did not prol-ide defiiite results perhliing to the
individual agents.
However, some generai conclusions can be drawn upon the
incorporation of an Al%. The three air enualiiog agents produced no adverse effeas
on the senhg and hydration properties of the cernent when used done, or in
ISSUES tN ADMUCTURE COMPATIBILIW
CONCLUSIONS & RECMMENDArioNS
combination with water-redu-
101
and superplasticizing aetures.
The reason for this
bekg is that the amount of actual agent used is but only a s m d l h c t i o n of the total
volume of the cernent paste or concrete.
Any detrimental influences that these
admiunires may possess simply do not emerge due to th& smail volume in the whole of
the mix. Aithough they may not have any definite effcts on the secMg characteristics of
the cernent they do have the effect of impmving the workability of the mix-
The
incorporation of the air enuaining agents has the effect o f Licreasing the measured minislump pat area orer non-air-ennalied mixtures ofequal proportions.
The Follo~vngrecommendations are made for continued research in this field:
1.
The study should be expandeci to d e t d e the influences of other waterredung and superplastiang admixture types have on rapid slump loss;
2.
Further study should be devoted to the effects of soluble alkali contents of
cements on cement/~perplasticizercompatibility
3.
~Uthough not investigated in this paper the influences of the phase

composition (namely the C d content) and the sdphate content of
cements should be analpsed;
4.
Testing o f cernent-admkture combinations should be repeated in order to

check the reproducibilitp of the results;
5.
The use of a conduction calorimeter is better suited for investgatng the

heat produced during hydration and should be used to replace the ad-hoc,
serni-adiabatic calorimeter apparatus set up in this work;
6.
The influences of supplementary cernenEng systems on compatibility

issues should be investigated by eupandkg the test program;
7.
A simple and suitable method for the determination of the air content in
cernent pas tes should be derised; and
ISSUES IN ADMIXTURE COMPATlBltlTY
102
CONCLUSIONS & REWniiMENDArioNS
8.
Mdmuth's suggestions to shorten the mixing regime so that flow loss due
to false
set can be ini-estigated, and that a cooling system be used
to
counteract the resulting temperature inaease redting from the high shear
mi*
9.
should be followed.
Further work should be conducted to correlate the mini-slump of pastes to
the slump o f concrete.
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Khalii, S.M. and Ward, K A . 1978. Influence of SO, and C,A on the Early Reaction
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Heat Evolution and Slump Loss of Concretes Confs;ri;ng High-range Water-Reducers,
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Quantity of Hydrates Needed to Ob& a Given Strength For Veq Young Concrete,
Materials and Structures, Vol. 27.pp 135-137.
Lee, Edwin. 1998. Determination of the Minimum Optimum Superplasticizer Dosage
of Concrete and Loss in Workability With k e .
University of Toronto Undergraduate thesis.
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Portland Cernent Pastes, Proceedings of the AmePcan Soery for TesMg M a t e d s ,
Vol. 46. pp. 1252-1292
MacInnis, C. and Racic, D. 1986. The Effect of Superplasticizers o a the Entrained

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International Conference On Superplasticizers and Other Chwiicd Admiytuzes in
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Rheologicai Behaviour of Cernent Paste Conminkg a Superplasucizer,
Superplasticzers and 0th- Chemicd Admixtures in Concrete; Proceedings of the
ISSUES IN ADMIXTURE COMPATlBlLlfY
REFEREENCES
fO7
T k d In temational Con ference, Ottawa, Canada, 1989. Amencan Concrete Institute,

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Odler, 1. and Wonnemaun, R. 1983. Effect Of ~Zikalies On Portland Cernent
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R a ~ i a a D.
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ISSUES IN ADMIXTURE COMPATlblLllY
REFEREENCES
108
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W h i ~ g David.
,
1980. Effect of Pc..fiuing Temperature oa Slump h s s and SeMng
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Aggregates, VOL2, No. 1. pp. 31-38.
ISSUES IN ADMIXTURE COMPATllLlTY
APPENDIX A: MIX DESIGNS
Table A-1
110
h&-slump
tests performed on admistuce enhanced pastes
utilising Eucon WR as the water reducer..............---.-.-...--.-...-.
1 11
Table A-2
Lirnited mini-slump tests performed on admi.xme mhanced

pastes utilising Conchem 25XL as the water reducer ................................. 1 12
Table A-3
hlini-slump control tests (admixture free &es)
Table A 4
Test program cattied out for the measurement of heat

de\-elopment in hydrating cernent pastes .............................................. 1 1 3
.............................. ...........
112
ISSUES IN ADMIXTURE COMPAflBlLliY
~ a ~ n p 3 .I;>~VAI
.1
aqi st!*IXZ U I ~ ~ J U O :S) L. ,I.I SS I; )~I S ~P J ~ U B L ~~ UI I~S ! U I ~ I uo

! ~
2-V alq'!,I.,
J U U ~ SJSW
~ J J) ~~ U ~ I S - !pLqI u~ ~
~
Table A-4
Test program carrieci out for the measuzement of heat developmt in Eiydrahng cement pastes.
Water
1%
Eucon W R
250 d / 1 0 0 k g
350g
STMARrSTlO
4
LAFARCE
Tl0
Cernent
t
S
ISSUES IN ADMlXtCIRE WMPATiBlLlTY
LOSS OF WORKABILITY
WITH TIME
APPENDIX B: im1-SLUMP RESULTS
115
LISTOF RESULTS
................................................................... 116
RheobuiId 2000B. Eucoa WR & N o
117
KLieobuild 2000B,Eucon WR & LCLB VR II .....................................................................
Rheobdd 2000B, Eucon WR & Darex II ...................~~~~~~.~~....~~~~~~~.........................
118
Rheobuild 2000B, Eucon WR & Micro AIR ....................................................................119
Eucon 37. Eucon W R & N o AELA ..................................................................................... 120
Eucon 37, Eucon W R & PvfB VR II .......................
.
.
........................................................ 121
Eucon 37, Eucon WR & Darex LI ......................................................................................122
Eucon 37, Eucoa WR & biicro AlR .................................. ............................................... 123
Rheobuild 2000B. Eucoa WR & N o MX ....................................................................... 124

Rheobuild 2000B, Eucon WR & MB VR II .....................................................................
125
Rheobdd 2000B, Eucon WR & Darex II ...................~~~~~~.~~~~~..~~~~~~..~
126
Iibeobuild 2000B, Eucon WR & Micro hIR ................... .
.............................................. 127
Eucon 3 .
1. Eucon WR & N o AEA .....................................................................................
VR II ....................-..............................................................
Eucon 37, Eucon WR & LW
Eucon 37, Eucon. WR
. & .Darex
. II...............................
. . . .
Eucon 37, Eucon W R & Micro AIR ..................................................................................
128
129
130
131
Lafarge T l O. Rheobuild 2000B. Conchem 25 XL & N o AEA ...................

.
.
.
......... 132
St. Rlarv's Tl O, Rheobuild 20008. Conchem 25 XL & N o AEA ................................. 133
Rheobuild 3000B. Eucon W R & N o AEA .......................................................................134

. AEA
. .................................
. . . ..
.
Eucon 37, Eucon WR .& No
.
135
APPENDIX B: MINI-SLUMP RESULTS
116
Mix Design:
Gmenc: Low-alka.iiType IO (Lfarge)
Air Entrainhg Agent: No AEA

Water Reducer: Eucon X R
Super Pbticizer: Rheobdd 2000B
Acti~-eAgmc Aq- Solution of Na Lignosulfoaate

Active
Melamine Based
WC
Table B-1
Loss of Workability \-S. T h e
Time
a
","ng
5
15
O
1808
1631
O. 1?O'
2676
21 73
Superpiasticizer Dosage
0-29/0
0.4%
0.6Oh
14065
3288
3769
3402
2718
8355
lime (min)
Figure B-1
bLini-Sluoip Area (mmA2)
Mini-slump Area vs. Time
0.8?/0
22849
20847
1
1
f
1.00'0
21410
20929
Mix Desimi:
Cernent:
Air Entru'n;rlP Agen=
Water Reducer:
Super Pfasticizer:
Low-nllrlli Type 10 (LaEuge)

MB VR
Active Agenc Neutralized Viasol Resins
Active Agenc Aq. Solution of Na Lignosulfonate
Eucon WR
Rheobuild 2000B Active Agenc Melamine Based
Results:
Table B-2
Loss of Worb.ab&ty vs. Time
Te
miuiap;
O.l0/o
mi ni-Slump Area (mmA2)

Superplasticizer Dosage
0.2?/0
0.494~
0.69'0
0.89'0
10
20
30
40
50
60
70
80
l.OO/o
Time (min)
Figure B-2
Mini-slump Area r s . T h e
Mix Design:
Gmenc
Air Entrainhg Agenc
Water Reducer:
Super Plasticizet:
Low-alkali Type 10 (Lafiuge)

Actit-e Agent Neutralized Vinsol Reslns
Darex II AEA
Active Agent Aq. Solution of Na Lignosulfonate
Eucon EX
Rheobuild 2000B Active Agenr, Melamine Based
Results:
Table B-3
Loss of Workability m. Time
Tic
afier
","ng
5
15
30
45
1
1
&hi-Slump Area (mmA2)

O
1587
1381
1299
1269
1
1
O.lO~'O
1843
1 433
1306
1279
0.Z029'0 1 0.4Yu 1 0.6?'0
2627
3170 [ 10620
1805
139
1381
2626
2264
l GGG
5498
5625
5240
0.8941
1.OOh
22283
20063
19868
18565
33909
2171 1
20764
20180
Tirne (min)
Figure B-3
b4.in.i-slumpArea vs. Time

ISSUES IN ADMIXTURE C O M P A ~ X l ' Y
Mix Design:
Cement:
Air Enuaitng Agent:
Water Reducer.
Super Piasacizec
Low-allrati Type 10 (Lhrge)

Mino Air
Actic'c A g c w Synthetic
Eucon
A c t i r c Ag&
Aq. SoIution of N a Lgnosulfonate
Rheobuild ? W B
A c h e A g c e Mehmne Based
Results:
Table 8-4
Loss ofWorkability vs-Time
Tie
afier
mking
15
O
1343
1328
O.19'0
1690
1496
mi ni-Slump Ares (mmA2)

~ u ~ e r ~ I a s & e~ro s a g e
02?6 1 0.4?0 1 0.6%
2766 1 4855 1 17401
2073 1 4105
12761
I
O.S0/o
20574
19650
1.O910
21519
20771
Time (min)
Figure B-4
&Fini-slumpArea vs. Time

ISSUES M ADMIXTURE COMPATIBILITY
-.
.WPENDIX B: MIM-SLUMP RESULTS
120
Mix Design:
Cernent=
Air Entrainhg Agenc
Water Reducex
Super Piasticizcc
L o w - Type
~
10 (Latrge)
No AEA
Eucon WR
Eucon 37
A c h e -4gcnt Aq. Solution of N a Lignosdfonate

A&v Agtmt Napthalene Based
Results:
Table B-5
Loss of WorkabXty \-S. Tme
Tiie
after
m t ! ~
0,l0/o
Mini-Slump Area (mmA2)

02?'0
1 00.40/t 1 0.5%
1
1
0.6?/0
0.8%
Time (min)
Figure B-5
mi ni-slump Area rs. Tune

ISSUES IN ADMMTURE COMPATIBILITY
Mix Design:
Cernent: Low-ahii Type 10 (Lahge)
Air Entraining A g e n ~ MB VR
Actirc Agenk Neuhralized Vinsol Resins
Adic'cAgen,? Aq. Solution of Na Lignosulfonate
Water Reducec Eucon W X
Super Piasticizec Eucon 37
Actizv Agent Napthalene Based
Results:
Table B-6
Loss of Workabihy m. Tune
T i e
afier
mising
5
15
30
15
60
1
1
0.19'0
2072
1855
1453
1373
1367
1288
1748
2418
1454
1304
1269
1286
75
*
O
mi ni-Slump Area (rnmA2)

~ u ~ e ~ l a sDosage
~ ~ z e r
0.2'/0
1 0.4?'0
o.soi>
3862
8673
19143
768 1
18809
2331
17933
6822
1811
17633
6278
1562
5023 1 14269 1
1373
4701 1 11723 1
1350
0.S0'o
21 673
20529
19143
18855
17220
14050
0.6?'0
19893
19587
19179
18712
16336
12940
10
20
30
40
50
60
70
80
Time (min)
Figure B-6

ISSUES IN ADMIXWiU3 COMaATIBILlTY
Mix Design:
Cernent:
Air Entraining Agent:
Water Reducec
Super Piasticizer:
Low-aikah Type 10 (Lafrge)

Actirc A g e e Neurtalized Vtnsol Resins
Darex II Ai54
AchCe A ~ MAq. Solution of Na Lignodonate
Eucon WR
Eucon 37
A c b i v Agen/= Napthaiene Based
Results:
Table 5 7
Loss o f Workabili~vs. Time
O
0.10;0 I
0.2%
0.4%
0.59'0
0.6O/o
0.8O/0
Time (min)
Figure B-7
ISSUES M ADMIXTURE COMPATIBLLITY
Mk Design:
Cernent= Low-aUtal; Type 10 (lafirge)
AU Entrs;n;nP Agent= Micro i\ir
Acfire Age& Synthetic

Aaiv Agm. Aq- Solution of Na Lignosulfonate
Water Reducer: Eucon W R

Super Plasticizer= Eucon 3 7
Act& Agent Napthalene
Based
Table B-8
Loss of Workabiliry vs- Time
Tie
afier
""ng
5
15
30
1
O
1343
1328
1305
O.19'0
1376
1335
1342
~ u ~ e r ~ l a s ~ cDosage
izer
0.29'0 1 0.49'0
lm9
9755
1387
8602
1372
7614
40
30
Tirne (min)
Figure B-8
bLini-sliimp Area vs. Time
50
0.5?/0
14145
1044
7588
0.60%
203443
19589
20475
0.8%
24053
23881
22698
APPENDIX 8: MINI-SLUMP RESULTS
124
Mix Design:
Cernent:
Air Entraiaing Agent:
Water Reducer:
Super Piasticizer:
High-aika.I Type 10 (SL Mary's)
N o AEA
AcLic Age&
Eucon \WR
Rheobuild 20008
A c t i r c Age&
Aq. Solution of Na Lignosuifonate

Melamine Based
Results:
Table B-9
Loss of Workabiliq vs- T i i e
&Fini-SlumpArea (mm"2)
afier
mt"ig
5
15
30
45
O
2097
1932
1543
1458
0.1?O
2818
235 1
1931
1710
1
1
Superplasticizm Dosage
0.296 1 0.4!o 1
3358
5553 1
2842
4846
3781
2201
1974
3441
,
0.6%
0.89'0
7134
6117
5349
7659
6557
5448
4781
4855
1 .OO'i
8409
6965
6112
5375
Time (min)
Figure B-9

ISSUES IN ADMIX-
COMPATIBUITY
Mix Design:
Cemenc
Water Reducer,
Super Piasticizec
Hgh-alkali Type 10 (St Pvhfs)
MB VR
Eucon WR
A n i t v Agt& Neutralized Vinsol Resins

A r n e Age& Aq. Solution of Na Lgnosulfonate
Ac~ic'eAgent: Melamine Based
Rheobuiid 2000B
Results:
Table B-10
Loss of Workability vs. Time
afier
i1LUtng
5
1572
15
1385
0.1%
3126
2645
~ u ~ ~ l a s ~ cDosage
izer
0.69'0
0.246
0.4?/0
7406
31 56
541 9
3490
5804
4615
0.80'0
7956
6777
1.000
8086
6288
1.5%
7647
7475
10
20
50
40
30
60
70
80
Time (min)
Figure B-10 Mini-slump A x a vs. Time
APPENDIX B: MIM-SLUMP RESULTS
U6
Mix Design:
Cernent:
Air Entrainhg Agenc
Water Reducer.
Super Piasticizer:
High-alkali Type 10 (St Mary's)

Acfice Agcw Neutralized Vinsol Resins
LI AEA
Acticv A g c k Aq- SoIution of Na Lignodonate
Eucon W X
Rheobuild 2B
Artire Agcnr= Melamine Based
Dar-
Table B-fi
Loss of Wohbility vs. Tme
O
1 908
1688
1 423
1403
1407
1360
0.1%0
2106
2 81 2
1499
1517
141 1
1369
Mini-Slump Ares (mmA2)

O.6?,6
02?%
0.4?/0
2840
5249
3408
4318
1710 1 1938
1617
1872
3363
1477
3575
1616
1423
1615
2275
2070
1460
1551
30
1
1
0.8?/0
6657
5131
4357
3484
3273
3117
1.O?/O
71 56
5637
4209
3680
3797
2970
50
40
Time (min)
Figure B-il
Mini-siump Area vs. Time

ISSUES M ADMIXTURE COMPATIBILI'W
Mix Design:
Cemenc
Water Reducer:
Super Plasticizec
H@-alkal; Type 10 (St Mary's)

Acfitv Agen/= Synthetic
Acrice Agenk Aq. Solution of N a Lrgaosdfonate
Eucon W R
Rheobuild 2000B
Actice Agent Melamine Based
M i a o Pur
Results:
Table 8-12
Loss of Wohbilit). vs- Time
Superphticker Dosage
afier
0.1Yo
O.2?43
0.4?/0
O.G?'o
0.80/0
l.OO:O
Time (min)
Figure B-12 Mini-slump Area vs. Time

Mix Design:
Cernene
Air Entrainhg Agent:
Water Reducer:
Super Plasticizer:
High-alkai Type 10 (St Mary's)
No AEA
Acrirv Agenk Aq. Solution of N a Ltgnosdfonate
Attire Agen[: Napthalene Based
Eucoa WR
Eucon 37
Table B-W
Loss of Workability 53. Time
aner
mi..^
O.l0/o 1
0.29'0
30
0.3?./0 1
40
50
0.6?,0
1 0.8'/0
l.OO/b
Erne (min)
Figure B-13
mi ni-slump k e a vs. Time

ISSUES IN ADMIXTURE COMPATIBILiTY
Uix Design:
Cemenc
Air Entraining Agent
Water Reducer:
Super Plasticizer:
Hi&-alkali Type 10 (St Mary's)

Mi3 VR
Anire Agent Neuaalized Visol Resins
A c r h Agent Aq. Solution of N a Lignosulfonate
Eucon WX
Eucon 37
Actit'e Agent Napthalene Based
Results:
Table 8-14
Loss of Workabili~m. Tme
Time
after
biiving
5
15
30
45
1
60
1
75
1
1350
0.1?/0
3463
2814
2413
2163
1996
1
/
1329
1963
O
1572
1485
1469
1378
mi ni-Slump Area (mmA2)

Supetplasticizer Dosage
0.2'0
1 0.4?'0
0.69'0
12677
5895
18872
5508
12223
16755
15922
4290
11155
3920
10605
3826
9334
14859
14104
8710
12899
3395
Time (min)
Figure B-14
mi ni-slump Area vs. Time
0.8%
18133
18054
17604
16840
15071
14477
1-09'0
18955
18732
18639
18441
17879
17835
Mix Design:
Cernent=
Air Entraining Agent=
Water Reducett
Super Plasticizec
High-alkal; Type 10 (St M e s )

Adit'c A g c n ~Neurraiized '~~msolResins
Actiue A g m ~Aq- Solution of Na lignosulfonate
Acti..e A g c n ~Napthalene Based
Darex II AEA
Eucon WR
Eucon 37
Results:
Table B-15
Loss of WorkabilZty vs-Time
1Min;-Slump Area (mmSuperplasticizer Dosage
O
1908
1688
1423
1403
1407
O. 1Oo'
2278
1915
1585
1438
1459
0.2?/0
0.49%
4075
3431
2546
2297
2127
10161
9594
8304
7741
6751
30
40
0.69'6
15924
15813
15576
15001
14854
1
1
0.8%
19918
18146
18103
17973
16803
1
1
l.OO'to
20581
20210
19223
lm99
18615
50
Time (min)
Figure B-15 hhi-slump Area w. Tirne

ISSUES J k ~ M I X T U R E
COMPATIBILITY
APPENDIX B: MINI-SLUMP RESULTS
131
Mix D e s a :
Cernent:
Air EnaahhgAgent:
Water Reducer,
Super Plasticizct:
E-hgh-aikali Type 10 (SL Mary's)

h k o Air
Eucon WR
Eucon 37
Actit'c Agete Synrhetic

Acrizv Agcnr- Aq. Solution of Na Lgnosulfonate
Act& Agcnk Napthalene Based
Resuits:
Table 5 1 6
Loss ofWorWiliy r s - T m e
mi ni-Slump Area (mm"2)
Time
afier
Mixklg
O.lO/o
O.SO/o
0.49'0
0.6?/0
I 0.8?/0 I
1.0%
Time (min)
Figure B-16 f i - s l u m p Area vs. Time

ISSUES IN ADMDITITRE COMPATIBIILITY
Mix Design:
Cernent: Low-alkal; Type 10 (lafarge)
Air Entraining Agent: No AEA
A&t Agent: Aq. SoIution of Ca Lignosulfonate
Water Reducs Conchem 25 XL
Super Plasticizs Rheobuild 2000B
Adict Agent Melanime Based
Results:
Table B-17
Loss of Workabitity VS. Time
Tie
after
MX-Slump Area (mrnA2)

50
40
30
Tirne (min)
Figure B-17
mi ni-slump Area vs. Time

ISSUES IN ADMIXTURE COMPATIBlLITY
Mix Design:
Cernent:
Water Reducer:
Super Plasticizer:
St Mary's (Bowmande)
No AEA
Actirc Ag&
Conchem 25 XL
Rheobuild 30008
A c t i m Agc&
Aq, Solution of C a Ligaosulfonate

MPlamirie Based
Results:
Table B-18
Loss of Workability vs. Tme
Mini-Slump tbea (mmA2)
Tie
afier
iMiuing
5
15
30
35
1999
1825
1534
1439
1
1
1
1
02?/0
O.6?'0
0.4?'0
O.lO/o
2180
1912
1709
1488
2676
2244
1901
1627
30
493 1
4353
3856
3467
40
50
5522
5084
4772
4261
0.B0/o
1.OO/o
6104
5722
7463
6822
6235
5984
5236
4998
Time (min)
Figure B-18
mi ni-slump Area w. T m e
ISSUES IN ADMIXTURE COMPATIBILiTY
Mix Design:
Cernent:
Air Entraining Agent=
Water Reducec
Super Plasticizet:
High-alkal; Type 10 (St Lawrence)

N o AEA
Adire Agenk Aq. Solution of Na Lrgiosulfonate
Eucon WR
Rheobuild 200B
Artire Agen& Melsmirie Based
Resuits:
Table B-19
Loss ofWorkabil~rs-T e
Mini-Slump Area (&2)
O !
O
0.10/0
Superplastiazer Dosage
0.2?/0 1 0.47'0 1 0.6%
10
20
30
40
Time (min)
l
vs. T i e
Figure B-19 ~ M k - s Area
0.8%
50
60
70
80
1.04.h
Mix Design:
Cernent: H&-ahh Type 10 (SL Lawrence)
Air Entraining Agent= No A i 3

Water Reducer: Eucon WR
Super Plasticizer: Eucon 37
A c l r i c Agent:
Adire Agm:
Aq- Solution of Na Lqposulfonace

Naphthalene Based
Results:
Table B-20
Loss ofWodcability vs-Tme
Time
after
Mkkg
5
15
30
45
60
75
1
O
--
--
--
0.1?0
---
mia ai-Slump Area (mmA2)

0.6O/o
0.40/0
02'?!0
9049
12147
7728
1 1988
7012
6507
6018
--
---
--
30
5672
40
Tirne (min)
Figure B-20 Mini-slump Ares vs. Time
50
IO824
10830
10149
9947
'
0.8?6
l.OO/o
137
APPENDlX C: HYDRATlON TEMPERATURE PROFILES
LaEirge Tl0 cernent absent of chernical admiYnire .....................................................
139
Rheobdd 20008. Eucon W R & No AEA .....................................................................

Rheobdd 2000B,Eucon W U & MB VR II....................................................................
Rheobudd 2000B, Eucon WR & Dar- LI ......................................................................
Rheobdd 2000B,Eucon WR & PvLicm AIR ..................................................................
1-K)
141
142
143
Eucon 37. Eucon WR & No AEA ...................................................................................

1-44
Eucon 37,Eucon WR & MB
. VR II ................................................................................. 145
Eucon 37,Eucon WX & Dare.~IT .................................................................................... 146
Eucon 3 1 , Eucon WR & Micro AIR ................................................................................ 147
Rheobuild 2000B.Eucon WR & NOAEA .....................................................................

Rheobuild 2000B,Eucon ER & MB VR II....................................................................
RheobuiId 30OB, Eucon WR & Darev II ...................................................................
Rheobudd 2000B,Eucon WR & Micro AIR .................................................................
149
130
151
153
Eucon 37. Eucon WR & No AEt4 ...................................................................................

153
Eucon 37,Eucon WR & Ml3 VR LI ................................................................................. 154
-Eucon 37, Eucon WR & Darex II .................................................................................... l x
Eucon 37, Eucon %'R& Micro AIR ..............................................................--..............136
ISSUES IN ADMIXTURE COMPATlBlliTY
APPENDM. C: EIYDRATlON TEMPERATCIRE PROFILES
138
APPENDIX C: aYDRATION T E M P E R A m PROFILES
139
APPENDIX C: EZYDRATION TEMPERATURE PROFILES
140
APPENDIX C: EYDRATION TEMPERATCTRE PROFILES
ISSUES N ADMIXI
141
142
APPENDIX C: EYDRATION TEMPERATRE PROFILES
ISSUES IN ADMIXTURE C
APPENDIX C: HYDRATION TEMPERATURE PROFILES
143
APPENDIX C: aYDRATlON TEMPERATURE PROFILES
144
U P E N D M C: HYDRATION TEMPERATURE PROFILES
145
ISSUES M ADMIXTURE COMPATIBUITY
146
Figure C- 10 Temp. rise vs. time for varied doses of Eucon 37 on Lafarge Tl0 cement with Micro Air AEA and Eucon WR.
Note: SP doses are expressed as % solids by mass of cernent.
148
ISSUES MADMIXTURE COMPATIBILITY
APPENDlX C: ENDRATION TEMPERA'IVRE PROFILES
149
APPENDDS C: EIYDRATION TEMPERATURE PROFILES
150
ISSUES M ADMIXTURE CO~PATIBILM
APPENDM C: HYDRATION TEMPERATURE PROFILES
151
APPENDIX C: EYDRATION TEMPERATURE PROFILES
152
Figure C-16
Temp. rise vs. time for varied doses of Eucon 37 on St Mary's Tl0 cernent with no AEA and Eucon WR.
Note: SP doses are expressed as % solids by mass of cernent
APPENDIX C: EYDRATION TEMPERATURE PROFlLES
154
APPENDIX C: EYDRATION TEMPERATURE PROFILES
155
APPENDIX C: ECYDRATXON TEMPERAT DRE fROFILES
156
158
APPENDIX O: AGGREGATE SlEVE ANALYSlS
COARSEAND FINE
AGGREGATE
GRADATIONCURVES
Sieve hnalysis of coarse aggregate (10 mm) grdation and LZST~MC 33-93 l;mifs...-. 160
Sieve Anaiysis of coarse aggregate (20 mm) gradation and ASTM C 33-93
Limits ................................................................................
............................. 162
i59
APPENDIX O: AGGREGATE SIRIE ANALYSIS
Table D-1
Sieve Analysis of Fine Aggregate and S T M C 33-93 Gnding Requirements
A p m e Size
Sieve Size
IO mm
No. 6
No. 8
No. 13
No. 16
No.-40
No. 30
No-50
No. 60
No- 80
(mm>
Percent Passing
(9'0)
IO
100
!
t
Lower M
(9'0)
Upper Limit
(?,a>
-
--
335
2.362
932
IO0
84.2
77.4
80
1.7
1.18
0.425
0.6
03
0-35
0.18
50
83
33.3
33
10
30
14.2
6.5
GO
Gradation (mm)
Figure D-1
Semi-log plot of fine aggregate gradation and ASTM C 33-93 imits

ISSUES IN ADMIXTURE COMPATlBlUW
160
APPENDIX O: AGGREGATE SIWE ANALYSIS
Table D-2
Sieve Analysis of Coarse i\ggregate (10 mm nominal s k e ) and ASrPvf C 33-93 Grading Requirements
A p m e Size
Sieve Size
(mm)
1"
3/4"
1/2"
3/8"
3/16
No. 8
pan
25
19
125
9.5.
4.75
336
(4.75
LoWrLGnit
p-m;"" ,/O
200
99.8
(?O
')
95.6
55.7
4.5
Cpper Limit
(96)
100
100
90
100
-40
70
13
O
-
100
100
Grdation (mm)
Figure D-2
Semi-log plot of coatse aggregate (10 mm) gradation and A m i C 33-93 Iunits
161
APPENDIX O: AGGREGATE SIEVE ANALYSIS
Table D-3
Sieve Anailis of Coarse Aggregate (20 mm nominal size) and ASTM C 33-93 Gradmg Requirements
Sieve Size
J
3/8"
3/16
No. 8
pan
90-
20
Aperture Size
(mm)
+cum% passing
(96)
(?O
')
(?O
')
9.5
4.75
2.36
-3-75
Upper Limit
Lower Lrnilt
Percent Passing
20
3381888
3.399684
O
O
55
IO
3
10
Graation (mm)
Figure D-3
Semi-log plot o f coarse aggregate (20 mm) gradation and ASTM C 33-93
iimits

Cement Compatibility

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T E S T I N G FOR

A Thesis Submitted in Conformity With the Requirements

For the Degree o f Master o f Applied Science in Civil Engineering

O Copyright by Edgar Furtado 1999

395 Wellington Str-t

395, rue Weflington

The author has granted a nonexclusive licence ailowing the

L'auteur a accord une licence non

The author retains ownership of the

L'auteur conserve la proprit du

TESTING FOR CEMENT-ADMIXI'URE INCOMPATIBILITY

Although chefnicd admi~turesare not an essentiai component in the production

of concrete they do prove to be induable ingredients whm produckg a h g h qualirg

and physiral hece5rr.

However, it is important that an understandmg of their

The aLn of this project is to determine the cornpatibility of commerady

1w-ould E e to express my gratitude to Professor R. D. Hooton, P.Eng., of the

guidance during the course o f this thesis.

donated for use in this thesis.

Acknowledgements ........................................................................................................................ rrr

List Of Tables ....................

List of Abbreviations and Symbois............................................................................................

Plan of Organisation .......................................................................................................

CHAPTER 2. LITERATURE REVIEW

2.2. Eady Reaaion Chemistry and Stiffening.............................................~~......................

2.3. Wockability .........

2.4. Chernical Admiunires and Their Use in Coacrete ...............................-................... 10

Factors Influenciag Air Entrainment.................-..-.--..---.--.-........

3-42. Water-reducing Admtvtures.............................................................................

3.4.3. Superplasticizers ...............................................................................................

H o w Superphsticizers Work In Concrete...................................

2.5. Slump Loss and S t i f f k g of Coacrete .....................................................................

T h e Effect of C3A o n Early Stiffening.......................................2

Effect of Sulphate Content ................................................................26

Influence o f Water reducers & Superpkticzer on the

Rok of Sulphates ..........................................................................

Suiphate Form ...............................................................................

Fineness of the Cement and Excessive Fines.....................

ALkali Content ................................................................................. 3 2

Effect o f Molecular Weight ...............................................................

Reduced Cernent Paste and Water Content............................................ 38

36.6. Initial SIump ......................................................................................................

2.7. Influmces of Admixtures on the Hydration and SetMg Properties o f

Ettringite Formation .........................................................................................

CHAPTER 3 EXPERIMENTAL PROCEEDURES

3.2 Introduction ................... .-.......................................................................................

Cement Propedes ..........................................................................

Air Entraining Admi.xtures ......................... ..,

3-3 Aggregate ...................

3.4 Foam Index Test ....................................................................................................

hLini-Slump Test Program ...........................................................................

3.6 MeasuDng Heat Rise of Hydrating Cernent Pastes..............................................55

3.1 Coacrete Trial Mixes....................................................................................................

3.8 ~MeauringSoluble Alk ali. Contents .....................

3.9 Determining Air Content.............................................................................................

CHAPTER 4 OBSERVATIONS & RESULTS

3.2 Foam index Tests.......................................................................................................

3.3 LLIUll-Slump Resuin ....................................................................................................

4.5 Slump Loss In Concrete...............................................................................................

4.6 hfid-slurnp w .Concrete Slump ..............................................................................

4.7 Heat Rise Li Cement Pastes ....................... .

The Influences of the Water Reducer ........................................................ 83

The Influences of Superplasticizers.........................................................

Influence of Air-Entrainiog Agents ...................................................... 8