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Penko, Mihael
SOME EARLY HYDRATION PROCESSES IN CEMENT PASTE AS
MONITORED BY LIQUID PHASE COMPOSITION MEASUREMENTS
Purdue University PH.D. 1983
University
Microfilms
I n t Br n f l t l On Sl I 300 N. Zeeb Road, Ann Arbor, Ml 48106
SOME EARLY HYDRATION PROCESSES IN CEMENT PASTE AS
MONITORED BY LIQUID PHASE COMPOSITION MEASUREMENTS
A Thesis
Submitted to the Faculty
of
Purdue University
by
Mihael Penko
In Partial Fulfillment of the
Requirements for the Degree
of
Doctor of Philosophy
May 1983
)
Grad School 7. -i ~) <J/.
Form No 9 <_^ A ' / ^
Revised
P UR DUE UNI VE RS I T Y
Graduate School
Thi s is to certify that t he t hesi s prepared
By Mihael Penko
Entitled Some Early Hydration Processes in Cement Paste as Monitored by
Liquid Phase Composition Measurements
Complies with the Uni versi t y regulations and that it meets the accepted
st andards of the Graduat e School with respect to originality and quality
For the degree of:
Doctor of Philosophy
Signed by the final examining commi t t ee:
^ ^Ccu^ uncu^^o^-
tchairman
Approved by the head of school or depart ment :
To the l i brari an:
t s -
This thesis is not to be regarded as confidential
Pr of essor un charge of the t hesi s
1
ACKNOWLEDGEMENTS
The author would like to express his sincere appreciation to his
major professor, Sidney Diamond, for his advice, continuous support,
and encouragement throughout his period of graduate study. The author
wishes to thank Professor W. L. Dolch and Professor D. N. Winslow for
consultations. Gratitude is due to Professor A. Angell for serving-on
the Advisory Committee.
The author is grateful for the financial support provided by the
Joint Highway Research Project of the Indiana State Department of
Highways and Purdue University. Without it his study at Purdue
University would have not been possible.
Finally, thanks are extended to Mrs. Janet Love 11 and Mr.
Federico Lopez-Flores for their technical assistance in some of the
experimental work and to Agnes Meyers for making the thesis readable.
Ill
TABLE OF CONTENTS
Page
LIST OF TABLES v
LIST OF FIGURES vii
ABSTRACT ix
CHAPTER ONE - REVIEW OF THE LITERATURE 1
1.1 I n t r o d u c t i o n 1
1.2 C
3
A - CS - CH System 2
1.3 Cl i nker-Gypsum System in Cont act wi t h Water 5
1.4 Al k a l i e s i n Cement and Thei r I nf l uence on
Gypsum Ef f e c t i v e n e s s 8
1.5 Pore Sol ut i ons 12
1.6 Optimum Gypsum Cont ent 15
CHAPTER TWO - MATERIALS AND EXPERIMENTAL METHODS 18
2. 1 Par t One - Ma t e r i a l s 18
2 . 1 . 1 . Cements 18
2 . 1 . 2 . Chemi cal s 20
2. 2 Par t Two - Exper i ment al Methods 20
2 . 2 . 1 . Cement Pa s t e Pr e pa r a t i on 20
2 . 2 . 2 . De t a i l s of Mixing 20
2 . 2 . 3 . Se t t i ng Time 21
2 . 2 . 4 . Temperat ure Evol ut i on 22
2 . 2 . 5 . Expr es s i ng of Pore Sol ut i ons 24
2 . 2 . 6 . Non-Evaporabl e Water Det er mi nat i ons 29
2 . 2 . 7 . Chemi cal Anal ys i s of Pore Sol ut i ons 29
2 . 2 . 8 . X-Ray Di f f r a c t i on 31
2 . 2 . 9 . Se mi qua nt i t a t i ve Anal ys i s by Energy
Di s pe r s i ve X-Ray Anal ys i s 33
CHAPTER THREE - RESULTS AND DISCUSSION 35
3 . 1 I n t r o d u c t o r y Remarks 35
3 . 2 De s c r i pt i on of Syst ems under Study 35
3 . 3 Temperat ure Evol ut i on and Se t t i ng Time 36
3.4 Non-Evaporabl e Water 48
3 . 5 Li qui d Phase Exami nat i on 51
3. 6 Sol i d Phase Exami nat i on 77
IV
Page
CHAPTER FOUR - DISCUSSION AND IMPLICATIONS 99
4.1 Transformation of Alkali Sulfates into Alkali
Hydroxides 99
4.1.1. Systems Without Gypsum 100
4.1.2. Systems With Gypsum 102
4.2 The Alkalinity of the Liquid Phase and Its Influence
on Setting 105
4.3 Optimum Gypsum 108
4.4 Experimental Evidence with Respect to the Protective
Layer Theory 110
CHAPTER FIVE - CONCLUSIONS 114
LIST OF REFERENCES 118
VITA 124
V
LIST OF TABLES
Tabl e Page
2 . 1. 1 Anal yses of Cements Used ' 19
3 . 3 . 1 Time of Se t t i ng of Cement Pa s t e s 46
3 . 3 . 2 Re l a t i ons Between Maximum Temperat ure Ri se and Al ka l i and
SO Cont ent s of Cement Systems ( a l l at w:c 0. 50) 47
3 . 4 . 1 Non-Evaporabl e Water Cont ent , % 50
3 . 5 . 1 Sol ut i on Concent r at i ons i n Or di nar y Por t l and Cement Pas t e
( w: c 0. 50) 54
3 . 5 . 2 Sol ut i on Concent r at i ons I n Or di nar y Por t l and Cement Pas t e
(w:c 1.00) 56
3 . 5 . 3 Sol ut i on Concent r at i ons in High Al ka l i Por t l and Cement
Past e (w:c 0. 50) 59
3 . 5. 4 Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pa s t e *
(w:c 0. 50) ' 62
3 . 5 . 5 Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Past e
Cont ai ni ng 5% Added Gypsum (w: c 0. 50) 65
3 . 5. 6 Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pas t e
Cont ai ni ng 2% Added K.SO (w: c 0. 50) 68
3 . 5 . 7 Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pas t e
Cont ai ni ng 10% Added Gypsum and 2% Added KS0 (w: c 0. 50) . 71
3 . 5 . 8 Sol ut i on Concent r at i ons i n Or di nar y Por t l and Cement Pas t e
As Adj ust ed for Change i n Water Cont ent ( w: c=0. 50) 78
3 . 5 . 9 Sol ut i on Concent r at i ons i n Or di nar y Por t l and Cement Pas t e
As Adj ust ed for Change in Water Cont ent (w: c=1. 00) 79
3. 5. 10 Sol ut i on Concent r at i ons i n High Al ka l i Cement Pas t e As
Adj ust ed for Change i n Water Cont ent (w: c=0. 50) 80
3. 5. 11 Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pas t e As
Adj ust ed for Change i n Water Cont ent (w: c=0. 50) 81
V I
Tabl e Page
3 . 5. 12 Sol ut i on Conc e nt r a t i ons in Fi nel y-Ground Cl i nker Past e
Cont ai ni ng 5% Added Gypsum As Adj ust ed for Change i n
Water Cont ent ( w: c=0. 50) 82
3 . 5. 13 Sol ut i on Conc e nt r a t i ons i n Fi nel y-Ground Cl i nker Pas t e
Cont ai ni ng 2% Added KSO, As Adj ust ed for Change In
Water Cont ent ( w: c=0. 50) 83
3 . 5. 14 Sol ut i on Conc e nt r a t i ons i n Fi nel y-Ground Cl i nker Pas t e
Cont ai ni ng 10% Added Gypsum and 2% Added KS0 As Adj ust ed
for Change i n Water Cont ent (w: c=0. 50) 84
VI
LIST OF FIGURES
Figure Page
2. 2. 1 Temperature Evolution Device 23
2. 2. 2 Cal i brat i on Line for Temperature Evolution 25
2. 2. 3 Mi l l i pore Pressure Fi l t er i ng System 26
2.2.4 Isometric Half-Section of the Pore Solution Expression
Apparatus 28
3 . 3 . 1 Temperature Evolution Curve for Ordinary Portland Cement
Paste (w:c=0.50) 37
3. 3. 2 Temperature Evolution Curve for Ordinary Portland Cement
Paste (w:c=1.00) 38
3. 3. 3 Temperature Evolution Curve for High Al kal i Cement Paste
(w:c=0.50) 39
3.3.4 Temperature Evolution Curve for Finely-Ground Clinker
Paste (w:c=0.50) 40
3. 3. 5 Temperature Evolution Curve for Finely-Ground Clinker
Paste with 5% Gypsum (w:c=0.50) 4 1
3. 3. 6 Temperature Evolution Curve for Finely-Ground Clinker
Paste with 2% KS0. (w:c=0.50) 42
2 4
3. 3. 7 Temperature Evolution Curve for Finely-Ground Clinker
Paste with 10% Gypsum and 2% KSO (w:c=0.50) 44
3 . 4. 1 Non-Evaporable Water vs . Time for Seven Di fferent
Cement Past es 4 9
3 . 5. 1 Concentration vs . Time for K , Na , Ca , OH , and SO,
Ions in Pore Solutions of Ordinary Portland Cement
Paste, w:c=0.50 55
+ + 2+ - 2
3.5.2 Concentration vs. Time for K , Na , Ca , OH , and SO,
Ions in Pore Solutions of Ordinary Portland Cement
Paste, w:c=1.00 58
Vlll
Figure +
+
2+ - 2-
P a g e
3.5.3 Concentration vs. Time for K , Na , Ca , OH and SO,
Ions in Pore Solutions of High Alkali Portland
Cement Paste, w:c=0.50 61
+ + 2+ -
3 . 5. 4 Concent r at i on v s . Time for K , Na , Ca , and OH I ons i n
Pore Sol ut i ons of Fi nel y- Gr ound Cl i nker Pa s t e , w: c=0. 50 . 64
+ + 2+ - 2-
3 . 5 . 5 Concent r at i on v s . Time for K m Na , Ca , OH and SO
I ons i n Pore Sol ut i ons of Fi nel y- Gr ound Cl i nker
Pas t e wi t h 5% Gypsum, w: c=0. 50 67
+ + 2+ - 2-
3 . 5 . 6 Concent r at i on v s . Time for K , Na , Ca , OH and SO,
I ons i n Pore Sol ut i ons of Fi nel y- Gr ound Cl i nker
Past e wi t h 2% K
o
S0. , w: c=0. 50 70
2 4
3 . 5 . 7 Concent r at i on Vs. Time for K
+
, Na
+
, Ca
+
, 0H~, and SO,
I ons in Pore Sol ut i ons of Fi nel y- Gr ound Cl i nker
Pas t e wi t h 10% Gypsum and 2% K
2
S0, , w: c=0. 50 73
3 . 5 . 8 X-Ray Di f f r a c t i on Pa t t e r n of Ear l y Pr e c i p i t a t e d Ca( 0H)
2
. . 74
3 . 6. 1 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for Or di nar y Por t l and
Cement Pas t e ( w: c=0. 50) 86
3 . 6. 2 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for High Al ka l i Cement
Pas t e ( w: c=0. 50) 87
3 . 6. 3 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for Fi nel y-Ground
Cl i nker Past e ( w: c=0. 50) 88
3 . 6. 4 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for Fi nel y-Ground
Cl i nker Pas t e wi t h 5% Added Gypsum ( w: c=0. 50) . . . . . . . 89
3 . 6. 5 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for Fi nel y-Ground
Cl i nker Pas t e wi t h 2% Added KS0. (w: c=0. 50) 90
2 4
3 . 6. 6 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s for Fi nel y- Gr ound
Cl i nker Past e wi t h 10% Added Gypsum and 2% Added KS0
( w: c=0. 50) 92
4 . 2 . 1 OH Ion Concent r at i on Changes i n Cement Pas t e
( Schemat i c) 107
IX
ABSTRACT
Penko, Mi hael , Ph. D. , Purdue Un i v e r s i t y , May 1983. Some Ear l y
Hydr at i on Pr oces s es i n Cement Pa s t e as Moni t ored by Li qui d Phase
Composition Measurement s. Major Pr o f e s s o r : Si dney Diamond.
A number of cement p a s t e s were pr epar ed i n or der t o st udy t he
hydr at i on pr oces s es t aki ng pl a c e wi t hi n t he f i r s t 24 hour s . In some
cas es c ont r ol l e d dosages of r e a ge nt gypsum, pot assi um s u l f a t e , or bot h
were added t o ground c l i n k e r f or use i n f or mul at i ng t he cement p a s t e s ;
ot he r s were pr epar ed from commerci al por t l and cement s. The wat er : cement
r a t i o used was o r d i n a r i l y 0. 5 0.
Most of t he exper i ment al work i nvol ved expr es s i ng and anal yzi ng
por t i ons of t he l i qui d phase pr e s e nt i n t he pa s t e s at cl os el y- s paced
time i n t e r v a l s wi t hi n t he f i r s t da y. I n a d d i t i o n , t he hydr at i on was
moni t ored by x- r a y d i f f r a c t o me t r y , t emper at ur e e vol ut i on measurement s,
and non- evapor abl e wat er d e t e r mi n a t i o n s . Cor r e l a t i ons were sought
between c onc e nt r a t i on changes i n t he l i qui d phase and t he pr oces s es
under l yi ng s e t t i n g , t emper at ur e e v o l u t i o n , and changes i n t he s ol i d
phase compos i t i ons .
In t hes e measurements i t was confi rmed t ha t s e t t i n g i s not a s s o c i -
at ed wi t h any sudden changes i n t he s o l u t i o n chemi s t r y of t he l i qui d
phas e. The onl y i n t e n s i f i e d chemi cal pr oces s de t e c t e d at or s h o r t l y
a f t e r s e t t i n g i s enhanced p r e c i p i t a t i o n of Ca(0H). However, smal l
but we l l - c r y s t a l l i z e d mi c r o c r y s t a l s of Ca(0H) were found t o be pr es ent
i n expr essed pore s o l u t i o n s at ver y e a r l y a ge s , f ar i n advance of s e t t i n g .
X
The major finding in this work concerns the effect of solid gypsum
on the alkalinity of the paste pore solution. It has been established
that early concentrations of dissolved sulfates are higher than expected
from the known solubility product of gypsum, and reflect the content of
alkali sulfate provided by the cement. These levels of concentration
are maintained as long as solid gypsum remains present; when the gypsum
is exhausted by continued ettringite production the sulfate concentra-
tion rapidly declines. When this occurs the hydroxyl ion concentration
increases in parallel with the decline of the sulfate concentration, in
effect converting dissolved alkali sulfate into alkali hydroxide. The
time at which this transformation begins can be extended by additional
gypsum.
CHAPTER ONE - REVIEW OF THE LITERATURE
1. 1 Introduction
The hydration reactions of portland cement have been studied for
many decades. It has been found that reactions that occur during the
first few hours, or the first day or so, are of particular importance
in their influence of the final properties of the concrete. The nature
of these early reactions has been most difficult to unravel - much
remains to be investigated but much has been learned. The various
investigators who have studied specific and isolated aspects of these
early reactions used a number of different techniques and it is only
now that we are able to draw much of this information together and to
obtain a reasonably clear picture of these early reactions.
In a limited space it is impossible even to attempt to make a
complete resume of these researches. Therefore, the present chapter
includes only the most important findings pertinent to this thesis,
that is, different sulfates present in cement and their role in the
early hydration process.
In the last century portland cement was produced which, without
any additives at all, set slowly enough that it could be used without
difficulty. It was only when the appreciable effect of cement fineness
on the rate of its strength development was discovered, and when the
fineness was progressively increased, that some problems occurred -
flash set being most serious one. It was therefore a considerable step
2
forward in cement technology when the discovery was made that a small
addition of gypsum could overcome this trouble. That discovery led
to the manufacture of finely ground, and consequently rapid hardening
cements, the setting time of which still remained long enough to enable
proper placing and consolidation of concrete.
However, the addition of gypsum, or generally calcium sulfates,
does not affect only the setting time. It can considerably alter the
shrinkage and also the strength characteristics of the cement. It was
established that there is an amount of gypsum called an "optimum gypsum
content" that produces minimum shrinkage and maximum strength, but this
optimum is sensitive to the clinker characteristics and to the hydration
temperature. However we still need to know more about the mechanism by
which gypsum influences shrinkage and strength and how clinker composi-
tion and curing temperature influence their mechanism.
1.2 C A - CS - CH System
From the classical work of Lerch (1,2) we know that CA in contact
with gypsum reacts spontaneously after mixing with water. By measure-
ments of the amount of hydration performed calorimetrically, he could
detect that after the first evolution of heat the reaction was strongly
retarded, and that after perhaps 40 hours a renewed strong reaction
began,-after which the total amount of gypsum had been converted into
ettringite. Schwiete (3) had reported similar observations as early as
1932, but was not able to explain them at that time. Stein (4) obtained
similar results. After an initial strong heat release, heat evolution
decreased continually up to the complete utilization of the gypsum, then
underwent a very strong increase and then fell again. Ettringite formed
3
up to the complete u t i l i z a t i o n of the gypsum pr esent . After the second
strong peak of heat r el ease St ei n observed t r i cal ci um aluminum mono-
sul fat e hydrate in the X-ray pat t er n. He came t o the conclusion t hat
in the space of time i n which gypsum r et ar dat i on influences the hydrat i on
of the CA, e t t r i n g i t e forms on the surfaces of the CA gr ai ns ; f ur t her -
more since the volume of e t t r i ngi t e formed i s great er than t hat of the
C-A portion consumed, the process probably must r es ul t in sloughing off
the e t t r i ngi t e l ayer .
Due to many r epor t s t hat e t t r i ngi t e was found in cement past es at
ear l y stages of hydrat i on (references are given in the next sect i on) the
theory developed by St ei n was accepted and furt her development of i t was
encouraged. Schwiete, Ludwig and Jager (5) made an ext ensi ve study of
the CA-CS-CH system and reached very si mi l ar conclusions as St ei n did
with thermochemical and X-ray methods. By el ect r on- opt i cal examination
of the system, small e t t r i n g i t e needles were found on the surface of
CA c r ys t a l s . A st rong r et ar dat i on of the react i on r at e they expl ai n
by t hi s el ect r on- mi cr oscopi cal l y observed formation of an e t t r i n g i t e
coating over the C.A c r ys t a l s . The same mechanism of e t t r i ngi t e forma-
t i on around the C-A cr ys t al s was assumed for the r et ar di ng ef f ect of
gypsum on the hydrat i on of portland cement. In t hei r opinion the
formation of e t t r i n g i t e i s a topochemical r eact i on and whenever a
rupture in the coat i ng occurs i t i s immediately sealed by penet r at i ng
calcium and s ul f at es and immediately new e t t r i ngi t e i s formed. This
process could expl ai n the e t t r i ngi t e formation even during the dormant
peri od. When the gypsum content of the sol ut i on phase of the r eact i on
mixture i s no longer suf f i ci ent for e t t r i n g i t e formation, the rupt ures
consequently can no longer be seal ed. The second strong r eact i on then
4
begins, which leads to a decrease of ettringite and the formation of
calcium monsulfate aluminate hydrate, or even tetracalcium aluminate
hydrate (C,AH._). In contrast to Stein, in their opinion this second
reaction can occur even in the presence of a small amount of gypsum in
the solid phase.
The weakest point of the above mentioned theory seems to be the
ettringite coating, that is whether ettringite formed in the way
described, really can prevent the penetration of molecules of water, and
thus protect the covered CA from the further reaction. The data on the
dissolution and electrokinetic behavior of C_A suggested an alternate
mechanism for retardation of C.A hydration by sulfate ions (6, 7). On
contact with water CA dissolves incongruently, leaving an Al-rich sur-
face. Ca ions chemisorb on the surface producing positively-charged
particles. The formation of such a structure decreases the number of
active dissolution sites and, thus, the rate of CA dissolution
decreases. Sulfate ions adsorb on the positively-charged C_A particles
resulting in further reduction of dissolution sites. The blocking effect
of sulfate ions on coordination sites prevents hydrogen or hydroxyl ions
from catalyzing the dissolution of alumina.
Holten (8) reported that the addition of quartz to the C_A-CS-CH
2-
system counteracts the retarding action of SO on the hydration off A.
He explained that quartz surfaces present additional sites for ettringite
crystallization. Strong retardation requires the presence of ettringite
near the CA, influencing the local concentration there.
Mehta (9), ten years after Schwiete et al.'s paper on CA-CS-H
system also studied the same system. He, however, disagreed in many
respects with their conclusions. He also noticed that ettringite
c r ys t a l s were formed near the surface of C_A gr a i ns . However, he
bel i eved t hat t hi s i s due t o the limited s ol ubi l i t y of C,A in presence
of s ul f at es and not due t o topochemical r eact i on. The i ndi scri mi nat e
formation of e t t r i ngi t e anywhere and everywhere in the system seems t o
r ul e out the topochemical r eact i ons being responsi bl e for e t t r i ngi t e
formation. He al so suggests t hat the deposi t s of e t t r i n g i t e cr ys t al s
around CA grai ns do not appear t o be dense enough t o account for the
r et ar dat i on of hydrat i on as a r es ul t of pr ot ect i ve coat i ng mechanism.
The r et ar dat i on phenomenon is explained by him on the basi s of reduced
s ol ubi l i t y of CA in sol ut i ons sat urat ed with s ul f a t e s .
1.3 Clinker-Gypsum System in Contact with Water
Long before Stein proposed hi s mechanism of r et ar dat i on t here had
been many r epor t s t hat e t t r i ngi t e had been found in cement past es at
di f f er ent ages. Just a few out of many si mi l ar experiments and findings
are mentioned her e.
Kalousek, Davis and Schmertz (10) observed t hat e t t r i n g i t e i s
formed in the hydrat i on of cement immediately af t er water i s added.
They used the DTA t echni que. With the same t echni que, Greene (11) could
det ect e t t r i n g i t e af t er a hydration time of only 5 minutes and could
det ect monosulfate hydrate af t er 7 days. Taylor (12) det ect ed
e t t r i n g i t e in the past e af t er 1 day. Richartz (13) found t hat in
addi t i on t o e t t r i n g i t e , Ca(0H)
?
cr ys t al s are al so formed ( t o a minor
ext ent ) af t er a few minutes of hydrat i on.
Budnikov (14) i nvest i gat ed the amount of SO bound in a cl i nker
with 11% CA as a function of t i me. The i n i t i a l gypsum content in t hat
i nves t i gat i on amounted t o 6.3% which dropped af t er 6 hours t o 2.9%,
6
aft er 24 hours t o 1.87%, aft er 3 days t o 1.1% and af t er 28 days t o 0.1%.
For the det ermi nat i ons of the free gypsum he ut i l i zed the ext r act i on
method in which the SO not bonded in e t t r i ngi t e i s ext ract ed through
agi t at i on with l i me-sat urat ed wat er.
In 1964 Seligmann and Greening (15, 16) developed continuous X-ray
di f f r act i on scanning methods for studying wet past es during the ear l y
stages of hydr at i on. They used t hi s method for examining wet past es
made of s ynt het i cal l y prepared di f f er ent mixtures of cement components.
Monitoring only C A, CS, and CH, the t ypi cal feat ures of the
hydration found by them were as follows. At 15 minutes, strong peaks
of C-A, CH and gypsum were observed. By two hours the gypsum peak has
been consi derabl y reduced and peaks appeared for e t t r i n g i t e . During the
next few hours the gypsum has completely reacted - thus the f i r s t stage
of aluminate r eact i on was completed. The second stage occurred even
more r api dl y. Al l of the e t t r i ngi t e reacted with remaining unhydrated
CA to form calcium monosulfate hydrat e. After t hat , the t hi r d stage of
aluminate hydrat i on s t a r t e d. A low-sulfate calcium sulfoaluminate. peak
at 9.2 degrees 2- t het a increased but al so shi ft ed as calcium hydroxide
and CA i nt e ns i t i e s decreased. These changes were explained by the
formation of a sol i d sol ut i on of the C,AH, and C, AS H, , and al so
4 13 4 11
C
4
AH
]g
.
The time needed for each stage to be completed depended on the
mixture preparation and gypsum content.
In ordinary portland cement there is another phase that is expected
to react with gypsum. This is a solid solution phase which composition
sometimes approximates C.AF, and is known as tetracalcium alumino-
ferrite. In portland cement it has not been considered to contribute
7
significantly to the strength. This is the reason that there are fewer
reports on the hydration of the ferrite phase than other cement phases
as summarized by Copeland and Kantro (17, Ludwig (18) and Kalousek (19).
An extensive study on the pure system C.AF-CS-H was made by Jawed,
Goto and Kondo (20). Their finding was that ettringite is formed on the
surface of the ferrite phase even faster than on C.A phase (after 30
seconds of hydration), but to a lesser extent. The hydration of the
ferrite phase was retarded as in the case of CA. When all the sulfate
was used monosulfate was produced, resulting in breaking the ettringite
layer and accelerating the hydration of C,AF. It follows that C.AF
forms the same sequence of hydration products as does CA.. The reactions
are slower and involve less heat.
There is, however, one important difference between cements that
are rich in C.AF and cements that are high in C-A. Cements low in C A
but high in C.AF are resistant to sulfate attack according to Mindess
and Young (21). It has not yet been completely established why this
is so.
Lerch (1, 2) in his pioneering work observed that gypsum does not
only react with CA and C.AF but influences the hydration rate of other
cement components too. He noticed that the second heat evolution peak,
which was attributed to the continued slow hydration of C_A and
particularly to the increasingly rapid reaction of CS, was accelerated
on increasing the amount of gypsum. The conclusion drawn from this
experiment suggested that gypsum is not required only to avoid flash
set but also to prevent a severe retardation of the normal silicate
reaction. The retarding effect of depletion of gypsum prior to the
silicate reaction was explained by the deposition of a severely-retarding
8
coating from aluminate and f er r i t e phases on the s i l i c a t e s .
From the above i t follows t hat a cl ear di s t i nc t i on must be made
between the r et ar dat i on of the chemical r eact i on and the r et ar dat i on of
s e t t i ng. Locher, Ri chart z and Sprung (22, 23) offered the following
expl anat i on for gypsum influence on s e t t i ng. The s et t i ng of cement
depends on the r i gi d st r uct ur e formed by the r eact i on product of C,A
and calcium sul fat e hydrat i on. This r eact i on product i s general l y a
fine grained e t t r i ngi t e forming a t hi n cover on the surface of cement
p a r t i c l e s . This t hi n e t t r i ngi t e layer does not hinder the ear l y
mobi l i t y of the cement par t i cl es and the past e remains workable. Set t i ng
i s caused by r ecr ys t al l i zat i on of t hi s mi cr ocr yst al l i ne e t t r i ngi t e i nt o
long needles bridging and i nt erl ocki ng the space between cement pa r t i c l e s ,
thus forming the r i gi d st r uct ur e r esul t i ng in s e t t i ng. For normal
s e t t i ng, the amount of sul fat e in sol ut i on should be in the r i ght
proport i on with CA dissolved in the f i r s t minutes af t er mixing cement
with water so as t o form e t t r i n g i t e . A shortage of sul f at e ions in
sol ut i on can lead t o formation of calcium monosulfoaluminate, C.ASH
and even C.AH.,, while an excess can cause pr eci pi t at i on of secondary
gypsum. All these are coarse cr yst al s and can cause premature
s t i f f eni ng, e . g. , "fal se s et " .
1.4. Al kal i es in Cement and Their Influence on Gypsum Effect i veness
The ef f ect i veness of gypsum as a r et ar der i s influenced by the
fi neness and al kal i content of the cement. Lerch (2) made the f i r s t
det ai l ed study of the ef f ect of al kal i es in cl i nker on the r at e of
hydrat i on of portland cement. From the cal or i met r i c t r aces he noted
t hat the presence of al kal i accel erat ed the hydrat i on pr ocess. The
9
gypsum requirement for proper r et ar dat i on of cements was affected by
a l ka l i e s ; cements with high al kal i content required more gypsum.
I nt er es t in al kal i es has increased in recent years as the percent -
age of al kal i es in cements get s hi gher. Skalny and Jawed (24)
published a comprehensive review on forms of al kal i es and t hei r effect
on cl i nker formation. Al kal i es in portland cement cl i nker occur as
sul f at es and, depending on the amount of S0 avai l abl e, may al so be
present in calcium s i l i c a t e and aluminate phases. As al kal i sul f at es
t here are t hree major compounds: KSO, ( a r c a ni t e ) , NaS0-3KS0
( a pht hi t a l i t e ) , 2 CaSO KSO (calcium l angbei ni t e) . Similar solid
sol ut i ons can al so e xi s t . As al kal i aluminates t here are NC A and
O J
suggested KC
0
A (25, 26). As al kal i s i l i c a t e s t here are KCS,
o j z j 11
(potassium st abi l i zed form of a-CS) and suggested NC
?
S ( 25, 26).
Again, sol i d sol ut i ons are possi bl e. The formation of K0>4SiO and
Na
o
0' 2Si0 at 600C and Na
o
Ca(C0
o
)
o
and KNa (S0. ) at 700C are al so
I I I 3 I 3 4 2
reported (27, 28). Under di f f er ent condi t i ons some other forms of
al kal i compounds may be found. For example, the ki l n dust cont ai ns
al kal i hal i des in addi t i on t o s ul f at es , the most common being KC1
( s y l v i t e ) . Formation of lumps in cement during storage has been
at t r i but ed t o another al kal i calcium s ul f at e, KSO, CaSO -H^O (syngeni t e),
When al kal i - cont ai ni ng cement i s mixed with water, the al kal i metal
ions from the soluble al kal i sul f at es r eadi l y go i nt o sol ut i on in the
l i qui d phase of the hydrating system and influence the r at e of cement
hydrat i on and the morphology of the hydrat i on product s. Di fferent
cements have been found to vary widely in the f r act i ons of t hei r al kal i
content t hat are r eadi l y sol ubl e, (29, 3 0) . McCoy and Eshenour (30)
concluded t hat even af t er one year a consi derabl e port i on of al kal i in
10
cement might not be di ssol ved. However, when r el at i vel y large amounts
of S0 are present in cl i nker a s ubs t ant i al fract i on of t ot a l al kal i es
passes i nt o sol ut i on wi t hi n a few minutes ( 3 1, 3 2). A slow but cont i n-
uous r i se in al kal i concent r at i on follows with time ( 3 3 , 34, 35) and
aft er 28 days or so, almost a l l of al kal i es are found t o be dissolved
( 3 6) . Abbassi (36) found t hat sodium di ssol ved more completely than
potassium in the absence of gypsum, whereas the opposite was observed in
i t s presence. Lawrence (37) noted a furt her sharp r i se in the concen-
+ + . 2- .
t r at i on of Na and K ions when a l l the SO. ions were removed from the
4
sol ut i on and at t r i but ed t hi s to increased hydration of alkali-doped CA.
I t i s considered gener al l y t hat upon hydration of the cement, the
al kal i sul f at es and double sul f at es are rapi dl y dissolved in the aqueous
phase, whereas al kal i es present in the al umi nat e, f er r i t e and s i l i c a t e
phases are released more slowly over a period of days or even weeks and
months ( 3 8) .
Yanev and Mircheva ( 3 9) , however, did not find any si gni fi cant
difference in s ol ubi l i t y between al kal i sul f at es and al kal i es incorpo-
rated in aluminates and s i l i c a t e s of hynt het i c laboratory-produced
cl i nker s . Diamond (40) considered t hat t hi s might have been due t o
di fferences in sample pr epar at i ons . Under normal ki l n burning condi t i ons,
the sul f at es are presumably condensed on the cl i nker surface (41) and are
r eadi l y accessi bl e t o wat er . In Yanev and Mitcheva' s experiments the
sul f at es were thoroughly mixed with the raw mat er i al s and thus were not
added vi a deposi t i on from the ki l n atmosphere.
Kryzhanovskaya (42) found t hat al kal i es from NC_A were released
i nt o sol ut i on more r eadi l y than from KC~S
11
A number of authors have reported t hat a l ka l i sul f at es accel erat e
the hydration of cement (43 , 44, 45, 46, 4 7) . Mander and Skalny (43)
showed t hat the main heat evol ut i on peak associ at ed with a l i t e hydration
appeared e a r l i e r in the presence of KSO . They al so noted t hat
i ncreasi ng the KSO content decreased the t o t a l heat evolved in the
f i r s t minutes of hydrat i on. Mori et aL (48) studied the effect of
a l ka l i compounds on the hydration of calcium s i l i c a t e s and reached the
same conclusion - a l ka l i sul f at es increased the hydrat i on in the accel -
er at i on period and increased the r at e of heat evol ut i on towards i t s
peak.
Skalny and Klemm (38) summarized di f f er ent suggestions as follows:
Al kal i sul f at es influence Ca(OH) s ol ubi l i t y, decrease the act i vat i on
energy of CS di ssol ut i on or hydrat i on, and prevent the poisoning of
CS hydration by alumina from the CA. There are not many r epor t s on
the influence of al kal i sul f at es on pure CA hydr at i on. Collepardi et
aL (4 9) reported t hat in the absence of gypsum and in the presence of
sodium sul fat e the hydration of C A i s ret arded by C AH coat i ng.
Experimentally they measured heat evol ut i on and DTA; X-ray di f f r act i on
anal ysi s was used only occasi onal l y.
Reports on e t t r i ngi t e formation in high a l ka l i cement past es are
conf l i ct i ng. Sheikin (50) noted t hat al kal i es in cement decreased
i n i t i a l e t t r i ngi t e formation. The r at e of conversion of e t t r i ngi t e t o
monosulfate increased af t er a l l gypsum was chemically combined and
when t here was a si gni f i cant decrease in Ca(0H) concent r at i on. Accord-
ing t o these authors the e t t r i ngi t e c r ys t a l l i z a t i on can be cont rol l ed
by sui t abl e addi t i on of al kal i es .
12
Ershov and Timofeeva (51) found that alkalies increase the form-
ation of ettringite and decrease the amount of Ca(OH) .
Sprung and Rechenberg (52) noted that high alkali contents of
cement, while suppressing the solubility of Ca(OH), promote the dis-
solution of CA. They indicated that in these alkali-rich solutions,
if the gypsum content is low, quick setting due to formation of aluminate
hydrate would occur. With too much gypsum, on the other hand, quick
setting due to formation of ettringite would occur.
1.5 Pore Solutions
Very ear l y r epor t s i ndi cat e t hat di f f er ent i nvest i gat or s have t r i ed
to examine the l i qui d phase of the cement paste for a long t i me. Works
of Roller ( 53 ) , Lerch ( 54) , Hansen and Pr essl er ( 55) , Kuhl ( 56) ,
Hedin (57), Budnikov and Strelkov (58) should be mentioned her e. The
effect i ve study of the l i qui d phase of hardened past es was hampered by
the immense di f f i cul t y of ext r act i ng the l i qui d from the hardened pas t e.
Inadequate methods and unr e a l i s t i c a l l y high water-cement r a t i os were
used. There were no dat a avai l abl e on pore sol ut i ons of older past es
(1 day and more). An appropri at e method was developed by Longuet et a l .
( 59) . By t hi s method the hydrating paste i s mechanically compressed
which allows the pore sol ut i on t o be squeezed out of the paste under
high pr essur e. The pore sol ut i on can then be immediately di l ut ed and
analyzed by the appropri at e means such as atomic absorpt i on.
However, as mentioned, some work had been done before t hi s method
was developed. Two experimental techniques for separat i ng the aqueous
phase from the solid phase before f i nal set were us e d- cent r i f ugal and
pressure f i l t r a t i o n . Discussion by Greenberg and Mehra ( 60) , given at
13
Washington Congress (1960), conci sel y reviews the most important f i ndi ngs.
At t hat time the dat a were avai l abl e mostly for the f i r s t two hours of
hydration and only Takemoto and Suzuki (61) had some information about
the liquid composition as old as five hours, e . e . almost up t o the
fi nal set t i ng of the cement pas t e.
In the i n i t i a l st ages of hydrat i on the pH values of the aqueous
phases were found from 12.6 t o 12.9, but for high al kal i cements pH
values as high as 13.45 were reported ( 62) . The sol ut i ons were found
to be supersat urat ed with respect t o calcium hydroxide very soon af t er
the beginning of hydrat i on with a slow decrease of calcium concent rat i on
afterwards. The removal of Ca from the sol ut i on was explained by the
formation of hydrated calcium s i l i c a t e s , calcium aluminates, calcium
sul foal umi nat es, calcium hydroxide and calcium s ul f at e. The concen-
t r at i on of sul f at e was found t o be at the equi l i bri um val ue, so t hat
the aqueous phase was regarded as being composed es s ent i al l y of a super-
sat urat ed calcium hydroxide sol ut i on sat urat ed with calcium sul f at e
di bydrat e. Sodium and potassium ions were present at concent rat i ons t hat
are more or l ess pr opor t i onal to the t ot a l amount of al kal i es in cement.
Their concent rat i ons remained nearl y constant during the earl y hydrat i on
processes. Si l i con- and aluminum-bearing ions were al so reported t o be
found in the aqueous phase, but at concent rat i ons which are very low and
can be di sr egar ded.
In 1964 Lawrence (63) made a more extensive study of the l i qui d
phase of di f f er ent cement systems and of the pure C-A-CS system. He
2-
noticed a slow removal of SO, ions from the sol ut i ons ext ract ed from
4
the past es without gypsum added. In the cases where gypsum or even
al kal i sul f at es were added he did not not i ce any appreciable di fference
14
in the r at e of uptake of s ul f at e. His suggestion was t herefore t hat
e t t r i ngi t e forms a prot ect i ve layer on the surface of C_A grai ns and
2-
t hat the decrease of SO, i s cont rol l ed by di ffusi on of sul fat e ions
through the bar r i er of e t t r i ngi t e on the surface of the anydrous C A.
At the same time the bar r i er of e t t r i n g i t e per i odi cal l y spal l s off as
fresh e t t r i ngi t e i s formed. His fi ndi ngs are in agreement with these
of Schwiete et a l . ( 5) .
As mentioned previ ousl y, an important cont ri but i on t o pore sol ut i on
i nvest i gat or s was the development of the method for expressing the pore
sol ut i on from hardened cement past es by Longuet et a l . (59). They found
t hat low al kal i cements may give r i s e t o combined al kal i concent rat i ons
of the order of 0.2M or more.
Normal cements, with higher al kal i - cont ent s , may give pore sol ut i on
of the order of 0.7M or even higher wi t hi n a month or so. They showed
t hat such sol ut i ons r et ai n t hei r hi gh, concent rat i ons of al kal i cat i ons
i ndef i ni t el y. Locher' s (3 3 ), Lashschenko and Loganina' s (64) and Diamond
and Barneyback' s (65) r es ul t s are s i mi l ar .
Longuet et a l . al so proposed a mechanism through which the neut r al
al kal i s al t s increase the pH of the pore s ol ut i ons , expressed as:
Ca(OH)
2
(sol) + K
2
S0
4
(sol) t KOH(sol) + CaSO^sol)
Ca(OH)
2
+ CaS0
4
l
At the same time they mentioned t hat the sul f at e does not have t o be
pr eci pi t at ed as calcium sul fat e and can be used for formation of sul f o-
al umi nat es. The above scheme has not been studied since then and
developed f ur t her .
Perhaps t hi s can be ascribed t o the somehow cont radi ct ory finding
t hat the addi t i on of gypsum to cement has l i t t l e ef f ect on pH value of
15
pore solution (64). Although it seems to be true for pH of old pore
solutions, it is not true at the beginning of the hydration.
The oversaturations of pore solutions with respect to Ca(OH) at
early stages of hydration has been discussed frequently in recent times
and also used for interpreting the setting phenomenon (66). Diamond's
calculations (67) suggest that the degree of oversaturation is usually
overestimated.
The solubility of gypsum is very sensitive to alkalies as proved
by Hansen and Pressler (55). They measured the solubility of Ca(OH)
and CaSO,
#
2H0 in dilute alkali solutions. At different alkali con-
4 2
centrations (K , Na and combined) they measured Ca and SO ion
concentrations and expressed them in moles of CaO and SO . The results
2+ . . .
show a slight decrease of Ca concentration with increased alkali
concentration but only in the low alkali concentration region. At higher
2+
alkali concentrations the Ca concentration becomes independent of
2- . .
alkalies. On the other hand, the SO, concentration is very sensitive
to alkalies in the whole concentration region. If S0 and alkali con-
centrations are expressed in equivalents the slope of the curve is
approximately 1. This suggests that some kind of complex ion is formed.
1.6 Optimum Gypsum Content
One of the main purposes of investigating the reactions between
gypsum and other cement components during the hydration period is to
find a reliable way to design the optimum amount of gypsum for a
particular clinker. As mentioned before, gypsum is added to cement to
prevent its flash setting. However, with its addition some properties
of the final product change, most important being the final strength
16
(usual l y 28 day st r engt h i s measured) and shri nkage. The optimum
gypsum content i s defined as one t hat produces minimum shrinkage and
maximum st r engt h. But the optimum i s sensi t i ve t o the cl i nker char act er -
i s t i c s and can be al so affect ed by the hydration temperature, the mixing
procedure, the water-cement r a t i o , the use of water reducing admixtures,
e t c .
Limiting t hi s review only t o cl i nker char act er i zat i ons , Lerch (12)
was the f i r s t t o show t hat the most important fact ors t hat influence
the gypsum requirements are the CA cont ent , the fi neness, and the
al kal i cont ent . Some speci f i c st udi es have been done since t hen.
Copeland (17) determined the optimum gypsum l evel for maximum r at e of
hydration of a l i t e and al so the var i at i ons in compressive st rengt h with
the ext ent of sul f at e s ubs t i t ut i on at a constant degree of C_S hydr at i on.
Bentur (68) expl ai ned the influence of gypsum content on the
i nt erconnect i on between the compressive st r engt h, the degree of hydrat i on
and C/S r a t i o of the hydrated product of t r i cal ci um s i l i c a t e past es.
Jel eni c et a l . (69) studied how the ef f ect of gypsum on the hydra-
t i on and st rengt h development in cement past es i s influenced by al kal i
s ul f at es .
Using Lerch' s da t a , Haskel l (70) obtained the following l i near
regressi on equation for optimum S0 content of cements (for cement
pas t e) : Optimum SO % = 1.84 1 + 0.0950 (CA%) + 1.6364 (equivalent
%Na~0). This cor r el at i on i s si mi l ar t o one obtained from Me i s s uer ' s
dat a (71): Optimum SO % = 0.789 + 0.1149 (C.jA%) + 1.872 (equi val ent
% Na0). An i nt er es t i ng observat i on i s the magnitude of the coef f i ci ent
for al kal i cont ent s, which i s about 16 times the coeffi ci ent for CA.
17
Recent l y, Ost (72) extended the Haskell treatment to include
cement f i neness. Using Lerch' s dat a he obtained an equation according
t o which the most important fact ors in determining the optimum SO-
content were cement fineness and the equi val ent Na0 and Fe.O cont ent s:
Optimum S0
3
% = 0.5560 (Na
2
0%) + 0.0017659 (Blaine fi neness) - 0.1072
(Fe
2
0
3
%) - 3.6004.
With a l l t hat i s known about the chemistry of gypsum in cement i t
i s di f f i c ul t to account for the absence of the coef f i ci ent for CA in
the above cor r el at i on. On the other hand, however, the strong cor r el a-
t i on between the optimum SO and the al kal i es (found in a l l the equat ions)
gives some addt i onal importance to the very simple scheme, proposed
by Longuet ( 59) , through which the neut r al a l ka l i s a l t s ( s ul f at es in
par t i cul ar ) increase the pH of the pore s ol ut i ons .
These r es ul t s are of considerable importance to the present
i nvest i gat i on and the i nt er pr et at i on of the hydrat i ng cement system
which wi l l be made l a t e r . They may be i nt er pr et ed as cast i ng consi der-
able doubt on the pr ot ect i ve layer t heor y, and on the theory based on
incongruent di ssol ut i on of CA as wel l . The importance of gypsum in
cement technology, these basi c disagreements on the physico-chemical
mechanisms and Longuet' s experimentally not - yet - st udi ed scheme provided
the impetus for the present work.
As a major experimental method we took advantage of the recent l y
developed pressuri ng technique t hat allows t o express pore sol ut i ons
from cement pas t es . Because the method i s f ai r l y new, t here are not
many published dat a on the pore sol ut i on avai l abl e and t hi s work
t herefore cont ri but es some new r es ul t s and conclusions regarding gypsum
a c t i vi t y in ear l y st ages of cement hydr at i on.
18
CHAPTER TWO - MATERIALS AND EXPERIMENTAL METHODS
2 . 1 . Par t One- Ma t e r i a l s
2 . 1 . 1 . Cements
The s p e c i f i c cement ma t e r i a l s used i n t h i s st udy were as
f ol l ows :
1. An ordinary Type I portland cement, moderate in a l ka l i
cont ent , produced by the Lone Star I ndus t r i es , I n c . ,
Greencast l e, Indi ana. The chemical anal ysi s was furnished
by Martin Mari et t a Labor at or i es, Baltimore, Maryland and i s
given in Table 2 . 1 . 1 .
2. A finely-ground Type I portland cement cl i nker , made
during a normal production run at the Holly Hi l l , South
Carolina pl ant of the Giant Cement Company in December-1974.
This cl i nker was ground in a speci al l y cleaned gri ndi ng mi l l
free of cont act with gypsum, t o a Blaine fineness of approx-
2 . . . .
imately 5,400 cm / g. A t ypi cal chemical anal ysi s of cl unker,
supplied by the pl ant i s given in Table 2 . 1 . 1 . From the
anal ysi s i t follows t hat the al kal i content i s extremely low.
3 . A high al kal i Type I portland cement, produced by the At l ant i c
Cement Company, St anford, Connecticut. The chemical anal ysi s
of i t i s supplied by the company and i s given in Table 2 . 1 . 1 .
19
Tabl e 2 . 1. 1 Anal yses of Cements Used
Component
si o
2
A1
23
Fe
2
0
5
CaO
Mgo
SO.
Na
2
0
K
2
0
Tot al Al k a l i s , as Na0
Sol ubl e Na
2
0
Sol ubl e K 0
Ignition loss
Insoluble
Free CaO
Or di nar y
Type I
Cement
20. 95
4. 98
2. 42
64. 4 7
1.19
2. 96
0. 10
0. 69
0. 45
2. 15
__
Fi ne l y Ground
Type I
Cl i nker
22. 17
6. 18
2. 63
67. 57
1.06
0. 13
0. 07
0. 17
0. 18
0. 01
0. 04
0. 3 5

High Al k a l i
Type I
Cement
21. 14
5. 81
2. 25
63. 24
3 . 45
2. 70
0. 3 0
0. 91
0. 90
0. 29
0. 50
0. 73
0. 22
0.69
Potential Compound
Composition
c
3
s
c
2
s
C
3
A
C.AF
4
Speci f i c Surface
2
cm / g ( Bl ai ne)
57.81
16.54
9. 11
7. 36
3760
58. 20
19.70
11.90
8. 00
5400
4 6. 8
25. 3
11.6
6. 8
3680
20
2. 1.2. Chemicals
s
The chemical addi t i ons used in t hi s work were as follows:
1. Calcium Sul f at e, CaSO .2H0, powder AR (Anal yt i cal Reagent ),
Mal l i nckrodt , I nc. , Pa r i s , Kentucky.
2. Potassium Sul f at e, KS0 , powder AR (Anal yt i cal Reagent),
Mallinckrodt Chemical Works, St . Loui s, Mi ssouri .
3 . Deionized water, passed through both cat i oni c and anionic
exchange r es i ns , was used throughout t hi s work.
2. 2. Part Two-Experimental Methods
The descr i pt i on of sample preparat i on and t he' experi ment al methods
used t o i nvest i gat e the pr oper t i es i nferred are presented in t hi s part
of Chapter I I .
2 . 2 . 1. Cement Paste Preparat i on
The cement past es studied in t hi s work were made with t hree di f f e r -
ent cements, previ ousl y descri bed. In speci f i c cases chemically pure
potassium s ul f at e, gypsum, or both were added. As mix wat er, only
dionized water was used. A 0.50 water-to-cement r a t i o was used, except
t hat in one case cement past es with water-to-cement r a t i o 1.00 were
al so st udi ed.
Whenever the addi t i on of gypsum was made, i t was made pr i or t o
mixing with water. On the other hand, the potassium sul fat e was
dissolved in the mix water before mixing i t with cement.
2. 2. 2 Det ai l s of Mixing
3
A standard Hobart mixer, Type N-50, capaci t y 4. 73 dm was used
in mixing the pas t es . ASTM Method C 305-80 for mechanical mixing of
21
hydraul i c cement past es was followed. In t hi s procedure the mix water
was f i r s t poured i nt o the mixer bowl, cement was added, and a period of
30 seconds was allowed for the cement t o absorb the mix wat er. After t hat
peri od, mixing was done at the low speed set t i ng for 30 seconds, followed
by 15 seconds r e s t . The paste was then scraped down from the si des of
the bowl and the system was mixed again at the medium speed s et t i ng for 60
seconds. Immediately af t er mixing the paste was poured i nt o pl a s t i c
ointment j ar s of 5.1 cm diameter and 6.5 cm hei ght . The j a r s were then
placed on a Syntron Jogger vi br at i ng t abl e and vi br at ed for 30 seconds
and then seal ed. The j a r s were stored in the l aborat ory at 'v, 23 C tem-
per at ur e. Past es mixed and stored in these pl as t i c cont ai ner s were used
for a l l det ermi nat i ons described in the present t he s i s . This includes
det ermi nat i ons of s et t i ng time, temperature evol ut i on, and expressi on of
pore s ol ut i ons . Paste from the same j a r s was used al so for X-ray di f f r ac-
t i on anal ysi s and SEM s t udi es .
2. 2. 3 Set t i ng Time
Determinations of i n i t i a l and f i nal set of the cement past es were
carri ed out usi ng the Vicat needle apparat us. The c r i t e r i a and proce-
dures complied e s s e nt i a l l y with ASTM Method C 191-79, sect i on 6. 2, except
t hat measurements were taken at w:c 0. 50, not at normal consi st ency.
These det ermi nat i ons were carri ed out on the standard pl a s t i c
ointment j a r s . The cont ai ner s were f i l l ed with the past e in one
si ngl e layer t o about 2 mm below the t op. They were then vi brat ed on
the vi br at i ng t abl e t o smooth the surface, and seal ed. The cap of the
cont ai ner was removed subsequently only while the act ual penet r at i on
t e s t s were being car r i ed out .
22
2. 2. 4 Temperature Evolution
The temperature evol ut i on over the f i r s t day of hydrat i on of
the cement past e was measured on r epl i cat e port i ons of the same batch
of paste on which the set was determined. The time at which the set
was reached was recorded on the ongoing temperature evol ut i on cur ve.
A device developed by Prof. D. N. Winslow was used in t hi s
experiment. The general arrangement consi st s of a styrofoam i nsul at i ng
system, two standard pl a s t i c ointment j ar s (one for the paste under,
study, and one for the reference mat er i al ) , a set of two matched
t her mi st or s, a Wheatstone bridge and a r ecor der . The set up i s shown
schematically in Figure 2 . 2 . 1 .
Immediately af t er the paste was prepared and cast in one si ngl e
layer in the pl a s t i c cont ai ner , i t was placed i nt o the styrofoam
i nsul at i ng system. The reference mat er i al used in t hi s work was Ottawa
sand mixed with wat er , having water:sand r a t i o equal t o t he water:cement
r at i o of the past e under t e s t . This reference mat er i al , equi l i br at ed
to room t emperat ure, was put in the other pl as t i c cont ai ner and al so
i nsul at ed wi t hi n the styrofoam i nsul at i ng system. The t her mi st or s
were then immersed in copper tubes t hat had one end crimped shut and
t hat were embedded in the reference mat er i al and in the cement pa s t e ,
r espect i vel y. Approximately 1 ml of mercury had been previ ousl y poured
i nt o the copper t ubes t o provide adequate thermal conduct i vi t y between
the copper tube wal l and the t her mi st or .
The hydrat i on r eact i ons increase the temperature of the cement
past e, which in t urn i ncr eases the temperature of the t hermi st or
embedded in i t . A vol t age di fference i s thus produced between t he two

T h e r m i s t o r -
C o p p e r T u b e
P l a s t i c
C o n t a i n e r
I n s u l a t i n g
C h a m b e r
^
C e m e n t P.aste
M e r c u r y
R e f e r e n c
T h e r m i s t o
S a m p l e
T h e r m i s t o r
V o l t a g e
S o u r c e
Fi gur e 2 . 2 . 1 Temperat ure Evol ut i on Devi ce,
ro
24
branches of the Wheatstone bridge ci r cui t t o which the t hermi st ors
are connected. This vol t age di fference i s fed i nt o a s t r i p chart
r ecor der . Before the t es t i s run the vol t age di f f er ences corresponding
t o speci fi ed temperature di fferences are cal i br at ed. The cal i br at i on
l i ne for the t hermi st ors and Wheatstone bri dge used in our experiments
i s given in Fi gure. 2. 2. 2. The time needed for t r ansf er r i ng the paste
from the mixing bowl i nt o the pl as t i c cont ai ner and i nt o the temper-
at ure evol ut i on device was about 3 mi nut es; thus the record of
temperature begins at approximately 5 minutes af t er water i s added to
the cement. In t hi s apparatus temperature i ncr eases are i nt erpret ed as
a consequence of net exothermic r eact i ons in the hydrat i ng cement past e;
temperature decreases are at t r i but ed t o the imperfect i s ol at i on, the
system being only quasi - adi abat i c. Time i nt er val s with approximately
const ant temperature were considered as t i mes when very slow heat
evolving r eact i ons go on, and the amount of heat rel eased i s compen-
sated by approximately the. same amount of heat escaping through the
heat leakage of the system.
2. 2. 5 Expressing of Pore Sol ut i ons
Two methods were used for expressi ng the l i qui d phase from
hydrat i ng cement. For hydrat i on peri ods l es s than the time of the
i n i t i a l set a Mi l l i pore pressure f i l t e r i ng system was used. The
source of pressure was ni t rogen gas from a cyl i nder , regul at ed t o a
pressure of 15 P. S. I . Mi l l i pore f i l t e r s of 0.8 ym pore diameter
and 47 mm over al l diameter were used. A diagram of the set -up i s
shown in Figure 2 . 2 . 3 . This method was preferred for expressi ng the
l i qui d phase in the ear l y stages of cement hydrat i on because i t i s
r**>
O
25 -
20 -
15 -
10 -
0
1 I I
0 20 40 60 80 100
VOLTAGE CmV:>
Figure 2. 2. 2 Cal i br at i on Line for Temperature Evolution. t o
26
N
2Cg)
Paste
F\Iter membrane
Recep t or v i al
Figure 2. 2. 3 Mi l l i pore Pressure Fi l t er i ng System.
(
27
quick, and the exact age of the paste at the moment of expression can
be more pr eci sel y estimated than with hi gh-pressure method.
The past es t hat reached set were subjected t o high pressures from
a hydraul i c loading machine t o express the pore sol ut i on. The
apparatus and procedure were described by Barneyback and Diamond ( 65) .
The pore sol ut i on expressi on device consi st s of a cyl i ndr i cal
s t eel die with a concent ri c bore for the i nser t i on of a s t eel pi st on.
This r es t s on top of a s t e e l pl at en provided with a ci r cul ar col l ect i ng
groove in i t s upper surface so as t o col l ect and di r ect the pore
sol ut i on through a fl ui d dr ai n channel t o a col l ect i ng syri nge. Heavy
pl as t i c tubing i s used as a connection between the pl at en and the
syri nge. Figure 2.2.4 shows an i somet ri c hal f sect i on of t hi s
apparat us. Before each use a l l the surfaces of the apparatus were
cleaned with et hanol and dr i ed. A coat i ng of film-bonding grade
fluorocarbon was sprayed on i nt er act i ng sur f aces. The die was placed
on the center of pl at en and the cement paste recovered from the pl a s t i c
cont ai ner was placed in the por e. A t i ght l y f i t t i ng t efl on di sc was
positioned over the sample and the pi st on introduced i nt o the bore
above i t . The apparatus was then centered under the loading pl at e
of a Forney t est i ng machine (Model No. FT 40DR). The pl as t i c tubing
was i nsert ed i nt o the dr ai n channel and a syringe attached t o i t . The
load was slowly applied u n t i l the pore sol ut i on was obtained. ,200,000
lbs was the l i mi t i ng load for safet y r easons.
Because no sudden changes in the l i qui d phase composition were
detected on switching from one method of expression t o another, we
considered t hat the r e s ul t s are not influenced by t he method of
expressi on.
28
PISTON
ASSEMBLY
DIE BODY
Figure 2.2.4 Isometric Hal f-Sect i on of the Pore Solution
Expression Apparat us.
29
2. 2. 6. Non-Evaporable Water Determinations
After the expressi on of the pore sol ut i on a port i on of the
compressed or f i l t er ed paste was immediately immersed in acetone t o
stop the hydration pr ocess. The sample was then l ef t in the oven t o
dry overnight at 105 C. Approximately 5g port i on of the oven dri ed
mat eri al were weighed in porcel ai n cr uci bl es and placed in a muffle
furnace overnight at 1050 C. The weight di fference due t o the muffle
furnace treatment r epr esent s the t ot a l l oss of i gni t i on, which af t er
subt ract i ng the l oss of i gni t i on of the cement al one, provides a
measure of the amount of non-evaporable wat er. The non-evaporable
water r epr esent s t hat par t of the or i gi nal water added t o the cement
t hat can not be removed from the cement paste by oven dryi ng, i . e . , the
"bound wat er". If measured at di f f er ent times of hydrat i on t hi s
quant i t y can be used as a measure for the degree of hydrat i on.
Since the specimens were seal ed, the di fference between the
or i gi nal water content and the bound water content can serve as a
measure of the "f r ee" or "sol vent " water remaining in the paste at the
time hydrat i on was stopped.
2 . 2 . 7 . Chemical Anal ys i s of Pore Sol ut i ons
In s p i t e of t he l a r ge number of el ement s t h a t can be de t e c t e d in
por t l and cement , not many ar e found i n t he pore s ol ut i on i n a ppr e c i a bl e
c onc e nt r a t i on dur i ng cement h y d r a t i o n . In our exper i ment s onl y t he
+ + 2+ 2 - - 3+
f ol l owi ng i ons were d e t e c t e d : K , Na , Ca , SO, , OH , and Fe
I r on was de t e c t e d onl y i n a few of t he s o l u t i o n s expr essed wi t hi n t he
f i r s t day of h y d r a t i o n , and was al ways at c onc e nt r a t i on t oo low t o
be qua nt i f i e d wi t h our equi pment (<10 m). Aluminum and magnesium
30
were never det ect ed despi t e repeated ef f or t s to do so.
Because of presumed i ns t a bi l i t y of the pore sol ut i ons from cement
past e, the det ermi nat i on of the hydroxyl ion concentration was made in
each case immediately af t er obtaining the pore sol ut i on. Other por t i ons
of the pore sol ut i ons were immediately di l ut ed 100 tiroes t o avoid the
pr eci pi t at i on of calcium and sul fat e i ons.
To determine the hydroxyl ion concent rat i on, 1 ml al i quot s of
the pore sol ut i on were t i t r a t e d with HC1 (0.05N) using methyl red as
i ndi cat or . The HC1 was standardized agai nst 0.2N NaC0.
For the remaining det ermi nat i ons a 1 ml al i quot of the pore
sol ut i on was placed in a 100 ml volumetric fl ask. Two mi l l i l i t e r s
of a 50,000 ug/ml La(N0 ) sol ut i on were added to the fl ask, followed
by 2 drops of concent rat ed HC 1. The cont ent s were then di l ut ed t o the
mark with deionized water and shaken. The hundred-fold di l ut ed pore
sol ut i on so prepared was the stock sol ut i on for a l l other det er mi nat i ons,
which were car r i ed out with a Perkin-Elmer 503 Atomic Absorption
Spectrophotometer.
The det ermi nat i on of potassium and sodium was done di r e c t l y from
the stock sol ut i on in the flame emission mode of the spect rophot omet er.
A lean ai r - acet yl ene mix was used as f uel .
The working condi t i ons fro potassium were: wavelength - 383:5 ym;
s l i t - 4 ; f i l t e r ; chopper; el evat i on of the burner - 2.0 mm. The working
condi t i ons for sodium were: wavelength - 294.7ym; s l i t - 3 ; chopper;
el evat i on of the burner - 2.0 mm.
Calcium was determined di r e c t l y from the stock sol ut i on in the
atomic absorption mode of the spectrophotometer. The condi t i ons set
for t hi s det ermi nat i on were: wavelength - 422.7 pm; s l i t - 4 ;
31
el evat i on of the burner - 4. 8 mm. A lean N0 -acet yl ene mix was used
as fue1.
The sul fat e was determined i ndi r e c t l y. The following method was
used: To 40 ml stock pore s ol ut i on, 40 ml of a 200 yg/ml BaCl
sol ut i on, 4 ml of a 5% KC1 s ol ut i on, and four drops of concentrated
HC1 were added. This was then di l ut ed t o 100 ml, shaken vigorously
and aft er t hat allowed t o r es t over ni ght . Sulfate was then quantified
by determining the excess barium af t er the r eact i on t hat had pr eci pi -
t at ed sul fat e as BaSO.. Barium was determined in the flame emission
4
mode. The condi t i ons were: wavelength - 277ym; s l i t - 2 ; chopper;
el evat i on of the burner - 2 mm. A r i ch N0 -acet yl ene flame was used.
2. 2. 8 X-Ray Di ffract i on
The X-ray di f f r act i on pat t er ns of the cement past es were obtained
using a Siemens D-500 X-ray di f f r act omet er . The r adi at i on used was
copper K r adi at i on. The vol t age and amperage were ,continuously set
at 50 kV and 20 mA r es pect i vel y. The s l i t s going from the X-ray tube
t o the det ect or were arranged in the following manner: 1 ; 1 ; ];
0.15 ; 0.15 . All samples were run at an angular speed of 2 20 per
minute. The angular range was from 5 t o 60 20. The recorder speed
was set at 2 cm per minute so t hat 1 20 corresponded t o 1 cm on the
char t . The time constant used was 2 seconds or 3 seconds depending
on the r esol ut i on desi r ed. The preparat i on of the sample was not
convent i onal .
The usual way of preparing cement past es samples for X-ray
examination in t hi s l aborat ory i s t o immerse the cement paste i nt o
acetone af t er the desi red time of hydrat i on in order t o stop the
32
hydrat i on. After the immersion the sample i s dr i ed, ground, and
sieved onto a rough-t ext ured piece of paper in the sample arrangement.
The paper i s subsequently removed and randomly ori ent ed pa r t i c l e s on
the sample' s surface are obt ai ned.
In the present work there was a par t i cul ar i nt er es t in studying
calcium sul fat e di s s ol ut i on, e t t r i ngi t e formation and calcium hydroxide
pr eci pi t at i on. The usual sample preparat i on procedures might i nt e r -
fere with each of these f eat ur es, and i t was decided t o get X-ray
pat t er ns of wet cement pas t es .
X-ray di f f r act i on of the surfaces of wet cement past es i s accom-
panied by vari ous experimental di f f i c ul t i e s , stemming from the
presence of a l i qui d film on the surface of the cement paste at ear l y
stages of hydrat i on and especi al l y during the bleeding peri od. With a
liquid film on the surface the r esol ut i on and the qual i t y of the X-ray
pat t er n i s s i gni f i cant l y worse than i t would be i f the sample were
dr y. However, drying of the surface was not desi r ed, t o avoid possi bl e
pr eci pi t at i on or c r ys t a l l i z a t i on on the surface t hat would not have
occurred at t hat time in the bulk cement past e. In the time s er i es of
the di f f r act i on pa t t e r ns , a fresh sample was taken from the bulk cement
paste for each run.
Another problem associ at ed with t hi s technique was the s peci f i -
cat i on of hydrat i on t i me. While the X-ray di f f r act i on pat t er n was
being run, the hydrat i on was continuing t o take place in the sample.
Since some 30 minutes was needed t o complete one X-ray pat t er n, the
end of the pat t er n (around 60 29) showed the pat t er n of a sample
t hat had been necessar i l y hydrated for 30 minutes longer than the
beginning of the pa t t e r n. While for older cement past es hal f an hour
33
does net make a si gni f i cant di f f er ence, at the earl y st ages of hydrat i on
such a di f f er ence can be s i gni f i cant , especi al l y where rapid changes
might be expect ed, such as at s e t t i ng. Fort unat el y, for our purposes
t hi s time speci f i cat i on problem was not too ser i ous, because the
compounds t hat we were i nt er est ed in (gypsum, e t t r i n g i t e , and calcium
hydroxide) a l l have di agnost i c peaks in a low range of 20 val ues , t hat
i s , between 5 and 20 20.
Fi nal l y, a major problem i s t hat in handling wet cement past e
atmospheric carbonat i on can occur. IR spectroscopy, which i s a very
sensi t i ve method for det ect i ng carbonat es, shows a sl i ght carbonat i on
within a few minutes of hydrat i on when fresh cement past es are
exposed. X-ray di f f r act i on i s not so sensi t i ve t o carbonation and no
changes in X-ray pat t er ns were usual l y observed when wet cement past e
was exposed t o the ai r for time peri ods of the order of 30 mi nut es.
However, even a small quant i t y of carbonat es, t hat might be s t i l l
undetected by X-ray di f f r act i on, could have an accel er at i ng ef f ect on
cement hydr at i on. By t aki ng a fresh sample from the sealed bulk cement
paste for each run t hi s problem was minimized.
2. 2. 9. Semi quant i t at i ve Analysis by Energy Dispersive X-Ray Anal ysi s
This method was used only t o determine whether t here i s i ron
present in the e t t r i n g i t e cr ys t al s which are formed in cement past e
during the hydrat i on pr ocess. This anal ysi s was obtained using an
ISI Super 111A scanning el ect r on microscope (SEM) equipped with an
EEDS Energy Di spersi ve X-Ray Analyzer (E. G. and G. Ortec Co. , I n c . ) .
An accel er at i ng vol t age of 30 kV was used in the SEM. In t hese
det ermi nat i ons a small piece of dry cement paste (si ze approximately
a quart er of an inch) was glued onto an SEM sample stub with s i l ver
paste and l i ght l y coated with a gold-palladium al l oy using a s put t er -
type coat er (Technics Hummer I ) . The coating was carri ed out for 2
minutes at 150 mi l l i t or r , with the current set at 10 amp. and the
vol t age at 1IV.
Well developed e t t r i ngi t e cr ys t al s were chosen for anal ysi s.
Spot analyses were carri ed out on a number of di f f er ent e t t r i ngi t e
c r ys t a l s , and on several spots on the l ar ger c r ys t a l s .
35
CHAPTER THREE - RESULTS AND DISCUSSION
3 . 1 . I nt r oduc t or y Remarks
The bul k of t he e xpe r i me nt a l da t a on t he components of t he pore
s ol ut i ons of por t l a nd cement pa s t e s i n t he l i t e r a t u r e da t e from pe r i ods
p r i o r t o t he devel opment and a p p l i c a t i o n of hi gh pr e s s ur e por e s o l u t i o n
e xpr e s s i on d e v i c e s . In consequence, such da t a are l i mi t e d t o t he per i od
bef or e s et oc c ur s , at l e a s t for normal wat er : cement r a t i o p a s t e s .
High pr es s ur e pore s o l u t i o n expr es s i on devi ces per mi t t he
c ont i nua t i on of such s t u d i e s t o an i n d e f i n i t e per i od a f t e r s e t . However,
most of t he a p p l i c a t i o n s of such devi ces so f ar have been t oward s t u d i e s
aimed at c l a r i f y i n g a l k a l i - a g g r e g a t e r e a c t i o n , s t e e l c or r os i on in con-
c r e t e , or ot her l ong- t er m e f f e c t s , and d e t a i l e d s t u d i e s of changes i n
pore s o l u t i o n s at c l o s e l y spaced i n t e r v a l s e a r l y in t he hydr a t i on
pr oces s have not pr e vi ous l y been r e p o r t e d .
The focus of t h i s work was t o c a r r y out such s t u d i e s i n a v a r i e t y
of hydr a t i ng cement syst ems over t he hydr at i on per i od of t he f i r s t day
or so as t o pr ovi de new i n s i g h t and i nf or mat i on on t he s o l i d - l i q u i d
r e a c t i o n s t aki ng p l a c e .
3 . 2 . De s c r i p t i o n of Systems under St udy
The f ol l owi ng cement pa s t e s have been s t udi e d:
1. Or di nar y por t l a nd cement (Type I ) ; w:c = 0. 50
2 . Or di nar y por t l a nd cement (Type I ) ; w:c = 1.0C
36
3 . High al kal i cement (Type I ) ; w:c = 0.50
4 . Finely-ground cl i nker (Type I ) ; w:c - 0.50
5. Finely-ground cl i nker (Type I ) + 5% gypsum; w:c = 0.50
6. Finely-ground cl i nker (Type I ) + 2% K-SO,; w:c = 0.50
7. Finely-ground cl i nker (Type I) + 10% ypsum + 2% K-SO ; w:c = 0.50
Relevant pr oper t i es of the cements are given in .Table 2 . 1. 1. The
Type I finely ground cl i nker i s from a batch prepared for low-porosity
cement formulation, but does not contain the l i gnosul fonat e and al kal i
carbonate admixtures necessary for low-porosity cement funct i ons. In
cal cul at i ng water:cement r a t i os a l l of the solid components above are
considered part of the cement.
3.3 Temperature Evolution and Set t i ng Time
As mentioned in Chapter Two, Part Two, where experimental methods
are di scussed, i nst ead of heat evol ut i on curves the temperature changes
of the hydrated systems were measured. The port i ons of the temperature
evol ut i on curves t hat show an increase of temperature are i nt erpret ed as
time i nt er val s in the process of hydration during which heat i s produced
the port i ons of the curve where temperature decreases occur are i nt er -
preted as periods duri ng which heat leakage from the system exceeds the
heat being generated by the hydrat i on processes. Figures 3. 3. 1 - 3.3.7
show the temperature evol ut i on curves for the systems under study. The
temperature measurements were cont i nuous; the bars i ndi cat e when pore
sol ut i ons were expressed. The general shapes of a l l the curves are
si mi l ar . The temperature r i s e s immediately af t er mixing cement with
wat er, and then remains approximately constant for a period of time
which i s char act er i s t i c for each system. This time period of so-cal l ed
t
0
20
15
10
5
a
T
-
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i
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s
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T
1 ( 1 1 1 1 1 1 1
0 8 12 16
20 24
TI ME, HOURS
Figure 3. 3. 1 Temperature Evolution Curve for Ordinary Portland Cement Paste (w:c=0.50),
a
0
%s
UJ
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X
o
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20
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12 16
20 24
TI ME, HOURS
Figure 3.3.2 Temperature Evolution Curve for Ordinary Portland Cement Paste (w:c=1.00).
w
CO
Tt-
39
CJ
_ <o
CJ
CO
CD
LO
CO CO
LO
CJ
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i 1 1 r 1 r | 1 1 i j-
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t 1
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-
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8 12 16 20
24 28
TI ME, HOURS
Figure 3.3.4 Temperature Evolution Curve for Finely-Ground Clinker (w:c=0.50).
o
" 1 ' 1 1 \""T
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i
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I I I ,
', ' 1 '
i i i i i i r- i i i
" J ^ ^
i
1
i
m
I
}


i
/

/
{
< i i


\

\
\
\
\
\
V -
V
1 1 1 t 1 I 1 1 1 1
0 4 8 12 16 20 24
TIME, HOURS
3 . 5 Temperat ure Evol ut i on Curve f or Fi nel y-Ground Cl i nker Pas t e With 5% Gypsum ( w: c=0. 50) . f]
Tiir~iiiiiriiiiii:iiii i i
Si
/
\
- J
f
^*
/ "
t 1 f t t . 1 I T I I t f I | I I t 1 I . t L
0
8 12 16 20 24
TIME, HOURS
3. 6 Temperat ure Evol ut i on Curve for Fi nel y-Ground Cl i nker Past e With 2% K30 ( w: c=0. 50) ,
Fi gur e 3 . 3 . 7
Temperat ure Evol ut i on Curve for Fi nel y-Ground Cl i nker
Past e wi t h 10% Gypsum and 2% KS0 ( w: c=0. 50) .
40
35 h-
30
25
20
15 [
10
1 1 1
5
0
I I
T i r
T r
> *
....^il'S-I"
I I I I . . . I
I 1 I
Tr~r
T f
r
* - . ,
**-.*
J _ I L
j l
0 4 8 12
TIME, HOURS
16
23 24
Figure 3. 3. 7
45
"dormancy" can be very di fferent with di f f er ent cement systems: The
shor t est period detected was pr act i cal l y zero, and the longest period
about 10 hours. The speci fi c length of dormancy depends on many f act or s:
the type of cement, the water t o cement r a t i o and the volume of addi t i ves
are j us t a few. After the period of dormancy i s completed, the temper-
ature i ncreases again, and the i ncrease i s maintained for some hours,
const i t ut i ng the major ear l y hydrat i on per i od. I t i s known t hat the
onset of the r i se cor r el at es with an i nt ensi ve Ca(0H) pr eci pi t at i on
and with mechanical changes in the cement pas t e. I n i t i a l s e t , as
defined by ASTM C-191, occurs usual l y near the beginning of the sl ope,
and f i nal set often occurs close t o the time of the maximum t emperat ure,
Table 3. 3. 1 gives val ues for the i n i t i a l and f i nal set for our systems.
As wi l l be seen from the diagram for hydrat i on of the ordinary cement
at water:cement r a t i o 1.00 the i n i t i a l and f i nal set do not always
have t o have the same r el at i on with regard t o the temperature evol ut i on,
and can sometimes be delayed. The i n i t i a l set in t hi s case i s close
to the time of the maximum temperature r i s e .
The posi t i on of maximum temperature peak, i t s hei ght , and i t s
broadness vary from one system t o anot her. I t i s observed t hat at
constant water:cement r a t i o the maximum temperature developed depends a
great deal on the amount of al kal i es and gypsum in the cement as can be
seen in Table 3 . 3 . 2. For example, the finely-ground cl i nker Hydrated
at watencement r a t i o 0.50 el evat es the temperature only 12.5 C. If
5% gypsum i s added, the temperature i ncr eases t o 23.5 C at maximum. A
2% addi t i on of K.SO t o the finely-ground cl i nker i ncreases the maximum
temperature at 21 C, about the same val ue. If both gypsum (at 10%) and
2% K
2
S0, are added to the finely-ground cl i nker at the same time, the
temperature r i se reaches 35 C, a very much enhanced val ue.
46
Tabl e 3 . 3 . 1
Time of Se t t i n g of Cement Pa s t e s
Cement Past e
Or di nar y por t l a nd cement , w:c 0. 50
Or di nar y por t l a nd cement , w:c 1.00
High a l k a l i cement , w:c 0. 50
Fi nel y- gr ound c l i n k e r , w:c 0. 50
Fi ne l y ground c l i n k e r + 5% gypsum,
w:c 0. 50
Fi nel y- gr ound c l i n k e r + 2% K. SO, ,
w:c 0. 50
Fi nel y- gr ound c l i n k e r + 10% gypsum
+ 2% K
2
S0
4
, w:c 0. 50
Initial Set
3 hrs 30 min
6 hrs 30 min
4 hrs 20 min
10 hrs
10 hrs
3 hrs
7 hrs 15 min
Final Set
5 hrs 10 min
10 hrs 30 min
4 hrs 50 min
11 hrs 40 min
10 hrs 30 min
3 hrs 45 min
8 hrs 10 min
47
Tabl e 3 . 3 . 2
Re l a t i ons Between Maximum Temperat ure Ri se and Al ka l i and SO,
Cont ent s of Cement Systems ( a l l at w:c 0 . 5 0 ) .
At Al ka l i SO,
Cement Past e
Or di nar y por t l and cement
High a l k a l i cement
Fi nel y- gr ound c l i n k e r
Fi nel y- gr ound c l i nke r
+ 5%" gypsum
Fi nel y- gr ound c l i n k e r
+ 2% KS0.
2 4
Fi nel y- gr ound c l i n k e r
+ 10% gypsum + 2% K SO
Maximum Cont ent , Cont ent ,
o
C ' % %
22
31
12.5
0. 45
0. 90
0. 18
2. 96
2. 70
0. 13
23.5
21
35
0. 98
0. 90
0. 90
2.45
2.42
4.74
48
3 . 4. Non-Evaporable Water
In Table 3. 4. 1 are given the dat a for non-evaporable water for the
systems under study during the f i r s t 24 hours of hydr at i on. The dat a
are pl ot t ed vs . time in Fi g. 3 . 4 . 1.
The observat i ons made can be summarized as fol l ows:
1. The values for non-evaporable water are very low during the
f i r s t hours of hydration and they do not exceed 2% by the time of
s et t i ng for any of the systems st udi ed. However, the hydration r at e
i ncreases af t er the f i nal set and the non-evaporable water cont ent s
general l y increase t o up t o 8 or 9% by the end of the f i r s t day of
hydrat i on. The finely-ground cl i nker sample, however, i s an except i on.
For t hi s mat er i al the increase i s much more modest than in the other
systems st udi ed, and af t er the f i r s t day the measured content of
non-evaporable water i s only about 4%.
2. I t wi l l be shown in Section 3.6 t hat af t er set i ncreasi ng
amounts of pr eci pi t at ed C.a(OH) are detected in X-ray pat t er ns of the
cement pas t es . The i ncreasi ng percentages of non-evaporable water
found af t er set cor r el at e ni cel y with the i ncreasi ng content of
Ca(OH). as indicated by the increasing i nt e ns i t i e s of the di f f r act i on
peak at 18 20 (Cu r a di a t i on) .
3 . Similar val ues for non-evaporable water content are found at
the same ages for the ordinary portland cement hydrated at two very
di f f er ent water:cement r a t i o s , 0.50 and 1.0. This i ndi cat es t hat the
r at e of development of non-evaporable water i s independent of water:
cement r a t i o , at l east during the f i r s t day of hydr at i on.
4 . The 5% addi t i on of gypsum, the 2% addi t i on of KSC,, and the
combined addi t i on of 10% gypsum and 2% K.SO. a l l i ncrease the non-
a:
ui
<
UJ
_J
<
O
CL
<
>
UJ
o
10
8
6
4 -
0
T i r
"T THr
TT
o
e
A
SO,
w: c=0. 50
w: c=0. 50
Fi ne l y ground c l i n k e r + 10% Gypsum + 2% KSu ,
Fi ne l y ground c l i n k e r + 2% KS0 ,
F i n e l y ground c l i n k e r + 5% Gypsum,
Fi ne l y ground c l i n k e r , w: c=0. 50
Or di nar y por t l and cement , w: c=0. 50
Or di nar y por t l and cement , w: c=1. 00
High a l k a l i cement , w: c=0. 50
w
c= 0.50
ir i r
J U_L
I ' l l l ) i i
0 8
12 16
20 24
TI ME, HOURS
Fi gur e 3 . 4 . 1 Non-Evaporable Water v s . Time for
Seven Di f f er ent Cement Pa s t e s .
c~
Table 3 . 4 . 1
Non-Evaporable Water Cont ent , %
Time,
Hr s .
1
2
4
6
8
12
18
24
Or di nar y
Por t l and
Cement
(w:c 0. 50)
1.7
1.8
2. 5
3. 4
4 . 2
5. 7
8. 2
8. 9
Or di nar y
Por t l and
Cement
(w:c 1.0)
1.6
1.5
2. 2
3 . 1
4 . 2
5. 8
8. 2
9. 0
Hi gh-
Al ka l i
Cement
(w:c 0. 5)
0. 6
0. 5
0. 9
1.6
4 . 0
5. 8
7.4
8. 0
Fi n e l y -
Ground
Cement
(w:c 0. 50)
1.2
1.4
1.1
1.5
1.6
1.9
3 . 2
3 . 8
Fi n e l y -
Ground
Cl i nker
+ 5%
Gypsum
(w:c 0. 50)
0. 9
1.1
1.1
1.3
1.6
2. 2
7. 5
8. 3
Fi ne l y-
Ground
Cl i nker
+ 2%
K
2
S0
4
(w. c 0. 50)
1.0
1.1
1.7
1.4
1.9
4. 4
6. 9
8. 3
Fi ne l y-
Ground
Cl i nker
+10% Gypsum
and 2%
K
2
S0
4
(w: c 0. 5)
1.4
1.5
1.4
1.7
1.7
4 . 5
7. 8
8. 6
O
51
evaporable water content present af t er one day of hydration by a
factor of 2 or more. However, i t i s i nt er est i ng to note t hat no
increase of non-evaporable water was observed during the f i r s t hal f
of the day.
This observat i on and the previ ousl y mentioned cor r el at i on between
non-evaporable water content and pr eci pi t at ed Ca(OH). suggest t hat the
non-evaporable water contents.measured in these st ages of hydrat i on are
strongly influenced by the amount of Ca(OH) act ual l y pr eci pi t at ed,
rat her than being pr eci sel y proport i onal i ndi cat or s of the degree of
hydration of the cement compounds.
3 . 5 . Liquid Phase Examination
As previ ousl y mentioned, t here i s a r el at i onshi p between the
heat evol ut i on pat t er n and the pat t er n of mechanical changes in cement
past e.
In the present work we are s peci f i cal l y concerned with possi bl e
cor r el at i ons between the mechanical changes, the heat evol ut i on, and
the concent rat i on changes in the l i qui d phase of the hydrated cement.
Thus a port i on of the l i qui d phase was expressed from the cement paste
frequently enough t o follow the changes in the concent rat i on of
di f f er ent ions over the f i r s t 24 hours. The numerical r e s ul t s of the
analyses of t hese expressed sol ut i ons are given in Tables 3. 5. 1 t o
3.5.7 and the gr aphi cal r el at i onshi ps between concent rat i ons and time
are shown in Fi gures 3 . 5. 1 t o 3 . 5. 7. Except for iron i ons, a l l ions
detected have been measured. These include K , Na , Ca , SO, , and
0H~.
52
The i ron concent rat i on was not determined quant i t at i vel y, since i t
was too low t o be determined with the methods and equipment avai l abl e .
However, an est i mat i on was made and the i n i t i a l concent rat i ons of iron
ions were about 1 x 10 M. The iron was associ at ed with a yellow col or
in the pore sol ut i ons in which i t was pr esent . A gradual fading of t hi s
yellow color with time of hydration occurred and the col or was l ost
within the f i r s t 24 hours of hydrat i on.
I t i s of i nt er es t t o mention here, and of importance for the l at er
di scussi on, t hat aluminum ions were never det ect ed in the pore sol ut i ons
of any of the hydrated cement pas t es .
An experimental di f f i cul t y encountered at the beginning in f i l t e r -
ing cement past es during the f i r s t few hours of hydrat i on (before set )
and which led us t o an unexpected fi ndi ng, i s worth mentioning her e.
The problem was t hat the sol ut i ons expressed from the ear l y aged cement
past es and f i l t er ed through nominally 3 ympore diameter Nuclepore
f i l t e r s were cloudy af t er f i l t r a t i o n . I t was or i gi nal l y thought t hat
the sol ut i ons were unst abl e and t hat rapid pr eci pi t at i on was taking
place af t er the f i l t r a t i o n . This seemed especi al l y l i kel y since the
concent rat i ons of calcium and of sul fat e ions were very high in most
cases in t hese ear l y pore s ol ut i ons . However, i t was found t hat f i l t e r -
ing these cement paste pore sol ut i ons with a more r e s t r i c t i v e membrane
f i l t e r (Mi l l i pore f i l t e r s of nominal 0.22 ym pore di amet er) r esul t ed
in cl ear s ol ut i ons . This i ndi cat ed t hat the sol ut i ons themselves were
s t a bl e , but t hat some very fine sol i d substance was suspended in them
from the very beginning of hydr at i on.
A double f i l t e r i ng technique was used t o obt ai n enough of t hi s
substance t o examine by X-ray di f f r act i on and i nfrared spect roscopy.
53
The pore sol ut i on was f i r s t f i l t er ed using the 3 ym pore diameter
f i l t e r , and the cloudy sol ut i on again f i l t er ed on a 0.22 ym pore
diameter f i l t e r , with the sol i d mat er i al recovered. This was carri ed
out for pore sol ut i ons expressed from past es of both the ordinary
portland cement and the finely-ground cl i nker s t ar t i ng at 1 hour of
hydrat i on. The substance proved to be pure calcium hydroxide. Fi g.
3. 5. 8 shows one of the X-ray di f f r act i on pat t er ns obtained; the X-ray
peaks are quite sharp, i ndi cat i ng t hat t hi s fine suspended calcium
hydroxide i s well c r ys t a l l i z e d.
The ionic concent r at i ons given in Tables 3 . 5. 1 t o 3. 5. 7 and shown
in the corresponding f i gur es , are experimentally-determined concentra-
t i ons act ual l y pr esent , without adjustments for progressive reduction
of water content due t o cement hydr at i on. However, non-evaporable
water contents i ndi cat i ng the amount of water progressi vel y bound t o
hydration product were det ermi ned, and are given in Table 3 . 4 . 1.
From the concent rat i on vs . time curves of Fi gs. 3. 5. 1 t o 3 . 5. 7, i t
i s easy to see t hat the general shape of al kal i ion concent rat i on curves
and of calcium ion concent r at i on curves are very much the same for a l l
the systems t hat were s t udi ed. Most of the al kal i es of the cement are
rel eased i nt o sol ut i on very r api dl y, wi t hi n minutes and perhaps seconds.
Subsequently, a more or l ess progressi ve increase i s observed during the
f i r s t day of hydrat i on.
The calcium ion concent r at i on al so bui l ds up rapi dl y at f i r s t .
However, i t sooner or l a t e r reaches a maximum value and then s t a r t s to
decrease. I t i s important t o note t hat the maximum had been always
reached much sooner than the s t a r t of s e t t i ng. For example, the
2+
maximum Ca concent rat i on (of about 0.06N) for ordinary portland
54
Tabl e 3 . 5 . 1
Sol ut i on Concent r at i ons i n Or di nar y Por t l and
Cement Pas t e (w:c 0. 50)
Time ,
Hours
1.05
1.62
2. 18
2. 73
3. 16
3 . 50
4 . 00
5. 43
6
12
15
18
21
24
Ca
2 +
(N)
0. 0688
0. 0692
0. 0680
0. 0652
0. 0638
0. 0610
0. 0628
0. 0592
0. 0570
0. 0087
0. 0058
0. 0057
0. 0051
0. 0050
K
+
(N)
0. 265
0.264
0. 275
0. 265
0. 265
0. 265
0. 267
0.274
0.284
0. 300
0. 3 05
0. 315
0.324
0. 340
Na
+
(N)
0. 0285
0. 0285
0. 0297
0.0284
0. 0282
0. 0292
0. 0292
0. 0300
0. 0413
0. 0435
0. 0435
0. 0435
0. 0457
0. 0457
OH (N)
0. 148
0. 148
0. 150
0. 150
0. 155
0. 149
0. 148
0. 148
0. 143
0. 245
0. 285
0. 3 23
0.354
0. 3 90
S0
4
2 _
( N)
0. 166
* 0. 166
0. 175
0. 166
0. 173
0. 176
0. 178
0.
0. 203
0. 145
0. 093
0. 047
0. 000
0. 000
> -
H
- J
<
Q
O
H
<
h-
Z
UJ
o
z:
o
o
0 . 4
0 . 3
0 . 2
0. 1 -
0
T~Tr
mi i r l KLW.11
0 8 12 16 20 24
TIME, HOURS
Figure 3.5.1 Concentration vs. Time for K
+
, Na
+
, Ca
2+
, 0H~, and S O
2
~ Ions In Pore
Solutions of Ordinary Portland Cement Paste, w:c=0.50
56
Tabl e 3 . 5. 2
Sol ut i on Concent r at i ons i n Ordi nary Por t l a nd
Cement Pas t e (w:c 1.00)
Ti me,
Hours
0. 2
0. 5
1
1.4
2. 3
3. 4
4. 4
5. 5
6. 5
9. 5
15. 2
24
Ca
2 +
(N)
0. 523
0. 0511
0. 0568
0. 0583
0. 0606
0. 0578
0. 0568
0.054 2
0. 0529
0. 4 16
0. 0207
0. 0106
K
+
(N)
0. 147
0. 145
0. 143
0.14 3
0.14 1
0. 142
0. 143
0.144
0. 143
0. 147
0. 148
0.16 1
Na
+
(N)
0.0167
0. 0160
0. 0158
0.016
0. 016
0. 0165
0.0174
0. 0173
0. 0175
0. 0182
0. 0186
0. 0200
0H~(N)
0. 084'
0. 095
0. 108
0. 111
0. 113
0. 114
0. 110
0. 108
0. 107
0. 112
0. 13 7
0. 190
S0
4
2
"( N)
0. 169
0. 149
0. 123
0. 123
0. 100
0. 104
0. 106
0. 104
0. 106
0. 091
0. 048
0. 000
Figure 3.5.2 Concentration vs. Time for K , Na , Ca , OH , and SO Ions
In Pore Solutions of Ordinary Portland Cement Paste,
w:c=1.00.
58
4-
C\f
CM
CM


LO
rr-

<S>

CO
CM
CO
Q
LO G>
CO
o
X
Ld
H
0)
M
3
00
H
AlI~WWaON ' N0IJLVyiN30N03
59
Tabl e 3 . 5 . 3
Sol ut i on Conc e nt r a t i ons i n High Al ka l i
Por t l a nd Cement Pas t e (w: c 0. 50)
Time,
Hours
0. 3
1
2
3. 16
4 . 5
6. 6
12
18
24
Ca
2+
(N)
0. 0399
0.04 16
0. 0420
0.0407
0. 0392
0. 0268
0. 0142
0.0106
0. 0050
K
+
(N)
0. 4 23
0. 43 60
0. 440
0. 44 1
0. 442
0. 486
0. 502
0. 514
0. 522
Na
+
(N)
0. 130
0. 13 0
0. 150
0. 150
0. 150
0. 160
0. 160
0. 173
0. 203
0H~(N)
0. 142
0. 174
0. 176
0.176
0. 165
0. 217
0. 308
0. 460
0. 605
S0
4
2
"(N)
0. 402
0. 396
0.404
0. 390
0.394
0. 367
0. 271
0. 163
0. 065
(
o
Fi gur e 3 . 5 . 3 Concent r at i on v s . Time for K , Na , Ca , OH , and SO^
I ons In Pore Sol ut i ons of High Al ka l i Por t l and Cement
Pa s t e , w: c=0. 50.
61
CO
UL
ZD
O
X
UJ
2:
H
0)
u
3
00
H
(0


U>

G>
^
a

CO


CM


Q

AlIlVWyON 'N0IlVaiN30N03
Tabl e 3 . 5. 4
Sol ut i on Concent r at i on i n Fi nel y- Gr ound
Cl i nker Pas t e* (w:c 0. 50)
Time,
Hours
0. 5
1
2
3 . 25
4
5
7
9
30.58
12. 92
15.58
24. 67
28
Ca
2 +
(N)
0.0784
0. 0736
0. 0613
0. 0600
0.0574
0.0574
0.0569
0. 0556
0. 0550
0.0534
0.0534
0. 0499
0. 0409
K
+
(N)
0. 0229
0. 0261
0. 0281
0.0284
0. 0291
0. 0291
0. 0291
0.0294
0. 0302
0. 0312
0. 0317
0. 0330
0. 0382
Na
+
0. 0025
0. 003 3
0. 0040
0. 004 2
0. 004 2
0. 0042
0. 0043
0. 0045
0. 0046
0. 0052
0. 0052
0. 0069
0. 0096
0H~
0. 0721
0. 0739
0. 0696
0. 0734
0. 0716
0. 074 1
0. 0701
0. 0664
0.0714
0. 0726
0. 0726
0.0744
0. 0771
*No gypsum was added t o t h i s ground c l i n k e r and s i nce t he SO cont ent
2- .
of the clinker was small, no analysis was made for SO, ions
+ + 2+ -
Fi gur e 3 . 5. 4 Concent r at i on v s . Time for K , Na , Ca , and OH I ons
In Pore Sol ut i ons of Fi nel y-Ground Cl i nker Pa s t e , w: c=0. 50.
64
- I
O
CO
z:
o +oo x o
H ^ Z O Q W
, :
:
l
: : -
s : -
c o
CM
CM

CM
<D
CM
CO

CO
o
X
UJ
2:
H
CD
u
3
00
CO

CD
Q
CM



(
AlIlVWyON ' N0HVyi N3 0N00
65
Table 3 . 5. 5
Sol ut i on Concentrations in Finely-Ground
Clinker Past e Containing 5% Added Gypsum (w:c 0.50)
x
'" ' 2+ + + 2-
Hours Ca (N) K (N) Na (N) OH' (N) SO, (M)
4
1
2
3
4
5 -
6
7
8
9
10
11
12
15
18
22
25
28
0. 073
0. 068
0.064
0. 069
0. 067
0. 066
0. 067
0. 065
0. 065
0. 063
0.064
0. 062
0. 053
0. 051
0. 049
0. 042
0.04 1
0. 023
0. 026
0. 026
0. 028
0. 028
0. 028
0. 029
0. 029
0. 03 0
0. 03 1
0. 03 1
0.034
0. 03 7
0. 03 7
0. 03 9
0. 03 9
0. 040
0. 003
0. 003
0. 004
0. 004
0.004
0. 004
0.004
0. 005
0. 005
0. 005
0. 005
0. 005
0. 006
0. 006
0. 007
0. 007
0. 010
0. 073
0. 073
0. 071
0. 073
0. 071
0. 072
0. 072
0. 076
0. 073
0. 075
0. 071
0. 069
0. 073
0. 091
0. 091
0. 092
0. 092
0. 021
0. 022
0. 022
0. 022
0. 022
0. 021
0. 022
0. 025
0. 025
0. 025
0. 026
0. 027
0. 026
0. 005
0. 000
0. 000
0. 000
c ^
0>
+ + 2+ -
Fi gur e 3 . 5 . 5 Concent r at i on v s . Time for K , Na , Ca , OH , and SO^
I ons i n Pore Sol ut i ons of Fi nel y-Ground Cl i nker Past e
wi t h 5% Gypsum, w: c=0. 50.
> -
H
<
SI
O
Z
o
H
<
H
UJ
o
2:
Q
O
0. 1
0. 08
0. 06 -
0. 04 -
0. 02
0
TIME, HOURS
Figure 3. 5. 5
crv
^1
Tabl e 3 . 5 . 6
Sol ut i on Concent r at i ons i n Fi nel y- Gr ound
Cl i nker Past e Cont ai ni ng 2% Added KSO (w: c 0. 50)
' ?+ + + - 7
Hours Ca (N) K (N) Na (N) OH (N) SO, (N)
4
0. 2
1.6
3. 6
6. 3
8. 0
12.0
18.3
28. 3
0. 0576
0. 0517
0.0434
0.0219
0. 010
0. 0091
0. 008
0. 005
0. 487
0. 497
0. 576
0. 577
0. 596
0. 602
0.616
0.634
0. 14 7
0. 196
0. 202
0. 203
0. 203
0. 201
0. 202
0. 202
0. 121
0. 190
0. 222
0. 321
0. 408
0.484
0. 583
0. 648
0. 402
0. 369
0. 3 42
0. 277
0.204
0. 170
0. 102
0. 017
+ + 2+ -
Fi gur e 3 . 5. 6 Concent r at i on v s . Time for K , Na , Ca , OH , and SO
I ons i n Pore Sol ut i ons of Fi nel y-Ground Cl i nker Pas t e
wi t h 2% K.SO , w: c=0. 50.
r
0.64
0.56
1 -
H
- 1
<
S
OS
O
Z
%
2
O
H
H
<
Q :
I
0.48
0.4
0.32
0.24
0. 16
0.08
I 1 I
TIME, HOURS
Figure 3. 5. 6
o
71
Tabl e 3 . 5 . 7
Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Gypsum Pas t e Cont ai ni ng
10% Added Gypsum and 2% Added K SO (w:c 0. 50)
J
-
X1
"
t i
' ?+ + + - ? -
Hours Ca (N) K (N) Na (N) OH (N) SO. (N)
0. 25
1.25
1.70
2. 25
4 . 0
6. 0
7. 25
13.5
19.6
24. 0
0. 0432
0. 0492
0.0514
0.0504
0.0514
0. 0509
0. 0509
0. 0491
0.0464
0. 0462
0. 525
0. 525
0. 525
0. 532
0.54 1
0. 54 1
0. 551
0. 562
0. 570
0. 578
0. 0065
0. 0071
0. 0072
0.0074
0. 0078
0. 0083
0. 0086
0. 0087
0. 0091
0. 0093
0. 149
0. 169
0. 203
0. 208
0. 208
0. 203
0. 202
0. 203
0. 203
0. 201
0. 44 1
0. 430
0. 401
0.4 11
0. 402
0. 406
0. 4 10
0. 3 98
0. 401
0. 403
^ J
NJ
Fi gur e 3 . 5 . 7 Concent r at i on v s . Time f or K , Na , Ca , OH , and SO
Ions I n Pore Sol ut i ons of Fi nel y-Ground Cl i nker Past e
wi t h 10% Gypsum and 2% K SO , w: c=0. 50.
CONCENTRATION, NORMALITY
*i
tw
c
ro
u>
Ol
^ j
H
H
2
rn
%.
x
o
c
73
CO
o

i:
I S- !>
: : !>
00
ro
O)
ro
ro
:c l >
:c t >
<S>
ro

w

^

en

0)
( )
C 0 O O 2 A H
0 2fl CH -CfO
jr e 8 t z
s
f &>XB3
2
CD
O
r
5:
1
I]
I rfi
L
yrAmw*
^ WV^ YH- W* *
Figure
3. 5. 8 X-Ray Di ffract i on Pat t er n of Early Pr eci pi t at ed Ca(OH)
2
75
cement of low al kal i content hydrated at water:cement r a t i o 1.00
occurred at 2 hours; as previ ousl y mentioned, the set t i ng time for t hi s
mat eri al was b\ hours.
Although small quant i t i es of suspended fine calcium hydroxide can
be separated from the pore sol ut i ons expressed from cement pastes qui t e
soon aft er the s t ar t of hydr at i on, as indicated e a r l i e r , det ect i on of
cr ys t al l i ne calcium hydroxide in the paste mass by X-ray di f f r act i on
does not begin before s e t t i n g , as wi l l be indicated l a t e r . Thus
2+ .
attainment of the peak in Ca ion concent rat i ons of the pore sol ut i on
does not si gnal the onset of s e t t i ng, and i t i s not immediately followed
by massive pr eci pi t at i on of calcium hydroxide.
Nevert hel ess, the pat t er n observed i ndi cat es t hat aft er the maximum
concent rat i on was reached, the Ca ion concent rat i on progressi vel y
decl i ned. The r esi dual concent rat i on in the pore sol ut i ons by 24 hours
was general l y found t o be very low.
The time pat t er ns observed for sul f at e and hydroxyl ion concent ra-
t i ons in these pore sol ut i ons suggest t hat two possi bl e types of
behavior e xi s t .
The f i r s t type i s observed t o occur with most of the systems
st udi ed. At some def i ni t e time af t er t he s t a r t of hydration a sudden
t urni ng point occurs at which the OH ion concent rat i on s t a r t s t o i n-
2
crease r api dl y, and the SO, ion concent rat i on t o decrease at approxi -
mately the same r a t e . The magnitude of t hi s sudden OH ion jump
depends on the al kal i cont ent of the cement. For example, for the low
al kal i finely-ground cl i nker with 5% gypsum added, t hi s jump was only
0.02N. For the high a l ka l i cement, on the other hand, the jump was more
than 0.4N.
76
The posi t i on of the jump on the time scal e depends on several
f act or s , but mostly on the amount of gypsum pr esent . I f t here i s no
gypsum at a l l as in the case of the finely-ground cl i nker with 2%
addi t i on of K~SO , the jump i s observed from the very beginning of
hydr at i on. For the usual l evel of gypsum addi t i on the jump occurs wi t h-
in the f i r s t day of hydrat i on. For the system with an overload of
gypsum ( f i nel y ground cl i nker with 2% KSO and 10% gypsum), the turning
point i s not observed t o occur during t he 24 hour period st udi ed.
This i s one i l l us t r a t i on of the second type of behavi or, t hat i s ,
r el at i vel y steady concent rat i on l evel s for OH and the absence of any
jump. Presumably in t hi s case the t urni ng point i s simply postponed
beyond the period of observat i on. However, the second type i s al so
observed where es s ent i al l y no al kal i es are present in the cement, since
the jump observed in the f i r s t type i s pr opor t i onal in magnitude t o the
a l ka l i content of the cement.
The occurrence of the turning point did not coincide with s et t i ng.
With the ordinary portland cement past es the t urni ng point occurred
about two or t hree hours aft er the f i nal set was achieved. However,
t hi s does not have t o be the r ul e , as for example in the paste containing
the finely-ground cl i nker with 2% of added KS0
4
. Here the t urni ng point
was reached soon af t er mixing and long before the occurrence of s et t i ng.
Fi nal l y, i t should be recal l ed t hat the concent rat i ons pl ot t ed
in Fi gs . 3. 5. 1 t o 3. 5. 7 and provided in the corresponding t abl es are
act ual concent rat i on val ues as determined exper i ment al l y. For some
purposes i t i s of i nt er es t t o adjust t hese experimental concent rat i on
val ues t o the concent rat i ons t hat cal cul at i on i ndi cat es would have been
present i f some of the solvent water had not been immobilized and
77
converted t o non-evaporable water by the chemical react i ons of cement
hydr at i on. For example, i t i s of i nt er es t t o determine whether the
i ncreases in al kal i ion concent rat i ons observed over the time period
examined r ef l ect the reduct i on in free water content onl y, or whether
t here i s evidence of addi t i onal di s s ol ut i on of al kal i ions from the
sol i d cement phases. The comparison can be made only af t er adjustment
for the water content change.
The cal cul at ed adjustments, based on the observed non-evaporable
water cont ent s of Table 3 . 4 . 1 , have been determined' , and the r esul t i ng
adjusted concent rat i ons provided in Tables 3. 5. 8 t o 3 . 5. 14. In some
cases the age of the paste at the time of expressi on of the pore
sol ut i on was di f f er ent from t hat when non-evaporable water cont ent s
were de-termined; in these cases non-evaporable water content est i mat es
were secured by i nt er pol at i on.
I t appears t ha t , judging from the r e s ul t s of Tables 3. 5. 8 t o 3.5.14,
the increase in concent rat i on of a l ka l i ions general l y does involve the
di ssol ut i on of addi t i onal a l ka l i from the cement in addi t i on t o the
concent rat i ng ef f ect of the progressi ve reduct i on in water content due
t o hydr at i on.
3.6 Solid Phase Examination
As i ndi cat ed e a r l i e r , X-ray di f f r act i on pat t er ns of hydrat i ng
cement past es of the seven systems studied were obtained per i odi cal l y on
wet specimens freshl y prepared at i nt er val s through the f i r s t day of
hydr at i on. These examinations were car r i ed out pri mari l y t o observe
changes in the sol i d phases t hat might correspond with or otherwise be
associ at ed with the changes in concent rat i ons of the pore sol ut i ons of
the same pastes=
78
Tabl e 3 . 5 . 8
Sol ut i on Concent r at i ons i n Or di nar y Por t l a nd Ce'ment Past e
As Adjusted f or Change i n Water Cont ent (w: c=0. 50)
Time,
Hours
1.05
1.62
2. 18
2. 73
3. 16
3 . 50
4. 00
5. 43
6. 00
12.00
15.00
18.00
21. 00
24. 00
Ca
2+
(N)
0. 68
0. 068
0. 067
0.064
0. 062
0. 060
0. 061
0. 057
0. 055
0. 008
2
0. 005,
4
0. 005
0. 005
0. 005
K
+
(N)
0. 260
0. 259
0. 270
0. 260
0. 259
0. 260
0. 260
0. 266
0. 274
0. 283
0. 283
0. 289
0. 3 00
0. 3 10
Na
+
(N)
0. 028
0. 028
0. 029
0. 028
0. 02
0. 028
0. 028
0. 029
0. 040
0. 04 1
0. 040
0. 040
0. 042
0. 04 2
OH"(N)
0. 145
0. 145
0. 14 7
0. 147
0. 152
0. 176
, 0. 144
0. 143
0. 13 8
0. 23 1
0. 265
0. 297
0. 324
0. 3 55
S0
4
2
"(N)
0. 162
0. 163
0. 172
0. 162
0. 169
0. 172
0. 173
0. 187
0. 201
0. 137
0. 086 '
0. 043
0. 000
0. 000
79
Table 3 . 5. 9
Sol ut i on Concent r at i ons i n Ordi nary Por t l a nd Cement Pas t e
As Adj ust ed for Change in Water Cont ent ( w: c=1. 00)
Ti me,
Hours
0. 2
0. 5
1.0
1.4
2 . 3
3. 4
4. 4
5. 5
6. 5
9. 5
15. 2
24. 0
Ca
1+
(N)
0. 052
0. 051
0. 056
0. 057
0. 059
0. 056
0. 055
0. 052
0. 051
0. 040
0. 019
0. 010
K
+
(N)
0.146
0.14 1
0. 140
0. 140
0. 139
0. 139
0. 139
0. 13 9
0. 138
0. 140
0.138
0. 147
Na
+
(N)
0. 016
0.016
0. 015
0. 016
0. 016
0. 016
0. 017
0. 017
0. 017
0. 017
0. 017
0. 018
OH (N)
0. 084
0. 096
0. 106
0. 109
0. 111
0. 111 ,
0. 107
0. 105
0.104
0. 107
0. 127
0. 173
S0
4
2
(N)
0. 168
0. 148
0. 121
0. 121
0. 098
0. 102
0. 103
0. 107
0. 103
0. 086
0. 045
0.
Tabl e 3 . 5 . 10
Sol ut i on Concent r at i ons i n High Al k a l i Cement Pas t e
As Adj ust ed f or Change i n Water Cont ent (w: c=0. 50)
Time
Hours Ca
2 +
(N) K
+
(N) Na
+
(N) 0H~(N) SO.
2
~(N)
0. 3
1
2
3. 16
4 . 5
6. 6
12
18
24
0. 040
0. 041
0. 042
0. 040
0. 039
0. 026
0. 013
0. 010
0. 005
0. 4 23
0.434
0. 437
0. 437
0. 437
0.474
0. 472
0. 476
0. 480
0.
0.
0.
0.
0.
0.
0.
0.
0.
130
130
149
148
148
156
151
160
187
0. 142'
0. 173
0. 175
0. 175
0. 163
0. 211
0. 290
0. 426
0. 557
0. 402
0.394
0. 402
0. 386
0. 389
0. 358
0. 255
0. 151
0. 059
81
Table 3 . 5. 11
Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pas t e
As Adj ust ed for Change i n Water Cont ent ( w: c=0. 50)
X J.11IC ,
Hours
0. 5
1.
2
3 . 25
4
5
7
9
10.58
12. 92
15.58
24. 67
28
Ca
1+
(N)
. 0. 078
0. 073
0. 060
0. 059
0. 057
0. 057
0. 056
0. 055
0.054
0. 052
0. 052
0. 048
0. 039
K
+
(N)
0. 023
0.026
0. 028
0. 028
0. 029
0. 029
0.029
0. 029
0. 030
0. 031
0. 031
0. 032
0. 037
Na
+
(N)
0. 002
0. 003
0. 004
0. 004
0. 004
0. 004
0.004
0. 004
0. 005
0. 005
0. 005
0. 007
0. 009
0H~(N)
0. 072
0. 073
0. 069
0. 072
0. 071
0. 073
0. 069
0. 065
0. 070
0. 071
0. 070
0. 072
0. 074
Tabl e 3 . 5. 12
Sol ut i on Conc e nt r a t i ons i n Fi ne
5% Added Gypsum As Adj ust ed for
T i n e
' 2+ +
Hours Ca (N) K (N)
1
2
3
4
5
6
7
8
9
10
11
12
15
18
22
25
28
0. 072
0. 067
0. 067
0. 068
0. 066
0. 065
0. 066
0. 064
0.064
0. 062
0. 063
0. 069
0. 050
0. 047
0. 045
0. 03 8
0. 03 7
0. 023
0. 026
0. 026
0. 028
0. 028
0. 028
0. 029
0. 029
0. 029
0. 03 0
0. 03 0
0. 03 3
0. 035
0.034
0. 035
0. 036
0. 036
-Ground Cl i nker Pas t e Cont ai ni ng
lange i n Water Cont ent ( w: c=0. 50)
Na
+
(N) 0H~(N) S0,.
2
~(N)
0. 003
0. 003
0.004
0. 004
0. 004
0.004
0.004
0. 005
0. 005
0. 005
0. 005
0. 005
0. 006
0. 006
0. 006
0. 006
0. 009
0. 072
0. 072
0. 070
0. 072
0. 070
"0. 071
0. 071
0. 075
0. 072
0.074
0. 070
0. 067
0. 069
0.084
0. 084
0. 084
0. 084
0. 021
0. 002
0. 022
0. 022
0. 022
0. 021
0. 022
0. 025
0. 025
0. 025
0. 025
0. 026
0. 025
0. 005
0. 000
0. 000
0. 000
83
Tabl e 3 . 5 . 13
Sol ut i on Concent r at i ons i n Fi nel y- Gr ound Cl i nker Pas t e Cont ai ni ng
2% Added K.SO As Adj ust ed for Change i n Water Cont ent (w: c=0. 50)
Hours
0. 2
1.6
3 . 6
6. 3
8
12
18. 3
28. 3
Ca
2 +
(N)
0. 057
0. 051
0. 043
0. 022
0. 010
0. 009
0. 007
0. 005
K
+
(N)
0. 486
0. 491
0. 519
0. 569
0. 585
0. 575
0. 573
0.574
Na
+
(N)
0. 147
0.194
0. 199
0. 200
0. 199
0. 192
0. 188
0. 183
0H~(N)
0. 121
0. 188
0. 219
0. 3 16
0. 400
0. 462
0. 543 .
0. 587
S 0
4
( N )
0. 401
0. 365
0. 338
0. 273
0. 200
0. 162
0. 095
0. 015
84
Table 3 . 5 . 14
Sol ut i on Concent r at i ons in Fi nel y-Ground Cl i nke r Pas t e
Cont ai ni ng 10% Added Gypsum and 2% Added KS0 As Adj ust ed
for Change i n Water Content ( w: c=0. 50)
Ti me,
Hours
0. 25
1.25
1.70
2. 25
4
6
7. 25
13. 5
19.6
24
Ca
1+
(N)
0.04 3
0. 049
0. 051
0. 050
0. 051
0. 050
0. 050
0. 046
0. 043
0. 042
K
+
(N)
0. 523
0. 518
0. 518
0. 525
0. 53 3
0. 53 2
0.54 2
0. 53 2
0. 524
0. 528
Na
+
(N)
0. 006
0. 007
0. 007
0. 007
0. 008
0. 008
0. 008
0.008
0. 008
0. 009
0H~(N)
0. 148
0. 166
0. 200
0. 205
0. 205
0. 200
0. 198
0. 192
0. 187
0. 184
S0
4
2
"( N)
0. 439
0.424
0. 400
0. 405
0. 600
0. 3 99
0. 403
0. 3 76
0. 369
0. 368
85
Since the more dr a s t i c changes in the l i qui d phase during the f i r s t
day of hydration were shown t o involve the concent rat i ons of the sul f at e
and hydroxyl ions and t o a l esser ext ent the calcium i ons, speci f i c
concern was evidenced with observing changes in the sol i d calcium
sul fat e and calcium hydroxide phases, and of course with hydrated c a l -
cium aluminate s ul f a t e s . While X-ray di f f r act i on pat t er ns were run t o
60 26 (copper r a di a t i on) , i t appeared t hat the best region for
observing such changes i s between 5 and 20 28, which cont ai ns the
major peaks for a l l of the substances concerned, and in which range the
peaks are not s i gni f i cant l y overlapped by di f f r act i on peaks of ot her
cement phases. Unfort unat el y, even in t hi s region a few weak peaks of
the calcium s i l i c a t e and possi bl y aluminate phases show up and in some
cases make the i nt er pr et at i on more di f f i c ul t . For example, t r i c l i n i c
o
C.S (JCPDS pat t er n 31-301) shows minor but appreciable peaks at 5.98A,
3.89A, and 3.55A.
To provide for proper i nt er pr et at i on of the r es ul t s of t hi s phase
of the i nvest i gat i on, t r aces of each of the pat t er ns obtained in the 20
region 5 t o 25 (copper r adi at i on) are provided in Fi gs. 3. 6. 1 t o 3 . 6. 6.
Pat t erns were not obtained for the w:c 1.00 ordinary portland cement
paste system, because of the di f f i cul t y in handling t hi s mat er i al .
The pat t er ns for the w:c 0.50 paste made with ordinary port l and
cement are provided in Fi g. 3 . 6 . 1 , and represent scans taken of the
dry mat eri al and of past es at 2, 4 , 6, 8, 12, 18, and 24 hours of
hydrat i on. I n i t i a l s et t i ng of t hi s mix occurred at 3h hours and f i nal
set at s l i ght l y beyond 5 hours.
As occurs with some commercial cements, despi t e the addi t i on of
gypsum l i t t l e or no X-ray di f f r act i on evidence for t hi s phase can be
86
u As->K
i . _ i _
25 20 15 10
DEGREES 2o Cu RADIATION
- J _ J
Figure 3 . 6. 1 Traces of X-Ray Di f f r act i on Pat t er ns
for Ordinary Cement Past e (w:c=0.50),
(
87
8
^^Aw' M/ w
' ' VVAAW^ A/ J
25 20 15 10 5
DEGREES 2 H CU RADIATION
Figure 3 . 6. 2 Traces of X-Ray Di ffract i on Pat t er ns
for High Al kal i Cement Paste (w:c=0.50),
88
14 M^OWS^A^V. ^AL- - ^* '
. t JL JL.
25 20 15 10
DEGREES 2o Cu RADIATION
Figure 3 . 6. 3 Traces of X-Ray Di ffract i on Pat t er ns
for Finely-Ground Clinker Paste (w:c=0.50).
v . 89
3Hr w u
V v
^
v
J r \ . ^ l ^ ^ ^
^ A i ^ ^ ^
8 W*V^v^'
18
24
" "^^AA^K^
AvJ v^w^
_ i _
25 20 15 10
DEGREES 2 G Cu RADIATION
Fi gur e 3 . 6. 4 Tr aces of X-Ray Di f f r a c t i o n P a t t e r n s
f or Pas t e of Fi nel y- Gr ound Cl i nker
wi t h 5% Added Gypsum ( w: c =0. 5 0) .
90
8 %
w
tA^i * Vi / 'V^^-"A/

25 20_ 15 10 5
DEGREES 20 Cu RADIATION
Figure 3 . 6. 5 Traces of X-Ray Di ffract i on Pat t er ns
for Paste of Finely-Ground Clinker
with 2% Added KS0, (w:c=0.50).
2 4
(
91
Fi gur e 3 . 6. 6 Tr aces of X-Ray Di f f r a c t i on Pa t t e r n s
f or Pas t e of Fi nel y- Gr ound Cl i nker
wi t h 10% Added Gypsum and 2% Added
K
o
S0, ( w: c=0. 5 0) .
92
-^
25
i l l ! I ' l l I
20 15 10
DEGREES 2 e Cu RADI ATI ON
Figure 3. 6. 6
93
found in the dry cement. Presumably in the i nt ergri ndi ng process some
of the cr ys t al l i zat i on water i s l ost and much of the mat er i al may be
converted t o calcium sul f at e hemihydrate or even soluble anhydri t e.
Unfortunately, calcium sul f at e hydrat es poorer in cr yst al water than
gypsum do not have i nt ense di f f r act i on peaks in the region free of
o
di f f r act i on peaks of ot her cement components. Even the peak near 6.0A
o
coincides with the minor t r i c l i n i c C,S peak at 5.98A previously
mentioned.
In any case, the pat t er n for the dry cement in Fi g. 3. 6. 1 shows no
def i ni t e peaks a t t r i but a bl e t o gypsum, and only an ambiguous peak at
o
5.95A which diminishes only slowly through the 1-day hydration peri od.
On the other hand, some prehydrat i on seems to have occurred even
in the ost ensi bl y dry cement, since small but def i ni t e e t t r i ngi t e peaks
can be observed. These remain about constant in i nt ensi t y over the
f i r s t four hours, then i ncrease somewhat. A small and r el at i vel y indef-
i ni t e peak for calcium monosulfoaluminate can f i r s t be detected at 8
hours and t hi s does not i ncrease in i nt ens i t y.
Calcium hydroxide i s f i r s t def i ni t el y observed for the pat t er n at 4
hours, i . e . , coi nci dent with the s et t i ng processes and the i nt ens i t y of
the pat t er n i ncreases r api dl y t her eaf t er .
Corresponding t r aces for the X-ray pat t er ns of the high al kal i
cement paste are provided in Fi g. 5. 6. 2. There i s comparatively l i t t l e
di fference observable between these pat t er ns and those discussed pr e-
vi ousl y. Again the dry cement shows no det ect abl e gypsum by X-ray
di f f r act i on, some e t t r i n g i t e formed presumably by exposure t o water
o
vapor, and the weak peak near 5.95A.
94
The low angle regi on for the pat t er n at 2 hours shows ext r aor di nar y
scat t er i ng t hat may be an a r t i f a c t of imperfect specimen geometry.
Wel l - cr yst al l i zed e t t r i n g i t e i s present in si gni f i cant amount by 4
hours, and calcium monosulfoaluminate i s det ect ed, somewhat ambiguously
at 18 hours and very def i ni t el y at 24 hours. The i n i t i a l and f i nal
s et t i ng times for t hi s paste are af t er 4 hours and before 5 hours, and
again sol i d calcium hydroxide i s observed f i r s t at 4 hours.
Traces of the X-ray pat t er ns for the paste of the finely-ground
cl i nker without any added components are provided in Fi g. 5 . 6. 3 . Here
because of lack of any added sul f at e and very modest sul f at e content of
the cl i nker i t s el f , no peaks for gypsum, hemihydrate, or e t t r i n g i t e are
o o o
expect ed. The dry ground cl i nker shows peaks at 5.98A, 3.86A, and 3.56A,
a l l at t r i but abl e t o C.S. None of these show appreciable reduct i ons in
i nt ens i t y over the 24 hour hydrat i on peri od.
The ser i es of pat t er ns of Fi g. 5. 6. 3 al so shows the development
o
over the f i r s t day of a peak at 9.8A, the usual posi t i on for the main
peak of e t t r i n g i t e . This remains somewhat of a mystery, since the
cl i nker cont ai ns no added gypsum. I t i s possi bl e t hat the peak i s
e t t r i n g i t e , since t here i s a small content of sul f at e in the cl i nker
i t s e l f . The sul f at e cont ent , i f completely di ssol ved, in the w:c 0.50
paste should produce a 0.065N sol ut i on. However, as i ndi cat ed e a r l i e r ,
no sul f at e was found in the pore sol ut i ons of the fi nel y ground cl i nker
pas t e. This suggests t hat the sul f at e reacted very r api dl y t o produce
e t t r i n g i t e . If a l l of the sul f at e i ndi cat ed as being present in the
cl i nker were used t o produce st oi chi omet ri c e t t r i n g i t e , the amount of
e t t r i ngi t e produced would be 0.7% by weight of the cl i nker , a r at her
small amount t o det ect by X-ray di f f r act i on. On the ot her hand, a l l of
95
the e t t r i n g i t e would presumably be located on the surfaces of the
hydrating cl i nker gr ai ns , and t herefore within easy reach of X-ray
r adi at i on.
SEM examination of the paste samples did not show appreci abl e
amounts of elongated AFt par t i cl es normally associated with the
e t t r i ngi t e in hydrat i ng cement systems, only a very few being found.
The pos s i bi l i t y e xi s t s t hat more e t t r i ngi t e than cal cul at ed above
may have been produced, with the e t t r i ngi t e being of a hi ghl y s ubs t i -
tuted var i et y def i ci ent in sul f at e i ons, or even an i nt ergrade between
e t t r i ngi t e and t haumasi t e.
The i n i t i a l and f i nal set t i ng times for t hi s paste were 10 hours
and a l i t t l e l ess than 12 hours, r espect i vel y. Solid calcium hydroxide
i s cl ear l y at 18 hours, although the pos s i bi l i t y of i t s presence at 12
hours as a peak -just on the borderl i ne of det ect abi l i t y cannot be ruled
out .
X-ray di f f r act i on pat t er ns for the paste of the finely-ground
cl i nker with 5% added gypsum are shown in Fi g. 3 . 6. 4. Here a pat t er n
i s provided at 3 hour s, r at her than at the 2 hour and 4 hour peri ods
as in previous f i gur es .
The r e s ul t s for t hi s system are r el at i vel y simple and cl ear t o
i nt er pr et since the added reagent gypsum shows di f f r act i on peaks t hat
are st rong and sharp, and changes are easy t o follow.
There i s an i ndi cat i on in the pat t er n for the "dry" mix t hat as
soon as the gypsum i s added t o the cl i nker some e t t r i ngi t e i s formed,
presumably due to the ef f ect of atmospheric humidity. This e t t r i n g i t e
pat t er n cont i nues t o grow in i nt ens i t y over the f i r s t hours of hydration.
At the same time the gypsum peaks grow progressi vel y weaker. The peak
96
i s es s ent i al l y gone af t er 18 hour s, at which time the e t t r i ngi t e peak i s
at a maximum. Table 3 . 5. 5 shows t hat t hi s coincides with rapid de-
creasi ng of sul fat e ion concent rat i on in the pore sol ut i on. At 24 hours
the e t t r i ngi t e peak has l ost some of i t s i nt ens i t y and the presence of
calcium monosulfoaluminate i s det ect ed.
The effect of the added gypsum on set t i ng time was-almost negl i gi bl e,
i n i t i a l set being i dent i cal with t hat of the ground cl i nker alone at 10
hours and f i nal set reduced s l i ght l y t o 10-^ hours. In these pat t er ns
there seems t o be a t race of sol i d calcium hydroxide vi s i bl e at 8 hours,
but si gni f i cant content of calcium hydroxide i s f i r s t detected at 12
hours and the amount i ncreases r api dl y t her eaf t er .
X-ray di f f r act i on pat t er ns for the paste of the finely-ground
cl i nker with 2% added K.SO, are shown in Fi g. 3 . 6. 5.
2 4
In the dry mix the K.SO, does not have strong enough di f f r act i on
peaks in the region examined t o i t s e l f be observed. The pat t er n for the
dry mix i s thus t hat of the ground cl i nker i t s e l f , and i s i dent i cal t o
the "dry" pat t er n of Fi g. 3 . 6. 3 .
Pat t er ns for some, but not a l l , of the wet paste samples show
pronounced scat t er i ng between 5 and 9 29 (copper r adi at i on) . These
"humps" are present in pat t er ns for 2, 6, and 8 hours, but not for 4
r
hours, and not af t er 8 hour s. This ef f ect i s t ent at i vel y considered t o
be an a r t i f a c t of specimen pr epar at i on, perhaps due t o a sl i ght mounding
up of a port i on of the surface of the fresh paste above the plane of the
di ffract omet er c i r c l e .
There does not appear t o be any e t t r i n g i t e det ect abl e in t hi s
paste unt i l 12 hours, although a small peak might be hidden in the
background hump at 6 hour s. However, i t should be noted t hat a 2%
97
K.SO, addi t i on enri ches the cl i nker with SO. only up t o 0.55%, which
i s s t i l l a very low SO l evel , and would be expected t o produce only a
l i t t l e bi t of e t t r i n g i t e . The e t t r i ngi t e peak, once det ect ed at 12
hours, remained approximately constant in i nt ensi t y through the r est of
the 24 hour peri od, and no unambiguous peak for calcium monosulfo-
aluminate was ever observed.
In cont rast with the almost negl i gi bl e effect of gypsum on the
s et t i ng time, addi t i on of the K.SO produced very strong set accel er -
at i on, i n i t i a l and f i nal set t i ng times being reduced r espect i vel y t o 3
hours and s l i ght l y l ess than 4 hours, r es pect i vel y. Defi ni t e formation
of Ca(OH). in t r ace amounts was detected only af t er 6 hours, and a
subst ant i al peak for t hi s compound was found only at 8 hours of hydra-
t i on, which i s qui t e a bi t af t er the completion of s e t t i ng.
Fi nal l y, X-ray di f f r act i on pat t er ns of past es of ground cl i nker
with 10% added gypsum and 2% added K.SO are provided in Fi g. 3 . 6. 6.
Here pat t er ns are provided for the dry mix and for the past es at 2, 6,
8, 12, 18, and 24 hours.
The amount of gypsum added to t hi s ground cl i nker was del i ber at el y
higher than would normally be found in portland cement. The dry mix
does indeed show a st rong gypsum pat t er n. I t appears t hat a t race of
e t t r i ngi t e i s present even in the dry mix. The gypsum peaks diminish
progressi vel y over the whole of the 24 hour peri od, but t here i s some
gypsum l ef t even at 24 hours: since the i n i t i a l gypsum content was so
l ar ge, t hi s i s expect ed. The e t t r i ngi t e peaks do not diminish at a l l
by 24 hours, and accordi ngl y, no calcium monosulfoaluminate was detected
even at 24 hours.
98
The s et t i ng time for t hi s mix was in between those for the mix with
gypsum addi t i on, and the hi ghl y accel erat ed mix with K.SO addi t i on
al one, i n i t i a l set being at j ust over 7 hours and f i nal set at 8 hours.
Calcium hydroxide was f i r s t detected unambiguously at 8 hours and i t s
amount increased progressi vel y t her eaf t er .
('
99
CHAPTER FOUR - DISCUSSION AND IMPLICATIONS
4 . 1 . Tr ans f or mat i on of Al ka l i Sul f a t e s i nt o Al ka l i Hydr oxi des
Si nce t he devel opment of t he t echni que for e xpr e s s i on of pore
s ol ut i ons from har dened cement p a s t e s , publ i shed da t a ar e a v a i l a b l e on
t he composi t i on of pore s o l u t i o n s of ol der p a s t e s , even up t o one year
or' more ( 6 5 ) . Al l t he a v a i l a b l e r e s u l t s ar e unanimous t h a t t he s e pore
s ol ut i ons ar e r e l a t i v e l y pure a l k a l i hydr oxi de s o l u t i o n s , wi t h
c onc e nt r a t i ons r e l a t e d p r i ma r i l y t o t he t o t a l a l k a l i c ont e nt of t he
cement us ed. Al l ot he r c a t i o n s and ani ons i n i t i a l l y pr e s e nt l eave t he
s ol ut i on sooner or l a t e r . While not p e r t i n e n t t o t h i s work, i t i s
i n t e r e s t i n g t o ment i on t h a t some r ecent da t a (73) show t h a t t he r e may
be some e xc e pt i ons t o t h i s r u l e . I f c h l o r i d e s , for exampl e, ar e
i nt r oduced i n t o cement p a s t e s , t hey can remai n i n t he pore s o l u t i o n
for a ver y l ong t i me . The da t a show t h a t i n 3 month ol d cement pa s t e
t her e i s s t i l l c ons i de r a bl e c hl or i de r emai ni ng i n t he pore s o l u t i o n .
However, c hl or i de i s nor mal l y not a component of or di na r y cement .
As t he d a t a produced i n t h i s i n v e s t i g a t i o n show, most of t he
a l k a l i e s go i n t o s o l u t i o n ver y soon a f t e r mi xi ng cement and wa t e r . ' I n
t h i s work we ar e concerned onl y wi t h t he s e r e a d i l y s ol ubl e a l k a l i e s ,
si nce s o - c a l l e d i ns ol ubl e a l k a l i e s i n cement can t ake weeks and months
bef or e t hey go i n t o s o l u t i o n . As des cr i bed i n t he i n t r o d u c t i o n ,
s ol ubl e a l k a l i e s ar e pr i ma r i l y d i f f e r e n t forms of a l k a l i s u l f a t e s . I t
coul d be s ai d t h a t a t t he begi nni ng of cement hydr a t i on t he f l ui d i s
100
most l y an a l k a l i s u l f a t e s o l u t i o n , wi t h some di s s ol ved cal ci um hydr oxi de .
Calcium hydr oxi de p r e c i p i t a t e s dur i ng t he s e t t i n g and for a few hour s
af t er war d. Al ka l i s u l f a t e s on t he ot her hand ar e t ransformed i n t o
a l k a l i hydr oxi des . The s u l f a t e i ons l eave t he s ol ut i on and are
d i r e c t l y r epl aced by hydr oxyl i o n s .
Longuet e t a l (59) f i r s t pr oposed a mechanism for t h i s t r a ns f or ma -
t i o n as f ol l ows :
Ca(OH). ( s o l ) + K.SO, ( s o l ) t KOH + Ca(S0 ) s ol
I 2. 4 t
H I f
Ca( 0H) . l CaSO, I
2 4
As t hey ment i oned, t he s u l f a t e does not have t o be p r e c i p i t a t e d as
cal ci um s ul f a t e and can be used f or f or mat i on of s ul f oa l umi na t e s .
The above scheme has not been s t udi ed and devel oped si nce t he
i n i t i a l s ugge s t i on. I t i s obvi ous t h a t i f such an e qui l i br i um e x i s t s
i t must be i nf l uenced by t he a d d i t i o n of gypsum t o t he syst em.
4 . 1 . 1 . Systems Wi t hout Gypsum
Among t he seven pa s t e syst ems s t udi ed i n t he pr es ent r e s e a r c h , onl y
two were wi t hout added gypsum, t he f i ne l y ground c l i n k e r pas t e of w:c
0. 50 and t he pas t e of t he f i n e l y ground c l i n k e r wi t h 2% added K.SO ,
a l s o at w:c 0. 5 0. The c l i n k e r i t s e l f cont ai ned onl y a smal l cont ent of
a l k a l i e s , onl y 0.17% K.O and 0.07% Na.O bei ng i ndi cat ed i n t he a n a l y s i s
of Tabl e 2 . 1 . 1 . An a d d i t i o n of 2% K.SO e qua l s appr oxi mat el y 1.1% of
added K.O, so t he t o t a l K.O c ont e nt a f t e r t he a ddi t i on i s 1.26 K0.
The low a l k a l i c l i n k e r was t hus i n e f f e c t t r ansf or med i nt o a hi gh a l k a l i
c l i n k e r , wi t h t he added a l k a l i i n t he form of K. S0
4
.
Tabl e 3 . 5 . 6 shows t h a t t he pot as s i um s ul f a t e di s s ol ved i mmedi at el y
a f t e r t he cement was mixed wi t h wa t e r , and t he t r ans f or mat i on of a l k a l i
101
sul fat e i nt o al kal i hydroxide st ar t ed t o take place almost immediately.
That i s , the sul fat e concent r at i on decreased soon af t er mixing and the
OH ion concent rat i on i ncreased at the same t i me. The l i qui d composi-
t i on changed dr a s t i c a l l y with t i me, implying i nt ensi ve chemical changes
in the system. There are no regi ons of constant l i qui d phase concen-
t r a t i on, and the term "dormant peri od" can not properl y be applied t o
t hi s system, although the past e s t i l l required 3 hours t o s et .
The X-ray di f f r act i on pat t er ns show t hat e t t r i ngi t e i s formed in
t hi s system, and by 12 hours of hydrat i on the major e t t r i ngi t e peak i s
well developed. I t appears t hat a small peak might be hidden in the
background as ear l y as 6 hour s. This confirms t hat the formation of
e t t r i ngi t e i s the expl anat i on for the progressive decrease in the
sol ut i on concent rat i on of sul f at e i ons, even though no gypsum was
pr esent .
Calcium is required for the formation of e t t r i n g i t e , however, and
i t s concentration in the pore sol ut i on was low compared t o t hat of
s ul f at e. Calcium i s of course a major const i t uent of C.S and C.S;
addi t i onal calcium ions needed for e t t r i n g i t e formation must come from
more rapid hydration of the calcium s i l i c a t e phases.
That the hydrol ysi s of the cement phases i s i nt ensi f i ed in the
presence of al kal i es i s corroborat ed by the dat a for non-evaporable
wat er. Comparison of the dat a for non-evaporable water for past es of the
fi nel y ground cl i nker and of the cl i nker with 2% added K.S0
4
show t hat
a remarkable increase in non-evaporable water content i s produced when
the al kal i sul fat e i s added. This rapid hydrol ysi s of the cl i nker
minerals does produce OH ions and unl ess they are pr eci pi t at ed by some
other mechanism the a l ka l i ni t y of the sol ut i on would i ncr ease.
102
In contrast to the pattern that develops with the added K.SO,, the
finely ground clinker by itself develops a pore solution whose chemical
composition does not change very much over the period concerned. This
implies very sluggish chemical reaction in the paste - a long dormant
period. However, in spite of the approximately constant liquid compo-
sition, all other features of characteristic hydrating cement paste
response are observed. The paste sets, solid calcium hydroxide is
observed at the same time, and heat is evolved. Certainly the setting
time is much later (10 hours) than for the previous system, and the
temperature increase much lower.
4.1.2 Systems With Gypsum
Five gypsum-containing past es were st udi ed: the ordinary portland
cement (with moderate a l ka l i content) at w:c 0. 50, the same cement at
w:c 1.00, the high a l ka l i cement at w:c 0. 50, the finely-ground cl i nker
with 5% added gypsum at w:c 0. 50, and the finely-ground cl i nker with 10%
added gypsum and 2% added K.SO at w:c 0. 50.
The finely-ground cl i nker i s e s s e nt i a l l y without a l ka l i e s . Addition
of 5% gypsum in ef f ect convert s i t t o a very low al kal i portland cement,
and i t i s of i nt er es t t o see how the gypsum addi t i on influences the be-
havi or. Actually the behavior of t hi s paste does not di f f er very muck
from t hat of the paste of ground cl i nker without gypsum. The i n i t i a l
set remains the same, the f i nal set i s somewhat more r api d, and more
heat i s evolved.
The gypsum addi t i on does not influence the l i qui d phase composition
very much e i t he r . Cert ai nl y the sul f at e ions const i t ut e a new component
now present in the pore s ol ut i on, but t he i r concent rat i on i s very low.
103
Here i t appears t hat the concent rat i on of sul f at e ions i s being con-
t r ol l ed by the s ol ubi l i t y product of gypsum. Comparatively l i t t l e
change i s seen t o take place in the composition of the pore sol ut i on
over t i me, although set occurs and the heat i s evol ved. The sul fat e
i ons, however, di sappear from the sol ut i on af t er 18 hours of hydrat i on.
This coi nci des with the disappearance of sol i d gypsum from the past e,
as the X-ray pat t er ns in Fi g. 3. 6. 4 i ndi cat e. As the sul f at e ion
concent rat i on reduces, t hat of hydroxyl ions i ncr eases. However, due
t o t h e low sul f at e concent rat i on present from the begi nni ng, the
magnitude of the decrease in sul fat e ion concent rat i on i s necessar i l y
smal l ; thus the increase in al kal i ni t y i s al so smal l .
The r e s ul t s for t hi s system suggest t hat the increase in hydroxyl
ion concent rat i on af t er the sol i d gypsum i s gone i s st rongl y r el at ed t o
the a l ka l i content of the cement past e. If the a l ka l i content i s low,
so i s the i ncr ease, and in the l i mi t i ng case of cement paste without
al kal i es no increase at a l l i s t o be expect ed.
I f al kal i es and gypsum are simultaneously added t o the cl i nker t o
dupl i cat e the usual s i t uat i on in portland cements, the s i t uat i on i s
much more complex. The i ndi cat i ons of what occurs are provided in
Fi gs . 3 . 51, 3. 52, and 3 . 53 . After mixing t here i s a period of approxi-
mately const ant sul f at e and hydroxyl ion concent r at i on l ast i ng a few
hours. Then suddenly the hydroxyl ion concent r at i on s t a r t s t o increase
and the sul f at e ion concent rat i on t o decr ease. This t urni ng point does
not coincide with s e t t i ng, as might be expect ed, but s t a r t s one or two
hours af t er the f i nal s e t .
X-ray di f f r act i on pat t er ns , especi al l y of past es made from
commercial cements, are not very hel pful in understanding what i s
104
going on. In cement manufacture gypsum i s added usual l y t o hot cl i nker
before gr i ndi ng, and par t l y dehydrat es, i nt er f er i ng somewhat with the
i nt ens i t y and sharpness of i t s peaks in the regi on of the X-ray pat t er n
free of other di f f r act i on peaks. Wel l - cr yst al l i zed hemihydrate or
anhydrate are not usual l y produced e i t he r . However, despi t e the
di f f i c ul t y of following the di ssol ut i on of the added gypsum by X-ray
di f f r a c t i on, the production of e t t r i ngi t e can r eadi l y be monitored. The
e t t r i n g i t e s t a r t s to form very soon aft er mixing, and can be det ect ed
wi t hi n an hour or so. This being so, the production of e t t r i n g i t e
alone can not be the expl anat i on for the t urni ng poi nt observed in the
' sul f at e and hydroxyl ion concent rat i ons. Something el se must, be
i nvol ved.
The behavior can be regarded as a combination of ef f ect s in two
previ ousl y dissolved systems, vi z:
a. Clinker + al kal i sul fat e
b. Clinker + gypsum
As mentioned previ ousl y, i f there i s no gypsum in a system containing
a l ka l i s ul f a t e s , the l a t t e r di ssol ve qui ckl y, supplying sul f at e ions
for e t t r i n g i t e product i on. Furthermore, rapid hydr ol ysi s of the
calcium s i l i c a t e s takes pl ace, and the a l ka l i ni t y of the sol ut i on
i ncr eas es .
' I f gypsum i s added to low al kal i cement, gypsum par t i ci pat es in
e t t r i n g i t e product i on. However, the gypsum does not di ssol ve i ns t ant l y,
and the calcium and sul f at e ions used for synt hesi s of e t t r i n g i t e are
repl aced in sol ut i on only by slow di ssol ut i on of an equi val ent amount
of sol i d gypsum. Therefore, no changes in the l i qui d composition are
observed.
105
On the ot her hand, when both a l ka l i sul f at es and gypsum are
pr esent , i t appears t hat the sul f at e l evel in sol ut i on i s maintained
at a higher concent rat i on l evel but gypsum s t i l l suppl i es the sul fat e
needed t o repl ace t hat l ost from sol ut i on in e t t r i ngi t e production as
long as some sol i d gypsum remains undi ssol ved. Only when i t i s a l l
used up do the di ssol ved al kal i sul f at es s t a r t t o transform t o a l ka l i
hydroxi des. This marks the turning poi nt , at which sul f at e concent ra-
t i ons s t a r t t o f a l l and hydroxyl ion concent rat i ons s t a r t t o r i s e .
In one of the systems st udi ed, the paste with added gypsum and
K.S0
4
, the amount of gypsum added was 10%, thus const i t ut i ng a large
overdose. The X-ray pat t er ns show t hat e t t r i n g i t e i s const ant l y
i ncreasi ng during the hydr at i on, but t hat despi t e t hi s the large amount
of gypsum present could not ful l y di ssol ve during the f i r s t day of
hydr at i on. Figure 3. 5. 7 shows the l i qui d composition as a function of
time during t hi s peri od. No changes whatsoever occurred in al kal i ni t y
or sul f at e concent rat i on during the f i r s t day. The presence of an
overdose of gypsum thus " k i l l " , or at l east del ays, the transformation
of a l ka l i sul f at es i nt o al kal i hydroxides.
4. 2 The Al kal i ni t y of the Liquid Phase and I t s Influence on Set t i ng
I t has long been known t hat al kal i hydroxides accel er at e s e t t i ng.
Our own experiments confirm t h i s , and al so show t hat so-cal l ed "fl ash
set " can be induced by a large enough addi t i on of al kal i hydroxide t o
hydrat i ng cements.
Al kal i metals in cement, in whatever form, wi l l sooner or l at er
be di ssol ved during the hydrat i on process and ent er the pore sol ut i on
along with other i ons. However, other ions are used up in di f f er ent
106
chemical processes, and only al kal i and hydroxyl ions are event ual l y
l eft in the s ol ut i on. The over al l process i s a conversion of a l ka l i
s al t s - mostly s ul f at es - i nt o a l ka l i hydroxides. The mediating
process i s e t t r i n g i t e product i on. The speed of the process, however,
depends on the a l ka l i concent r at i on, the r eact i vi t y of the C.A phase of
the cement, the r at e of hydrol ysi s of the calcium s i l i c a t e s of the
cement, and the amount of gypsum pr esent .
All of the var i ous al kal i ni t y changes in the liquid phase duri ng
the hydration of cement det ect ed in our experiments can be descri bed
with a generalized curve such as t hat shown in Fi g. 4 . 2 . 1 .
Almost i ns t ant l y af t er mixing cement with water a hydroxyl ion
concentration of the order of perhaps 0.1N (depending on the a l ka l i
content) i s reached, and then maintained approximately const ant at the
l evel reached for some hours depending on the gypsum cont ent . I f t here
i s no gypsum in the system at a l l , t hi s region of constant a l ka l i ni t y
i s missing. When a l l of the gypsum has passed i nt o sol ut i on the
hydroxyl ion concent r at i on s t a r t s to build Up again. This i s the regi on
of al kal i sul f at e conversi on. After a day or so a l l of the sul f at e ions
are used up. Although the hydroxyl ion concent rat i on may continue t o
increase with t i me, i t then does so at a considerably lower r a t e . This
extended slow buildup i s at t r i but ed t o insoluble al kal i es in cement t hat
are slowly l i ber at ed from the vari ous cement phases as hydrat i on
progresses.
If an exaggerated overdosage of gypsum i s added to the cl i nker no
second increase of a l ka l i ni t y i s observed, at l east within the f i r s t
day of hydr at i on, since as i ndi cat ed by X-ray pat t er ns , consi derabl e
sol i d gypsum remains undi ssol ved.
i
0. 4 r
i-
H
<
o
o
H
<
h-
"Z.
O
O
O
0. 3
0. 2 -
0.1
0
0 6 ' 12 18 24
TI ME, HOURS
Figure 4.2.1 0H~ Ion Concentration Changes in Cement Paste (Schematic)
o
108
The absence of the second increase i s observed al so in cl i nker s
or cements without a l ka l i e s . The f i r s t increase in hydroxyl ion
concent rat i on can t herefore be at t r i but ed t o the hydrol ysi s of the
di f f er ent cement phases, which always t akes pl ace. The second increase,
where i t occurs, r ef l ect s the t ransformat i on of di ssol ved a l ka l i
sul f at es t o al kal i hydroxides following the completion of di ssol ut i on
of gypsum. The time requi red t o begin t hi s t ransformat i on i s thus
regul at ed by the amount of gypsum in the system.
4 . 3 . Optimum Gypsum
The amount of gypsum needed to pr ot ect a cl i nker from fl ash set t i ng
and at the same time r e s ul t s in the optimum balance of st r engt h
development and shrinkage char act er i s t i cs i s cal l ed the optimum gypsum
content of t hat cl i nker . This optimum gypsum content i s determined
purely empi r i cal l y, and i s t ypi cal l y about 5% by weight for Type I
cl i nker s . There has been l i t t l e t heor et i cal expl anat i on of t hi s
parameter.
Although there i s no doubt t hat the major chemical r eact i on t hat
the gypsum par t i ci pat es in i s the formation of e t t r i n g i t e , no r el at i on
has ever been est abl i shed between the optimum gypsum content and the
percentage of the C.A phase in the cl i nker . Even f ur t her ,
experi ment al l y-deri ved numerical equat i ons for the pr edi ct i on of
optimum gypsum content show t hat the content of the C.A phase i s of
l i t t l e si gni f i cance. In Haskel l ' s equat i on, given in the i nt r o-
duction on page 16, which i s derived from Lerch' s experimental dat a
( 1 , 2) , the coef f i ci ent for C.A i s very smal l . In Ost ' s equation on
the same page, based on the same experimental dat a but including
109
fineness as a variable, the coefficient for C A content is zero.
Although the optimum gypsum content as normally formulated depends on
factors such as fineness, C.S content, and iron content, all of these
are practically insignificant compared to the expressed dependence on
the alkali content. The coefficient for alkalies is so large compared
to the other regression coefficients that the others can, in practical
terms, be completely disregarded. For example, the regression co-
efficient for alkali content in Ost's equation is 300 times larger
than that for cement fineness.
These equations have generally been given less importance than
they deserve, perhaps because of the lack of ability to interpret the
significance of the alkali content coefficient.
The experiments reported here show a strong relation between
gypsum content, alkali content, and the alkalinity of pore solutions
within the first day of hydration. If the alkali content is small or
zero gypsum appears to lose its function and effectiveness when added
to the clinker. It does not affect setting significantly, even though
ettringite is produced. Analysis of the liquid phase reveals that the
hydroxyl ion concentration, i.e., the alkalinity of the liquid, is not
altered if gypsum is added. On the other hand, gypsum added to the
same clinker when it is also enriched with alkalies produces marked
changes. The setting time now depends strongly on the amount of gypsum,
and so does the alkalinity of the liquid phase. The presence of solid
gypsum serves to keep alkalinity low and to delay the transformation of
alkali sulfates to alkali hydroxides, the latter process starting only
when the solid gypsum is used up. The amount of gypsum added regulates
whether this transformation will take place before the set or after it.
110
Examining ordinary cements, it turns out that the transformation
begins approximately one or two hours after the final set. Assuming
that the experimentally-determined optimum amount of gypsum was added
at the cement plant, it appears that the optimum gypsum content is one
that prevents the alkali sulfates from transforming into alkali
hydroxides until the paste is completely set. At that point the
optimum ampunt of gypsum will have dissolved completely and the
transformation takes place. If the amount of gypsum added is too
small the tranformation will start before the completion of setting, or
even before initial set. Once the transformation starts the alkalinity
starts to build up rapidly, the rate depending on the amount of alkali
ions present, the reactivity of the calcium silicate and C.A present,
and perhaps other factors. If the rate of accumulation of hydroxyl ions
is rapid enough, the concentration of these ions may build up to a level
sufficient to induce so-called flash setting before the normal setting
can take place.
4.4. Experimental Evidence With Respect to the
Protective Layer Theory
The protective layer theory was discussed in Chapter 1 of this
thesis. The theory suggests that gypsum present in the hydrating cement
paste reacts at the surfaces of C.A forming a thin layer of ettringite
which subsequently protects the underlying C.A, otherwise the most
reactive phase present, from further reaction with water. In conse-
quence the whole process of hydration slows down and the set is delayed.
Although the theory is remarkably simple and logical, studies by
various authors have cast doubt on some details, and various
I l l
modifications have been suggested. However, the di scussi ons are mostly
concerned with the C.A phase, i t s r e a c t i vi t y, and the pr ot ect i on of i t s
exposed sur f aces.
One of the more t e l l i ng arguments against the theory i s the
general f ai l ur e t o deomonstrate the exi st ence of the proj ect ed t hi n
layer of . e t t r i ngi t e on C.A surfaces by scanning el ect r on microscopy.
On the other hand, more or l ess well developed needles of e t t r i n g i t e
are found in di f f er ent pl aces in cement past e, most usual l y concentrated
in capi l l ar y pores or attached t o cement cl i nker grai ns i ndi vi dual l y or
in small c l us t e r s . The pr ot ect i ve layer theory implies t hat the
formation of e t t r i ngi t e should be a topochemical r eact i on, but i t i s
cl ear from the usual observat i ons t hat most e t t r i ngi t e i s produced by
t hrough-sol ut i on pr ocesses. The problem cannot be regarded as sol ved,
and general opinion i s divided t oday.
Some of the present r e s ul t s may be i nt erpret ed as bearing on the
problem. The concent rat i on of aluminum ions found in the pore sol ut i ons
examined was always negl i gi bl e. The presence of iron in sol ut i on was
observed ear l y in the l i qui d phases examined, but the concent rat i ons
r api dl y diminished t o ef f ect i vel y zer o. Thus a sink for both aluminum
and iron ions must e xi s t .
The formation of e t t r i n g i t e might cer t ai nl y be expected t o pr o-
vide such a si nk, e t t r i n g i t e produced in cements usual l y being
somewhat deviant in composition from the t he or e t i c a l , and at l east
sometimes cont ai ni ng iron s ubs t i t ut i ng for some of the aluminum.
To i nvest i gat e the pos s i bi l i t y t hat e t t r i ngi t e forming by
t hrough-sol ut i on processes was act i ng as an iron sink as wel l as an
( aluminum si nk, a few wel l developed e t t r i ngi t e cr ys t al s were located
112
in SEM mounts of several of the past es examined and then analyzed with
respect t o iron content by energy-di spersi ve X-ray anal ysi s (EDXA).
The content of iron found in these e t t r i ngi t e cr ys t al s was pr act i cal l y
zer o, only t r ace amounts being detected at the var i ous spot s examined.
Thus i t appears t hat whatever the sink for di ssol ved i ron may be, i t i s
not the formation of e t t r i n g i t e .
One might argue t hat t hi s i s a point in favor of the topochemical
formation of e t t r i n g i t e , and consequently of the pr ot ect i ve layer
t heor y. However, the general import of the experi ment al r e s ul t s
obtained in t hi s i nvest i gat i on i s very much agai nst the pr ot ect i ve layer
t heor y, as det ai l ed in the five poi nt s ci t ed below.
1. An additon of gypsum to cl i nker low in al kal i es or without
al kal i es i s completely i neffect i ve in cont r ol l i ng the s e t ,
although X-ray di f f r act i on i ndi cat es the usual formation of
e t t r i n g i t e has occurred.
2. Addition of gypsum t o such cl i nker s speeds up the r at e of
accumulation of non-evaporable water (at l eas t wi t hi n the
f i r s t day of hydr at i on) . This suggests t hat the general r at e
of hydration i s not slowed down by the presence of the gypsum.
Such a slowdown i s a necessary feature of the formation of
the hypot het i cal pr ot ect i ve layer of e t t r i n g i t e .
3 . Even cl i nker s r i ch in C.A apparently wi l l not undergo fl ash
set in the absence of a l ka l i e s . Rat her, the opposite i s t r ue ,
and s et t i ng times in such circumstances are long and not
r el at ed t o the amount of C.A pr esent .
4 . The X-ray di f f r act i on pat t er ns seem t o i ndi cat e t hat normally
the production of e t t r i ngi t e in hydrat i ng cement past es seems
113
t o be at a const ant r a t e , at l east as long as t here are sul f at e
and calcium ions avai l abl e.
5. I f some C.A i s present and gypsum i s avai l abl e, the production
of e t t r i n g i t e always t akes place in cement hydr at i on. However,
the ef f ect i veness of the gypsum in influencing the set t i me,
hence the length of the "prot ect ed" peri od, depends on the
content of a l ka l i ions - which i s not easy t o r el at e t o
formation of a pr ot ect i ve l ayer .
I t i s bel i eved t hat these findings suggest t hat -the pr ot ect i ve
layer theory i s at the very l e a s t , incomplete, and may be bas i cal l y
i ncor r ect .
114
CHAPTER FIVE - CONCLUSIONS
The f ol l owi ng concl us i ons ar e drawn from t he r e s u l t s of t h i s
i n v e s t i g a t i o n .
1. The l i qui d phases of hydr a t i ng cements cont ai n measurabl e
c onc e nt r a t i ons of K , Na , Ca , SO, , OH , and o c c a s i o n a l l y ,
3+ . . .
Fe i ons . The c onc e nt r a t i ons of t hes e i ons bui l d up ver y
qui ckl y a f t e r mi xi ng and l a t e r onl y r e l a t i v e l y smal l changes
are obs er ved.
2 . The phenomenon of s e t t i n g i n por t l a nd cement pas t e does not
r e pr e s e nt t he at t ai nment of some l e ve l or st age of c onc e nt r a -
t i o n of any of t he i ons i n t he pore s o l u t i o n ; cement pa s t e s
may undergo s e t at wi del y va r yi ng c onc e nt r a t i ons of t he
va r i ous component s.
3 . The time t r e nds r e f l e c t i n g t he c onc e nt r a t i ons of t he d i f f e r e n t
i ons i n t he l i qui d phase ar e not at a l l i nt e r r upt e d or
modi fi ed by t he occur r ence of s e t .
4 . Se t t i ng i s al ways accompanied by a major t emper at ur e r i s e
of t he pas t e and by i nt e ns i ve p r e c i p i t a t i o n of Ca(OH). .
The pr esence of c r y s t a l l i n e Ca(OH). i s found at much e a r l i e r
t i mes of h y d r a t i o n , al t hough of t en in amounts t oo smal l t o be
de t e c t e d by X-ray d i f f r a c t i o n of t he bul k s o l i d s .
5 . The i n i t i a l s e t u s u a l l y occur s near t he begi nni ng of t he
t emper at ur e r i s e , but t h i s i s t r ue only f or normal or
115
moderate water:cement r a t i o systems. If water:cement r at i os
are unusually hi gh, i n i t i a l set i s delayed with respect t o
temperature evol ut i on.
6. Although the s et t i ng time i s influenced by many var i abl es ,
the al kal i content of the cement i s of the gr eat est s i gni f i -
cance. High a l k a l i cements wi l l set rapi dl y and low al kal i
cements wi l l set sl owl y, even i f they are of high fineness and
C.A cont ent .
7. Calcium ion concent r at i ons at t ai n a maximum values quickly, but
then s t ar t t o di mi ni sh at a slow and approximately constant
r a t e . Sur pr i si ngl y, s et t i ng does not i nt er f er e with or
appreciably i nfl uence the progress of t hi s slow decrease.
Calcium ion concent r at i ons are almost zero by the end of the
f i r s t day, r egar dl ess of the al kal i content or other chemical
parameters of the hydrat i ng cement system.
8. Sulfate ions concent r at i ons rapi dl y at t ai n a l evel t hat depends
on the content of a l ka l i sul f at es pr esent . They maintain t hi s
l evel as long as undissolved gypsum i s pr esent . On di ssol ut i on
of the l ast of the sol i d gypsum, a t urni ng point i s reached and
sul fat e concent r at i ons r api dl y and progressi vel y diminish t o
near-zero l e ve l s .
9. The hydroxyl ion concent r at i on r i s es quickly in a l l cements
to a l evel which r epr esent s the ef f ect s of i n i t i a l hydrol ysi s
of the cement cl i nker compounds. A second increase i s
observed with past es cont ai ni ng al kal i s ul f at es , st ar t i ng at
the turning poi nt marking the exhaustion of sol i d gypsum. This
increase r epr esent s t he conversion of dissolved al kal i sul f at e
116
t o al kal i hydroxide. Addi t i onal long-term hydrol ysi s may
increase the hydroxyl ion concent rat i on addi t i onal l y aft er
completion of t hi s pr ocess, but at a lower r a t e .
10. The turning point i s delayed i ndef i ni t el y i f a large excess
of gypsum i s provided t o the cl i nker . In t hi s case the sul f at e
and hydroxyl ions continue at approximately constant l evel s
although set t i ng and the onset of rapid cement hydration may
take place .
11. The magnitude of the jump in hydroxyl ion concent rat i on af t er
the turning point depends on the amount of a l ka l i e s , or more
s peci f i cal l y, on the a l ka l i sul f at e content of the cement. In
low al kal i cement pas t es , the jump i s small; in high al kal i
past es i t i s large in magnitude. Therefore, no t urni ng point
i s expected for cements without a l ka l i e s .
12. If the cement has a small or near zero content of al kal i es
gypsum loses i t s ef f ect in r egul at i ng cement set t i ng t i me.
13. Et t r i ngi t e forms in the very ear l y stages of cement hydrat i on
i f sul fat e i s avai l abl e, but the i neffect i veness of such
e t t r i ngi t e formation in i nfl uenci ng the s et t i ng time of
cements with l i t t l e or no a l ka l i cont ent s may be taken as
evidence agai nst the pr ot ect i ve layer t heory.
14. Al kal i hydroxides accel er at e s e t , and i f present in large
enough concent r at i on, can t r i gger fl ash s e t . The a bi l i t y of
gypsum t o delay the production of al kal i hydroxides unt i l
af t er normal s et t i ng i s seen as the foundation of i t s a bi l i t y
t o cont rol s et t i ng in normal cements. For ordinary commercial
cements, t hi s large scal e i nt er nal production of al kal i
117
hydroxide i s delayed and s t a r t s at about 2 hours aft er f i nal
s e t t i ng. I t i s suggested t hat the optimum gypsum content i s
pr i mar i l y the amount of gypsum necessary t o accomplish t h i s .
15. Addition of gypsum, al kal i s ul f at e, or both at the same time
r e s ul t s in i ncreasi ng the r at e of accumulation of non-
evaporable wat er. The rat e i s not changed unt i l af t er s et t i ng,
but af t er s e t t i ng, past es with added a l ka l i or calcium sul fat e
accumulate non-evaporable water more r api dl y than past es where
the cl i nker alone i s pr esent . The amount of increase cor r e-
l at es ni cel y with the pr eci pi t at i on of Ca(OH)..
LIST OF REFERENCES
(
118
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of Por t l and Cement Pa s t e s " . PCA Res . Dept . Bu l l . 12 ( 1946) .
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VITA
(
124
VITA
Mihael Penko was born on September 24, 1946, in Mari bor,
Yugoslavia. He r ecei ved hi s elementary and secondary educat i on in
Yugoslavia. He recei ved hi s B. Sc. degree in Physi cal Chemistry from
the Uni versi t y of Lj ubl j ana, Yugoslavia in 1971. After t hat he worked
as a research a s s i s t a nt at the I n s t i t u t Boris Ki dri c in Department for
St r uct ur al Chemistry. There he took hi s M.Sc. degree in 1976; hi s
major being Infrared and Raman Spect roscopy. He was accepted t o
Purdue Uni ver si t y i n January 1979 as a research as s i s t ant t o pursue
hi s Ph.D. st udi es in Ma t e r i a l s .