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Differential thermal method of estimating calcium hydroxide in calcium

silicate and cement pastes
Ramachandran, V. S.

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https://doi.org/10.1016/0008-8846(79)90062-0
Cement and Concrete Research, 9, November 6, pp. 677-684, 1979-11-01

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I

National Research Council of Canada

- Conseil national d e recherches du Canada
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I no. 869
cop. 2

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CALCIUM kIYDROXIDE IN CALCIUM STLXCATE
AND CEhENT PASTES
by V. S. Rmachandran

CN L L Y Z ' ~

Reprinted from:
Cement and Concrete Research
Val. 9, No. 6 , November 1979
p. 677 - 684

DBR Paper Ma. 869

Division of Building Research

Price $2.00 NRCC 17861

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CEMENT and .CONCRETE RESEARCH. Vol. 9 , pp. 677-684, 1979. P r i n t e d i n the U.S.A.
0008-88461791060677-08$02.00/0 Copyright ( c ) 1979 Pergamon Press, L t d .

DIFFERENTIAL THERMAL METHOD OF ESTIMATING CALCIUM

HYDROXIDE I N CALCIUM SILICATE AND CEMENT PASTES

..
V S Ramachandran
D i v i s i o n of B u i l d i n g Research
N a t i o n a l Research c o u n c i l of Canada AN A L ~ Z E ~
Ottawa, Canada

(Communicated by P. J. Sereda)
(Received J u l y 30, 1979)

AB STRAC T

DTA i s a p p l i e d t o e s t i m a t e Ca(OH)2 i n c e m e n t i t i o u s phases by d e t e r m i n i n g

t h e peak a r e a s caused by t h e decomposition of Ca(0H) 2 t o CaO+H20. I n
t h e h y d r a t i o n of C3S g e n e r a l l y , t h e chemical method y i e l d s s l i g h t l y
h i g h e r v a l u e s . DTA i s a l s o u s e d a s a monitoring t e c h n i q u e i n p r e p a r i n g
a p r a c t i c a l l y Ca(OH)2-free p r o d u c t from h y d r a t e d p o r t l a n d cement o r
h y d r a t e d C3S. Hydrated p o r t l a n d cement o r C3S h a s now b e e n exposed t o an
u n s a t u r a t e d Ca(OH)2 s o l u t i o n and e x t r a c t i o n c o n t i n u e d u n t i l t h e sample
i n d i c a t e no endothermal peak f o r Ca(OH)2. The thermal method p e r m i t s
d e t e r m i n a t i o n of t h e r a t e of f o r m a t i o n of Ca(OH)2 i n p o r t l a n d cement
h y d r a t e d i n t h e p r e s e n c e of 0, 1, 2 and 31 p e r c e n t CaC12.

L ' a u t e u r u t i l i s e l a t e c h n i q u e thermique d i f f g r e n t i e l l e pour 6 v a l u e r la

t e n e u r e n Ca(OH)2 d e s phases l i a n t e s e n dgterminant l e s s e c t e u r s p i c s
caus6s p a r l a d6composition du Ca(0H) 2 e n CaO + H20. Pour l ' h y d r a t a t i o n
du C3S, l a mgthode chimique donne gGn6ralement d e s v a l e u r s 16gSrement
p l u s 6 l e v g e s . La m6thode thermique d i f f g r e n t i e l l e s e r t a u s s i de
technique de c o n t r g l e dans l a p r 6 p a r a t i o n d'un p r o d u i t pratiquement
exempt de Ca(OH)2 2 p a r t i r de ciment p o r t l a n d ou de C3S h y d r a t 6 .
L ' a u t e u r expose du ciment p o r t l a n d o u du C3S hydrati5 5 une s o l u t i o n de
Ca(0H) 2 non s a t u r g e e t c o n t i n u e l ' e x t r a c t i o n j u s q u ' s c e que 1 1 6 c h a n t i l l o n
ne p r o d u i s e p l u s de p i c s endothermiques e n p r g s e n c e de Ca(OH)2. La
m6thode thermique permet de dgterminer l a v i t e s s e de f o r m a t i o n du Ca(OH)2
dans l e ciment p o r t l a n d h y d r a t 6 e n pr6sence de 0, 1, 2 e t 33 pour c e n t
de CaC12.
 Vol. 9, No. 6
V.S. Ramachandran

Introduction

A knowledge of t h e amount of f r e e CH formed d u r i n g t h e h y d r a t i o n of C3S,

C2S and p o r t l a n d cement i s e s s e n t i a l i n following t h e k i n e t i c s and
determining t h e composition of calcium s i l i c a t e h y d r a t e . Calcium hydroxide,
a s one of t h e major phases c o n s t i t u t i n g hydrated cement and hydrated calcium
s i l i c a t e s , e x e r t s a s i g n i f i c a n t i n f l u e n c e on t h e i r physico-mechanical
c h a r a c t e r i s t i c s . I n t h e s y n t h e s i s of calcium s i l i c a t e h y d r a t e s t h e
d e t e r m i n a t i o n of Ca(OH)2 permits monitoring of t h e r e a c t i o n s . Estimation of
Ca(OH)2 s e r v e s a s a method of measuring t h e r e a c t i v i t y of pozzolanic m a t e r i a l s .

S e v e r a l methods have been suggested f o r e s t i m a t i n g t h e amount of Ca(OH)2

i n c e m e n t i t i o u s m a t e r i a l s . Although c a l o r i m e t r i c , X-ray, conductometric
t i t r a t i o n , and thermal techniques have been used s p o r a d i c a l l y , t h e chemical
e x t r a c t i o n method, i n v o l v i n g s o l v e n t s such a s e t h y l e n e g l y c o l , a c e t o a c e t i c
a c i d + isobu'tyl. ~ l c o h o l(Franke method) and o t h e r s , seems t o b e most popular.
I n t h e chemical 'mdihiid, however, t h e r e i s concern t h a t t h e s o l v e n t , i n
a d d i t i o n t o e x t r a c t i n g f r e e Ca(OH)2, may a t t a c k c o n s t i t u e n t s such a s calcium
aluminates, high sulfoalurninates, MgO, and t h e hydrated products of t h e
f e r r i t e phase and calcium s i l i c a t e h y d r a t e ( 1 - 3 ) . I t i s a l s o recognized t h a t
i n t h e chemical method a l a r g e number of parameters a f f e c t t h e r e s u l t s and it
i s somewhat time consuming. As a r e s u l t , t h e r e i s a c o n s t a n t s e a r c h f o r a
r e l i a b l e a l t e r n a t i v e method of e s t i m a t i n g f r e e Ca(0H) 2 .

I n r e c e n t years t h e thermogravimetric technique (TG) has been suggested

f o r e s t i m a t i n g f r e e Ca(OH)2 (4-11). A l i m i t a t i o n i s t h a t it i s not always
easy t o d e l i n e a t e t h e temperature i n t e r v a l s corresponding t o t h e weight l o s s
due t o Ca(OH)2 decomposition. A s w e l l , hydrated products o t h e r t h a n Ca(OH)2
may a l s o l o s e weight i n t h e same temperature range a s Ca(OH)2. Although t h e
technique of DTA has been recognized a s a v a l u a b l e t o o l f o r t h e i d e n t i f i c a t i o n
of v a r i o u s hydrated and unhydrated phases i n cement systems, it has n o t been
a p p l i e d widely f o r q u a n t i t a t i v e purposes ( 1 2 ) . A r e c e n t paper published by
Midgley shows t h e thermal a n a l y s i s technique t o be v e r y r e l i a b l e f o r
e s t i m a t i n g Ca(0H) 2 i n s e t p o r t land cement (13) .
I n a n o t h e r r e c e n t i n v e s t i g a t i o n , an e s t i m a t i o n of t h e components i n white
c o a t p l a s t e r s , v i z , CaS04. 2H20, hlg (OH) 2 , Ca(0H) 2 , CaC03 and MgO, was
accomplished by applying t h e d i f f e r e n t i a l thermal technique ( 1 4 ) . Estimated
v a l u e s corresponded c l o s e l y t o t h o s e determined by chemical a n a l y s i s . I t was
t h e r e f o r e of i n t e r e s t t o extend t h e method by e s t i m a t i n g Ca(OH)2 i n o t h e r
c e m e n t i t i o u s systems. I n t h e p r e s e n t paper t h e r a t e of h y d r a t i o n of C3S i s
followed by e s t i m a t i o n of Ca(OH)2, u s i n g d i f f e r e n t i a l thermal and chemical
methods of a n a l y s i s . The d i f f e r e n t i a l thermal technique i s a l s o a p p l i e d t o
i n v e s t i g a t i n g t h e e f f e c t of CaCl2 and w a t e r / s o l i d r a t i o on t h e formation of
Ca(OH)2 during h y d r a t i o n of C3S. I t s a p p l i c a b i l i t y f o r monitoring t h e r a t e o f
e x t r a c t i o n of Ca(0H) from a c o m p l e t e l y ~ h y d r a t e dC3S and cement u s i n g under-
s a t u r a t e d Ca(OH)2 s o l u t i o n i s a l s o examined.

Experimental

Materials

The sample of t r i c a l c i u m s i l i c a t e used i n t h i s work was made a v a i l a b l e

by t h e P o r t l a n d Cement A s s o c i a t i o n , U.S.A., and had t h e f o l l o w i n g composition
expressed a s a percentage i g n i t e d b a s i s :
V o l . 9, No. 6 ,679
DTA, Ca(OH)*, CEMENT PASTES, UNDERESTIMATION

CaO, 73.88; S O 2 , 26.17; A1203, 0.08; f r e e CaO (ASTM), 0.18; f r e e CaO (Franke),
0.46. Mineralogical a n a l y s i s : C3S, 99.33; C2S, 0.00; C3A, 0.21; CaO (Franke),
0.46. Fineness : B l a i n e 3310 cm2/g.

Calcium hydroxide used f o r c a l i b r a t i o n purposes was o b t a i n e d by c a l c i n i n g

Analar Grade CaC03 t o 1000°C f o r 3 h and h y d r a t i n g t h e r e s u l t i n g CaO i n
d i s t i l l e d w a t e r . The p u r i t y of Ca(OH)2 was checked by TGA and c o n s i d e r e d
s a t i s f a c t o r y f o r drawing t h e c a l i b r a t i o n curve.

P o r t l a n d cement, Type I , of t h e following compound composition was used

f o r s t u d y i n g t h e e f f e c t of CaC12 on i t s h y d r a t i o n c h a r a c t e r i s t i c s : C3S = 51.5
p e r c e n t , C2S = 19.8 p e r c e n t , C3A = 12.8 p e r c e n t and C4AF = 6.6 p e r c e n t .
The completely h y d r a t e d p o r t l a n d cement, Type I , from which t h e Ca(OH)2-free
product was prepared had o r i g i n a l l y t h e f o l l o w i n g compound composition:
C3S = 46.5 p e r c e n t , C2S = 24.6 p e r c e n t , C3A = 10.4 p e r c e n t and C4AF = 9 . 3
per cent.

Calcium c h l o r i d e hexahydrate of a n a l y t i c a l r e a g e n t q u a l i t y was d i s s o l v e d

i n water t o o b t a i n an approximate c o n c e n t r a t i o n of 15 p e r c e n t . The e x a c t
c o n c e n t r a t i o n was determined by t h e a r g e n t o m e t r i c method and d i l u t i o n s were
made t o any r e q u i r e d c o n c e n t r a t i o n f o r s t u d y i n g t h e e f f e c t o f CaC12 on t h e
h y d r a t i o n c h a r a c t e r i s t i c s o f p o r t l a n d cement.

Hydration

The h y d r a t i o n of C3S was i n v e s t i g a t e d by mixing i t with d o u b l e - d i s t i l l e d

water a t a w a t e r - t o - s i l i c a t e r a t i o of 0 . 3 . The h y d r a t i o n was c a r r i e d o u t i n
~

t i g h t l y covered p o l y e t h y l e n e c o n t a i n e r s r o t a t e d c o n t i n u o u s l y over r o l l e r s .
A t s p e c i f i c i n t e r v a l s of time each sample was d r i e d a t 110°C i n vacuum f o r
3 h.

The h y d r a t i o n of p o r t l a n d cement i n t h e presence of CaC12 was s t u d i e d by

making cement cubes o f 5.1 cm and exposing them a t a w/c r a t i o of 0.25 o r 0.4
f o r 6 h and 12 h, and 1, 2, 3 , 7 , 14, 28 and 90 days. The c o n c e n t r a t i o n s of
CaC12 i n t h e mixing water were a d j u s t e d i n such a way t h a t t h e p a s t e s
c o n t a i n e d 0, 1, 2 and 3% per c e n t CaC12 with r e s p e c t t o p o r t l a n d cement.

E x t r a c t ion of Ca (OH) 2

Discs 0.64 t o 0.76 mm t h i c k were c u t from c y l i n d e r s prepared by

h y d r a t i o n of C3S o r p o r t l a n d cement a t a w a t e r l s o l i d r a t i o 0.5 f o r about 10
y e a r s . They were placed i n a cage and exposed t o 5 l i t r e s o f an aqueous
s o l u t i o n c o n t a i n i n g 9 . 5 mmol/L of CaO. The s l i c i n g and e x t r a c t i o n were
c a r r i e d o u t i n a C02-free atmosphere.

Analysis

A d i f f e r e n t i a l scanning c a l o r i m e t r i c (DSC) c e l l s u p p l i e d a s a module t o

a Du Pont 990 thermal a n a l y s i s system was used t o o b t a i n thermograms from room
temperature t o 550°C. I n each experiment 20 mg of sample was heated i n a i r a t
a r a t e of loOc/min. For c a l i b r a t i o n purposes Ca(OH)2 of known p u r i t y was
mixed with C3S i n d i f f e r e n t p r o p o r t i o n s and endothermal peak a r e a s were
p l o t t e d a g a i n s t Ca(OH)2 c o n c e n t r a t i o n s . The endothermal peak a r e a s were
determined by a p l a n i m e t e r . A l l samples were d r i e d a t llOOc f o r 3 h i n
vacuum p r i o r t o thermal a n a l y s i s .
 Vol. 9, No. 6
V.S. Ramachandran

5 1 1 I I I I d The s o l v e n t v a r i a t i o n method

/-
(SVM) was used t o e s t i m a t e Ca(OHl2
4 -
- i n some samples ( 1 ) . I t consisted
= - of e x t r a c t i o n w i t h a mixture of
4
r
U)

-
+. e t h y l a c e t o a c e t a t e and i s o b u t y l
25 3 a l c o h o l i n a 3 t o 20 r a t i o byvolume.
;= The r a t i o o f t h e s o l v e n t volume t o
£ 2 - sample weight was v a r i e d from 1000
-Z
u-
=
Im
-
LI
2
t o 3000 mL p e r gm and t h e time of
-
5
1
; / O 8 O
- each e x t r a c t i o n was maintained a t
30 min. A p l o t of t h e volume of
s o l v e n t a g a i n s t Ca(OH)2 e x t r a c t e d
a I 1 I t t 1 gave a s t r a i g h t l i n e whose i n t e r c e p t
5 LO 15 20 25 30 35
r e p r e s e n t e d t h e f r e e Ca(OH)2 con-
CaIOH12. %
t a i n e d i n t h e sample.
Fig. 1 C a l i b r a t i o n curve f o r
e s t i m a t i o n of Ca(0H) 2 by R e s u l t s and Discussion
d i f f e r e n t i a l thermal technique
Figure 1 r e p r e s e n t s t h e c a l i b r a -
25 I I I I I I t i o n curve of t h e endothermal peak
a r e a s due t o Ca(0H) 2 decomposition
CHEMICAL METHOD- _,
__ __----- i n Ca(OH)2-C3S mixtures c o n t a i n i n g
a THERMAL METHOD '
20
pa-- d i f f e r e n t amounts o f Ca(OH)2. A
good l i n e a r r e l a t i o n f o r samples
4
l5 c o n t a i n i n g up t o about 33 p e r c e n t
z 'J
l? Ca(OH)2 a t t e s t s t o t h e a p p l i c a b i l i t y
-
0

: lo of t h e d i f f e r e n t i a l thermal t e c h -
nique f o r t h e e s t i m a t i o n of Ca(OH)2.
A t a high s e n s i t i v i t y an amount a s
5 - low a s 0 . 1 p e r c e n t Ca(OH)2 can be
estimated.
Oo Ib A o:
TIME, days
4IO O: 6b 10 The r e l a t i v e amounts o f Ca(0H) 2
formed a t d i f f e r e n t p e r i o d s during
Fig. 2 Amounts o f Ca(0H) 2 formed t h e h y d r a t i o n o f C3S were estimated
i n t h e hydration of C3S by both d i f f e r e n t i a l thermal and
chemical methods of a n a l y s i s and
t h e r e s u l t s a r e compared i n Figure
2. Both show t h a t t h e r a t e o f
formation of Ca(OH)2 i s r e l a t i v e l y
40 high i n t h e f i r s t 7 days, a f t e r
which it becomes more g r a d u a l .
IDEAL LINE
Although t h e general t r e n d s a r e
s i m i l a r , t h e v a l u e s r e s u l t i n g from
t h e use of chemical a n a l y s i s a r e
h i g h e r t h a n those from t h e thermal
method. The d i f f e r e n c e becomes
l a r g e r a s hydration p r o g r e s s e s .
This, however, can be expected
s i n c e t h e chemical method i n v o l v e s
,b 2b O: ao 50 a t t a c k o f t h e C-S-H phase by t h e
Ca10H12. % B Y C H E M I C A L M E T H O D s o l v e n t . Figure 3 g i v e s t h e
r e l a t i o n between Ca(0H) 2 v a l u e s
Fig. 3 Comparison of chemical and e s t i m a t e d by t h e d i f f e r e n t i a l
thermal methods o f e s t i m a t i n g thermal method and t h e chemical
Ca(OH) 2 method; t h e p o i n t a t about 40 p e r
 VoF. 9, No. 6 681
DTA, Ca(OH)2, CEMENT PASTES, UNDERESTIMATION

c e n t Ca(OH)2 r e p r e s e n t s a v a l u e f o r an almost
completely hydrated C3S. Although a l l t h e
points l i e close to t h e ideal l i n e , there i s
unmistakable evidence t h a t chemical a n a l y s i s
y i e l d s s l i g h t l y higher v a l u e s .

In t h e C3S samples hydrated f o r d i f f e r e n t

p e r i o d s t h e endothermal e f f e c t due t o decom-
p o s i t i o n of Ca(OH)2 (of d i f f e r e n t c r y s t a l
s i z e s ) occurs i n t h e temperature range 450 t o
550°C. S i m i l a r o b s e r v a t i o n s have a l s o been
made i n p o r t l a n d cement p a s t e s . As no o t h e r
compound i n t h e hydrated cement e x h i b i t s
thermal e f f e c t s i n t h e temperature range 450
t o 550°C, i n t e r f e r e n c e e f f e c t s a r e l a r g e l y
avoided .

One method o f examining t h e r o l e o f Ca(OH)2

i n hydrated cementitious systems c o n s i s t s of
s t u d y i n g t h e hydrated product from which
Ca(OH)2 i s s e l e c t i v e l y e x t r a c t e d . Any
technique adopted t o remove f r e e Ca(OH)2
should not b e d e t r i m e n t a l t o t h e chemical
s t r u c t u r e of t h e h y d r a t e s c o n s t i t u t i n g t h e
system. I t appears t h a t t h e l e a s t s e v e r e
t r e a t m e n t , coupled w i t h a good monitoring
technique, c o n s i s t s of p l a c i n g t h e m a t e r i a l i n
an u n s a t u r a t e d Ca(OH)2 s o l u t i o n and monitoring
from time t o time t h e amount o f remaining f r e e
Ca(OH)2 by t h e d i f f e r e n t i a l thermal technique. TEMPERATURE. "C
D i f f e r e n t i a l thermal curves o f t h e sample
subjected t o extraction f o r d i f f e r e n t periods Fig. 4 Endothermal effect
i n d i c a t e t h a t a s t h e f r e e Ca(OH)2 is d i s s o l v e d due t o Ca(OH)2 i n
t h e i n t e n s i t y of t h e endothermal peak a r e a due hydrated C 3S exposed
t o Ca(0H) 2 d e c r e a s e s gradual l y ( F i g u r e 4) . t o d i f f e r e n t times
The amount of Ca(OH)2 remaining a t d i f f e r e n t of extraction
times i s p l o t t e d i n Figure 5 . Almost a l l
Ca(OH)2 i s e x t r a c t e d i n about 12 days. F u r t h e r
c o n t a c t of t h e m a t e r i a l w i t h t h e e x t r a c t i n g
s o l u t i o n i s not d e s i r a b l e because t h e
p o s s i b i l i t y e x i s t s t h a t lime i n t h e calcium
s i l i c a t e h y d r a t e may b e a t t a c k e d by t h e
u n s a t u r a t e d lime s o l u t i o n . The s t e e p curve
a t e a r l i e r p e r i o d s i n Figure 5 r e p r e s e n t s a
f a s t e r r a t e o f e x t r a c t i o n o f Ca(OH)2 s i t u a t e d
c l o s e t o t h e s u r f a c e of t h e sample. I f a
t h i c k e r sample had been used, t h e time
i n t e r v a l between e x t r a c t i o n o f Ca(W) 2
s i t u a t e d c l o s e t o t h e s u r f a c e and t h a t
s i t u a t e d i n t h e i n t e r i o r of t h e specimen would
have been much longer, and t h e tendency o f t h e
e x t r a c t i n g s o l u t i o n a t t a c k i n g t h e C-S-H phase TIME, days
would have i n c r e a s e d .
Fig. 5 I n f l u e n c e OF time on
Calcium hydroxide-free p o r t l a n d cement e x t r a c t i o n of Ca(0H)
p a s t e was a l s o prepared from a f u l l y hydrated from hydrated C 3s
 Vol. 9, No. 6
V.S. Ramachandran

I I I

-.
2
.r
30

-
I
0

rn
U

-
20

", _._._._A-.-.-.-.-.--
-I..

+
: -
i
5 1 0
-1 - -
-
\b,I
0 6 12 24 48 72 01 3 1 14

0 TIME. h TIME. d
5 10 I5 10

T I M E . days Fig. 7 I n f l u e n c e of calcium c h l o r i d e on

t h e formation of calcium hydroxide
Fig. 6 I n f l u e n c e of t i m e on d u r i n g t h e h y d r a t i o n of p o r t l a n d
e x t r a c t i o n o f Ca(0H) 2 cement (w/c = 0.25)
from hydrated cement

cement sample by t h e t e c h n i q u e
d e s c r i b e d above. The r e s u l t s _.-.-
_._.-.
__-.
a r e shown i n Figure 6. A f u l l y a
/-
hydrated p o r t l a n d cement c o n t a i n s
l e s s f r e e Ca(OH)2 t h a n a f u l l y
hydrated C3S p a s t e . I t t a k e s
-IT% CaC12
somewhat l o n g e r , however, t o
e x t r a c t a l l t h e f r e e Ca(0H) 2 .......
from p o r t l a n d cement p a s t e . I t
has a h i g h e r p o r o s i t y and lower
microhardness than does C3S 0 6 1 2 2 4 48 72 0 1 3 7
I
14
i
28' 9 0
p a s t e b e f o r e e x t r a c t i o n , and
TIME, h TIME, d
t h e s e f a c t o r s would b e expected
t o f a c i l i t a t e r a t h e r than F i g . 8 I n f l u e n c e of calcium c h l o r i d e on
r e t a r d t h e e x t r a c t i o n of Ca(OH)2 t h e formation o f calcium hydroxide
from t h e cement p a s t e . I t i s d u r i n g t h e h y d r a t i o n of p o r t l a n d
p o s s i b l e t h a t i n cement p a s t e s cement (w/c = 0.4)
c o n t a i n i n g aluminate and
f e r r i t e phases ( i n a d d i t i o n t o
s i l i c a t e phases) t h e hydrated lime i s enveloped by h y d r a t i o n p r o d u c t s much
more e f f i c i e n t l y t h a n it i s i n C3S p a s t e s ; t h u s t h e p e r m e a b i l i t y o f t h e s o l i d
t o t h e e x t r a c t i n g s o l u t i o n would b e reduced.

One method o f f o l l o w i n g t h e r a t e o f h y d r a t i o n of cement and C a - s i l i c a t e s

i n v o l v e s d e t e r m i n a t i o n o f f r e e Ca(OH)2 formed a t d i f f e r e n t times, applying
chemical t e c h n i q u e s . The a p p l i c a b i l i t y o f t h e d i f f e r e n t i a l thermal technique
of e s t i m a t i n g f r e e Ca(OH)2 produced d u r i n g t h e h y d r a t i o n of p o r t l a n d cement
c o n t a i n i n g d i f f e r e n t percentages of CaC12 i s i l l u s t r a t e d i n F i g u r e s 7 and 8
( 1 5 ) . I n each sample t h e amount o f Ca(OH)2 formed i n c r e a s e s w i t h time, t h e
h i g h e s t r a t e o c c u r r i n g i n t h e f i r s t 24 h. A t a w/c = 0.25 a l l samples show
lower amounts of Ca(OH)2 t h a n do t h o s e hydrated a t w/c = 0 . 4 . T h i s can b e
e x p l a i n e d by t h e r e l a t i v e l y lower degree of h y d r a t i o n i n samples made a t a
w/c = 0.25. Rate o f h y d r a t i o n , based on amount of Ca(OH)2, depends on t h e
t o t a l p e r i o d of h y d r a t i o n and t h e dosage of t h e admixture. A t 28 days and a
w/c = 0.40 t h e r a t e of h y d r a t i o n i n terms o f Ca(OH)2 formation i s a s follows:
cement + 1 t o 2 p e r c e n t CaC12 > cement + 0 t o 3 4 p e r c e n t CaC12; a t a
V o l . 9, No. 6 683
DTA, Ca(OH)*, CEMENT PASTES. UNDERESTIMATION

w/c = 0.25 t h e o r d e r i s : cement + 1 p e r c e n t CaC12 > cement + 2 p e r c e n t

CaC12 > cement + 0 p e r c e n t CaC12 >cement + 34 p e r c e n t CaC12. I f t h e r a t e
of h y d r a t i o n i s based on t h e non-evaporable water c o n t e n t , which r e f l e c t s t h e
t o t a l amount of a l l hydrated p r o d u c t s , t h e r a t e of h y d r a t i o n i s i n t h e o r d e r :
cement + 2 t o 3 s p e r c e n t CaC12 > cement + 1 p e r c e n t CaC12 > cement + 0 p e r
c e n t CaC12 (15). This d i s c r e p a n c y h a s a l s o been observed i n t h e C3S-CaC12-
H20 system ( 1 6 ) . I t can be explained by t h e formation o f t h e C-S-H product
w i t h a h i g h e r t h a n normal C/S r a t i o i n samples c o n t a i n i n g 34 p e r c e n t CaC12.
Caution should t h e r e f o r e be e x e r c i s e d i n u s i n g t h e e s t i m a t i o n o f Ca(OH)2 a s a
b a s i s f o r comparing t h e degree of h y d r a t i o n of d i f f e r e n t m a t e r i a l s . The
method can be a p p l i e d t o follow t h e h y d r a t i o n o f a p a r t i c u l a r m a t e r i a l p e r s e
and t o determine t h e composition o f t h e C-S-H p r o d u c t .

Conclusions

The d i f f e r e n t i a l thermal technique a p p e a r s t o b e a u s e f u l a l t e r n a t i v e t o

chemical methods o f e s t i m a t i n g Ca(OH)2 i n c e m e n t i t i o u s systems; it i s l e s s
time consuming, needs only small amounts o f sample, and appears t o b e more
r e l i a b l e . The d i f f e r e n t i a l thermal method p e r m i t s e s t i m a t i o n of CaO a f t e r
conversion t o Ca(0H) 2 by a u t o c l a v i n g .

The chemical method o v e r e s t i m a t e s Ca(OH)2 by i n c l u d i n g o t h e r h y d r a t e s i n

t h e hydrated cement o r calcium s i l i c a t e ; and t h e X-ray method u n d e r e s t i m a t e s
Ca (OH) 2 by n o t r e g i s t e r i n g t h e presence of m i c r o c r y s t a l l i n e or n e a r amorphous
Ca(0H) 2 .

Acknow ledeements

The a u t h o r wishes t o thank G.M. Polomark f o r t h e experimental a s s i s t a n c e .

This paper i s a c o n t r i b u t i o n from t h e Division of Building Research, N a t i o n a l
Research Council o f Canada, and i s published w i t h t h e approval o f t h e
D i r e c t o r of t h e D i v i s i o n .

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