CEMENT and CONCRETERESEARCH. Vol. I , pp. 607-620, 1971.

Pergamon Press, Inc

Printed in the United States.

D I F F E R E N T I A T I O N O F I N T E R L A Y E R AND A D S O R B E D
W A T E R IN H Y D R A T E D P O R T L A N D C E M E N T BY
THERlvlAL ANALYSIS

R. F . F e l d m a n and V. S. R a m a c h a n d r a n
D i v i s i o n of B u i l d i n g R e s e a r c h , N a t i o n a l R e s e a r c h C o u n c i l of C a n a d a
O t t a w a 7, O n t a r i o , C a n a d a

(Communicated by G. L. Kalousek)

ABSTRACT
W o r k l e a d i n g to t h e n e w m o d e l of h y d r a t e d p o r t l a n d c e m e n t h a s
s h o w n t h a t m u c h of t h e w a t e r p r e v i o u s l y c o n s i d e r e d t o r e s i d e on
f r e e s u r f a c e s e x i s t s a s i n t e r l a y e r w a t e r . In t he p r e s e n t w o r k
samples were conditioned at various relative humidities for
t i m e s v a r y i n g f r o m 1½ t o 14 m o n t h s and w e r e d r i e d t o t w o d i f f e r -
e n t l e v e l s b e f o r e c o n d i t i o n i n g , one b e i n g d - d r y . Conditions
w e r e c h o s e n , b a s e d on t he m o d e l , so t h a t t h e d i f f e r e n t s t a t e s of
w a t e r c o u l d be c l e a r l y i l l u s t r a t e d . It w a s c o n c l u d e d t h a t t h e r m a l
a n a l y s i s a l l o w s d i f f e r e n t i a t i o n of i n t e r l a y e r and p h y s i c a l l y
a d s o r b e d w a t e r and t h a t t he d i f f e r e n t d e g r e e s of d r y i n g and v e r y
lo n g t i m e s a l l o w e d f o r e q u i l i b r a t i o n s u p p o r t al l s o r p t i o n r e s u l t s
on w h i c h t he n e w m o d e l of h y d r a t e d p o r t l a n d c e m e n t w a s b a s e d .
SOMMAIRE
L e s t r a v a u x m e n a n t ~ la n o u v e l l e f o r m u l e de c i m e n t p o r t l a n d
h y d r a t ~ ont d ~ m o n t r ~ q u ' u n e g r a n d e p a t t i e de l ' e a u q u ' o n c r o y a i t
qui d e m e u r a i t a u p a r a v a n t s u r l e s s u r f a c e s l i b r e s , e x i s t e s o u s
f o r m e d ' e n t r e c o u c h e d ' e a u . Dans la p r ~ s e n t e ~tude, les ~ c h a n t i -
l l o n s ont ~t~ c o n d i t i o n n ~ s h d i v e r s e s h u m i d i t ~ s r e l a t i v e s p o u r d e s
p ~ r i o d e s de t e m p s v a r i a n t e n t r e 1 ½ t o o l s ~ 14 t o o l s , et f u r e n t
s o u r n i s au s ~ c h a g e h d e u x n i v e a u x d i f f ~ r e n t s a v a n t le c o n d i t i o n n e -
m e n t , un d e s n i v e a u x ~tant " d - d r y . " Les conditions furent
c h o i s i e s , b a s ~ e s s u r la n o u v e l l e f o r m u l e , a f i n que l e s d i v e r s
~ t a t s de l ' e a u p u i s s e n t ~ t r e c l a i r e m e n t i l l u s t r ~ s . On en a c o n c l u s
que l ' a n a l y s e t h e r m i q u e p e r m e t la d i f f ~ r e n c i a t i o n d e s e n t r e -
c o u c h e s et de lZeau a d s o r b ~ e p h y s i q u e m e n t , et que l e s d i f f ~ r e n t s
d e g r ~ s de s ~ c h a g e e t l e s t r h s l o n g u e s p ~ r i o d e s de t e m p s p e r m i s e s
p o u r l ' ~ q u i l i b r a t i o n s u p p o r t e n t t o u s l e s r ~ s u l t a t s de d 4 s o r p t i o n
s u r l e s q u e l s . l a n o u v e l l e f o r m u l e de c i m e n t p o r t l a n d h y d r a t ~ ~ t a i t
bas~e.

P r e s e n t e d at t h e S e c o n d C e m e n t S y m p o s i u m h e l d as p a r t of t h e 7 3 r d A n n u a l
M e e t i n g of t h e A m e r i c a n C e r a m i c S o c i e t y , C h i c a g o , A p r i l 1971.

607
608 Vol. I , No. 6
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

Introduction

A n e w m o d e l for hydrated portland c e m e n t has been recently

described (I). Portions of the m o d e l w e r e based on results f r o m water

sorption experiments (2) and conclusions w e r e m a d e with regard to the state

of the water and its role in the system. T h e m o d e l recognizes that the

hydrated calcium silicates in hydrated portland c e m e n t are layer-structured

but poorly oriented, and with a spacing b e t w e e n layers that m a y vary f r o m

region to region. Much of the water which had previously been considered

to reside on free surfaces is n o w considered to exist as interlayer water,

and m a n y of the physical and m e c h a n i c a l properties of hydrated portland

c e m e n t are ascribed to this.

T h e m o d e l has aroused considerable interest but doubts have been

e x p r e s s e d (3). In a continuing research p r o g r a m at the National R e s e a r c h

Council on the n e w m o d e l , significant n e w evidence w a s developed on the

manner in w h i c h water occurs in C - S - H . In w o r k on c e m e n t s so far reported

no systematic w o r k s e e m s to have been done on the t h e r m a l analysis of

s a m p l e s at controlled conditions of humidity (4, 5). However, thermal

analysis of s a m p l e s equilibrated at different relative humidities, based on

the model, clearly differentiates b e t w e e n adsorbed and interlayer water.

T h e results are presented in this report.

Experimental

M ate rial s

A T y p e I portland c e m e n t w a s bottle-hydrated for 1½ years at a

water-to-solid ratio of 5. It w a s almost completely hydrated; carbon
dioxide content w a s I % and the surface area by nitrogen adsorption w a s
ZZm2/gm. T h e bottle-hydrated p o w d e r w a s dried to 1 1 % R . H . and screen-

ed over a 1 0 0 - m e s h sieve. T h e residue of large C a ( O H ) 2 crystals w a s

ground and r e m i x e d with the powder.

S a m p l e Conditioning

T h e bottle-hydrated p o w d e r w a s restored at 1 1 % R . H . (over sat-

urated solution of LiCI) in a desiccator for 6 m o n t h s and designated prep-
Vol. l , No. 6 609
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

aration A. One portion of A was spread 2 to 3 m m thick in dishes andplaced

in a large desiccator with a large-diameter tube fixed to the lid. The tube
led to a p u m p i n g system which consisted of a trap cooled with solid C O 2 and
a two-stage rotary pump. This corresponds to the well-known d-drying
procedure. After 5 weeks of pumping the material was placed in a v a c u u m
vessel and heated for 3 hr at 100°C. This sample is designated preparation
B. Another portion of A designated preparation G w a s placed in a v a c u u m
vessel and heated to 70°C for approximately 2 hr. It was found to contain
approximately 3 % m o r e water than the d-dried sample. Small amounts of
preparations A , B and C w e r e placed in desiccators over saturated salt
solutions (intermittently stirred by magnetic stirrers) to control at l l, 3Z,
44, 58, 66, 76, 84 and 1 0 0 % R . H . , respectively. After a period of time
samples of preparations B and C exposed at different humidities as described
above w e r e placed in another v a c u u m desiccator conditioned at 1 I% R . H .

These reconditioned samples w e r e designated B(R) and C(R). The s c h e m a

below illustrates h o w the samples were designated and their history.

Preparation A

Preparation B Preparation C
d-dried 3 % m o r e H z O than
preparation B

> <
ii 32, 44, 58, 66, 76, 84 and 100% m. H°

Ii% R.H. 1%RH.

Preparation B(R) Preparation C(R)

Table I shows the length of time samples of preparations A, B, C,

B(R) and C(R) were held at each condition before they w e r e analyzed. As
can be seen, the times w e r e usually about several months. Entries in the
columns under T G A and D T A show w h e n samples were tested by each
te chnique.
610 Vol. l , No. 6
WATER, INTERLAYER, ADSORBED,THERMALANALYSIS

TABLE I

P e r i o d s (in M o n t h s ) D u r i n g Which S a m p l e s W e r e

Conditioned at Respective Relative H u m i d i t i e s

Exposed at
A B C(R)
%R.H. B(B.){, TGA C
DTA TGA DTA TGA DTA I DTA TGA DTA TGA

11 12-14 14-16 3-6 i. 25 4.25-6.25 2.75 7-9 9-11 3 3

Back to 11% R . H . 3-5 I. 50 ! -- -- 4-6 7
32 7-9 3-6 i. 25 1.25 1.25 7-9 9-Ii 3 3
Back to 11% R . H . 3-5 i. 50 -- -- 4-6 7
44 7-9 9-11 3-6 1.25 1.25 1.25 7-9 9-Ii 3 3
Back to 11% R . H . 3-5 1. 50 -- -- 4-6 7
58 7-9 9-II 3-6 i. 25 1.25 1.25 7-9 9-ii 3 3
Back to 11% R . H . 3-5 I. 50 -- -- 4-6 7
66 7-9 9-11 3-6 1.25 1.25 1.25 7-9 9-11 3 3
Back to 11% R . H . 3-5 I. 50 -- -- 4-6 7
76 7-9 9-11 -- -- 7-9 9-11 3 3
B a c k to 11% R . H . . . . . 4-6 7
84 7-9 9-11 3-6 I. 25 1.25 1.25 7-9 9-11 3 3
B a c k to i i % R . H . 3-5 I. 50 -- -- 4-6 7
i00 7-9 9-11 3-6 1. 25 1.25 1.25 7-9 9-11 3 3
B a c k to i i % R . H . 3-5 I. 50 -- -- 4-6 7

Thermal Analysis

In t h i s w o r k D T A and T G A w e r e c a r r i e d out u n d e r c o n t r o l l e d c o n -
d i t i o n s of h u m i d i t y , t he d e t a i l s of w h i c h h a v e b e e n p u b l i s h e d e l s e w h e r e (6).

(1) Thermogravimetric Analysis

A specially constructed gloved environmental box was used with a

Calm R . H . electrobalance (6). S a m p l e s c o u l d be w e i g h e d and l o a d e d ont o
t h e b a l a n c e and r u n s p e r f o r m e d w i t h o u t t h e s a m p l e s b e i n g e x p o s e d to o u t s i d e
conditions. N o r m a l TGA runs w e r e p e r f o r m e d at a h e a t i n g r a t e of 1 0 ° C / m i n
under vacuum. Static runs were performed b y h e a t i n g at 100°C f o r 3 h r .
S a m p l e s w e r e c o m p a c t e d at 5000 p s i to p r e v e n t b l o w i n g and l o s s of p o w d e r
d u r i n g e v a c u a t i o n and h e a t i n g .

(2) Differential Thermal Analysis

T h e 900 Du P o n t t h e r m a l A n a l y s e r w a s u s e d f o r d i f f e r e n t i a l t h e r m a l
measurements. This unit has a r e m o t e p l u g - i n m o d u l e called the c a l o r i -
metric cell. T h e c e l l is p l a c e d in a g l o v e d b o x c o n t r o l l e d at the r e q u i r e d
h u m i d i t y and c o n n e c t e d to t he r e c o r d e r t h r o u g h a l e n g t h of s h i e l d e d w i r e .
S a m p l e s of r e q u i r e d quantity (16 milligrams) w e r e w e i g h e d in a balance in
 Vol. l , No. 6 611
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

the g l o v e d box. Thermal c u r v e s w e r e o b t a i n e d at h e a t i n g r a t e s of b o t h 10

and gO ° C / r a i n . R e s u l t s a r e r e p o r t e d h e r e f o r l O ° C / r n i n only.

Re sults

(i) Thermo~ravirnetric Anal)rsis

The dynamic T G A runs did not show as clear a delineation of differ-

ent types of water as the D T A curves. Hence, the T G A equipment w a s also

used under static conditions, where the samples equilibrated at every con-
dition w e r e heated in v a c u u m for 3 hr at 100°C. It w a s found previously (2)

that this condition w a s equivalent to the d-dry condition, and thus the results
would yield quantitative information with regard to the a m o u n t of water in
each sample above the d-dry condition. A s a result the intensity of each
DTA curve could be well defined for the region of "evaporable" water (7) on
the basis of the above.

A n advantage gained by performing the static thermal gravimetric

analysis is that sorptlon isotherms can be constructed. These are shown in
Fig. I for-the preparations A, B and C. Another advantage is that these
isotherms are constructed f r o m samples that have been conditioned simulta-
neously at various hurnidities for 1¼ to Ii m o n t h s (see Table I). This m e a n s
that each point on the isotherm has been at its respective condition for that
period. To accomplish this by a n o r m a l v a c u u m balance, the period involved
would have been increased several-fold. A s it turns out, these lengths of
time are unnecessary in the regions investigated.

The points enabled outer boundary sorption curves to be d r a w n for

preparations B and C, i.e. B(ads) and C(ads) respectively. From the points
obtained f r o m samples that had been exposed to various relative humidities
and returned to 1 I% R . H . and the adsorption curve for preparation A,
approximate scanning curves could be outlined. From the sample that had
been returned f r o m I00 to 11% R.H. the outer boundary desorption curve
could be estimated. (This estimate is based on previous w o r k with an
identical sample (2).) The adsorption curve for preparation A w a s d r a w n on
the isotherm loop of both preparations B and Co Its slope is very low, m u c h
lower than the outer boundary sorption curves for preparations B and C. As
612 Vol. I, No. 6
WATER, INTERLAYER, ADSORBED, THERMAL ANALYSIS

18 I I I I I [ 1
0 0

17
16

15

,4 /. ,,tl
15 -
,
/' // Ill /"
,/ I/ I I
i2 - ,," 11 .," I!
/ e i / I l

,i- ,,'PREP:9'/ ,' ,-" PRep: B I , I

_ ,' ,"/,' ,' /i/
0
0 ,u - / /4'/ oi,'/
,' /
X , i ,,"/I ,' ..' /,'I
91-,PREP:A ,,' ." o'] ,' . . " PREP:A 4 ' /
o
/ \
L
,,__.o--_;¢..,'/,",,-
o.~'---"~-'~"~----_~
-'-
_Lo~."
. - .., ./ o - - ' - - ' - - - " - -
../
./ ,~/
0 X-f-- -" I'1 .I "" i'/
X¢ J i l l I " 1~ Z'lll

7- x ...,- .i,,, ~ ,<'7

L--2:--:~'~
^>r'C~>~?-'",." ~---,_--.~.-Z--B
--';'" '(ads/'

4 - I / PREP: C
:5 ~
//
Initial dry state
/ "

I-
d-dry level
I I I I I
0o 20 4O 6( 80 I00
0 20 40 60 8O I00
PER CENT, RH

FIG. 1
Isotherms of h y d r a t e d cement from static thermal balance.
Vol. l , No. 6 613
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

m e n t i o n e d above, the scanning c u r v e s w e r e p a r t i a l l y located by o b s e r v i n g

t h e s l o p e of t h i s c u r v e . P r e v i o u s w o r k {2) h a s a l r e a d y n o t e d t he d i f f e r e n c e
in s l o p e of t h e o u t e r b o u n d a r y c u r v e s a nd t he s c a n n i n g c u r v e s . Also shown
in F i g . i is th e f a c t t h a t a l i t he w a t e r { i n c l u d i n g h y d r a t e w a t e r ) r e m o v e d
w h e n th e s a m p l e s a r e d - d r i e d (B) o r p a r t i a l l y d r i e d (C) f r o m 11% R . H . is
r e t u r n e d a f t e r the s a m p l e has been r e w e t t e d . The scanning curves show that
t h i s r e t u r n t a k e s p l a c e o v e r t h e r a n g e of h u m i d i t i e s 11 t o 100% R . H . DTA
w i l l s h o w t h a t p a r t of t h e w a t e r is r e t u r n e d b e l o w 11% R . H .

In c o m p a r i n g the two isotherms for preparations B and C it can be

observed that the sorption boundary curve for B (d-dried) has a greater
slope. T o illustrate this, the latter is d r a w n on the s a m e axis as the C
preparation.

Preparation C contained approximately 3 % m o r e moisture than prep-

aration B at the start of the isotherm, but this difference w a s regained
completely by preparation B at higher humidities. This w a s apparent be-
cause both preparations had completely regained all the water lost after
being exposed to 1 0 0 % 1%.H. This lack of recovery at the low humidities of
all the extra water r e m o v e d explains the m u c h larger hysteresis loop of
preparation B (d-dried).

Several points m a y be taken f r o m these results:

(a) T h e C preparation w h i c h w a s not d-dried did not allow complete

regain of water w h e n exposed at low or intermediate humidities, even after
extended periods. This is explained by interlayer hysteresis described in
the n e w model°

(b) If the B E T calculations are applied to the boundary sorption

curve of preparations B or C, results would be completely fictitious since
interlayer water is re-entering in the 0 - 3 3 % I%. H. range. Values would be
controlled by h o w the interlayer water re-entered the sample. Conclusive
evidence that water enters in the B E T region is derived f r o m the scanning
curves and the fact that preparation B (d-dried) has a steeper curve in that
region. If the extra water r e m o v e d f r o m preparation B w a s solely phys-
ically adsorbed, it would have readsorbed below 1 0 % I%.H., w h e r e it w a s
614 Vol. I , No. 6
WATER, INTERLAYER, ADSORBED,THERMALANALYSIS

removed. T h e increased steepness in the curve in the B E T region is due to

increased interlayer re-entry in this region.

A calculation for surface area could be m a d e f r o m the curve for the

A preparation, since no interlayer water appears to be entering on this

curve in the B E T region. H o w e v e r , the position for zero adsorbed water is

not known. Special procedures involving simultaneous m e a s u r e m e n t of

sorption and length change can be used to determine this. T h e y have been

used by H e l m u t h (8) and referred to as the B a n g h a m , Freundlich, F e l d m a n

and Sereda m e t h o d . T h e surface area obtained by H e l m u t h for the curve

equivalent to curve C w a s similar to the area obtained by N 2 adsorption.

(2) Differential Thermal Analysis

The samples u s e d in t h i s s t u d y w e r e in s o m e cases conditioned for

longer periods at the various relative humidities. The times are also tab-

u l a t e d on T a b l e I.

For preparation B and B(R) a therrnogram is presented on F i g . 2 for

every condition on the sorption boundary curve series (A) a s w e l l a s f o r a l l

the points returned to ll% R. H., i . e . , t h e p o i n t s on t h e s c a n n i n g curve

series (B) a t a h e a t i n g r a t e of 1 0 ° C / r a i n . For series A it m a y b e o b s e r v e d

that two e n d o t h e r m i c peaks with peak t e m p e rature s varying in the range 65-80

and 9 0 - I 0 5 ° C f o r m and g r o w simultaneously with increasing humidity. It

should be m a d e clear here that these temperatures are not exactly definable

and are k n o w n to vary to s o m e extent depending on the experimental con-

ditions. T h e peaks for the heating rate of 10°C/rain are very clearly

recognizable although the baseline shifts greatly at this rate. Of the two
peaks the 9 0 - I 0 5 ° C peak is larger up to 8 4 % R . H . ; at ii and 3 2 % R . H . , the
6 5 - 8 0 ° C peak is small, showing that in the region up to 1 1 % Ro H. m o s t of
the water sorbed is associated with the higher t e m p e r a t u r e peak.

Series B s h o w s clearly h o w 1 1 % R . H . on the sorption isotherm is

not a uniquely defined point as also can be seen in Fig. 1, w h e r e the a m o u n t
of water contained at 1 1 % R . H . varies with the conditions of exposure. The
higher t e m p e r a t u r e peak g r o w s bigger as the relative humidity to w h i c h the
Vol. I , No. 6 615
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

'l'l'l' ' I' I ' I ' I

I
PREPARATION B
f REPARATION B (R)
eries B

RH 0 *B4% #

Rlt 0 - t O O t

, ]_.a~ .._L I , I , l ,
I00 200 3OO 4O0 0 I00 200 300 400
TEMPERATURE, 'C
TEMPERATURE,"C

FIG. Z

D T A t h e r m o g r a m s of p r e p a r a t i o n B and B(l~)
S e r i e s A - P r e p a r a t i o n B e q u i l i b r a t e d at I~. H. of 0 to 100%;
S e r i e s B - P r e p a r a t i o n B(R.) f r o m R . H . of 0 t o 100%,
e q u i l i b r a t e d at 11% R. H.

s a m p l e w a s exposed increases. T h e 6 5 - 8 0 " C peak, on the other hand, is

always reduced to a very small size on return to 1 I % R . H . T h u s it is
evident that the hysteresis effect manifested by the scanning curves observ-
ed on the sorption isotherm is associated with the high t e m p e r a t u r e peak.
This hysteresis effect has been previously attributed to interlayer water
616 Vol. I , No. 6
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

re-entry {2), and it is apparent that the two peaks distinguish b e t w e e n inter-

layer water and water adsorbed on free surfaces.

The thermograms for preparations A, C(R) and C are presented on

Fig. 3. Series A for preparation C(R) shows the curves for the samples
that had been all returned to 11% R.H. after exposure to various humidities.
It is clear that this preparation contained more water after drying than
preparation B since an extended endothermal effect is visible below 100°C
for the 0% R.H. curve. Subsequent exposure to higher humidities and back
to 11% R.H. causes the 90-I05°C peak to grow. The 65-80°C peak is small
or not visible. This series is thus similar to that for preparation B. Series
B, the samples exposed at different humidities shows, as for preparation B,
a simultaneous growth of both peaks, the higher temperature peak not be-
ing surpassed in intensity by the lower temperature peak until 76% R. H.

Series C represents p r e p a r a t i o n A e x p o s e d to v a r i o u s r e l a t i v e
humidities. T h i s s a m p l e s h o w s a w e l l - d e v e l o p e d p e a k at 9 0 - I 0 5 ° C and a
s m a l l p e a k at 6 5 - 8 0 ° C . A s t he r e l a t i v e h u m i d i t y is r a i s e d t h e 6 5 - 8 0 ° C
peakincveases, s u r p a s s i n g t he 9 0 - 1 0 5 ° C p e a k at 76% R . H . The latter
a p p e a r s to r e m a i n r e l a t i v e l y c o n s t a n t , and t he 6 5 - 8 0 ° C p e a k now a p p e a r s to
g r o w i n d e p e n d e n t l y of t h e h i g h e r t e m p e r a t u r e peak. T h i s e x p l a i n s the
s o r p t i o n c u r v e f o r p r e p a r a t i o n A w h i c h h a s a v e r y low s l o p e in c o n t r a s t to
t h a t of p r e p a r a t i o n B or C (Fig. 1). For preparationA al l t h e w a t e r a s s o c i -
a t e d w i t h th e 9 0 - 1 0 5 ° C p e a k is a l r e a d y p r e s e n t , w h i l e f o r B and C it i s s o r b -
ing as th e h u m i d i t y is i n c r e a s i n g . T h e s o r p t i o n h y s t e r e s i s is e x p l a i n e d a l s o
by t h i s p e a k , and s i n c e p r e p a r a t i o n C h a s s o m e of t h i s w a t e r a l r e a d y p r e s e n t

its hysteresis is n o t a s l a r g e .

C o m p a r i n g s e r i e s B a n d C on F i g . 3, it a p p e a r s t h a t t h e l o w e r t e m -
p e r a t u r e p e a k f o r C i s l a r g e r f o r t he s a m e h u m i d i t y . T h i s m a y be due to a
larger s u r f a c e a r e a of t h e u n d r i e d s a m p l e . Some other experimental
r e s u l t s c o n f i r m i n g t h i s h a v e b e e n o b t a i n e d and w i l l be p u b l i s h e d l a t e r .

Discussion

Despite the extraordinary lengths of time allowed for equilibrium at

the various conditions described above these results are essentially the s a m e
Vol. I, No. 6 617
WATER, INTERLAYER, ADSORBED, THERMAL ANALYSIS

' I ' I ' I '

/ /
PREPARATIO~ C

RIt 01L
"7
RH0°1 I%

, I , I , I , 11
0 IO0 200 300 400 0 I00 200 300 400 0 100 200 300 400
TEMPERATURE,"C TEMPERATURE."C TEMPERATURE,"C

FIG. 3

DTA thermograms of p r e p a r a t i o n s A, C(R) and C

Series A - Preparation C ( R ) f r o m R . H . of 0 t o 100%,
e q u i l i b r a t e d a t 11% R . H .
Series B - Preparation C e q u i l i b r a t e d a t R . H . of 0 t o 100%.
Series C - PreparationA e q u i l i b r a t e d a t R . H . of 0 t o 100%.
618 Vol. I , No. 6
WATER, INTERLAYER, ADSORBED,THERMALANALYSIS

a s t h o s e o b t a i n e d b e f o r e w h e n t he e q u i l i b r a t i o n p e r i o d s w e r e m u c h l e s s (2).
T h e r e s u l t s c l e a r l y s h o w t he f o l l o w i n g :

(a) adsorption and desorption curves are well defined by

the experimental points and a large hysteresis loop is
confirmed;

(b) scanning curves exist and are the result of re-

entrance of interlayer water;

(c) practically all water r e m o v e d on first drying f r o m

1 1 % i~. H. is regained by r e w e t t i n g ;

(d) interlayer water re-enters t h r o u g h o u t the B E T r a n g e ;

thus conventional surface area calculations from water
s o r p t i o n a r e not v a l i d .

In t h i s p a p e r it w a s p o s s i b l e t o c o r r e l a t e t h e 9 0 - 1 0 5 ° C p e a k w i t h
i n t e r l a y e r w a t e r a nd t h u s it w a s p o s s i b l e to o b s e r v e d i r e c t l y how t h e a m o u n t
of i n t e r l a y e r w a t e r c h a n g e s w i t h h u m i d i t y . Progressive re-entry of i n t e r -
l a y e r w a t e r i n t o t he d - d r i e d m a t e r i a l t a k e s p l a c e in s t a g e s b e g i n n i n g w i t h
e x p o s u r e at v e r y low h u m i d i t i e s and is not c o m p l e t e u n t i l it e x c e e d s a b o u t
75% R . H . T h e r e s e e m s t o be a f o r m of e q u i l i b r i u m at e a c h h u m i d i t y ; t h i s
w a s d i s c u s s e d in an e a r l i e r p a p e r (2). F r o m t h e c o r r e l a t i o n of t h e 9 0 - 1 0 5 ° C
p e a k w i t h i n t e r l a y e r w a t e r and f r o m p r e p a r a t i o n C, t h e p a r t i a l l y d r i e d p r e p -
aration, it w a s p o s s i b l e t o o b s e r v e t h a t i n t e r l a y e r w a t e r e n t e r e d w h e n the
s a m p l e s w e r e e x p o s e d f r o m t he d r y to 1 1 % R . H . by a g r o w t h in t he 9 0 - 1 0 5 ° C

p e a k ; t h i s g r o w t h a l s o o c c u r r e d in t he B E T r e g i o n .

T h e s i g n i f i c a n c e of t he 11% h u m i d i t y p o s i t i o n is o b v i o u s in t he
thermograms. F o r an i d e a l a d s o r p t i o n s y s t e m the a m o u n t a d s o r b e d at 11%
R.H. s h o u l d be u n i q u e l y d e f i n e d . At a b o u t 11% R . H . a monolayer usually
e x i s t s w i t h o u t the c o m p l i c a t i n g f e a t u r e s of c a p i l l a r y c o n d e n s a t i o n . A l s o in
t h i s r e g i o n a d s o r p t i o n is e x p e c t e d to be r e v e r s i b l e a l o n g t he a d s o r p t i o n
curve. H o w e v e r , in the c e m e n t s y s t e m a n y n u m b e r of p o s i t i o n s e x i s t b e -
t w e e n the u p p e r and l o w e r b o u n d a r i e s of t he h y s t e r e s i s loop. T h i s is a l s o
e v i d e n t f r o m the p e a k i n t e n s i t i e s at 9 0 - 1 0 5 ° C in t he t h e r m o g r a m s . The
9 0 - 1 0 5 ° C p e a k in p r e p a r a t i o n A at 11%1%.H. is s i m i l a r to t h a t in p r e p a r a -
Vol. I , No. 6 619
WATER, INTERLAYER, ADSORBED,THERMALANALYSIS

t i o n s B and C e x p o s e d t o 84 o r 100% R . H . and r e t u r n e d to 1 1 % R . H . Ex-

p o s u r e of p r e p a r a t i o n A t o d i f f e r e n t h u m i d i t i e s c a u s e s o n l y p e a k 6 5 - 8 0 ° C t o
grow. An e x p l a n a t i o n b a s e d on the r e a s o n i n g t h a t t he 9 0 - I 0 5 0 C p e a k is due
to t h e d e s o r p t i o n of a m o n o l a y e r of a d s o r b e d w a t e r c a n be r e j e c t e d f o r t he

following reasons.

(i) W h e n the peak is r e m o v e d by drying it can only

be restored by exposure to high humidities.

(2) Samples can be prepared by exposure to different

hurnidities and maintained at 11% R.H. even though
they contain different amounts of water. This is
also manifested by the 90-I05°C peak being of
different sizes. The 11% R.H. position is not
unique. This situation is well explained by the n e w
m o d e l of hydrated portland cement.

(3) T h e r m a l analysis of porous glass at different

humidity conditions (6) shows that the monolayer
cannot be differentiated from the multilayers.

The higher temperature peak is explained as due to the expulsion of

interlayer water. This m a y not necessarily be due only to a higher energy
of binding of these H z O molecules over those physically adsorbed but also
due to the mechanical barrier imposed on the interlayer water because of
their interlayer positions. Although two peaks can be observed it is clear

that there m u s t be s o m e overlap in the interaction energies.

Conclusions

T h e r m a l analysis allows differentiation of interlayer and physically

adsorbed water.

D i f f e r e n t d e g r e e s of d r y i n g of s a m p l e s and long p e r i o d s a l l o w e d f o r
e q u i l i b r a t i o n s u p p o r t a l l s o r p t i o n r e s u l t s on w h i c h t h e n e w m o d e l of h y d r a t e d
p o r t l a n d c e m e n t is b a s e d .
620 Vol. l , No. 6
WATER, INTERLAYER, ADSORBED, THERMALANALYSIS

Acknowledgement

The a u t h o r s a c k n o w l e d g e the v a l u a b l e a s s i s t a n c e of M e s s r s . G.
P o l o m a r k , M . L e G e y t and S. Dods in p e r f o r m i n g the e x p e r i m e n t s and
gathering data. T h i s p a p e r is a c o n t r i b u t i o n f r o m the 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 R e s e a r c h C o u n c i l of C a n a d a , and is p u b l i s h e d w i t h the
a p p r o v a l of the D i r e c t o r of the D i v i s i o n .

T h i s p a p e r w a s p r e s e n t e d at the S e c o n d C e m e n t S y m p o s i u m h e l d as
p a r t of the 7 3 r d A n n u a l M e e t i n g of the A m e r i c a n C e r a m i c Society, C h i c a g o ,
A p r i l 1971.

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i. R. F . F e l d m a n and P . J . Sereda. Mater. Constr., 1, 509 (1968).

2. R. F . F e l d m a n . P r o c e e d i n g s , F i f t h I n t e r n a t i o n a l S y m p o s i u m on the
C h e m i s t r y of C e m e n t h e l d in T o k y o , 1968, P a r t III, Vol. III, 53 (1968)

. S. B r u n a u e r , I. O d l e r and M . Y u d e n f r e u n d . Highway Res. Board

R e c o r d No. 38, 89 (1970).

. V. S. R a m a c h a n d r a n . A p p l i c a t i o n s of DTA in C e m e n t C h e m i s t r y .
C h e m i c a l P u b l i s h i n g C o . , New Y o r k (1969).

5. G. E n g l e r t and F . W i t t m a n n . Mater. Constr., 1, 535 (1968).

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7. T. C. Powers and T.L. Brownyard. J. Amer. Conc. Inst. Proc.,

4_~3, 276 (1947).

. R. A. Helmuth, Dimensional Changes and Water Adsorption of

Hydrated Portland Cement and Tricalclum Silicate. M.Sc. Thesis,
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