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SESSION A model for hydrated Portland cement paste as deduced from sorption-length change and mechanical properties

R. F. F E L D M A N

and P. J. SEREDA ~

R~SUM~
Des r6sultats obtenus r & e m m e n t ~ la Division des Recherches sur le B~timent et dans d'autres laboratoires ont rendu n6cessaire une r~vision du rnod~le jusquqci acceptS, pour representer la p~te de ciment Portland hydrat6. Ce module admet comme valeurs les plus sfires et les aires superficielles et les porosit6s d&ermin6es par adsorption d'azote, et fait d~pendre un grand nombre des ph6nom6nes observes du compcrtement de I'inter-couche d'eau d'hydratation. La nature des liaisons dans les ~r cristallites ~, et entre elles, sont clairement d6finies ; on voit que les liaisons ~ inter-cristallites >~ ne sont pas affect6es par adsorption d'eau. Ce r a p p o r t expose quelques-unes des 6quations t h e r m o d y namiques relatives aux ph~nom~nes de I'adsorption, variation de Iongueur et fluage, ainsi que quelques principes de base qui r6gissent I'adsorption et des types d'hyst6r~sis. Les r6sultats ont 6t~ fournis par deux s6ries de travaux : A. des experiences sur la chimie des surfaces; B. la mesure des propri&~s m&anique~ des syst~mes compact6s et coul6s de ciment hydrat6 et de pl~tre. Les experiences (A) int6re~saient les ph6nom6nes d'adsorption, et les modifications de Iongueur des r6seaux d'isothermes ou de I'eau et du m&hanol, et les r~sultats de ces exp6riences aboutissaient aux conclusions suivantes : (i) L'isotherme de I'eau pour le ciment hydrat6 amen~ siccit6 est irreversible en toute partie des courbes primaires, la cause 6rant la r~-introduction d'une intercouche d'eau d'hydratation. (ii) Les calculs de Brunauer, Emmett et Teller de I'eau isot h e r m e ne sont pas valables. Les aires super~cielles et les porosit6s obtenues par I'adsorption d'azote sont des valeurs plus sfires. (iii) A I'aide du r6seau d'isothermes et du calcul, il esr possible de s6parer I'inter-couche et I'eau physique (adsorb6e) ; les

SUMMARY Recent findings in DBR and other laboratories has made it necessary here to revise the accepted model for hydrated portland cement paste. The model recognizes surface areas and porosities obtained by N~ adsorption as the most reliable values, and attributes'many of the phenomena observed, to the behaviour of interlayer hydrate water. The bonds between and within individual "' crystallites " are clearly defined; it is shown that the "' inter-crystallite "' bonds do not separate when exposed to physically adsorbed water.

The paper describes some of the thermodynamic equations pertinent to the phenomena of adsorption, length change and creep, and some basic principles governing physical adsorption and types of hystereses. The results were obtained from two areas of work : A. Surface chemical experiments. B. Measurement of mechanical properties of compacted and cast systems of hydrated cement and gypsum. The experiments in (A) included sorption and length change scanning isotherms of water and methanol and led to the follow!ng conclusions : (i) The water isotherm for "' d-dried "' hydrated cement is irreversible at all regions of the primary curves, due to the re-entry of inter-layer hydrate water. (ii) B.E.T. calculations on the water isotherm are invalid. Surface areas and porosities obtained from N~ adsorption are more reliable values. (iii) By use of the scanning isotherms and calculation it is possible to separate interlayer and physical water; each of these were used to describe properties of the hydrated cement.

Q) National Research CunciI Building Research, Ottawa.

of Canada, Division of

509

VOL,

| - - N ~ 6 - - 1968 -- M A T I ~ R I A U X

ET C O N S T R U C T I O N S

deux mSthodes ant 6t6 utilis6es pour d6crire les propri6tSs du ciment hydrat6.
Les mesures (B) comprenaient celles du module et de la r~sistance en fonction de I'humidit6 relative et de la porosit~; elles a n t conduit aux conclusions suivantes :

The experiments in (B) included measurements of modulus and strength versus relative humidity, and porosity, and led to the following conclusions :

(i) L'eau adsorb6e ne se trouve cristallites >>.

pas aux limites <( inter-

(ii) Les liaisons form6es au cours de I'hydratation ne sont pas plus fortes que celles form6es par compactage, c o n t r a i r e m e n t ce qui se passe avec le plgtre. Pourtant, les liaisons sont assez fortes et impliquent des proportions variables de forces agissant long terme et 5. court terme. L'eau adsorb6e normalement n'influence pas cette r6partition. (iii) Le fluage r6versible et une partie du fluage irreversible sont probabtement associSs ~ la lente d6composition de I'intercouche hydrat6e due ~ I'application d'une charge. (iv) Le fluage irr6versible est probablement le rSsultat de la r u p t u r e et de la reconstitution des liaisons << inter-cristallites >) dens des conditions de contrainte contrari6e.

(i) Physically adsorbed water is not present at '" inter-crystallite "' boundaries. (ii) The bonds formed during hydration are not stronger than those formed by compaction, in sharp contrast to the gypsum system. However, the bonds are fairly strong and involve a varying proportion of long-range and short-range forces. Physically adsorbed water does not normally influence these bands. (iii) The reversible and part of the irreversible creep is probably associated with the slow decomposition of the interlayer hydrate due to application of stress. (iv) The irreversible creep is probably the result of breaking and re-making of " inter-crystallite "" bonds under confining stress conditions.

The d e v e l o p m e n t of the p r e s e n t 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 has b e e n largely, b a s e d on s u r f a c e c h e m i c a l c o n s i d e r a t i o n s ; this i n v o l v e d the establishm e n t of criteria for distinguishing b e t w e e n c h e m i c a l l y c o m b i n e d a n d p h y s i c a l l y a d s o r b e d water. The d e t e r m i n a t i o n of the s t o i c h i o m e t r y of the t o b e r m o r i t e gel, its w a t e r s u r f a c e a r e a a n d its p o r o s i t y was b a s e d on the a b o v e criteria. R e c e n t findings in D.B.R. a n d o t h e r l a b o r a t o r i e s i n v o l v e d m e a s u r e m e n t s of s o r p t i o n a n d lengthc h a n g e relationships, a n d variations of m e c h a n i c a l p r o p e r t i e s with r e l a t i v e h u m i d i t y a n d with p o r o s i t y of c o m p a c t s of bottle h y d r a t e d c e m e n t a n d small p r i s m s of p a s t e h y d r a t e d cement. This has p r o v i d e d n e w e v i d e n c e , m a k i n g it n e c e s s a r y to m o d i f y the a c c e p t e d m o d e l for h y d r a t e d p o r t l a n d c e m e n t paste. This n e w m o d e l allows the p o s s i b i l i t y of n e w a p p r o a c h e s to, a n d explanations for, s o m e wellknown phenomena.

1. T H E O R Y
S o m e of the b a s i c t h e o r i e s r e l a t e d to p h y s i c a l adsorption, adsorption hysteresis, and adsorption a n d l e n g t h - c h a n g e p h e n o m e n a will first b e d i s c u s s e d . The v a r i o u s e x p e r i m e n t a l results a n d i n t e r p r e t a t i o n s will then b e p r e s e n t e d with the aim of d e v e l o p i n g a n e w model. Final discussion will c o n c e r n the r e l a t i o n of c r e e p to this m o d e l .

a d s o r b e d m a t e r i a l as a function of its v a p o u r p r e s s u r e at constant t e m p e r a t u r e . This i s o t h e r m for a g i v e n s o l i d - g a s s y s t e m s h o u l d b e r e v e r s i b l e if t h e r e is no i r r e v e r s i b l e c h a n g e in the n a t u r e of the solid a n d / o r gas, s i n c e t h e r e thus can b e o n l y o n e state of e q u i l i b r i u m at a g i v e n v a p o u r p r e s s u r e . At l o w e r p r e s s u r e s this is usually the case, b u t at h i g h e r p r e s s u r e s the p r o b l e m of p r i m a r y h y s t e r e s i s arises. This is c o m m o n l y r e l a t e d to the p o r e s t r u c t u r e of the solid a n d a c h a n g e in n a t u r e of the a d s o r b a t e . This c h a n g e , it is postulated, manifests itself in the formation of a m e n i s c u s ; the d i f f e r e n c e in the p r o c e s s of formation a n d r e c e s s i o n of this m e n i s c u s c a u s e s the hysteresis. Brunauer, E m m e t t a n d T e l l e r [1] with s o m e simplifications a n d a s s u m p t i o n s d e r i v e d their famous B.E.T. equation. This e q u a t i o n was g e n e r a l l y a p p l i c a b l e in the interval of p a r t i a l p r e s s u r e s 0.05 to 0.35, a n d a s s u m e s r e v e r s i b i l i t y a n d a constant s u r f a c e area. F r o m this e q u a t i o n the amount of a d s o r b a t e r e q u i r e d to form a c o m p l e t e m o n o l a y e r can b e calculated; thus, from a k n o w l e d g e of the size a n d p a c k i n g of the a d s o r b a t e m o l e c u l e , the surface a r e a can b e evaluated.

b) Adsorption hysteresis
F i g u r e 1 illustrates t h r e e f o r m s of h y s t e r e s i s that h a v e b e e n o b s e r v e d on v a r i o u s m a t e r i a l s [2]. A l o o p of t y p e I is f o r m e d o v e r a limited r a n g e of p r e s s u r e s a n d is g e n e r a l l y c o n s i d e r e d (as s t a t e d a b o v e ) to b e a s s o c i a t e d with the formation of a m e n i s c u s . S c a n n i n g of the l o o p m a y b e p e r f o r m e d b y d e s o r b i n g after r e a c h i n g X on the a s c e n d i n g b o u n d a r y c u r v e ; thus, one r e a c h e s Y on the d e s c e n d i n g b o u n d a r y c u r v e a n d m a y r e t u r n to X b y r e a d s o r p t i o n . T y p e II h y s t e r e s i s , w h e r e the l o o p e x t e n d s o v e r the w h o l e p r e s s u r e r a n g e , has b e e n o b s e r v e d for w a t e r on c e l l u l o s e o r p r o t e i n fibres a n d also for p o l a r a d s o r b a t e s o n montmoriltonite. In t y p e III, which c o m b i n e s the c h a r a c t e r i s t i c s of the o t h e r t y p e s , the a s c e n d i n g a n d d e s c e n d i n g b r a n c h e s only join at v e r y low o r z e r o p r e s s u r e . The d o t t e d lines s h o w the p a t t e r n f o l l o w e d if a d s o r p t i o n r e c o m m e n c e s at X. T y p e III l o o p s a r e f o u n d with s o m e graphites,. c l a y m i n e r a l s a n d h y d r a t e d p o r t l a n d cement.

a) Physical adsorption at lower humidities


P h y s i c a l a d s o r p t i o n is a s s o c i a t e d with the attachm e n t of the a d s o r b e d m o l e c u l e to the s u r f a c e of the solid. The e n e r g y of the r e a c t i o n for p h y s i c a l a d s o r p t i o n is usually similar to that of c o n d e n s a t i o n of the p a r t i c u l a r gas, a l t h o u g h it m a y b e c o n s i d e r a b l y h i g h e r on active p o i n t s of the solid. The amount of g a s o r v a p o u r a d s o r b e d w h e n e q u i l i b r i u m is e s t a b l i s h e d at a g i v e n t e m p e r a t u r e a n d p r e s s u r e is a function of the nature of the a d s o r b e n t and adsorbate. The e x p e r i m e n t a l o b s e r v a t i o n most f r e q u e n t l y m a d e for s o r p t i o n s y s t e m s is of the a d s o r p t i o n isot h e r m ; this is the m e a s u r e m e n t of the quantity of 510

R. F. F E L D M A N ,

P. J. S E R E D A

IT[

4
FIG. I. --

Types of sorption hysteresis.

/
P/Po pip o plp o ]~ C
Fro.
2 . - - Basic length change - adsorption hehaviour : I . Adsorption isotherm;

_J

/o.
pip o
A W/W The l o w - p r e s s u r e hysteresis p h e n o m e n o n is usually a t t r i b u t e d to i r r e v e r s i b l e intercalation of a d s o r b a t e within the structure of the solid. Quite often the solids h a v e a l a y e r structure a n d a c h a n g e in the s p a c i n g of these layers has b e e n o b s e r v e d .

H. Lengthchange vs.weightchange plot.

c) Adsorption length-change phenomenon


Some of the basic c o n s i d e r a t i o n s of this p h e n o m e n o n are well illustrated b y the work on p o r o u s glass b y A m b e r g a n d Macintosh [31. In the r e g i o n OA, s h o w n on both g r a p h s of figure 2 for A W / W vs. p/P0 a n d AL/L vs. AW/W, r e v e r s i b l e a d s o r p t i o n occurs u p to about two m o l e c u l a r l a y e r s at A. In this r e g i o n it was found that the G i b b s ' a d s o r p tion equation held.

illustrating differences in the treatment of the homog e n e o u s b u l k a n d surface phases. C o n s i d e r the differential p r o c e s s nlB (gas)--~-n 1 moles of a d s o r b e d B on A; n3/n 2 is the c o n c e n t r a t i o n of B on A a n d is not affected b y the addition of nL moles. If B is a n e a r l y p e r f e c t gas, the f r e e - e n e r g y c h a n g e for this p r o c e s s is AF = + n l R T In t5/Po. P0 is the s a t u r a t e d v a p o u r p r e s s u r e of the a d s o r b a t e B. The i n t e g r a l p r o c e s s

n2A + nlB ~ (n~A + nlB)


results in a s y s t e m c o m p o s e d of n 1 moles of B a d s o r b e d on n 2 m o l e s of A. Here the c o n c e n t r a t i o n is c o n s i d e r e d to b e c h a n g ing-thus nl/n 2 is the n e w concentration. In this p r o c e s s G i b b s ' a d s o r p t i o n e q u a t i o n r e p r e s e n t s the d e c r e a s e of surface free e n e r g y . The following is a n outline of the d e r i v a t i o n of G i b b s ' e q u a t i o n as p r e s e n t e d b y Flood [5]. With the statement of the various t h e r m o d y n a m i c restrictions n e c e s s a r y , a n d the basic a s s u m p t i o n that " A s s e m b l i e s of v o l u m e s of the p u r e a d s o r b e n t a n d a d s o r b a t e can each exist separately, in equilib r i u m with e x t e r n a l l y a p p l i e d forces, in states that a r e t h e r m o d y n a m i c a l l y identical with their states in the a d s o r b e n t - a d s o r b a t e s y s t e m " the e q u a t i o n dF 1 + d F 2 = dF n was p r e s e n t e d as the condition for the p r o c e s s of 511

AF = + R T
o

n I/pdp

nl is the concentration of adsorbate in g m moles/gin of solid and p is the vapour pressure of the adsorbate. AF is the decrease in free energy of pure adsorbent from its initialstate under its o w n vapour pressure to its combining state, i.e. adsorbent plus adsorbate. Gibbs' equation is extremely important in theories of length-change and adsorption but its application is apparently not completely understood [4]. Thermodynamic equations d e r i v e d for dilute solutions in the " b u l k state " h a v e b e e n e r r o n e o u s l y u s e d b y s o m e w o r k e r s [11] to m a k e calculations a n d a n a l y s e data. With the aim of p r e s e n t i n g a c l e a r e r picture, an analysis of two t h e r m o d y n a m i c p r o c e s s e s a n d a s i m p l e d e r i v a t i o n of G i b b s ' equation, first p r e s e n t e d b y F l o o d [5], is g i v e n below. In (d) of this section, m o r e detail of the t h e r m o d y n a m i c s will b e given,

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transformation of the s e p a r a t e systems 1 a n d 2 into the c o m b i n e d s y s t e m 12 to b e r e v e r s i b l e at a n y point a l o n g a path of variation of the t h r e e systems. At constant t e m p e r a t u r e , a n d m a k i n g the customa r y assumptions, o n e can write

The equation easily d e r i v e d is AL/L c = k 2AP = k2!9-T/pM, InF2/Pl w h e r e ,AL Lc is the c o n t r a c t i o n d u e to the p r e s s u r e of the m e n i s c i (AP) c h a n g i n g r a d i u s as v a p o u r p r e s s u r e c h a n g e s from p~ to P2. D is the d e n s i t y of the adsorbate. The surface free e n e r g y must still c h a n g e h o w e v e r , b e c a u s e the v a p o u r p r e s s u r e of the a d s o r b ate changes. If we a s s u m e n o c h a n g e in c o n c e n tration of a d s o r b e d water w h i c h is within the field of force of the solid, G i b b s ' e q u a t i o n b e c o m e s Ay = R T / z . n I

vldlz 1 +dF2

vndP12

w h e r e v~ is the v o l u m e of the p u r e gas at the equilib r i u m p r e s s u r e pl, c o r r e s p o n d i n g to the n u m b e r of m o l e s of gas n 1 a d s o r b e d , a n d v n a n d P12 are the v o l u m e a n d hydrostatic p r e s s u r e of the c o m b i n e d system. Note that the c o m b i n e d s y s t e m is not further d e f i n e d here. It will b e s h o w n in (d) h o w c o n v e n t i o n a l t h e r m o d y n a m i c s treats the c o m b i n e d s y s t e m as a surface phase. The a b o v e e q u a t i o n is i n t e g r a t e d for a constant mass of solid n ' 2 b e t w e e n a p p r o p r i a t e limits:

/p

a n d the equation for total l e n g t h c h a n g e in CD is AL/LT = (klRT /~.nl +kzRT /M,~) in P2/Pr Moderately successful a t t e m p t s h a v e b e e n m a d e to relate Ay a n d AL/L to the elastic constants of the material. Calculations in r e g i o n s AB a n d DA a r e g e n e r a l l y not attempted b e c a u s e of the i r r e v e r s i b l e n a t u r e of the process.

f t21 = p l , nl =n'j [ P ~ d F 2 CP,~(nl ='n',,n,a:n% ) vidE. 1 + : IvndPr2


/[]1
=

0, n 1 = 0

gPz~

JP2s (nl = 0, n., -- n',,)

Po s, the p r e s s u r e of the solid, is a s s u m e d to b e v e r y low a n d in the case of l a r g e adsorptions, v 1 will b e m u c h l a r g e r than vlo. In n e g l e c t i n g the third integral a n d i n t e g r a t i n g the following is o b t a i n e d :
AF 2

= -- f

v,d

= --RT f [ln'ldpl,/p~

d) S o m e aspects of h o m o g e n e o u s bulk and surface phase t h e r m o d y n a m i c s


Usually in t h e r m o d y n a m i c s it is a s s u m e d that e v e r y system consists of o n e or m o r e c o m p l e t e l y homogeneous phases b o u n d e d by sharply defined g e o m e t r i c a l surfaces. This is of c o u r s e an o v e r simplification, for the i n t e r f a c e b e t w e e n a n y two p h a s e s will rather b e a thin l a y e r across which the physical p r o p e r t i e s v a r y c o n t i n u o u s l y from those of the i n t e r i o r of o n e p h a s e to those of the i n t e r i o r of the other p h a s e . - I n a d s o r p t i o n p h e n o m e n a , it is n e c e s s a r y to c o n s i d e r the t h e r m o d y n a m i c p r o p e r t i e s of these surface l a y e r s b e t w e e n two phases. In a n y h o m o g e n e o u s bulk p h a s e the force across a n y unit area is e q u a l in all d i r e c t i o n s a n d is called p r e s s u r e ; but in the " surface p h a s e " this is not so. The effective p r e s s u r e will v a r y with its distance from the surface. In a d s o r p t i o n of v a p o u r s or g a s e s on solids, the a d s o r b e d p h a s e is in fact in c o m p r e s sion n o r m a l to the surfaces. T h e r e is a two d i m e n sional p r e s s u r e (much s m a l l e r than the a b o v e ) tangential to the surface a n d e q u a l in m a g n i t u d e but opposite in sign to the c h a n g e in surface e n e r g y of the solid. In o r d e r to allow for this c h a n g e in free e n e r g y r e s u l t i n g from an i n c r e a s e o r d e c r e a s e of surface e n e r g y , it is n e c e s s a r y to i n c l u d e a t e r m ' y~ in the G i b b s - D u h e m equation, A p a r t from the surface contribution, the free e n e r g y of a system of two c o m p o n e n t s is g i v e n b y
G = ~In1

AF2 is the c h a n g e in free e n e r g y of p u r e a d s o r b e n t from its initial state u n d e r its own v a p o u r p r e s s u r e to its c o m b i n i n g state, p r o v i d e d that this i n t e g r a l r e p r e s e n t s a path of t h e r m o d y n a m i c reversibility. If it is a a s s u m e d that the constant solid surface a r e a m ~-/gm has u n d e r g o n e a c h a n g e in surface tension, Ay, we can write
AF2 = Thus ~Ay.

Ay = --RT /~ fi~n'~dPl/pr

,',y in fact m e a s u r e c h a n g e s in states of stress of the solid, b r o u g h t a b o u t b y an interaction of the a d s o r b e d m o l e c u l e with forces on the solid surface; these forces have p l a c e d the solid in a state of c o m p r e s s i v e stress. The B a n g h a m [61 e q u a t i o n p r o v i d e d a basis for testing G i b b s ' e q u a t i o n on solids
AL/L = k l A y . A plot of the e x p e r i m e n t a l l y m e a s u r e d AL/L against Ay o b t a i n e d from G i b b s ' equation y i e l d e d a straight line t h r o u g h zero. In s u m m a r y , in r e g i o n OA w h e r e the p r o c e s s is an i n t e g r a l one, G i b b s ' e q u a t i o n must b e u s e d for e v a l u a t i n g c h a n g e s in stress of the solid. In r e g i o n CD, which is r e v e r s i b l e a n d is postulate d as r e p r e s e n t i n g the c h a n g i n g of the radius of m e n i s c i without r e v e r s i b l e desorption, one m a y c o n s i d e r , as an approximation, that this r e p r e s e n t s a differential process. In effect a c h a n g e in c o n c e n tration with r e s p e c t to the a d s o r b e n t is not taking place, if the capillary water is d e f i n e d as b e i n g r e m o t e from the surface forces. The capillary water maintains e q u i l i b r i u m with different v a p o u r p r e s s u r e s b y c h a n g i n g the radius of its meniscus. This in turn i m p o s e s a t e n s i o n on the w a t e r a n d a comp r e s s i o n on the solid; thus the a b r u p t contraction CD in figure 2, II. 512

+~2n2

w h e r e n 1, n~. are the r e s p e c t i v e n u m b e r of moles; ~1, I-~2a r e the r e s p e c t i v e c h e m i c a l potentials, ' y ' is the surface e n e r g y p e r sq. cm. a n d ' ~ ' is the surface area (cm2); addition of the ' y ~ ' t e r m yields G = y~ + ~ l n l -~.2n2 for a constant t e m p e r a t u r e a n d p r e s s u r e . F r o m this can b e d e r i v e d the s u r f a c e - p h a s e anal o g u e for the G i b b s - D u h e m equation:

~dy + nld~ t + n,2d~2 = O,

R. F. F E L D M A N ,

P. J. S E R E D A

the

bulk p h a s e

e q u a t i o n is
nl~ + n.z~ = 0

w h e r e nz ~ n~~ are the r e s p e c t i v e n u m b e r of m o l e s for the b u l k phases. The f u n d a m e n t a l differential e q u a t i o n for the total c h a n g e in free e n e r g y of a h o m o g e n e o u s b u l k p h a s e is: dGh,lk : V d P - - S d T + ~-xdn 1 + ~.~dn 2. The analogous differential e q u a t i o n for a surface p h a s e is:

tion that the w a t e r b e y o n d some distance from the surface e.g. two m o l e c u l a r layers, is in e s s e n c e b u l k water. That this is an a p p r o x i m a t i o n is clear w h e n one c o n s i d e r s that w a t e r in p o r e s as g r e a t as 100 A U in d i a m e t e r are i n f l u e n c e d b y surface forces.

2. EXPERIMENTAL EVIDENCE FOR TIrE MODEL, TAKEN F R O M SURFACE CHEMISTRY CONSIDERATIONS a) Adsorption, l e n g t h - c h a n g e and surface area
W a t e r a d s o r p t i o n e x p e r i m e n t s have b e e n u s e d to m e a s u r e the surface a r e a of h y d r a t e d p o r t l a n d c e m e n t a n d computations h a v e y i e l d e d values in e x c e s s of 200 m 2/gin. The v a l u e was of g r e a t i m p o r t a n c e , a n d was u s e d to estimate the n u m b e r of layers in the t o b e r m o r i t e gel " crystallites "; it also p r o v i d e d the basis for calculating other physical p a r a m e t e r s . Kalousek [7] o b s e r v e d that the surface a r e a u s i n g N2 as a d s o r b a t e y i e l d e d v e r y low values c o m p a r e d with those of water; the N 2 value was s h o w n b y Mikhail et al. [8] to d e c r e a s e with the water c e m e n t (W/C) ratio to values b e l o w 30 m2/gm. Similar results w e r e o b t a i n e d w h e n o r g a n i c v a p o u r s such as CH~.OH w e r e u s e d as a d s o r b a t e s [9]. It must b e p o i n t e d out that the d e t e r m i n a t i o n of surface a r e a b y a d s o r p t i o n of N2, t o g e t h e r with a calculation b a s e d on the B.E.T. equation, has b e c o m e a s t a n d a r d m e t h o d in the r e a l m of surface chemistry. C a r b o n s with v e r y high surface areas a n d v e r y small p o r e s have y i e l d e d n i t r o g e n surface a r e a s that a p p r o a c h 1,000 m 2/gin. Yet, in the case of h y d r a t e d p o r t l a n d cement, the " water a r e a " has b e e n the o n e g e n e r a l l y h e l d " true a n d valid ". It was c o n s i d e r e d that the N2 m o l e c u l e could not e n t e r small p o r e s a n d a d s o r b on the whole surface b e c a u s e of its l a r g e size. The d i a m e t e r s of the water, nitrogen, a n d m e t h a n o l m o l e c u l e s a r e a p p r o x i m a t e l y 3.25, 4.05 a n d 4.4 A r e s p e c t i v e l y ; it s e e m s difficult to allow for the situation w h e r e u p to 90 % of the a r e a is e x c l u d e d to N2 b e c a u s e of the small difference in diameters. If the holes w e r e part of the crystal structure like certain " m o l e c u l a r sieves " which are cage-like m o l e c u l e s with small e n t r a n c e s , it w o u l d b e realistic, but h y d r a t e d c e m e n t is not of this nature. Several y e a r s ago it was found in this l a b o r a tory [10], d u r i n g s t u d y of the l e n g t h - c h a n g e a n d s o r p t i o n isotherms of w a t e r on bottle h y d r a t e d cement, that it was p o s s i b l e to detect characteristic differences in the type of water that was b e i n g r e m o v e d on d r y i n g . T h e s e characteristics p r o v i d e d a m e a n s to study, a n d formulate an hypothesis on the e x p a n s i o n a n d contraction of h y d r a t e d p o r t l a n d c e m e n t on sorption a n d d e s o r p t i o n of water. It must b e emp h a s i z e d that this t h e o r y did not relate to the p h e n o m e n a that o p e r a t e d u r i n g first d r y i n g ; this will b e d i s c u s s e d in a later section. The t h e o r y e m p h a s i z e d the role of the G i b b s a n d B a n g h a m equations in the lower p r e s s u r e r e g i o n s a n d it was c o n c l u d e d that the e x p a n s i o n on s o r p t i o n was d u e in the first i n s t a n c e to the d e c r e a s e in surface e n e r g y of the solid. It was not n e c e s s a r y to i n t r o d u c e the c o n c e p t that individual crystallites could not m o v e b a c k a n d forth with r e s p e c t to each other in a r e v e r s i b l e m a n n e r as a function of the v a p o u r p r e s s u r e . O n c e a solid-solid contact was m a d e the l a r g e force r e a l i z e d from this proximity w o u l d m a k e the b o n d difficult to break. E v i d e n c e for this is available from other a d s o r b e n t - w a t e r 513

dGsurrace = phase

VdP--SdT

+ ~dy

+~idnl +~,2dn 2

' S ' is as usual the e n t r o p y term. Since the a d s o r b e d p h a s e is not a h o m o g e n e o u s b u l k phase, b u t is part of the surface phase, the last differential e q u a t i o n is the o n e that d e s c r i b e s the c h a n g e in free e n e r g y d u e to the p r o c e s s of physical adsorption. At constant t e m p e r a t u r e , a n d a s s u m i n g that the a m o u n t of solid in the surface p h a s e is constant, o n e obtains:
dG~race = VdP--Gdu

~.idnl

phase

w h e r e ' d n l ' is the c h a n g e in n u m b e r of m o l e s of a d s o r b a t e p e r unit surface mole of a d s o r b e n t . If one a s s u m e s that the a d s o r b e d water is b u l k water, a n d t h e r e is no surface e n e r g y t e r m to b e c o n s i d e r e d , o n e obtains: dGwater
=

VdP +[hdnl.

If t h e r e is no alteration in the n u m b e r of m o l e s of w a t e r or n e a r I y so, then:

dGwater

--

VdP.

This is the e q u a t i o n u s e d b y o n e author [i1] a n d others in d e a l i n g with adsorption, l e n g t h c h a n g e a n d c r e e p p h e n o m e n a in the system, h y d r a t e d p o r t l a n d c e m e n t a n d water. (This e q u a t i o n is in fact the o n e u s e d in d e r i v i n g the potential osmotic p r e s s u r e of a solution.) Looking a g a i n at the a s s u m p t i o n s that w e r e m a d e implicitly on a p p l y i n g the a b o v e e q u a t i o n to the h y d r a t e d p o r t l a n d - w a t e r system: a) it was a s s u m e d that a d s o r b e d water is not a d s o r b e d , a n d t h e r e is no surface e n e r g y involved; b) there is no alteration in the n u m b e r of m o l e s of a d s o r b e n t or adsorbate. Alternatively this last a s s u m p t i o n m a y b e r e s t a t e d - - the original c o n c e n t r a t i o n of a d s o r b a t e to a d s o r b ent is so high that any further a d d i t i o n of a d s o r b a t e is n e g l i g i b l e ; in other words, 100 g m s of d r i e d h y d r a t e d p o r t l a n d c e m e n t with 1 g m of a d s o r b e d w a t e r on it, is e q u i v a l e n t to a dilute solution a n d that this I g m of a d s o r b e d w a t e r can b e c o n s i d e r e d as b u l k water. The a b o v e a s s u m p t i o n s a r e of c o u r s e u n t e n a b l e . It m a y b e stated h e r e that the Kelvin equation, a form of which relates the t e n s i o n in capillary w a t e r to the v a p o u r p r e s s u r e ,
AP = RT / p M . I n P 2 / P l

is d e r i v e d for a h o m o g e n e o u s b u l k liquid. H o w e v e r , its use in surface chemistry has i n v o l v e d the a s s u m p -

VOL.

I --

N ~ 6 --

'1968 --

MATE~RIAUX

ET

CONSTRUCTIONS

b) S c a n n i n g

loops

on the isotherm

(i)

(ii)

(iii)

In the e x p e r i m e n t s o u t l i n e d a b o v e , the s a m p l e s w e r e not d r i e d c o m p l e t e l y to t h e " d - d r y i n g " point. It has b e e n s u g g e s t e d [13] that the i n t e r l a y e r w a t e r will n o t . r e - e n t e r if that p o i n t is attained b e c a u s e it is p o s t u l a t e d that at this p o i n t , most of this w a t e r has b e e n r e m o v e d a n d the l a y e r s h a v e c l o s e d tightly together, m a k i n g r e - e n t r y i m p o s s i b l e .
o o (v)
.

(iv)

o
,

(vi)

oo

\-..t-'~oQo o o 8~i.~ \'~?.Y, o o o o ~ ' , q


O0
0

A d e t a i l e d s t u d y of the l e n g t h - a n d w e i g h t - c h a n g e i s o t h e r m s for w a t e r on h y d r a t e d c e m e n t d r i e d to s e v e r a l conditions i n c l u d i n g t h e e q u i v a l e n t of ' d d r y i n g ' has b e e n c a r r i e d o u t r e c e n t l y [14], u s i n g bottle a n d p a s t e h y d r a t e d c e m e n t s , a n d r e - e n t r y of w a t e r has b e e n s h o w n to o c c u r . In e s s e n c e , s c a n n i n g l o o p s h a v e b e e n o b t a i n e d as low as 5 % r e l a t i v e h u m i d i t y (R.H.) a n d to as h i g h as 100 % R.H. (fig. 4.I). H e r e it is s e e n that the i s o t h e r m is i r r e v e r s i b l e at a n y p o i n t in the r a n g e of 5 to 100 % a n d p r o b a b l y l o w e r . Also, plotting AL/L vs. A W / W (fig. 4. II) for OA on the a s c e n d i n g b o u n d a r y c u r v e a n d AB the d e s c e n d i n g s c a n n i n g c u r v e , it is o b s e r v e d that t h e s e c h a r a c t e r i s t i c s a r e different. This i m p l i e s that t h e m e a n location of the w a t e r s o r b e d is different to that d e s o r b e d . The i s o t h e r m with the s c a n n i n g l o o p s e n a b l e d with s o m e justifiable a s s u m p t i o n s a c o m p l e t e s e p a r a tion of the r e v e r s i b l e w a t e r ( p h y s i c a l l y a d s o r b e d ) a n d i r r e v e r s i b l e w a t e r ( i n t e r l a y e r - h y d r a t e ) . This l e d to the construction of r e v e r s i b l e a n d i r r e v e r s i b l e isotherms 9 T h e r m o d y n a m i c e q u a t i o n s a p p l i e d to the f o r m e r l e d to AL/L vs. f~W/W, AL/L vs. A-~ r e l a t i o n s h i p s a n d e n a b l e d an e v a l u a t i o n of Y o u n g ' s m o d u l u s which p r o v i d e d c o m p l e t e justification for this a p p r o a c h . The i r r e v e r s i b l e i s o t h e r m p r o v i d e d the basis for an h y p o t h e s i s (to b e d e s c r i b e d later) on the w a y i n t e r l a y e r w a t e r l e a v e s a n d e n t e r s the crystal. E x p e r i m e n t s to m e a s u r e the variation of Y o u n g ' s m o d u l u s with v a p o u r p r e s s u r e , which will b e d e s c r i b e d in a l a t e r section, p r o v i d e firm s u p p o r t for the hypothesis. T h e s e results then l e a d to the f o l l o w i n g conclusions: a) The w a t e r i s o t h e r m for t h e d r y i n g conditions u s e d is i r r e v e r s i b l e at all r e g i o n s , a n d as such cannot b e u s e d for B.E.T. calculations. b) U n d e r t h e s e d r y i n g c o n d i t i o n s , s o m e i n t e r l a y e r w a t e r is e n t e r i n g at all r e g i o n s of the isotherm. c) Since a l a r g e b u t u n k n o w n p o r t i o n of the " s o r b e d " w a t e r in the low p r e s s u r e r e g i o n is interl a y e r r e h y d r a t i o n , the s u r f a c e a r e a must b e consid e r a b l y l o w e r than the o r i g i n a l v a l u e c a l c u l a t e d for water. d) The surface a r e a s c a l c u l a t e d from N2 a d s o r p t i o n m u s t b e c o n s i d e r e d a m o r e r e l i a b l e figure. The N 2 m e a s u r e s m a i n l y the " e x t e r n a l " surface while the w a t e r in a d d i t i o n has g o n e b e t w e e n the layers 9 e) I n t e r l a y e r w a t e r can b e s e p a r a t e d from p h y s i c a l w a t e r a n d e a c h of t h e s e s e p a r a t e l y can b e u s e d to e v a l u a t e a n d d e s c r i b e p r o p e r t i e s of the h y d r a t e d cement 9 This thus l e a v e s us with a c o n s i d e r a b l y a l t e r e d m o d e l of the dried h y d r a t e d p o r t l a n d c e m e n t . It has a m u c h l o w e r s u r f a c e a r e a w h i c h c h a n g e s with the W / C ratio a n d the b o n d s b e t w e e n crystallites d o not n o r m a l l y part. In a d d i t i o n , i n t e r l a y e r w a t e r p l a y s an i m p o r t a n t r o l e on the s o r p t i o n a n d l e n g t h c h a n g e p h e n o m e n o n . This m o d e l will b e f u r t h e r d e s c r i b e d w h e n the different s e c t i o n s a r e d i s c u s s e d .

FiG. 3. - - Simplified model for adsorption of molecules in cylindrical pores.

s y s t e m s , a n d results, d i s c u s s e d in a l a t e r s e c t i o n on m e c h a n i c a l p r o p e r t i e s , h a v e s u p p o r t e d this c o n c e p t . The i d e a of m o v i n g crystallites was c o n c e i v e d t o g e t h e r with that of ' r e s t r i c t e d a d s o r p t i o n ' [11]. The latter is c o n s i d e r e d unrealistic. A s u r f a c e attracts a m o l e c u l e to it b y f o r c e s e m a n a t i n g from it that fall off r a p i d l y with distance. If this s u r f a c e is in a p o r e (fig. 3 (i-vi)), the m o l e c u l e s diffuse g r a d u a l l y into the p o r e a n d a r e a t t r a c t e d to the surface. If small p o r e s (3, iv) b e c o m e full at low p r e s s u r e s , a d d i t i o n a l gas m o l e c u l e s will b e p r e v e n t e d from c o m i n g into the r e g i o n of the force field a n d b e i n g a t t r a c t e d b y the surface 9 A l a r g e r p o r e (3, v), after b e c o m i n g full, will form a m e n i s c u s w h o s e r a d i u s of c u r v a t u r e will d e p e n d on the e q u i l i b r i u m v a p o u r p r e s s u r e . This less tightly h e l d w a t e r in the m i d d l e of the p o r e c o m e s u n d e r a tension. If the size of the p o r e is v e r y c l o s e to the size of the m o l e c u l e (3, vi), the m o l e c u l e will b e a d s o r b e d from b o t h surfaces. This has b e e n t e r m e d ~ m o l e c u l a r b r i d g ing' a n d at l o w v a p o u r p r e s s u r e s , contractions h a v e b e e n o b s e r v e d (e.g. m o l e c u l a r s i e v e s [12]). At the i n t e r m e d i a t e a n d - h i g h p r e s s u r e r e g i o n s e v i d e n c e for m e n i s c i f o r c e s influencing the l e n g t h c h a n g e s was o b t a i n e d . Similarly, c h a r a c t e r i s t i c s w e r e o b s e r v e d similar to those d i s c u s s e d in Section

1 (c).
F r o m the AL/L vs. A W / W c h a r a c t e r i s t i c s it was r e c o g n i z e d that the exit a n d e n t r y of the i n t e r l a y e r h y d r a t e w a t e r b e t w e e n the s h e e t s of the t o b e r m o r i t e g e l p l a y e d an i m p o r t a n t role in e x p a n s i o n a n d contraction. This last point can b e e a s i l y illustrated b y the s k e t c h of the i s o t h e r m s h o w n for the t y p e III i s o t h e r m d i s c u s s e d in Section 1 (b). Unfortunately, b e c a u s e of the n a t u r e of the t o b e r m o r i t e g e l with r e g a r d to the c-axis, it has not b e e n p o s s i b l e to c o n f i r m the i n t e r l a m e l l a r p e n e t r a t i o n b y X - r a y m e t h o d s . It is c l e a r that s o m e w h e r e a l o n g the a s c e n d i n g b r a n c h of the isotherm, w a t e r is s o r b e d i r r e v e r s i b l y . This w o u l d affect the o v e r - a l l m e c h a n i s m for the s o r p t i o n - e x p a n s i o n p h e n o m e n a , a n d the u s e of the a s c e n d i n g c u r v e for B.E.T. calculations if i n t e r l a y e r w a t e r r e - e n t e r s in the 0 to 35 % r e l a t i v e h u m i d i t y r a n g e . It was c o n c l u d e d on the b a s i s of l e n g t h - c h a n g e a n d s o r p t i o n c h a r a c t e r i s t i c s that w a t e r d i d e n t e r the l a y e r s at b o t h low a n d h i g h humidities. As a result, p a r t of the l e n g t h - c h a n g e t h r o u g h o u t the i s o t h e r m is d u e to i n t e r l a y e r r e h y d r a t i o n , a n d a B.E.T. a r e a calculation from the w a t e r i s o t h e r m s h o u l d y i e l d a s m a l l e r value, if c o r r e c t i o n for i n t e r l a y e r hydration could be made. 514

R. F. F E L D M A N ,

P. J. S E R E D A

20

I
rr

16

9 40

<l

8
x .

36

.32 2

I
10

I
30

I
.50 pip o x 100

I
70

I I
90

-I
5 ~W/W X 100

i
6

FIG. 4. - - Sorption of water on hydrated Portland cement : I. Isotherm with scanning loops; IX. Length change vs. weight change plot over OAB.

c) S o r p t i o n

and length-change

of methanol

The s o r p t i o n i s o t h e r m of m e t h a n o l on h y d r a t e d p o r t l a n d c e m e n t was o b t a i n e d b y Mikhail [9]; this e x p e r i m e n t was r e p e a t e d in the D.B.R. l a b o r a t o r i e s in m o r e detail, a n d also i n c l u d e d m e a s u r e m e n t s of the a s s o c i a t e d l e n g t h - c h a n g e s . The result s h o w s similarities to the i s o t h e r m s of both n i t r o g e n a n d water. It r e s e m b l e d N~ s o r p t i o n in that the a m o u n t s o r b e d was low a n d the c a l c u l a t e d surface a r e a was similar to that o b t a i n e d b y N2. It y i e l d e d , h o w e v e r , a s e c o n d a r y h y s t e r e s i s m u c h l a r g e r than that for N 2 (which is r e l a t i v e l y small but p r e s e n t ) but not as l a r g e as for w a t e r ; s c a n n i n g Ioops w e r e o b s e r v e d at low as well as h i g h p r e s s u r e s . AL/L vs. A W / W c h a r a c t e r i s t i c s of the a s c e n d i n g a n d d e s c e n d i n g p o r t i o n s of the l o o p s a g a i n s h o w e d e v i d e n c e of the CH~.OH b e i n g s o r b e d in different r e g i o n s . CH3.OH has a d i p o l e m o m e n t of m a g n i t u d e c o m p a r a b l e to w a t e r but, as a l r e a d y shown, is l a r g e r than w a t e r a n d n i t r o g e n . P o l a r m o l e c u l e s , d u e to a m e c h a n i s m d i s c u s s e d in ref. 14, t e n d to p e n e t r a t e l a y e r e d c r y s tals m o r e effectively than n o n - p o l a r ones, b u t it b e c o m e s m o r e difficult the l a r g e r the m o l e c u l e becomes. T h e s e results a r e d i s c u s s e d h e r e as further evid e n c e of the i m p o r t a n c e of the l a y e r e d s t r u c t u r e of t o b e r m o r i t e gel, a n d its low s u r f a c e area. As w o u l d b e e x p e c t e d , the e x p a n s i o n d u e to the a d s o r p tion of m e t h a n o l is m u c h less than that for water, s i n c e a m u c h s m a l l e r amount has e n t e r e d the l a y e r s .
d) F i r s t d r y i n g of hydrated portland cement

l e n g t h cannot b e attained. This i r r e v e r s i b i e s h r i n k a g e is g r e a t e r the h i g h e r the W / C ratio; this m a y b e d u e to the fact that the d e g r e e of d i s p e r s i o n o r s u r f a c e a r e a of the w e t c e m e n t v a r i e s with W / C ratio a n d first d r y i n g is a manifestation of a m a j o r rearrangement of the l a y e r s o r s h e e t s of t o b e r m o r i t e gel. The r e m o v a l of w a t e r b e t w e e n s o m e i n d i v i d u a l s h e e t s m a y b r i n g a b o u t a l a y e r i n g of t h e s e s h e e t s o r further l a y e r i n g of others. A further e x p e r i m e n t a l result from this l a b o r a t o r y ( u n p u b l i s h e d data) m a y illustrate the i m p o r t a n c e of this rearrangement of l a y e r s o r s h e e t s of t o b e r m o rite g e l on first d r y i n g . F i g u r e 5 s h o w s the first d r y i n g (A) of a h y d r a t e d p o r t l a n d c e m e n t p a s t e p r e p a r e d at a W / C of 0.8

0.00

0.16 - -

0.32

--

0.48
X

0.64 <] 0.80


O. 96
-

The d i s c u s s i o n thus far has i n v o l v e d h y d r a t e d c e m e n t that has b e e n d r i e d f r o m the o r i g i n a l w e t state f o r m e d from the h y d r a t i o n p r o c e d u r e . The first time that the h y d r a t e d p a s t e is d r i e d is r a t h e r a s p e c i a l case, a n d m e a s u r e m e n t s t a k e n at this time a r e v e r y p e r t i n e n t to p r o b l e m s e n c o u n t e r e d in the field. The h i g h c h a n g e in s u r f a c e e n e r g y of the solid, a n d r e m o v a l of w a t e r b e t w e e n crystallites for the first time might c a u s e s o m e p e r m a n e n t c h a n g e . R e c e n t s t u d i e s b y Helmuth [15] h a v e s h o w n that the first d r y i n g d o e s in fact y i e l d a l a r g e i r r e v e r s i b l e s h r i n k a g e . On s u b s e q u e n t wetting, the o r i g i n a l

]
20

I
40
pip

i
80

I
100

60 o X 100

FIG. 5. - - Contraction on first drying for paste hydrated Portland cement. Water cement ratio is 0.8: I. Without additive; II. With additive.

515

VOL.

1 --

N o 6 --

1968

MATI6RIAUX

ET

CONSTRUCTIONS

a n d (B) the s a m e c e m e n t p r e p a r e d at the s a m e W / C with a d o s e of 0.0075 g i n s / g m of c e m e n t of a calcium l i g n o s u l p h o n a t e additive, This d o s e was t h r e e times l a r g e r than normal. It is b e l i e v e d that this effect can b e e x p l a i n e d b y the influence of the a d d i tive on the initial d e g r e e of l a y e r i n g of the h y d r a t e p r o d u c t ; a m o r e d r a s t i c c h a n g e m a y then take p l a c e on the first d r y i n g i n v o l v i n g the l a y e r i n g a n d r e a r r a n g e m e n t of the t o b e r m o r i t e g e l sheet. This l a y e r i n g might not result in a well o r d e r e d p r o d u c t ; orientation a n d s p a c i n g might b e i r r e g u l a r a n d t w i s t e d a n d naturally the l a y e r s might v a r y in thickness. T h e r e are, then, two different l e n g t h c h a n g e p r o c e s s e s for w h i c h one might h a v e to d e r i v e a m o d e l , o r from which one m i g h t obtain information with r e g a r d to a m o d e l . It is also e v i d e n t that in b o t h p r o c e s s e s the w a t e r b e t w e e n the l a y e r s of the t o b e r m o r i t e g e l p l a y s an i m p o r t a n t role. How t h e s e effects fit into this m o d e l of p o r t l a n d c e m e n t p a s t e a n d the m e c h a n i s m of c r e e p will b e d i s c u s s e d later after its m e c h a n i c a l p r o p e r t i e s a r e d e s c r i b e d in the n e x t sections.

b o n d b e p o s t u l a t e d which w o u l d i n v o l v e a solid-tos o l i d contact r e s u l t i n g f r o m t h e b r i n g i n g t o g e t h e r of s u r f a c e s ( b y p r e s s u r e e x t e r n a l l y o r i n t e r n a l l y g e n e r a t e d b y the reaction), f o r m i n g a p a r t i c l e b o u n d a r y h a v i n g little o r no r e g u l a r atomic a r r a n g e m e n t o r spacing. Atoms at such a b o u n d a r y w o u l d e n g a g e a v a r y i n g p r o p o r t i o n o f the l o n g - r a n g e a n d s h o r t - r a n g e f o r c e s d e p e n d i n g on the d e g r e e of d i s o r d e r a n d the a v e r a g e s p a c i n g . It can b e visuali z e d that this i n t e r p a r t i c l e b o n d can b e b r o k e n a n d subsequently remade under appropriate loading conditions. This t y p e of b o n d differs from the " c h e m i c a l " b o n d just d e f i n e d , w h i c h has a m o r e r e g u l a r atomic a r r a n g e m e n t a n d the s p a c i n g of m o r e of the atoms m a y a p p r o a c h that of the lattice s p a c i n g in the crystal. If w a t e r is i n v o l v e d in s u c h a b o n d (it will b e e i t h e r c h e m i - s o r b e d o r h y d r a t e d ) , it is c o n s i d e r e d a constituent p a r t o f the crystal. R e c e n t w o r k at this l a b o r a t o r y i n g g y p s u m [17] a n d c e m e n t has s h o w n that b o t h m o d u l u s o f n e s s a r e r e l a t e d to p o r o s i t y b y r e l a t i o n h a v i n g the form: E = Eoe-bP (fig. 6 a n d 7 ) i n v o l v p a s t e s a m p l e s [18] elasticity a n d h a r d a semi-logarithmic

EVIDENCE FOR TIlE 3. EXPERIMENTAL FROM MECHANICAL MODEL, TAI~EN BEHAVIOUR M e c h a n i c a l b e h a v i o u r of c e m e n t p a s t e s h o u l d f u r t h e r r e v e a l what p a r t w a t e r p l a y s in the structural m o d e l . Before this is d i s c u s s e d , a c l o s e r look must b e t a k e n at the s y s t e m of b o n d s which b i n d the l a y e r e d s t r u c t u r e of the p a r t i c l e a n d also the interparticle bonds. a) I n t e r p a r t i c l e b o n d s Philleo [16] d i s c u s s e d the v a r i o u s t y p e s of b o n d s a n d p o i n t e d out that the limited s w e l l i n g in w a t e r of the c e m e n t p a s t e has b e e n c o n s i d e r e d e v i d e n c e for the e x i s t e n c e of s o m e c h e m i c a l ( p r i m a r y ) b o n d s b e t w e e n the g e l p a r t i c l e s , but that the s e c o n d a r y b o n d s a c c o u n t e d for most of the s t r e n g t h of the c e m e n t paste. It is r e c o g n i z e d that the t e r m s " c h e m i c a l " a n d " s e c o n d a r y " b o n d s h a v e b e e n u s e d in d e s c r i b i n g the s t r u c t u r e of h y d r a t e d c e m e n t s y s t e m s without a strict definition of t h e i r m e a n i n g . This has l e d to c o n s i d e r a b l e m i s u n d e r s t a n d i n g . It is b e l i e v e d that what was m e a n t b y the " c h e m i c a l " b o n d b e t w e e n the p a r t i c l e s was a solid-to-solid contact similar to that of a g r a i n b o u n d a r y in a p o l y c r y s t a l l i n e m a t e r i a l w h e r e s o m e atoms a p p r o a c h the s p a c i n g a n d a r r a n g e m e n t in the crystal. Such " c h e m i c a l " b o n d s c o u l d b e f o r m e d d u r i n g a crystallization p r o c e s s a c c o m p a n y i n g a c h e m i c a l r e a c t i o n w h e r e the m o b i l ity of atoms allows for a r e g u l a r a r r a n g e m e n t resulti n g in an i n t e r g r o w t h of crystals. It follows that these bonds would be strong and when broken w o u l d not b e r e m a d e in n o r m a l c i r c u m s t a n c e s . It is b e l i e v e d that the t e r m " s e c o n d a r y " b o n d s as a p p l i e d to the h y d r a t e d c e m e n t s y s t e m a r o s e out of the a s s u m p t i o n that p h y s i c a l l y a d s o r b e d w a t e r was a constituent p a r t of the i n t e r p a r t i c l e b o n d ; thus the g e n e r a l t e r m of van d e r W a a l s f o r c e s was considered appropriate. P r e v i o u s w o r k in this l a b o r a t o r y has i n d i c a t e d that n e i t h e r of t h e s e definitions w o u l d a d e q u a t e l y fit the i n t e r p a r t i c l e b o n d s in the h y d r a t e d c e m e n t system. It is s u g g e s t e d , t h e r e f o r e , that a different i n t e r p a r t i c l e 516

where E a n d E 0 a r e the m o d u l i of elasticity at a g i v e n p o r o s i t y a n d at Zero p o r o s i t y r e s p e c t i v e l y , b is the e m p i r i c a l constant a n d P is the p o r o s i t y . W h e n the a b o v e relation for m o d u l u s of elasticity was d e t e r m i n e d for s a m p l e s of g y p s u m a n d c e m e n t p a s t e r e p r e s e n t i n g t h r e e different structural systems, the following conclusions w e r e m a d e . At 30 % porosity, the in-situ h y d r a t e d g y p s u m h a d a m o d u l u s about 10 times g r e a t e r than c o m p a c t e d g y p s u m a n d a b o u t 5 times as g r e a t as s a m p l e s of in-situ h y d r a t e d a n d l a t e r c o m p a c t e d s a m p l e s , in c o n t r a s t with the results for c e m e n t p a s t e w h e r e the t h r e e different s e r i e s of s a m p l e s aI1 g a v e virtualIy the s a m e plot of m o d u l u s vs. p o r o s i t y . T h e s e results s u g g e s t that the i n t e r p a r t i c l e b o n d s a r e the s a m e in all the s e r i e s of s a m p l e s of c e m e n t p a s t e a n d a r e solid-to-solid contacts w h i c h a r e m a d e b y b r i n g i n g the s u r f a c e s t o g e t h e r with the a p p r o p r i a t e p r e s s u r e resulting e i t h e r from the e x t e r n a l l y a p p l i e d l o a d as in c o m p a c t i o n o r i n t e r n a l l y g e n e r a t e d d u r i n g the h y d r a t i o n reaction. The significant fact l e a r n e d f r o m t h e s e results is that the b o n d s f o r m e d d u r i n g the h y d r a t i o n r e a c t i o n a r e not s t r o n g e r than those f o r m e d b y c o m p a c t i o n , in s h a r p contrast with what h a p p e n s in the c a s e of the g y p s u m system. In the latter case, the interg r o w t h of crystals s e e m s to o c c u r d u r i n g h y d r a t i o n , forming " chemical " bonds which are very much s t r o n g e r than t h o s e f o r m e d b y c o m p a c t i o n . Similarly, s o m e r e c e n t w o r k i n v o l v i n g c o m p a c t s of Ca(OH)2 d u r i n g a g e i n g [19] a n d d u r i n g c a r b o n a tion [20] s h o w s h o w t h e s e i n t e r p a r t i c l e b o n d s can b e i n c r e a s e d b e c a u s e of r e c r y s t a l l i z a t i o n of the m a t e r i a l o r b e c a u s e of n e w p r o d u c t s f o r m e d as the result of the reaction. F u r t h e r e v i d e n c e for the n a t u r e of the i n t e r p a r t i c l e c e m e n t b o n d c o m e s from the e x p e r i m e n t s w h e r e h y d r a t e d c e m e n t p a s t e was c o m p a c t e d to l o w e r p o r o s i t i e s i n v o l v i n g a r e d u c t i o n of p o r o s i t y v a r y i n g from as little as 5 % to as m u c h as 45 %. In all c a s e s the m o d u l u s v a l u e s fitted the s a m e relation as for the h y d r a t e d p a s t e s a m p l e s . If a " c h e m i c a l " b o n d w e r e to b e f o r m e d d u r i n g h y d r a t i o n , such a b o n d would be broken during subsequent compaction and w o u l d not b e r e m a d e , r e s u l t i n g in a l o w e r m o d u l u s

R. F. I : E L D M A N ,

P. J. S E R E D A

>_i,--

100
40

<,o
~.~
o ~' :::) v.

20 10
4

o ~E

FI FI-I

Compacted Cement Paste \ Compacts of Bottle Hydrated


Cement

FIG. 6. - - Modulus o f elasticity as a function of total porosity for v a r i o u s hydrated c e m e n t samples.

I
20

I
40

1
60

TOTAL POROSITY, PERCENT 100 >7~


40

l
I~..

I Cast Gypsum I I YI Compacted Cast Gypsum I]Z Hydrated Plaster Compacts


Compacts of Bottle

Hydr.ated P la ster
~-o
.__jo
223 '-4

10
4

FXG. 7. - - Modulus o f elasticity as a function o f total porosity for various g y p s u m samples.

20 40 60 'TOTAL POROSITY, PERCENT

for c o m p a c t e d paste. This was not the case, which is e v i d e n c e of the a b s e n c e of " chemical " b o n d s a n d leads to the conclusion that the i n t e r p a r t i c l e b o n d s are solid-to-solid contacts which are r e s p o n s ible for the limited s w e l l i n g of c e m e n t paste. T h e s e b o n d s a p p e a r to b e of such a n a t u r e that they can b e b r o k e n a n d r e m a d e without suffering p e r m a n e n t d e c r e a s e in modulus. The most important q u e s t i o n relating to the interparticle b o n d is w h e t h e r physically a d s o r b e d w a t e r zs a constituent part of the interparticle b o u n d a r y , as has b e e n postulated b y m a n y w o r k e r s . It s h o u l d b e r e m e m b e r e d that the a r e a of actual contact betw e e n particles is p r o b a b l y no g r e a t e r than 5 % of the a p p a r e n t cross-sectional a r e a w h e n the porosity is about 50 %. If this is the case, it w o u l d result in g r e a t stress c o n c e n t r a t i o n at areas of contact d u r i n g loading. For example, a load of 5,000 psi d u r i n g c o m p a c t i o n (about the lowest u s e d to obtain a stable sample) would i m p o s e a load of a p p r o x i m a t e l y 100,000 psi on the b o n d area. It is unlikely that a n y a d s o r b e d water w o u l d r e m a i n b e t w e e n the particles d u r i n g t h e application of such high unit load. (Van O l p h e n [21] caJculated that a p r e s s u r e of 60,000 psi w o u l d r e m o v e a m o n o l a y e r of water from b e t w e e n clay particles.) E x p e r i m e n t a l e v i d e n c e for the c o n c l u s i o n that a d s o r b e d water is not p r e s e n t at an i n t e r p a r t i c l e b o u n d a r y is available from the work at DBR [22]. Bottle h y d r a t e d c e m e n t p o w d e r was c o m p a c t e d after c o n d i t i o n i n g to 0 % R.H. as well as 30 % R.H. The

c o m p a c t i o n c u r v e s (fig. 8) w h e r e porosity was plotted against log c o m p a c t i o n p r e s s u r e are parallel a n d only slightly displaced. The d i s p l a c e m e n t b e t w e e n these two c u r v e s could b e e x p l a i n e d on the basis of lower friction w h e n a m o n o l a y e r of water is p r e s e n t which allows far e a s i e r sliding a n d a c c o m m o d a t i o n of particles. If water r e m a i n e d at the interparticle b o u n d a r y in the o n e case a n d not in the other, then the c o m p a c t i o n c u r v e s w o u l d b e e x p e c t e d to b e significantly different. The only

L~ r

0-

50--

>_0

o _~
<

Bottle Hydrated Cement ~


25 I l-f -

O~o R.H.
30% R . H .

\ \

--

~-

Io

10

100

COMPACTION PRESSURE PSIX10 -3


FIG. 8 . - - Total porosity as a function of compaction pressure for bottle hydrated cement: I. Dried to 0 per cent relative humidity: II. Dried to 30 per cent relative humidity.

517

VOL

- -

N~ 6

- -

1968

- -

MATI~RIAUX

ET C O N S T R U C T I O N S

>.i--

20 --

\\

f
\\

<,o"
t/3 0 ',I

\\ \\
Cement Paste
, I
Sat. 0 R.H.
50

.~o10
O

WlC = O. 30
I00

F I G . 9. - -

Modulus

of elasticity

as a

function of relative httmidity.

(0) X X X X X (b) xxxxx

Saturated

o7,,
oO~
ooO ~

~ o

B
(d)

Desorpti0n

"
x )~_,w~A

Dry

cf)
(g) A X B o
FIG. iO. --

XN

"

NX

l
Saturated]

Adsorption

xx215
F~o. li. --

- I n t e r p a r t i c l e Bonds - I n t e r l a y e r .Hydrate Water - T o b e r m o r i t e Sheets - Physically Adsorbed Water


Simplified

Simplified model for the exit and e n t r y of water into the layers of tobermorite g e l .

model for hydrated Portland cement.

d i f f e r e n c e is o b s e r v e d at v e r y h i g h p r e s s u r e , h o w e v e r , w h e r e the c u r v e for the c e m e n t c o n d i t i o n e d to 30 % R.H. (containing a b o u t 6 % m o i s t u r e content) flattens, p o s s i b l y b e c a u s e this amount of water, w h i c h is l a r g e in relation to the low p o r o s i t y , is t r a p p e d a n d p r e v e n t s further c o m p a c t i o n u n d e r r a p i d ] o a d application. P e r h a p s the most c o n c l u s i v e e v i d e n c e in s u p p o r t of the i d e a that i n t e r p a r t i c l e b o n d s d o not h a v e a d s o r b e d w a t e r at the b o u n d a r y c o m e s from the m e a s u r e m e n t s of elastic m o d u l u s at different c o n d i tions of r e l a t i v e h u m i d i t y [22] (fig. 9). It has b e e n s h o w n that the m o d u l u s r e m a i n s u n c h a n g e d w h i l e r e l a t i v e h u m i d i t y is i n c r e a s e d from 0 to 50 %. This is the r e g i o n of h i g h a d s o r p t i o n a n d c o r r e s p o n d i n g l y l a r g e d i m e n s i o n a l c h a n g e . If the a d s o r b e d w a t e r w e r e e n t e r i n g the i n t e r p a r t i c l e b o n d a r e a the net r e s u l t s h o u l d b e a d e c r e a s e in m o d u l u s , as o c c u r s in the c a s e of cellulosic m a t e r i a l [23].
b) S t r u c t u r e particle
and bonds within the cement gel

A d s o r p t i o n s t u d i e s h a v e r e v e a l e d that the g e l p a r ticle of t o b e r m o r i t e is a l a y e r e d s t r u c t u r e into which 518

w a t e r enters, not as a p h y s i c a l l y a d s o r b e d , b u t as a structural a n d " c h e m i c a l " c o m p o n e n t that c o u l d b e d e s i g n a t e d as an i n t e r l a y e r - h y d r a t e water. If this is true, then the m e c h a n i c a l b e h a v i o u r s h o u l d e x h i b i t certain p e c u l i a r i t i e s to suit this s p e c i a l m o d e l of the g e i particle. It has b e e n f o u n d that the m o d u l u s of elasticity has the h i g h e s t v a l u e w h e n t h e p a s t e is h y d r a t e d a n d t e s t e d in the s a t u r a t e d state ( b e f o r e first d r y i n g ) (fig. 9). As the p a s t e is d r i e d the m o d u l u s d e c r e a s e s to a m u c h l o w e r v a l u e ( d e p e n d i n g on the initial W / C ratio). W h e n w a t e r is a d s o r b e d the m o d u l u s r e m a i n s e s s e n t i a l l y constant until a b o u t 50 % R.H. c o n d i t i o n is r e a c h e d ; after f u r t h e r a d s o r p t i o n the m o d u l u s then i n c r e a s e s until at saturation the v a l u e is n e a r l y the s a m e as w h e n the p a s t e was s a t u r a t e d originally. T h e r e is e v i d e n c e that this i n t e r l a y e r w a t e r is r e m o v e d p r o g r e s s i v e l y as the s a m p l e is d r i e d , b u t m o s t l y in the last p a r t of the d r y i n g r e g i o n . D u r i n g s o r p t i o n from the d r y state the i n t e r l a y e r w a t e r g o e s into the crystallites p r o g r e s s i v e l y . T h e effect of this i n t e r l a y e r w a t e r o n m o d u l u s , h o w e v e r , b e g i n s to b e of s i g n i f i c a n c e o n l y in the h i g h e r r e g i o n of the isotherms. In this r e g i o n the e n t r y of interlayer water causes a much smaller length change

R. F. F E L D H A N ,

P. J. S E R E D A

p e r unit of i n t e r l a y e r w a t e r g a i n e d . In Section 4 this will b e s h o w n to b e consistent. It is i m p o r t a n t to c o n s i d e r w h e t h e r the i n t e r l a y e r w a t e r w o u l d b e e x p e l l e d d u r i n g c o m p a c t i o n of the h y d r a t e d c e m e n t p a r t i c l e s as was s u g g e s t e d for the c a s e of the i n t e r p a r t i c ] e b o n d a r e a . First the a r e a b e t w e e n l a y e r s m u s t b e l a r g e r e l a t i v e to the interp a r t i c l e a r e a a n d c o n s e q u e n t l y unit p r e s s u r e w o u l d not b e high. S e c o n d , the interlaT}'er w a t e r finds itself c o n f i n e d o r b l o c k e d b e t w e e n the l a y e r s , a n d so w o u l d r e q u i r e c o n s i d e r a b l e time to b e e x p e l l e d . Thus in the r a p i d a p p l i c a t i o n of p r e s s u r e d u r i n g compaction, v e r y little of this w a t e r w o u l d b e e x p e l led, w h e r e a s d u r i n g the s u s t a i n e d l o a d a p p l i c a t i o n r e s u l t i n g in c r e e p , a c o n s i d e r a b l e a m o u n t of the i n t e r l a y e r w a t e r m a y b e e x p e l l e d . This p o s s i b i l i t y p r o v i d e s the link b e t w e e n d r y i n g s h r i n k a g e a n d c r e e p deformation. Thus the r e v e r s i b l e p a r t of c r e e p is p r o b a b l y a s s o c i a t e d with the slow d e c o m p o s i t i o n of the h y d r a t e a n d l i b e r a t i o n of water, w h i c h s h o u l d r e t u r n to its o r i g i n a l position after the r e m o v a l of the stress. The i r r e v e r s i b l e p a r t of c r e e p c o u l d b e a s s o c i a t e d with the d i s p l a c e m e n t of o n e l a y e r r e l a t i v e to the other, but m o r e likely i n v o l v e s a p r o c e s s of b r e a k i n g a n d r e m a k i n g the i n t e r p a r t i c l e b o n d s . Just as c o m p a c t i o n of p a s t e is p o s s i b l e without a n y loss in s t r e n g t h w h e n this is d o n e u n d e r triaxial stress, so will s u s t a i n e d s t r e s s at a lev~i c o n s i d e r a b l y b e l o w the b r e a k i n g stress, i n d u c e the b r e a k i n g of c e r t a i n highly stressed bonds and subsequent remaking after s o m e r e o r i e n t a t i o n of the p a r t i c l e s . As l o n g as t h e r e a r e as m a n y - b o f l d s b e i n g r e m a d e as a r e b e i n g b r o k e n , no net loss in s t r e n g t h will b e e x p e rienced.
4. M O D E L F O R H Y D R A T E D C E M E N T PASTE

sible p h y s i c a l l y h e l d water. It is the o u t e r s u r f a c e s that h a v e b e e n m e a s u r e d d u r i n g N2 a d s o r p t i o n , although at times d u r i n g the s t r u c t u r e formation s o m e of t h e s e contacts m a y r e p r e s e n t the i n t e r l a y e r situation e x i s t i n g i n s i d e the p a r t i c l e d e s c r i b e d a b o v e . The r e a s o n for the Nz a r e a c h a n g e s with W / C ratio is found in the c o n c e p t that g e l f o r m e d in m o r e confined s p a c e ( l o w e r W / C ratio) is f o r c e d to b e " p r e s s e d " t o g e t h e r a n d that m o r e of the s p a c e s b e t w e e n p a r t i c l e s b e c o m e effectively i n t e r p a r t i c ] e s p a c e s w h e r e w a t e r is p r e f e r e n t i a l l y a d m i t t e d a n d b e c o m e s h y d r a t e water. The l a y e r e d i r r e g u l a r s t r u c t u r e is consistent with the v a r i o u s d e s c r i p t i o n s of e l e c t r o n m i c r o g r a p h s of t o b e r m o r i t e as c r u m p l e d sheets. A n a t t e m p t is m a d e to r e p r e s e n t d i a g r a m m a t i c a l l y a m o d e l of a t o b e r m o r i t e p a r t i c l e in f i g u r e 10, w h e r e the two t y p e s of w a t e r a r e differentiated. The i n t e r p a r t i c l e b o n d i n g is r e p r e s e n t e d as a s o l i d - t o - s o l i d contact, although at times d u r i n g the s t r u c t u r e formation s o m e of t h e s e contacts m a y r e p r e s e n t the i n t e r l a y e r situation existing i n s i d e the p a r t i c l e d e s c r i b e d above. The r e m o v a l of the i r r e v e r s i b l e w a t e r d u r i n g d e s o r p t i o n is found to b e different than its r e - e n t r y d u r i n g s o r p t i o n a n d this can account for the v a r i a tion of Y o u n g ' s m o d u l u s a n d l e n g t h c h a n g e with v a p o u r p r e s s u r e (or i r r e v e r s i b l y s o r b e d w a t e r ) (fig. 11). This m o d e ] s h o w s in (a) a n d (b), the g r a d u a l r e m o v a l of i n t e r l a y e r w a t e r from the e d g e s . This p r o b a b l y o c c u r s f r o m 30 to 10 % R.H. a n d little c h a n g e in m o d u l u s a n d l e n g t h c h a n g e occurs. F u r ther removal, from (b) to (c), i n v o l v e s a l a r g e r l e n g t h c h a n g e , u p to a b o u t 2 % R.H., b u t still no c h a n g e in m o d u l u s . O n l y the final r e m o v a l of the w a t e r in the m i d d l e s h o w s a l a r g e d e c r e a s e in m o d u l u s a n d a g a i n a l a r g e l e n g t h c h a n g e . On r e s o r p t i o n l a r g e l e n g t h c h a n g e s o c c u r u p to a b o u t 50 % R.H. (states (e) a n d (f)) with no c h a n g e in modulus; a b o v e 50 %, to 100 %, state (g) is r e a c h e d , i.e., a filling of the m i d d l e of the l a y e r , y i e l d i n g an i n c r e a s e in m o d u l u s a n d l o w e r rate of i n c r e a s e of length with i n t e r l a y e r w a t e r . This m o d e l e x p l a i n s the l a r g e h y s t e r e s i s f o u n d for the variation of modulus, i r r e v e r s i b l e water, a n d l e n g t h c h a n g e of h y d r a t e d c e m e n t p a s t e with r e l a t i v e p r e s s u r e .

E v i d e n c e has b e e n p r e s e n t e d in s u p p o r t of the c o n c e p t that the h y d r a t e d c e m e n t p a r t i c l e o r crystallite is a l a y e r e d s t r u c t u r e of no definite n u m b e r a n d of i r r e g u l a r configuration o r a r r a n g e m e n t . It n o w a p p e a r s c e r t a i n that w a t e r constitutes a structural p a r t (a c r o s s l i n k oi" w e b ) b e t w e e n l a y e r s a n d that this w a t e r is the i r r e v e r s i b l e w a t e r o b s e r v e d from the s c a n n i n g isotherms, distinct from the r e v e r -

ACKNOWLEDGEMENTS

This p a p e r is a c o n t r i b u t i o n of the Division of Building R e s e a r c h , National R e s e a r c h Council of C a n a d a a n d is p u b l i s h e d with the a p p r o v a l of the D i r e c t o r of the Division.

519

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MATI~RIAUX

ET

CONSTRUCTIONS

REFERENCES

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calcium silicate and tricalcium silicate at room temperature. J. Phys. Chem., 80, 761-767, 1958.

[14] FELDMArr R. F., Sorption and length change scanning isotherms of methanol and water on hydrated portland cement. Submitted to 5th International Symposium on (:hem, of Cement, Tokyo, t968. [15] I-Ir:LMUTrLR. A., and T~RK, D. H., The reversible and irreversible drying shrinkage of hardened portland cement and triealcium silicate pastes. J. Portland Cement Assoc., Research and Development Lab. 9, p. 8-21, May t967. [16] PHILLEO, R. E., The origin of strength of concrete. Highway Research Board Spec. Report 90, 175185, 1966. [17] SOROKA, I., and SEnEDA, P . J . , The inter relation of hardness, modulus of elasticity and porosity in various gypsum, systems J. Amer. Ceram. Soc., 51, 337-340, 1968. [18] SOROKA, I., and SEREDA, P. J., The structure of cement-stone and the use of compacts as structural models. Submitted to the 5th International Symposium on the Chemistry of Cement, Tokyo, 1968. [19] SWENSON, E. G., and SEREDA, P. J., Some ageing characteristics of lime. J. Appl. Chem., 17, 198202, t967. [20] SWENSON, E. G., and SEREDA, P. J., A mechanism for carbonation shrinkage of lime and h) drated cement. J. Appl. Chem. In press. [21] OLI~HEN, H. vAIN., A n introduction to clay colloid chemistry. Interscience Publishers, New York, 1963. [22] SCJtEDA, P. J., FELD~AIN., R. F. and SWENSON, E. G., Effect of sorbed water on some mechanical roperties of hydrated cement pastes and coml: acts. Highway Research Board Spec. Report 90, p. 5873, 1966. [23] ZrIvnKOV, S. N., Dokl. Akad. Nauk SSSR 49, 198, 1945.

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