CEMENT and CONCRETERESEARCH. Vol. I , pp. 367-383, 1971.

Pergamon Press, Inc

Printed in the United States.

MORPHOLOGY AND MICROSTRUCTURE OF HYDRATING

PORTLAND CEMENT A N D ITS C O N S T I T U E N T S
IV. CHANGES IN H Y D R A T I O N O F A CsS, C=S, CsA, C 4 A F
AND GYPSUM PASTE WITH AND WITHOUT THE ADMIXTURES
TRIETHANOLAMINE AND CALCIUM LIGNOSULPHONATE'~

T. D. Ciach and E. G. S w e n s o n
Division of Building Research, National Research Council of Canada
Ottawa 7, Ontario, Canada

(Communicated by G. M. Idorn)

ABSTRACT
Systematic sequential observations with the electron microscope
w e r e m a d e of morphological changes which occurred during
hydration of a paste mixture of C3S ~ , C2S, C~A, C ~ A F and
gypsum. The pronounced effect on rate of hydration of each of
two organic admixtures was clearly observed. Differences
could be seen also in the stability and habit of hydration products
and in the microstructure itself. The electron micrographs
shown illustrate the forms of the products at different hydration
time s.
SOMM AIRE
Des observations au microscope ~lectronique ont ~t~ faites en
s~quence syst~matique pour observer les changements m o r p h o -
logiques qui prenaient place au cours de l'hydratation d'une p~te
de C3S ~:~, C2S, C3A, C 4 A F et de gypse. Les effets prononc~s
de deux adjuvants organiques sur la vitesse d'hydratation ont
~t~ nettement observes. On a pu constater des differences dans
la stabilit~ et l'habitus des produits d'hydratation de m ~ m e que
dans la microstructure elle-m~me. Les r~sultats de la micro-
graphie qui sont pr~sent~s illustrent la forme des produits
cliff,rents stages de l'hydratation.

- , ~ P r e s e n t e d a t t h e C e m e n t S y m p o s i u m of t h e A m e r i c a n Ceramic Society,
72 A n n u a l M e e t i n g , P h i l a d e l p h i a , May, 1970.

~:';:~Standard c e m e n t n o m e n c l a t u r e is used; CaS = 3CaO. SiOa; C2S = 2CaO.~C~;

C 3 A = 3 C a O . A ~ 2 O a ; C ~ A F = 4CaO. A Z 2 0 3 . F e 2 0 3 ; w / c = w a t e r : c e m e n t
ratio by weight.
367
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MICROSTRUCTURE,CEMENT PASTE, ADMIXTURES

T h i s is the f o u r t h of a c o n t i n u i n g s e r i e s of p a p e r s w h i c h r e p o r t the
m o r p h o l o g i c a l c h a n g e s o c c u r r i n g d u r i n g the h y d r a t i o n of p o r t l a n d c e m e n t
and i t s p u r e c o n s t i t u e n t s in the a b s e n c e and in the p r e s e n c e of a d m i x t u r e s .
The f i r s t d e a l t w i t h C s A ( I ) , the s e c o n d w i t h CsS and C~S (2), and the t h i r d
w i t h CsS and C s A (3); in e a c h c a s e the c h a n g e s w i t h and w i t h o u t g y p s u m w e r e
noted.

The present paper deals with the morphological changes that occur
during the hydration of a synthetic cement: a mixture of CsS, C~S, C s A ,
C~AF and gypsum, in the absence and in the presence of two admixtures,
triethanolamine and calcium lignosulphonate.

Intr oduction

Studies that describe the morphological changes occurring during

the hydration of simple systems of cement minerals have been referred to in
the previous papers in this series (l, Z, 3). Experiments with the multi-
component mixture used in the present study, C s S , C~S, C s A , C ~ A F and
gypsum, apparently have never been performed. Chatterji and Jeffery (4)
used electron optical and x-ray diffraction techniques in a study of the
hydration to three m o n t h s of a mixture of alite, C s A , C 4 A F and gypsum.
This and other simpler systems have been reviewed relatively recently by
Copeland and Kantro (5), Taylor (6) and de Jong (7). These studies would
lead one to expect considerable differences to occur in the rates of reaction
and in the nature of products formed, as a result of varying the conditions or
combining the components.

Certain forms of alumina, iron and sulphate, such as C s A in CsS

systems, can enter the C S H lattice structure; such penetrations are reported
to affect the rate of hydration of the silicates and possibly also the m i c r o -
structure (5, 6, 7). Rather than being isomorphous, penetrations m a y be
due to additions to the lattice (5); for example, SO~ m a y be added by an
extension of the C S H lattice.

The presence of g y p s u m appears to accelerate the hydration of alite

but only during the first day or so of C s S hydration (5). Water-to-solids
Vol. I , No. 4 369
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

ratio in a C 3 S component system affects the formation of lime and this is

believed to effect changes in the rates of formation of silicate hydrates.

With admixtures like sucrose and calcium lignosulphonate, no n e w

solid phases appear to occur (8) but the rates of hydration of the m a j o r
components are sharply affected. The retardation of C 3 S by such admixtures
is believed to be due to the inhibition of the release of lime. The presence
of C 3 A , however, accelerates the hydration of C3S due to a preferential
adsorption of calcium lignosulphonate into the f o r m e r (8, 9, 10, ll). A
lignosulphonate is also able to delay the precipitation of gypsum. Some
question exists as to the effect of calcium lignosulphonate in retarding the
change of C ~ A H s and C 4 A H I ~ to the C 3 A H 6 f o r m (12, 13).

The various effects reported above were kept in m i n d w h e n examin-

ing the systems in this study.

Materials and Procedure

The sample materials used, C3S , C2S , C s A , gypsum, triethanol-

amine and calcium lignosulphonate, are the s a m e as those described in
previous papers (i, 2) dealing with the m o n o m i n e r a l pastes. The C 4 A F
had been prepared s o m e years ago at the University of Saskatchewan by
Dr. T. Thorvaldson.

The dry mixture of the synthetic cement used consisted of 44 per

cent C 3 S , 34 per cent C~S, 12 per cent C 3 A , 5 per cent C 4 A F and 5 per cent
gypsum. These proportions w e r e considered reasonably in line with those
occurring in n o r m a l portland cement. T h e y w e r e ground together in a
pot celain-alumina ball-mill.

Pastes w e r e prepared based on a ratio of 0.5 per cent by weight

water-to-dry powder. Admixture dosages w e r e 0.5 per cent by weight of
the dry mixtures.

At intervals of 5 minutes, 1 and 6 hours, l, 2, 3, 7 and 14 days

and i, 2 and 3 months, samples w e r e taken. Hydration was stopped by
treating the paste with acetone at about -18°C, and then drying the frozen
samples in vacuum.
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MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

Single stage replicas from broken surfaces of the paste were m a d e

using the platinum-carbon technique. Only those electronmicrographs
which depict the average and general morphology are presented in this paper

Results and Observations

i. Hydration of synthetic cement paste with no admixture present

The microstructure of synthetic cement (w/c ratio 0.5) after 5

minutes of hydration displayed a mixture of unhydrated grains of cement
minerals and a m o r p h o u s films of hydration products. Also present were
the rod-like particles of ettringite and s o m e irregular plates on the surfaces
of grains (Fig. I).

B y 6 hours the a m o r p h o u s films and the ettringite particles were the

m a i n hydration products, but small rounded particles on the surfaces of
grains appeared as well (Fig. Z).

At the end of l day of hydration, large thin plates of hydration

products and small fibrous particles of C S H had formed between unhydrated
grains of cement minerals (Fig. 3).

At 3 days hydration the microstructure displayed a closely knit

structural form, with needles of ettringite, plates of hexagonal C A H and
s o m e small fibres of C S H radiating from calcium silicate grains (Fig. 4).

During the next 2 weeks, m a n y different types of hydration products

were formed, the dominant being platelet aggregations (Fig. 5). Fibrous
particles of C S H were present between them, and sometimes a fibrous
structure developed on the surface of plates (Fig. 6).

At I m o n t h of hydration the synthetic cement paste had a dense

microstructure in which p s e u d o m o r p h s of calcium silicate grains
surrounded by fibrous particles or irregular forms of parallel cleavage
could be distinguished (Fig. 7). S o m e of the plate-like forms of the
hydration products displayed fibrous fracture on the surfaces.

During the second and third months of hydration the microstructure

is very dense, although no n e w forms of hydration products appeared.
Vol. I, No. 4 371
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

FIG. 1 FIG. 2
Microstructure of synthetic cement Microstructure of synthetic cement
paste, w / c = 0.5. Age 5 rain. M i x - paste, w / c = 0. 5. A g e 6 hr. Rod-
ture of unhydrated grains of c e m e n t like ettringite and small rounded
constituents cemented by a m o r p h o u s particles of hydration products.
hydration products. Note rod-like
ettringite particles and s o m e irreg-
ular, plate-like products on the
surfaces of grains.

FIG. 3 FIG. 4
Microstructure of synthetic c e m e n t Microstructure of s y n t h e t i c c e m e n t
paste, w / c = 0.5. Age 1 day. Large paste, w/c = 0.5. Age 3 days.
thin plates of hydration products and D e n s e s t r u c t u r e of n e e d l e s a n d
small fibrous particles of CSH. plates of CAH and some small
f i b r o u s p a r t i c l e s of C S H r a d i a t i n g
from calcium silicate grains.
372 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

FIG. 5 FIGo 6
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste, w / c = 0.5. A g e 14 days. paste, w / c = 0. 5. A g e 14 days.
M a n y different types of hydration S o m e plates of hydration products
products with the dominant f o r m s display an oriented two-dimensional
being platelet aggregations. fibrous structure.

FIG. 7
Microstructure of synthetic c e m e n t
paste, w / c = 0. 5. A g e 1 month.
Various types of hydration products
with closely packed structure.
Vol. I , No. 4 373
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

P l a t e s a r e the p r e d o m i n a n t f o r m , w i t h p s e u d o m o r p h s of c e m e n t m i n e r a l s
a l s o a p p e a r i n g p l e n t i f u l l y ( F i g . 8).

X - r a y d i f f r a c t i o n s t u d i e s done on t h i s s y n t h e t i c c e m e n t p a s t e a f t e r 1,
3 and 7 d a y s of h y d r a t i o n , s h o w e d t h a t the 4 . 9 A p e a k f o r CH a p p e a r e d a f t e r
one d a y of h y d r a t i o n . L a t e r the p e a k s of the c e m e n t m i n e r a l s d i s a p p e a r e d
but none of the d i f f r a c t o g r a m s s h o w e d m u c h c h a n g e due to the p o o r c r y s t a l -
l i n e h a b i t s of the h y d r a t i o n p r o d u c t s .

2. Hydration of synthetic c e m e n t paste with 0. 5% triethanolatnine present

The first hydration products developed between 5 minutes and l hour

of hydration as short rod-like particles of ettringite type, and rounded,
unoriented plates on the surfaces of unhydrated grains of cement minerals
(Fig. 9).

At 6 hours' the m a i n hydration products w e r e plates and single rod-

like particles (Fig. 10). After 1 day of hydration the microstructure was
a closely knit structure consisting mainly of plates (Fig. ll). During the
next period up to 3 days, the amorphous, fibrous particles of C S H w e r e
radiating grains of calcium silicates and in s o m e places w e r e in the f o r m of
plates (Fig. 12).

The dominant f o r m s of hydration products at 7 days' hydration w e r e

large fibres of C S H , radiating grains of calcium silicates, and aggregates of
plates, s o m e of which displayed a fibrous structure (Fig. 13).

The microstructure at 14 days consisted of irregularly shaped

hydration products which w e r e forming an un0riented structure (Fig. 14).
Fibrous particles of C S H w e r e gradually changing to plates having a three-
directional fibrous fracture or cleavage.

Many different f o r m s of hydration products w e r e present after 1

m o n t h of hydration. Among t h e m the p s e u d o m o r p h o u s grains of cement
minerals, fibres and plates could be distinguished. Some of the plates also
displayed fibrous fracture (Fig. 15).
374 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

FIG. 8 FIG. 9
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste, w / c = 0. 5. A g e Z months. paste with 0. 5 % triethanolamine,
Several f o r m s of hydration products w / c = 0.5. A g e 1 hr. Hydration
a m o n g w h i c h one can distinguish products appear as plates, a m o r -
m a n y platelets and fibrous forms. phous films and short rods between
the unhydrated grains of c e m e n t
minerals.

FIG. 10 FIG. Ii
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste with 0. 5 % triethanolamine, paste with 0. 5 % triethanolamine,
w / c = 0.5. A g e 6 hr. M a i n hydra- w / c = 0.5. A g e I day. Various
tion products are plates and single f o r m s of hydration products dis-
rods or needle-like particles. playing a s o m e w h a t dense struc-
ture, m a i n l y of platelets.
Vol. I , No. 4 375
MICROSTRUCTURE, CEMENT PASTE, ADMIXTURES

FIG. 12 FIG. 1 3
Microstructure of synthetic cement Microstructure of synthetic cement
paste with 0 . 5 % triethanolamine, paste with 0 . 5 % triethanolamine,
w / c = 0.5. Age 3 days. Semi- w / c = 0. 5. Age 7 days. Dominant
a m o r p h o u s fibrous particles of C S H f o r m s are fibres, large radiating
in s o m e cases a s s u m e a plate-like aggregates and plates which s o m e -
form. times display fibrous fracture.

" I Fm

FIG. 14 FIG. 1 5
Microstructure of synthetic c e m e n t Microstructure of synthetic cement
paste with 0 . 5 % triethanolarnine, paste with 0. 5% triethanolamine,
w / c = 0.5. Age 14 days. Irregular w / c = 0.5. A g e 1 month. B e t w e e n
forms of hydration products display the various forms of hydration prod-
an unoriented structure. ucts are p s e u d o m o r p h s of cement
minerals, fibres and plates. S o m e
plates display three-directional
fibrous fracture.
376 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

At Z and also at 3 m o n t h s the microstructure w a s very dense, with

the m a i n forms of the hydration products being plates and fibres (Fig. 16).
In s o m e instances small rounded platelets appeared to be growing on the
larger plates.

X - r a y diffraction patterns of the synthetic cement paste with

triethanolamine w e r e taken after 4 hours, 1 day, 3 days and 90 days hydra-
tion time, and the results are presented in Figure 17. It is very significant
that peaks of calcium hydroxide appeared after 3 days of hydration and that
after this time, there was very little change.

3. Hydration of synthetic cement paste with 0 . 5 % calcium li~nosuIphonate

The first hydration products at 5 m i n u t e s were a m o r p h o u s foils and

small rod-like ettringite-type particles between unhydrated grains of cement
minerals. These were the m a i n hydration products also during the next 6
hours of hydration (Fig. 18). In s o m e cases these rod-like particles ap-
peared as a sort of irregular plate.

At 1 day hydration the products appeared as unoriented platelets and

fibres located around the grains of the calcium silicates (Fig. 19). After 3
days of hydration, the spaces between the unhydrated grains of cement
minerals w e r e nearly filled by these platelets and fibres (Fig. 20).

At 7 days of hydration the microstructure had b e c o m e a closely

knit structure with m a n y different forms of hydration products. From this
period up to 14 days the m a i n hydration products w e r e fibrous particles
(Fig. 21).

At i, 2 and 3 m o n t h s the microstructure looked dense and un-

oriented. P s e u d o m o r p h s of cement minerals appeared to be cemented to-
gether by platy and fibrous forms of the hydration products. S o m e of these
platy forms had a striated cleavage and s o m e t i m e s a fibrous fracture as
well {Fig. Z2).

X - r a y diffraction patterns of the synthetic cement paste with calcium

lignosulphonate were obtained at 4 hours, i, 3 and 90 days of hydration. It
Vol. I , No. 4 377
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

FIG. 16 FIG. 1 8.
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste with 0. 5 % triethanolamine, paste with 0o 5 % calcium ligno-
w / c = 0. 5. A g e 3 months. Fibres sulphonate, w / c = 0. 5. A g e 6 hr.
and platelets forming a dense Rod-like particles of ettringite are
structure, the dominant f o r m of hydration
products.

,,, • ,z I , . I

I 90 day

~ 3 day

~ 1 day

.... 4 hr

I I I I I I I I ] I J [ ] I I l I ] I I I I I I I I I I I
60 56 52 48 44 40 36 32 28 24 20 16 12 8 4
2@

FIG. 17
X - r a y diffractograms at various times
of hydration of synthetic c e m e n t paste
with 0. 5 % triethanolamine, w / c = 0. 5.
(Gu/Ni, 45KV, 25mA. )
378 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

FIG. 19 FIG. 2O
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste with 0. 5 % calcium ligno- paste with 0. 5 % calcium ligno-
sulphonate, w / c -- 0. 5. A g e l day. sulphonate, w / c -- 0. 5. A g e 3 days.
Unoriented platelets and a fibrous Fibrous particles of hydration prod-
structure of hydration products. ucts fill spaces between grains of
c e m e n t minerals.

~i¸~ ~

FIG. 21 FIG. 22
Microstructure of synthetic c e m e n t Microstructure of synthetic c e m e n t
paste with 0. 5 % calcium ligno- paste with 0. 5°/o calcium ligno-
sulphonate, w / c = 0. 5. A g e 14 days. sulphonate, w / c = 0. 5. A g e i month.
Different f o r m s of hydration prod~ D e n s e microstructure with m a n y platy
ucts, m a i n l y of fibrous habit. f o r m s of hydration products.
Vol. I , No. 4 379
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

w a s observed that the m a j o r change occurred in the peaks representing

calcium hydroxide; this peak appeared after i day of hydration {Fig. 23)
instead of after 3 days as had been the case w h e n triethanolamine had been

pre sent.
o~
,~ o<
o.~
~x

I "'; ~ 90 day

~ 3 day

1 day

4 hr

I [ [ I 1 I I I 1 I I I I ] I [ I I 1 1 I ] J I I ] I I I
60 56 52 48 44 40 36 32 28 24 20 ]6 12 8 4
2@

FIG. 23
X - r a y diffractograms at various
times of hydration of synthetic
cement paste with 0.5% calcium
lignosulphonate, w/c = 0.5.
(Cu/Ni, 45KV, 25mA.)

Discussion

The products formed by this multicomponent system with no organic

admixture present, and the times at which these products formed, when it
was hydrated over a period of 3 months, were very similar to those formed
by the simpler system, CsS , C s A and gypsum, described in the preceding

paper of this series (3). Again the early product after a few minutes of
hydration was an a m o r p h o u s film, possibly corresponding in G / S ratio to
the original C s S. The irregular, fibrous material probably corresponded
to the lower C/S stage, and the plate-like forms to the later, higher C/S
product reported by others (6, 7). The failure to positively identify Ca(OH) e
suggests that the lime liberated in the early reaction, in very finely divided
form, is taken into the C S H lattice in s o m e m a n n e r (2, 3, 7). It is clear
380 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

f r o m these studies and the previous investigations (i-3) that both the C A H

and C S H hydrates can and do take on crystal habits very like those of well-

crystallized lime, and that all such crystallites have in the past been m i s -

takenly believed to be C a ( O H ) ~ . T h e free lime can occur m o r e readily, of

course, in suspensions than in pastes (5}. Other w o r k has indicated that

similarly oriented lattices of foils of C S H link readily to the three-dimen-

sional n e t w o r k of C a ( O H } ~ (14).

Significant a m o u n t s of the plate-like C S H products apparently do not

develop as early in this s y s t e m as in s o m e w h a t similar s y s t e m s with alite in

place of C s S (4). This m a y be due to the claimed higher activity of the alite

(5) or to the differences in conditions, materials or proportions.

A relative abundance of p s e u d o m o r p h s of original C ~ S particles in

later stages of hydration, and apparently forming an integral part of the

finalmicrostructure of the paste, w a s observed in this study. Such

pseudomorphs do not appear to be m e n t i o n e d by other researchers as a

m a j o r component. Their occurrence m i g h t be interpreted as indicating that

hydration does not occur as a through-solution process.

In this m u l t i c o m p o n e n t s y s t e m the cubic f o r m of C A H did not appear

as it does in a hydrating portland c e m e n t system. It has been observed (7)

that the presence of large a m o u n t s of C s S retards the formation of C s A H s ;

this m a y be the explanation. Chatterji and Jeffery (4) did not report the
cubic f o r m in their s y s t e m of alite, C s A , C4AF and g y p s u m , but did report

it in the s a m e s y s t e m with no g y p s u m present, with or without the presence

of alkali. It is concluded that in their s y s t e m s the g y p s u m has taken up so
large a proportion of the C s A hydrate in producing the sulpho-alurninates

that not enough C A H is left to produce significant or noticeable quantities of

the cubic C s A H s . T h e s y s t e m in the present study appears to support this.

T h e present study did not reveal the rather extensive variations in

m o r p h o l o g y and rates one m i g h t have expected f r o m the literature on
simpler systems. It is b.elieved that the low diffusion rates in such a low
w a t e r - c e m e n t ratio s y s t e m m a y have been a contributory factor. Also,
the various interactions reported m a y tend to d a m p e n out in a m u l t i c o m p o -
Vol. I , No. 4 381
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

nent system s u c h a s w a s u s e d in t h i s s t u d y . It s h o u l d b e r e c a l l e d that only

the predominant products were s t u d i e d in t h i s s e r i e s , and also that the

proportions of o r i g i n a l constituents of m i x t u r e s in t h i s s y s t e m , as well as

in t h e p r e v i o u s l y reported systems, were in t h e s a m e order as normally

f o u n d in p o r t l a n d cement.

There were definite differences between the pastes with the two

different organic admixtures, triethanolamine and calcium lignosulphonate,

in t h e i r rates of r e a c t i o n , a n d in t h e p r o d u c t s they formed, but no significant

difference c o u l d be d e t e c t e d in t h e f i n a l m o r p h o l o g y of t h e p a s t e s .

The pastes, with and without the admixtures, ultimately t a k e on a

close-packed microstructure; the filling-in process occurs in m u c h t h e

same w a y in b o t h p a s t e s although the timing varies. A characteristic of

this dense structure is the cleaved, tabular mass made u p of t h e c o m b i n e d

hydration products, CH, CSH and CAH and pseudomorphs of o r i g i n a l constit-

uents. Further interpretation of t h e a p p a r e n t l y pseudohexagonal plates that

form the tabular masses is provided in a s e p a r a t e publication (15} w h i c h i s

based on t h e p r e s e n t and previous studies (1-3).

Conclusions

1. T h e effect of e a c h of the admixtures, triethanolamine and

calcium lignosulphonate, on the hydration p r o c e s s e s of the synthetic c e m e n t

w a s very pronounced, but not as definite as the effects w h i c h w e r e apparent

during the hydration of the m o n o m i n e r a l pastes. This w a s probably due to

the different action of each a d m i x t u r e on each of the m i n e r a l c o m p o n e n t s as

well as to the influence of one m i n e r a l on the other.

2. T h e hydration p r o c e s s e s with no a d m i x t u r e s present a p p e a r e d

to be very similar to those occurring with triethanolamine and calcium

lignosulphonate pre sent.

3. With c a l c i u m lignosulphonate it w a s noted that during the entire

time of hydration there w a s considerably less hydration of the c e m e n t

m i n e r a l s than w h e n either no a d m i x t u r e or triethanolamine had been used.

T h e s e hydration products, h o w e v e r , displayed better crystal habit. With

382 Vol. I , No. 4
MICROSTRUCTURE, CEMENTPASTE, ADMIXTURES

triethanolamine m o r e hydration products appeared, but at a lower level of

c rystallinity.

X - r a y diffraction examinations s h o w e d that the presence of calcium

lignosulphonate produced peaks of crystalline C H at 1 day of hydration,

c o m p a r e d with 3 days for the triethanolamine paste. P e a k s of C H w e r e

smaller with triethanolamine than those w h i c h occurred with calcium

lignosulphonate (Figs. 17 and Z3).

4. The m o r p h o l o g y of the hydration products, and the sequence in

w h i c h they f o r m e d during the hydration process, did not differ significantly

f r o m the products of the simpler systems, but the times of their appearance
w e r e dependent upon the admixture present.

5. A l m o s t all changes occurred within the first 7 days of hydra-

tion, and during this time differences in microstructure of synthetic c e m e n t

paste as c o m p a r e d with the m o n o m i n e r a l pastes w e r e m o s t significant.

Acknowledgements

We acknowledge gratefully the invaluable contribution of M r . E.

Q u i n n in preparing replicas f r o m the s a m p l e s for electron m i c r o s c o p i c
examination. T o Portland C e m e n t Association for supplying the pure

constituents of c e m e n t w e are also m o s t grateful.

This paper is a contribution of the Division of Building Research,

National R e s e a r c h Council of C a n a d a and is published with the approval of

the Director of the Division.

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