CEMENT and CONCRETERESEARCH. Vol. I , pp. 143-158, 1971. Pergamon Press, Inc.

Printed in the United States.

M O R P H O L O G Y AND M I C R O S T R U C T U R E O F H Y D R A T I N G
P O R T L A N D C E M E N T AND I T S C O N S T I T U E N T S
I. C H A N G E S IN H Y D R A T I O N O F T R I C A L C I U M A L U M I N A T E
A L O N E AND IN T H E P R E S E N C E O F T R I E T H A N O L A M I N E
OR CALCIUM LIGNOSULPHONATE

T.D. Ciach and E,G. S w e n s o n

Division of Building Research, National Research Council of C a n a d a
Ottawa 7, Ontario, Canada

(Communicated by G. M. Idorn)

ABSTRACT
Morphological changes which occur during the hydration of C s A *
paste were observed by electron m i c r o s c o p y f r o m the age of 5
minutes to 3 months. X - r a y analyses were used to identify
phases. The effects of the admixtures, triethanolsxnine and cal-
c i u m lignosulphonate, were investigated with and without gypsum.
The dosage of admixture w a s 0.5%; the water to C s A ratio was
i. 0. The results showed clearly the morphological changes that
took place as hydration proceeded, and showed the specific
influences of each of the two admixtures.

SOh~M AIRE
Les changements morphologiques qui prennent place au cours de
l'hydratation d'une pgte de C s A ont ~t~ observes par microscopie
~lectronique ~ partir de l'~ge de 5 minutes jusqu'~ l'~ge de 3
tools. Les analyses aux rayons-X ont servi ~ identifier les
phases. L'effet, avec et sans gypse, des adjuvants tri~thanola-
m i n e et lignosulfonate de calcium a ~t~ exarnin~. Le dosage de
l'adjuvant ~tait de 0.5% et la fraction eau: C s A ~tait de I. 0. Les
r@sultats ont clairement d~montr~ les changements morpholo-
giques qui ont pris place au cours de l'hydratation et ont aussi
m o n t r ~ l'influence particuli~re de chacun des deux adjuvants.

* S t a n d a r d c e m e n t n o m e n c l a t u r e i s u s e d ; C s S = 3 C a O . SiO~; C2S = 2 C a O . SiO~;

C s A = 3CaO. AL$Os; C 4 A F = 4CaO. A L s O s . F e m O s ; w / c = water:cement ratio
by weight.

143
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MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

This is the first of a series of papers reporting the results of long-term

studies on the relationship between morphological changes in hydrating
portland cement and its microstructure in the hardened state. The ultimate
a i m is to identify particular morphological changes and the corresponding
changes in microstructure with changes in the physical and mechanical
properties.

The m e t h o d consisted of taking electron-micrographs on a sequential

basis, being careful to select representative and characteristic structures
and formations. X - r a y was employed to identify phases w h e r e initial doubt
existed. W h e r e changes occur, the corresponding series of electron-micro-
graphs are shown. W h e r e no change occurs, one or two only m a y be
shown. Although the formations given are representative, they constitute
a qualitative picture.

Although m a n y micrographs showing m o r p h o l o g y changes in hydrating

cement compounds, with and without admixtures, have been published,
m o s t have s o m e w h a t limited value in the practical sense for several rea-
sons: hydration has usually been carried out in excess water; clear-cut
crystalline formations w e r e often selected in preference to indefinite,
a m o r p h o u s m a s s e s which m a y have been predominant; and hydration has
often been largely completed w h e n the electron micrographs w e r e taken,
thus earlier changes w e r e missed. This systematic study is expected to
provide a better understanding of the practical consequences of the presence
of an admixture in concrete, and the methods followed are expected to f o r m
a better basis for studies of n e w systems.

The study of C s A described in this paper is being followed by similar

studies of the other pure c o m p o u n d s of portland cement, combinations of
these, and portland c e m e n t itself. These first several papers will consist
mainly of observations of morphological changes. Other studies attempt
to show a correlation between microstructure and mechanical properties (i).

Intr oduction

Studies of the hydration process of C 3 A indicate that the presence of

small amounts of certain organic chemicals affects the rate of reactions,
Vol. I , No. 2 145
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

but a p p a r e n t l y n o t t h e b a s i c n a t u r e of t h e h y d r a t i o n p r o d u c t s ( 2 - 1 0 ) . Such
agents may, however, p r o d u c e m o d i f i c a t i o n s of t h e crysta.1 h a b i t s of t h e s e
h y d r a t e s (2, 3, 7).

S o m e o r g a n i c c o m p o u n d s a p p e a r t o b l o c k t h e c o n v e r s i o n of C ~ H s
a n d C 4 A H ~ to C s A H s w h i l e o t h e r s f a c i l i t a t e t h e r e a c t i o n (6), Ligno-
sulphonates, for example, a r e s h o w n to i n h i b i t t h e c h a n g e f r o m t h e h e x a g o n a l
hydroaluminates to C 3A H s u n d e r n o r m a l c o n d i t i o n s (2). A d d i t i o n of g y p s u m
a nd l i m e d o e s n o t a p p a r e n t l y a l t e r t h e c o u r s e of t h e r e a c t i o n ( 2 , 4 , 5, 9).
D a u g h e r t y and K o w a l e w s k i r e v i e w , in t h e i r 1968 T o k y o S y m p o s i u m p a p e r
(6), t h e m a j o r researches in t h i s a r e a .

A n y c h a n g e s in t h e m o r p h o l o g y of h y d r a t i o n p r o d u c t s of p o r t l a n d
cement compounds, of w h i c h C s A i s o n e , m u s t n e c e s s a r i l y affect both the
n a t u r e of t h e p l a s t i c s t a t e and t h e m i c r o s t r u c t u r e and p r o p e r t i e s of t h e
h a r d e n e d s t a t e of c e m e n t p a s t e .

T h e p r e s e n t p a p e r is i n t e n d e d p r i m a r i l y to d e m o n s t r a t e t h e v a l u e of
a systematic sequential study using the electron microscope for direct
o b s e r v a t i o n of t h e m o r p h o l o g i c a l c h a n g e s . It is l i m i t e d to t w o c o m m e r c i a l l y
used concrete admixtures, triethanolamine and c a l c i u m l i g n o s u l p h o n a t e ,
in t h e a b s e n c e a nd in t h e p r e s e n c e of g y p s u m . In c o n c r e t e t e c h n o l o g y ,
triethanolamine is u s e d in f o r m u l a t i o n s to r e d u c e e x c e s s i v e r e t a r d a t i o n of
other admixtures agents, and l i g n o s u l p h o n a t e is one of s e v e r a l b a s i c c o m p o -
n e n t s of s e t - r e t a r d e r s and w a t e r - r e d u c e r s . In t h i s f i r s t s t u d y , t he h y d r a -
t i o n of C3A w a s c a r r i e d out in t h e a b s e n c e of a d d e d l i m e .

Materials and P r o c e d u r e s
The tricalcium a l u m i n a t e u s e d in t h e e x p e r i m e n t s w a s m a d e in t h e
Materials Section Laboratory of t h e D i v i s i o n of B u i l d i n g R e s e a r c h (2): it
c o n t a i n e d 2 p e r c e n t f r e e l i m e and h a s a s p e c i f i c s u r f a c e a r e a of a b o u t
3000 cm2/gm Blaine.

T h e C3A p a s t e s w e r e p r e p a r e d on t h e b a s i s of w a t e r to C3A b y w e i g h t
= 1.0, and a d m i x t u r e d o s a g e s of 0. 5 p e r c e n t b y w e i g h t of d r y CsA . The
r a t i o of C s A t o g y p s u m w a s Z:I. The gypsum was prepared from large,
clear, n a t u r a l c r y s t a l s w h i c h w e r e g r o u n d t o p a s s 200 DIN. A s in t h e c a s e
146 Vol. l , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

of portland cement, g y p s u m in these studies w a s considered as an additive,

and is to be distinguished f r o m the organic chemical admixtures added.

T h e triethanolamine used w a s a chemically pure reagent grade. The

calcium lignosulphonate w a s a commercially prepared product chemically
treated to destroy excess sugars. Total sugars averaged 0.08 per cent
and total reducing bodies about 4 per cent.

T h e paste consisted of 5 g r a m s CaA, 5 g r a m s water and 0.0Z5 g r a m s

admixture, the latter always p r e m i x e d with the water. T h e choice of dosage
of admixture w a s m a d e on the basis of probable availability to C a A in the
cement paste, rather than on the actual proportion of admixture to C a A in

the paste. T h e paste w a s kept at 23 + I°C in tightly stoppered plastic tubes

which w e r e rotated continuously to prevent segregation.

At intervals of 5 minutes, 1 and 4hours, I, 2, 3 and 7 days, and I,

Z and 3 months, samples are taken out and tested. Hydration was stopped
by treating with acetone at about -18°C, then drying the frozen samples in
a vacuum.

Single stage replicas of the broken surfaces of the C a A paste w e r e

m a d e using the platinum-carbon technique (11 ).

Electron microscopic examinations w e r e done at different times

during hydration f r o m 5 minutes to 3 months, and at significant times X - r a y
examinations w e r e made.

T h e electron micrographs shown are those that depict the general

morphology. Exceptional forms and structures are not taken into account.

Observations and Discussion

1. Hydration of C ~ A in A b s e n c e of G y p s u m
(a) N o Admixture Present

T h e first hydration products w e r e hexagonal phases of C A H i n the

f o r m of semicrystalline foils and plates (Fig. I). A m o n g these it w a s
possible to distinguish by X - r a y examination C s A H o which w a s probably
the m a i n f o r m present.
Vol. I , No. 2 147
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

After 1 hour's hydration the cubic hydrogarnet phase, which has a

crystal size of about 1 micron, m a d e its appearance a m o n g the hexagonal
phases of C A H , and after one day's hydration it was the dominant phase
(Figs. 2 and 3). The crystals of hydrogarnet w e r e twinned m a n y times and
displayed a very compact structure. Starting at about 3 days these hydro-
garnet crystals b e c a m e partly covered by s o m e small particles which
slowly transferred to the hexagonal plates (Fig. 4). X - r a y examination
showed these hexagonal or pseudohexagonal phases to be AI(OH)s and
Ca(OH) 2, and also revealed the presence of very small quantities of the
hexagonal C A H , mainly C 2 A H 8 (Table I). This pseudohexagonal phase of
AI(OH)s and the hexagonal phase of Ca(OH)2 w e r e formed probably by the

d e c o m p o s i t i o n of t h e c u b i c p h a s e of C s A H s u n d e r t h e s e c o n d i t i o n s , but s o m e
m a y h a v e r e s u l t e d d i r e c t l y as h y d r a t i o n p r o d u c t s of C3A.

After 1 month's hydration there appeared more hexagonal-like plates

of A I ( O H ) s and C a ( O H ) e w h i c h c o v e r e d t h e l a r g e h y d r o g a r n e t crystals
(Fig. 5). A f t e r 3 m o n t h s t h e s t a b l e p r o d u c t s a p p e a r e d to be t h e c u b i c
p h a s e of C s A H s and t h e h e x a g o n a l o r p s e u d o h e x a g o n a l p h a s e s of A l ( O H ) s
and Ca(OH)~ (Table I).

(b) With T r i e t h a n o l a m i n e

For the first few days, the hydration process of C s A p a s t e w i t h

triethanolamine was s i m i l a r to the p a s t e without a d m i x t u r e s , but a f t e r 7
d a y s of h y d r a t i o n t h e h y d r o g a r n e t c r y s t a l s h a d t h e c u b e h a b i t ( F i g . 6).

A f t e r 7 d a y s t h e s i z e of t h e s e c u b e s w a s a b o u t 2 m i c r o n s and t h e y
occurred as l o o s e a g g r e g a t i o n s of i n d i v i d u a l s i n g l e c r y s t a l s , in c o n t r a s t
w i t h t h o s e f o r m e d w i t h o u t a d m i x t u r e w h i c h w e r e t w i n n e d and s h o w e d c l o s e
structure. S o m e of t h e s e c r y s t a l s w e r e c o v e r e d b y a m a t e r i a l appearing
l i k e h e x a g o n a l p l a t e s of c a l c i u m h y d r o x i d e and a l u m i n u m h y d r o x i d e . After
a b o u t 1 m o n t h of h y d r a t i o n t h e c u b e f o r m w a s t r a n s f o r m e d to t h e r i c h c u b i c
form.

The very fast transformation t o t h e c u b i c f o r m ( b e t w e e n t h e a g e s of 4

h o u r s and 1 d a y ) , a p p e a r s t o h a v e b e e n r e s p o n s i b l e f o r d e l a y i n g t h e s e t t i n g of t h e
C3A p a s t e w i t h t r i e t h a n o l a m i n e in t h e a b s e n c e o f g y p s u m . A c t u a l l y t h e p a s t e did
148 Vol. I , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

TABLE I

Results of Hydration of Tricalcium Aluminate Paste with

Admixtures as Determined by X-ray Examination

Storage C s A Paste + CsA Paste +

Cs A Paste
Time T riethanolamine Ca Lignosulphonate

C3A CaA CsA

4 hours C~AH a C2AH~ C eA H s
C a AH6 C~AH8 C 4 AHis

CaA CsA CsA

C s AH8 C sAH8 C2AHg
3 days
C2AH s C2AH 8 C 4AH~ g

CH, AH CH, A H CH

C s AH6 CaAHa
CsAH6
CH CH
3 months CH, A H
AH AH
CsA. C a C O s. 1 2 H ~ O
C3A CsA

FIG. 1 FIG. Z

C s A paste. Age 5 rain. Small C a A paste. Age lhr. Large, loosely

particles of wrinkled foils and wrinkled plates of hexagonal C A H and
plates of hydration products. s m a l l cubic h y d r o g a r n e t c r y s t a l s .
Vol. I, No. 2 149
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

FIG. 3 FIG. 4
C a A paste. Age i day. The rich C s A paste. Age 3 days. Twinning
cubic habits of hydrogarnet crystals. hydrogarnet crystals covered by very
small particles of other hydration
products.

FIG. 5
C s A paste. Age 1 month. Large
cubic crystals of hydrogarnet
often covered by precipitations of
hexagonal form.
FIG. 6
C a A paste with triethanolamine. Age
7 days. Large hydrogarnet crystals
o£ cube habit with some hexagonal-
like particle s.
150 Vol. l , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

FIG. 7 FIG. 8
C ~ A paste with calcium lignosulphonate. Age 4hrs. The
large aggregates of very thin plates of hexagonal C A H . The
clustering of their edges can be likened to bundled ribbons.

n o t b e g i n to h a r d e n s i g n i f i c a n t l y u n t i l a f t e r a b o u t 2 m o n t h s , at w h i c h t i m e it w a s
observed that the twinning, rich cubic form ofhydrogarnet, as w e l l as h e x a g o n a l
plates ofCH andAH, appeared. T h u s , w i t h w a t e r o n l y and w i t h t r i e t h a n o l a m i n e ,
t h e f i r st h y d r a t i o n p r o d u c t s of C s A p a s t e w i t h o u t g y p s u m w e r e m e t a s t a b l e
p h a s e s of h e x a g o n a l CAH, w h i c h w e r e t h e n v e r y q u i c k l y t r a n s f o r m e d to
t h e c u b i c h y d r o g a r n e t p h a s e w h i c h is m o r e s t a b l e at r o o m t e m p e r a t u r e .
The latter, however, a p p e a r e d t h e n to be p a r t l y t r a n s f o r m e d under these
t e s t c o n d i t i o n s t o t h e h e x a g o n a l p h a s e s of A I ( O H ) s and C a ( O H ) 2 .

(c) W ith L i g n o s u l p h o n a t e
T h e f i r s t h y d r a t i o n p r o d u c t s of C s A w i t h 0 . 5 p e r c e n t c a l c i u m
l i g n o s u l p h o n a t e a p p e a r e d as w r i n k l e d f o i l s or p l a t e s of h e x a g o n a l p h a s e s
of CAH s i m i l a r t o t h e C s A p a s t e w i t h o u t a d m i x t u r e s (Fig. 1).

After 4hours of h y d r a t i o n t h e r e a p p e a r e d l a r g e a g g r e g a t e s (of a b o u t

11 m i c r o n s ) of v e r y t h i n p l a t e s ; a f t e r 2 d a y s of h y d r a t i o n t h e s e d i s p l a y e d
an e d g e - f r a c t u r e surface (Figs. 7 and 8). The X-ray examination showed
t h a t b e t w e e n t h e s e h e x a g o n a l f o r m s of CAH one c a n d i s t i n g u i s h o n l y C2A H s
and C 4 A H l s . T h e e d g e s of t h e s e plates were cluster-like bundled plates
( F i g . 9). T h e h e x a g o n a l p h a s e of CAH r e m a i n e d stable for about 7 days.
Vol. I , No. 2 151
MICROSTRUCTURE, TRICALCIUM-ALUMINATE,HYDRATION

FIG. 9 FIG. 10
CsA paste with calcium ligno- C s A paste with calcium ligno-
sulphonate. Age 2 days. The sulphonate. Age 7 days. The
c l u s t e r s of e d g e s of t h i n h e x - large hydrogarnet crystals of
agonal plates are displayed in the cubic form a m o n g aggre-
the interlocking structure. gates of hexagonal phases.

After 7 days atransformationtoa close-packed tabular structure

o c c u r r e d , and a l s o t h e c u b i c f o r m of h y d r o g a r n e t p h a s e w a s o b s e r v e d
(Fig. 10). T h e c a l c i u m l i g n o s u l p h o n a t e is t h u s s h o w n to r e t a r d t h e t r a n s -
f o r m a t i o n of t h e h e x a g o n a l p h a s e of t h e c a l c i u m a l u m i n a t e h y d r a t e to t h e
c u b i c p h a s e of C s A H s ; t h i s p h a s e r e m a i n e d s t a b l e f o r t h e n e x t s e v e r a l d a y s .

A f t e r h y d r a t i o n f o r 1 m o n t h , and up to 3 m o n t h s , t h e m a j o r h y d r a t i o n
product was the r i c h cubic f o r m o f h y d r o g a r n e t . This form was partly
t r a n s f o r m e d to c a l c i u m h y d r o x i d e and a l u m i n u m h y d r o x i d e , and t h e s e
products covered the hydrogarnet crystals.

2. H y d r a t i o n of C s A in P r e s e n c e of G y p s u m

(a) No A d m i x t u r e P r e s e n t
T h e f i r s t h y d r a t i o n p r o d u c t s of C s A p a s t e w i t h g y p s u m and no o t h e r
a d m i x t u r e a p p e a r e d a f t e r a f e w m i n u t e s of h y d r a t i o n ; t h e y d i s p l a y e d p a r t l y
rolled, s e m i c r y s t a l l i n e f o i l s and r o d s w h i c h f o r m e d f l o w e r - l i k e a g g r e g a t e s
on t h e s u r f a c e s of t h e g y p s u m c r y s t a l s ( F i g . 11).
 152 Vol. l , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

FIG. 11 FIG. Il

C 3 A paste with g y p s u m . A g e 5 C s A paste with g y p s u m . A g e

rain. R o u n d e d plates and rods of i day. Unoriented rods of
first hydration products on sur- ettringite and a large crystal
face grains of C 3 A and g y p s u m . of g y p s u m .

After 1 day's hydration this flower-like f o r m disappeared and the

m a i n hydration products w e r e seen to be short, rod-like particles of the
high sulphate f o r m of C A H (ettringite); large crystals of g y p s u m w e r e

also present (Fig. 12). X - r a y diffraction patterns s h o w that there w a s

a large proportion of high sulphate C A H , s o m e a m o u n t of the low sulphate

CAH, gypsum and unhydrated C s A (Fig. 13, curve I).

I I I I I I I I I I [ l I ! I I [ I

L FIG. 13
X - r a y diffraction pattern
of C a A paste with g y p s u m
after different times of
hydration. E = high
sulpho C A H , L = low
sulpho C A H , C u r v e I = l
day, and C u r v e II = 8 days.
I I I I I I i I I i I ]~, I ], I [ I i
40 38 36 34 32 30 28 26 24 22 20 18 16 14 12 I0 8 6 4 2
2@
Vol. I , No. 2 153
MICROSTRUCTURE, TRICLACIUM-ALUMINATE, HYDRATION

FIG. 1 4 FIG. 15

C3A paste with gypsum. Age 8 C 3 A paste with gypsum. A g e I

days. Plates of the low sulphate month. Unoriented plates of the
f o r m of C A H . low sulphoalurninate of C A H .

At 3 days of hydration the paste showed signs of setting and the

hydration products appeared as a loose m a s s of u n k n o w n m o r p h o l o g y partly
covered by rod-like particles of ettringite of the "coin-in-coin" type.

After 8 days of hydration the paste had set, and the microstructure
appeared as a loose structure of unoriented, thin hexagonal plates (Fig.
14). X - r a y diffraction patterns showed that these plates, which comprised
the dominant form, w e r e low sulphate C A H crystals of apparently different
types. Some ettringite w a s also present (Fig. 13, curve If).

For the first 3 months, the microstructure of the C 3 A paste with

g y p s u m w a s seen to be plates and a partly striated structure, which had
been f o r m e d f r o m the plates of the low-sulphate products, and also rods
of ettringite (Fig. 15).

(b) With Triethanolamine

The hydration processes that occurred in t h e p a s t e of C3A with
gypsum and triethanolamine were very similar to those that took place in
the paste of C3A with gypsum only. Thus, in p a s t e s of C 3 A w i t h g y p s u m
without admixture, and with both gypsum and triethanolamine, the hydration
154 Vol. I , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

FIG. 16 FIG. 17
C3A p a s t e w i t h g y p s u m and c a l - C 3 A p a s t e w i t h g y p s u m and c a l -
c i u m l i g n o s u l p h o n a t e . A ge 1 day. cium lignosulphonate. Age 3
B e t w e e n t h e s m a l l r o d s of e t t r i n g - days. Small, rod-like particles
ite a r e l a r g e c r y s t a l s of s e c o n - a r e s o m e t i m e s f o r m e d in l ong
d a r y g y p s u m of v e r y good h a b i t . fibres.

p r o d u c t at e a r l y s t a g e s of h y d r a t i o n w a s t h e h i g h - s u l p h a t e CAH w h i c h
a p p e a r e d as r o d - l i k e e t t r i n g i t e - t y p e p a r t i c l e s . It w a s t h e d o m i n a n t p h a s e
d u r i n g t h e f i r s t 3 d a y s of h y d r a t i o n . At t h i s t i m e t h e p a s t e s s h o w e d s i g n s
of s e t t i n g , and p l a t e - l i k e p a r t i c l e s of l o w - s u l p h a t e CAH a p p e a r e d . The
pastes had set after 7 days, at w h i c h t i m e t h e m a j o r h y d r a t i o n p r o d u c t s
w e r e h e x a g o n a l p h a s e s of l o w - s u l p h a t e CAH.

(c) With L i g n o s u l p h o n a t e
Q u i t e d i f f e r e n t r e s u l t s w e r e o b t a i n e d f o r t h e p a s t e of C s A w i t h
g y p s u m and c a l c i u m l i g n o s u l p h o n a t e . The first hydration products
a p p e a r e d a f t e r a f e w m i n u t e s as s m a l l r o d - l i k e p a r t i c l e s on t h e c r y s t a l
s u r f a c e s of t h e g y p s u m . Up t o 1 d a y ' s h y d r a t i o n t h e r e a p p e a r e d l a r g e r
crystals of v e r y good h a b i t ( F i g . 16). X-ray diffraction showed that these
c r y s t a l s w e r e d i f f e r e n t f o r m s of t h e e t t r i n g i t e t y p e , i . e . , the high-sulphate
CAH; t h i s w a s t h e m a i n h y d r a t i o n p r o d u c t up to 14 d a y s of h y d r a t i o n ( F i g .
17 , F i g . 18, c~trves III and IV).

A f t e r 14 d a y s t h e p a s t e s h o w e d s i g n s of s e t t i n g , and thin, u n o r i e n t e d
Vol. I , No. 2 155
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

I I r r r l I { I I I { { I ~ I r

FIG. 18
X-ray diffraction pat-
t e r n of G3A p a s t e witli
g y p s u m and c a l c i u m
lignosulphonate after
d i f f e r e n t t i m e s of h y -
dration. E : high sulpha
C AH, L = l o w s u l p h o
C AH, C u r v e I l l = 8 d a y s
a nd C u r v e IV = 14 d a y s .
I I I I I I I I [ I I I I E
40 38 36 34 32 30 28 26 24 22 20 18 16 14 12 I0 8 6 4 2
28

hexagonal plates of low-sulphate C A H w e r e observed as well (Figs. 19 and

20). During the next period up to 3 months, both forms of calcium sulpho-
aluminate w e r e observed in the microstructure; the paste was only partly
set during this time.

3. General Observations
The initial presence of a c o m p a r a t i v e l y l a r g e a m o u n t of l i m e as in
the samples s t u d i e d b y S e l i g m a n n and G r e e n i n g (9) w o u l d u n d o u b t e d l y h a v e
s o m e d i f f e r e n t e f f e c t s on t h e r a t e s of c h a n g e s f o u n d in t h e p r e s e n t e x p e r i -
m e n t s w h e r e o n l y a s m a l l a m o u n t of l i m e w a s i n i t i a l l y p r e s e n t . Since
t h e s e i n v e s t i g a t i o n s w e r e i n t e n d e d to develop a p r o c e d u r e and t e c h n i q u e
t h a t w o u l d e n a b l e one to f o l l o w m o r p h o l o g i c a l changes clearly, it w a s

considered preferable to s t a r t with the s i m p l e s t s y s t e m s . Furthermore,

the initial presence of a l a r g e a m o u n t of l i m e , with its r e l a t i v e l y high
d e g r e e of c r y s t a l l i n i t y , is not c o m p a r a b l e to t h e n o r m a l g r a d u a l f o r m a t i o n
of e x t r e m e l y f i n e and a c t i v e l i m e d u r i n g t h e h y d r a t i o n of t h e s i l i c a t e p h a s e s
in p o r t l a n d c e m e n t .

The large initial acceleration of C s A h y d r a t i o n o b s e r v e d b y S e l i g m a n n

and G r e e n i n g m a y h a v e b e e n c a u s e d , a c c o r d i n g to t h e i r own s p e c u l a t i o n s ,
b y t h e i n h i b i t i o n of l i m e r e l e a s e (9). T h i s e f f e c t w a s a l s o o b s e r v e d in t h e
present experiments.

A l t h o u g h no a t t e m p t w a s m a d e to d e t e r m i n e and r e l a t e t h e t i m e w h e n
 156 Vol. I , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

x ' i / "<
/ /" /

#
,0
¥ !

~, I~m

FIG. 19 FIG. 20
CsA paste with gypsum and cal-
cium lignosulphonate. A g e 14 d a y s . C s A paste with g y p s u m and calcium
T h e s h o r t r o d s of e t t r i n g i t e a r e lignosulphonate. Age 3 months.
formed in large aggregations Grain of hydrated C s A with very
between some small rounded plates clear spherical structure of hydration
of t h e l o w s u l p h a t e f o r m of C A H . products.

the pastes u s e d in t h e s e studies set, one observation was of interest. The

triethanolamine in t h e a b s e n c e of g y p s u m appeared to delay stiffening

until the rich cubic form of t h e h y d r o g a r n e t appeared. The hydrogarnet

crystals have habits of d i f f e r e n t forms of t h e cubic system:

as icositetrahedra and rhombicdodeahedra (Fig. 3). It w a s

observed bySersale (3) t h a t t h e s e forms occur at a n e a r l y s t a g e in t h e

transormation of t h e h y d r a t i o n product of C s A t o t h e c u b i c p h a s e of C 3 A H e,
and that the last form is, in f a c t , the cube.

It is recognized that the comparatively small dosages of the organic

chemical used m a y have different effects on rates of change than would
larger dosages. These are, of course, subjects for separate study.

Considered in the light of previously published researches, these

experiments m a d e it clear that acceleration and retardation in rates of
reaction having to do with morphological changes, are not necessarily
related to acceleration and retardation pertaining to setting and hardening.
Vol. I , No. 2 157
MICROSTRUCTURE, TRICALCIUM-ALUMINATE, HYDRATION

It is the latter criterion that has established the accepted classification of

admixtures used in concrete.

Summary
Systematic sequential observations with the electron m i c r o s c o p e w e r e

m a d e of the morphological changes occurring during the hydration of C 3 A

in the absence and in the presence of selected admixtures. X - r a y analyses

w e r e m a d e to identify s o m e phases.

T h e effects of small dosages of the organic chemicals, triethanol-

a m i n e and calcium lignosulphonate, w e r e studied in the absence and in the

presence of gypsum.

T h e m e t h o d used showec~ clearly the m a n n e r in which hydration

proceeded and the accelerating or retarding effects of the presence of each

admixture. C h a n g e s in crystal habit w e r e observed.

Similar procedures are being used to study other c o m p o u n d s and

mixtures of c o m p o u n d s of portland c e m e n t with the ultimate a i m of deter-
mining which factors of microstructure influence mechanical properties,
dimensional change and durability of portland c e m e n t paste.

Acknowledgements

W e acknowledge gratefully the invaluable contribution of M r . E. Quinn

in preparing replicas f r o m the samples for electron microscopic 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 w a s presented to the Annual Meeting of the H i g h w a y R e s e a r c h

B o a r d in January, 1969, and is n o w a contribution of the Division of Building
Research, National R e s e a r c h Council of Canada, and is published with the
approval of the Director of the Division.

References

I. T.D. Ciach, J.E. Gillott, E.G. S w e n s o n , and P . J . S e r e d a , J. C e m e n t

and C o n c r . R e s . , 1 (1970).
158 Vol. I , No. 2
MICROSTRUCTURE, TRICALCIUM-ALUMINATE,HYDRATION

~o J.F. Young, M a g . Concr. Res. i__44,137 (1962).

3. R. Sersale, Ricerca scient. 2_~7,777 (1957).

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(1966).

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