CEMENT and CONCRETE RESEARCH. Vol. 18, pp, 911-922, 1988. Printed in the USA.

0008-8846/88. $3.00+00. Copyright (c) 1988 Pergamon Press plc.

KINETICS OF HYDRATION OF TRICALCIUM ALUMINATE

IN THE PRESENCE OF GYPSUM

James Pommersheim
Jemei Chang
Bucknell University
Lewisburg, PA 17837

(Communicated by D.M. Roy)

(Received March 31; in f i n a l form Sept. 9, 1988)

ABSTRACT

Based on a conceptual model for the stages of hydration of tricalcium alumi-

nate in the presence of gypsum, a mathematical model was developed for the
kinetics of hydration. The model was solved, i l l u s t r a t e d and compared to
experimental heat release data. Analytical equations were presented for the
f i r s t two stages, while the last stages of hydration reduced to a previously
developed model for the hydration of tricalcium aluminate in the absence of
gypsum. Results suggested that pore diffusion through a thickening
e t t r i n g i t e barrier layer controlled the f i r s t stage of hydration, while pore
diffusion through a thinning e t t r i n g i t e barrier layer controlled the second
stage. After the e t t r i n g i t e layer disappeared, the reaction of the remain-
ing tricalcium aluminlte proceeded more rapidly, but by a similar mechanism,
than in the absence og Rulfate containing species.

Introduction

The tricalcium aluminate (C3A)* in Portland cement is of great importance

owing to i t s high r e a c t i v i t y with water during the early stages of hydration.
It is common practice to add from 1 to 10% gypsum to suppress this reaction,
thereby preventing too rapid setting and heat release. An understanding of the
mechanism of the reactions and other phenomena occurring is desirable. Even
more useful would be a quantitative description of the process which would
enable design predictions of cement performance. However t h i s must await better
models for the rate at which the components of Portland cement hydrate, both as
single components and mixtures. Towards this end a number of quantitative kine-
t i c studies have been made examining the hydration of the constituents of
Portland cement. These include C3S [1,2,3], C2S [4,5], C3S/C2S mixtures

*Conventional cement industry nomenclature is used here:

C = CaO, A = A£203, H = H.,O, S = Si02, ~ = SO3.

911
912 Vol. 18, No. 6
J. Pommersheim and J. Chang

[ 6 , 7 , 8 ] , C3A [ 9 ] , and calcium s u l f a t e hemihydrate [ 1 0 ] . However l i t t l e work has

been done to form a q u a n t i t a t i v e basis f o r the behavior of mixtures of cement
constituents. This paper is r e s t r i c t e d to a q u a n t i t a t i v e d e s c r i p t i o n of
the h y d r a t i o n of C3A in the presence of gypsum. Hopefully studies such as t h i s
can help form a basis f o r Future modeling of Portland cement h y d r a t i o n .

Conceptual Model

As depicted in Figure i , the hydration of t r i c a l c i u m aluminate in the p r e -

sence of gypsum is conceived to occur in three d i s t i n c t stages. In each stage
a d d i t i o n a l consumption of C3A occurs but by a d i f f e r e n t c o n t r o l l i n g mechanism.
Figure 2 presents a general heat release rate curve (dQ/dt vs. t ) in which the
t h r e e stages are denoted.

STAGE I
SO 4 diffuses in

dissolves
~ , , forms ©
STAGE 2
---~Stege 1 ~ 2.
C3A species diffuse out
Stage

'~ ....mo.bo. .~.,os.,D..tefo~,..

A ~ t Aft dissolves

STAGE 3 TIME, t
Hexagonal ~heees form
H20 ~ ~'~

FIG. 2

Heat Release Rate vs. Time- showing

CubiC phesOS form
stages of hydration

FIG. i

Schematic Description of
Hydration Stages

First Sta~e

The f i r s t stage is marked by an ever decreasing heat evolution rate

corresponding to the gradual retardation of hydration by the formation of an
e t t r i n g i t e layer around the C3A particle [11-20]:

C3A + 3C~'H2 + 26H * C3A • 3L"S" • H32 (i)

In C3A - C-SH2 - H20 systems, gypsum dissolves rapidly in water, saturating

the solution. This is more a function of fine particles size than high solubi-
lity. Electrical conductivity data show no difference between systems prepared
with pure water and water previously saturated towards gypsum [21-22].
 Vol. 18, No. 6 913
C3A, HYDRATION, KINETICS, GYPSUM

E t t r i n g i t e crystals are believed to form by a through-solution mechanism

[19-26] near the C3A surface which may act as a catalyst for crystal nucleation
[27]. The crystals grow out as fine needles into solution. I t is generally
believed that e t t r i n g i t e formed on the anhydrous C3A surface retards the reaction
by decreasing the d i f f u s i o n of aluminate species could equally well l i m i t hydra-
tion rates. This would occur i f e t t r i n g i t e needles grew at t h e i r t i p s , while
sulfate ions would be most l i k e l y to l i m i t with growth at the needle base. The
thicker and denser the e t t r i n g i t e formed, the more d i f f i c u l t i t is for ions to
d i f f u s e . Collepardi et. a l . [25] have demonstrated that the retardation of C3A
hydration occurs only~he~ a r e l a t i v e l y large amount of e t t r i n g i t e is formed.
They also showed that the size and location of the second heat release peak is
closely related to the amount of gypsum added. Thus, there is ample evidence to
presume that diffusion of sulfate or aluminate ions through the e t t r i n g i t e
barrier layer is the c o n t r o l l i n g mechanism during the f i r s t stage of hydration.

Second Stage

The stoichiometry of e t t r i n g i t e formation (equation 1) shows that when the

i n i t i a l molar ratio of gypsum to C3A (g/a) is less than three all of the gypsum
is consumed. This is the case in practice for most Portland cements.

As sulfate ions in solution become depleted, they eventually reach a level

which is i n s u f f i c i e n t to form e t t r i n g i t e . The second stage begins when mono-
sulfate starts to c r y s t a l l i z e in solution withdrawing free calcium and sulfate
ions [28]:
m 1

C3A • 3CS • H32 + 2C3A + 4H + 3C3A • CS • H12 (2)

Simultaneously, the e t t r i n g i t e coating is removed by dissolution into solution

[30]. The r i s i n g part of the second heat evolution peak (figure 2) shows that
the reaction in the second stage accelerates. The C3A is considered to be pre-
sent in solution as an aluminate bearing ion, e.g., A~(OH)~, as well as
calcium and hydroxyl ions. Ghorab et. a l . [31] believe monosulfate is formed
through-solution after the d i s s o l u t ~ n o'oTettringite and the rapid reaction of
the residual C3A. Other evidence for a through-solution reaction for mono-
sulfate c r y s t a l l i z a t i o n is that large hexagonal plates grow from solution
rather than being formed between the interface of the unreacted C3A and
e t t r i n g i t e layer [15,30,32]. As the e t t r i n g i t e layer becomes thinner C3A spe-
cies can more easily diffuse through i t and reaction accelerates. This provides
evidence that the second stage is also controlled by a d i f f u s i o n mechanism.

Third Stage

L i t t l e e t t r i n g i t e is l e f t at the end of the second stage and most sulfate

ions are present in the monosulfate crystals. At the start of the t h i r d stage
the core of the C3A p a r t i c l e is once again exposed to the solution and reaction
rates are quite high. This corresponds to the sharp peak in the heat release
curve. The t h i r d stage corresponds to the f a l l i n g part of the second heat evo-
l u t i o n peak. During t h i s stage, the remaining C3A reacts with water in the pre-
sence of monsulfate, and, a mixed solid composedof a mixture of
monosulfate and hexagonal and cubic aluminate hydrates is formed:

2C3A + 21H + C2AHB + CwAH13 (3)

CgAH8 + CwAH13 ÷ 2C3AH6 + 9H (4)
 914 Vol. 18, No. 6
J. Pommersheim and J. Chang

A l t e r n a t i v e l y , C~AHI9 may be formed rather than C4AHI3 [ 3 3 ] . The transformation

tO a cubic hydrate (4) is usually delayed. During t h i s l a s t stage a hexagonal
phase b a r r i e r layer f i r s t builds up around the C3A core. I t then dissolves to
form c r y s t a l s of the cubic phase in s o l u t i o n . The presence of the monosulfate
can a l t e r rates s i g n i f i c a n t l y but is presumed to leave the basic mechanism unaf-
fected.

Further d e t a i l s of the conceptual and mathematical models for cnis stage

have been described elsewhere [ 9 ] for the C3A - H20 system. Comparison of the
mathematical model developed to experimental data showed d i f f u s i o n through the
hexagonal phase b a r r i e r l a y e r , d i s s o l u t i o n of t h i s layer and c r y s t a l l i z a t i o n of
the cubic phase were a l l c o n t r i b u t i n g resistances in the model, although pore
d i f f u s i o n through the b a r r i e r layer was the r a t e - c o n t r o l l i n g step.

I t is important to mention that there w i l l ~e no t h i r d stage i f all the

C3A is consumed in forming monosulfate. This w i l l occur whenever (g/a) is
greater than u n i t y .

Mathematical Models

The k i n e t i c models developed here are based on the conceptual model and
rate laws and conservation equations w r i t t e n for a dispersion of s i n g l e - s i z e d
p a r t i c l e s in s o l u t i o n . The s o l u t i o n is considered to be uniformly mixed and to
remain isothermal.

First S~age

In t h i s stage C3A reacts with s u l f a t e ions from s o l u t i o n to form

e t t r i n g i t e product. According to the conceptual model, the d i f f u s i o n of s u l f a t e
ion through the e t t r i n g i t e layer c o n t r o l s the reaction rate of C3A in the pre-
sence of the gypsum. Equally, the formation can be cast in terms of the d i f -
fusion of aluminate species. The f i n a l model w i l l have an equivalent form.
Based on the s t o i c h i o m e t r y :

dmA dme I
= - N (5)
dt dt 3 s

where

mA is the moles of C3A

me is the moles of e t t r i n g i t e

Ns is the d i f f u s i o n rate of s u l f a t e ions, mol/s.

Expressing the moles in terms of the p a r t i c l e r a d i i , and the d i f f u s i o n

rate in terms of the product of the d i f f u s i v e f l u x and the p a r t i c l e surface area
according to Fick's f i r s t law of d i f f u s i o n :

dr A i aCs re
(6)
dt = ~ LADsc dA rA(re _ rA)
Vol. 18, No. 6 915
C3A, HYDRATION, KINETICS, GYPSUM

dr e dr A
- (1 - d) (7)
dt re dt

dA
with d =
( i - c ) de

where

Ds is the d i f f u s i v i t y of sulfate ions, m2/s

ACs is the concentration difference of sulfate ion~ between the inside and
outside of the e t t r i n g i t e barrier ~ayer, mol/m~
dA is the molar density of C3S, mol/m
de is the molar density of e t t r i n g i t e , mol/m3
~A is the shape factor for C3A particles [9]
is the porosity (void space) of the e t t r i n g i t e phase.

The parameter d is a dimensionless density r a t i o . For d > I the particle

expands on reaction, as in the present case, where d ~ 10. ACs w i l l remain
constant u n t i l all the gypsum particles have completely dissolved. Because the
reaction is diffusion limited, i t w i l l be approximately equal to the saturation
concentration of gypsum in water.

Equations (6) and (7) can be solved simultaneously to give:

r 3 1/3
re
- [ I + (d - I ) ( I -(~))] (8)
rAO rAO

r, 2 i (rA) 3 2/3 t
1 - (~) + { [d + (1 - d) ] - I ~ = 2- (9)
rAO 1-d rAO ts

t s, the time constant for sulfate in diffusion, is defined by:

t s = 3 rAO2 dA/~ADs¢ ACs (10)

From the molar densities and i n i t i a l p a r t i c l e size, equations (8) and (9)
can be used to predict the particle size, re, and radius of the unhydrated par-
t i c l e core, rA, as a function of reduced time, t / t s. t s, defined by equation
(10), is a time constant for the diffusion of sulfate ions through the
e t t r i n g i t e layer. It is the only adjustable parameter in the analysis. Low
values of t s indicate rapid diffusion while high values predict low rates of
diffusion.

Equation (10) shows that the time constant varies with the square of the
i n i t i a l particle size. Thus, larger particles w i l l take s i g n i f i c a n t l y longer to
hydrate during t h i s period than smaller.
 916 Vol. 18, No. 6
J. Pommersheim and J. Chang

The conversion (m) of t r i c a l c i u m aluminate is given by:

3
rA
= I - ( ) (11)
rAo
This equation remains v a l i d throughout h y d r a t i o n . An expression for the
conversion rate can be obtained by d i f f e r e n t i a t i o n .

The model p r e d i c t s t h a t the f i r s t stage of h y d r a t i o n w i l l end a b r u p t l y

when:

rAi i i/3
- [i - ~ (g/a)] (12)
rAO
This occurs (at t l ) when a l l the gypsum has been consumed S u b s t i t u t i o n of
equation (12) i n t o equations (8) and (9) g i v e s , r e s p e c t i v e l y , the p a r t i c l e s i z e ,
r e l , and reduced time, t L / t s , at the end of the f i r s t stage.

Second Stage

In the second stage the e t t r i n g i t e reacts with C3A to form monosulfate.

The second stage begins at the p o i n t when a l l the gypsum has been consumed
(at t [ ) . Based on the s t o i c h i o m e t r y of equation (2):

dmA dme
= - 2 = NA (13)
dt dt

where

NA is the d i f f u s i o n rate of C3A species, mol/s.

I f the ions d i f f u s e as A~(OH)4- ions the f l u x needs to be twice t h a t given,

i . e . , 2NA. According to the conceptual model, the d i f f u s i o n of ions of
d i s s o l v e d C3A species through the e t t r i n g i t e l a y e r w i l l be the rate determining
step r a t h e r than the c r y s t a l l i z a t i o n of monosulfate from s o l u t i o n . This implies
t h a t the ions which are f i n a l l y i n c o r p o r a t e d i n t o the c r y s t a l s t r u c t u r e of the
monosulfate w i l l spend a r e l a t i v e l y long time d i f f u s i n g through the e t t r i n g i t e
barrier layer.

The d i f f e r e n t i a l equations of the model are analogous to those from the

first stage and have analogous s o l u t i o n s . Their s o l u t i o n y i e l d s :

i
r e = [ r e l 3 + (I + -- d) (r~ 3 - rAl3)] l/3 (14)
2

rA 2 I r 2 re I z 2(t - tl)
I - (-) + [ ( e ) ( ) ] - (15)
rAl I + i/2 d rAl rAl tA
Vol. 18, No. 6 917
C3A, HYDRATION, KINETICS, GYPSUM

During this stage r e remains greater than r A, and both the aluminate and
e t t r i n g i t e layers w i l l be shrinking. The time constant for diffusion of
dissolved C3A species through the e t t r i n g i t e layer is given by:

tA = rA~2 dA/~ADAACAC (16)

where
aCA is the concentration difference of C3A species~between the inside and
outside of the e t t r i n g i t e barrier layer, mol/m~

DA is the d i f f u s i v i t y of C3A species, mZ/s.

According to the conceptual model, ACA w i l l remain constant u n t i l all the

e t t r i n g i t e has disappeared, at time t2, the end of the second stage.

From the molar densities and i n i t i a l particle size, predictions can be

made of r e and r A as a function of the reduced time, t / t A . tA has a similar
physical meaning to t s. It is the only unknown or adjustable constant in the
second stage of hydration.

The model predicts that the second stage w i l l end abruptly when:

re2 _ rA2
Ll - ( g / a ) ] Z / 3 (17)
rA 0 rA 0
This occurs when all the e t t r i n g i t e has been consumed. Substitution of equation
(17) into equation (15) predicts the time t 2.

Third Stage

At the start of the t h i r d stage the e t t r i n g i t e has all been converted to

monosulfate and the C3A particles, now smaller, are once again exposed to the
solution. The mathematical models For the last stage are the same as those pre-
viously reported for the C3A - H2O system [9].

There are three time constants for the processes which occur during the
t h i r d stage, tw, for diffusion of water through the pores of a hexagonal phase
barrier layer formed adjacent to the C3A p a r t i c l e ; t x , for dissolution of t h i s
layer; and tc, for c r y s t a l l i z a t i o n of cubic phase from solution. These l a t t e r
steps take place through mass transfer films adjacent to p a r t i c l e surfaces.
Since the steps occur in series, the one with the longest characteristic time
w i l l control the hydration process. For the C3A - H2O system this has been
found to be t w [9].

Results and Discussion

In t h i s section graphical solutions are presented to the model, comparisons

are made to experimental heat release data and the results are discussed in
terms of r a t e - c o n t r o l l i n g phenomena.

Model Output

The model has five time constants as parameters: t s ( f i r s t stage), t a

(second stage) and t c , t x and t w ( t h i r d stage). Specifying these time constants
 918 Vol. 18, No. 6
J. Pommersheim and J. Chang

along with the s a t u r a t i o n concentrations, phase d e n s i t i e s , and water to s o l i d

and gypsum to C3A r a t i o s , completely determines model output. Only the time
constants are unknowns, so that during the f i r s t two stages there is one
adjustable constant while during the t h i r d stage there are three. All time
constants are proportional to times c h a r a c t e r i s t i c of the processes occurring
w i t h i n that stage. Use of smaller p a r t i c l e s lowers II time constants, espe-
c i a l l y those associated with pore d i f f u s i o n through )roduct layers ( i s , ta, and
tw), and predicts more rapid h y d r a t i o n .

Heat release rates (dQ/dt) were taken to be proportional to conversion

r a t e s , d a / d t , with the molar heat of reaction (&H) and s t o i c h i o m e t r i c r a t i o n as
p r o p o r t i o n a l i t y constants:

dQ da
- n (-AH)- (18)
dt dt

For the f i r s t stage n = 1, while during the second n = i / 2 . The corresponding

values of aH are -24.4 and -142,2 kcal/mol, r e s p e c t i v e l y . During the t h i r d
stage heat is released by the formation of the hexagonal phases and absorbed by
the formation of the cubic phases. Both must be considered when accounting for
the t o t a l heat release [ 9 ] .

Model Predictions

100 i i
2000

Parameter: (g/a) (g/a) = 0.25

• Oata [ 2 8 ] . 2 0 " C
75
tSO0
A

1000 3.05 2 2

S00 : 0.1S

2
*

t ' x tO 3
',

4
0.2S

6
25

o~ 10
i•AA
20
t(h)
•
3O
A ,
40
*
50

FIG. 3 FIG. 4

Effect of Gypsum to Comparison of Heat Release

C3A Molar Ratio Data [28] to Model Output

Figure 3 shows a o r e d i c t i o n of conversion rate d ~ / d t ' as a function of

dimensionless time t ' : t / t s, with the gypsum to C3A molar r a t i ~ (g/a) shown as
a oarameter. The other time constant r a t i o s are fixed at t s / t a : 5, t s / t w = 50,
and t s / t x = t s / t c = I000. Tne time scale can be matched with t y p i c a l experimen-
tal times by an aopropriate choice of t s. r i u l t i p l y i n g the coordinate axes by
t h i s value allows comparison to experimental data and also f i x e s the other time
constants. The end of the f i r s t stage is denoted bY a dashed v e r t i c a l l i n e
labeled ( I ) , while the end of the second stage is marked by l i n e (2). In the
f i r s t stage, a f t e r f i r s t contact of s u l f a t e ions and C3A , the reaction rate (and
heat release rate) is oredicted to be very large. As the e t t r i n g i t e layer beco-
Vol. 18, No. 6 919
C3A, HYDRATION, KINETICS, GYPSUM

mes thicker i t impedes the diffusion of ions through i t , and the reaction rate
turns lower u n t i l the point at which all the gyosum in the system has been con-
sumed (vertical dashed line I ) . An apparent induction period is entered as
indicated by the low f l a t region. This is common for all the curves u n t i l the
f i r s t stage ends. In the second stage, the conversion and heat release rates
rise again. As the e t t r i n g i t e layer becomes thinner, the diffusion of C3A spe-
cies outward through the e t t r i n g i t e to the solution also becomes easier, and the
reaction accelerates. The second stage ends when all the e t t r i n g i t e has reacted
( l i n e 2). Discontinuous break points on each curve show the switching from one
stage to another. The jumps are higher at lower values of (g/a). As shown,
lower gypsum to C3A ratios give shorter induction periods and higher heat
release peaks. Very large conversion rates are predicted to occur at the end of
the second stage, when the e t t r i n g i t e barrier layer is completely converted to
monosulfate, and the unreacted C3A again comes into direct contact with the
solution.

Comparison to Experimental Data

Figure 4 shows a comparison of the model f i t to experimental heat release

data reported by ~lori and !linegishi [28]. The curves produced by the model were
obtained by a computer program #hich linked two other programs, one a differen-
t i a l equations solver and the other a least squares optimization program. The
model constants used to regre~ the data were t s, ta, tw, tx, and t c.

For the f i r s t two staqes of hydration Table 1 oresents the results of this
analysis.

Table I. %del Time Constants (h) for First Two Stages, from
Regression Analysis of ~1ori and ~linegishi's Data [28].

P1ethod ts a
t t_~.l __tz ts/t a

1) heat release 520 2870 1.4 18+ 0.2

2) conversion 1880 2260 5.0 18+ 0.8

3) X-ray 4640 1030 12+ 18+ 4.5

+constrained

For the t h i r d stage the time constants were Found to be tw = 57, t x = 3,

and tc = 0.6 hrs. Data For the t h i r d stage were analyzed separately beginning
from the end of the seconJ stage (t 2 : 18 hrs).

As indicated in Table i , three different methods were used to find the

time constants. They were based on i) heat release data, 2) independent
measurement of the conversion at the end of one hour (~ = 0.036), and, 3) X-ray
d i f f r a c t i o n measurements [28] which gave the lenqths of the f i r s t and second
stages as 12 and 6 hours, respectively. A value of 18 hours was accepted for
the total time taken to complete the reaction in the First and second stages
because i t agrees with both the heat release and X-ray analysis data. In all
methods the total heat release was constrained to be equal to that calculated
from heat of reaction data [33].
920 Vol. 18, No. 6
J. Pommersheim and J. Chang

Figure 4 shows the model f i t for the X-ray diffraction method, where both
t l and t~ were set at their measured values before the regression analyses were
performea. This is the most constrained of the three methods, but even with
these constraints there is reasonable agreement. The sharp break at the end of
the second stage, corresponding to the dissolution of all the e t t r i n g i t e , is
steeper and occurs later than the experimental data shows. The model also pre-
dicts a jump at the end of the f i r s t stage ( t i = 12 hours, marked by the dashed
vertical line) which is not matched by the data. For the other methods (not
shown) this jump occurs earlier and is less pronounced. This could be a result
of the presence of an intermediate or transition stage. Chatterji [13] has
suggested that monosulfate may be formed in the presence of gypsum near the end
of the f i r s t stage of hydration. T h i s could also give the lower heat liberation
rates observed when e t t r i n g i t e disappears.

Discussion

Does the formation o~ disappearance of e t t r i n g i t e control the hydration of

C3A in the presence of gypsum during the early stages? The answer depends on
the relative magnitude of the ratio ( t a / t s ) . High values of this ratio
correspond to control by the formation of e t t r i n g i t e , while low values match its
disappearance. Values near unity would indicate no clear control by either
mechanism. As indicated in the l a s t column of table 1, the value of ( t a / t s)
depends on the method of data a n a l y s i s . Thus, no clear answer can be given to
t h i s question for the data we examined.

During the t h i r d stage the r e l a t i v e value of the time constants found

(tw >> t x > tc) suggest that pore d i f f u s i o n of water through the hexagonal
aluminate hydrate l a y e r surrounding the C3A (tw) is the rate l i m i t i n g or c o n t r o l
l i n g step in the h y d r a t i o n . D i s s o l u t i o n of the hexagonal phase ~tx) , and l a t e r ,
c r y t a l l i z a t i o n of the cubic phase ( t c ) , w i l l only control the hydration for a
short time near the end when the b a r r i e r layer of hexagonal phases is t h i n .
These conclusions are s i m i l a r to those reached for the hydration of C3A in a
s u l f a t e - f r e e environment [ 9 ] . However, a l l time constants are s i g n i f i c a n t l y
greater than before, e s p e c i a l l y tc. D i f f u s i o n rates are much reduced in the
presence of gypsum, perhaps because of the formation of denser product layers
and t h i c k e r mass t r a n s f e r f i l m s , which can r e s u l t from poorer mixing or p a r t i c l e
agglomeration. The formation of the hexagonal and cubic aluminate phases is
delayed by the presence of e t t r i n g i t e . Due to the s i m i l a r hexagonal s t r u c t u r e
of the monosulfate and hexagonal phases, part of t h i s l a t t e r phase may move
from the C3A p a r t i c l e and form a s o l i d s o l u t i o n with the monosulfate. Low
values of t c may r e f l e c t t h i s process. In a d d i t i o n , mpnosulfate can act as
nucleation s i t e s for c r y s t a l l i z a t i o n . In both cases ions are scavenged from
s o l u t i o n or from surfaces and the hydration accelerates.

Conclusions

The differential equations of the model predicted the size and amounts of
reaction products, and the rate and degree of hydration and heat release. Model
input included d i f f u s i v i t i e s , phase densities, water to solid and ~ypsum to alu-
minate ratios, and saturation concentrations. The remaining (unknown) model
parameters were time constants, for diffusion of ions through the pores of the
e t t r i n g i t e barrier layer (t s and ta) , and for hydration of C3A after the
e t t r i n g i t e had been consumed (tw, t x and t c ) .

Comparing the model to experimental heat release data using the time
constants as regression parameters a reasonable f i t was obtained. Results
 Vol. 18, No. 6 921
C3A, HYDRATION, KINETICS, GYPSUM

suggested that pore diffusion through a thickening e t t r i n g i t e barrier layer

controlled the First stage of hydration while pore diffusion through a thinning
layer controlled the second. The final stages of hydration were controlled by
pore diffusion of water through a hexagonal phase barrier layer surrounding the
C3A particle core. However, results were inconclusive as to whether e t t r i n g i t e
growth or disappearance controlled the earlier stages of hydration. The last
stage of hydration (formation of Afm phases) was significantly retarded when
compared to results obtained in a sulfate-free environment.

Acknowledgements

The authors appreciate helpful discussion with P. W. Brown and L. Struble

concerning the conceptual basis for the model, as well as help provided by L.V. Ng
of the department in verifying the analytical solutions.

Nomenclature
C& C3A conversion
CA C3A species concentration, mol/m~
Cs sulfate ion c,mcen~ration, mol/m~
d dimensionless density ratio, dA/(1-¢)d e
DA d i f f u s i v i t y of C3~, m2/s
dA molar density of C3A, mol/m3
de molar density of e t t r i n g i t e , mol/m3
£ porosity of e t t r i n g i t e layer
g/a gypsum-tricalcium aluminate molar ratio
~A shape factor of C3A particle
mA moles of C3A
me moles of e t t r i n g i t e
~ A, NS diffusion rate of C3A species and sulfate ions, mol/s
heat evolution, cal/mol
cA radius of C3A, m
re radius of C3A particle covered by e t t r i n g i t e phase, m
rAO i n i t i a l radius of C3A particle, m
rAi, rA2 radii of C3A particle at end of f i r s t and second stage, m
rel, re2 radii of C3A particle covered by e t t r i n g i t e phase at end of
f i r s t and second phases, m
t l , t2 duration of f i r s t stage, s, end of second "stage, s
tA, t c, t s, time constants, for diffusion of C3A species through e t t r i n g i t e ,
tw, t x for crystallization of cubic phase from solution, for diffusion of
sulfate ion through e t t r i n g i t e , for water diffusion through hexagon-
al phase, and for dissolution of hexagonal phase, s

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