CEMENT and CONCRETE RESEARCH, Vol. 20, pp. 453-460, 1990. Pr/nted in the USA.

0008-8846/90. $3.(X)+00. Copyright (c) 1990 Pergamon Prets plY,

A DILATATION MODEL FOR THE EXPANSION OF SILICA GLASS/OPC MORTARS

G. W. Groves and X. Zhang

Department of Metallurgy and Science of Materialst University of Oxford,
Parks Road, Oxford OXl 3PH.

(Communicatedby A.J. Majumdar)

(Received August 15, 1989)

ABSTRACT A model for the expansion of a silica glass/alkaline OPC mortar has
been developed which is based on the observation that the main
reaction product of the glass is a layer of CSH gel formed at its
surface. In the model, which takes into account the mechanical
- properties of the system, the increase in voltm~e of the glass plus
its reaction product layer above that of the original glass leads to
a predicted mortar expansion which is slightly less than that
observed, but of the correct order of magnitude.

i. Introduction

Although the alkali silica reaction, first recognized by Stanton (I) as

a source of distress in concrete, has been extensively studied, relatively
little work has been done to develop a quantitative model to describe it,
based on detailed microstructural observations and taking into account the
mechanics of the expansion process. Thus, although Hobbs develcged a
quantitative model to predict the effect of the mortar ccmposition on the
expansion (2), for example, the magnitude of the e ~ i o n in the model was
set by a disposable parameter and so was not predicted in any absolute
sense.

In this paper we develop a model based, on observations of the

microstructure of an expanded mortar cc~posed of silica glass particles in an
alkaline OPC paste. The details of the expansion and its dependence on the
mix parameters and the size of the silica glass particles as observed
experimentally will be presented elsewhere. For the purposes of this paper
we note that such mortars can expand by as much as 1% after 6 months and that
the typical reaction product observed at the interface between the silica
glass particle and the cement matrix is a layer of CSH gel which is
determined by microanalysis in the transmission electron microscope to have a
Ca:Si ratio of approximately 1.0. This is by far the commonest type of
reaction product. An example is shown in fig.I. The formation of a CSH gel
with Ca:Si ratio of order unity is what would be expected in a system in
effective contact with calcium hydroxide. Kalousek (3), in a study of
equilibria in the soda-lime-silica water system at 25°C showed that although
the presence of sodium in solution greatly reduced the equilibrium

453
454 G.W. Groves and X.Z.,hang Vol. 20, No. 3

concentration of calcium in solution, the gel coexisting with solid Ca(OH)2

and sodium-containing solutions had a Ca:Si ratio of about 1.0 and gels of
very low Ca:Si ratio were not obtained. It would appear that only in regions
effectively isolated from Ca(OH)2 can very low Ca:Si ratio gel be formed.
Such a gel, with Ca:Si ratio approximately 0.2 was only observed in a few
isolated instances in the T~4 examination of our mortars. Its presence might
be attributed to regions of poor mixing where a high local concentration of
silica glass gave an area at a considerable distance from any Ca(OH)2. It
might be argued that such regions even if few in number were nevertheless the
source of expansion in our mortars, according to the widely accepted
mechanism of an alkali-silicate gel of relatively low Ca content imbibing
water and swelling. However there is a difficulty with this explanation.
The swelling pressures which have been experimentally measured in such gels
typically give values up to about 10MPa (4). Such pressures, as has been
pointed out (4), exceed the tensile strength of ordinary concrete, and could
certainly produce crack propagation if present within large sharply angular
regions or pre-existing cracks. However it is questionable whether such
pressures within relatively small (say-100~m) isolated volumes could produce
fractures. If it is accepted that the strength of ordinary hardened cement
paste is determined by the presence of large flaws -imm in size (5), then
volumes of cement paste -100~m in size can be expected to have a much higher
strength than macroscopic samples of cement or concrete. This view is
supported by the large increases in strength obtained by eliminating large
flaws from the c~nent paste microstructure (6). If a pressure of 10MPa in a
few regions -100~m in size produces only elastic deformation and creep of the
surrounding matrix the expansion produced would be quite negligible compared
to the observed expansions of our mortar bars. Thus the elastic expansion of
a spherical volume containing a pressure p in a large volume of matrix of
shear modulus ~ is given by (7),
8v = 3~ (i)
v 4~

Creep of the matrix at this stress level would reduce the effective modulus
over a period of months, by roughly one-half (8). A value of ~ on the order

FIG. 1
T~M micrograph of 6 month old alkaline OPC/silica glass mortar showing
reaction layer at the surface of a glass particle.
V~,I. 20, N~. 3 Dilatation Model. $iO 2 Glass, Cement, Mortars 455

of 4GPa would be appropriate, giving an expansion -10-3 of the vol~m~ and a

negligible expansion overall. It is possible that the experimental
measurements of pressures generated by alkali-silica gels greatly
underestimate those which can occur in practice. Nevertheless it is
reasonable to examine the possibility of expansion arising from the formation
of the CSH gel of Ca:Si of order unity which is by far the commonest reaction
product in our system. The alkali content of this gel is relatively small (a
few percent) and could not be accurately measured in our analysis. We
consider the composition to be essentially CaOSi<hxH~, the main role of
the alkali being to accelerate the attack on the SiR and the formation of
reaction product. If all the reacted silica is assumed to be retained in the
layer of reaction product at the surface of the silica glass particle it is
evident that the reaction product layer will have a substantially larger
volume than that of the reacted glass leading to an effective expansion of
the particle. We first compare the volume of the reaction product with that
of the reacted glass.

2. Development of the Model

2.1 Increase in volume in forminq CSH reaction product

We define the parameter A as the ratio of the volume of reaction

product, including any contained porosity, to the volume of reacting silica.
The parameter A can only be estimated since neither the composition nor the
density of the CSH gel are completely known. The main uncertainty in
conposition lies in the bound water content. In the formula CaOSiChxHeO
we take x ~- 2, a value intermediate between the somewhat lower values
expected from the compositions of the crystalline hydrates jennite or
tobermorite (9) and the somewhat higher values implied by most experimental
determinations (10). Allowing for a gel porosity of -30% a density of the
gel including its porosity is taken to be 70% of a value of 2.3 g c ~ 3, the
density of jennite. This gives a density of 1.6 gcnr3. The ratio of the
mass of gel to the mass of reacting SiCh is then 2.53 and the ratio of the
volume of gel to the volume of glass, taking the density of silica glass as
2.2gcm-3, is 3.5. We therefore estimate A = 3.5. This implies that 71.4% of

FIG. 2
Optical micrograph of 3 month old OPC/silica glass mortar showing angular
glass particles.
456 G.W. Groves and X. Zh~tg Vo]. 20, No. 3

the observed volume of CSH reaction product layers on the surfaces of the
glass particles represents an increase in volume of regions within the
mortar. Although the value of A is an estimate, it should be noted that a
variation of A in the range say, 3 to 4, would produce a variation of only
from 67% to 75% in the percentage of reaction product volume representing a
volume increase. The uncertainty in the calculation of the volune increase
of the mortar introduced by the uncertainty in the exact composition and
porosity of the gel is probably smaller than the uncertainty of other
factors in the calculation, as discussed below.

2.2. The volume of CSH gel reaction product at the qlass particle surfaces

The thickness of the reaction product layer in a particular mortar can

be measured by T~M for various glass particles and a value at the lower end
of the range chosen to allow for the effect of sectioning on the apparent
thickness. The thickness will be expected to be a function of the
composition of the mortar, particularly the alkali-silica ratio, and possibly
the particle size. We have observed, for example, that the thickness, along
with mortar expansion, is much reduced by the an~ition of pozzolanas such as
precipitated silica (to be published elsewhere). If in a particular specimen
the thickness is t, then when t is much less than the particle size, the
volume of reaction product is given by

V = St (2)

where S is the total surface area of the particles. In our case, the glass
particles were prepared in a certain size range by grinding and sieving and S
was not measured directly. The estimation of S gives the greatest source of
uncertainty in our calculation. If the particles were spherical, tb~ value
of S could readily be calculated from the average particle size. However the
glass particles in our case are extremely angular as shown in fig.2. This
can be expected to introduce a much larger value of S. Thus for exanple
Shacklock and Walker, as quoted by Neville (ii) found that crushed granite
particles sieved to the same size range as rounded gravel particles had a
surface area between 1.6 and 1.9 times as great, over a wide size range from
300-600~m to 17.7 - 19.05ram. (Our particles are somewhat smaller than this
range, but there is no indication in Shacklock and Walkers' results of a
systematic change in the factor with particle size).

It is convenient when considering the mechanical aspects of the

expansion process to use a model of a spherical aggregate particle. However
we consider that our particles are likely to be at least as angular as
crushed granite and that the volume of the reaction product of the particles
calculated on the basis of a spherical model should be multiplied by a factor
of at least 1.9. we term this factor the shape factor (~. The volume of
reaction product is then given by

6~tv a
V = d (3)

where d is the average paricle size and V a is the total volLm~e of glass
aggregate. The factor 6Va/d arises from the surface : voltm~ ratio for a
Vol. 20, No. 3 DilatationModel, $iO2Glass, Cement,Mortars 457

sphere of diameter d. From the estimate of the volume increase AV made in

Section 2

AV = 0.71V (4)

4.26 ~ t V
or AV = d a (5)

2.3 The Increase in vol~ne of the Mortar

When a body contains regions which increase their unstrained volume by

~V the expansion of the body is in general different from ~V. If the
behaviour is elastic, then relatively compliant expanding regions within a
stiff matrix will produce an expansion of the body of less than AVwhereas a
stiff expanding inclusion within a ~ c h less stiff matrix will produce an
expansion of the body in excess of ~V. This latter result, at first sight
paradoxical, arises from the tensile image forces set up at the free outer
surface of the body in order to neutralize the compressive forces which would
act in an infinite matrix. These image forces produce a dilatation of the
matrix (7). The elasticity theory of a misfitting sphere of bulk modulus K'
in a matrix of shear modulus ~ and bulk modulus K shows that the vol~ne
increase of a composite sphere containing the sphere whose volume increases
from V s to V s + ~V s is given by (7)

AVm = ? ~Vs/~ (6)

where ?' 3K' + 4~

= 3K' (7)

3K + 4~ (8)
Y= 3K

which may be expressed alternatively as

3(i - v)
= (I + v) (9)

Using a value of 0.25 for the Poisson's ratio V of the c~ment paste
matrix (12) we calculate y to be 1.8. The bulk modulus of the glass
particle, modelled as a mis-fitting sphere should be corrected for the
reduced modulus of the reacted surface layer, although for the layer
thicknesses -i~ with which we are concerned the effective modulus is reduced
by only 3%, which is a relatively small factor. An effective bulk moch/lus
for the glass particle of 36(~a and a shear modulus for the matrix of 8GPa
gives a value of ~' of 1.3 and

AVm = 1.4 AV s (I0)

Thus in the elastic misfitting sphere model the expansion of the mortar is
40% greater than the effective increase in volume of a glass aggregate
458 G.W. Groves and X. Zhang \%1.20, No. 3

particle. The total increase in volume due to randomly distributed particles

is, from equation (5), estimated as

6~tV a
AV = (Ii)
d

or setting ~ = I. 9 for our highly angular particles

tV a
AVm -- ii.4 d (12)

In the above model it is assumed that the dilatation of the matrix is

elastic. The behaviour of the matrix cannot in fact in our case be wholly
elastic because the strains are too large to accommodate elastically. The
tensile stresses in the cement paste at the glass/cement interface would be
large enough to induce microcracking since according to the elastic
misfitting sphere model the pressure at the interface is given (for an
infinite matrix) by (7).

4
P =]~v (13)
s

with a tensile stress at the interface ac£ing parallel to the interface of

magnitude p/2. The relatively high free energy of formation of the hydrate,
probably on the order of 102 kJ/mol (13), would allow the expansion to
overcome high pressures and in fact the tensile strength of even small
volumes of cement paste would be exceeded by stresses of the order of that
given by equation (13) with AVs/Vs on the order of 10-I. It must
be expected therefore that the elastic dilatation of the matrix entering into
the expansion of the whole body given in equations (Ii) and (12) will be
largely replaced by dilatation due to microcracking. The physical picture is
that as the effective expansion of the glass particles increases by the
growth of the layer of reaction product at their surfaces, the cement paste
matrix dilates by microcracking, giving a total volume increase for the
mortar significantly greater than the increase in effective volume of the
aggregate particles alone. Microcracking was not in fact observed in our
mortars but this may be because it was on too small a scale to observe
optically. The presence of microcracking is consistent with the large loss
in bending strength which occurs at an early stage on the expansion (to be
published elsewhere). The dilatation of the microcracked matrix may not be
identical to that given by the elastic model, but it is reasonable to asst~ne
that it is of the same order of magnitude and at least as large. We
therefore consider that equation (12) can be used to estimate the linear
expansion of a mortar bar of vol~ne Vm containing a total volume Va
of angular glass particles of average diameter d having a reaction layer of
thickness t

i Arm V
-3 ( - T ) : (14)
a
m m
Vol. 20, No. 3 D~a~ationModel, SiO 2 Glass,Cement, Mortars 459

5. Comparison with experimental observations

Equation (14) is in a form which can readily be compared with the

measured expansions of mortar bars containing silica glass. For example,
particles sieved to between 50 and 125~m, giving an average value of d of
87.5~m give in a mortar bar with glass/cement mass ratio 3:7 (cement alkali
content 2% Na20 equivalent) and water:cement ratio 0.5 a 28 day expansion
of 0.8%. Thickness of reaction rims measured from electron micrographs
ranged from 0.61 to 0.75~m. Taking the lowest value to be correct to allow
for the effect of the section orientation we take t = 0.6~m. From the
densities of the cement paste determined from the masses of cement and water
and the volume of the mixed paste and the silica glass (2.2 gm c ~ 3) as being
1.9 gm cm-3 we estimate (Va/Vm) to be 0.2 giving from equation (14) a
linear expansion of 0.53%. The predicted expansion is of the correct order
of magnitude and considering the uncertainties of the model, particularly in
the shape factor and in the matrix dilatation term, can be regarded as in
reasonably good agreement with experimental observation.

Discussion and Conclusion

A quantitative model for the expansion of a mortar containing silica

glass particles in an alkaline cement matrix has been developed which is
based upon measurements of the composition and thickness of layers of CSH gel
which are formed by the reaction of glass particles at their surfaces. The
model shows that the effective expansion of the particles as the reaction
layers grow is able to account for the order of magnitude of the observed
expansion of the mortar and can therefore be said to meet the first criteron
for a successful quantitative model. There are two assumptions in the model.
The first is that the problem can be treated as one in continuum mechanics,
i.e. the matrix surrounding the particle is regarded as a solid continuum.
This assumption will clearly break down when the particle is so small as to
be comparable in size to the more numerous pores in the matrix, e.g. for the
case of silica fume particles where a significant proportion of the particles
may simply expand into pore space. However for the 50~m-125~m particles in
our mortar the continuum model would appear to be a reasonable one. The
second assumption is that all the silica in the reacted glass becomes located
in the CSH gel reaction product layer. The escape of any silica from this
layer would reduce the expansion.

Further confirmation of the model would require many further

measurements of reaction layer thicknesses for various compositions of the
mortar mix which produce varying expansions. An explanation for the effect
of the mortar mix would have to be found in its effect on the thickness and
composition of the reacted layer, on the amount of silica retained within it
and on the mechanical properties of the system. At present the model can
provide only a very incomplete explanation of the expansion. However even at
its present stage of development the model has certain advantages for our
case over the explanation for expansion due to alkali-aggregate reaction
which has become widely accepted. This is that an alkali-silicate gel of low
Ca content forms which, by imbibing water, expands to produce the observed
effects. The problerm with this explanation in our case are firstly that an
alkali-silicate gel of low Ca content is not the main reaction product, and
indeed would not be expected to form in a system in equilibrium (3), and
secondly that the pressures which such gels have been observed experimentally
to be capable of generating by imbibing water are too small to account for
the observed expansion. Although there may be much circumstantial evidence
460 G.W. Groves and X. Zhang Vol. 20, No. 3

in favour of the widely accepted explanation in other cases, the authors are
not aware that a detailed quantitative prediction of an expansion has ever
been compared with a measured value, using this explanation as a basis. In
view of the success of our alternative model in this respect, albeit, in a
particular case, it may be worth keeping an open mind about the mechanism of
expansion in some other instances.

Acknowledqement

One of us (X.Z.) is grateful to the Chinese Government for financial

support.

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(1982).
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