CEMENT and CONCRETERESEARCH. Vol. 3, pp. I-6, 1973. Pergamon Press, Inc.

Printed in the United States.

MECHANISM OF EXPANSIONASSOCIATED WITH ETTRINGITE FORMATION

P. K. Mehta
Department of Civil Engineering
University of California
Berkeley, California 94720

(Communicated by D. M. Roy)

ABSTRACT
Ettringite formation in portland cement concretes can be
responsible for both deleterious and beneficial phenomena.
Several hypotheses on the mechanism of expansion associated
with ettringite formation are reviewed, and a new hypothesis
is proposed. Experimental evidence is presented in support
of the new hypothesis. I t is shown that in the presence of
lime the nature of ettringite formed is colloidal, and not
long lath-like crystals. I t ~ proposed that colloidal
ettringite is able to attract a large number of water molecules which cause interparticle repulsion, thus causing an
overall expansion of the system.

Die Bildung von Ettringit in Portlandzement-Benton kann sich

sowohl vorteilhaft als auch sch~dlich auswirken. Verschiedene
Hypothesen ~ber den Ausdehnungsvorgang bei der Ettringitbildung
werden er~rtert, und eine neue Hypothese wird vorgeschlagen und
durch Experimente belegt. Es wird gezeigt, dass sich Ettringit
in Gegenwart von Kalk kolloidal bildet und nicht in Form l~nglicher
Kristallpl~ttchen. Es wird angenommen, dass ko~oidaler Ettringit
in der Lage i s t , eine grosse Anzahl von Wassermolek~len anzuziehen.
Dies bewirkt eine Abstossung der Teilchen und so eine Ausdehnung
des Gesamtsystems.

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ETTRINGITE, EXPANSION, THEORY, CONCRETE, SEM

Expansion associated with e t t r i n g i t e

(C6AS3H32) formation is known to be

responsible for both deleterious and beneficial

concretes.

phenomena in portland cement

In unrestrained hardened concretes, e t t r i n g i t e

formation can cause

cracking by development of t e n s i l e stresses which are frequently high enough to

overcome the tensile strength of concrete.

On the other hand, e t t r i n g i t e f o r -

mation under r e s t r a i n t can be u t i l i z e d to develop compressive stresses of e i t h e r

low magnitude in shrinkage-compensating concretes, or of high magnitude in s e l f stressing concretes. ( I )
Several hypotheses have been advanced on the mechanism of expansion associated with e t t r i n g i t e

formation. (2)

The d i f f i c u l t y

to ascribe expansions d i r e c t l y

to increased volume of solids, when the reactants are converted into e t t r i n g i t e ,

is explained by Mehta (3) on the basis of stoichiometric equations involving
ettringite

formation in three types of expansive cements.

In every case, instead

of volumetric increase, t h e o r e t i c a l l y there should be 7-8% reduction in volume on

completion of e t t r i n g i t e

forming reactions.

Lafuma (4) suggested that the aluminates are r e l a t i v e l y

insoluble in the

presence of calcium hydroxide, and that solid state conversion of calcium aluminates to e t t r i n g i t e could cause expansion.

Hansen(5) showed by computations that

solid state conversion of C3A to e t t r i n g i t e could cause e i g h t - f o l d volumetric increase.

However on the basis of electron microscopic studies of the hydrated

pastes, Chatterji and J e f f e r y , ~6)"" and more recently Mehta, (3) demonstrated that
the early hydration products in the cement pastes are formed by through-solution
reactions rather than s o l i d - s t a t e reactions.
Thorvaldson (7) suggested that volume changes in cement mortars and concretes
are controlled by osmotic forces, similar to those responsible for swelling or
shrinkage of gels and clays.

In certain c o l l o i d a l

clays osmotic pressure is iden-

t i f i e d with pressures arising from concentration differences of dissolved ions

between the clay plates and the surrounding l i q u i d phase.
reported that under a l a t e r a l

Mielenz and King (8)

r e s t r a i n t of 1 psi, sodium montmorillonite expanded

66% in 33 days of water adsorption, whereas Dawson(9) reported up to 15 tons per

sq. f t .

expansive pressure exerted by confined bentonite clays.

High specific

surface, peculiar flaky shape of c r y s t a l s , and proximity of a polar f l u i d are considered important by Van Olphen (I0) in explaining large expansions associated with
osmotic swelling or the double-layer repulsion shown by clay-water systems.
though there are some s i m i l a r i t i e s

between the e t t r i n g i t e - w a t e r system and the

Cement chemistry notations are used:

C = CaO;

A = A1203;

S = Si02;

Al-

S = S03;

H = H20.

Vol. 3, No. l

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ETTRINGITE, EXPANSION, THEORY, CONCRETE, SEM

clay-water system, Lea( I I ) doubts whether Thorvaldson's osmotic pressure theory

can account for large expansions that can be produced by ettringite formation in
hardened cement pastes.
Direct crystal thrust by anisotropic growth of ettringite crystals has
been advanced as another possibility because this is reported to be the mechanism
responsible for expansion of plaster of Paris on setting. Though the total volume
of solids and water present decreases on hydration, i t is argued that the effective space taken up by the mass of interlocking lath-like gypsum crystals is actually increased, while cavities are l e f t in the interior~

Kalousek and Benton(12)

proposed that lack of growth of ettringite crystals was probably responsible for
l i t t l e or no expansion observed in their studies on sulfate resisting portland
cement. However, Brown(13) believed that crystal growth from solutions cannot be
a source of significant mechanical energy. The thermodynamic property involved
with crystal formation and crystal growth is only the heat of solution, from which
there is no significant release of mechanical energy. Midgley and Pettifer (14)
reported in hydrated supersulfated cement pastes large quantities of long laths
of ettringite crystals, many in excess of 12O um long, yet mortars and concretes
made with this cement do not exhibit significant expansion.
On the basis of experimental work described below, the writer proposes the
following alternative hypothesis on mechanism of expansion associated with ettringite formation:
l)

Only colloidal ettringite is capable of developing large expansions.

In the presence of lime, the nature of ettringite formed is colloidal, and not
long lath-like crystals.
2)

For colloidal .ettringite to cause large expansions, i t must be in con-

tact with an outside source of water. High specific surface of colloidal ettringite, and its peculiar crystal structure with a negative net charge, as proposed
by Moore and Taylor, 15)'' are probably responsible for attracting a large number
of water molecules, which surround the ettringite crystals and cause interparticle
(perhaps double-layer type) repulsion, thus causing an overall expansion of the
system, without any change in crystal lattice of ettringite.
The experiment involved hydration of a mixture containing stoichiometric
amounts of C4A3S, CSH2, and quick lime for ettringite formation. Another mixture
was similarly hydrated in which the quick lime had beenreplaced by an equivalent
weight of additional CSH2. Fractured specimens of the hydrated pastes were exby scanning electron microscopy.
The scanning micrographs of hydration
products at 24 hours and 72 hours are shown in Fig. I. Comparison of Fig. IA

amined

A "Stereoscan"

Vol. 3, No. !
ETTRINGITE, EXPANSION, THEORY, CONCRETE, SEM

FIG. 1
Micrograph of C4A3S - CSH2 Hydrated Paste, with and without Lime
(A) in the presence of lime, 24 hours, 5000 X; (B) in the absence of lime, 24
hours, 5000 X; (C) in the presence of lime, 72 hours, 6000 X; (D) in the absence of lime, 72 hours, I000 X.

FIG. 2
Wet Cured vs Dry Cured C4A3S + 8CSH2 + 6C
Pastes, 7 Days
(A) micrograph, wet cured, 5000 X; (B)
micrograph, dry cured, 5000 X; (C) photoof wet cured (in the beaker) vs. dry cured
specimens.

Vol. 3, No. 1

5
ETTRINGITE, EXPANSION, THEORY, CONCRETE, SEM

with F~g. IB showed that at 24 hours the ettringite crystals formed in presence

of lime were about 1 ~m long and I/4 ~m wide, and that in the absence of lime
they were about 6-8 um long and I / 2 - I ~m wide.

Comparison of Fig. IC with ID,

which show e t t r i n g i t e crystals at 72 hours, confirmed that the e t t r i n g i t e crystals formed in the presence of lime needed about 6 times larger magnification to
reproduce approximately the c r y s t a l l i n e sizes that were seen in the absence of
lime.

Similar results were obtained when the experiment was repeated with CA

r a t h e r than C4A3S as a source of aluminate for e t t r i n g i t e formation.

In another experiment a stoichiometric mixture of C4A3S, CSH2, and quick
lime was hydrated with more than enough water to form e t t r i n g i t e (0.8 watersolids r a t i o ) , and the paste was cast into two Le Chatelier expansion molds.

At

6 hours when the paste had hardened, one of the molds was sealed completely with
paraffin wax while the other one was placed in a glass beaker and exposed to
moist curing in a fog room.

At 7 days both the dry and the wet-cured pastes

were examined for r e l a t i v e expansion, e t t r i n g i t e content (by X-ray d i f f r a c t i o n ) ,

and the size of e t t r i n g i t e crystals (by Stereoscan).
Fig. 2.

The results are shown in

The wet cured specimen swelled so much that i t could not be taken out

of the beaker, whereas thedry-cured specimen did not show s i g n i f i c a n t expansion

(Fig. 2C).

The micrographs of the wet-cured (Fig. 2A) vs. the dry-cured speci-

mens (Fig. 2B) did not reveal s i g n i f i c a n t differences in the size of e t t r i n g i t e

c r y s t a l s , although e t t r i n g i t e crystals in the wet-cured condition appeared to be
better formed and well separated from each other.

X-ray d i f f r a c t i o n analyses of

the two pastes showed some unhydrated C4A3~ to be s t i l l

present in the dry-cured

paste, but this was not considered s i g n i f i c a n t with regards to the large d i f f e r ences in the swelling characteristic of the two pastes.
The mechanism proposed here adequately explains why expansion and cracking
associated with e t t r i n g i t e formation is more common in portland cement concretes
rather than in concretes made from supersulfated, high alumina, and certain pozzolan or slag cements which contain l i t t l e

or no Ca(OH)2 after hydration.

It

also explains why the portland cement concrete f a i l u r e s due to sulfate attack
are generally found in the areas where concrete is exposed to wet environments,
for example concrete in sewage pipes, mine cribbings, foundations on sulfate
s o i l s , and seawater structures.
References
I.

Report of ACI Committee 223, Expansive Cement Concrete--Present State of

Knowledge, Jour. ACI, Proc. Vol. 67, No. 8, p. 585, 1970.

2.

Discussion on the ACI Committee 223 Report, Expansive Cement Concrete--Present State of Knowledge, Jour. ACI, Proc. Vol. 68, No. 4, pp. 293-296, 1971.

Vol. 3, No. 1
ETTRINGITE, EXPANSION, THEORY, CONCRETE, SEM
3.

P, K. Mehta, "Chemistry and Microstructure of Expansive Cements," Conference

on ExPansive Cement Concretes, University of C a l i f o r n i a , Berkeley, June 1972

4.

H. Lafuma, Revue Mater. Constr., Trav. Publ., 243, 441 (1929).

5.

W. C. Hanse, "Discussion on Significance of Test for Calcium Sulfate in Hydrated Portland Cement Mortar," Proc. ASTM, Vol. 61, p. 1039, 1961.

6.

S. Chatterji and J. W. J e f f e r y , Jour. Am. Ceram. Soc., 46, 187-191 (1963).

7.

T. Thorvaldson, "Chemical Aspects of the D u r a b i l i t y of Cement Products,"

Proc. Third I n t ' l . Sym. Chem. of Cements, Cement and Concrete Association,
London, p. 463, 1952.

8.

R. C. Mielenz and M. E. King, "Physical Chemical Properties and Engineering

Performance of Clays," C a l i f . Div. Mines B u l l . , 169, 196-254 (1955).

9.

L. S. Brown, "Discussion on Mechanism of Seawater Attack on Cement Pastes,"

Jour. ACI, Proc. Vol. 67, No. 8 pp.- 646-648, 1970.

I0.

H. van Olphen, "An Introduction to Clay Colloidal

Publ. Co., I n c . , pp. 146-149, 1963.

Chemistry," Interscience

II.

F. M. Lea, "The Chemistry of Cement and Concrete," Chemical Publ. Co., I n c . ,

p. 348, 1971.

12.

G. L. Kalousek and Eo J. Benton, "Mechanism of Seawater Attack on Cement

Pastes," Jour. ACl, Proc. Vol. 67, No. 2, pp. 187-192, 1970.

13.

L. S. Brown, "Discussion on Mechanism of Seawater Attack on Cement Pastes,"

Jour. ACl, Proc. Vol. 67, No. 8, pp. 646-648, 1970.

14.

H. G. Midgeley and K. P e t t i f e r ,
(1971).

15.

A. E. Moore and H. F. W. Taylor, Nature 218' , 1048 (1968).

Cement and Concrete Research, ~, 101-104