CEMENTand CONCRETERESEARCH. Vol. 13, pp. 401-406, 1983. Printed in the USA.

0008-8846/83/030401-06503.00/0 Copyright (c) 1983 Pergamon Press, Ltd.

MECHANISM OF SULFATEATTACKON PORTLANDCEMENT

CONCRETE - ANOTHERLOOK

by P. K. Mehta
Department of Civil Engineering
University of California
Berkeley, California 94720 U.S.A.

(Communicated by D.M. Roy)

(Received Nov. I I , 1982)

ABSTRACT
Sulfate-generated deteriorations in normal portland cement concretes
include expansion, cracking, loss of strength and stiffness, and
sometimes disintegration. The chemical phenomenonof ettringlte forma-
tion as a result of reaction between sulfate water and hydration pro-
ducts of portland cement does not adequately explain all the physical
manifestations of the sulfate attack. Furthermore, ettringite which
causes expansions in some cases is apparently responsible for high
strength in other cases. The published literature does not contain
satisfactory explanatiomfor this anomalous behavior of ettringite.
In this paper, the author has attempted to provide answers to some of
the questions.

Introduction

Normal portland cement concretes are known to expand and, at times, crack
on long exposure to sulfate waters containing more than lO00 ppm sulfate.
This phenomenon called, "sulfate attack", is generally attributed to ettrin-
gite formation. Whereas researchers have yet to agree on the mechanism by
which ettringlte causes expansion, i t is observed that ettringite is also the
primary source of strength in many cements. For example, i t is well estab-
lished that the rapid hardening property of supersulfated cements, regulated-
set cement (1), very high early strength cement (2), and certain energy-saving
cements (3) is derived mainly from ettringite. Large quantities of ettringite
are formed on hydration of these cements, yet this does not cause expansion
and cracking in concrete. Are there two kinds of ettringite -- one expansive
and the other cementitious, or is there only one ettringite which responds
differently to different environmental conditions?
In normally retarded portland cements containing 6-12% CgA, in the course
of hydration and subsequent sulfate exposure ettrlnglte forms~t~Ice -- once
during the very early hydration period {e.g. first 14 hours), and later when
the sulfate ions from aggressive water are able to penetrate into the well-
401
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P.K. Mehta

hydrated cement paste. Since the~/A ratio in the anhydrous cement favors the
formation of the monosulfate hydrate, the ettringite formed during the early
hydration period is gradually converted to the monosulfate, which being
unstable in aqueous environments with high concentration of sulfate ions, is
converted back to ettringite. Many researchers like to explain the physical
manifestations of ettringite forming reactions on the assumption of solid-
state hydration. Do experimental observations support this assumption?

There are other interesting questions. The sulfate-generated deteriora-

tion is not confined to the expansion-cracking phenomenon. Someti~nes strength
loss and mushiness or loss of the cementitious property is observed. For in-
stance, Thorvaldsen (4) reported disintegration of mortar bars made with a
high-C~A cement in a 2% Na~SO~ solution, with very l i t t l e expansion. No ex-
planatTon for strength los~ b~ the C-S-H was given. Furthermore, i t is well
known that the deteriorated specimens often contain both ettringite and gypsum
in abundance. Howeverthe effect of gypsum formation is not fully explained in
the literature. That with respect to sulfate attack the complex nature of
interplay between various chemical interactions and their physical manifesta-
tions is not properly understood is also evident from many laboratory observa-
tions which show a lack of direct correlation between expansion and the amount
of ettringite formed. In sulfate immersion tests on standard mortar or con-
crete specimens made with ASTMType I or II portland cement, the specimens
usually do not expand much during the f i r s t several months of exposure when
most of the ettringite is formed. Subsequently, there is an exponential rise
in expansion, with l i t t l e or no increase in ettringite. In the hope of stimu-
lating further discussion and research on the subject, the author has at-
tempted in this paper to offer some answers to the questions raised above.
Types of Ettringite

Although several types of ettringite crystals are known on the basis of

differences in the crystal habit and size, the internal structure corresponds
to only one type which shows strong XRD lines at 9.7, 5.61, 4.70 and 3.8B A.
In hydrated cements, ettringite is generally believed to form from solution
phase containing calcium, aluminum, sulfate and hydroxyl ions. From the stand-
point of expansion behavior, i t is proposed to categorize ettringite crystals
into two types:
Type l Ettringite ' Crystals
Large lath-like crystals, lO-lO0 ~m long and several micrometers thick,
are formed under conditions of low hydroxyl ions concentration which, for
instance, prevail during the hydration of supersulfated cements or rapid-
hardening cements composed of C2S, C4A3~, C4AF, and CT. Since hydrated
cements containing considerable amount of large ettringite crystals show
high strength but no expansion, i t is proposed that Type l Ettringite
crystals are not expansive.

Type ~ Ettringite Crystals

Small rod-like crystals, typically I-2 pm long and 0.I-0.2 pm thick as
observed by a scanning electron microscope, are formed under conditions
of high hydroxyl ions concentration which, for instance, exist during the
hydration of normal portland cements and many modified portland cements
including Type K, M, and S expansive cements. From high-magnification
electron microscopic observations and surface area measurements by small-
angle diffraction, i t is suspected that the actual size of the ettringite
Vol. 13, No. 3 403
SULFATE ATTACK, EXPANSION,MECHANISMS,ETTRINGITE, ADSORPTION

crystals may even be considerably smaller. Since large amounts of these

crystals are found in concretes deteriorated due to sulfate attack, i t is
proposed that Type 2 Ettringite crystals can either be expansive or a
source of strength, depending on the environmental conditions such as
restraint of the system, stiffness of the cement paste, and the type and
concentration of ions in the contact solution. Experimental observations
show that this microcrystalline ettringite is capable of adsorbing large
amounts of water on the surface, thereby causing considerable volume
changes.
Does Ettringite Form b~ Solid State Reactions?
Ettringite (CAA~'H~) forms prismatic crystals. According to Taylor (5),
broad features of ~he ~ystal structure are polygon-columns of the composition
ICa6[AI(OH)6]" • 24H2016+ whichsurround channels containing anions of the
composition [(~04)3.2H2016". On the basis of structural considerations and
experimental observations by many researchers, i t is generally believed that
during the early hydration period of portland cement ettringite forms by
through-solution reactions. However, from the standpoint of clarifying the
expansionmechanism associated with sulfate attack, i t is not the early reaction
of ettringite formation during the cement hydration but the latter reaction
during the sulfate exposure which is important.
In well-hydrated and moist cement pastes, the A13+ ions are tied up
mostly in the hexagonal-plate crystals of the monosulfate hydrate (C4A~'HI8)
and tetracalci~m aluminate hydrate (C~AH~^), or a solid solution of
the type C3A.CS.HIs- C3A.CN.CI8*. ~ '~ Although due to the limited ionic
mobility in well-hydrated pastes i t is tempting to consider that on sulfate
attack these compounds transform to ettringite by solid-state reactions,
again this does not appear to be the case when the differences in the crystal
structures are taken into account. The structure of the tetracalcium aluminate
hydrate (C4AHIg) consists of layers of the composition ~ Ca4[AI(OH)6] } 4+
between which are the anionic layers of the type [(OH)2.12H20]4". T~e layer
structure of the monosulfate hydrate (C4A~'HI8) is similar to the tetracalcium
aluminate hydrate structure except that the anionic layer is of the composition
[(S03).IZH20]4". According to TaYlor (5) the surface of the cation columns in
ettringite is composed entirely of H20 molecules and they contain more calcium
ions than the cation components of C4AHI9 or C4A~I8 structure. On the other
hand, the anion component of the latter contains many more water molecules than
ettringite. Evidently, due to the large differences in the structural compo-
nents, transformation of these layer-structure hydrates to ettringite by solid-
state is most unlikely.

*The Fss i n portland cement tends to form an iron analog of the type,
3CaO,(Al~O~.Fe~O~).Ca[SOa-(OH)~]-aq, which appears to be more stable i n s u l f a t e
solutionS. ~ . . . .
404 Vol. 13, No. 3
P.K. Mehta

Role of Gypsum in Sulfate Attack

Alkali-metal sulfates and calcium sulfate are the most common sources of
sulfate ions in soils and ground waters. In aqueous environments, the sulfate
ions gradually find their way into the interior of concrete and many complex
physical-chemical changes begin to take place. For instance, let us consider
the monosulfate hydrate f i r s t . I t becomes unstable when in contact with a
solution containing high concentration of sulfate ions where ettringite would
become the stable phase. The through-solution conversion of the monosulfate
to ettringite requires both sulfate and calcium ions from the solution. The
calcium ions concentration of the solution phase would be maintained i f , in
addition to the monosulfate hydrate, some solid CH from the hydrated cement
paste dissolves. This ensures high hydroxyl ion concentration during ettrin-
gite precipitation. Under these conditions Type 2 Ettringite crystals having a
high surface area tend to form, but carefully monitored experiments show that
only a l i t t l e or no expansion occurs during this period.

When adequate supply of the aluminate from the dissolution of C4A~HI8

and C4AHI9 is no longer maintained to the solution phase, the crystallization
of ettringite would cease and gypsum begins. In the advanced stages of the
sulfate attack, many researchers have reported considerable amounts of both
ettringite and gypsum present. At any area of the cement paste where the sul-
fate solution is being regularly replenished by an outside source, the con-
tinued removal of calcium from the solution through gypsum precipitation would
eventually deplete all the solid CH from the area, thus lowering the hydroxyl
ion concentration. What happens when C-S-H and ettringite are surrounded with
crystalline gypsum instead of crystalline calcium hydroxide or, in other words,
the hydroxyl ion concentration of the contact solution becomes low whereas the
sulfate ions concentration becomes high? On the basis of experimental observa-
tions described below, the authorwould like to propose that under these con-
ditions C-S-H starts losing strength and stiffness, and Type 2 Ettringite
crystals become expansive.

To clarify the role of gypsum formation in the sulfate attack, a simple

experimental study was carried out in which the sulfate resistance of two
cements was compared, using an accelerated sulfate immersion test. One cement
was a white portland cement having the calculated compound co~osition:
C3S = 58%, C2S = 22%, C3A = 12%, C~H2 = 4%. The other cement was a portland-
pozzolan cement prepared by blending 80% weight of the white portland cement
and 20% of a reactive pozzolan. The reactive pozzolan was a condensed silica-
fume composed essentially of amorphous s i l i c a , with 20 m2/g surface area by
nitrogen adsorption. Small specimens of neat cement paste (0.55 water-solids
ratio) were moist-cured for 7 days at 50oc before immersion in a 4% sodium-sul
fate solution held at a constant pH (7±0.5) and sulfate concentration. Cylin-
drical specimens were used for measurement of changes in the elastic ~dulus
and prisms were used for determination of linear expansions on sulfate exposure.
Intensity of selected peaks from the X-ray powder diffraction plots was measured
as a semi-quantitative estimate of ettringite, calcium hydroxide, and gypsum
contents. The relative intensitydata are shown in the Figure.
Before the sulfate immersion, no CRA paste was detected in either of the
cement pastes. The control portland cement paste contained considerable mono-
sulfate hydrate but no ettringite. The cement paste containing the reactive
silica showed that a l i t t l e ettringite was present. The monosulfate hydrate was
not detected; instead the presence of a silica analog of monosulfate hydrate was
Vol. 13, No. 3 405
SULFATE ATTACK, EXPANSION, MECHANISMS, ETTRINGITE, ADSORPTION

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AGE OF SULFATE IMMERSION (DAYS}

Effect of Sulfate Immersion on Hydration Products of Cements

suspected. Like the iron analog, the silica analog is known to be resistant to
sulfate attack. Also, as expected, the peak intensities due to crystalline
calcium hydroxide were much larger in the control portland cement paste than in
the paste containing the silica.

As a result of the sulfate immersion, in the control portland cement

paste a large amount of ettringite formed rapidly during the f i r s t 7 days of
immersion but only small linear expansions were recorded in the prisms (avg.
0.416% free expansion). During the 3-7 days immersion period, a large drop in
the calcium hydroxide content with a corresponding increase in gypsum was
probably responsible for a loss in the elastic modulus. Subsequently, during
the 7-I0 days period, the average expansion rose from 0.416 to 2.07%, with no
increase whatsoever in the ettringite peak intensities. The cement paste con-
taining the silica showed only a l i t t l e expansion (0.41%) throughout the entire
14-days immersion period, no loss in the elastic modulus, and much smaller
amounts of gypsum and ettringite. Manyresearchers have observed the loss of
strength in hydrated C3S or alite pastes exposed to sulfate environment. For
instance, alite pastes showed considerable strength deterioration in the
presence of 6% gypsum (6). The exact reason for this phenomenon is not known,
however i t is speculated that sulfate adsorption on C-S-H surfaces reduces
their adhesive ability. Any tendency for expansion on the part of ettringite
in a system which has suffered a loss of stiffness can easily lead to large
dilatations of the paste and cracking.
Concludtn 9 Remarks
Studies on the e t t r i n g t t e expansion phenomenon alone are inadequate to
explain the sulfate-generated deteriorations in portland cement concrete. For
a proper understanding of the deterioration process, possible physical-chemical
406 Vol. 13, No. 3
P.K. Mehta

effects of sulfate ions on all the phases of the hydrated cement paste must be
considered. I t seems that as a result of gypsum formation and sulfate adsorp-
tion by C-S-H, some reduction in the stiffness of the hydrated cement paste is
preceded by large expansions due to ettringite. Only poorly crystalline ettrin.
gite appears to be capable of expanding by water adsorption. I t is proposed
that a drop in the hydroxyl ions concentration and an increase in the sulfate
ions concentration of the environment lowers the stiffness of the cement paste
on one hand, and increases the water-adsorption capacity of the ettringite on
the other hand.
References
(1) H. Uchikawa and S. Uchida, "The Influence of Additives Upon the Hydration
of the Mixtures of II CaO.7AI~O~.CaFo, 3 CaO.SiO2, and CaSO4 at 20oc, ''
Cem. Concr. Res., V. 3, 607-6~4~(197~).
(2) G. Sudoh, T. Ohta, and H. Harada, "High Strength Cements in the C-A-S-~
System," Proc. 7th Inter. Congr. Chem. Cem., Paris, V . I I I , pp. V 152-157
(1980).
(3) P. K. Mehta, "Investigations on Energy Saving Cements," World Cem. Tech.,
V. I I , 166-177 (Ig8O).
(4) T. Thorvaldson, "Chemical Aspects of the Durability of Cement Products,"
Proc. 3rd Inter. Sy~p. Chem. Cem., London, 436-465 (1952).
(5) H.F.W. Taylor, "Crystal Structure of Some Double Hydroxide Minerals,"
Mineralogical Mag., V. 39, 277-389 (1973).

(6) P. K. Mehta, D. Pirtz, and M. Polivka, "Properties of Alite Cements,"

Cem. Concr. Res., V. 9, 439-450 (1979).