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Review
Abstract
Delayed ettringite formation (DEF) can damage concrete that has experienced a temperature above about 70C. Claims that slow release
of sulfate from the clinker can have a similar effect in concrete not thus heated are unsupported. Chemical and microstructural aspects of DEF
are reviewed. Expansion results from formation of ettringite crystals of submicrometre size in the paste, the larger crystals readily observed in
cracks and voids being recrystallisation products. The rate and ultimate extent of expansion are influenced by factors of three types:
chemistry, which determines how much ettringite can be formed; paste microstructure, which determines the stresses produced by its
formation; and concrete or mortar microstructure, which determines the response of the material to those stresses. Alkali present before the
end of the heat treatment can increase expansion, but when present subsequently, it decreases expansion by inhibiting ettringite formation.
Leaching therefore promotes expansion. D 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Delayed ettringite formation; Thermal treatment; Microstructure; Alkalis; Leaching
1. Introduction
Delayed ettringite formation (DEF) may be defined as
the formation of ettringite in a cementitious material by a
process that begins after hardening is substantially complete
and in which none of the sulfate comes from outside the
cement paste. It is known in some cases to have caused
damage in materials that have experienced temperatures
above about 70C. It has been claimed that DEF has caused
damage also in materials that have not been at such
temperatures, but as will be seen, these claims are not well
founded if one excludes the obvious case of cements
containing excessive proportions of total SO3.
Various cases of damage in field concretes have been
attributed wholly, or more often partly, to DEF. Most were
precast products made by elevated-temperature curing [1
4]. Some were mass concretes, in which the temperature
was believed to have risen excessively from the heat of
$
Paper presented by H.F.W. Taylor as the First Della Roy Lecture at
the 102nd Annual Meeting of the American Ceramic Society, St. Louis,
MO, on May 2, 2000.
* Corresponding author. Tel.: +44-15394-41485; fax: +44-1539441485.
E-mail address: hal.joant@lineone.net (H.F.W. Taylor).
0008-8846/01/$ see front matter D 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 8 - 8 8 4 6 ( 0 1 ) 0 0 4 6 6 - 5
684
Fig. 1. Linear expansion data for a mortar cured at 20C and at 100C
followed by storage in water at ordinary temperature. Adapted from Yang
et al. [15].
nate phase is formed at all, it is more likely to be monosulfate than ettringite [11]. Neither experimental data [11]
nor normative calculations [12] favours the view that either
excessive contents or the distribution of clinker SO3 is a
likely cause of damage from DEF in materials that have not
been subjected to an elevated temperature.
Various investigators have made parallel studies of
expansion in mortars or concretes cured at ordinary and
elevated temperatures [13 18]. Fig. 1 shows typical results.
The mortar cured at an elevated temperature expanded
markedly and that cured at about 20C did not. Many
similar results have been reported, even for cements containing more than 5% of total SO3 [16].
3. Ettringite in cement paste and concrete
It is often said that ettringite forms in the early stage of
cement hydration but is later replaced by monosulfate.
This is true up to a point, but with many cements, as
Copeland et al. [19] noted many years ago that ettringite
persists indefinitely. Small crystals are inherently unstable
relative to larger ones because of their greater surface
areas, and it follows that ettringite formed as small crystals
in a cement paste tends to recrystallise in any voids or
cracks that may exist in a mortar or concrete. It follows
that the presence of relatively large ettringite crystals, of
the kinds readily seen by petrography or SEM, does not
necessarily indicate distress. We have discussed this more
fully elsewhere [20]. Erlin [21] noted that the presence of
ettringite or other phases in bands at aggregate boundaries
shows only that the paste has expanded and that in order to
find why it has expanded, additional evidence is needed.
685
Fig. 2. S/Ca atom ratios vs. Al/Ca atom ratios for the outer C-S-H gel in two
mortars, in each case directly after heating at 90C and after a subsequent
200-day storage in water at ordinary temperature. Mortar B expanded
during storage; Mortar A did not. Mon = monosulfate; Ett = ettringite
(Famy [18]).
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687
688
689
690
691
Acknowledgments
We thank Professor G.W. Scherer for helpful discussions
and Professor R.J. Kirkpatrick for the provision of data in
advance of publication.
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