Ettringite

Ettringite (AFt) is primarily the product of the hydration reaction between tricalcium
aluminate (C3A) and the setting retarder (gypsum).

From: New Trends in Eco-efficient and Recycled Concrete, 2019

Related terms:

Calcium Silicate Hydrate, Carbonation, Compressive Strength, Aluminate, Calcium

Aluminate, Cement Paste, Hydration Product, Portland Cement, Portlandite, Sulfate
Attack

View all Topics

Calcium Aluminate Cements

Jason H. Ideker, ... Bruno Touzo, in Lea's Chemistry of Cement and Concrete (Fifth
Edition), 2019

12.4.4.2 Rapid Drying

Moisture reduction is a key function of self-levelling compounds used for flooring
applications, such as self-levelling underlay (SLU) (Section 12.5.2). This is usually
termed drying even when it is more a case of water combination in hydrates rather
than loss of water to the atmosphere. The ‘drying time’ is the time at for the
residual moisture (free water) to fall below a given threshold which depends on
the application (typically 3 wt%). Moisture reduction is driven by two mechanisms
(i) internal drying by binding free water within hydrates and (ii) external drying by
water evaporation at the upper surface or diffusion from the lower surface into the
substrate when it is porous (e.g. concrete).

Ettringite binders allows a rapid internal drying for two main reasons:

• For a given quantity of cement, the quantity of water combined in ettringite

crystals is higher than in other hydrates. This is shown in Table 12.6 which
compares the internal drying capacity of different hydrates. The capacity of
ettringite is 85%, meaning that 100 g of anhydrous phases can combine 85
g of water within the crystallised network of ettringite. As a comparison, the
capacity of gypsum is only 27%, whereas it is around 30% for C-S-H.Table •
12.6. Drying Capacity (wt% of Crystallised Water Over wt% of Anhydrous Phas-
es) of Ettringite Compared to Other HydratesDrying Capacity in wt%Ettringite C-
3A ∙ 3(CaSO4)·32H85CAH10113C2AH7.567C3A·(CaSO4)·12H54AH3 microcrystalline54AH3
gibbsite54C 2/3SH1.532C
Ettringite crystals 5/6S2/3Hform
typically 1.8332C 1.33SHquickly
more 2.1732C1.5 S0.67H
than 2.5532CaSO
other 4.2H27
hydrates.

> Read full chapter

Microscopic examination of deteriorat-

ed concrete
T.G. Nijland, J.A. Larbi, in Non-Destructive Evaluation of Reinforced Concrete Struc-
tures: Deterioration Processes and Standard Test Methods, 2010

Massive secondary ettringite (delayed ettringite formation,

DEF)
Ettringite is a primary constituent of hydration of Portland cement concrete. Its for-
mation plays an important role in the control of setting. Minor amounts of secondary
ettringite are often encountered in air voids of hardened concretes, regardless of
the type of cement used. This secondary ettringite, evidently developed in the walls
of the air void, become stable, but is not associated with any cracking. Individual
ettringite crystals are easily distinguished. Less commonly, massive secondary et-
tringite is encountered. Microscopically, this ettringite takes the form of massive
aggregates or bands at the aggregate–cement paste interface, causing debonding,
or filling cracks, accompanied by air voids (almost) completely filled by ettringite
(Fig. 8.19). The majority of the individual ettringite crystals in the aggregates cannot
be distinguished. Cracking may be intense, and, sometimes, massive secondary
ettringite occurs together with ASR (see previous subsection).

Massive secondary ettringite is often denominated as delayed ettringite formation,

DEF. Originally, this term was reserved for secondary ettringite formed in concretes
that are heat or steam cured above 70 °C (Taylor et al. 2001). Above this temperature,
primary ettringite is destabilized. Subsequently, massive secondary ettringite forms,
in which individual needle-like crystals cannot easily be distinguished with the aid of
an ordinary optical microscope. DEF may cause swelling of the hardened concrete,
increase microcracking, increase the capillary porosity, reduce the cohesiveness of
the cement paste and cause debonding of the cement paste from the aggregate par-
ticles. DEF should not be confused with secondary ettringite, which forms in cracks
or air voids in concrete by solution and re-precipitation of primary ettringite. This
secondary ettringite reaction may occur in concretes cured at normal temperatures.

Massive secondary ettringite may also be the result of other causes, either by
infiltration of sulfate from external sources like soils, groundwater, or materials
stored in or at the surface of the concrete (such as fertilizer or artificial manure),
or an excess of sulfate in the concrete itself, especially in historic concretes. Modern
ground granulated blast-furnace slag cements (CEM III/A, CEM III/B) show a good
resistance to sulfate attack. In the past, however, in similar cements (i.e. with similar
slag contents, not supersulfated cements) calcium sulfate was not added to control
setting, but in much higher amounts, as it was considered needed to activate the
slag (Van der Kloes 1924). This surplus of initial sulfate may be a cause of future
massive secondary ettringite.

> Read full chapter

Inorganic cementing materials

Qiang Yuan, ... Cong Ma, in Civil Engineering Materials, 2021

2.1.3.2.4 Ettringite
Ettringite is present as rod-like crystals in the early stages of reaction or some-
times as massive growths filling pores or cracks in mature concrete or mortar. The
chemical formula for ettringite is [Ca3Al(OH)6.12H2O]2.2H2O or, mixing notations,
C3A.3CaSO4.32H2O. Monosulfate: monosulfate tends to occur in the later stages
of hydration, a day or two after mixing. The chemical formula for monosulfate is
C3A.CaSO4.12H2O. Note that both ettringite and monosulfate are compounds of
C3A, CaSO4 (anhydrite), and water, in different proportions. Monocarbonate: the
presence of fine limestone, whether interground with the cement or present as fine
limestone aggregate, is likely to produce monocarbonate (C3A.CaCO3.11H2O) as
some of the limestone reacts with the cement pore solution. Other AFm phases that
may be present are hemicarbonate, hydroxy-AFm, and Friedel's salt. Hydrogarnet
forms mainly as the result of C4AF or C3A hydration. Hydrogarnets have a range of
compositions, of which C3AH6 is the most common phase forming from normal
cement hydration and then only in small amounts.

> Read full chapter

Cements Made From Blastfurnace Slag

Micheline Moranville-Regourd, Siham Kamali-Bernard, in Lea's Chemistry of Ce-
ment and Concrete (Fifth Edition), 2019

10.3.3 Sulfate Activation: Gypsum, Hemihydrate, Anhydrite,

Phosphogypsum
Ettringite and C-S-H are the first phases formed in the presence of sulfate. They
were observed either in SEM or in ESEM and detected by XRD44,45 (Fig. 10.12). AFm
was not observed at any time (in presence of an alkaline solution KOH 0.25 mol/L).
In presence of Ca(OH)2 like in super-sulfated cements, two C-S-H are found around
slag grains. The observed C-S-H is foil like. The inner layer contains higher Al and Mg
than the outer layer. After Brews D.M. and Glasser F.P.46 an M-S-H gel is possible.

Fig. 10.12. Hydration scheme for the hardening of ordinary SCC binder.45 The inner
layer has a lower Ca/Si ratio (Ca/Si = 1.2) than the outer layer (Ca/Si = 1.4).

According to Mobasher et al.,47 the structural evolution of sodium sulfate activated

slag cement corresponds to the formation of ettringite, and a hydrotalcite-like
Mg–Al layered double hydroxide. The most significant changes at advanced ages
were the growth of AFt phase and an increase in silicate chain length in the C-A-S-H,
resulting in higher strength.

> Read full chapter

Pozzolanas and Pozzolanic Materials

Michael John McCarthy, Thomas Daniel Dyer, in Lea's Chemistry of Cement and
Concrete (Fifth Edition), 2019

Ettringite and Monosulfate

The AFt phase ettringite forms rapidly in cements containing natural pozzolanas197
or fly ash.188,198 Ettringite has been observed from 5 h up to 28 days in cements
containing fly ash,188 and up to 1 year in cements containing natural pozzolanas.197
Ettringite can disappear after 3 days,9 being transformed into monosulfate. Its
conversion was noted in low-SO3, but not in high-SO3 fly ashes.177 The conversion
of ettringite into monosulfate depends on the amount of SO3 available and on the
CO2 content of the cement paste. In fact, carbon dioxide reacts with excess calcium
aluminate hydrate and gives monocarboaluminate, thus preventing it from reacting
with ettringite to form monosulfate.199 For this reason, ettringite is often found
co-existing with monocarbonate.

Similar results have been obtained with a cement containing 15% silica fume cured
for 10 years. AFt was associated with a medium content of calcium carbonate, where-
as monosulfate was associated with a low calcium carbonate content.200 Analysis us-
ing analytical electron microscopy revealed that this AFt phase significantly deviated
from the composition of pure ettringite. Table 9.15 shows that the atom ratio of
plain PC pastes and those with 15% silica substitution deviates from the theoretical
values.200 In particular, the ratio is significantly higher than the theoretical value of
2.0. These figures imply that a substitution in the SO4 sites by silica and, presumably,
anion has occurred.200

Table 9.15. Pastes of PC and PC + 15% Microsilica Produced by a Flame Hydrolysis

Process200

Atomic Ratios
Sample Ca/Al
PC 2.73 ± 0.15 2.66 ± 0.86 2.55 ± 0.78
PC + Si 3.06 ± 0.39 2.73 ± 0.69 2.39 ± 0.58
Theoretical pure phase 3.00 2.00 2.00

Atom ratios of the AFt phase for PC and PC + Si, as determined by analytical electron
microscopy.

> Read full chapter

Constituent Materials
Karen Scrivener, in Advanced Concrete Technology, 2003

2.10 Use of CACs in mixed binder systems

An increasingly important use of calcium aluminate cements today is as a compo-
nent of mixed binder systems for specialist applications. The ingredients are usually
blended dry and sold as mortars ready to mix with water. The applications are
typically non-structural finishing operations in buildings, such as floor levellers, tile
adhesives or fixing mortars. Another application is rapid-hardening repair mortars.

Such mixed binders are usually based on combinations of three reacting ingre-
dients – calcium aluminate cements, Portland cement and calcium sulfate. The
calcium sulfate may be in the form of gypsum, anhydrite or plaster (calcium sulfate
hemi-hydrate). Fillers such as limestone and supplementary cementitious materials
such as slag may also be present. In addition these mixes usually contain several
admixtures in dry form (accelerators, retarders, fluidifiers, plasticizers, thickeners).
Fine siliceous sands (and sometimes fine aggregate) are also normally used in these
special mortars as they would be in conventional mortars.

Figure 2.21 shows the common zones of formulation of the CAC, PC and C$

components. Zone 1 concerns blends based on binary mixtures of Portland and
calcium aluminate cement (with more of the former) to which smaller amounts of
calcium sulfate may be added. These mixtures are rapid setting and hardening.

Figure 2.21. Zones of formulation in ‘Building Chemistry’.

It has long been known that additions of CAC to Portland cement can induce flash
setting. The basis of this behaviour is that the added calcium aluminates combine
with the calcium sulfate in the Portland cement added during grinding. This disrupts
the normal set control process of the Portland cement, in which calcium sulfate re-
acts with the rapidly reacting C3A phase of the Portland clinker, producing products
which coat the surface of the C3A and block its further reaction for several hours.
The relative rates of dissolution of the various forms of calcium sulfate (anhydrite,
hemi-hydrate and gypsum) are different, so the amount of CAC that needs to be
added to give flash setting varies with the amount and type of calcium sulfate in the
Portland cement.

Such simple binary mixtures may show rather poor long-term strength develop-
ment. This can be improved by the addition of admixtures or gypsum. Further
discussion of the mechanisms occurring in such system can be found in Amathieu
et al. (2001). As an example a correctly formulated mixture in this zone can have a
working time of 2 hours and shows strength of around 20 MPa after 6 hours.

In such systems the hydrated micro structure is similar to that of Portland cement,
with calcium silicate hydrate being the dominant phase. The quantity of calcium
hydroxide will be decreased and the quantities of ettringite and/or monosulfate
increased according to the relative amounts of CAC and calcium sulfate contained in
the blend. For the amounts of CAC typically used, the metastable calcium aluminate
hydrates are not formed so there is no question of conversion.

The mixtures in Zone 2 are composed of roughly equi-molar amounts of monocal-

cium aluminate (CA) from CAC and calcium sulfate, with minor amounts of Portland
cement. The predominant hydration reaction in this zone is:

(2.6)

In equation (2.6) the formula AH3 for gibbsite is used for convenience, but this phase
is often poorly crystalline. Microstructural examination shows crystals of ettringite
dispersed in a dense alumina-rich matrix. Both these phases are stable phases and
will not spontaneously convert to other phases.

Such mixtures can be controlled to be fluid for a few hours to allow placing and then
harden rapidly. However the main difference, between the mixtures of this zone and
those of zone 1 is their capacity to combine water in the hydrates and so to rapidly
reduce the relative humidity. This leads to their major application as floor-levelling
compounds (Figure 2.22), where the rapid reduction of relative humidity (commonly
referred to as drying) allows them to be overlaid with carpet or floor tiles with a
minimum of delay (as little as 8 hours). Table 2.3 shows the percentage of combined
water by weight in various hydrate phases.
Figure 2.22. Application of floor-levelling compound.

Table 2.3. Percentage of water combined in various hydrates

Phases Formula % H2O

ettringite 3CaO · Al2O3 · 3CaSO4 · 32H- 46
2O

CAH10 CaO · Al2O3 · 10H2O 53

Monosulfate 3CAO · Al2O3 · CaSO4 · 12H- 35
2O

gibbsite Al(OH)3 35
C2AH8 2CaO · Al2O3 · 8H2O 40
C3AH6 3CaO · Al2O3 · 6H2O 28
CSH 1.7CaO · SiO2 · 4H2O 30
Portlandite Ca(OH)2| 24

2.10.1 Stability of ettringite-containing systems

As discussed, ettringite is an important component in all these mixed systems
and questions are posed as to its stability, regarding temperature, humidity, and
carbonation. On the first two issues, recent work published by Zhou and Glasser
(2001) confirms that ettringite has broadly similar stability to temperature and
humidity as C–S–H the principal hydrate found in hydrated Portland cement. It is
important to realize that ettringite occurs as part of a system of hydrates, existing as
a rigid, if porous, solid and not as an isolated powder. Thermogravimetric analysis
shows that the decomposition temperatures of ettringite and C–S–H are very similar,
around 110–130°C.
On the question of carbonation, analogies may also be drawn with conventional
Portland systems. Finely powdered ettringite will carbonate rapidly, as will finely
powdered C–S–H, but when either are part of a hydrate system the kinetics of the
reaction are controlled by the ingress of CO2 into a porous solid. The carbonation of
ettringite eventually leads to calcite, gypsum and alumina:

(2.7)

This reaction leads to the release of water, which helps to maintain a high relative
humidity inside the solid, which impedes the ingress of CO2 gas. However, the loss
of water corresponds to a decrease in the solid volume and an increase in porosity.
Therefore, there will be some loss of strength in materials containing ettringite
that become completely carbonated. For formulations in Zone 1, such strength
losses are negligible and will be compensated for by the continuing increase in
strength due to hydration. For formulations in zone 2 the loss in strength is more
significant, but not catastrophic. Laboratory studies (Scrivener et al., 1997b) of
accelerated carbonation of a composition which had a one-day strength of ~ 30 MPa
showed that the samples stored at 100% CO2 and 60% R.H. had stable strength
of 35 MPa at 3 months (corresponding to complete carbonation) as opposed to a
strength of 45 MPa for the reference sample stored at 60% R.H. with atmospheric
CO2.

2.10.2 Dimensional stability of ettringite-containing systems and

shrinkage compensation
Another issue related to ettringite is that of dimensional stability. By formulation it
is also possible to engineer the initial hydration reaction to produce controlled ex-
pansion and so compensate for the normally observed drying shrinkage of Portland
cement. This is similar to the actions of shrinkage compensation in type K cements.

It is well known that the formation of ettringite is also related to undesirable

expansion during external sulfate attack and in so-called internal sulfate attack or
delayed ettringite formation (DEF) which may occur after exposure to temperatures
> 70°C during curing. However, the relationship between ettringite formation and
expansion is extremely complex. For example, after exposure to temperatures > 70°C
during curing delayed ettringite forms in Portland cement mortars or concretes,
irrespective of whether expansion occurs or not. Extensive studies have shown that
the crystallization of ettringite only leads to expansive forces if it forms in small pores
(~ 50 nm) (Taylor et al., 2001).

Generally it can be said that the expansive formation of ettringite requires:

1 A source of alumina (e.g. calcium alumino monosulfate) distributed in small

pores
2 A source of sulfate, which can locally produce conditions that are supersatu-
rated with respect to ettringite formation.

In the formulated systems described above, such conditions may arise if there is an
excess of calcium sulfate present, such that this does not all react to form ettringite
during the initial reactions. Systems that are correctly formulated have been shown
to be dimensionally stable over several years, even if subject to wetting and drying
cycles.

> Read full chapter

Chemical degradation of concrete

J. Bensted, ... M.M. Page, in Durability of Concrete and Cement Composites, 2007

4.2 External sulfate attack involving expansive ettringite forma-

tion

4.2.1 Basic phenomena

The expansive ettringite form of sulfate attack in concrete exposed to aggressive
ground is probably the most familiar type that occurs in the field (Bensted, 1981a,b)
and was at one time regarded as the only serious phenomenon involved. Indeed
sulfate attack was given a formal definition by the American Society of Testing and
Materials (ASTM) in the 1970s as follows: ‘Sulfate attack can be defined as a chemical
or physical reaction, or both, between sulfates usually in soil or ground water and
concrete or mortar, primarily with calcium aluminate hydrates in the cement paste
matrix, often causing deterioration’ (Bensted, 1981a). Although thaumasite sulfate
attack has come into increased prominence recently (see Section 4.3) and involves
the silicate as well as the aluminate phases, this does not render the above definition
inappropriate insofar as what is now regarded as the conventional form of sulfate
attack is concerned.

Sulfate attack has attracted increasing interest over the years as its complexities
have become more apparent. There have been a number of recent review articles
(Skalny and Marchand, 2001; Santhanam et al., 2001; Bensted, 2002b; Neville, 2004)
and even books on the subject (Marchand and Skalny, 1999; Skalny et al., 2002).
Ettringite formation features prominently in many situations but there are several
other processes, such as the conversion of portlandite to gypsum and reversible
hydration/dehydration reactions of sulfate salts, such as the Na2SO4 (thenardite)
Na2SO4.10H2O (mirabilite) system, that have also been implicated. In this context
it may be noted that there has been disagreement over the terminology used to
classify these various phenomena and some authors consider processes such as the
thenardite/mirabilite transformation to be purely physical phenomena, as distinct
from chemical forms of attack. It is generally agreed that sulfate attack needs the
presence of moisture and it is believed to involve ‘through-solution’ mechanisms,
with transport of sulfate ions through the surface of the concrete or mortar. Normally
such transmission is of extraneous sulfate ions, but internal sulfates within the
structure can also contribute if the amounts contained in the concrete mix materials
are not controlled within acceptable limits (Skalny et al., 2002). An example of the
sort of degradation that may be produced is illustrated in Fig. 4.1.

4.1. Conventional sulfate attack associated with expansive ettringite formation in

a concrete prism (RHS) and non-degraded control prism (LHS).Photograph re-
produced from CEB Design Guide, Durable Concrete Structures, London, Thomas
Telford, 1989.

In its initial stages, sulfate attack may result in a general hardening of the cement
matrix. This usually arises from the pores and voids present becoming filled, through
the ingress of SO42– ions, by crystals of gypsum and/or ettringite, which tend to
increase the overall density of the concrete or mortar. These crystals, which are
formed in the pores and voids, may cause expansion directly by anisotropic growth or
indirectly by increasing the pore water pressure, giving rise to internal stresses that
might ultimately, in specific instances, destroy the concrete or mortar. For instance,
in transforming one mole of calcium hydroxide CH to gypsum CsH2, the volume of
solids is more than doubled (from 33.2 cm3 to 74.3 cm3) and the transformation
of calcium aluminate hydrate and gypsum to ettringite also involves more than
doubling of the volume of solids (Bensted, 1981a; Lea, 1970; Eglinton, 1998).

4.2.2 Exposure conditions

Groundwaters and soils containing sulfate salts may be liable to cause expansive
sulfate attack. Sulfuric acid can also occur naturally in groundwaters and soils
as a consequence of oxidative weathering of sulfide minerals such as pyrite and
marcasite, both of which have the chemical formula FeS2. Oxidation to ferrous sulfate
and sulfuric acid may arise in the presence of oxygen and moisture:

4.4

The reaction commonly stops here unless certain aerobic bacteria are present to
produce further oxidation cycles (see Section 4.7). In undisturbed soils, the position
of the water table is of great importance for determining access of air and therefore
the extent to which oxidation can take place. If the pyrite is always below the
water level, no oxidation occurs, whilst in areas of fluctuating water levels that
permit replenishment of oxygen to the soil, the reaction proceeds readily. If there is
sufficient calcium carbonate or other basic minerals in the soil, the sulfuric acid
is neutralised as gypsum is formed. If not, as in some instances where sulfuric acid
production is marked, the acid may persist in the groundwater (Eglinton, 1998).

Disturbance of natural ground conditions by excavation or drainage is a common

cause of pyrite oxidation by providing access for air. Rapid oxidation has been report-
ed when compressed air has been employed to keep back water during underground
work, as in tunnel construction (Lea, 1970). This can result in large increases of
acidity and in the sulfate content of groundwater. The oxidation of pyrite can be
followed by other reactions that cause expansion, such as production of gypsum
from any calcite present, which gives a solid volume increase of 103%, and the
reaction of gypsum with the monosulfate-hydrocalumite solid solution in hardened
concrete to re-form ettringite. The free sulfuric acid can also attack clay minerals
like illite to form jarosite KFe3(SO4)2(OH)6, a hydrated potassium iron (III) sulfate that
produces a volume 115% greater than that of pyrite. Ground heave can be caused
adjacent to buried concrete structures by production of gypsum and other hydrated
sulfates (Hawkins and Pinches, 1997; Cripps and Edwards, 1997). All these reactions
can give rise to expansive forces within the concrete, which lower the long-term
durability (Bensted, 1981a,b; Eglinton, 1998).
Ettringite is sometimes associated with thaumasite in aggressive ground when
the temperatures are low (normally below ca. 15 °C) and either or both may be
associated with expansion of the concrete if it arises (see Section 4.3). However, the
mere presence of ettringite in a hardened concrete is not per se proof that it has
produced expansion of the concrete. For instance, the ettringite which forms during
the early stages of hydration of Portland cement does not cause expansion as it is not
rigidly packed. Often, this ettringite is only partially converted to monosulfate-hy-
drocalumite solid solution (AFm) during the subsequent stages of cement hydration
(Bensted, 2002c). Thus observation of ettringite, particularly by techniques such as
SEM/EDXA spot analysis that sample only minute volumes within the specimens of
concrete examined, clearly does not provide conclusive evidence of sulfate attack, as
has been noted elsewhere (Bensted, 2002b; Neville, 2004).

Only a minority of the sulfate from the original gypsum ground in with the Portland
cement clinker during manufacture ends up as ettringite, and most of its formation
happens during the first day of hydration at normal ambient temperatures (Bensted,
1983). A substantial part of the sulfate derived from the gypsum actually ends up
in the calcium silicate hydrate (C-S-H phase) either sorbed or in solid solution.
Expansion of concrete takes place when the hardened mono-sulfate-hydrocalumite
solid solution reacts with gypsum (either from external sources or still present in
unhydrated parts of the cement along with unhydrated clinker minerals) to produce
ettringite.

4.2.3 Preventative measures

For concrete in contact with aggressive ground, it is obviously desirable that cement
with a good record of sulfate resistance is used, e.g. a suitable extended cement
containing ground granulated blastfurnace slag (ggbs) or pulverised fuel ash (pfa)
which has been adequately cured prior to exposure. The concrete should be of low
penetrability, having an appropriately low water/cement ratio, achieved through the
use of admixtures where necessary, to minimise the rate of ingress of extraneous
sulfates from the environment into the material. Detailed guidance applicable to
UK exposure conditions has been given in BRE Special Digest 1, which has already
undergone significant revisions since it was first introduced in 2001 and is
currently in its 3rd edition (Building Research Establishment, 2005), as discussed
in Section 4.5.

One of the many difficulties in formulating simple guidance rules stems from
the fact that the conditions to which concrete is exposed prior to coming in contact
with sulfate-bearing groundwater can have a marked influence on the severity of
sulfate attack. Thus even mild atmospheric carbonation can play a significant
role in modifying the surface pore structure of the material, thereby reducing its
penetrability. Current guidance recognises this effect in providing protection to
precast products which are exposed to non-acidic sulfate-bearing environments
(Building Research Establishment, 2005).

As already mentioned, a recent review has highlighted several other features that
contribute to the confused state of knowledge of sulfate attack (Neville, 2004).
Amongst these is the influence of the cation, with sodium, calcium and magnesium
sulfates all having different effects. Sulfate-resisting Portland cement (ASTM Type V
cement), which was developed to minimise reaction with hydration products of the
C3A (aluminate) phase does not offer special protection against attack upon C-S-H or
CH and the combined presence of Mg 2 + and S042– ions can result in the conversion
of these hydrates to magnesium hydroxide (brucite), silica gel and gypsum. The
concomitant lowering of the pore solution pH, due to the low solubility product of
brucite (for which a saturated solution has an equilibrium pH of~10.5), destabilises
the C-S-H and accounts for the fact that magnesium sulfate is more aggressive than
sodium sulfate or calcium sulfate. If the pH is maintained at an artificially high level,
however, as in some laboratory tests involving magnesium sulfate, unrealistic results
may be obtained because brucite can sometimes form an insoluble protective layer
upon concrete unless it becomes mechanically damaged.

Altogether the state of current knowledge of external sulfate attack under field
conditions remains inadequate and although the problem is generally avoidable by
following prescriptive guidance of the kind given in BRE Digest 1 (Building Research
Establishment, 2005) it is difficult to devise appropriate laboratory tests for
assessing the resistance of different types of concrete subject to different exposures;
this problem with performance tests is discussed in further detail in chapter 9 of the
book by Skalny et al. (2002). Various attempts to devise mathematical models that
might serve as aids in predicting performance have been made by researchers in this
field and a recent review of the work appears in chapter 7 of the book by Skalny et
al. (2002) – see also Section 4.6.4 of the present chapter. Unsurprisingly, however, it
is fair to say that progress to date has been rather limited.

> Read full chapter

Concrete Properties
Steve Kelham, in Advanced Concrete Technology, 2003

12.4.2 Delayed ettringite formation

In the alkaline environment of hydrating Portland cement ettringite is unstable at
temperatures above ~ 70 °C. If hydration takes place at higher temperatures, through
the use of steam curing of precast production or through self-heating in large pours,
then ettringite is not formed. Studies of mortars immediately after heat treatment
indicate either no sulfate containing phases or small quantities of monosulfate.
Much of the sulfate is absorbed by the C-S-H and some is in solution in the pore
fluid, particularly in high alkali systems. Similarly, no aluminate hydrates are visible.
The alumina content of the C-S-H is higher than usual and some hydrogarnet may
be detected.

When the concrete returns to ambient temperature this assembly of phases is not
stable and ettringite begins to form and crystals grow in available pore spaces in
the paste structure. In some cases this leads to expansion of the paste and cracks
form through the paste and particularly around aggregate particles. These cracks are
then also filled with ettringite crystals. This damage mechanism is termed Delayed
Ettringite Formation (DEF) and is a form of ‘internal’ sulfate attack. Although no
external sulfate or other ions are involved damage only occurs in wet concrete.

> Read full chapter

Deterioration of concrete in the marine

environment
M. Santhanam, M. Otieno, in Marine Concrete Structures, 2016

5.4 Physical mechanisms of deterioration

The formation of phases such as gypsum and ettringite lead to a lowering of the
quality of the concrete surface zone. The overall effect of the chemical attack is a
progressive reduction in the integrity of the concrete. In other words, the surface
concrete gets weaker and more prone to erosion by the splashing action of the
waves. In this manner, the chemical and physical mechanisms act together to cause
deterioration.

As shown in Fig. 5.1, the wick action created by drying, in addition to the drying and
wetting phenomena caused by the tidal action, creates abnormally high chemical
concentrations at the concrete surface in this zone. After the salt is deposited
on the concrete, there is subsequent evaporation of the water, and the resultant
nucleation and growth of the salt crystals can lead to expansive pressures in the
surface pores of the concrete (Scherer, 2004). The extent of damage created on the
surface depends on the available porosity, the supersaturation of the salt and the
existence of repulsive force between the salt and the pore surface (Scherer, 2004).

Salt weathering is greater in horizontal or inclined surfaces (Neville, 2013), as well as

in conditions where there are prolonged drying spells. Neville (2013) also suggests
 that the dissolution by dew of airborne salts that get deposited on the concrete, and
subsequent evaporation, can also cause salt weathering damage.

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Waste Materials in Construction

J.A. Stegemann, ... R.J. Caldwell, in Studies in Environmental Science, 1997

Calcium Sulphoaluminates
Depending on the tricalcium aluminate and gypsum content of ordinary portland
cement, the maximum ettringite content of the hydrated product at early ages
is approximately 15%; cementing systems containing industrial by-products, such
as fly ash, with lime and gypsum may have a higher ettringite content of, for
instance, 20% (Solem and McCarthy, 1992); expansive cements based on calcium
aluminates could have an ettringite content of up to approximately 50%. Because
of the potential for uptake of contaminants by ettringite mentioned above, use of
high ettringite systems for waste management has been advocated. However, such
systems can be expected to have a different pH response to acid addition than
cements based primarily on CSH.

Although the pH stability of ettringite has not been specifically addressed, some
studies, both in the areas of cement and concrete, and waste management, have
touched on this issue. Day (1992) cites existence of a crystalline ettringite in the pH
range from 11.5 to 11.8, and a non-crystalline phase with a similar composition from
pH 12.5 to 12.8. Ghorab and Kishar (1986) found the pH of an ettringite solution
to be 11.2, whereas a group of workers based at the University of North Dakota
have variously observed pH values from 9.8 to 12, although their most recent work
states that ettringite is not stable below pH 11 (McCarthy, Hassett and Bender, 1992,
Kumarathasan et al., 1990, and Hassett et al., 1989).

Literature values of the solubility product for ettringite range from 10-35 to 10-45
(Day, 1992, and Deng and Tang. 1994), from which the theoretical pH of a saturated
solution may be calculated as ranging between 11.0 and 11.6.

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