Magazine of Concrete Research, 1990, 42, No. 153, Dec.
, 249-264
Sulphate attack on concrete
C. D. Lawrence*
BRITISH CEMENT ASSOCIATION
The types ofdisruption observed during sulphate attack
on mortars or concretes, and thechemicalprocesses
involved, are summarized. Concrete mix design and
binder type have an important influence on concrete
performance in sulphate environments. The present UK
Codes of Practice (based on B R E Digest 250) reflect
the technical information available for various binders
currently used in the UK. Sulphate-resisting Portland
cement is apurpose-made cement designed to resist sul-
phates. The chemical factors giving rise to its sulphate
resistance are well understood, and its performance has
been uniformly good in experimental trials throughout
the world. This cement is the standard by which other
binders are judged, and should continue to be the
preferred binder for concretes expected to withstand
sulphate concentrations in ground waters greater than
3000mg S 0 4 - - / l . Althoughpartial replacement of
ordinary Portlandcement (OPC)by various latent
hydraulic binders can lead to improved sulphate resis-
tance, the mechanism by which these latent hydraulic
binders act is not established. There is well-documented
evidence of considerable variability of performance for
OPClpulverized fuel ash and OPClground granulated
blastfurnace slag combinations, and the ability of com-
posite cements to provide a guaranteed performance is
suspect. A more rigorous approach towards the selec-
tion of composite binder components in the appropriate
standardsis required before their use can be recom-
mended in ground waters where sulphate levels exceed
3000 mg SO,- - 11.
Introduction
The susceptibility of mortars and structural con-
cretes to attack by sulphate-bearing soils and ground
*British Cement Association, Wexham Springs, Slough SL3 6PL,
UK.
waters has been known formany years. Sulphate-
resisting Portland cement (SRPC) was developed in
the 1930s by modifying the chemical composition of
ordinary Portland cement (OPC). Many laboratory
and field studies have been carried out, all of which
have shown SRPC to be very successful in producing
highly resistant concretes.
SRPC hasadvantages which make it an ideal
cement in many ways. The alkali content is low, so
that careful choice of aggregate to minimize the risk of
alkali-silica reaction is unnecessary. It has a low rate
of heat evolution, and is less likely to produce con-
cretes that crack through thermal cooling effects in
massive structures. SRPCcan also beused where
reduced temperaturesduringcuringare likely, or
where only limited curing can be given.
In spiteof this success, newlaboratory studies relat-
ing to sulphate attack continueto appearin the litera-
ture. These contradictory perceptions of the need for
further research into sulphate attack arise from the
introduction ofnew ranges of binders that contain
OPC together with a proportion of a latent hydraulic
binder (usually a by-product or waste material from
another industry). Because the chemical analysis of a
composite cement does not yield a satisfactory esti-
mate of itssulphate resistance, there is a need to
develop reliable performance tests for use in sulphate
conditions.
TheEuropeanConcretePre-StandardENV 206
follows the German standard in specifying the use
of a sulphate-resisting binder where ground water
sulphateconcentrations exceed 500 mg SO,/l, but
leaves the choice of binderto individual national
codes. InGermany, high percentage ggbs/Portland
composite cements, made in the cement factory,
are regarded as equivalent toSRPC.In France,
plain Portland cements of limited C3A level are
regarded as closely similar in performance to factory-
249
Lawrence

Table 1. European cement standard (draft prENVl97, June 1989): cement

composition, spec1jication and conformity criteria
Cement Designation Proportion by mass excluding CaSO, : YO
type
Portland Natural PFA Filler
cement pozzolana
clinker

K S Z F
~~ -
CE I Portland cement 95-100 - -

CE I 1 Portland-composite cement 65-94 0-27 0-23

CE 11-S Portland-slag cement 65-94 6-35 -

CE 11-Z Portland-pozzolana cement 72-94 - 6-28

CE 11-C Portland-fly ash cement 72-94 - -

CE 11-F Portland-filler cement 80-94 - -

CE 111 Blastfurnace cement 20-64 36-80 -

CE IV Pozzolanic cement > 60 - 40

made CPJ composite cements, having restricted C,A
levels.
In the UK, there is significant production of com-
positecementsbutsecondarybindersare usually
added separately to the concrete duringmixing (mixer
combinations). The degree ofsulphate resistance estab-
lished for factory compositesis sometimes assumedto
be valid for mixer combinations; however, documented
field experience of sulphate exposure for mixer com-
bination concrete is limited. While this approach may
be justified in less onerous exposure conditions or in
less importantstructures,it may not be justified
where such decisions will adversely affect the life of a
structure.
European cement standard
Table 1 gives composition, specification and con-
formity criteria under draft prENV 197. Pozzolanic
cement,type CE IV,cancontaineithernatural
pozzolana or PFA. Up to5% addition of unspecified
bindermaterial (ggbs, natural pozzolana, PFAor
filler) can be made to all bindertypes, except type CE
11, with the proviso that further additions of a com-
ponent already present as a major constituent may
not be made.
The eight binder types can bespecified in two
strength classes (42.5 and 32.5), each of which may be
high early strength (R)or normal, making 32 binders
in all. OPC (BSI 2) is similar to type CE I strength class
42.5; RHPC (BS12) is similar to type CE I strength
class 42.5R; and CFPC (BS12) is similar to type CE I
strength class 32.5R.
The usual addition of calcium sulphate is required
for all binder types in order to regulate the setting
time. The maximum permitted level for SO, is gener-
ally 3.5'%0, exceptthat type CE I l l may contain up to
4.0%. Other binder types in the strength class 42.5R
may also contain up to 4.0% SO,. These limits are
characteristic values ratherthanabsolutemaxima,
250
and may be exceeded byup to0.5% SO, in 10% of the
samples taken.
There is noattemptto standardize SRPC in
ENV197 at the present time.
Concrete codes for sulphate environments
BRE Digest 250 recommendations (1986)
The recommendations are summarized in Table 2.
The cement contents in the table refer to concretes
having 20mm nominal maximum size aggregate. To
maintain the cement content of the mortar fraction at
similar values, the minimum cement content shouldbe
increased by 50 kg/m3 for 10 mm nominal maximum
size aggregate and decreased by 40 kg/m3 for 40 mm
nominal maximum size aggregate. The table recog-
nizes that for improved sulphate resistance, minimum
replacement levels for OPC of 25% PFA or 70% ggbs
are required.
Note that in class 2sulphateconditionsa lower
maximumwater/binderratio(anda higher binder
content) is required forcomposite cementswhere
mixer combinations with a lesser proportion of PFA
or ggbs are envisaged, as compared with composite
cementswith at least the recommendedminimum
proportions of PFA or ggbs.
In class 3 sulphate conditions, a higher maximum
water/binder ratio (and a lowercement content) is
permissible for SRPC than for OPC-PFA or OPC-
ggbs composites(havingmorethan the minimum
replacement levels of latent hydraulic binder suitable
for these sulphate conditions).
For class 4 and class 5 sulphate conditions, only
SRPC and SSC binders are allowed. Both OPC-PFA
composites and OPC-ggbs cements are excluded in
the UK codes for concrete exposed to these sulphate
conditions. Where the sulphate concentrationexceeds
6000mg SO,- -/l, the concrete must be protected by
being coated with a suitable paint or enclosed by an
impermeable membrane.
Magazine of Concrete Research, 1990, 42, No. 153
 Sulphate attack on concrete

Table 2. Summary of BRE Digest 250*

Severity of the environment Class 1 Class 2 Class 3 Class 4 Class 5

mg SO,- -/kg in soil 0-2400 2400-6000 6000- 12000 12000-24000 > 24000
mg SO,- -/I in ground water 0-360 360- I440 1440-3000 3000-6000 6000

Maximum water/binder ratio O.S/O.55 0.45/0.S 0.45 0.45 + protection

Minimum binder content : kg/m’ 330/310/280 380/330 370 370

Binder type OPCt

OPC-PFAt
OPC-ggbst
Blastfurnace Blastfurnace
cement1 cement11
(70-90% ggbs) (70-90% ggbs)
OPC-PFAS OPC-PFAII
(2540% PFA) (2540% PFA)
SRPCg SRPP SRPC SRPC

*RHPC can be substituted for OPC in this table. In class 1 sulphate conditions, there is no special requirement for binder type.
tMaximum water/binder = 0.5, minimum binder content = 330 kg/m’.
$Maximum water/binder = 0.55, minimum binder content = 310 kg/m’.
6Maximum water/binder = 0.55, minimum binder content = 280 kg/m’.
(/Maximum water/binder = 0.45, minimum binder content = 380 kg/m2.
’IMaximum water/binder = 0.50, minimum binder content = 330 kg/m’.

Cembureau recommendations (1978)
The current draft of the new European Standard
prENV 206 (Concrete-Performance, production,
placing and compliancecriteria) is based on the
recommendations of Cembureau (Table 3).
The CEN Pre-StandardENV 206 states that a
sulphate-resisting cement should be used (without
specifying the type of cement to be employed) where
sulphate concentration in the ground water exceeds
500 mg SO, -/l or where the sulphate concentration
-
in the soil exceeds 3000 mg SO,- -/kg. In France and
Germany, SRPC, SSC and high percentage blast-
furnace slag composite cements are regarded as equally
effective in resisting sulphate attack.
Nature of sulphate attack on concrete
Sulphateattack on concrete is characterized by
an expansion which eventually leads to cracking or
softening of the outer layers. Strength may increase
slightly during initial stages of the attack, but there is
some evidence that weakening of the microstructure
precedes overall expansion.’ A densification of the
microstructure is reported’ during sulphate attack on
Portland cement pastes by MgSO, solution (7900mg
SO,- -/l). A preferential softening of the outer layers
occurs on immersion in plain water if excess sulphate
is uniformly distributed within a mortar, suggesting
Table 3. Cembureau recommendations
Severity of the environment Class 1
that uptake of water may be a controlling factorin the
disruption process.
Chemical reactions between sulphate and set paste
It is usually- agreed that expansion of Portland
cement based products in sulphates can be associated
with the presence of ettringite, but the quantity of
ettringite produced does not correlate with the result-
ing e x p a n ~ i o n . ~
Work
. ~ on expansive cements’ also
showed a lack of correlation. Similar amounts of
ettringite have sometimes been reported to be
produced by SRPCandOPC pastes in sulphate
environments.6
Environmental sulphates must first diffuse into the
concrete, but, because of the much more rapid rate of
diffusion of hydroxyl anions as compared with both
sulphate anions and the associated cations, the dif-
fusion process approximates to oneof replacement of
hydroxyl within the concrete by sulphate. The nature
of the cation partlydetermines the rateof diffusion of
the sulphate into the concrete.
Individual chemical reactions between sulphate and
the various cement hydratescan be identified as
follows.
( a ) A reaction between the crystalline Ca(OH), in the
hydrated cement and the environmental sulphate
occurs, yielding soluble hydroxide together with
Class 2 Class 4 Class 3 Class 5

mg SO,/I in ground water < 400 400-600 6000 3000-6000 600-3000

Maximum water/binder ratio 0.55 0.5/0.55 0.5 0.45 0.45 + protection

Binder - - Sulphate-resisting cement

Magazine of Concrete
Research, 1990, 42, No. 153 25 1
Lawrence
.
crystalline CaSO, 2H,O-
2Na+ + SO,- + Ca(OH), + 2H20
-
= 2Na+ + 2 0 H - + CaSO,.2H,O
Calcium silicate hydrate in set cement reacts with
environmental magnesium sulphatesolutions
(and to a lesser extent sodium and calcium sul-
phate solutions), yielding crystalline CaSO,.
2H,O. The concrete maybe partlyaltered by
deposits of Mg(OH), in the surface,which form a
protective layer.
The gradual removalof calcium hydroxide and
its replacement with calcium sulphate in (a) and
(6) above result in loss of strength, but expansion
doesnot usually occur.However,substantial
depositsof CaSO,.2H,Owithin the silicate
hydrate structuremay cause expansion by gypsum
crystal growth in weakened pastes.
Environmentalsulphates react withthe
cal-
ciumaluminate/calciummonosulphoaluminate
hydrates in the hydratedcement, formingettringite
3Ca0. A1,0,. CaSO, . 12H,O + 4Naf
+ 2SO4-- + 2Ca(OH), + 2 0 H 2 0
= 3 C a 0 . A1,0,. 3CaS04.32H2O
+ 4Na+ + 4 0 H -
Theformation ofettringite usually results in
expansion and eventually in disruption.
Both ettringite and calcium monosulphoalu-
minate analogues are formed by the ferrite and
aluminoferrite phases (C2F, C4AF andC,A,F).7
The morphology of the ettringites obtained from
hydratingC,AF/Ca(OH),/CaSO, . 2H,Omix-
tures is somewhat different from that obtained
from the corresponding mixturesusing C, A, and
appears to be amorphous rather than acicular.*
The exact mechanism of expansion associated
with ettringite formation is disputed. A possible
process
is ettringite
crystal
nucleation and
growth. Expansion is thus avoidable by increas-
ing the solubility of the ettringite (by reducing
Ca(OH), levels, or increasing the temperature),
so allowing dissolution/recrystallization processes
to occur and encouraging redistribution of the
crystals to any available free pore volume.
An alternative hypothesis for sulphate expan-
ion'.^ is that finely divided or colloidal ettringite
forms in the early stages of sulphate attack, which
then attracts waterfromtheenvironment by
osmotic forces and so generates expansion.
Theformation of thaumasite, Ca,Si(OH), . mortars in saturated CaSO, solution
12H20.SO,. CO,,has been proposed as the
mechanism of expansion and disruption of auto-
claved dolomiticaggregate mortar in sodium
252
sulphate solutions at reduced temperatures (near
5OC)," and in exposed rendered brickwork.'' This
compound does not contain alumina; the disrup-
tion of pure silicate systems has been observed in
sulphate environmentsat reduced temperatures.I2
Penetration of sulphate into concrete
The penetration of chloride into mortars has been
foundto be dependenton the composition of the
~ e m e n t .Reported
'~ values for chloride diffusion coef-
ficients are 0.1-1.2 x 10-'2m2/sfor the various
binders.I4
The diffusion rate of SO4- - ions appears to be
muchlower thanforchloride,and may not be as
sensitive to binder type. OPC and SRPC pastes were
foundto give diffusivities of 0.6-0.9 x 1 0 - ' 4 m 2 / ~
after 3 months' water cure.I5 The depth of penetration
of sulphate ions into Portlandcement and OPC-30%
PFA pastes has been investigated:"j in 4% Na,SO,
solution (27 048 mg SO,- -/l) at pH7,a marked maxi-
mum in SO, level was obtained at a depth of pene-
tration of 0.5 mm." Diffusivity values for sulphate
ion ingress were calculated at 0.56-1.34 x m2/s
for both OPC andOPC-PFA pastes. The penetration
of Cl-, SO,- and Mg+ ions into SRPC concrete
- +
from sea water evaporators (runningat 50-1 10°C) in
desalination plants showed sulphate penetrating
further than chloride after 521 days."
Paste systems that werevulnerable to sulphate
attack tended to produce large quantities of ettringite
on exposure to sulphates; systems that were resis-
tant formed only minor amounts." Where sulphate-
resisting slag cementsweresuspendedin sulphate
solutions,ettringiteformed readily, indicating that
resistance to diffusion of sulphateinto the blast-
furnace cement paste microstructure was of primary
importance in determining the sulphate resistance of
slag cements.
Sulphate environments
CaSO, solution
The durabilityof lean mortar prisms has been inves-
tigated in saturated calcium sulphate solution and also
in Na,SO, and MgSO, solutions.2n.21 The expansions
in sodium and calcium sulphates were similar. The
effects of calcium and sodium sulphate solutions on
the compressive strength of 12.5mm cement paste
cubes havebeen reported,22 and similar reductions
in strength were reported in bothsolutionsfor
plain Portland, OPC-trass and OPC-slag composite
cements.
The performances of a group of Portland cement
(1440mg
S 0 4 - - / l ) and in 5% Na,SO, solution(33810mg
so4--/l) havebeencompared.,, The differences in
behaviour of certain cements in these two solutions
Magazine of Concrete Research, 1990, 42, No. 153

was attributedto differences in the mechanism of
disruption,thesodiumsulphatesolutionforming
gypsum within the pastes while the calcium sulphate
solution gave rise to ettringite.
Comparisons of the performanceof 130commercial
binders in saturated CaSO, solutionare given in
Ref. 24. The performance of binders in this sulphate
environment was usually good, except for the OPCs.
The C,A content of plain Portland cements could be
correlated inversely with performance. CPJ cements
andOPC with only 15% latenthydraulic binder
(ggbs, PFA or natural pozzolana), performed less
well. The blastfurnace slag content of slag cement
binders (15, 30 or > 70% slag) did not give a clear
relationship with performance.
N a 2 S 0 4and K 2 S 0 4solutions
The sulphate resistance of a large number of dif-
ferent binders has been examined using mortar bar
expansions and dynamic modulus tests.’ There was a
significant relationship between the C,A (Bogue) con-
tent of Portland cements and the rate of expansion.
The analysis of the performance of 3 x type I Portland
cements, using a group of 14 pozzolanas (nine class F
PFAs, two class C PFAs, two natural pozzolanas and cement clinkers, gypsum and blastfurnace slags has
one silica fume), showed that for high C,A Portland
cements (13-1 and 14.6% C,A) blending with
pozzolanas did not,in general, result in a performance
equal to that of type I1 Portland cements. For type I
Portland cement with 9% C,A, blending with 30%
pozzolana usually resulted in performance equal to
that of type I1 Portland cements. A relation between
C,A percentage and expansion for both plain Port-
land and OPC-PFA composite cement mortars was
noted.,’
After 10.5 years there was little evidence of disrup- wider range of replacement levels, notably where the
tion for slag mixes from the strength or expansion
tests in Na,SO, solution (3000 mg SO,- -/l), but the
type I1 cement concretes showed strength loss,26while
the Portland cement mixes showed varying degrees of
damage, which increased as the percentage of C,A in
the cement increased. In 50000mg SO,- -/l solution
(Na,SO, and K,SO,) a similar pattern was evident,
except thatthe 50% slag mixeswere beginning to
show accelerating expansionratesafter 2800 days.
The expansions were greater for thepotassium sulphate
solution.
The performancesof SRPC, OPC, blastfurnaceslag
cements (30 and60% slag), and aPortlandtrass
cement (26% trass) in 4% Na, SO, solution (27 040 mg C, A. The Germanflat prism test has been adopted in
SO,- -/l), controlled at pH7, have been compared.,,
The SRPC andthe 80% slag cement performed equally
well; thetrass cement andthe 30% slag cement
performed poorly. Mixer combinations of an ASTM
type I Portland cement were examined with 16 PFAs
of varying composition, at replacement levels of 25
and 40%.27 was It deduced that overall composition of
the PFA was not relevant to the sulphateresistance of
Magazine of Concrete Research, 1990, 42, No. 153
Sulphate attack on concrete
PFA blends. Two of the five bituminousPFAs,
having low CaO contents (Class F), did not improve
the sulphateresistance of the cement. Three out of the
eight sub-bituminous PFAs studied showed poor per-
formances, and analysis showed the presence of
monosulphoaluminate hydrate before exposure to the
sulphate solution.
The C,A content of the Portland cement was an
important factor determining the sulphate resistance
of composite cements containing PFA or ggbs.,* It
was concluded that replacement by PFA of the order
of 40% was required to transform the sulphate resis-
tance to 2% Na,SO, solution (1 3 524mg SO,- -/l) of
an OPC having 14% C, A to that of a 9% C, A OPC,
and that a > 50% replacement by blastfurnace slag
was required.
The addition of > 5% silica fume to a slag cement
increased sulphate resistance in Na,SO, solution
(0.26 mol/l, 24 980mg SO,- -/l).29 Where more than
5% replacement by silica fume was made, mortar bar
expansions were equal to or smaller than those for
similar SRPC cement mortars.
The influence of slag percentage on the sulphate
resistance of blends of separately ground Portland
been investigated, in Na,SO, solution (29 750mg
SO,- -/l), using the Koch-Steinegger method of
flexural strength determination.” Blending slag that
contained 17.7% A1,0, with Portland cement clinkers
containing 8 or 11YOC,A produced a sulphate-resisting
binder if the replacement level of the slag exceeded
60-70%, but below this replacement level the binder
remained non-resistanttosulphate.Certaincom-
binations of high Al,O, slag andPortland cement
clinker showed poor sulphate resistance over a much
slag was coarsely ground. Binders utilizing high
C,A Portland cement clinker were more sensitive
tothe slag composition, fineness and percentage
replacement.
Results from a co-operative programme to inves-
tigate the influence of A1,0, contents of blastfurnace
slags have beenreported,’ at replacement levelsof
Portland cement clinker by slag of55-70%,using
both theflat prism expansion test and flexural strength
measurement. Changes in percentage of Al,O, in the
slag from 10.5 to 18.7%, holding the slag replacement
value constant at 65%, resulted in no change in sul-
phate vulnerability, using clinker with 7.8 or 10.2%
investigation of the performance of slag cement^.^'
After 8 years, the data showed OPC-70% ggbs
cements having virtually zero expansion, while the
SRPC mortars disintegrated at this time in Na,SO,
solution (30000mg SO,- -/l).A detailed study of
the performance of plain Portland and slag cement
mortars has been published.,,
Tests carried out by the Portland Cement Associ-
253
Lawrence

1200 r

- l
E Q /
/ a

0 Ref. 38
0 Ref.41
Ref. 44
A Ref. 40

0 2000 4000 6000 8000

Sulphate concentration: mgA

Fig. 1. Concentration of magnesium ions plotted against concentration of sulphate

ions in representative selections of UK ground waters: analyses with > 100mg Sol/!

ation33.34In. natural Na,SO, soils involved wetting/
drying and absorption of sulphate solution into the
concretes. For plain Portland cements, the C,A con-
tent determined the levelof deterioration, which
increased as the C3A level increased from 0 to 12.6%.
For the blastfurnace Portland cement (40% ggbs), a
poorer performance was obtained than for the type I
Portland cements from whichit was derived. Slag
cements made from Portland cement clinker contain-
ing 7% C3Awere more durable than those containing shows how the magnesium content tends to increase as
10.2% C3A. The addition ofa type F PFA to a type
I cement gave improved performance at both 20 and
40% replacement levels, for all levels of cement con-
tent. Predictions of the long-term field performance
from laboratory tests, involving repeated wetting and
drying with Na,SO, solution, indicated that com-
posite cements derived from type I1 and type V Port-
landcements with pozzolanas should have greater
durability than the plain Portland cement concrete^.^'
However, 6 out of the 34 pozzolanas examined did not
showimprovedperformance, and wide variations
were observed even with pozzolanas from the same
source.
The durabilityof building mortars in terms of visual
appearance hasbeen investigated by allowing samples
to absorb K2S04(20000mg SO,- -/l) solution and
then subjecting a fraction of them to f r e e ~ e l t h a w . ~ ~continued
The test method was designed to simulate the factors
operating on a severely exposed face of a mortar bed
in external facing brickwork. SRPC was found to be
particularly effective under these conditions.
The flexural strength measurement hasbeen used to
examine theperformance of 41 cements, including
plain Portland cement and composite cement^.^' The
flexural strength reached a maximum for the speci-
mens exposed to Na,SO, solution (29 800mg SO,- -/l)
and the time taken to reach this maximum correlated
254
inversely with the C3A content of the plain Portland
cements. Composite cements containing PFA orggbs
showed much greater times to maximum strength.
MgSO, solution
Magnesium sulphate occurs widely in ground
waters in the UK and elsewhere, and is a major com-
ponent of sea-water. Fig. 1 summarizes data from
over 500 analyses of water samples from the UK, and
sulphate level increase^.^^.^' Concentrations of sul-
phate and otherions in ground waters tend to increase
during periods of dry weather.,'
The expansion of mortarbars containing either
OPC (Canadian type 10) or SRPC(Canadian type 50),
with or without 15% replacement by a sub-bituminous
fly ash, hasbeen reported.,, Specimens were immersed
in sulphatesolutions (Na,SO,, 6762 or 67 670mg
SO,- -/l and MgSO,, 7997 or 79970mg SO,- -11). In
6762mg SO,- -/l Na,SO, solution,OPC/fly ash
mortarbars expanded by 0-018% and0435% in
270 days, while the plain SRPC showed negligible
expansion (less than 0.02% in 300 days). In 7997mg
SO,- -/l MgS0, solution, the expansions were much
-greater-the two OPC/fly ash mortars expanded by
0.05% and 04)75% respectively; the SRPC mortars
.~~ to show negligible expansion (0.02%).
An OPC-20% PFA blend concrete was much more
resistant than the corresponding plain OPC concrete
in Na, SO, solution (1 8 000 mg SO, -/l), and equal in
performance to SRPC concretes. In MgS0, solution
(18 000mg SO,- -/l) they were less re~istant.,~
The performances of 130binders were compared by
measuring the strengthof half-immersed prisms in the
MgSO, solution (19490mg SO,- -/I) and sea-water.',
In MgSO, solution, the completely immersed half of
the specimens showed good performance for the
Magazine of Concrete Research, 1990, 42, No. 153

SRPC and type I1 Portland cement mortars, as did
theCPJ cements with 15% ggbs, PFAornatural
pozzolana. The CHF-CLK slag cements with > 70%
slag performed best of all, but CPF slag cements with
30% ggbs performed poorly, as did the OPCs. The
non-immersed half of the specimens normally per-
formed better than the immersed half, but in the case
of slag cements thenon-immersed half performed very
badly while the immersed part remained in excellent
condition. In sea-water the performance showed little
relationship to the C,A level in the cements. Cements
containing 15% latent hydraulic binder (ggbs, PFA or
natural pozzolana) performed well in sea-water, at a
level, on average, near to that of SRPCs. The blast-
furnace slag content of slag cement binders correlated
well with performance; the greater the slag content,
the more resistant was the binder.
Increasing the SO, level to 2-4% improved the
sulphate resistance of lean mortar prisms to MgSO,
solution.44 The C,A content of the Portland cement
was a significant factor.
The effectiveness of replacing 25% of OPC and
SRPC with PFA in MgSO, solution (4200mg SO,/l)
has been reported. Most plain OPC mixes suffered
totaldestruction; all SRPC mixes showed minimal
signs of attack and continued to show strengthgains;
bothOPC-PFAandSRPC-PFAcomposite mixes
showed minimal signs of attack but some strength loss
was apparent between 2and 5 years.45 In MgSO,
solution (18 000 mg SO,- -/l), most OPC mixes
suffered total destruction and all SRPC, OPC-PFA
andSRPC-PFA blend mixes suffered substantial
damage,the lower cement content mixes suffering
particularly. SRPC-PFA blends behaved worse than
plain SRPC at lower binder content; for the higher
bindercontent mixes, OPC-PFA,SRPC-PFA and
SRPC mixes performed similarly. In Na, SO, solutions
(18 000 mg SO,- -/l), OPC-PFA composite cements
and SRPCshowed no visible signs of attack, although
the strengthgains were not asgood as for water-stored
specimens.
Theexpansion of neat cement pastebarsmade
from type I (l 1.4% C, A) and type V (0% C, A)
Portland cements has been reported.Agelatinous
coating of Mg(OH), was always observed on speci-
mens stored in magnesium containing solutions. Two
competing factors were proposed: the efficiency of the
surface coating of Mg(OH), in preventing attack, and
the increased attackdueto increased sulphate ion
c~ncentration.,~
A good correlation was found between the C, A
content of plain Portland cements and the rate of
attack, with an upper limit for sulphate resistance of
5.5% C,A.,’ Pozzolanic cements formed from a range
of natural and artificial latent hydraulic binders per-
formed better in Na,SO, solutions than in MgSO,
solutions,but no relationship between theircom-
position and performance could be discerned. High
Magazine of Concrete Research, 1990, 42, NO.153
Sulphate attack on concrete
temperature
steam
curing was
very
effective
in
promoting sulphate resistance.
Sea-water and chloride solution
The results ofthe RILEM technical committee
32-RCA review ofsea-water attack onconcrete4*con-
cluded that, if the concrete was of good quality, all
binder types gave good service in marine environ-
ments; OPCs with C,A contents < 8% were par-
ticularly suitablefor sea-water conditions,as were
high slag blastfurnace slag cements and pozzolanic
cements.
A series of very long-term studies was reported:49
200mm cubes were exposed to sea-water in outdoor
sites. It was concluded that blastfurnace slag cements
with high slag contents (CLK slag > 80% and CHF
slag > 65%) have very good resistance to sea-water;
slag cements with less slag (CPF, ggbs = 35% and
CMM, ggbs = 50%) also had good resistance to sea-
water provided that the C,A content of the Portland
cement clinker component wasless than 8%. For
Portland cements the C,A content was important, an
upper limit of 8% being satisfactory.
Tests of mortar specimens in sea-water and MgSO,
solutions (5844mg SO,- -/l), using a wide range
of cement types, are summarized and discussed in
Ref. 50. These indicate a superior performance for
slag cements: the slag cement mortars were reduced to
55-100% of the water cured strength, while all the
Portland cement mortars were completelydisintegrated
(Fig. 2).
The effect of sea-water on a range of binders is
reported in Ref. 16: cement pastes were made at water/
cement (w/c) ratiosof 0.3 and 0.5 from type I, TI
and V cements after 14 days’ cure. The attack was
monitored by length change measurements over a
period of 254 days. Expansions shown by types I and
I1 cements were considerably greater thanforthe
type V cement in each case. The amounts of ettringite
forming in the three cement pastes did not correlate
with the different expansions produced. TheC3A con-
tent of aPortland cement was one of thefactors
determining level of
Although slag cements have usually been thought of
as providing high resistance to sea-water attack,
recent data suggest that slag cements do not perform
well in freezing sea-water condition^.^^ After 8 years
some specimens showed significant surface deterio-
ration, the amount of deterioration generally increasing
with increasing w/c ratio and increasing replacement
levels for the type I cement with slag.
The resistance of Portland cements to sea-water has
been analysed in terms of their compo~ition.’~ was It
deduced that the SO, content of the cement was the
dominant factorin the first two years of exposure, but
thatat later ages the C,A content became more
important, and thefineness of the cement finally deter-
255
Lawrence

&?l Blastfurnace slag cement

“
m
5 10

Storage tme. years

Fig. 2. Relative compressive strengths of mortars stored in sea-water (600 kg cement,

1500 kg sand, WIC= 0.39)’’

mined the resistance, i.e. the finer the cement the more
resistant were the mortars.
The disruption of concretes by the action of cold
sea-water has been examined.55Two non-air-entrained
concretesandthreeair-entrainedconcretes were
employed, with andwithout silica fume or blast-
furnace slag.Silica fume increased the resistance of the
concretes and was moreefficient than ggbs. Attack by
MgCl, solution (2000mg Mg+/l) caused a coarsening
of the pore structure of Portland cement pastes.,
A method of examining the behaviour of cement
mortars exposed to hot sea-water has been de~cribed.’~
The Portland cementstested (with both high and low
C,A) by thistechnique behavedverywell;
they
retainedstrength and failed toexpand.Theslag
cements, however, lost strength and expanded to a
great extent.
The salinity of the Dead Sea is reported to be 10
times that of ocean water but sulphate concentration
- mortars andconcretes are reportedin Ref. 59. For SO,
is only 1/4 that of ocean sea-water.” Prisms of typeI
Portlandcementcracked and
their
outer shell
crumbled. Prismsof type V Portland cementremained
hard and showed only rounding of the edges. The
addition of chloride to thesulphateenvironment
increased theexpansions whichwere obtained in
simple chloride environments for sulphate-containing
cements but not for the corresponding sulphate-free
ground clinkers.
Tests for strength and expansion on mortars found
thatPortlandcementmortar prismsexplosed to
MgCl, solutions in a range of concentrations deterio-
rated by amechanism involvingleaching of the
Ca(OH),.I3 The C,A content of the Portland cement
had no influence. Blastfurnace slag cement mortars
retained strength for 1 year in 25g MgCl,/I solution,
and were almost immune to attack.
Measurements of chloride penetrationinto the sur-
face of the specimensshowed that the slag cement
256
mortar contained chloride only in the outer few milli-
metres, while the Portland cement mortars contained
chloride all the way to the centre of the specimens.
The resistance ofsmall concrete cubes to strong
chloride solutions (NaCI, CaCl,, MgCl, and NH,Cl)
has been i n ~ e s t i g a t e d .Blastfurnace
~~ slag cement
(75% slag), SRPC (1% C,A) and OPC (12% C,A)
wereexamined. The blastfurnace cementconcretes
were unaffected by CaCl,solutions, but both Portland
cements suffered severedamage within ’16 weeks. Satu-
rated NaCl solution also had more drastic effects on
the Portlandcement concretes than onthe slag cement
concretes. hlgC1, solutions caused severe damage to
all concretes.
Sulphate incorporated into the concrete mix
The effects of added gypsum on Portland cement
additionsaboveacertainminimum,acommon
expansion curve against time was obtained. Two test
procedures, measuring expansion and involving the
incorporation of CaSO,. 2H,O into the test speci-
mens, are described in the literature-the Le Chatelier-
Anstett-Blondiau cement paste test and the ASTM
C452 mortar bar expansion test. The Le Chatelier-
Anstett-Blondiau test sulphate
for resistance
measures the expansion of a compact composed of
two parts of hydrated cement paste and one part of
gypsum. This procedure is a very severe test of sul-
phate resistance, and only SRPC and certain PFA
blendsmeet the accepted criteria of resistance of
< 1.8% expansion at 28 days. Blastfurnace slag
cements behave badly in this test.60
In the ASTM C452 test, the Portland cement sul-
phate content is increased to 7% by adding gypsum.
The mortarprisms are stored underdistilled water and
the expansion is noted after 28 days. A good corre-
lation between the Bogue C,A content and expansion
Magazine
Research,of Concrete 1990, 42, No. 153

forplainPortlandcementshas been r e p ~ r t e d . ~ ' . ~ ' temperature reduced the time for a given expansion;6s
OPC-ggbs composite cements were expansive when
used inthistest,but PFAand silica fume blends
performed well.
The standards give maximum limits for sulphate
contents in concrete and aggregates-BS8110 : 1985
sets a limit of 4% by mass of cement for concrete;
BS877 : 1973 (Foamed or expanded blastfurnace slag
lightweight aggregate for concrete) sets a limit of 1%
SO,, asdoes BSI 165 : 1985 (Clinkerandfurnace
bottom ash aggregate for concrete).
Investigation of theexpansion of mortar prisms
containingadded gypsum showed that expansion
more than -
continued at laterages where the mixes contain
6% SO, for sulphate-resisting cement
concretes.62Pozzolaniccementsshowedgood resis-
tance to sulphates addedin the mixing. It was pointed
out that the maximum sulphate allowable in a con-
crete was dependent on many factors, including C, A
content,curingtemperature,particle size of the
gypsum, and presence of chloride in the mix.63
The expansion of mortar bars made with various
percentages of gypsum as aggregate showed the influ-
ence of C,A content of the Portland cement: and
largeexpansions were found with 5% gypsum (by
mass of aggregate) for Portland cements containing 9 varioustemperaturesfor
and 14% C3A, whilevery smallexpansions were
obtained with SRPC.
The expansion of mortar prisms using aggregate
contaminated with 1 or 2%gypsum, by mass of aggre-
gate,andalsomadeentirely with crushed gypsum
aggregate, hasbeen investigated.@At 2% gypsum, the 40°C. The reverse situation obtained when aluminate-
slag cements showed high rates of expansion but the
SRPC showed slow expansions. When all the aggre-
gate was gypsum, the high slag cement expanded freely
while the SRPC expanded very slowly, and only
showed significant expansion after 3years under water
at 20 f 2°C.
It has been claimed6' that ettringite formation can
take place withoutthe presence of C3A when the
aggregatecontainsweathered(kaolinzed)granite.
The substitution of 40% of the Portland cement by
pozzolana improved the resistance. Clays stabilized
with 10% cement (boulder
clay,
weatheredand
unweatheredOxfordclay) have been examined for
effects of sulphate contamination.66 Clay containing
more than 1% SO, was found to show wet strengths
of only - 1/4 of that without sulphate. The use of
SRPC did notimprovethestrengthperformance.
Cement-stabilized colliery shale (8-10Y0 cement) has
occasionally been found to swell after 1 or 2 years'
service due to the oxidation of the pyrite present to
form acidic ferric sulphate^.^'
Temperature of exposure
Lean mortar bar expansions in 0.15 and 0.50 mol/l
Na,SO, and MgSO, solutions, carried out at 0.5, 22
and 40°C show that for Na,SO, solution, a rise in
Magazine of Concrete Research, 1990, 42, No. 153
Sulphate attack on concrete
the effect of temperature change in MgSO, solution
was similar between 0-5 and 22"C, but at40°C the rate
of expansion fell away at later ages, so that later
expansion values were higher at 0.5 and 22°C than at
40°C.
Both Portland andslag cement mortars (20,35, and
80% slag) showed reducedexpansion as thetem-
perature of exposure to sea-water was increased from
5 to 20 to 40°C.5' The effects of 5% Na,SO, solution
at 5 and 22°C on the expansion behaviour of OPC
mortars (having 7 or 14% C, A) after curing at room
temperature or under autoclave conditions are reported
in Ref. 69. Autoclaved specimens deteriorated rapidly
at 5°C butremainedsound at 22°C.All theroom
temperature cured specimens were attacked, but the
7% C, A cement mortar bars showed lower rates of
attack at 22°C than at 5°C.
Thaumasite forms during sodium sulphate attack
on autoclaved mortarsat 5"C, and this compound has
been held responsible for the observed disruption."
Exposure of this material at 25°C did not result in
disruption (the autoclaved mortar was made with a
dolomitic aggregate).
Theeffect of exposuretosulphatesolutions at
SRPCmortars has been
rep~rted.~'In Na,SO, solutions,expansions were
greatest at 1O"C, and reduced somewhat at 20"C,
falling to negligible values at 40°C. In contrast, for
MgSO, solutions expansion was moderate at 10°C,
increased at 20°C but again fell to negligible values at
containing rock was used in the aggregatewith SRPC
in 5% Na,SO, ~olution;~' in this case exposure at
higher temperatures resulted in increased expansions.
Type of hydraulic binder
Plain Portland cement
The sulphate resistanceof Portland cements canbe
estimated from the calculated value of the C3A per-
centage, using the Bogue formula, or from a direct
C3A determination by X-ray diffraction. Cement stan-
dardsforPortlandcementsthroughoutthe world
have adopted the Bogue formula approach to identi-
fying SRPCs, placing limits on the calculated C,A
content in the region of 3-5%.
An upper limit of 5.5% C3A eliminated all cements
of lowsulphate resistance:' Satisfactory data correlat-
ing calculated C, A levels with expansion, using the Le
Chatelier-Anstett-Blondiau test, have been found@ . '
Approximate relationships
have been obtained
between mortar bar expansion data and calculated
C,A levels in Portland cement^^'.^^,^' (Fig. 3).
The C3Acontent is thus well established asan
important composition parameter for plain Portland
cementconcretesdeterminingsulphate resistance.
257
Lawrence

phate andsea-water environments show highstability,

but that a significant minority show poorer resistance;
5% Na2SO4
he is at pains to point out that ‘unsuitable mixtures of
0 Portlandcement
clinker and very slightly hydraulic slags’ were
R = 0.970 + Slag
mixes
employed in the latter tests.
(Portland cements only) (equipment C A )
1000
One way of increasing the reactivity of a slag is to
800 + deliberately add alumina to the feed stock, but the
,I 600 resulting cement may exhibit a lower sulphate resis-
Proposed limit for tance (BRE Digest 250, ASTM C989-88). A minimum
type V equivalence
c
._ glass content of the slag ( > 61 YO)was found to be
v)

m necessary for sulphate resistance of the blend,” but

9 changing theSO, content or the fineness had noeffect.
European field experience is largely confined to fac-
toryproduced slag cementswhichhave SO, levels
considerably higher thanthose ofmixer combina-
a,
E
F tions. Increasing the SO, level from -
1 % to
improved the sulphate resistance significantly.M
3% -
OPC-PFA composite cement
The performance of OPC-PFA composite cements
is dependent on theC,Acontent of thePortland
2 4 6 8 10 12 14 cement (Fig. 4). BRE74state that the net sulphate
Bogue &A. %
resistance of OPC-PFA composite cements depends
‘Ages from best fit line for ASTM limits on C3A to some extent on the C,A content of the OPC, and
Fig. 3. Time.for ASTM mortar prisms to expand 0.1% in 5% BRE Digest 250 in its current form makes allowance
day?‘ Na,SO, solution: forthis by notequating the performance of these
composite cements with that of SRPCs.
Different behaviour has been observed with com-
SRPC is sometimes referred to as C,A-free Portland posite cements made with PFAs from different sources
cement. but the composition changes bringing this about have
not been identified. Using the ASTM C1012-84 test (a
Blastfurnace slag cement plot of themortarbar expansion after 180 days
Smolc~yk’~ commented that the vast majority of against C,A content for both plain Portland cements
laboratory reports of blastfurnace slag cementin sul- and blended cements) the data showed that blended

X X

--C
X
X
X
X

X
xxc-
X

X X

X
X

I I
- - - - _ - - - _ _ - _ ____ ____
XX ? X &
:
-
0.00
l1 V RC 714 RC 756 RC744
With pozzolans
Material

Fig. 4. Comparison of rates of expansion in 5% Na,SO, solution of mortar bars

made with ASTM type I1 and type V cements, and composite cements using three
ASTM type I cements with 13, 9 and 15% C, A (RC714, RC744, RC756: C+
marks the expansion of the plain type I cement mortars)’
258 Magazine of Concrete Research, 1990, 42, No. 153
 Sulphate attack on concrete

cements in general performed better than would be 1-

expected if only simple dilution for the C, A present in
390 kg
the Portland cement component applied, but the rela-
tionship between expansion and calculated C, A level
was poorly defined.25

OPC-silica fume composite cement

2-

3-
i
307

The literature contains a numberof reports on the

sulphate resistance of reactive silica-containing mixes. -
0)
.-
-?!
Earlier
indicated that expansions in Na2S0, J -
.v,
> 4
and MgSO, solutions were reduced by blending up to
20% silica gel with the OPC where the C3A level was
intermediate, but this was ineffective when high levels
of C3A were examined. The resistance to Na,SO, 5- Cement no. 12
12.6% CBA
solutions of typeI Portland cement mixes is improved
223
by incorporating 15% silica fume but the resistance to
strong MgSO, solution is worsened,76 the specimens
losing 20-25% of theirmass. Type V Portland cement l I I I
0 20 40
mixes were made less resistance, especially to MgSO, Fly ash replacement: % by weight of cement
solution, by incorporating silica fume. The reason for
the improvement in performance of silica fume com- Fig. S . Visual ratings of concrete prisms stored in sulphate
posites is still a subject of speculation. The formation contaminated soils for I 1 years of d@erent binder contents
and different replacement levels of ASTM type I cement by
of a finer pore structure, the reduction in Ca(OH), PFA”
content, and the removal of the aluminate fraction of
thecement by incorporationintotheextra silicate
hydrate being formed have all been proposed as Replacement of ASTM type I Portland cement by
explanations. 20 and 40% class F PFA increased the sulphate resis-
tance of theconcretes with 223, 307 and 390kg
Mix design cement/m3concrete after 11 years’ exposure insulphate-
contaminated soils, the most significant improvement
The normal effect of increasing the cement content being for the leaner concretes,, (Fig. 5). Replacement
is to improve durability. After25 years’ exposure, high of 20% ASTM type I1 or type V Portland cements by
slag blastfurnace slag cements showed practically no PFA also produced an improvedperformance at
deterioration at cement contents of 250-390 kg/m3 223 kg cement/m3, butresulted in little change for the
concrete; to obtainsimilardurabilities with OPCs richer mixes.
required a cement content of 350 to 375 kg/m3; for The performance of concretes with 225, 285, 335
concretes containing an erzzement (SRPC) or a slag and 375 kg/m3 binder contentsat two levels of work-
cement with 30%slag,asimilarperformance was
-
attained at 300 kg/rn3.’,
The effects of changes in cement content of concrete
ability or water/binder ratio hasbeen reported:43there,
was a clear differentiation between thecastand
trowelled faces of the cubes, the cast faces deteriorat-
are more significant at the leaner end of the range. ing more slowly. For OPC mixes at 335 and 375 kg
The Portland Cement Association examined the effect cement/m3, there was a trend to increased disruption
of sulphate attack on concrete specimens stored half- in sulphateenvironments as the water/binderratio
buried in sulphate soils (contaminated with high per- was increased. ForSRPC concretestherate of
centages of Na,SO,or Na,S0,/MgS04):33 after 6 years, deterioration was much less than for OPC concretes,
for rich mixes (390kg cement/m3) the attack was slow and it was more difficult to establish the effects of mix
and little difference in behaviour was detected between proportions.
cements with high and low C,A contents; forlean and
intermediate mixes (223 and 307 kg cement/m3), the Period and temperature of cure
attack was more rapid and the importance of cement An increased period ofwater cure greatly dim-
composition became apparent, a limit of 7% C,A inished sulphate attack in Na,SO, s~lutions.~’ In con-
(Bogue) separatinggoodandbadperformance.At trast,sulphateattack byMgSO, solution was not
20 years, theconclusionsreported at 6 yearswere influenced by increasing the period of cure.
confirmed, but the performance of the rich mix (390 kg A drastic reduction in period of cure before expo-
cementlm’) concretescouldnow be differentiated sure to sulphatesolutionshas been investigated:26
according tothecomposition of thecement used: immediately aftercasting,permeable plastic film
again theC,A level wasfound to correlate with degree plates were clampedoverthe mortarbar moulds
of attack. whichwere then immersed in Na,SO, solution
Magazine of Concrele Research, 1990, 42, No. 153 259
Lawrence
(50000mg SO,- -/l). The OPC mortar (12.2% C,A)
failed quickly (in 3 months); the SRPC (2.2% C3A)
eventually failed also-however, a 50: 50 slag blend
with the 12.2% C,A Portland cement performed as
well as when allowed the normal cure in fresh water
before exposure.
The effectsof extending the curing period under
water before exposure to sulphate solutions has been
examined. OPC-PFA and high slag/PFA blends given
21 or 112 days precure were examined in tests using
mortar prisms immersed in Na,SO, solution
(25 000 mg SO,- -/I). The results show that the rela-
tively low sulphate resistance of the plain cements can
be improved by partial replacement with fly ash and
by longer term curing.
It was found that low pressure steam curing did
not influence the performance of mortars in sul-
phates significantly, except for those with 20%
colloidal silica, whichshowed improved perfor-
mance.20 Curing at 100°C78and high pressure steam
curinggreatlyimprovedthe resistance of Portland
cement mortarsand concretes to sulphates;sub-
stitution of dolomitic aggregate forsiliceous aggregate
in Portland cement mortars increased their resistance
to MgS0, solution.
Carbonation
Ettringite is unstable when pH is reduced, and is
decomposed by carbonation, therefore no expansion
of carbonated mortars can take place in sulphates.
Theouter layer ofcarbonatedconcreteformeda
protectivebarrieragainstsea-water attack6' over
a 20year period.Osbornehasreportedasimilar
effect of carbonation against the attack by sulphate
solutions.79
Thecarbonation of mortarsmadefrom ASTM
type I Portland cement was found to be benefici,al to
specimens cured both at room temperature and under
autoclaveconditions, in both Na,SO, and MgSO,
solutions.69 Accelerated carbonation of dried OPC
mortars before immersion in sulphate solutions (10%
(NH,),SO, (72750mg SO,- -/l)) rendered them
resistant to sulphate attack.80
Discussion and conclusions
The process of sulphate attack is complex and the
chemical interactions between hydrated cement and
sulphatesareprobablydependent on the precise
environmental conditions. Different accelerated tests
yield different results: for example, strong MgSO,
solutions
are
more
harmfultowards
composite
cements thantowardsSRPCs,andstrong Na,SO,
solutions arepossibly biased in the opposite direction.
Tests limited to measurements of expansion are not as
satisfactory as those which also include measurements
of mass and strength loss.
260
Excess sulphate in the mix aggregate is unlikely to
occur in the UK, except possibly where waste filler
material is involved; thissituation is particularly
damaging to slag cements. Concretes with excess sul-
phate may prove particularly unstable under marine
conditions.
It is clear that the calculated C3A level provides a
good indication of the expansiveness of a plain Port-
land cement in sulphate conditions; SRPC (low C,A
Portland cement) usually performs as well or better
than any other binder type., The C3A content of the
OPC is also a determining factor for the behaviour
of OPC-PFA and OPC-ggbs composite cements in
sulphate environments.
A wide range of performances has been reported for
OPC-PFA and OPC-ggbs composite cements; it has
notproved possible to predict sulphate resistance
from the chemical or physical compositions of the
secondarybinder. Blastfurnacecementsmay derive
their sulphate-resistant properties from a number of
possible mechanisms (a similar list can be compiledfor
OPC-PFA cements).
The quantity of Ca(OH), present is reduced by
absorption during the initial hydration, increas-
ing the solubility of ettringite and making it less
expansive.
The Ca(OH), present is reduced by absorption
duringthe initial hydration, reducing therate
of ingress of SO,- - into the concrete by reduc-
ing the concentration of OH- ions available for
counterdiffusion.
The solubilities of the aluminate hydrate phases
are reduced by incorporating silicate into their
crystalstructuresand delayingconversion to
ettringite in the presence of sulphate.
The hydrate pore structure is refined, increasing
the physical resistance to diffusion and reducing
the rate of ingress of sulphate into the concrete.
Which of these possibilities operate in particular
instances is not yet established. This uncertainty con-
cerning the basic reasons controlling their sulphate
resistance limits confidence in the performance of
these secondary binders.
The following conclusions can be drawn.
( a ) Concrete mix design has a largeeffect on concrete
performance in sulphate environments, and an
increased binder content or reduced water/
binder ratio usually leads to improved resistance.
(b) The relative performance of hydraulic binders
depends, to a degree, onthesulphatesolution
composition and concentration employed. If tests
are limited to concentrations below 3000mg
SO,- -/l, it is possible to formulatesulphate-
resisting cements from a wide range of materials,
including binders containing PFA and blast fur-
nace slag.
Magazine of Concrete Research, 1990, 42, No. 153

It is well established that the C3Acontent of plain
Portland cements is themajorfactor affecting
susceptibility to sulphates. Recently reported
studies confirm the pre-eminent position of C,A-
free cements in the range of available sulphate
resisting binders, and their guaranteed resistance
to sulphate concentrations up 6000 to mgSO4- -/l.
Satisfactory performance of composite cements
and mixer combinations in sulphateenviron-
ments of 3000 mg SO,- -/l is critically depen-
dent on thecorrect choice of material properties
andproportions. In view of the variability of
PFA and slag composition, the existing British
Standards for compositecements, while satisfac-
tory in regulating general purpose concrete, are
inadequate as specifications for materials to be
usedin sulphateenvironments of > 3000mg
SO4- -/l.
The present evidence from various parts of the
world is that a wide range of performances are
produced when PFA is incorporated with Port-
landcement. Althoughthe
range of PFAs
presently available in the UK is limited to the
generally more satisfactory bituminous coal ash,
it is recommended that PFAcomposites continue
to be restricted to modestly aggressive sulphate
environments, as detailed in BS 8 1 10 : 1985 and
BRE Digest 250 (1986).
The sulphate resistance of OPCmortars can
be improved by theaddition of silica fume.
Additions of 10-25% have been shown to be very
effective inincreasing sulphate resistance, both in
short-term tests in the laboratory and in long-
term field trials, where sodium sulphate solutions
are present. However, strong MgSO, solution
attacks silica fume blends much more vigorously
than plain Portland cement mortars.
More comprehensive tests of blended cement
combinations are required, covering wider ranges
of materials. A number of sulphate solution con-
centrations and types, and a range of tempera-
tures of exposure, including reduced temperatures,
should be studied, as well as the effect of partial
immersion in sulphatesolution.Testsshould
investigate both strength loss and expansion.
Appendix 1: Standards and abbreviations
A standardglossary of terms foruse in building and
civil engineering has been published by BSI-BS6100 :
Section 6.1 : 1984.
Active hydraulic binders ( U K )
O P C . OrdinaryPortland cement; BS12: 1989. A
factory-produced binder made by grinding Portland
cement clinker together with a controlled amount of
calcium sulphate (max. 3.5% SO,) (type I in ASTM
C150-89).
Magazine of Concrete Research, 1990, 42, No. 153
Sulphate attack on concrete
R H P C . RapidhardeningPortland cement; BS12:
1989. Similar in composition to OPC but more finely
ground together with a controlled amount of calcium
sulphate (max. 3.5% SO,) (type I11in ASTM Cl 50-89).
CFPC. Controlled fineness Portland cement; BS12 :
1989. Similar in composition to OPC butmore coarsely
ground with a controlled amount of calcium sulphate
(max. 3.0% SO,).
S R P C . Sulphate-resisting Portland cement; BS4027 :
1980. A factory-produced binder similar to OPC but
prepared by grinding selected clinker, having low
levels of C,A (max. 3.5% C3A), with a controlled
lower amount of calcium sulphate (max. 2.5% SO,).
(Roughly equivalent to type V in ASTM C150-89,
ASTM type I1 being between type I and type V in
sulphate resistance and C3Acontent).
L H P C . Low heat Portland cement; BS1370 : 1979. A
factory-produced binder similar to OPC, but prepared
by grinding selected clinker of low C,S level together
with a controlled amount of calcium sulphate (max.
3.0% so,).
Latent hydraulic binders (UK)
PFA. Pulverized fuel ash (fly ash in the American and
continentalEuropeanliterature); BS3892 : part 1 :
1982, 'Specificationf o r pulverized-fuel ashf o r use as a
cementitiouscomponent in structuralconcrete’. The
solid waste produce extracted frompower station flue
gases by electrostatic precipitation isselected and,
where necessary, processed. An upper limit of 2.5% is
placed on SO, level. (American Standard ASTM
C618-87, ‘Specijication forfly ash and raw or calcined
natural pozzolan for useasamineraladmixture in
Portland cement concrete’. This standard recognizes
two types of fly ash-class F, the type normally used
in the UK and produced by burning anthracite or
bituminous coal, and class C, produced by burning
lignite or sub-bituminous coal which may contain a
lime content of > 10% CaO. Amaximum level of 4%
SO, is placed on class F fly ash, and of 5% SO, on
class C fly ash).3
ggbs. Ground granulated blastfurnace slag; BS6699 :
1986, ‘SpeciJicationf o r groundgranulated blasqurnace
slag f o r use withPortlandcement’. Selected blast-
furnace slag, a by-product from the manufacture of
pig iron, is quenched from themolten state, and finely
ground. (American Standard ASTM C989-88, ‘Spec$-
cation for groundgranulated blastfurnace slagusefor
in
concrete and mortars’).
Composite hydraulic binders ( U K )
PBFC. Portland-blastfurnace cement. BS146 : part
2 : 1973. Factory cement (granulated blastfurnace slag
not exceeding 65% of total compositebinder) contain-
ing selected Portland cement clinker (complying where
appropriate with BS12 cement clinker) and selected
granuatedblasfurnace slag; eitherintergroundor
blended after separate grinding; SO, level brought to
261
Lawrence

Table 4 . British Standards for U K cements

Standard Date Cement Max. % C,A Max. % SO,

BS4027 1980 SRP 3.5 2.5

BSI2 1989 OP - 3.5 (2.5 if C,A < S o / )
RHP - 3.5 (2.5 if C,A < S o / )

an optimum value by including calcium sulphate in The inclusion of an additional limit on the total
the formulation (max. 3.0% SO,). A1,0, by the USA, Germany and the Netherlands has
LHPBFC. Low heat Portland-blastfurnace cement. the effect of limiting the percentage C,AF, so recog-
BS4246 : part 2 : 1974. Factory cement (granulated nizing theimportance
blastfurnace slag 50 to 90%of total compositebinder) interaction of ferrites with sulphates.
containing selected Portland cement clinker (comply-
ing where appropriate with BSI 2 cement clinker) and
selected granulatedblastfurnace slag; eitherinter-
References
1.
ground or blended after separate grinding; SO, level
brought to an optimum value by including calcium
sulphate in the formulation (max. 3.0% SO,).
SSC. Supersulphated cement; BS4248 : 1974. Fac- 2.
tory cement. Composite binder containing high a level
of granulatedblastfurnace slag (minimum 75% of
3.
totalcomposite binder) groundor blended with a
Portland cement clinker and a controlled increased
proportion of calcium sulphate (minimum 4.5% SO,). 4.
This binder is not available in the UK at present.
P P F A C . Portland-PFA cement. BS6588 : 1985. Fac-
5.
tory cement (PFA 15-35% of total composite binder)
formed by blending or intergrinding Portland cement
clinker (complying where appropriate with BS12 6.
cement clinker) with PFA; SO, level adjusted to an
optimum value by incorporating calcium sulphate in 7.
the formulation (max 3.0% SO,).
P O Z C . Pozzolanic cement. BS6610 : 1985. Factory
cement (PFA 35-50% of totalcomposite binder) 8.
formed by blending or intergrinding Portland cement
clinker (complying where appropriate with BS12
cement clinker) with ground pozzolana (PFA); SO,
level adjusted to an optimum value by incorporating 9.
calcium sulphate in the formulation (max.3.0% SO,).
10.
Appendix 2: Standards for sulphate resisting
Portland cements
The Bogue calculation for compound composition 11.
isused universally to define Portland cements. The
percentage of C,A is obtained from 12.
'?LO C,A = (2.65 x %A1,0,) - (1.692 x YoFe,O,)
13.
In the USA and Germany, the % AI,O, used in this
formula includes % TiO, and % P,O,, while in the
14.
UK YOA1,0, represents the pure aluminium oxide.
Similar standardsforSRPCstothose given in
Table 4 have been drawn up in countries with back-
grounds and economies very different from the UK; 15.
these cements are generally accepted as a solution to
16.
the problem of sulphate attack on concrete. The local
product can be expected to perform in a well-defined
manner. 17.
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Discussion contributions on this Paper should reach the Editor by
28 June 1991.

264 Magazine of Concrete Research, 1990, 42, No. 153