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CEMENT and CONCRETERESEARCH. Vol. 2, pp. 79-89, 1972. Pergamon Press, Inc.

Printed in the United States.


G. L. Kalousek, L. C. Porter, and E. J. Benton

Engineering and Research Center, Division of General Research
Bureau of Reclamation, Denver, Colorado 80225

(Communicated by Sir Frederick M. Lea)

Data on concretes soaked continuously in a 2.l percent sodium
sulfate solution and alternately soaked and dried served for
predicting service l i f e . Sixteen out of 19 concretes made
with Type V and II cements showed l i f e expectancies of less
than 50 years. Concretes containing different pozzolans showed
a spectrum of effects ranging from deleterious to highly bene-
f i c i a l . Only 6 out of 33 pozzolan concretes had l i f e expect-
ancies of less than 50 years. Fly ash, pumice, and two calcined
products markedly improved sulfate resistance. Seven of II con-
cretes having a l i f e expectancy in excess of lO0 years, some
possibly up to 200 years, contained f l y ash. Revision of present
day specifications for sulfate resisting concrete is recommended.

Ergebrisse, die durch kontinuierliches Tr~nken und alternierendes •

Tr~nken und Trocknen von Beton in 2.1% NatriumsulfatIBsung erhalten
wurden, dienten zur Bestimmung der zu erwartenden Lebensdauer. 16
von 19 Betonsorten, die mit Typ V- und II Zementen gemacht waren,
ziegten Lebenserwartungen von weniger als 50 Jahren. Verschiedene
Pozzolane in Beton bewirkten eine Vielfalt von sch~dlichen bis
sehr n~tzlichen Effekten. Nur 6 von 33 Pozzolan enthaltenden
Betonsorten hatten Lebenserwartungen von weniger als 50 Jahren.
Durch Flugasche, Bimsstein und zwei kalzinierte Produkte wurde
der Widerstand gegen Sulfate betr~chtlich erh~ht. 7 von II
Betonsorten, die Lebenserwartungen bis Uber lO0 Jahre-, einige
m6glicherweise bis zu 200 Jahren zeigten, enthalten Flugasche.
Ein Berichtigung der gegenw~rtigen Spezifikationen fur gegen
Sulfate widerstandsf~higen Beton wird empfohlen.

80 Vol. 2, No. l

Results of research in Bureau of Reclamation laboratories have shown that
concrete designed to resist sulfate attack (in a 2.1 percent sodium sulfate
solution) may remain stable for only. a few years, several decades, or indefin-
itely. These large variations in behavior of high quality concrete made with
Type V and Type II cements remain unexplained. Research has been handicapped
by lack of a theory to give direction to applied research. Also, the long times
of exposure required for obtaining meaningful results have been a deterrent to
progress. Various accelerated tests to give results in a few weeks or months
to permit long-time predictions of expected service have not materialized.
Results being obtained in a few years by the Bureau in a partially accelerated
test (1) permit an approximate prediction of service l i f e of concrete in excess
of 20 years and, possibly with s~fficient r e l i a b i l i t y , into the range of lO0 to
200 years.
The failures of some high quality concretes made with Type V and Type II
cements after only a few years of sulfate solution attack prompted a long-time
research program on the problem at the Bureau. These investigations included
effects of pozzolans, water and cement contents, admixtures, variations in
porosity, special cements, moist curing and drying, etc. The improvements ob-
tained with some pozzolans are highly significant, and the report is therefore
restricted to this part of the program.
The severity of sulfate attack on concrete in the field (2) as related to
concentrations of sulfate (as SO4) in solutions extracted from soils is as
follows: negligible at 0.00 to 0.015 percent, positive at 0.015 to O.lO0 per-
cent, considerable at O.lO0 to 0.200 percent, and severe over 0.200 percent.
Soil water may contain up to l.O percent total sulfate salts (about 0.65 to
0.80 percent S04) (3). In isolated locations, and also i f concrete resting on
wet sulfate-bearing soils is subject to surface drying, the sulfate salt con-
centrations in the interior may exceed l.O percent and, in rare instances, may
be 5.0 percent or more. The concentration of 2.1 percent (0.15 molar) Na2SO4,
or 1.4 percent SO4, long a standard in laboratories, causes more severe attack
than generally encountered in the field. The time to predicted failure at this
concentration may generally be shorter than for concrete in the f i e l d , depending
on soil-water sulfate concentration and other conditions of exposures.
The results of Bureau research on concrete with and without pozzolans and
covering a span of 18 to 24 years of testing are presented in this report. In-
cluded are the service l i f e expectancies of various concretes stored continu-
ously in 2.1 percent Na2SO4, and the l i f e expectancies for this condition of
Vol. 2, No. l 81

exposure computed from accelerated test results.

The Bureau criterion of concrete failure in sulfate solution is 0.5 percent
expansion which corresponds approximately to 40 percent loss in elastic modulus
for 3- by 3- by 16-1/4-inch prisms. The plot of the extrapolated values, in
years, to 0.5 percent expansion in continuous Na2SO4 solution exposure versus
the corresponding computed times from accelerated test data comprise the basis
for comparison. The plot of data is divided into three zones (or groups). As
w i l l be apparent in plot of the data Zone A is bounded on the 2 axes with mini-
mum l i f e expectancies of lO0 years. Concretes of shortest l i f e expectance, 50
years maximum, are contained in Zone C. The remainder of the data f a l l i n g be-
tween Zones A and C represents concrete of intermediate to long-life expectan-
cies and comprise Zone B.
The choice of age limits for the three groups is partly arbitrary. However,
a maximum l i f e expectancy of 50 years would probably be considered short accord-
ing to most c r i t e r i a . (In Bureau long-range planning the 50 years is considered
to be a highly inadequate l i f e of service.) Swenson (4) reported ". . . . . failures
have occurred where all precautions were taken" such concrete would have been in
service for about 35 years or less. I t is recognized, as already mentioned, that
most concretes in service are not exposed to as severe an exposure, as the 2.1
percent Na2SO4 solution in the laboratory. In field exposure, however, factors
such as freezing and thawing, shrinkage and other cracking, etc., may contribute
to accelerated sulfate attack. Because of these factors, the effects of which
are d i f f i c u l t to evaluate, and to provide assurance against the infrequent most
severe exposure, the 50-year minimum l i f e expectance is considered j u s t i f i e d .

Materials and Procedures

The cements were obtained from producers who supplied or were potential
suppliers of Bureau needs. Type I cements, included in all early tests, are no
longer considered for use in sulfate environments. Results are reported only
for Type V and Type II cement concretes. The pozzolans originated from many
sources and for several potential uses. I t was impractical to make complete
chemical, mineralogical, and physical tests on all the several hundred samples
received. Various tests were initiated and samples of pozzolans set aside. It
was some lO to 15 years later before the spectrum of effects of pozzolans on
sulfate resistance became apparent. In the interim most of the samples had been
discarded. Accordingly, the pertinent mineralogical compositions, expecially of
the shales and clays, cannot be supplied. Chemical analysis and physical prop-
erties, available for some of the pozzolans are not recorded, because these did
not correlate with the pozzolans behavior, with one exception. Fly ashes high
82 Vol. 2, No. l

in carbon, and not meeting present day specifications, did not give maximum
improvement observed for low-carbon f l y ashes. Pozzolans from a specific source
occasionally Showed wide variations in mineralogical compositions and performan-
ces. This generally precludes classification of pozzolan according to origin.
The aggregate was either from the Brett Pit, Grand Coulee Project, or Clear
Creek in the v i c i n i t y of Denver, Colorado. Both are sound and high quality
aggregates. The specimens were 3- by 6-inch cylinders provided with reference
points in the end faces. Aggregate was graded to 3/4-inch (l.91 cm) maximum
size. The W/C ratio or W/(C+P) (water to cement or cement plus pozzolan ratio
by weight) was either maintained constant at 0.51 or varied as job concrete
design dictated. Slump was maintained in the 3- to 4-inch range. Pozzolans
were added as replacement for cement by weight or volume. The specific details
are given as these apply.
The concrete principally was cured in the molds for 24 hours, then, after
stripping, for 13 days in the fog room followed by exposure to 50 percent rela-
tive humidity air at 73.4°F (23°C). The cylinders were then measured for i n i t -
ial ("zero") length and placed in a 2.1 percent Na2SO4 solution at room tempera-
ture which ranged between 70° and 80QF (21 ° and 27°C) and measured periodically.
This is called the continuous soaking test. The accelerated test, also called
the alternate soaking-drying test, consisted of soaking-and-drying cycling of
the specimens. Each cycle consisted of soaking of the specimens for 16 hours
in 2.1 percent Na2SO4 solution at 70° to 80° F (21 ° to 27°C) followed by 8 hours
of forced air drying at 130°F (54°C). One year of accelerated testing equals
365 cycles.
Many concretes of three specimens each were under continuous soaking testing
for about 2 to 4 years before the accelerated test was placed in operation, At
this time one cylinder from each lot was moved into the accelerated test, the
other two remaining in the continuous soaking test. The time of i n i t i a l expos-
ure in continuous soaking divided by eight (for reasons given below) was added
as a correction to the time in the accelerated test. In early tests comparison
of the number of years to reach 0.5 percent expansion showed that l year of
accelerated testing equaled 6 years of continuous soaking. This ratio of 1:6,
based in part on extrapolated data and some results on Type I cements was con-
servative. The updated results (18 to 24 years) showed that a l:lO ratio is
more r e a l i s t i c , but to maintain a conservative approach to l i f e expectancy, a
1:8 ratio was selected. The data presented are based on this ratio.
The results obtained in the continuous soaking test through 18 to 24
years were also used for estimating the time to the 0.5 percent expansion by
Vol. 2, No. l 83

straight-line extrapolation. Obviously the shorter the time of extrapolation,

the higher is the accuracy of the results. Extrapolation extending from 20 to
the order of lO0 years may be in substantial error. I f the volume of the speci-
man stabilizes at some nearly constant volume, the predicted value will be un-
derestimated. Conversely, i f expansion accelerates with time of exposure, the
predicted value will be overestimated.
The plots of data from the accelerated test show (1) that as the 0.5
percent expansion is approached the rate of expansion accelerates. The pre-
dicted l i f e expectancies from the accelerated test take into account, at least
partly, the accelerated rate of expansion as the terminal value is approached.
In view of the possible inherent errors in each of the two methods of
predicted service l i f e the most realistic prediction possibly would appear to
be from a comparison of plots of data obtained by the two methods. Such pre-
sentation of data is made.

Results on nonair-entrained concretes, of 3- to 4-inch slump at constant
W/C ratio of 0.50 ~ .02, made with Type V and II cements and Grand Coulee aggre-
gates are given in Table I. The f i r s t five Type V cement concretes were put
under continuous soaking test over 24 years ago for the Columbia River Basin
Project. Attention is directed to the last column in the table which shows the
actual l i f e , i f available, or the predicted l i f e of the concretes computed from
the accelerated test data. The early failures after 1.5 and 6.7 years in the
soaking test and other similar data, prompted the investigations already men-
The tests on the other Type V and II cements in Table l were parts of
other investigations started 18 to 21 years ago. A comparison of actual or pre-
dicted service l i f e of all cements listed in Table l reveals no critical differ-
ence in sulfate resistance of the types of cements shown. These and other re-
lated data are discussed later.
Starting about 18 to 21 years ago, extensive series of tests were
started using pozzolans and slag. The concretes were made withGrand Coulee
aggregate with a 3- to 4-inch slump and W/(C+P) ratios as shown in Table 2.
The volume of cementitious materials was maintained constant, 35 percent being
pozzolan. The C3A and C4AF contents, in percent, of the cements were, respect-
ively, 6.0 and 13.8 for No. 9458, 5.2 and 13.5 for No. A777, 4.2 and 12.3 for
No. 9249, and 4.1 and 7.1 for No. A-570.
For purposes of clarity in graphical presentation in Figure l , the 52
concretes are combined into groups as follows (individual pozzolans are identi-
84 Vol. 2, No. 1

Table 1

Results on Concretes Without Pozzolan in Sulfate Tests

Continuous Soakin9 Accelerated

Predicted Time to Predicted
Cement C3~ C.AF, Exp. Time life 0.5% Iife
Type number ' ~% % yrs. yrs. exp., yrs. yrs.

V 6347 2.8 9.9 0.45 24.0 27 2.7 22

V 6350 4.1 8.8 .26 24.0 46 5,5 44
V 6352 4.5 7.7 .50 (I .5) a_/ (I.5)
V 6355 3.8 9.3 .50 (6.7) (6.7)
V 6358 3.4 7.8 .30 24.0 40 3.6 29

V A-672 3.1 8.7 .08 20.0 125 5.9 47

V 1366 3.9 9.8 .23 18.0 39 1.5 12
V 1212 3.9 I0.0 .37 18.4 25 2.4 19
V 1214 4.0 I0.I .30 18.4 31 2.3 18
V 9830 I. 8 I l. 6 .16 21.0 66 I0.3 82

II 6344 5.8 9.5 .50 (2.1) (2.1) (2.1)

II 9284 5.1 10.6 .40 21.0 26 1.9 15
II 9229 5.7 14.0 .24 21.0 44 3.4 27
II A-240 4.6 13.4 .I0 20.3 I02 9.3 74
II 9348 7.3 7.4 .45 18.0 20 1.3 lO

~/ Numbers in parentheses are actual l i f e in years.

f i e d in Table 2): ( I ) w i t h o u t pozzolans, (2) w i t h f l y ash, pumice, and vol-

canic ash as glassy-phase pozzolans, (3) with clays and shales grouped as cry-
stalline pozzolans, (4) w i t h calcined c l a y s , shales, d i a t o m i t e - c l a y and dia-
tomite-shale as clacined pozzolans, and (5) w i t h slags. The i d e n t i f i c a t i o n of
the groups is given in Fig. I . This f i g u r e , as explained, is divided i n t o Zones
A, B, and C.
The p l o t t e d r e s u l t s reveal no c r i t i c a l d i f f e r e n c e between Type V and
Type I I cements in resistance to s u l f a t e attack. These concretes, w i t h o u t
pozzolans, as a group generally show the lowest l i f e expectancy; 16 out of 19
fall i n t o Zone C w i t h maximum l i f e expectancy of less than 50 years. In Group
C also are found 6 concretes made with pozzolans. Concretes, in Group A of
longest l i f e expectancy, c o n s i s t of 7 made with f l y ash, 2 w i t h shale, one each
with clay and pumicite. Most of these have not expanded to 0.5 percent in the
accelerated t e s t , and t h e r e f o r e have a longer l i f e expectancy than i n d i c a t e d ,
some probably in excess of 200 years. Seven of the concretes in Group B have
a life expectancy of I00 years or more by one or the other method of p r e d i c t i o n .
Vol. 2, No. l 85

Table 2

Tests on Concretes Containing 35 Percent Pozzolans

(Cement type) W Cont. soakin~ Accelerated

or pozzolan
Predicted Predicted
Kind Ratio Age, Exp. life Age, Exp. life
yrs. % yrs. yrs. % yrs.

(II No. 9458) .49 21.0 0.25 42 4.6 0.50 37

Fly ash .47 21.4 .06 180 17 .18 140+
Fly ash .46 20.6 .08 130 17 .17 140+
Fly ash .49 20.6 .07 150 17 .25 140+
Fly ash .47 20.5 .07 150 17 .lO 140+
Fly ash .49 17.8 .09 lO0 15 .35 120+
B. F. Slag • 48 18.0 .50 (18) 1.8 .50 14
B. F. Slag .49 20.3 .13 80 16 .50 130
B. F. Slag .48 20.3 .06 170 .6 .35 130+
G. B. F. Slag .52 1.8 .50 (I.8) (l .8)
G. B. F. Slag .53 2.4 .50 (2.4) (2.4)
Shale .45 20.0 .06 170 17 .12 140+
Calc. shale .58 21.4 .12 90 3.8 ,50 30
Shale .55 20.4 .I0 lO0 16 .50 130
Calc. clay .53 19.8 .13 80 6.2 .50 50
Calc. bentonite .56 21.3 .16 66 6.0 .50 48
Calc. diat-shale .56 19.8 .ll 90 16.4 .39 140+
Volc. ash .57 20.6 .15 70 6.1 .50 49
Volc. ash .53 19.8 .ll 90 lO.O .50 80
(II No. A777) .50 19.7 .21 47 3.3 .50 26
Fly ash .53 18.4 .ll 80 5.7 .50 46
Fly ash .51 18.4 .lO 90 6.7 .50 54
Fly ash .50 18.4 .10 90 6.0 .50 48
Pumicite .52 18.4 .lO 90 15.5 .39 120+
(II No. 9249) .49 20.I .24 42 4.8 .50 38
Fly ash .44 19.0 .07 140 16.4 .19 130+
Fly ash .48 19.8 .09 llO 16.4 .39 130+
Shale .58 19.0 .21 45 5.7 .50 46
Clay .53 17.0 .21 41 4.8 .50 36
Calc. diat-shale .55 19.0 .07 135 8.9 .50 72
Pumicite .53 19.0 .07 135 16.4 .50 130
(V No. A570) .69 15.4 .50 (15) 1.5 .50 12
Fly ash .67 19.8 .ll 90 16.3 .41 130+
Shale .87 19.8 .21 47 6.1 .50 49
Clay .82 19.8 .19 52 5.8 .50 47
Calc. diat-shale .78 19.8 .ll 90 4.0 .50 32
Volc. ash .75 19.8 .15 66 5.8 .50 47

This subgroup consists of two concretes without pozzolans, two with calcined
diatomite-shale pozzolan, and one each with f l y ash, pumicite, and slag. Of
the remaining concretes in Group B, with less than lO0-year l i f e expectancy,
five were made with calcined pozzolans, three with f l y ashes, three with vol-
canic ashes, and one each with clay and without pozzolan.
Six out of the 34 pozzolans did not improve sulfate r e s i s t i n g over that
exhibited by the nonpozzolan concretes. Two granulated blast furnace slags
86 Vol. 2, No. l

TyN V cemeet
Type ~ cement
x Giossy-phose pozzoion
L~ Crystolllne
V Colcined
D 51o9

i4G x
q 120


xv B D

xV •
~ 6C


4C~ •

o:" C
o 0

L 1 I I J I J 1 I I
2O 40 ~ 60 60 I00 120 i40

FIG. l
Life Expectancies of Concretes in 2.1 Percent Na2SO4 Solution

caused a marked decrease in sulfate resistance. The effects of pozzolans range

from deleterious to highly beneficial in relation to sulfate attack. Infor-
mation was not available, nor was i t possible to develop data, to explain the
widely varying effects of pozzolans within a given group such as shales and
clays. These two kinds of pozzolans generally increase water requirements of
concrete and increasing amounts of mixing water relates to decreasing resist-
ance to sulfate attack. Pozzolans, such as some shales, bentonite, kaolin, and
diatomaceous earth, which increased the W/(C+P) ratio above 0.70 from the nom-
inal 0.5 W/C of concrete without pozzolan, caused rapid sulfate deterioration.
These data are not presented. The effect of high water requirement, W/C of
0.69, necessitated by a lean concrete design to simulate concrete for a dam is
shown in Table 2 for cement No. A570. Four pozzolans which substantially in-
creased the water requirements of this concrete increased significantly the
predicted service l i f e of the concrete. The beneficial effect of fly ash, which
decreased the ~W to 0.67 to 0.69 W/C increased remarkably the predicted ser-
vice l i f e . Other similar anomalies on effects of amount of mixing water have
been observed in Bureau research. Therefore, under certain s t i l l undefined
Vol. 2, No. 1 87

Table 3
Accelerated Sulfate Test on Air-Entrained Concretes

Pozzolan Results
Water, Predicted
Amt., % of Exp., Time life
Kind % standard % yrs. yrs.

(standard) ~ 0.0 (lO0) .50 2.7 22

Fly ash 15 93 0.40 13.4 I05+
Fly ash 30 88 .19 13.4 I05+
Shale 15 I02 .31 13.4 I05+
Shale 30 I09 .28 13.4 I05+
Pumicite 15 lOl .16 13.4 I05+
Pumicite 30 I04 .23 13.4 I05+
Calc. diat-clay 15 I06 .37 13.4 I05+
Clac. diat-clay 30 125 .50 5.4 43
Calc. diat-shale 15 I03 .36 13.4 I05+
Calc. diat-shale 30 ll6 .41 13.4 I05+

a_/ Standard concrete without pozzolan.

conditions a high W/C or C+P ratio per se may not be deleterious.
Following the early promising results of the accelerated test, other ser-
ies of pozzolan concretes were tested by this method. In one series, five pozzo-
fans were used at 15 and 30 percent by weight replacements of a Type II cement
with C3A content of 6.7 percent and C4AF of I0.8 percent. The concretes con-
tained 6.0 ~0.5 percent entrained air. The slump was maintained at 3.0 ~0.2
inches and the W/(C+P) at 0.51. Clear Creek aggregate was used. Three cylind-
ers ofeach concrete were subjected to the accelerated test immediately following
Both amounts of pozzolans as shown in Table 3 increased the predicted l i f e
from 22 years without pozzolan to more than I05 years except for the 30 percent
addition of the calcined diatomite-clay pozzolan which was 43 years. No one of
these concretes, with the cited exception, expanded to 0.5 percent and, there-
fore, the l i f e expectancy is in excess of I05 years. The pozzolans had varying
effects. The expansions with 30 percent addition were larger for pumicite, cal-
cined, diatomite-clay, and calcined diatomite-shale, and lower for f l y ash and
shale than for the 15 percent addition.
The results in Table 3 substantiate those presented in Tables l and 2 for
the accelerated test. The expansions of the three cylinders were generally in
close agreement. I t is concluded that the results on the single specimens used
in earlier tests are a reliable measure of performance.
88 Vol. 2, No. l

SummarX and Conclusions

Some high quality concretes made with sulfate-resisting cements have deter-
iorated prematurely in the field (3). This observation is in agreement with
laboratory results reported here. The present results further confirm that
limitations on C3A and C4AF contents are not the ultimate answer to the problem
of sulfate attack. Present updated data permit drawing more definite conclusions
on the highly beneficial effects of some pozzolans than was possible previously.
In drawing conclusions, particular attention is given to the large variations in
effects of pozzolans and effects of water requirements. Most pozzolans that de-
crease sulfate resistance have high water requirements.
This report is concerned only with sulfate attack on concrete. I t is ob-
vious that a pozzolan which improves sulfate resistance must also meet other
requirements governing properties such as strength, durability, alkali-aggregate
reaction, etc. The present conclusions on effects of pozzolans therefore apply
only i f other properties are not impaired. The mechanism by which pozzolans de-
crease sulfate attack is not fully understood. Lea (4) reviewed related hypoth-
eses and suggested that the C-S-H formed by reaction of the pozzolan and Ca(OH)2
deposited as an impervious coating over the surfaces of the Al~OR-bearing phases.
Any other inactivation of the Al203 such as substitution of the Al 3+ in the C-S-H
structure might have a similar effect.
Results, and interpretations based on criteria defined in this report, of
Bureau of Reclamation investigations permit the following conclusions:
I. Eighty-four percent of Types V and II cement concretes without pozzolans
showed a l i f e expectancy of less than 50 years.
2. Certain pozzolans increased very significantly the l i f e expectancy of
concrete exposed to 2.1 percent sodium sulfate solution. Fly ashes meeting
present day specifications were prominent among the group of pozzolans showing
the largest improvements.
3. Concretes for long-time survival in a sulfate environment should be made
with high quality pozzolans and a sulfate-resisting cement. The pozzolan should
not increase significantly, but preferably decrease, the amount of water required
4. Cementto be used in making sulfate-resisting concrete with pozzolan of
proven performance should have a maximum C3A content of 6.5 percent and maximum
C4AF content of 12 percent. Restrictions of cements to those meeting present day
specifications for Type V cement does not appear justified.
5. The actual effects of high mixing water content on sulfate resistance
is not clearly understood.
Vol. 2, No. l 89

The authors gratefully acknowledge the general direction of E. C. Higginson
who was Chief of the Concrete and Structural Branch and the help of many Bureau
scientists and technologists for gathering the results over many years.

I. J. T. Dikeou, "Fly Ash Increases Resistance of Concrete to Sulfate Attack,"
A Water Resources Technical Publication Res. Report No. 23, U. S. Department
of the Interior, Bureau of Reclamation, Denver, Colorado.
2. Concrete Manual, U. S. Department of the Interior, Bureau of Reclamation,
Denver, Colorado, Seventh Edition (1966).
3. E. G. Swenson, "Concrete in Sulphate Environments," Canadian Building Digest,
pp. 136-I to 136-4, April 1971.
4. Frederick M. Lea, "The Chemistry of Cement and Concrete," Third Edition (1970)
Edward Arnold, Publ. (London).