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ABSTRACT
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.
79
80 Vol. 2, No. l
LONG-TIME, SULFATE-RESISTANCE, CONCRETE
Introduction
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
LONG-TIME, SULFATE-RESISTANCE, CONCRETE
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
LONG-TIME, SULFATE-RESISTANCE, CONCRETE
Results
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-
tioned.
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
LONG-TIME, SULFATE-RESISTANCE, CONCRETE
Table 1
Table 2
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
LONG-tIME, SULFATE-RESISTANCE, CONCRETE
IOC X
TyN V cemeet
Type ~ cement
x Giossy-phose pozzoion
L~ Crystolllne
V Colcined
D 51o9
x~
i4G x
x
X
A
q 120
x
x
o
I00
VV XX X x X V
xv B D
X
xV •
~ 6C
5C
o
4C~ •
o:" C
o 0
,
L 1 I I J I J 1 I I
2O 40 ~ 60 60 I00 120 i40
TIME TO FAILURE. Y R ( C A L C I
FIG. l
Life Expectancies of Concretes in 2.1 Percent Na2SO4 Solution
Table 3
Accelerated Sulfate Test on Air-Entrained Concretes
Pozzolan Results
Water, Predicted
Amt., % of Exp., Time life
Kind % standard % yrs. yrs.
W
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
curing.
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
LONG-TIME, SULFATE-RESISTANCE, CONCRETE
Acknowledgments
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.
References
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).