EXPANSION OF ALITE PASTE CAUSED BY GYPSUM FORMATION

DURING SULFATE ATTACK

By Bing Tian1 and Menashi D. Cohen2

ABSTRACT: This paper introduces a study carried out to investigate sulfate attack caused by gypsum formation.
The aim, specifically, was to study whether gypsum formation can be a factor leading to expansion in concrete
exposed to solutions containing sulfate ions. It was found from the laboratory study that alite paste specimens
(0.48 water-to-alite ratio) expanded and cracked significantly in 5% Na2SO4 solution after a ‘‘dormant’’ period
of about 1 year. X-ray diffraction confirmed that gypsum was the main product—ettringite does not form in the
system, because of the lack of aluminate. The detailed study of the mechanism for expansion and cracking is
continuing. These findings confirm the long-term understanding that sulfate attack mechanism is a complicated
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process. A highlight of the study, therefore, reveals that expansion and cracking of portland cement concrete
may not be attributed solely to ettringite formation. Gypsum formation may be a cause leading to expansion
and subsequent cracking. More research is needed in this area.

INTRODUCTION MgO, Al2O3, Fe2O3, and alkali. A commercial-grade bulk silica

Sulfate attack on concrete is a destructive and corrosive pro-
cess. It is caused by the formation of expansive salts within
concrete structures that are exposed to external sulfate ions.
The damage is usually believed to be caused by each of two
major sulfate reactions: (1) The sulfate ions react with C3A
and its hydration products to form ettringite with increase in
volume, which results in expansion and subsequent cracking
of the concrete; (2) the sulfate ions react with CH to form
gypsum. It is generally accepted that gypsum formation is to
be harmful, but the specific mechanism is not well understood.
It is often believed that the gypsum formation has only a soft-
ening effect and causes mass and strength loss (Cohen and
Mather 1991). As to the theory that gypsum formation leads
to expansion, there is some literature published with contro-
versial conclusions regarding this issue. Some publications
(Bonen and Cohen 1992; Mehta 1992; Ping and Beaudoin
1992; Bonen and Sarkar 1993) supported this theory—that
gypsum formation leads to expansion—while others (Hansen
1966; Mather 1996) contradicted this theory. However, these
studies were conducted on specimens of portland-cement-
based concrete—all containing aluminate source (i.e., C3A).
The expansion has always been attributed to ettringite for-
mation (Gonzalez and Irassar 1997). There has been no clear
evidence that gypsum formation can lead to expansion.
In this investigation the experimental part was carried to
study the sulfate attack on alite paste. Intentionally, this system
was selected so ettringite was absent during sulfate attack. The
alite paste specimens were exposed to 5% Na2SO4 solution.
The physical properties and chemical reactions were studied
to find out if gypsum formation, by itself, could cause expan-
sion.
MATERIALS AND TESTING
In order to simplify the chemical reaction process and elim-
inate the effects of ettringite formation, the cement mineral
alite was used. A gray powder alite was provided by Concrete
Materials Laboratory at Purdue University; it consisted of
monoclinic crystals with small amounts of impurities such as
1
PhD Candidate, School of Civ. Engrg., Purdue Univ., W. Lafayette,
IN 47907.
2
Prof., School of Civ. Engrg., Purdue Univ., W. Lafayette, IN.
Note. Associate Editor: J. J. Beaudoin. Discussion open until July 1,
2000. To extend the closing date one month, a written request must be
filed with the ASCE Manager of Journals. The manuscript for this paper
was submitted for review and possible publication on September 7, 1999.
This paper is part of the Journal of Materials in Civil Engineering, Vol.
12, No. 1, February, 2000. 䉷ASCE, ISSN 0899-1561/00/0001-0024–
0025/$8.00 ⫹ $.50 per page. Paper No. 21799.
24 / JOURNAL OF MATERIALS IN CIVIL ENGINEERING / FEBRUARY 2000
fume (SF) was used to study the role of silica fume on gypsum
formation and the mechanism of sulfate attack. The chemical
compositions of the materials as obtained by EDXA are shown
in Table 1.
The mixture proportion for the alite paste was alite:water =
1:0.48 by mass. The mixture proportion for the alite/SF paste
was alite:SF:water = 0.9:0.1:0.48 by mass. Prisms (8 mm ⫻
16 mm ⫻ 80 mm) with acrylic resin end pieces were used for
expansion measurement. The specimens were demolded after
one day and then cured at 20 ⫾ 1⬚C in saturated limewater
solution. After 14 days of curing, the specimens were divided
into several categories and exposed to different solutions. The
sulfate solutions were made by dissolving the reagent-grade
sodium sulfate (Na2SO4) in deionized water with the level of
SO2⫺
4 concentration of 33,800 ppm (5% Na2SO4), similar to
the solution concentration in ASTM C 1012. The solution and
specimens were kept in plastic containers with ample space
between specimens. The containers with the specimens were
stored in a constant-temperature (20 ⫾ 1⬚C) room. The solu-
tions were replaced with a fresh supply periodically—once a
week for the first month after the start of the exposure and
then once every two months.
RESULTS AND DISCUSSION
The expansion of alite paste specimens, with and without
silica fume, exposed to Na2SO4 solution is shown in Fig. 1.
In 5% Na2SO4 solution, alite paste specimens showed no ex-
pansion for a period of approximately 360 days. After this
‘‘dormant’’ period the specimens began to show significant
expansion. The expansion reached 0.10% at 480 days. Alite/
SF paste specimens showed no expansion during the exposure
period.
As to the physical appearance of alite paste specimens in
Na2SO4 solution, as shown in Fig. 2, there were cracks visible
along the edges of the specimens. The surfaces were scaled.
The alite/SF paste specimens showed no visible damage. The
physical appearance was consistent with the expansion results.
The specimens with large expansion magnitude had visible
cracks and scaling. Those with little or negligible expansion
exhibited no such distress.
The solid phases in the specimens after different exposure
period were examined by X-ray diffraction. Fig. 3 shows the
X-ray diffraction patterns of the specimens after 480 days of
exposure. As expected, the main product formed from sulfate
attack was gypsum. There was more gypsum formed in the
alite paste specimens without SF. For instance, alite paste spec-
imens showed the presence of intense gypsum peaks in their
X-ray patterns, while alite/SF paste specimens showed the

J. Mater. Civ. Eng. 2000.12:24-25.

 TABLE 1. Chemical Compositions of Materials—Mass Percent
Material CaO SiO2 Al2O3 Fe2O3 MgO SO3 K2O Na2O P2O5 MnO2 Total
(1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12)
Alite 72.34 24.76 0.65 0.34 0.92 0.64 0.00 0.24 0.04 0.14 100
SF 0.19 98.25 0.36 0.21 0.00 0.62 0.28 0.14 0.00 0.00 100
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FIG. 3. X-ray Diffraction Patterns of Specimens after 480 Days

of Exposure [G: Gypsum; C: C3S; CH: Ca(OH)2].

FIG. 1. Expansion of Alite Paste and Alite with SF Paste in ing in alite paste specimens subjected to sulfate attack. It is
Na2SO4 Solution not clear that gypsum formation follows either the topochem-
ical reaction mechanism or the through-solution mechanism.
But the experimental results suggest that the sulfate attack
mechanism is complicated and the expansion and cracking of
portland cement concrete is probably not exclusively attributed
to ettringite formation. More research is needed in this area.

ACKNOWLEDGMENTS
This research was supported by the National Science Foundation’s
Center for Advanced Cement-Based Materials. The insightful comments
provided by Dr. Bryant Mather are thankfully acknowledged.

FIG. 2. Physical Appearance of Alite Paste and Alite/SF Paste
Specimens
presence of small gypsum peaks. The X-ray patterns also in-
dicated that some unhydrated C3S remained in all specimens.
SUMMARY
The experimental results showed that gypsum formation
during sulfate attack could be a source of expansion and crack-
APPENDIX. REFERENCES
Bonen, D., and Cohen, M. D. (1992). ‘‘Magnesium sulfate attack on
portland cement paste—I. Microstructural analysis.’’ Cement Concrete
Res., 22, 169–180.
Bonen, D., and Sarkar, S. L. (1993). ‘‘Replacement of portlandite by
gypsum in the interfacial zone and cracking related to crystallization
pressure.’’ Ceramics Transactions, American Ceramics Society, Wes-
terville, Ohio, Vol. 37, 49–59.
Cohen, M. D., and Mather, B. (1991). ‘‘Sulfate attack on concrete—
research needs.’’ ACI Mater. J., 88(1), 62–69.
Gonzalez, M. A., and Irassar, E. F. (1997). ‘‘Ettringite formation in low
C3A portland cement exposed to sodium sulfate solution.’’ Cement
Concrete Res., 27(7), 1061–1072.
Hansen, W. C. (1966). ‘‘Attack on portland cement concrete by alkali
soil and water—a critical review.’’ Hwy. Res. Rec., No. 113, 1–32.
Mather, B. (1996). ‘‘Discussion of ‘The process of sulfate attack on ce-
ment mortars.’’’ Adv. Cement Based Mat., 5, 109–110.
Mehta, P. K. (1992). ‘‘Sulfate attack on concrete—a critical review.’’
Materials science of concrete III, American Ceramics Society, Wester-
ville, Ohio, 105–130.
Ping, X., and Beaudoin, J. J. (1992). ‘‘Mechanism of sulfate expansion
I. Thermodynamic principles of crystallization pressure.’’ Cement Con-
crete Res., 22(4), 631–640.

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J. Mater. Civ. Eng. 2000.12:24-25.