Calcium Sulfoaluminate

Cement
Benefits and applications

by Robert J. Thomas, Marc Maguire, Andrew D. Sorensen, and Ivan Quezada

C
alcium sulfoaluminate (CSA) cements were first
introduced around 1960,1 and they have been
produced at industrial scale in China—where they are
known as the Third Cement Series—since the 1970s.
Nevertheless, they have only recently emerged on the North
American market as a high-early-strength, potentially
sustainable alternative to portland cement. This article
provides an overview of the unique features and benefits of
CSA cement, the durability of CSA cement concrete, and
ongoing and potential applications within the concrete industry.
Composition and Chemistry
The chemical composition of CSA cement is very different
from that of portland cement and other common cementitious
and pozzolanic materials (Fig. 1). The oxide composition of
portland cement is dominated by calcium oxide (CaO), silica
(SiO2), and, to a lesser extent, alumina (Al2O3). In cement
chemistry terminology, these oxides are present in the form of
alite (C3S), belite (C2S), aluminate (C3A), and ferrite (C4AF);
refer to Table 1. These compounds hydrate in the presence of
water, forming calcium silicate hydrate (C-S-H) and calcium
hydroxide (also known as CH, portlandite, or slaked lime).
CSA cements are richer in alumina and poorer in calcium
oxide and silica than portland cement; they are also abundant
in sulfate (SO3). These oxides appear mainly in the form of
Ye’elimite (C4A3Ŝ or Klein’s compound, after Alexander
Klein), belite, ferrite, and calcium sulfate. The latter is often
inter-ground with CSA clinker in the form of gypsum or
anhydrite at 15 to 20% by mass, which is significantly higher
than the 3 to 5% typically added to control early hydration of
C3A in portland cement clinker. The main reaction products
are ettringite (C6AŜ3H32), amorphous aluminate, and
monosulfate (C4AŜH18).4-6 The relative abundance of
ettringite depends on the sulfate content of the cement, and

SiO2 Table 1:
Typical phase composition of CSA and portland
Silica cements (% mass)4-11
Fume
Type of portland cement
I II III IV V CSA
F
C3S
Fly Ash Alite
55 50 60 30 35 —

C C2S
20 25 20 50 45 0 to 20
Belite
Slag
Natural C3A
10 <8 10 5 5 —
Pozzolans Aluminate
Portland C4AF
7 10 7 12 10 5 to 15
Cement Ferrite

CSA C4A3Ŝ
— — — — — 50 to 60
Lime Ye’elimite
CŜH2
CaO A12O3 Gypsum
2 to 3 15 to 25
Fig. 1: Oxide composition of CSA and other common cementitious CŜ
Anhydrite
materials (% by mass)2,3

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Fig. 2: Precipitation of ettringite in CSA cement (image courtesy of CTS
Cement)
Fig. 3: ASTM C403/C403M14 setting times for CSA mortar with citric
and boric acid retarders (Note: w/cm = 0.40; admixture dosage by
mass of cement)
therefore on the amount of added calcium sulfate.4
The amount of added calcium sulfate also affects the water
demand for CSA hydration.4 Powers and Brownyard12 showed
that complete hydration of portland cement requires a
water-cementitious materials ratio (w/cm) near 0.42. Complete
hydration of CSA cement can require w/cm as high as 0.78.13
However, the inclusion of belite or other phases in commercial
CSA cements may reduce the overall water demand. Many
researchers report success with water dosages comparable to
those used for portland cement (that is, 0.35 to 0.5).1,4,5,7,8,13
Ettringite precipitates in a needle-like form (Fig. 2) and its
formation at very early age contributes to rapid strength
development. Ettringite often has a negative connotation for
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Fig. 4: Typical compressive strength development in CSA and portland
cement concretes (normalized by 28-day compressive strength)
many practitioners, who associate it with one of two related
deleterious effects—delayed ettringite formation or false set.
The former is discussed in more detail later in this article. The
latter refers to the early formation of ettringite during hydration
of portland cement, which results in premature slump loss. In
CSA cements, this rapid ettringite formation is advantageous
as it contributes significant early-age strength development.
Setting Time and Strength Development
The rapid crystallization of ettringite in hydrating CSA
cements leads to very short setting times. At low water
dosages, initial setting times of 10 minutes or less can be
expected. As in portland cement, increased water dosage and
reduced temperature can extend working times. Citric acid is
effective as a retarding admixture, as shown in Fig. 3. Boric,
gluconic, and tartaric acids have also shown promise as
retarding admixtures.9 With sufficient admixture dosages, cool
mixing temperatures, and sufficient water dosage, setting
times of around 1 hour can be achieved. Nevertheless, setting
times in CSA cements are sometimes prohibitively short, and
setting times longer than 1 hour are difficult to achieve.
Developing effective retarding admixtures is therefore one of
the main research needs related to CSA cements.
As the needle-like ettringite crystals precipitate, they form
a dense interlocking matrix, which produces considerable
early-age strength. As shown in Fig. 4, the rate of strength gain
of concrete produced using CSA cement is extremely fast, even
compared to mixtures made with Type III high-early-strength
portland cement. Mixtures produced with CSA cements gain
about 50% of their ultimate strength within a few hours and
about 90% of their ultimate strength within the first 3 days.
Ultimate compressive strengths of at least 10,000 psi (68.9 MPa)
are easily attained.
Durability
CSA cement pastes, mortars, and concretes seem to exhibit
good durability in comparison with portland cement-based
materials, although the available information is limited. The
rapid precipitation of ettringite in CSA cement pastes forms a
dense microstructure with low porosity and permeability.8,13
As a result, the freezing-and-thawing durability is good.13
Some evidence suggests that the resistance to chloride ion
penetration is also very good, although there is some
disagreement in the literature.4,15,16 There is a need for more
research in this area.
The volume stability of CSA cement is the result of the
expansive precipitation of ettringite. This is the same
mechanism by which Type-K cements (which are blends of
portland cement, CSA, calcium sulfate, and lime) derive their
shrinkage-compensating properties. The volume stability
therefore depends on the relative abundance of ettringite in
the reaction product which, in turn, depends on the amount of
calcium sulfate interground with the clinker.4,5,10 An optimum
addition of calcium sulfate may exist (perhaps near 25%4), at
which the CSA reaction product is volumetrically stable. The
reaction product is expansive above this optimum and will
shrink below it.4 Furthermore, higher water demand in CSA
cement4,6,13 means that CSA cements may exhibit autogenous
shrinkage, even in mixtures with relatively high water content.
This is evidenced by the authors’ previously unpublished data
(Fig. 5), which also indicates that internal curing with
saturated lightweight aggregate can at least partially mitigate
this problem.
The resistance of CSA cements to acid attack has not been
studied. However, due to the absence of lime and reduced
alkalinity,13 CSA cements are less prone to alkali-silica
reaction than portland cement.18-20 It should be noted that,
while the pore solution alkalinity is less in CSA than in
portland cement, it is still sufficient to form a passive layer on
embedded steel reinforcement.13 CSA cement concrete
carbonates at about the same rate as portland cement concrete.4,6
Finally, the high sulfate content of CSA cement ensures that
the reaction products cannot accommodate additional sulfate
ions. Because the reaction products contain neither lime nor
surplus aluminates (that can react with sulfate contaminants),
CSA cement concretes are highly resistant to sulfate attack.4,15
Lastly, the high rate of hydration in CSA cements results in
rapid pore structure refinement, so many of the discussed
durability properties are realized from a very early age.
Production, Sustainability, and Economy
In China, industrial-scale production of CSA cement has
been underway for several decades—production exceeded
1 million tons (907,200 tonnes) per year by the early 2000s.4
CSA cements are produced by clinkering in traditional rotary
kilns. Raw materials can include limestone, gypsum, and
Fig 5: ASTM C169817 autogenous shrinkage in CSA mortar. Internal
curing (IC) was achieved using 100% replacement of fine aggregate
with saturated lightweight fine aggregate
alumina-rich bauxite. A variety of repurposed industrial and
municipal wastes are also appropriate as feedstocks.11 Using
materials such as incinerated municipal waste, recycled
alumina, red mud (bauxite tailings), and flue gas
desulfurization byproduct (synthetic gypsum) reduces the
depletion of natural resources and diverts waste from landfills.21
The clinker phases in CSA cement form at lower
temperatures1,4,7,13,21 than those in portland cement (1250 to
1350°C versus 1450°C [677 to 732°F versus 788°F]). This,
combined with the inclusion of up to 20% calcium sulfate
(which requires no pyroprocessing), reduces the energy demand
for manufacturing CSA cements by up to 60% relative to
portland cement. Because the feedstock and clinker phases are
much lower in calcium oxide, the carbon emissions due to
calcination are reduced by 30 to 50%. Increased friability in
CSA clinker also reduces grinding energy requirements.1,4,11,21
The market price for CSA cement in North America in
2017 is about four times the market rate for Type I/II portland
cement. A portion of the price differential can be explained by
economy of scale; even the millions of tons of CSA produced
in China per year are a mere fraction of portland cement
production. More significant, however, are the increased
quality control demands for CSA cement production. CSA
cements are more sensitive to changes in chemical
composition, which necessitates more frequent and extensive
quality assurance testing. The increased material cost
associated with CSA cement can be offset—at least in
part—by reductions in construction costs (associated with
rapid strength gain) and improved service life.22 Although
CSA cement is still perceived as a niche product, there are
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Fig 6: Placing CSA cement concrete using a volumetric mixer (photo
courtesy of CTS Cement)
producers and distributors on six continents, including at least
three major producers in North America. Several leading
international cement manufacturers have undertaken corporate
efforts to bring CSA cement products to a wider market.
These efforts, combined with increased research into
applications, are expected to greatly increase the market share
of CSA cement in coming years.
Applications
CSA cements and similar materials (for example, Type-K
cement) can be used as additives to ordinary portland cement
to improve volume stability or accelerate setting times. The
present discussion is not concerned with the use of CSA as an
additive or mineral admixture, but instead focuses on CSA
cement as the primary binder in concrete.
The rapid setting and strength gain in CSA cements make
them well suited to infrastructure repair applications. The
California Department of Transportation (CalTrans) has
employed CSA-based materials in pavement repair for at least
a decade.22 Because short setting times can be problematic for
ready mixed concrete applications, these repairs are often
completed using on-site mixing in volumetric mixers (Fig. 6).
The Port of Seattle used CSA-based materials for extensive
pavement rehabilitation at the Seattle-Tacoma International
Airport in 1995. CSA cement-based materials can easily meet
the “4x4 requirement” (4000 psi [27.6 MPa] in 4 hours) of
rapid repair media; consequently, the use of CSA cements in
68 APRIL 2018 | Ci | www.concreteinternational.com
pavement repair is becoming increasingly common.23
Another potential use for CSA cement is in precast
concrete. Precasters typically mix concrete on site, so short
setting times are less of a hindrance than in other ready mixed
concrete operations. In fact, the rapid hydration and strength
gain provided by CSA cements could reduce the need for
steam curing and increase bed turnover by significant margins.
Lastly, the resistance of CSA cement to sulfate attack also
suggests an immunity to biogenic sulfide corrosion, indicating
that there should be potential applications in wastewater
infrastructure. This market could include precast as well as
site-cast products.
Conclusions and Future Directions
Despite high cost relative to portland cement, CSA cement
offers several important benefits such as:
•• Rapid hydration and high early strength without the use of
chemical admixtures or steam curing;
•• Lower carbon footprint and embodied energy compared
with ordinary portland cement; and
•• Potentially good durability.
Currently, CSA cement concrete is employed in a
relatively limited capacity (primarily as a rapid pavement
repair material), but further applications will likely be
realized soon. The primary barrier to widespread application
of CSA cement within the concrete industry is difficulty
extending the setting time beyond 1 hour, which hinders its
use in ready mixed concrete batch plants. Effective retarders
for CSA cement hydration remain the most significant
research need in this area.
References
1. Hargis, C.W.; Telesca, A.; and Monteiro, P.J.M., “Calcium
Sulfoaluminate (Ye’elimite) Hydration in the Presence of Gypsum,
Calcite, and Vaterite,” Cement and Concrete Research, V. 65, Nov. 2014,
pp. 15-20.
2. Lothenbach, B.; Scrivener, K.; and Hooton, R.D., “Supplementary
Cementitious Materials,” Cement and Concrete Research, V. 41, No. 12,
Dec. 2011, pp. 1244-1256.
3. Burris, L.E.; Alapati, P.; Moser, R.D.; Ley, M.T.; Berke, N.; and
Kurtis, K.E., “Alternative Cementitious Materials: Challenges and
Opportunities,” Durability and Sustainability of Concrete Structures,
SP-305, M.A. Chiorino, L. Coppola, C. Mazzotti, R. Realfonzo, and
P. Riva, eds., American Concrete Institute, Farmington Hills, MI, 2015,
pp. 27.1-27.10.
4. Glasser, F.P., and Zhang, L., “High-Performance Cement Matrices
Based on Calcium Sulfoaluminate-Belite Compositions,” Cement and
Concrete Research, V. 31, No. 12, Dec. 2001, pp. 1881-1886.
5. Péra, J., and Ambroise, J., “New Applications of Calcium
Sulfoaluminate Cement,” Cement and Concrete Research, V. 34, No. 4,
Apr. 2004, pp. 671-676.
6. Winnefeld, F., and Lothenbach, B., “Hydration of Calcium
Sulfoaluminate Cements – Experimental Findings and Thermodynamic
Modeling,” Cement and Concrete Research, V. 40, No. 8, Aug. 2010,
pp. 1239-1247.
 7. Coumes, C.C.D.; Courtois, S.; Peysson, S.; Ambroise, J.; and Pera, 23. Guan, Y.; Gao, Y.; Sun, R.; Won, M.C.; and Ge, Z., “Experimental
J., “Calcium Sulfoaluminate Cement Blended with OPC: A Potential Study and Field Application of Calcium Sulfoaluminate Cement for
Binder to Encapsulate Low-level Radioactive Slurries of Complex Rapid Repair of Concrete Pavements,” Frontiers of Structural and Civil
Chemistry,” Cement and Concrete Research, V. 39, No. 9, Sept. 2009, Engineering, V. 11, No. 3, Sep. 2017, pp. 338-345.
pp. 740-747.
8. García-Maté, M.; Santacruz, I.; De la Torre, á.G.; León-Reina, Received and reviewed under Institute publication policies.
L.; and Aranda, M.A.G., “Rheological and Hydration Characterization
of Calcium Sulfoaluminate Cement Pastes,” Cement and Concrete
Composites, V. 34, No. 5, May 2012, pp. 648-691.
9. Zajac, M.; Skocek, J.; Bullerjahn, F.; and Haha, M.B., “Effect of ACI member Robert J. Thomas is a
Retarders on the Early Hydration of Calcium-Sulpho-Aluminate (CSA) Postdoctoral Research Associate in the
Type Cements,” Cement and Concrete Research, V. 84, June 2016, Department of Civil and Environmental
pp. 62-75. Engineering at Utah State University
10. Telesca, A.; Marraccoli, M.; Pace, M.L.; Tomasulo, M.; Valenti, (USU), Logan, UT. His research focuses
G.L.; and Monteiro, P.J.M., “A Hydration Study of Various Calcium on development and characterization
of novel and advanced materials to
Sulfoaluminate Cements,” Cement and Concrete Composites, V. 53,
improve sustainability in the concrete
Oct. 2014, pp. 224-232.
industry. Thomas is a member of ACI
11. Xu, L.; Wu, K.; Li, N.; Zhou, X.; and Wang, P., “Utilization of
Committee 123, Research and Current Developments. He
Flue Gas Desulferization Gypsum for Producing Calcium Sulfoaluminate
received his PhD in civil engineering from Clarkson University,
Cement,” Journal of Cleaner Production, V. 161, 2017, pp. 803-811.
Potsdam, NY, in 2016.
12. Powers, T.C., and Brownyard, T.L, “Studies of the Physical
Properties of Hardened Portland Cement Pastes,” ACI Journal
Marc Maguire is an Assistant Professor
Proceedings, V. 43, No. 9, Dec. 1946, pp. 469-504. in the Department of Civil and
13. Bernardo, G.; Telesca, A.; and Valenti, G.L., “A Porosimetric Environmental Engineering at USU. His
Study of Calcium Sulfoaluminate Cement Pastes Cured at Early Ages,” research has focused on concrete, in
Cement and Concrete Research, V. 36, No. 6, June 2006, pp. 1042-1047. all of its manifestations, and he was
14. ASTM C403/C403M-16, “Standard Test Method for Time the 2017 Precast/Prestressed Concrete
of Setting of Concrete Mixtures by Penetration Resistance,” ASTM Institute Educator of the Year. His recent
International, West Conshohocken, PA, 2016, 7 pp. research has focused on accelerated
15. Dachtar, J., “Calcium Sulfoaluminate Cement as Binder for bridge construction, rapid concrete
Structural Concrete,” PhD dissertation, University of Sheffield, Sheffield, repair, and partially composite sandwich wall panel behavior.
UK, 2004, 232 pp. He received his PhD in civil engineering from Virginia Tech,
16. Jen, G.; Stompinis, N.; and Jones, R., “Chloride Ingress in a Blacksburg, VA, in 2013.
Belite-Calcium Sulfoaluminate Cement Matrix,” Cement and Concrete
Research, V. 98, Aug. 2017, pp. 130-135. Andrew D. Sorensen is an Assistant
17. ASTM C1698-09, “Standard Test Method for Autogenous Strain Professor in the Department of Civil
of Cement Paste and Mortar,” ASTM International, West Conshohocken, PA, and Environmental Engineering at USU.
2009, 8 pp. His research focuses on the behavior
of cementitious infrastructure and
18. Zang, L.; Su, M.; and Wang, Y., “Development of the Use of
building materials under extreme and
Sulfo- and Ferroaluminate Cements in China,” Advances in Cement
multi-hazard loading events as well
Research, V. 11, No. 1, Jan. 1999, pp. 15-21.
as providing improved, sustainable
19. Quillin, K., “Performance of Belite-Sulfoaluminate Cements,”
materials for their repair. He received his
Cement and Concrete Research, V. 31, No. 9, Sept. 2011, pp. 1341-1349.
PhD in architectural engineering from the
20. Juenger, M.C.G.; Winnefeld, F.; Provis, J.L.; and Ideker, J.H.,
University of Nebraska–Lincoln, Lincoln, NE, in 2009.
“Advances in Alternative Cementitious Binders,” Cement and Concrete
Research, V. 41, No. 12, Dec. 2011, pp. 1232-1243. Ivan Quezada is a PhD Student in the
21. Arjunan, P.; Silsbee, M.R.; and Roy, D.M., “Sulfoaluminate- Department of Civil and Environmental
Belite Cement from Low-Calcium Fly Ash and Sulfur-rich and Other Engineering at USU. His PhD work
Industrial Byproducts,” Cement and Concrete Research, V. 29, No. 8, is focused on rapid repair media for
Aug. 1999, pp. 1305-1311. concrete pavements. He received his
22. Wang, T.; Lee, I.S.; Harvey, J.; Kendall, A.; Lee, E.B.; and Kim, C., MS in structural engineering from USU
“UCPRC Life Cycle Assessment Methodology and Initial Case Studies in 2014.
on Energy Consumption and GHG Emissions for Pavement Preservation
Treatments with Different Rolling Resistance,” Research Report:
UCPRC-RR-2012-02, Caltrans, Sacramento, CA, 2012, 1144 pp.

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