Cement
Benefits and applications
C
alcium sulfoaluminate (CSA) cements were first chemistry terminology, these oxides are present in the form of
introduced around 1960,1 and they have been alite (C3S), belite (C2S), aluminate (C3A), and ferrite (C4AF);
produced at industrial scale in China—where they are refer to Table 1. These compounds hydrate in the presence of
known as the Third Cement Series—since the 1970s. water, forming calcium silicate hydrate (C-S-H) and calcium
Nevertheless, they have only recently emerged on the North hydroxide (also known as CH, portlandite, or slaked lime).
American market as a high-early-strength, potentially CSA cements are richer in alumina and poorer in calcium
sustainable alternative to portland cement. This article oxide and silica than portland cement; they are also abundant
provides an overview of the unique features and benefits of in sulfate (SO3). These oxides appear mainly in the form of
CSA cement, the durability of CSA cement concrete, and Ye’elimite (C4A3Ŝ or Klein’s compound, after Alexander
ongoing and potential applications within the concrete industry. Klein), belite, ferrite, and calcium sulfate. The latter is often
inter-ground with CSA clinker in the form of gypsum or
Composition and Chemistry anhydrite at 15 to 20% by mass, which is significantly higher
The chemical composition of CSA cement is very different than the 3 to 5% typically added to control early hydration of
from that of portland cement and other common cementitious C3A in portland cement clinker. The main reaction products
and pozzolanic materials (Fig. 1). The oxide composition of are ettringite (C6AŜ3H32), amorphous aluminate, and
portland cement is dominated by calcium oxide (CaO), silica monosulfate (C4AŜH18).4-6 The relative abundance of
(SiO2), and, to a lesser extent, alumina (Al2O3). In cement 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
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 Fig 5: ASTM C169817 autogenous shrinkage in CSA mortar. Internal
addition of calcium sulfate may exist (perhaps near 25%4), at curing (IC) was achieved using 100% replacement of fine aggregate
with saturated lightweight fine aggregate
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 alumina-rich bauxite. A variety of repurposed industrial and
cement4,6,13 means that CSA cements may exhibit autogenous municipal wastes are also appropriate as feedstocks.11 Using
shrinkage, even in mixtures with relatively high water content. materials such as incinerated municipal waste, recycled
This is evidenced by the authors’ previously unpublished data alumina, red mud (bauxite tailings), and flue gas
(Fig. 5), which also indicates that internal curing with desulfurization byproduct (synthetic gypsum) reduces the
saturated lightweight aggregate can at least partially mitigate depletion of natural resources and diverts waste from landfills.21
this problem. The clinker phases in CSA cement form at lower
The resistance of CSA cements to acid attack has not been temperatures1,4,7,13,21 than those in portland cement (1250 to
studied. However, due to the absence of lime and reduced 1350°C versus 1450°C [677 to 732°F versus 788°F]). This,
alkalinity,13 CSA cements are less prone to alkali-silica combined with the inclusion of up to 20% calcium sulfate
reaction than portland cement.18-20 It should be noted that, (which requires no pyroprocessing), reduces the energy demand
while the pore solution alkalinity is less in CSA than in for manufacturing CSA cements by up to 60% relative to
portland cement, it is still sufficient to form a passive layer on portland cement. Because the feedstock and clinker phases are
embedded steel reinforcement.13 CSA cement concrete much lower in calcium oxide, the carbon emissions due to
carbonates at about the same rate as portland cement concrete.4,6 calcination are reduced by 30 to 50%. Increased friability in
Finally, the high sulfate content of CSA cement ensures that CSA clinker also reduces grinding energy requirements.1,4,11,21
the reaction products cannot accommodate additional sulfate The market price for CSA cement in North America in
ions. Because the reaction products contain neither lime nor 2017 is about four times the market rate for Type I/II portland
surplus aluminates (that can react with sulfate contaminants), cement. A portion of the price differential can be explained by
CSA cement concretes are highly resistant to sulfate attack.4,15 economy of scale; even the millions of tons of CSA produced
Lastly, the high rate of hydration in CSA cements results in in China per year are a mere fraction of portland cement
rapid pore structure refinement, so many of the discussed production. More significant, however, are the increased
durability properties are realized from a very early age. quality control demands for CSA cement production. CSA
cements are more sensitive to changes in chemical
Production, Sustainability, and Economy composition, which necessitates more frequent and extensive
In China, industrial-scale production of CSA cement has quality assurance testing. The increased material cost
been underway for several decades—production exceeded associated with CSA cement can be offset—at least in
1 million tons (907,200 tonnes) per year by the early 2000s.4 part—by reductions in construction costs (associated with
CSA cements are produced by clinkering in traditional rotary rapid strength gain) and improved service life.22 Although
kilns. Raw materials can include limestone, gypsum, and CSA cement is still perceived as a niche product, there are