Chap. 9.3-Innovative Cements PDF

Chapter 9.
3 1149
Innovative Cements
by J. Francis Young* and Musarrat Ullah Khan Afridi**
While the production of portland cements and blends with pozzolans and slags dominates
commercial manufacturing, there exists a variety of innovative cements whose production is quite
limited on a worldwide basis. These can be divided into two main categories: low energy cements
and cements for specialty niche markets. Included in the former are belite cements, which have
received considerable attention worldwide. The latter category encompasses cements with such
diverse properties as rapid hardening, expansive characteristics, low alkalinity, and compatibility
with high temperatures and pressures. This chapter is confined to consideration of modified port-
land cements, which is the emphasis of this volume, despite some interesting innovative cements
based on other chemistries.
Figure 9.3.1. Microstructure of a low-energy cement showing sintered α'-C2S, stabilized with BaO,
showing Ba-rich grain boundary phases and exsolutions.
*Professor, University of Illinois, Urbana, IL 61801

**Executive Director, Dadabhoy Construction Technologies (Pvt) Limited, Maqbool Commercial Complex, Block 7&8,
J.C.H.S. Shahrah-e-Faisal, Karachi – 75350, Pakistan, Ph: 092 21 455 4749, e-mail: mukafridi@hotmail.com.
1150 Innovations in Portland Cement Manufacturing
LOW ENERGY CEMENTS

The use of modern cyclone preheater dry process kilns have brought energy consumption down to
less than 3100 kJ/kg (740 kcal/kg) (Locher, 1986). In order to make further energy reductions, three
strategies can be considered:
1. Reduction of the burning temperature by the use of mineralizers and fluxes or other
approaches
2. Reduction of the calcium carbonate content in the raw mix to reduce the energy demands
associated with calcination
3. Blending of clinker with supplementary cementing materials, such as slag or fly ash
A typical low energy cement is shown in Figure 9.3.1. Fluxes and mineralizers are often used in
normal cement manufacture but usually for the purposes of improving the burning characteristics of
specific compositions. Klemm and Skalny (1977) claim that reductions of 100-200°C in the clinkering
temperature can be achieved in this way with an energy savings as high as 625 kJ/kg (150 kcal/kg).
However, this estimate is considered too high by Christensen and Johansen (1979) and Gardeik
(1981), who calculate a savings of only 100-150 kJ/kg. However, if the calcining temperature is also
reduced, the energy savings will be slightly greater.
The second strategy involves the formation of reactive lower lime compounds, such as alinite,
reactive belite, C4A3Æ, or C11A7 ·CaF2 (see Table 9.3.1) which will be discussed in the following
sections. However, the use of fluxing agents to form several of these compounds also allows
clinkering temperatures to be reduced (see Table 9.3.2).
Table 9.3.1. Overview of Low Energy Clinkers (Klemm and Skalny, 1977)
Main clinker minerals Properties applications

Active belite-cement α'-C2S Lower early age strength and higher
C3S later age strength compared to
C3A por tland cement.
Pilot scale experiments in former
East Germany, India and former USSR.
Belite-sulofaluminate β-C2S High early strength, expansive, shor t
–
C4A3S setting time, good chemical durability.
–
or CA, C12A7, CS Special cements in USA, Japan
and former USSR.
Belite-sulfoferrite β-C2S Shor t setting time, high early
cement C4AF strength.
–
C4A3S Industrial production in
–
CS Peoples Republic of China.
Alinite-cement Alinite Chloride content up to 2.5%, high
C11A7·CaCl2 hydraulic activity, steel corrosion
Industrial production in the
former USSR.
Innovative Cements 1151
Table 9.3.2. Reduction of Clinkering Temperatures
Approach Temperature range, °C Remarks

Fluxes and mineralizers 1300–1400 See Ref. 5, for example
Belite-rich cements 1350–1400 Formation of α'-C2S
or rapid cooling required
Formation of alinite 1000–1100 chloride or fluoride-based
Sol-gel processing 600–1100 Not commercially viable
ALINITE CEMENTS
Alinite cements were developed in the 1970s in the former USSR using a special salt flux technol-
ogy and have been used commercially (Chatterjee, 1992). Alinite is a chlorosilicate closely related
to C3S with the approximate formula Ca21Mg(Si0.75Al0.25O4)8O4Cl2 (Locher, 1986 and Bikbauo,
1986) or C21MS6A·CaCl2 in cement chemistry notation. Chlorine ions (Cl –) partially replace O2– in
the original alite structure (Ilukhin and others, 1977) and Mg is essential to the structure (von
Lampe and others, 1986). An alinite clinker contains 3%-4% by weight of chloride (Bikbauo, 1980)
and forms 60-80 wt.% alinite, 10-30 wt.% belite, 5-10 wt.% calcium chloroaluminate
(C11A7 ·CaCl2), and 2-10 wt.% calcium ferrite (C2F). Clinkering studies of alinite compositions
have been reported (Bikbauo, 1980; Agarwal and others, 1986); CaCl2 lowers the calcination
temperature for CaCO3 and promotes the formation of spurrite and C11A7 ·CaCl2 at low tempera-
tures. Alinite crystallizes at 1000-1100°C from a chloride-rich liquid of composition (wt. %):
CaO = 35-45, SiO2 = 18-23, Al2O3 = 2-3, Fe2O3 = 2-5, MgO = 1-2, and CaCl2 = 20-35. It is
unstable at higher temperatures, decomposing to alite.
Alinite reacts vigorously with water and is considerably more reactive than alite (Bikbauo, 1986)
but forms similar hydration products. However, chloride is released during hydration and will
promote corrosion of reinforcing steel. For this reason the fluorine analog would be more suitable
and can be formed at a similar temperature to regular alite (Agarwal and others, 1986; Ludwig and
Urbonas, 1993). However it only has a relatively slow rate of hardening. A sulfide analog,
jasmundite, is only weakly hydraulic (Ludwig and Wolter, 1979).
BELITE CEMENTS
There has been considerable interest over the past 20 years in developing useful cements that have
belite as the major calcium silicate component. The advantages of such a cement are 1) lower
clinkering temperatures, 2) smaller quantities of carbon dioxide are formed per ton of clinker, 3)
use of lower grade limestone, 4) use of lower calorific-value fuels, and 5) a more durable cement
paste, since less calcium hydroxide and more C-S-H is formed. The major drawback is the low rate
of strength gain due to the more sluggish hydration of β-C2S. The strategies that have been
explored to overcome this problem are:
1. Very rapid cooling to form more reactive β-C2S

2. Stabilization of α'-C2S
3. Formation of highly reactive β-C2S at low temperature
4. Presence of sufficient amounts of highly reactive compounds, such as alite or calcium sulfo-
aluminate (C4A3Æ), to provide adequate early strength
Rapid Cooling
Stark and co-workers (1980-a, 1980-b, 1981, 1984, 1985) have shown that very rapid cooling of
belite-rich clinkers can increase the reactivity of the belite and hence the rate of strength develop-
ment. The effect is most noticeable in clinker compositions with a lime saturation factor (LSF) in
the range 78-83 (Stark and others, 1981) (see Figure 9.3.2), since the reactivity of alite is little
changed. Cooling rates investigated (Stark and others, 1980-a) ranged from 100°C/min (normal
cooling) up to 3000°C/min (quenching in water or liquid nitrogen). Cooling down to 900°C at a
rate in excess of 1000°C/min (Ludwig and Wolter, 1979; Stark and others, 1981) is sufficient to give
strength development comparable to conventional portland cement (Figure 9.3.3); this can be
achieved by forced air cooling. Clinkering temperatures as low as 1350°C are sufficient, allowing an
energy reduction of 300 kJ/kg (70 kcal/kg).
60
50
3000
Compressive strength, MPa
°C/min
40
100
°C/min
30
20
10
0
70 80 90 100
Lime saturation factor (LSF)
Figure 9.3.2. Effect of lime saturation factor (LSF) on compressive strength (28 days) after rapid
cooling (Stark and others, 1981).
70
60
28d
Compressive strength, MPa 50
40
30
20 7d
3d
10
0
10 102 103 104
Rate of cooling, °C/min
Figure 9.3.3. Effect of rate of cooling on development of compressive strength (LSF = 80) (Stark and
others, 1981).
It has been shown by Jost and others (1984) that rapid cooling stabilizes α'-C2S, probably by limit-
ing the exsolution of impurities that will occur during slow cooling (von Lampe and Seydel, 1989).
The other phases are not greatly affected by the cooling rate (Table 9.3.3) except at 3000°C/min
when substantial amounts of glass are formed (Stark and others, 1980-a). However, it should be
noted that as cooling rates are increased, the sum of the crystalline phases decrease. High cooling
rates can be obtained on a pilot plant scale (Muller and others, 1985) to give good performance
(Table 9.3.4).
Stark and co-workers (1987) have considered the effects of some specific minor components on the
formation and properties of rapidly cooled belite cements. Alkalis affect strength development in a
manner similar to ordinary portland cements, increasing early (3-day) strengths and lowering
Table 9.3.3. Compound Composition (Wt. %) of a Belite-Rich Clinkers (LSF = 80 Free

Lime <1%) After Different Rates of Cooling (Stark and Others, 1980-a)
Cooling rate,
°C/min Alite α'-Belite β-Belite Glass C 3A C4AF MgO
3000 34 9 0 12 5 1 3
2000 27 33 0 0 10 9 3
1000 30 27 0 0 10 9 3
800 29 31 8 0 11 10 4
20 24 6 44 0 15 6 4
Table 9.3.4. Effect of Cooling on a Pilot Scale Clinker (Alite = 30% α'-Belite = 20-30%,
β-Belite = 15-30%, Interstitials = 17%) (Stark and Others, 1980-b)
Cooling rate, 28-day strength,

Cooling regimen °C/min MPa
Rotar y cooler only 300 43
Fluidized trough → rotar y cooler 1500 54
Hot comminution (impact mill) → 5000 59
fluidized trough → rotar y cooler
28-day strengths. Addition of SO3 (as sulfate) during clinkering promotes the formation of β-
belite at low levels, but α'-belite at higher additions. In these mixes C2S forms from the decompo-
sition of intermediate sulfo-spurrite (2C2S · CÆ).
Stabilization of α'-C2S
Considerable attention has been paid to the formation of cements in which α'-C2S is stabilized by
the presence of foreign ions. Although α'-C2S is also a reactive phase, it is much more difficult to
stabilize at room temperature. Most reactive belite cements rely on the formation of a stable α'
polymorph stabilized by an excess amount of an impurity element. A comparison of reactivities of
the different polymorphs is given in Table 9.3.5. Chemical stabilization of C2S polymorphs (Ghosh
and others, 1979; Moranville-Regourd and Biokova, 1992), and their relative reactivity (Stark and
others, 1979; Young, 1998), have been reviewed.
However, the stabilization of high temperature polymorphs by impurity elements have physical as
well as chemical mechanisms. On cooling, complex microstructures develop as a result of poly-
morphic transformation (Moranville-Regourd and Biokova, 1992; Chan and others, 1992).
Lamellar structures form during the α → α' transformation and twinning during α' → β, while
the β → γ transformation is martensitic and hence strongly dependent on crystal size and matrix
restraint (Matkovic and others,1981). Stabilization of α' by rapid cooling must be due in large part
to inhibiting the nucleation of β or γ structures. Ghose and others (1983), and Chan and others
(1988) observed that during cooling, exsolution of impurity atoms form second phases at grain
boundaries or between lamellae (see Figure 9.3.1). These second phases can be glassy or crystalline
and must play an important role in determining reactivity, since the behavior of a particular poly-
morph depends on the nature of the stabilizer (Young, 1998). For a given stabilizer, α' is always
more reactive than β, but some preparations of β-C2S may be more reactive than certain α'-C2S
preparations, depending on the nature of the stabilizer. Belite-rich clinkers have been prepared in
the laboratory by Bobesic and others (1981), Matkovic and others (1986), and Gies and Knöfel
(1986), but although some pilot scale studies have been carried out, there appear to be no belite-
rich clinkers produced that do not contain calcium sulfoaluminate to provide high early strength.
Table 9.3.5. Comparison of Reactivities of Different Polymorphs of C2S

Compressive strength, MPa
Stabilizer Polymorph 3 days 28 days
BaSO4 α' + β 12 30
β 4 18
Ba2SiO4 α 17* 57
α' 6* 44
β 0* 27
Ca5(PO4)3OH α' + β — 14
β — 3
Na2CO3 + Fe2O3 α 13 34
α + α' 7 20
β 2 6
α' + β 4 12
β 1 5
(Al,Fe)2O3 + (Na,K)2O α 3 21
α' 1 7
β 2 4
*Strengths after 1 day.
Reactive Dicalcium Silicates

During the 1990s, considerable interest has focused on the preparation of highly reactive forms of
β-C2S, spurred by reports (Ishida and others, 1992) on the hydration of β-C2S formed from the
thermal decomposition of hillebrandite (β-C2SH). The subject has been reviewed in detail by
Ishida and Mitsuda (1998). Since then, Nettleship and others (1993), and Hong and Young (1999),
have prepared reactive C2S by the Pechini method of sol-gel processing. Reactive β-C2S is more
reactive than C3S prepared by conventional solid state sintering. The very high surface areas
(> 5 m2/g) are indicative of small crystallite size which probably have high defect concentrations.
Although sol-gel processing is used successfully to produce advanced ceramics, it cannot be the
commercial basis of cement production, which is a commodity market. Nevertheless a modified
version of the Pechini method has been used to prepare the four major clinker compounds
(Lee and others, 1999). The possibility of using this approach for specialty products cannot be
entirely ruled out as a future production approach.
Additions of Reactive Components

The reactivity of even the most reactive forms of α'-C2S cannot reach that of C3S without a very
rapid cooling regimen. Therefore the strength development of belite cements will remain lower
than that of ordinary, alite-rich portland cements unless a reactive component is included in the
formulation. Alite can serve that purpose for both β-belite (Ludwig and Pohlman, 1986) and
α'-belite cements (Bobesic and others, 1981). In the latter case, strengths are comparable to ordi-
nary portland cements by 3 days. According to Mehta (1980), and Raina and others (1978), the
inclusion of reactive aluminates (eg. CA, C12A7, C4A.3 Æ) is a more widely used approach. The use
of C4A3Æ is discussed more fully in the section on sulfoaluminate-belite clinkers.
CALCIUM SULFOALUMINATE CEMENTS

Cements which contain anhydrous calcium sulfoaluminate (C4A3 Æ) as an important constituent
are produced commercially in several countries. China, in particular, has pursued this technology
vigorously as a means of making optimal use of available raw materials. C4A3 Æ is a very reactive
compound and combines with calcium sulfate to form ettringite, which can provide high early
strength in the matter of a few hours. Alternatively, in the presence of free lime, ettringite forma-
tion will be slower but more expansive, and forms the basis of expansive or shrinkage compensat-
ing cements.
Phase Equilibria
The phase equilibria underlying C4A3 Æ formation are reviewed by Blanco-Varela, and others
(1998). In the C-A-CÆ system the only stable ternary compound is calcium sulfoaluminate
(C4A3Æ), and it can readily be formed from mixtures of bauxite, gypsum, and lime at 1350°C. At
this temperature, C4A3Æ has a much lower dissociation than CÆ, but it is not stable at temperatures
greater than 1400°C. When silica is added to the system, calcium sulfoaluminate forms below
1200°C (and perhaps as high as 1400°C), while C3S does not appear as a stable phase in the lime-
rich region. The compatible phases above 1200°C are C, C2S, and C4A3Æ. At lower temperatures,
sulfospurrite (2C2S·CÆ or C2S2Æ) occurs as a stable phase and can co-exist with C4A3Æ, as can C3A.
When iron is added to the system, C4AF is the stable iron phase; an iron analog of C4A3Æ cannot be
formed although there is limited solid solution of iron in the latter.
Therefore, clinkering mixtures of iron-containing bauxites with limestone and gypsum in the
range of 1300°C-1440°C readily produces mixtures of sulfato-belite cements containing “C4AF,”
C4A3Æ, and C2S. The ferrite phase composition will vary depending on the A/F ratio in the raw
mix, but generally tends to an iron-rich composition even when the A/F ratio is high because of
the consumption of Al in C4A3Æ (Boikova and others, 1992). The α'-C2S polymorph is favored by a
combination of Al2O3 and SO3 (the latter being a particularly influential component), but appar-
ently is destabilized by MgO.
Over the past 20 years or so, the formation and properties of belite-sulfoaluminate cements have
been widely examined by several workers including Ikeda (1980), Sudoh and others (1980), Deng
and others (1980), Ali and others (1992), Beretka and others (1993), and Majling and others (1993).
Appropriate mixtures of limestone, bauxite, and anhydrite (or gypsum) can yield a wide variety of
compositions covering binary (C4A3Æ-C2S), ternary (C4A3Æ-C2S-CÆ) and quaternary
(C4A3Æ-C2S-CÆ-C), formulations by firing at 1300°C. This temperature seems to be optimum for
burning. Above 1350°C, C4A3Æ decomposes to C3A, while below 1200°C sulfospurrite (2C2S·CÆ ) is
the major silicate phase and is non-hydraulic. These clinkers can be prepared using industrial by-
product materials such as fly ash or slag as sources of alumina as well as silica and phosphogyp-
sum. Dolomitic limestones can also be used since up to 10% of MgO can be fixed as merwinite
(C3MS2) without deleterious expansion.
Deng and others (1980) blended clinkers with appropriate amounts of gypsum in order to control
the early formation of ettringite, which is responsible for rapid hardening, and later formation,
which provides expansive properties. The presence of free lime is not necessary for early strength,
although an optimum amount has been identified in one study. Early strengths, as might be
expected, increase with decreasing C2S content; this latter phase is primarily responsible for long
term strength. Optimum compositions appear to lie in the range of 40%-50% C4A3Æ, ~35% C2S,
and 15%-25% CÆ. The proportions of C4A3Æ and C2S are controlled by the A/S ratio.
Chinese scientists Deng and others (1980), and Wang and others (1985-a, 1985-b, 1986, 1993), have
developed a suite of calcium sulfoaluminate cements with fairly low belite contents. The cements are
now widely used in China (~ 1 million tons in 1995) and have been called “The Third Series.” Table
9.3.6 shows the compositional range of the two classes of cements which are produced. Widely avail-
able low grade limestones and bauxites with high contents of silica and iron are used for clinker for-
mation, together with natural anhydite or gypsum. The clinkers are burned at 1300°C, and this low
temperature, combined with good grindability, reduces energy requirements. The sequence of clink-
ering reactions is summarized in Table 9.3.7. The clinker is ground with varying proportions of gyp-
sum (and sometimes limestone) to provide appropriate high early strength or expansive properties.
Table 9.3.6. Composition (wt. %) Ranges of Chinese Calcium Sulfoaluminate Clinkers

(Sudoh and Others, 1980)
–
Clinker type C4A3S Ferrite C 2S CS
Sulfoaluminate 55–75 3–6 15–30 <5
Ferroaluminate 35–55 15–30* 15–35 <5
*Ferrite has a composition close to C6AF2
Table 9.3.7. Sequence of Compound Formation in Clinkering (Ikeda, 1980)

Temperature, °C Reaction
830 Decomposition of limestone
–
1000 Formation of intermediatics; C4A3S first appears.
1100 Formation of C2F
1150 Formation of C2S and C4AF begins
1200 Decomposition of C2AS; Formation of C4AF
– –
1250 Formation of C6AF2; C4AS is at a maximum; 2C2S · CS
decomposes to C2S
1300 Compound formation is complete
CALCIUM FLUOROALUMINATE CEMENTS

The influence of calcium fluoride on the phase equilibria has been extensively reviewed by Blanco-
Varela and co-workers (1998). In the lime-rich field fluoro-spurrite (2C2S · CaF2) exists below 1000°C,
while the ternary compound 3C3S · CaF2 exists in a narrow temperature range (1050-1175°C). The
ternary calcium fluoro-aluminate (C11A7 · CaF2) forms in preference to C3A. This compound is
isostructural with C12A7 (or C11A7 · CH) and can form a complete solid solution with it. The fluorine
analog of C4A3S (3CA· CaF2) is a much more stable compound than its sulfate analog, melting at
about 1500°C. The reduction in the temperature of liquid formation (about 40°C) due to the pres-
ence of CaF2 is expected. Furthermore, the phase field of C3S is extended and can form below
1250°C. Therefore portland cement compositions with C11A7 · CaF2 replacing C3A are readily
obtained.
This is the basis of calcium fluoroaluminate cement first developed and patented as regulated set
cement by Greening (1971). Subsequent development of this cement took place most extensively in
Japan under the tradename of Jet® cement. The high reactivity of C11A7 · CaF2 produces a flash set
which can be controlled by the addition of varying amounts of calcium sulfate hemihydrate. Rapid
formation of ettringite causes set and allows useful strength to be developed within an hour or two.
The A/F ratio needs to be optimized in order to maximize early strength and minimize expansion.
To achieve this, the burning temperature should be maintained in the range of 1250°C-1350°C.
According to Knöfel and Wang (1994), Liu and others (1992), and Ikabata and others (1994), rapid
Table 9.3.8. Calcium Fluoroaluminate Clinkers
Clinkering
Clinker temperature, °C C3S C2S C11A7 ·CaF2 Ferrite
Alite-based 1250–1350 50–70 — 20–30 5–10
Belite-based 1250–1450 — 15–30 60–75 < 10
setting belite-fluoroaluminate cements can also be produced (see Table 9.3.8). The reactivity of
C11A7 ·CaF2 depends on the burning temperature and the lime content of the clinker. Above
1300°C C11A7 ·CaF2 will decompose to C3A so the burning temperature should not exceed 1350°C.
In low-lime belite compositions, burning temperatures up to 1400°C can be used.
SPECIAL INORGANIC CEMENTS

In addition to the cements covered above, several other innovative cements and cementitious
materials also exist for special applications. A number of these materials are already in commercial
applications but some are still in the developmental stage that do carry significant scientific inter-
est (Odler, 2000). These cements/cementitious materials are listed in 4 broad categorized as
follows:
• Special portland cements
• Sulfoaluminate, fluoroaluminate, alinite cements
• Aluminous cements, phosphate cements, inorganic binders, and
• Polymer-modified cementitious materials
The types, composition (major phases/components), and applications of these materials are
summarized in Tables 9.3.9 – 9.3.12. Towards the end, two sections, one each on polymer-modified
cementitious materials and superplasticized cements are included. Therein the commercial devel-
opment of these materials and data on salient properties extracted from on-site case studies are
also presented to benefit the readers.
Table 9.3.9. Types, Composition, and Applications of Special Portland Cements

Special portland cements
Types High C3S High C2S Elevated C2S High C3A Low C3A
Major phase
C3S + – – = =
C2S – + + = =
C3A = = = + =
C4AF = = = = –
Parameters LSF=100, LSF=80-90 High alumina High silica
Blaine, modulus modulus
400-500 m2/kg
Applications High early Improved Low heat of Expansive Frost
strength fludity hydration resistance
= equal, + higher, – lower than ordinar y por tland cement (OPC)
Table 9.3.10. Types, Composition, and Applications of Sulfoaluminate, Fluoroaluminate, and

Alinite Cements
Sulfoaluminate, fluoroaluminate, alinite cements
Types Sulfobelite Sulfoalite Sulfoaluminate

–
Major phase C2S (10-60%), C3S (80%), C5S2S (25-77%),
– – –
C4A3S (10-55%) C4A3S (10%) C4A3S (15-55%)
Applications Easy grind non- Easy grind, favorable Rapid early strength
expansive high early strength development
strength, or,expansive
Table 9.3.11. Types, Composition, and Applications of Aluminous Cements, Phosphate

Cements, and Inorganic Binders
Aluminous cements, phosphate cements, inorganic binders
Strontium Barium Magnesium Calcium Aluminate Zinc

Types aluminate aluminate phosphate phosphate phosphate phosphate
Major phase SrO·Al2O3 BaO·Al2O3 MgO, Ca5(PO4)·3OH Al(PO)4 ZnO,
(major), (major), (NH4)2HPO4 H3PO4
SrO·6Al2O3 3BaO·Al2O3
(minor) (minor),
BaO·6Al2O3
(minor)
Applications Refractory Improved High Dentistry, Refractory Dentistry
properties refractory temperature medicine properties applications
properties applications applications
Special portland cements

High specific Low specific
High iron High MgO Low alkali surface surface Mineralized
= = = = = =
= = = = = =
_ = = = = =
+ = = = = =
Low alumina MgO>5% Alkalies Blaine, No CaSO4, SO3 and F
modulus reduced 400-500 m2/kg Blaine, added
<250 m2/kg
Sulfate Blended For use with Accelerate Special Energy
resistance cement subgrade d hydration applications benefits
applications aggregates
Sulfoaluminate, fluoroaluminate, alinite cements

Belite
fluoroaluminate Belite
(iron rich) fluorosulfoaluminate Fluoroalinite Ecocement
C2S (10-50%), C2S (0-23%), C19S7 · CaF2 (35-80%) C11A7· CaCl2, C4AF
C2(A,F) (20-80%), C2(A,F) (30-75%),
C11A7CaF2 (5-60%) C11A7· CaF2 (0-32%),
–
C4A3S (17-34%)
Longer setting time, Very fast setting, Corrosion resistant Fast hardening, low
final strength rapid initial strength strength, used in soil
comparable to OPC stabilization
Aluminous cements, phosphate cements, inorganic binders

Calcium
phospho- Oxychloride/ Belite
silicate oxysulfate aluminate Ferrite Sulfoferrite Borate
–
Hydroxyapatite, MgO·MgCl2eq, βC2S (55-75%), C4AF, C4F3S (10-55%), K2B4O7·4H2Oeq,
–
C2S, MgO·MgSO3eq CA (15-30%), C6AF2 C3FS (0-60%), Na2B8O13·4H2Oeq,
amorphous C12A7 (1-10%) C2S (25-40%) CaCl2
C-S and C-P
High flexural Indoor use, High sulfate Binder in Corrosion Quick setting
strength partition walls, resistant iron ore resistant properties
fire-protection pellets properties
boards
Table 9.3.12. Types, Composition, and Applications of Polymer-Modified Cementitious

Materials
Polymer-modified cementitious materials
Polymer-cement composites
Macro
Polymer- OPC-blast defect-free
modified Calcium furnace (MDF)
Types cement mixes cement based OPC-based slag based cement
Calcium OPC-blast Calcium
aluminate furnace aluminate
OPC, organic cement (86%) OPC (86%) slag (86%) cement (84%)
Major polymer phenol phenol phenol polyvinyl
components dispersion resin (11%) resin (11%) resin (11%) alcohol (6%)
Exceptional Reduced Reduced
Suitable for strength and strength and strength and Exceptional
repair work, mechanical mechanical mechanical mechanical
chemical and properties, properties, properties, properties,
steel corrosion special special special special
Applications resistant applications applications applications applications
POLYMER-MODIFIED CEMENTITIOUS MATERIALS

Portland cement is mostly used in the form of mortars and concretes in field applications.
However, mortars and concretes made by cement have some disadvantages because of the inor-
ganic nature of the material. Such limitations include 1) low tensile, flexural, shear, impact and
bond strengths, 2) large drying shrinkage, 3) tendency to crack with changes in temperature and
moisture, 4) relatively high moisture absorption and permeation, 5) low resistance to corrosive
agents, and 6) rapid loss of gauging water in thin surfacings by evaporation and substrate absorp-
tion. Figure 9.3.4 is an electron micrograph of a hardened unmodified cement mortar where an
abundance of cracks and pores is evident. Mortar constituents i.e. cement hydration products and
sand grains are loosely joined suggesting weak adhesion among themselves (Afridi and others,
2003).
Polymer-modified cementitious mate-

rials are developed to mitigate these
limitations (Omaha, 1998-a). These
materials are mostly developed by using
Figure 9.3.4. SEM photomicrograph

of hardened unmodified cement
mortar showing an abundance of
pores and cracks. Mortar constitu-
ents are loosely connected resulting
in brittle and inferior water-proof-
ness and durability characteristics.
the following polymers, 1) aqueous polymers in dispersion form (latexes and emulsions) like
styrene-butadiene rubber (SBR) latex, poly(ethylene-vinyl acetate) (EVA) emulsion, and poly-
acrylic ester (PAE) emulsion, 2) redispersible polymer powders based on poly(ethylene-vinyl
acetate) emulsion and poly(vinyl acetate-vinyl carboxylate) (Va/VeoVa) emulsion, 3) water-soluble
polymers like cellulose derivatives of methyl cellulose (MC), hydroxyethyl cellulose (HEC),
polyvinyl alcohol (PVAL), polyacrylamide and acrylate monomer, and 4) liquid polymers like
epoxy and unsaturated polyester resins. Among these polymers, usage of latexes and emulsions for
modifying cementitious mixes is growing fast. In general, properties of polymer-modified cemen-
titious materials depend significantly on the type of polymer used, polymer content or polymer-
cement ratio, P/C (defined as the mass ratio of polymer solids in a polymer-based admixture to the
amount of cement in the polymer-modified cementitious material) rather than the water-cement
ratio as considered in conventional cement mixes or both (Omaha, 1998-a, b).
Latexes and emulsions are added to cementitious mixes in ranges 5% to 20% as a polymer-cement
ratio. Process technology of mixing and using the polymer-modified cementitious mixes is similar
to the conventional cement mixes. However, polymer-modified cementitious mixes are usually
moist cured for a few days, and then air cured under their service conditions (Omaha, 1989). Upon
hardening, a monolithic matrix phase with a network structure is developed in them in which
cement hydrate phase and polymer phase (polymer films) interpenetrate. Figures 9.3.5 (a-e) shows
scanning electron micrographs of several polymer films developed in various polymer-modified
cementitious mixes after hardening [Afridi and others, 2003]. These polymer films are responsible
for improved mechanical and durability characteristics of such systems that results in enhanced
properties compared with conventional cement mixes (Omaha, 1998-a).
(a) (b)
Powdered Va/VeoVa-Modified, P/C= 20% Aqueous EVA-Modified, P/C=10%
Figure 9.3.5. SEM photomicrographs showing polymer films developed in various hardened poly-
mer-modified cementitious mixes. The films and cement hydration products interpenetrate and
result in improved mechanical and durability properties. (Continued on next page.)
(c) (d)
Aqueous SBR – Modified, P/C=10% Aqueous SBR– Modified, P/C=20%
(e)
Aqueous EVA – Modified, P/C=20%
Figure 9.3.5. SEM photomicrographs showing polymer films developed in various hardened poly-
mer-modified cementitious mixes. The films and cement hydration products interpenetrate and
result in improved mechanical and durability properties.
COMMERCIAL PRODUCTION OF POLYMER-MODIFIED

CEMENTITIOUS MATERIALS
Availability of polymers as redispersible polymer powders has helped to develop prepackaged poly-
mer-modified cementitious mixes requiring only water to be added at construction site prior to
applications. Prepackaged polymer-modified cementitious mixes are highly helpful in improving
the handling procedures and to avoid mixing errors (Afridi and others, 2003). Figure 9.3.6 (a-c)
shows various types of pre-packaged polymer-modified cementitious materials being produced
commercially in Pakistan. Their typical applications have been in the areas of 1) in-situ water-
Figure 9.3.6. Various types of prepackaged polymer-modified cementitious materials commercially

produced in Pakistan.
proofing, 2) as adhesives, 3) coating, 4) water-proof patching, 5) repairs, and maintenance, and

6) durability improvement. A comparison of typical properties between prepacked polymer-
modified mortar and unmodified mortar cement is given in Table 9.3.13. Evidently the data shows
improved engineering properties of the prepacked polymer-modified mortar than the unmodified
one. Because of the availability of high quality redispersible polymer powders, it has now being con-
templated that aqueous polymer dispersions will be replaced by the redispersible polymer powders
for the production of polymer-modified cementitious mixes in near future (Omaha, 1999).
Table 9.3.13. Comparison of Engineering Properties of Prepacked Polymer-Modified

and Unmodified Mortars
Polymer-
Properties modified mortar Unmodified mortar
Fresh mortar
Air content, % 8.2 6.1
Water retention, % 97 70
Hardened mortar
28-day compressive strength, Mpa 32 23
28-day flextural strength, MPa 13 7.4
28-day tensile strength, MPa 4.7 2.4
Maximum tensile strain, x10-6 1231 385
Flextural modulas of elasticity, x103 Mpa 6.31 7.36
Tensile modulas of elasticity, x103 Mpa 2.27 2.67
Crack coefficient 0.020 0.037
Adhesion in tension, MPa 2.2 0.5
Water absorption, % 9.3 12.2
Water permeation, % 6 66
91-day carbonation depth, mm 10 21
91-day chloride ion penetration depth, mm 10.5 22.5
Freeze-thaw durability factor 72 10
SUPERPLASTICIZED CEMENTS
Superplasticizers (SP) or high range water reducing admixtures (HRWRA) are chemicals which are
mostly added on the job site to concrete mixes in modern concrete technology throughout the
world due to the great benefits attainable with their use in terms of performance, reliability and
economy. Superplasticizers are now available in both liquid and powdered form [Ramachandran,
2001]. The basic advantages of using superplasticizers in concrete mixes include, 1) high workabil-
ity of concrete without additional water, resulting in easy placement without reduction in cement
content and strength, 2) high strength concrete with normal workability but lower water content,
and 3) a concrete mix with less cement but normal strength and workability. Use of superplasti-
cizers in concrete mixes may also produce increased rate of strength development at early ages.
Nonetheless, on-site addition of superplasticizers to concrete mixes may have critical limitations
such as the possibility of wrong dosage administration in the field and therefore lesser assurance of
a centralized quality product, pilferage in the admixture, extra costs due to usage of dispensing
equipment and labor, etc. To mitigate the above limitations, the latest concept is the development
and use of superplasticized cements (SPCs) that have preblended, powdered superplasticizers in
them and hence there is no need for separate addition of a superplasticizer (Ramachandra and
others, 1998; Rossetti and others, 1992).
Rossetti and others [1992] and Afridi and others (2003) have reported regular industrial produc-
tion of superplasticized cements (SPCs) in Italy and Pakistan respectively. Superplasticized
concrete made by such superplasticized cements has consistently shown improved and reliable
performance.
SUPERPLASTICIZED CEMENT DEVELOPMENT AND

APPLICATIONS – A PAKISTANI EXPERIENCE
Both superplasticized ordinary portland cement (SPOPC) and superplasticized sulfate resistant
cement (SPSRC) are produced commercially in Pakistan and are supplied in market. They are
produced as 50-kg bags similar to those of portland cement (Figure 9.3.7).
There are two ways of producing SPSRC and SPOPC, 1) either the powdered superplasticizer is
introduced in the ball mill along with the grinding of clinker and gypsum or, 2) powdered super-
plasticizer is mixed with finished cement in separate mixers specially designed for this purpose. As
regards the quantity of powdered superplasticizer to be added, it depends upon the type of
powdered superplasticizer and is adjusted according to the instructions from the manufacturer of
such powdered superplasticizer and after proper testing at plant laboratories. Afridi and others
[2003] have evaluated the newly developed SPSRC and SPOPC and made recommendations for
their usage.
Figure 9.3.7. Pre-packed Superplasticized Ordinary Portland Cement (POPC) and Superplasticized
sulfate Resistant Cement (SPSRC).
On-Site Applications
Both SPSRC and SPOPC have been used in field successfully. They show improved flowability at
reduced water requirements without segregation and produce high strength/high performance
concretes. Comparison of flowability in terms of flow areas for pastes and mortars); and slump for
concrete batches made with SPSRC (superplasticized sulfate resistant cement) vs SRC (sulfate
resistant cement), and SPOPC (superplasticized ordinary portland cement) vs OPC (ordinary
portland cement), are shown in Tables 9.3.14, 9.3.15, and 9.3.16 respectively. Data in Table 9.3.14
clearly shows that the pastes made with SPSRC has higher flow than those made with SRC at each
stage of testing. The pastes prepared with SPSRC are workable for longer periods than those made
with SRC. Table 9.3.15 shows the effect of water on the flow of mortars made with SPSRC vs SRC
as a function of water demand. Mortars made with SPSRC are more flowable as compared to the
mortars made with SRC at the given w/c ratios. Furthermore mortars made by SRC achieve a flow
of 114 mm at a w/c ratio of 0.45 while the mortars made by SPSRC achieve the same at a signifi-
cantly reduced w/c ratio of 0.35; thus confirming high workability for SPSRC mortars at lower
water contents. Table 9.3.16 shows data on concrete mixes made with SPSRC vs SRC and SPOPC
and OPC. Concrete mixes made with SPOPC and SPSRC have significantly higher slumps than
those made with OPC and SRC respectively at the given w/c ratios; for improved performance such
concretes are preferred in situations where flowing concretes are desired.
Table 9.3.14. Flow of SPSRC vs SRC Pastes By Mini Slump Cone Method (as
Workability Indicator) with Elapsing Time
SPSRC paste SRC paste

Elapsed Average Average
time, min flow dia, mm Observation flow dia, mm Observations
0 79 Fast flowing 46 Slow flowing
10 64 Flowing 43 Slow flowing
60 50 Flowing 39 V. slow flowing
75 44 Slow flowing 38 V. slow flowing
90 42 Loosing flow Sticky to Cone No flow but
v. soft
120 Proper test Stiff but
not possible workable
A strength comparison of concrete prepared with SPSRC and SRC (see Table 9.3.17) confirms that
SPSRC are capable of developing economical mixes by lowering cement content or by partially
replacing it with aggregates. As can be seen, the 7-day compressive strength of concrete made with
SPSRC is higher than the 28-day compressive strength of concrete made with SRC, that strongly
suggests a potential for developing high early strength concretes with the given mix design. Hence,
SPSRC could also potentially be used in situations where high early strength development is
required with the same mix design and slump (Table 9.3.14). In case, higher compressive strengths
are not desired, cement content can be reduced or the mix can be extended by addition of aggre-
Table 9.3.15. Flow of Mortars Made with SPSRC vs SRC as Function of Water to
Cement Ratio
Water to Average flow dia of mortars Average flow dia of mortars

cement ratio made with SPSRC, mm made with SRC, mm
0.35 114 Crumbled
0.40 129 Crumbled
0.45 147.5 114
0.485 161 141
Table 9.3.16. Slump Comparison of Concretes Made with OPC vs SPOPC, and SRC vs
SPSRC Using Varying Mix Designs
Water to
Cement Mix design* cement ratio Slump, mm
OPC 1:2:4 0.52 35
SPOPC 1:2:4 0.52 90
SRC 1:3:3 0.54 102
SPSRC 1:3:3 0.54 178
*1:2:4 = 1 par t cement : 2 par t fine aggregates : par t 4 coarse aggregates
1:3:3 = 1 par t cement : 3 par t fine aggregates : 3 par t coarse aggregates
Table 9.3.17. Strength Properties of Unextended and Extended Mixes of Concrete

Made with SRC and SPSRC
Compressive strength, psi
Cement Mix design* w/c ratio Slump, mm 3-day 7-day 28-day
SRC 1:3:3 0.62 75 1953 2542 3813
SPSRC 1:3:3 0.50 75 2945 3844 4743
SPSRC 1:3.5:3.5 0.62 75 2134 2635 3844
*cement : fine aggregates : coarse aggregates
gates. The concrete made by extended SPSRC mix 1:3.5:3.5 (cement:fine aggregates:coarse aggre-
gates), shown in Table 9.3.17, has achieved higher strengths at all ages than the concrete made by
un-extended mix (1:3:3) of SRC. Therefore, such extended concrete mixes, because of lesser
cement contents, would produce lesser heat of hydration and may as well be useful for large
concreting operations. Furthermore, with proper mix alteration(s), they can also be highly useful
where pumped or flowing concrete is required.
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Chapter 9.

by J. Francis Young* and Musarrat Ullah Khan Afridi**

*Professor, University of Illinois, Urbana, IL 61801

LOW ENERGY CEMENTS

Main clinker minerals Properties applications

Table 9.3.2. Reduction of Clinkering Temperatures

Approach Temperature range, °C Remarks

1. Very rapid cooling to form more reactive β-C2S

Table 9.3.3. Compound Composition (Wt. %) of a Belite-Rich Clinkers (LSF = 80 Free

Cooling rate, 28-day strength,

Table 9.3.5. Comparison of Reactivities of Different Polymorphs of C2S

Reactive Dicalcium Silicates

Additions of Reactive Components

CALCIUM SULFOALUMINATE CEMENTS

Table 9.3.6. Composition (wt. %) Ranges of Chinese Calcium Sulfoaluminate Clinkers

Table 9.3.7. Sequence of Compound Formation in Clinkering (Ikeda, 1980)

CALCIUM FLUOROALUMINATE CEMENTS

Table 9.3.8. Calcium Fluoroaluminate Clinkers

SPECIAL INORGANIC CEMENTS

Table 9.3.9. Types, Composition, and Applications of Special Portland Cements

= equal, + higher, – lower than ordinar y por tland cement (OPC)

Table 9.3.10. Types, Composition, and Applications of Sulfoaluminate, Fluoroaluminate, and

Types Sulfobelite Sulfoalite Sulfoaluminate

Table 9.3.11. Types, Composition, and Applications of Aluminous Cements, Phosphate

Strontium Barium Magnesium Calcium Aluminate Zinc

Special portland cements

Sulfoaluminate, fluoroaluminate, alinite cements

Aluminous cements, phosphate cements, inorganic binders

Table 9.3.12. Types, Composition, and Applications of Polymer-Modified Cementitious

POLYMER-MODIFIED CEMENTITIOUS MATERIALS

Polymer-modified cementitious mate-

Figure 9.3.4. SEM photomicrograph

COMMERCIAL PRODUCTION OF POLYMER-MODIFIED

Figure 9.3.6. Various types of prepackaged polymer-modified cementitious materials commercially

proofing, 2) as adhesives, 3) coating, 4) water-proof patching, 5) repairs, and maintenance, and

Table 9.3.13. Comparison of Engineering Properties of Prepacked Polymer-Modified

SUPERPLASTICIZED CEMENT DEVELOPMENT AND

SPSRC paste SRC paste

Water to Average flow dia of mortars Average flow dia of mortars

Table 9.3.17. Strength Properties of Unextended and Extended Mixes of Concrete

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