CEMCON-04975; No of Pages 14

Cement and Concrete Research xxx (2015) xxx–xxx

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Cement and Concrete Research

journal homepage: http://ees.elsevier.com/CEMCON/default.asp

Research review of cement clinker chemistry

Horst-Michael Ludwig a,⁎, Wensheng Zhang b
a
Finger-Institute for Building Materials Science, Bauhaus-Universität Weimar, Weimar, Germany
b
State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100024, China

a r t i c l e i n f o a b s t r a c t

Article history: This paper aims to review the progress in cement clinker chemistry since the last International Conference on the
Received 12 May 2015 Chemistry of Cement in 2011. Although Portland cement clinker is still, by far, the most important compound of
Accepted 13 May 2015 modern cements we show that there is a strong development of alternatives. This is mainly due to the emission of
Available online xxxx
carbon dioxide during the calcination of calcium carbonate as raw material whose reduction is the goal of inter-
national activity due to anthropologically caused climate change. Furthermore, it is an objective to use both more
Keywords:
Clinker
raw materials that are located close to the concrete plants and alternative fuels. Developments in the field of ce-
Ca3SiO5 ment clinker chemistry show a potential for alternatives. Thereby we discuss both old and new ideas. But it has
Ca3SiO4 been shown that the substitution of Portland cement clinker has to consider not only reduction in CO2 emission
Sulfoaluminate during fabrication: For practical solutions the performance in both in terms of strength development and dura-
Blended cement bility has to be adequate compared to the ordinary Portland cement clinker.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction classical Portland cement. The main component of Portland-composite

Since the first Portland cement with the present definition was pro-
duced in 1843 by William Aspdin there has been a continuous process of
evolution in cement process technology and cement itself. Compared
with other industries the speed of development has been moderate,
which can certainly be explained by the huge efforts needed to achieve
safe and standardized concrete construction. However, since some
years there has been a significant increase in the development rate of
new cementitious binders. The main impulse for this development is
given by the international agreement linked to the United Nations
Framework Convention on Climate Change to reduce global CO2 emis-
sion (i.e. Kyoto Protocol). Due to the fact that cement production is
responsible for 5% of the global CO2 emission (i.e. 0.95 tons of CO2 per
ton of Portland cement) and also the introduction of the European
Union Emission Trading System the cement industry is facing the chal-
lenge to reduce CO2 emission. Furthermore concrete production has
joined the debate on sustainability of the material and production
processes.
To date the most effective way to reduce CO2 emission of cement
production is to reduce the clinker content by blending cements with
Supplementary Cementitious Materials (SCMs). These SCMs typically
are ground granulated blast furnace slag, fly ash, silica fume and lime-
stone. In several countries and for several applications these Portland-
composite cements (CEM II according to EN 197-1 and type IS, IP and
IT according to ASTM C595/C595M) have already partly replaced the
⁎ Corresponding author.
E-mail address: horst-michael.ludwig@uni-weimar.de (H.-M. Ludwig).
cements remains the Portland cement clinker that is burnt in a rotary
kiln.
In the light of these facts, the fundamental understanding of clinker
chemistry remains an important issue and will become even more im-
portant if, as often desired, the SCM percentage further increases. The
main drawback of cements containing a high percentage of SCM is the
low early strength. Additionally, the durability of concretes is affected
by SCMs. Optimisation of SCM characteristics can only partly improve
these issues. A more effective option could be to target an increase in
performance of the clinker fraction in blended cements. Thus, either
the search for SCM specific accelerators or improved clinker reactivity
is needed. To improve clinker reactivity a detailed characterization of
clinker phases starting from chemical composition of clinker phases
including minor components, crystallographic and microstructural
characterization is a fundamental prerequisite.
Aside from the development of cement composition also the
production conditions of Portland cement clinker have changed sig-
nificantly. Following the rising social demand for CO2 reduction and
sustainability an increasing amount of secondary fuels and raw ma-
terials are used in the cement production process. Who would have
thought two decades ago that today some cement plants use up
to 100% secondary fuels for production and in some countries (e.g.
Germany, Switzerland, Austria) the mean proportion of secondary
fuels reaches 70%. These developments have induced important chang-
es not only to process technology but also to product composition
(chemical and mineralogical composition of clinkers). To ensure the
quality of the product the potential changes with respect to reactivity
have to be understood. In this way it may also be possible to identify

http://dx.doi.org/10.1016/j.cemconres.2015.05.018
0008-8846/© 2015 Elsevier Ltd. All rights reserved.

Please cite this article as: H.-M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr. Res. (2015), http://dx.doi.org/
10.1016/j.cemconres.2015.05.018
2 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
advantages of secondary raw and fuel materials (e.g. increased reactiv-
ity to due incorporation of minor components introduced by secondary
materials).
In addition to reduction of cement clinker content by blending
cements with SCMs a couple of other alternative ideas to reduce the
CO2 footprint of cements exist. There are binary or ternary cementitious
materials composed of SCMs and activators (geopolymers, sulfate
containing slag cements etc., which is the subject of another paper in
this volume) or cements based on complete different materials.
Intensive research and development is currently carried out on
Calcium Sulfoaluminate and binders based on reactive C2S polymorphs
(Ca-Si-Bi) or hydraulic calcium hydro silicates (Celitement).
Our review starts with the main compounds of OPC clinker alite and
belite. Then we focus on the alternative fuels and raw materials (AFR)
for the cement production. Finally we report on alternative binders.
2. Research on tricalcium silicate (alite)
2.1. Polymorphism, crystal structure and stabilization of alite
2.1.1. Polymorphism and crystal structure of alite
Tricalcium silicate (C3S) has a nesosilicate structure with isolated
[SiO4] tetrahedra which are connected by Ca–O polyhedra. Because of
the importance of alite, much research work has been done on the
crystal structure of C3S in the past 80 years. C3S exhibits a complex
polymorphism depending on temperature or impurities [1]. Due to
the complicated structure and the difficulty in preparing single crystal
of C3S, it is difficult to obtain crystal structure information of individual
polymorphs. The analysis of the crystal structure of C3S has been mainly
based on powder XRD, DTA and optical microscopy. Only three
polymorphic structures (R, M3 and T1) of C3S have been determined
by synthesizing single crystals [2–5]. In order to perform accurate
Rietveld quantitative phase analysis (QXRD), several studies in the last
decade have focused on the crystal structure of alite [6–10]. Various
models are available for T1, T2, T3, M1, M3 and R polymorphs, however,
there is still no structural model for the M2 polymorph. Since various
models are available for the polymorphs normally found in clinker,
few studies have been done on the crystal structure of alite in the past
five years.
The XRD pattern permits the determination of the dimensions and
symmetries of the various lattices, but little information can be derived
about precise atomic positions in the structure. To resolve these prob-
lems and to learn more details about the structure of C3S we recently
synthesized single crystals of suitable size (4 mm) using the high tem-
perature optical floating zone furnace [11]. The single crystal of pure
C3S was tested using a CCD single crystal diffraction. 736 atomic param-
eters were refined. The final crystallographic R factor is 3.58%, which is
much smaller than that reported by Golovastikov (R = 9.7%) [12].
This is by far the most exact determination for the structure of C3S.
Space group: P-1(No.2), Lattice parameters: a = 13.719(2) Å, b =
14.291(3) Å, c = 11.745(2) Å, α = 90.235(3)°, β = 94.395(3)°, γ =
104.306(4)°, V = 2224.1(7) Å3, Z = 18. The structure is shown in
Fig. 1. It can be seen from Fig. 2 that the structure of C3S can be consid-
ered as a three-dimensional assemblage of [O3Ca12] trimers. Three
[OCa6] octahedra are connected to form a [O3Ca12] trimer, the trimer
extends along the [112] direction and has a zigzag conformation. It
can be seen in Fig. 3 that oxygen atoms are present in two different
coordination environments. Among the 45 atomic sites, nine are
present in special coordination environment such as O(5), O(6) and
O(9). They are octahedrally coordinated by 6 calcium ions. It is believed
that these special oxygen atoms account for the high reactivity of C3S.
The ordinary O in SiO4 is subject to sp3 hybridization, which is a
covalent bond, whereas, the special O in [OCa6] is not connected with
small radius Si, and the Ca–O–Ca is an ionic bond. The latter O would
be likely to have higher activity.
Please cite this article as: H.-M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr. Res. (2015), http://dx.doi.org/
10.1016/j.cemconres.2015.05.018
Based on the known structure, the different polymorphs differ by the
silicate tetrahedral orientations. It is known that a higher symmetry of
[SiO4] tetrahedron is attained as the structural symmetry of alite in-
creases [13]. In any case, the accurate structure (atomic position) of dif-
ferent polymorphs (especially for T2, T3, M1 and M2) is still not fully
understood.
2.1.2. Stabilization of high temperature polymorphs of alite
Pure C3S exhibits polymorphism when heated and can be triclinic
(T1, T2, or T3), monoclinic (M1, M2, or M3), or trigonal (R). While at
room temperature pure C3S only exists in the T1 (triclinic) form, the
higher temperature forms (T2, T3, M1, M2, M3 and R) are not stable
even if C3S is quenched [1]. A practical way to stabilize high temperature
polymorphs is doping with foreign ions. Because the hydraulic reactivity
of C3S polymorphs can be enhanced by doping with foreign ions, this
subject has gained great attention in recent studies.
2.1.2.1. Individual ions. The influence of individual ions on the structure
of C3S has been extensively studied in the past decades [8]. It was
found that the higher the crystal symmetry of C3S, the less stabilizing
ions can be incorporated. Based on the chemical structure of the ions,
the basic patterns of substitution are summarized in Table 1. By defining
a quantity called structure difference factor D [8], in which the structural
parameters, such as radius, electrovalence and electronegativity of the
substituent ion were taken into account with respect to Ca2+, the rela-
tionships between the chemical structure parameters of substituent
ions and their substitution patterns and abilities to stabilize the
higher-temperature forms of C3S have been established and quantified.
As is shown in Table 1, the substitution position changes gradually from
Ca to Si as the value of D increases, and at D ≥ 0.676 (D value for Ti4+)
foreign ions start to replace silicon.
The presence of MgO has a stabilizing effect on C 3 S formation
(decrease in temperature of formation, acceleration of the process,
smaller crystals, M3 alite modification). Also an increase in C 4AF
content was observed in the presence of MgO [14–16]. A small
amount of Al2O3 was shown to be effective in stabilizing the M3-type
polymorph of alite [17]. Alite with a high P5 + concentration
(P2O5 ≥ 0.5 m.-%) can be stabilized as R-type alite [18]. The phase trans-
formations of alite during reheating are mainly correlated with the
polymorphic form of alite and the kind and amount of foreign ions in-
corporated. For example, for alite stabilized as M3 type and with high
Mg2+ concentration (2% MgO), the reversion to triclinic at 600 °C on
the reheating was blocked. The presence of Fe3+ has a reverse effect,
i.e. the presence of Fe3 + promotes the transformation from M3 to T
type [13]. In addition, it was also shown that the lattice parameters of
alite vary linearly with the amount of foreign ions up to their limits. A
Fig. 1. T1 structure of pure C3S.
 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
Fig. 2. Schematic illustration of the structural elements for T1.
discontinuity at particular concentration for phase transformation
boundary or changes in the substitution pattern is observed that follows
Vegard's law [19,20].
The stabilization of C3S polymorphs by guest ions is shown schemat-
ically in Fig. 4.
As shown in Fig. 4 the stabilization range of C3S polymorphisms is
dependent on the D value suggesting that higher symmetry polymorphs
can be stabilized with the increase in the difference between the sub-
stituent ion and the parent ions.
Besides the nature of the foreign ions also the level of substitution
plays an important role in the stabilization of high temperature poly-
morphs. Accordingly, it is known that higher temperature polymorphs
are stabilized with increasing amounts of guest ions. Thus, the lattice
distortion caused by ionic substitution could readily account for the sta-
bilization of high temperature polymorphs.
Fig. 3. Schematic illustration of the coordination of O atoms.
Please cite this article as: H.-M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr. Res. (2015), http://dx.doi.org/
10.1016/j.cemconres.2015.05.018
3
2.1.2.2. Multiple ions. As constituents of the raw materials and fuels used
in the production of cement clinker, foreign ions such as Na2O, K2O,
MgO, SO3, and P2O5 are unavoidably present during the formation of
alite. As a result, a limited amount of these oxides are introduced into
the chemical structure of alite. When several foreign ions are jointly
present in alite, the structure and reactivity of alite are not additively
changed but depend on the mutual interactions of these ions [13,18,
21,22] which can be significantly different from the individual effects
of each ion. Due to the complexity of clinker, a vast number of
interacting factors such as the amount of liquid formed, its appearance,
temperature, viscosity, surface tension and other clinker minerals can
be involved in the effect of foreign ions on alite. Recently, the effect of
the combined doping of the seven typical foreign ions (Na+, K+,
Mg2+, Al3+, Fe3+, S6+ and P5+) in clinker has been studied systemati-
cally by synthesizing pure alite phase. Compared with single doping,
multiple foreign ions can more easily stabilize the higher temperature
forms of alite [13]. The combined doping with normal concentrations
of all the doped foreign ions could favor the formation of alite and pro-
mote the M3-type alite stabilization. In this respect, Mg2 + and Al3 +
seem to have the most significant effect on the stabilization of the
higher-temperature forms of alite. The absence of either Mg2+ or Al3+
resulted in the stabilization of T2-type alite.
2.1.2.3. Influence of minor or trace elements on clinker and alite formation.
As stated before, the impact of foreign ions incorporated into the struc-
ture of C3S influences the reactivity, but this effect depends strongly on
the incorporation level. Likewise the impact of foreign ions on the prop-
erties of cement clinker is modified. It is known that minor or trace
components derived from raw materials or fuels affect both clinker for-
mation and reactivity. During the past years, continuous efforts have
been made to study the incorporation of various foreign ions (alone or
in combinations) in the cement clinker and their effects on the clinker
formation and cement properties.
MgO and SO3 are the most common minor components of cement
clinkers. Recently, the effects of MgO, SO3, temperatures and sintering
times (alone or in combination) on the clinker formation and alite poly-
morphisms were studied by applying ex-situ XRD quantitative analysis
[14,15]. It was found that the C3S and C2S contents were linearly related
to the SO3/MgO ratio. MgO can enhance the formation of C3S both by ac-
celerating the clinkerization reactions and by lowering the formation
4 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx

Table 1
[8] Chemical structure parameters of average ions incorporated in alite and their substitution patterns in C3S.

Ions Ionic radius (pm) Coordination number Electronegativity Substitution pattern D* value

O2− 140 – 3.44 – −2.021

F− 136 – 3.98 F→O −1.114
Li+ 60 6* 0.98 Li → Ca/interstitial or Ca/Si [6] −0.008
Na+ 95 12 0.93 Na → Ca/interstitial −0.003
Ca2+ 99 6,8 1 – 0
Sr2+ 113 8* 0.95 Sr → Ca 0.014
K+ 133 12 0.82 K → Ca 0.062
Ba2+ 138 12 0.89 Ba → Ca 0.087
Mn2+ 80 6 1.55 Mn → Ca 0.211
Mg2+ 65 6 1.31 Mg → Ca 0.213
Zn2+ 74 4 1.65 Zn → Ca 0.328
Cu2+ 72* 4 1.9 Cu → Ca 0.491
Ti4+ 68 6 1.54 Ti → Si 0.676
Cr3+ 64 6 1.66 Cr → Ca/Si 0.7
Al3+ 50 4,6 1.61 Al → Ca/Si/ hole 0.906
Ga3+ 62 6 1.81 – 0.908
Fe3+ 60 6 1.83 2Fe → Ca + Si 0.981
Mn4+ 52* 4* 1.55 Mn → Si 1.044
Si4+ 41 4 1.9 – 2.109
P5+ 34 4 2.19 P → Si 3.907
S6+ 29 4 2.58 S → Si 6.703

*Structure difference factor D (referred to Ca2+), D = Z*△x*(Rc − R)/Rc, where Z and R = the charge and radius of a ion respectively; △x = electronegativity difference between the el-
ement and Ca; Rc = Ca2+ radius.

temperature of C3S. Although SO3 hindered the formation of C3S, its neg-
ative effects can be compensated by the addition of MgO. The amount of
C4AF can be increased with the addition of both MgO and SO3. Besides, it
was also found that MgO can favor the formation of M3 type alite,
whereas SO3 promoted the stabilization of M1 type alite, just as it has
been described in the literature [23,24].
Another study on the use of fines and sludge generated out of the
production of porphyry and dolomitic limestone for Portland clinker
production has shown that these alternative raw materials have some
additional advantages because of their higher MgO content. MgO com-
bined in combination with alkali and SO3 has fluxing activities whereby
the alite formation is promoted which could improve the burnability of
the alternative clinkers [25]. In high sulfate low alkali clinker, the
amounts of the tricalcium aluminate (C3A) and alite as well as the
alite/belite ratio were decreased, which however leads to a modification
in the cement quality [26].
The distribution of P2O5 in the clinker minerals after the addition of
bone meal (BM) ash to the basic raw mixture was studied. It has been
found that belite and alite accommodate nearly all the phosporousus
in the clinker. P5 + enters the structure of calcium silicates with Al3+
and Fe3+ [27].
Fig. 4. [8] The relationship between D values* of substituent ions and their abilities to sta-
bilize the higher-temperature forms of C3S.
2.2. Reactivity of alite
The fine changes in the chemical composition and structure inevita-
bly lead to changes in the reactivity of alite with water. Because the re-
activity of C3S and its polymorphs is too complex to be handled in the
present review only principles on reactivity are discussed in the
following.
The hydration kinetics of alite with foreign ions may deviate signifi-
cantly from that of pure C3S. Because many variables are involved, it is
difficult to compare the reactivities of different polymorphs. As a result,
it is difficult or nearly impossible to handle these parameters indepen-
dently. Back in the 1970's Fierens and Verhaegen [28,29] found that
the influence of substituent ions on the reactivity of C3S was due to
the presence of defects, which could be studied by the irradiation in-
duced thermoluminescence (TL). The complex relations between con-
tent of substituent ions, polymorphism, defects and reactivity were
recently studied again [19,30,31]. As a result the findings of Fierens
and Verhaegen [28,29] (relation between defect concentration and the
hydration behavior of alite) remains open for discussion.
The impact of foreign ions within the structure of C3S was investigat-
ed by Stephan et al. [32] on Cr, Zn and Ni. It was found that Cr and Ni
lead to an accelerated C3S reaction whereas Zn shows retarding effects.
But these effects were only evident at very high addition levels. In fact
Bazzoni et al. [33] found an accelerating effect of Zn incorporated into
the structure of alite (0.98 and 1.16 wt.%). In another study it was
found that the addition of Fe2O3 leads to a significant decrease in the hy-
dration reactivity of alite [34]. The addition of phosphor containing ma-
terials leads to a decrease in viscosity of the melt and thus to the
formation of larger alite crystals. This in turn may reduce the reactivity
of the cement. The performance of cements obtained by adding
phosporousous during clinker production is also varied. Early compres-
sive strengths are slightly reduced due to incorporation of P (b1.0 m.-%)
and corresponding decreased amounts of alite and C3A. The 28d com-
pressive strength is slightly increased (1.0 m.-% P2O5) and decreases
again at increasing concentrations of phosphate (2.0 m.-% P2O5) on ref-
erence values [35]. These results are in accordance to findings by others
[36]. As a result of reduced C3A content the demand of calcium sulfate
(as set regulator) decreases.
These findings are parts of the discussion on the causes of the induc-
tion period during hydration of C3S or alite in general. This period occurs
after first wetting of C3S and lasts for several hours before during the

Please cite this article as: H.-M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr. Res. (2015), http://dx.doi.org/
10.1016/j.cemconres.2015.05.018
 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx 5

Fig. 5. Recently discussed theories on the cause of the induction period.

main hydration period the majority of C3S reacts to C-S-H phases and 3.1. Polymorphism, crystal structure and synthesis of belite
portlandite. Today's most discussed theories are the protective layer
theory (first stated by Kantro et al. [37] and Stein and Stevels [38]), 3.1.1. Polymorphism and crystal structure of belite
slow dissolution step hypothesis (Juilland et al. [39] and Nicoleau et al. Belite is known to exist in six crystalline polymorphs. The poly-
[40] adapted from investigations on the dissolution rate of minerals morph present at very high temperatures is α-belite that transforms
[41,42]) and the aluminum induced formation of C-A-S-H phases [43]. into the αH′-polymorph at 1425 °C which is stable down to 1160 °C
Fig. 5 gives an overview on the principles of the different theories. being transformed to αL′-belite. The latter is replaced by the β-form at
According to the protective layer theory the surface of C3S is covered approx 650 °C. Polymorphs from the α-family and the β-form have an
by a product layer that is claimed to be an intermediate phase in the pre- almost identical crystal structure. When further cooled, β transforms
cipitation process of C-S-H phases [44–47]. The overall reaction process into γ that is stable at room temperature and the only polymorph
is believed to be controlled by that layer. with a clearly distinct structure [1]. Recent results showed that two
The slow dissolution step hypothesis on the other hand postulates other belite polymorphs exist. These two forms of belite are claimed
that the slow reaction during the induction period is caused by a slow to have a reactivity higher than alite. The most reactive polymorph is in-
dissolution rate of C3S in conditions characterized by high ion concen- deed an XRD-amorphous phase [52] with the same composition as the
trations that are expected during the induction period [39,40,48]. In crystalline polymorphs. The other very reactive polymorph is x-C2S
this case the formation of a layer is not necessary. Numerical modeling [53]. These polymorphs have the identical chemical composition but a
[49] of the hydration process that combines dissolution [50] and precip- much higher reactivity than polymorphs known from common cement
itation reactions may contribute to understanding the mechanism dur- manufacture. The crystal structure of x-C2S is different to all other poly-
ing the early hydration stage of C3S and alite. morphs [54]. A particularity of x-C2S is the presence of small “tunnels”
Besides these theories, the impact of aluminum on the early reaction
of C3S has been investigated [43,48,51]. It is claimed that the formation
of C-A-S-H phases lowers the number of C-S-H nuclei. Consequently, a Table 2
longer period is needed to precipitate C-S-H phases that lead to the Stabilization effect of foreign ions on β-C2S.
end of the induction period. The role of aluminum is of interest in partic- Ion addition Stabilization
ular in cases when cement hydration is concerned including the use of
P5+ Yes1,2
AFR. Further work is needed to clarify the role of aluminum in the hy- B3+ Yes1,2
dration process. As3+, As +5 No2, Yes1
V5+ Yes1,2
Al3+ No1,2
3. Research on dicalciumsilicate (belite) Cr2+, Cr3+, Cr+6 No2, No1,2, Yes1,2
Fe2+, Fe3+ No2, No1,2
Sr2+ Yes2
The need to reduce carbon dioxide emissions leads to a special focus
Mg2+ No1,2
on the reactivity of belite. By using alternative binders (e.g. calcium Ba+2 No1, Yes2
sulfoaluminate) the reactivity of belite is of central importance for the Na+ No1, Yes2
early strength development of cements with low alite content. As a re- K+ No1, Yes2
sult a number of works is published that aims at gaining new efforts Mn2+, Mn3+, Mn4+, Mn6+ No1,2, No2, No2, No2

in understanding the reactivity of belite. Data taken from [55,56].

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10.1016/j.cemconres.2015.05.018
6 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx

phases [60,61]. Other researchers found that SO3 promotes C2S forma-
tion at the expense of C3S [14,15]. It was documented that an SiO2 sub-
stitution by SO3 of up to 4.4 wt.% stabilizes monoclinic β-C2S. By this
mechanism the hydraulic activity increases up to 3 times with respect
to the pure β-C2S [62]. This result is in contrast to observation that in-
creasing sulfur additions decreases hydraulic reactivity of β-C2S [26,36].
Again by NMR spectroscopy [60,61] it was found that phos-
porousous can enter the belite (β-C2S) structure which leads to its sta-
bilization. The role of phosphates on clinker formation and reactivity
was studied in detail [35]. It was found that at low clinkering tempera-
tures phosporousous leads to the formation of hydroxylapatite which is
associated with the consumption of calcium. At increased temperatures,
decomposition of hydroxylapatite occurs. Thereby solid solutions
between C2S and C3P are formed. If the consumption of calcium is com-
pensated in the raw mix then alite (with incorporations of P) is formed.
If a higher amount of phosporousous is present in the mix then also a
destabilization of C3A is observed because aluminum is increasingly in-
corporated into C2S.
Similar to aluminum, also the addition of boron leads to a variation
in the chemical structure of C2S polymorphs [60,61]. In this case silicate
tetrahedra are substituted by borate tetrahedra. For charge compensa-
tion also calcium is partly substituted by boron. In the same study, the
impact of Na/B was investigated showing a large variation in chemical
structures of belite. For Rietveld refinement a new structure of boron
activated belite was proposed. It was further stated that the stabilization
of belite is most effective in the presence of boron.

3.1.2.2. Synthesis of highly reactive belite polymorphs. The production of

Fig. 6. Phase diagram of the sub-system C2S - 7CaO-P2O3-2SiO2 [59].
running parallel to the c-axis. These tunnels are possibly responsible for
the high reactivity.
highly reactive C2S polymorphs was pioneered by Ishida [53] and
Garbev et al. [63]. Supported by the presence of foreign ions it is based
on a two-step process that involves the synthesis of α-Ca2SiO4⋅ H2O in
an autoclave at 150–200 °C as a first step and its conversion into highly
reactive belite polymorphs by tempering at 400–800 °C in a second step,
see Fig. 7. It was later shown by Link et al. [52] that a number of poly-
morphs can be present in the same sample. The concentration of the

3.1.2. Synthesis and stabilization of belite polymorphs

3.1.2.1. Stabilizing of high temperature polymorphs of belite. Despite being

unstable in the pure form at low temperatures, high temperature mod-
ifications can be stabilized by rapid cooling, appropriate particle size
and the incorporation of foreign ions. It was shown that Ba is beneficial
for α, P for αH′, Sr for αL′ whereas the β-polymorph can be stabilized by
a broad range of elements. An overview of stabilization effects of foreign
ions on β-C2S polymorph is given in Table 2. It becomes evident that be-
sides foreign element also the oxidation state influences the stabilizing
effect.
From the point of view of thermodynamics, the incorporation of for-
eign ions leads to a slight reduction of the Gibbs free energy. Since the
phase with the lowest Gibbs free energy is the stable one; the incorpo-
ration of foreign ions could extend the zone of thermodynamic stability.
This results in a changed phase diagram with increasing content of for-
eign ions, cf. Fig. 6.
Active belite cements produced by incorporation of foreign ions and
fast cooling consist of β- and the various α-polymorphs [57]. However,
sufficient cooling rates are difficult to realize and reactivity is also low
compared to x- and amorphous-belite.
The addition of aluminum during burning of belite has been investi-
gated by several researchers. It is found that silicate tetrahedra are
substituted by aluminate which stabilizes β-C2S [36]. Furthermore it is
argued that oxygen vacancies are generated which leads to an increase
in water uptake and ionic conductivity. It is shown that even at high
temperatures protons or water remains in minor fractions in the crystal
structure [58].
Results gathered by NMR show that addition of sulfur during cement
clinker production can cause also an increase in aluminum in silicate Fig. 7. Production of highly reactive belite in a 2-step process.

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10.1016/j.cemconres.2015.05.018
 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
25
Heat release rate [J7(gh)]
20
15
10
5 C3S. Both C2S samples contain a high concentration of amorphous C2S
0
0 6 12 18 24
Time [h]
Fig. 8. Heat release rates for two samples with highly reactive C2S in comparison with C3S
analyzed by isothermal calorimetry (modified from [52]).
individual polymorphs depends on synthesis parameters of the two
process steps such as temperature, fineness, water vapor pressure and
other details. It was also established that an amorphous belite material
can be present in the samples after the dehydration step.
Alternative attempts to produce highly reactive belite with a
two-step autoclave process are also published. It is possible to produce
fly ash belite cements [64,65] or thermally activated hillebrandite
(Ca2SiO4⋅ H2O) [66–68]. These procedures result in the familiar β-α′-
polymorphs and the reactivity is much lower compared to amorphous-
and x-C2S.
3.2. Hydraulic reactivity of belite polymorphs
3.2.1. Reactivity of high temperature polymorphs of belite
Belite polymorphs in OPC clinker have a low reactivity which de-
pends on crystallographic modification, fineness, foreign ion substitu-
tion and other parameters in the order α N α′ N β ≫ γ [69]. The β-C2S
polymorph commonly present in OPC reacts slowly whereas α-poly-
morphs are higher in reactivity and γ-C2S is nearly inert.
Based on the chemical structure of C2S polymorphs the differences in
reactivity are discussed [70]. According to the authors the difference in
charge density of active O atoms in α′L- and β-C2S results in higher
reactivity against water. In contrast γ-C2S exhibits no active O atoms
and thus its reactivity is low. This finding can be the basis for under-
standing the impact of foreign ions into the chemical structure of C2S.
Nicoleau et al. [40] investigated the dissolution rate of C3S, C2S and
CaO. They found that the dissolution rate decreases with an increase
of the ion concentration in the aqueous phase. Based on this, they
claimed that dissolution theory is suitable to describe hydration kinetics
under paste conditions. Moreover, the decrease in dissolution rate is
proposed to be caused by a superficially hydroxylated surface [71] of
the silicates.
The role of foreign ions in the chemical structure of C2S was investi-
gated with special focus on reactivity. It is known from earlier investiga-
tions that the reactivity of C2S can be enhanced by mechanical
treatment [72], fast cooling rate and incorporation of guest ions [73–76].
Along with the improvement of the reactivity of belite polymorphs
due to the presence of foreign ions during clinkerization, also mechani-
cal activation of γ-C2S is of interest. This C2S polymorph is the main
compound of slags that originated from the production of stainless
steel [77] which may be used as alternative raw material. It was found
that high energy milling improves the reactivity of γ-C2S. However, by
means of high energy milling only a slight improvement (9.1 MPa
after 90 days) of the γ-C2S reactivity can be achieved (sand:binder
ratio = 3, w/b = 0.75). Chemical activation by adding NaOH
and Na2CO3 causes adequate effects. A combination between water
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10.1016/j.cemconres.2015.05.018
7
quenching and addition of mineralizer (NaF, Fe2O3) was shown to im-
C3S prove reactivity of belite [78].
A420
B500 3.2.2. Reactivity of highly reactive belite polymorphs
It was first demonstrated by Ishida et al. [67] that dehydration prod-
ucts from α-Ca2SiO4⋅H2O can react very fast with water. This was also
confirmed in the study by Link et al. [52]. In this study the process pa-
rameters were investigated that have a direct impact on reactivity.
Fig. 8 shows calorimetric data from two materials and conventional
and x-C2S. Contrary to C3S, the two highly reactive C2S samples show
an increased heat release rate during the induction period which indi-
30 36 cates that the reaction to products occur. However other C3S samples
can show increased reactivity with respect to the C3S sample used
here. According to the annealing conditions the maximum during the
main stage of hydration is observed after approx. 12 h. This first maxi-
mum of the main hydration period is related to the reaction of the amor-
phous phase. The second maximum after approx. 24 h is associated to
the reaction of the x-polymorph. Thus, in relation to the C3S sample
used in this study amorphous C2S shows increased reactivity whereas
with respect to C3S the heat release rate of x-C2S is slower. It was also
shown that the degree of hydration after 3 days is approximately 90%
and thus higher than that of C3S after similar hydration times (37%). It
is expected that this high reactivity will result also in very high early
strengths. Some of these samples contain β- or γ-C2S as a contamination
and investigations by X-ray diffraction confirm the low reactivity of
these polymorphs.
Highly reactive belite cements have also other advantages com-
pared Portland cements with alite as a major phase such as low spe-
cific heat development required for mass concrete [1]. It is expected
that highly reactive C 2S will form a denser matrix with respect to
OPC which results in good durability [79] (reduced capillary trans-
port, higher frost resistance, etc.). Furthermore, the absence of AFm
and AFt-phases is believed to be beneficial in terms of sulfate and
frost–thaw resistance. Based on unpublished work of the group at
Weimar this binder is compatible with superplastisizers and stimulates
the reactivity of latent hydraulic components. Finally, an intense grind-
ing process is not required due to the high process related fineness of
the material. Considering these properties, highly reactive belite ce-
ments are a promising candidate to replace Portland cement clinker
containing alite as main component.
4. Effect of AFR
A great amount of wastes from industrial, municipal, agricultural
sectors are used as AFR in the production process of cement clinker
nowadays, for the reason of both lowering the consumption of natural
resources and reducing the emissions in cement industry and waste dis-
posal for other industrial sectors. These wastes are used for alternative
fuels or alternative raw materials, depending on the characteristics
such as compositions. Generally, wastes mainly consisting of combusti-
ble organics contain a lot of energy and usually are used as alternative
fuels for firing system, and wastes composed of CaO, SiO2, Al2O3, Fe2O3
and so on are usually used as alternative raw materials in the raw
meal preparation.
Coal is the primary fuel burned in cement kiln in most areas of the
world, but alternative fuels are commonly used in cement plants.
Worldwide alternative fuels are used at a rate of below 10% (Fig. 9,
[80]). Although in some European countries such as Germany, an aver-
age of above 60% fuels used in cement kiln are alternative fuels [81]. Pe-
troleum coke, used plastics and rubbers such as used tires, meat and
bone meal, biomass, solvent and waste oil are traditional typical alterna-
tive fuels used in cement industry. However, associated with large scale
waste disposal, sewage sludge and municipal wastes have become in-
teresting alternative fuels in the cement industry.
8 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
Fig. 9. Solid Recovered Fuel (SRF)-substitution rate in cement industry (time period: 2000–2011, CPP = cement production plant) [80].
4.1. Impact of alternative fuels on the production process and the clinker
quality
In contrast to primary fuels, significantly more ash is produced by
the combustion of most secondary fuels [82]. The amounts of ash are,
particularly at high application rates of secondary fuels, of a scale that
makes it necessary for them to be considered in the raw meal. In situa-
tions where the corresponding ashes contain less calcium and more sil-
icon, raw meals with higher lime saturation factor have to be used.
Without this correction, this would lead to a significant decrease of
the alite content in the clinker.
The resulting ashes can also have further implications, as they may
contain other property modifying oxides depending on the secondary
fuel. Through the use of meat and bone meal, as well as sewage sludge
more phosphorous may enter the clinker. The consequence of this is,
as discussed in Section 2.1.2.1, the stabilization of belite a mixed crystal
formation C2S and C3P and a decrease of the content of alite [35]. This is
accompanied by changes in the strength characteristics of correspond-
ing cements. For example, the utilization of sewage sludge leads to
60 Alite
Belite
Aluminate phase
Ferrite phase
phase contents/%
40
20
0 metals in cement clinker.
0 10 20
(sewage sludge)/(raw meal) rate/%
Fig. 10. Phase content of clinker with the (sewage sludge)/(raw meal) ratio increasing
[80].
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10.1016/j.cemconres.2015.05.018
variation in the content of clinker minerals as, for example, shown in
Fig. 10 [83], mainly due to phosphorous stabilizing belite phase and
inhibiting the formation of alite from belite and CaO in clinker formation
process.
Fortunately, industrial trials suggest that the substitution of 10% of
the heat demand by sewage sludge has an acceptable effect on the qual-
ity of clinker [84]. It is believed that the addition of sewage sludge, ani-
mal meal or bone meal has no negative impact on the development of
strength when the phosphate content remains below 0.60 m.-% in the
clinker [82].
Using different secondary fuels also leads to a size increasing of alite
crystals, which usually leads to a reduction in the early age compressive
strengths (12 h, 1d) and to an increase of the 28d compressive strength
[85]. A large amount of sewage sludge used as AFR can lead to an in-
crease of the alite size [86] (Fig. 11). Minor constituents, such as phos-
phorous, sulfates, heavy metals, lead to changes in the properties of
liquid phase in clinkering process, the viscosity decreases and it be-
comes easier for ions to diffuse in the liquid phase which leads to
grain growth. Similar results are also reported by other authors [84,87].
Alite may also grow large and quite perfect with long and lazy flames
most observed in the case of high levels of secondary fuels [80].
Minor amounts of alternative fuels in the range of amounts below
20% usually do not alter much the properties of the clinker.
Alternative fuel derived from municipal wastes that has been buried
for years was used in a cement manufacturing line in Beijing [88] to re-
place about 10% of coal. The results show that strength of clinker, as well
as consistency, remains at the same level as without alternative fuel, be-
sides setting time prolonged a little.
4.2. Heavy metals
The use of alternative raw and fuel material in clinker can also intro-
duce various heavy metal ions, which could be dangerous to human
health and cause environmental problems. Significant attention has
been paid to the solidification and solidification mechanisms of heavy
For waste with a high Zn content, the use of OPC as a binder for the
solidification/stabilization process can cause deleterious effect on ce-
ment property. The validity of the alternative method to introduce Zn
into the raw material before clinkerisation was assessed [89]. It has
 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
Fig. 11. Alite phase in clinker with (sewage sludge)/(raw meal) ratio of 0 and 20% [80].
been shown that the immobilization during clinkerisation is a good al-
ternative to treat waste with a high Zn content in Ordinary Portland Ce-
ment (OPC).
Besides these components also the effect of heavy metals in traces
on cement clinker production was investigated. Therefore threshold
limits of Cu, Sn, Zn in a cement clinker (65% C3S, 18% C2S, 8% C3A, 8%
C4AF) were defined as 0.35%, 0.7% and 1 wt.%, respectively [90] which
are quite high with respect to the current contents in clinker. It ap-
peared that beyond the defined threshold limits, these elements had
different behaviors. Ni was associated with Mg as a magnesium nickel
oxide (MgNiO2) and Sn reacted with lime to form a calcium stannate
(Ca2SnO4). Cu changed the crystallization process and affected therefore
the formation of C3S. A high content of Cu in clinker led to the decompo-
sition of C3S into C2S and of free lime. Zn, in turn, affected the formation
of C3A. Ca6Zn3Al4O15 was formed while a tremendous reduction of C3A
content was identified. Cements made with the clinkers at the threshold
limits were at least as reactive as the reference cement. By others it was
shown that up to 6% Zn can be incorporated in C-S-H phases [91].
In leaching tests it was found that Cu, Cr and Ni are trapped in clinker
phases and were not liberated into the environment [92]. In general the
stabilization of β-C2S increases (Cr3+ N Ni2+ N Zn2+), whereas copper
has a negative effect [93]. The incorporation of Sn in C3A causes changes
in early hydration behavior. This effect depends on the level of Sn incor-
poration. Therefore, additions of 0.5 and 1% Sn increase and 2% Sn de-
crease C3A reactivity at early hydration period (up to 3 h). Sn also
stabilized the hydration products. Moreover, if C3A is mixed with gyp-
sum the incorporation of Sn into the chemical structure of C3A leads to
enhanced formation of AFt and AFm without changing the performance
of the mixture [94].
The solidification mechanisms for Cd and Ni during cement kiln co-
processing of hazardous wastes were of three types [95]. One was the
formation of a new solid. Substitution of the Ca in CaO to form a Ca–
Cd–O solid was the main mechanism for Cd solidification in cement
clinker. In the case of Ni, the metal tended to form a new inert com-
pound, MgNiO2. A second process was the formation of an interstitial
solid solution; Cd and Ni could partly enter and be sited in the spaces
of the C4AF lattice. The third type was isomorphous replacement. There-
by a small number of Cd2 + and Ni2+ ions substitute for Ca and Fe in
C4AF, respectively, and are incorporated into the C3S crystal lattice by
replacement of Ca2+.
5. Alternative binder
5.1. SCMs
Due to the CO2 emissions in the traditional production of Portland
cement and the fact that forecasts project a doubling of cement con-
sumption by 2050 [96], great efforts are being made to replace the tra-
ditional Portland cement. Currently the most important option is the
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10.1016/j.cemconres.2015.05.018
9
use of so-called SCMs. Particularly through the use of the three compo-
nents limestone, coal fly ash and blast furnace slag cement producers
could reduce CO2 emissions by about 18% with respect to the year
1990 [97]. In some regions and for different applications Portland
cement has been largely replaced by cement with SCMs, whereas
Portland cement clinker remains the basic material of these cements.
Currently higher use rates of SCMs in the composite cements are
hampered by problems in the early strength and durability [98].
Furthermore, the availability of SCMs limits their use. Against this back-
ground, researchers intensively investigate potential new SCMs cur-
rently. Particularly promising SCMs are calcined clays [99–101] and
modified steelmaking slag [102–104].
5.2. Calcium Sulfoaluminate cements (C$A)
Besides the use of SCMs which today is the main instrument to re-
duce material-related CO2 emissions, researchers are also investigating
cement production based on alternative clinkers. Further development
of C$A cements and the production of novel cements based on α-C2SH
are seen to be of special potential.
C$A cements have been known since the patent by Alexander Klein
in 1963 [105]. The classic C$A cements with ye'elimite as the main
phase have been produced and used in China since the 1970s [106].
Fields of application are specific applications that exploit the special
properties of the C$A cements such as rapid setting, high early strength
and shrinkage compensation. In addition, these cements were also used
sporadically for construction purposes [107,108]. Due to the high levels
of aluminum in the classical C$A cements (30–40%) and the required
very expensive bauxite as raw material, these cements are not compet-
itive as mass cements from an economic point of view. With regard to
the reduction of CO2 emissions C$A cements provide, however, a high
potential, since the formation of the main phase ye'elimite is associated
with the release of significantly less CO2 compared to the clinker phases
of Portland cement:
Alite C3 S ¼ 0:578 gCO2 =gphase
Belite C2 S ¼ 0:511 gCO2 =gphase
Aluminateferrite C2 ðA; FÞ ¼ 0:362 gCO2 =gphase
Calciumsulfoaluminate C4 A3 $ ¼ 0:216 gCO2 =gphase
The low burning temperatures (about 1250 °C) and the improved
grindability of C$A also reduce the energy consumption and CO2
emissions. All in all, depending on the composition C$A cements emit
about 25 to 35% less CO2 during manufacturing compared to an OPC
[109].
As already mentioned, with respect to total amounts these savings
are, however, currently not realizable in light of the high cost and avail-
ability of raw materials. Therefore, recent research and developments
focus on so-called belite calcium sulfoaluminate cements (BC$A) with
10 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
Patents:
1. Klein US3251701 (1964)
2. Mehta US4036657 (1977)
3. Lafarge EP1781579 (2009)
4. Cemex EP0812811 (2003)
5. Ost US3860433 (1975)
6. JP 57-200252 (1982)
7. Italcementi EP1306356 A1 (2003)
Fig. 12. Patents in the system C4A3$-C2S-others [97].
belite as main phase and not ye'elimite. To lower the aluminum content
in the system, still mostly materials containing iron are added, so that
larger amounts C4AF are formed and the Al2O3 content of cements can
be lowered to values between 14 and 17% [110].
Much of the ternary system C4A3$-C2S-others has now been covered
by different patents (Fig. 12).
A major problem of the belite rich cements is the gap in reactivity be-
tween the extremely fast reacting ye'elimite and the slow-reacting
belite. To solve this problem, a number of ideas have been developed
and partially implemented in recent years.
An important starting point for closing the gap in reactivity is the
stabilization of more reactive high-temperature modifications of belite,
such as α-C2S and α′-C2S. For stabilization purposes B2O5 is particularly
suitable, but also Na2O and P2O5 [111]. Technically, the concept was
implemented as part of a large-scale experiment in which 5500 t BC$A
(AETHER™) with the composition 55% α′-C2S, 25% C4A3$ and 15%C4AF
were prepared [112].
A different approach is the technology of the so-called belite
calciumsulfoaluminate-ternesite (BCT), in which besides belite,
ternesite (C 5 S2 $) is a main phase [97,113]. Ternesite as sulfate
spurrite has long been considered as not being hydraulically active.
However, recent studies show that in the presence of reactive alumi-
num ternesite is highly reactive. In the system BC$A ternesite is
therefore able to close the gap between the reactivity of ye'elimite
and belite.
Another way to close the gap between the reactivity of ye'elimite-
and belite is the introduction of alite-ye'elimite cements. The produc-
tion of such cements is, however, associated with significant challenges.
For the alite formation temperatures of 1450 °C are needed while
ye'elimite decomposes above 1350 °C. To guarantee the coexistence of
both phases it was previously proposed to either reduce the formation
temperature of the alite to a range between 1230 °C to 1300 °C by min-
eralizers (fluoride, CuO, MgO) or to stabilize ye'elimite by suitable
Table 3
Overview Celitement and Ca–Si–Bi.
Characteristics Binder
Celitement
Raw materials SiO2 and CaO containing materials (e.g. calciumhydroxide and quartz)
First production step Autoclave (150–200 °C, 5 bar)
Intermediate product Non-reactive α-C2SH
Second production step Activation grinding with a coarse SiO2-component (e.g. quartz)
Final reactive products Reactive calciumhydrosilicates (e.g. Ca2[SiO3OH](OH))
Hydration products C-S-H-phases
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10.1016/j.cemconres.2015.05.018
measures to higher temperatures (e.g. addition of barium/strontium)
[114,115]. A more recent approach proposes a two-stage burning meth-
od in which firstly alite is formed at 1450 °C in a sulfate-rich raw meal
and subsequently ye'elimite is obtained in a second burning step [116].
In addition to the change in the composition of the cements based on
calcium sulfoaluminate towards increased content of belite, the use of
waste materials containing high levels of aluminum and sulfates can
contribute to cost reduction [117,118].
Owing to the considerable relevance today to reduce CO2 emission
and the potential offered by the group of C$A cements a variety of pub-
lished studies on different aspects of these cements are available. Espe-
cially the high temperature chemistry of clinker production [119,120]
and the hydration of the BC$A and C$A cements [121–123] are the
focus of research. But also the possibility to include fly ash into C$A ce-
ments in order to reduce CO2 footprint has been evaluated [124,125].
Decisive for the application of new cements in the field of concrete
construction is the durability of concrete including also proper passiv-
ation of reinforcement. Here, there have been few studies that partly
contradict each part. Because of their low porosity (very dense micro
structure) concretes made with C$A cements possess a good resistance
against sulfate and chloride attack [126,127]. On the other hand resis-
tance towards carbonation is estimated by most authors to be lower
as compared to OPC concretes. One main issue seems to be the carbon-
ation of ettringite [126,128].
Regarding the pH value of the aqueous phase in C$A concretes and
therefore potential for proper passivation of reinforcement, divergent
statements can be found in literature. One reason for the wide variety
of given pH valued might be of course also that the cements and respec-
tive concretes differ largely in composition. The aqueous phase of C$A
cements was investigated in detail by [129]. Here it was found that
the pH value during the early hydration is low (approximately 10.5–
11.0). Over the course of hydration an increase to pH of 12.8 was mea-
sured. The maximum pH of 13.0 was found only by [130]. All other
Ca–Si–Bi
SiO2 and CaO containing materials (e.g. calciumhydroxide and quartz)
Autoclave (150–200 °C, 5 bar)
Non-reactive α-C2SH
Calcination (400–500 °C)
Highly reactive belite polymorphs (e.g. x-C2S) and amorphous C2S
C-S-H-phases and portlandite
 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
determined pH values were less than 13 [131]. Concrete investigations
in the field did not detect significant corrosion of reinforcement [128].
Overall it must be noted that systematic investigations on concrete
durability (especially with regard to composition of aqueous phase
and passivation of reinforcement) in dependence of systematic changes
in C$A composition are still missing. Especially requested is durability
data also for promising belite containing C$A cements and concretes
thereof.
5.3. Binder based on C-S-H
Another completely new technology of cement production is based
on the synthesis of initially nonreactive calcium silicate hydrate (for ex-
ample α-C2SH). Referring to the composition of these intermediate
products, the new binders are denoted as C-S-H binders. Currently,
there are two fundamentally different products on this basis. While in
case of “Celitement” the α-C2SH passes through a reactive grinding pro-
cedure with quartz to form reactive calcium hydrosilicate, during the
fabrication of the binder “Ca-Si-Bi” by calcination α-C2SH is converted
into reactive polymorphs of belite. An overview of both binders is
given in Table 3. Subsequently both binders will be discussed.
One of the first binders introduced of this type is the product called
Celitement (by Celitement GmbH, Germany) [132–134]. The produc-
tion process of this binder is dived into several steps. First quartz and
free lime (or other CaO and SiO2 containing materials) are brought to-
gether to a homogeneous raw mixture. The second step comprises reac-
tion of this mixture at 150 °C–210 °C at 5 bar in an autoclave. Thereby
non-hydraulic calcium-silicate-hydrates are formed. Preferential only
α-C2SH is used for further Celitement production. To transfer this
non-hydraulic material into a hydraulic binder a, so called, activation
grinding step is carried out. Thereby another SiO2 component (quartz
sand or similar) is added. During this activation grinding process stabi-
lizing hydrogen bonds of α-C2SH that are formed in the autoclave are
destroyed (“tribochemical” surface reaction). The newly formed hy-
draulic binder consists of reactive calcium hydrosilicate, and is loosely
attached to the added silicate component. The hydration starts after ad-
dition of water at these interfaces (Fig. 13).
These phases are amorphous, reactive and water containing.
Addition of mixing water induces a hydraulic reaction that further
transforms these precursor C-S-H phases into C-S-H similar to that
formed during OPC hydration. The Ca/Si ratio of the final C-S-H phase
is lower than C-S-H formed during OPC hydration. According to the
first studies on CO2 balance of the Celitement process up to 50% reduc-
tion of CO2-compared to OPC production- can be achieved [132].
C-S-H-phases after 7 d hydration
Silicat material
Fig. 13. Microstructure of the hydrated Celitement [133].
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11
Fig. 14. C-S-H formation in Ca–Si–Bi after 48 h.
Up to date the production of Celitement is limited to small scale pro-
ductions. The upscaling of this pilot plant is planned for the next years.
Also most of the performance parameters of the new binder are current-
ly not available. Especially durability might be an upcoming issue since
calcium hydroxide is not contained in the hydrated material. Thus in-
vestigations on corrosion protection by passivation of reinforcement
are urgently required. The question to be answered is if the low porosity
of the binder is maybe balancing the effect of a material inherent low pH
value that bears the main risk for reinforcement corrosion.
A further binder (Ca-Si-Bi) already mentioned in the Sections 3.1.2.2
and 3.2.2 based on α-C2SH is introduced by studies [52]. The Ca-Si-Bi
technology is characterized by a calcination process at temperatures be-
tween 400 and 500 °C after the autoclave without grinding. The product
of this calcinations step is a highly reactive polymorph of belite (i.e. x-
C2S) and amorphous C2S. During hydration of this binder C-S-H phases
similar to those obtained during OPC hydration are formed. Contrary to
Celitement, portlandite is additionally formed.
Interestingly, within the first 48 h hydration of the belite poly-
morphs is nearly completed (i.e. C-S-H phases are formed, Fig. 14).
This is a significant difference to the hydration of belite contained in
OPC, where after decades unhydrated belite is still found in concrete. In
contrast to the hydration of alite in OPC the reaction of the above de-
scribed C2S binder produces more C-S-H phases and less calcium hy-
droxide. Thus, a significant reduction in binder content can be
expected for concretes made with those newly developed C2S binders.
Similar to Celitement the development of this binder is at an initial
state, i.e. only small scale production is possible. Thus investigations
on durability of this binder and concretes made thereof are also urgently
required. Table 3 summarizes key points of Celitement and Ca-Si-Bi
binders.
The two approaches discussed – C$A and cements based on α-C2SH
precursor – are characterized by the fact that reaction products similar
to those of OPC hydration are formed. Completely different approaches
such as binders on the base of magnesium silicates [135], amorphous
calcium carbonates [136] or wollastonite [137] leave the area of hydrau-
lic binders and are not discussed in the present review.
6. Conclusions and outlook
The present paper aims to summarize the development in the field
of cement clinker chemistry in the last 4 years. Against the background
that on the global scale CO2 emissions have to be reduced, the main goal
of the cement industry is the reduction of the content of the Portland
12 H.-M. Ludwig, W. Zhang / Cement and Concrete Research xxx (2015) xxx–xxx
cement clinker in cements. But although promising approaches have
been proposed in order to find alternatives, it is expected that Portland
cement clinker cannot be fully substituted in the near future. However,
its content in cements can be reduced which results in the need of a
deeper understanding of the impacts on cement clinker reactivity. In
particular, a large amount of research is dedicated to understand the re-
activity of belite since its production is associated with lower emissions
of CO2 as compared to C3S. Additionally, the use of AFR can impact the
performance of cements. We expect that the future cement will be a
green cement tailored more and more to the planed performance pro-
duced with very different raw materials and fuels.
Acknowledgment
The authors would like to thank Thomas Sowoidnich and Dr. Frank
Bellmann for their support and helpful discussions.
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Please cite this article as: H.-M. Ludwig, W. Zhang, Research review of cement clinker chemistry, Cem. Concr. Res. (2015), http://dx.doi.org/
10.1016/j.cemconres.2015.05.018