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Article history:
Received 12 May 2015
Accepted 13 May 2015
Available online 3 June 2015
Keywords:
Clinker
Ca3SiO5
Ca3SiO4
Sulfoaluminate
Blended cement
a b s t r a c t
This paper aims to review the progress in cement clinker chemistry since the last International Conference on the
Chemistry of Cement in 2011. Although Portland cement clinker is still, by far, the most important compound of
modern cements we show that there is a strong development of alternatives. This is mainly due to the emission of
carbon dioxide during the calcination of calcium carbonate as raw material whose reduction is the goal of international activity due to anthropologically caused climate change. Furthermore, it is an objective to use both more
raw materials that are located close to the concrete plants and alternative fuels. Developments in the eld of cement clinker chemistry show a potential for alternatives. Thereby we discuss both old and new ideas. But it has
been shown that the substitution of Portland cement clinker has to consider not only reduction in CO2 emission
during fabrication: For practical solutions the performance in both in terms of strength development and durability has to be adequate compared to the ordinary Portland cement clinker.
2015 Elsevier Ltd. All rights reserved.
1. Introduction
Since the rst Portland cement with the present denition was produced 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 signicant 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 emission (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 challenge 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, y ash, silica fume and limestone. In several countries and for several applications these Portlandcomposite 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).
http://dx.doi.org/10.1016/j.cemconres.2015.05.018
0008-8846/ 2015 Elsevier Ltd. All rights reserved.
25
advantages of secondary raw and fuel materials (e.g. increased reactivity 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.
26
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 signicantly 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 systematically 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 promote the M3-type alite stabilization. In this respect, Mg2 + and Al3 +
seem to have the most signicant 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. Inuence of minor or trace elements on clinker and alite formation.
As stated before, the impact of foreign ions incorporated into the structure of C3S inuences the reactivity, but this effect depends strongly on
the incorporation level. Likewise the impact of foreign ions on the properties of cement clinker is modied. It is known that minor or trace
components derived from raw materials or fuels affect both clinker formation 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 polymorphisms 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 accelerating the clinkerization reactions and by lowering the formation
27
Table 1
[8] Chemical structure parameters of average ions incorporated in alite and their substitution patterns in C3S.
Ions
Coordination number
Electronegativity
Substitution pattern
D* value
O2
F
Li+
Na+
Ca2+
Sr2+
K+
Ba2+
Mn2+
Mg2+
Zn2+
Cu2+
Ti4+
Cr3+
Al3+
Ga3+
Fe3+
Mn4+
Si4+
P5+
S6+
140
136
60
95
99
113
133
138
80
65
74
72*
68
64
50
62
60
52*
41
34
29
6*
12
6,8
8*
12
12
6
6
4
4
6
6
4,6
6
6
4*
4
4
4
3.44
3.98
0.98
0.93
1
0.95
0.82
0.89
1.55
1.31
1.65
1.9
1.54
1.66
1.61
1.81
1.83
1.55
1.9
2.19
2.58
FO
Li Ca/interstitial or Ca/Si [6]
Na Ca/interstitial
Sr Ca
K Ca
Ba Ca
Mn Ca
Mg Ca
Zn Ca
Cu Ca
Ti Si
Cr Ca/Si
Al Ca/Si/ hole
2Fe Ca + Si
Mn Si
P Si
S Si
2.021
1.114
0.008
0.003
0
0.014
0.062
0.087
0.211
0.213
0.328
0.491
0.676
0.7
0.906
0.908
0.981
1.044
2.109
3.907
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 element and Ca; Rc = Ca2+ radius.
temperature of C3S. Although SO3 hindered the formation of C3S, its negative 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 nes 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 combined in combination with alkali and SO3 has uxing 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 modication
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 stabilize the higher-temperature forms of C3S.
28
main hydration period the majority of C3S reacts to C-S-H phases and
portlandite. Today's most discussed theories are the protective layer
theory (rst stated by Kantro et al. [37] and Stein and Stevels [38]),
slow dissolution step hypothesis (Juilland et al. [39] and Nicoleau et al.
[40] adapted from investigations on the dissolution rate of minerals
[41,42]) and the aluminum induced formation of C-A-S-H phases [43].
Fig. 5 gives an overview on the principles of the different theories.
According to the protective layer theory the surface of C3S is covered
by a product layer that is claimed to be an intermediate phase in the precipitation process of C-S-H phases [4447]. The overall reaction process
is believed to be controlled by that layer.
The slow dissolution step hypothesis on the other hand postulates
that the slow reaction during the induction period is caused by a slow
dissolution rate of C3S in conditions characterized by high ion concentrations that are expected during the induction period [39,40,48]. In
this case the formation of a layer is not necessary. Numerical modeling
[49] of the hydration process that combines dissolution [50] and precipitation reactions may contribute to understanding the mechanism during the early hydration stage of C3S and alite.
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
longer period is needed to precipitate C-S-H phases that lead to the
end of the induction period. The role of aluminum is of interest in particular in cases when cement hydration is concerned including the use of
AFR. Further work is needed to clarify the role of aluminum in the hydration process.
3. Research on dicalciumsilicate (belite)
The need to reduce carbon dioxide emissions leads to a special focus
on the reactivity of belite. By using alternative binders (e.g. calcium
sulfoaluminate) the reactivity of belite is of central importance for the
early strength development of cements with low alite content. As a result a number of works is published that aims at gaining new efforts
in understanding the reactivity of belite.
Table 2
Stabilization effect of foreign ions on -C2S.
Ion addition
Stabilization
P5+
B3+
As3+, As +5
V5+
Al3+
Cr2+, Cr3+, Cr+6
Fe2+, Fe3+
Sr2+
Mg2+
Ba+2
Na+
K+
Mn2+, Mn3+, Mn4+, Mn6+
Yes1,2
Yes1,2
No2, Yes1
Yes1,2
No1,2
No2, No1,2, Yes1,2
No2, No1,2
Yes2
No1,2
No1, Yes2
No1, Yes2
No1, Yes2
No1,2, No2, No2, No2
29
phases [60,61]. Other researchers found that SO3 promotes C2S formation at the expense of C3S [14,15]. It was documented that an SiO2 substitution by SO3 of up to 4.4 wt.% stabilizes monoclinic -C2S. By this
mechanism the hydraulic activity increases up to 3 times with respect
to the pure -C2S [62]. This result is in contrast to observation that increasing sulfur additions decreases hydraulic reactivity of -C2S [26,36].
Again by NMR spectroscopy [60,61] it was found that phosporousous can enter the belite (-C2S) structure which leads to its stabilization. The role of phosphates on clinker formation and reactivity
was studied in detail [35]. It was found that at low clinkering temperatures 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 compensated 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 incorporated 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 compensation 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 renement 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.
running parallel to the c-axis. These tunnels are possibly responsible for
the high reactivity.
30
25
quenching and addition of mineralizer (NaF, Fe2O3) was shown to improve reactivity of belite [78].
C3S
A420
20
B500
15
10
0
0
12
18
24
30
36
Time [h]
Fig. 8. Heat release rates for two samples with highly reactive C2S in comparison with C3S
analyzed by isothermal calorimetry (modied from [52]).
31
Fig. 9. Solid Recovered Fuel (SRF)-substitution rate in cement industry (time period: 20002011, CPP = cement production plant) [80].
4.1. Impact of alternative fuels on the production process and the clinker
quality
In contrast to primary fuels, signicantly 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 situations where the corresponding ashes contain less calcium and more silicon, raw meals with higher lime saturation factor have to be used.
Without this correction, this would lead to a signicant 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 corresponding cements. For example, the utilization of sewage sludge leads to
Alite
Belite
Aluminate phase
Ferrite phase
phase contents/%
60
40
20
0
0
10
20
The use of alternative raw and fuel material in clinker can also introduce various heavy metal ions, which could be dangerous to human
health and cause environmental problems. Signicant attention has
been paid to the solidication and solidication mechanisms of heavy
metals in cement clinker.
For waste with a high Zn content, the use of OPC as a binder for the
solidication/stabilization process can cause deleterious effect on cement property. The validity of the alternative method to introduce Zn
into the raw material before clinkerisation was assessed [89]. It has
32
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 alternative to treat waste with a high Zn content in Ordinary Portland Cement (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 dened as 0.35%, 0.7% and 1 wt.%, respectively [90] which
are quite high with respect to the current contents in clinker. It appeared that beyond the dened 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 decomposition 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 identied. 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 -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 incorporation. Therefore, additions of 0.5 and 1% Sn increase and 2% Sn decrease C3A reactivity at early hydration period (up to 3 h). Sn also
stabilized the hydration products. Moreover, if C3A is mixed with gypsum 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 solidication mechanisms for Cd and Ni during cement kiln coprocessing 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
CdO solid was the main mechanism for Cd solidication in cement
clinker. In the case of Ni, the metal tended to form a new inert compound, 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. Thereby 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 consumption by 2050 [96], great efforts are being made to replace the traditional Portland cement. Currently the most important option is the
use of so-called SCMs. Particularly through the use of the three components limestone, coal y 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 background, researchers intensively investigate potential new SCMs currently. Particularly promising SCMs are calcined clays [99101] and
modied steelmaking slag [102104].
5.2. Calcium Sulfoaluminate cements (C$A)
Besides the use of SCMs which today is the main instrument to reduce material-related CO2 emissions, researchers are also investigating
cement production based on alternative clinkers. Further development
of C$A cements and the production of novel cements based on -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 specic 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 (3040%) and the required
very expensive bauxite as raw material, these cements are not competitive 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 signicantly less CO2 compared to the clinker phases
of Portland cement:
Alite
Belite
Aluminateferrite
Calciumsulfoaluminate
C3 S
C2 S
C2 A; F
C4 A3 $
33
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)
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$-C2S-others has now been covered
by different patents (Fig. 12).
A major problem of the belite rich cements is the gap in reactivity between the extremely fast reacting ye'elimite and the slow-reacting
belite. To solve this problem, a number of ideas have been developed
and partially implemented in recent years.
An important starting point for closing the gap in reactivity is the
stabilization of more reactive high-temperature modications of belite,
such as -C2S and -C2S. For stabilization purposes B2O5 is particularly
suitable, but also Na2O and P2O5 [111]. Technically, the concept was
implemented as part of a large-scale experiment in which 5500 t BC$A
(AETHER) with the composition 55% -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 $) is a main phase [97,113]. Ternesite as sulfate
spurrite has long been considered as not being hydraulically active.
However, recent studies show that in the presence of reactive aluminum ternesite is highly reactive. In the system BC$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'elimiteand belite is the introduction of alite-ye'elimite cements. The production of such cements is, however, associated with signicant 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 mineralizers (uoride, CuO, MgO) or to stabilize ye'elimite by suitable
Table 3
Overview Celitement and CaSiBi.
Characteristics
Raw materials
First production step
Intermediate product
Second production step
Final reactive products
Hydration products
Binder
Celitement
CaSiBi
34
Silicat material
Up to date the production of Celitement is limited to small scale productions. The upscaling of this pilot plant is planned for the next years.
Also most of the performance parameters of the new binder are currently not available. Especially durability might be an upcoming issue since
calcium hydroxide is not contained in the hydrated material. Thus investigations 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 -C2SH is introduced by studies [52]. The Ca-Si-Bi
technology is characterized by a calcination process at temperatures between 400 and 500 C after the autoclave without grinding. The product
of this calcinations step is a highly reactive polymorph of belite (i.e. xC2S) 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 rst 48 h hydration of the belite polymorphs is nearly completed (i.e. C-S-H phases are formed, Fig. 14).
This is a signicant 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 described C2S binder produces more C-S-H phases and less calcium hydroxide. Thus, a signicant 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 -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 hydraulic binders and are not discussed in the present review.
6. Conclusions and outlook
35
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