Quantification of the

M1 and M3 polymorphs
of alite in OPC clinker

Introduction the crystal structure, introduced by the raw material and

The main component in industrial clinkers for the cement fuels. Most relevant in clinkers are two monoclinic
production is alite with the ideal composition Ca3SiO5, also polymorphs of alite, the M1 and M3 forms. In recent years the
written as C3S in the short cement notation. This compound quantification of these two polymorphs has become of more
can occur in crystallographic polymorphs. Their formation interest because of publications claiming differences in the
depends mainly on the burning conditions (temperature, reactivity of synthetic M1 and M3 alite.
burning time, cooling rates) and minor or trace elements in

1a
Pure C3S: T1 620º C T2 920º C T3 980º C M1 990º C M2 1070º C R

1b
Impure C3S: 990º C M2 1060º C M3 1070º C R
M1

Figure 1. Transition temperatures for alite polymorphs.

The alite polymorphs Quantitative Rietveld analysis of M1 and M3 polymorphs

Up to 1100°C, seven polymorphs of alite are known, three Generally, all alite polymorphs have nearly similar structures,
triclinic (called T1, T2 and T3), three monoclinic (M1, M2 and and accordingly, also the powder diffraction diagrams are
M3) and a rhombohedral (R) one. For pure C3S (Ca3SiO5) the nearly similar. Structure determinations exist for the M3,
reactions in Figure 1a are valid, for the impure C3S (stabilized whereas for the M1 two structure models are available. These
by minor elements especially Mg and Al) occuring in an data can be used for a quantification of the alite polymorphs.
industrial produced clinker the reactions in Figure 1b are Figure 2 shows a Rietveld refinement including the
valid. quantification of the M1-M3 polymorphs.

Most relevant in clinkers are two monoclinic polymorphs of

alite, the M1 and M3 forms. These two polymorphs have
come into focus during the last years, because differences
between the reactivity of synthetic M1 and M3 alite were
reported in the literature. Using Rietveld analysis, distinction
and individual quantification of M1-M3 polymorphs are
possible.
 Counts

C3S - M1 (Pc) 29.8 %

C3S - M3 (Nishi) 33.4 %
C2S - Belite 20.2 %
6000 C4AF - Ferrite 6.6 %
C3A - Aluminate cubic 2.2 %
C3A - Aluminate ortho 6.0 %
Calcium oxide - Lime 0.5 %
Calcium hydroxide - Portlandite 0.7 %
Magnesium oxide - Periclase 0.1 %
4000 Potassium sulfate, beta - Arcanite 0.3 %

2000

0
20 30 40 50 60
Position [°2θ] (Copper (Cu))

Fig. 2. Quantitative Rietveld phase analysis of clinker including M1- M3 polymorphs

Example results of the Rietveld analysis are shown in Fig. 3. The typical repeatability of the M1-M3 quantification values is
0.9 for 1σ and 2.9 for 3σ.

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C3S M1[%] C3S M3[%] C2S [%] C3A_SUM [%] C4AF [%] CaO [%] MgO [%] Ca (OH)2 [%]
10.1 52.8 21.8 4.8 7.6 1.4 0 0.7
39.4 33.2 14.4 4 6 1.2 0.4 0.8
31.3 40.2 15 4.8 6.1 0.9 0.5 0.7
19.8 49.3 17.7 5.1 6.5 1.1 0 0.5
16.3 52.5 15.9 4.7 7.2 1.4 0.5 0.8
35.1 39.3 11.9 5.6 6 1.1 0 0.9
32.6 38.1 14.4 6.4 5.5 1.6 0.4 0.6
12.7 50.7 21 5.8 6.9 1.3 0.6 0.6
32.4 38.4 15.1 6 6.1 0.9 0 0.6
30.5 40.5 14.7 4.6 6.5 1.5 0 0.9
41.6 33.4 10.3 5 5.4 1.8 0 0.8
40.8 34.2 11.3 5.7 5.3 1.5 0 0.7
15.5 50.6 16.6 6.8 7.9 1.6 0 0.9
22.8 47 13.3 4.8 7.1 1.9 0.3 0.8
11.2 60.2 16.5 5.4 8.4 2.3 0.4 0.8
12.4 53.7 17.9 4.9 77 1.7 0 0.9
10.6 57.4 15.8 4.5 8 2 0 0.9
17.5 49.5 19.4 4.3 6 1.5 0 0.8
30.1 40.8 14.4 6.1 5.8 1.6 0 0.7
30.3 42 13 5.9 6 1.3 0 0.7

Fig. 3. Quantitative Rietveld phase analysis of different clinker including M1 - M3 polymorphs.

Conclusion

In this data sheet we have shown that the M1 and M3 polymorphs in clinker can be quantified individually using the
Rietveld method. The repeatability of the method is such that it allows accurate process control of cement production.

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