Belite compositions

In general, clinker belite compositions indicate ratios of other atoms to oxygen above the theoretical value of 0.75. As Regourd et al. (R3) noted, the C2S structures are too densely packed for the presence of interstitial ions to appear likely, and it is more probable that vacancies occur in the oxygen sites, with possible concomitant shifts in the positions of other atoms. Table 1.3 includes atomic ratios, with a possible allocation of atoms to sites. 

Calculate the overall Ca and Si contents (expressed as CaO and Si02) of a Portland cement clinker that has 55% alite, 30% belite, 5% alumi-nate phase, and 10% ferrite (assume ideal compositions for the latter two). Would you expect this to behave as a fast or a slow setting cement ... 

The ferrite phase makes up 5 15% of normal Portland cement clinkers. It is tetracalcium aluminoferrile (CajAIFeOj) substantially modified in composition by variation in Al/Fe ratio and incorporation of foreign ions. The rale at which it reacts with water appears to be somewhat variable, perhaps due to differences in composition or other characteristics, but in general is high initially and intermediate between those of alite and belite at later ages. 

Studies on synthetic belites suggest the possible occurrence of modulated structures, i.e. ones in which compositional or structural variations occur with a statistical periodicity that is not a rational multiple of that of the basic structure (H5). Such effects might occur in clinker belites. 

Table 1.2 includes an average composition for belites in ordinary production clinkers, based on the results of many studies by X-ray microanalysis (T2,K1.G3,B2,G4,S1,H3,H4) or chemical analysis of separated material (Yl). As with alite (Section 1.2.3), most of the results from different laboratories are in relatively close agreement. Belites in white cement clinkers have also been analysed (B3). Pure C2S, for comparison, contains 34.9% of Si02 and 65.1% of CaO. 

Regourd et al. (R3) synthesized several belites of P-C2S type with compositions similar to those found in clinkers and determined their cell parameters. With increased substitution, the crystallinity tended to decrease, causing broadening of XRD powder peaks. Two of their results are given in Table 1.5. 

Rapid increase in temperature is desirable at temperatures below those at which substantial liquid formation occurs (C9,B27,S21,C11,W9,G26). Most of the belite, and almost all of the other product phases, subsequently either melt or react in the presence of the melt, and there is no merit in promoting crystal growth or removal of imperfections, which would impede these processes. Slow heating may also allow the decomposition products of the clay minerals to transform into less reactive phases. It can also lead to the formation of microstructures unfavourable to the later reactions Chromy (C9) found that it allowed the belite shells around the silica particles to thicken, producing composites slow to react with lime. In contrast, rapid heating increases movement of the liquid phase, when this forms, and thus improves the mixing of the calcareous and siliceous constituents (Cl 1). 

Nodulization, chemical reactions and evaporation of volatiles are interdependent. Alite formation and loss of volatiles affect nodulization, and the compaction that the latter entails must affect the kinetics of the former processes. Alite formation thus occurs in a changing environment. Initially, the clinker liquid is not a continuous and uniform medium enveloping the grains oflime, belite and other solid phases rather, it fills separate pores and capillaries, forming thin films on the particles, and there are large local variations in composition (Tl). As compaction proceeds, it becomes more continuous and more uniform. 

The reason why mixes with AR > 1.7 do not yield any CjjA, on independent crystallization is that the solid phases are not pure CjA, QAF and CjS. For AR = 2.71, the quaternary liquid in equilibrium with C,S, C S and CjA at 1400X contains 55.7% CaO, 27.1% AljOj, 10.0% FcjOj and 7.2% SiOj (S8). This composition can be closely matched by a mixture of aluminate (63%), ferrite (30%) and belite (7%) with the normal compositions given in Table 1.2, the bulk composition of this mixture being 54.4% CaO, 26.4% AI2O3, 9.7% Fe Oj, 5.6% SiO and 1.8% MgO, with <1% each of TiOj, Mn20j, NajO and KjO. Independent crystallization can thus yield a mixture of the three phases. The liquid composition cannot be matched by a mixture of pure CjA, C AF and CjS, which is relatively too high in CaO, so that if no ionic substitutions occurred, some C,2A7 would also be formed. A strict comparison would be with the actual composition of the clinker liquid, which is modified by minor components, but lack of adequate data precludes this. 

Because the constituent phases of a cement are not equally easy to grind, different particle size fractions differ in composition. Gypsum, and its dehydration products, are concentrated in the finer fractions. Osbaeck and Jons (08) concluded that each 1% of gypsum contributed about 10m kg to the specific surface area in a typical case, some 15% of the total specific surface area is thus due to gypsum. The content of alite decreases, and that of belite increases, with increasing particle size (R12,G30), the contents of aluminate and ferrite phases being little affected. 

The bulk composition affects the relative amounts of phases, the LSF, SR and AR affecting primarily the ratios of alite to belite, silicate phases to interstitial material and aluminate to ferrite phase, respectively. An LSF that is too high, either absolutely or in relation to the burning conditions, also gives rise to an excessive content of free lime. Belite may occur in such clinkers only as inclusions in alite. 

Applications of IR and Raman spectroscopy to the study of clinkers and unhydrated cements have been reviewed (B39,B40). The laser Raman microprobe, with which regions of micrometre dimensions on a polished surface may be examined, has been used to investigate structure and crystallinity, especially of the alite and belite (Cl9). Spectroscopic methods for studying the surface structures and compositions of cements are considered in Section 5.6.2. 

The hydrated material has been analysed by X-ray microanalysis and analytical electron microscopy. In a 3-day old paste, that formed in situ from alite or belite did not differ significantly in composition from the corresponding product in pure Portland cement pastes (H4). but at later ages Ca/ Si is lower and Al/Ca higher (R25,R26,T44,U 17,U 18,R42). Ca/Si is typically about 1.55, but the value decreases with age and ratio of pfa to clinker. Uchikawa (U20,U17) reported a value of 1.01 for a 4-year-old paste with 40% replacement of cement by pfa. Several of the studies (R25,T44,U20,U 17) showed that the C-S-H was higher in alkalis if pfa was present, but one cannot tell to what extent potassium or sodium apparently present in the C-S-H has been deposited from the pore solution on drying. For material close to the pfa particles in a 10-year-old mortar. Sato and Furuhashi (S92) found a Ca/Si ratio of 1.1-1.2. 

Regulated-set cement and jet cement are modified Portland cements in which the normal aluminate phase is replaced by CuA CaF, through the use of a raw mix containing CaF,. Uchikawa and Tsukiyama (U2I) gave chemical (Table 10.4) and phase compositions of two jet cements. Botli contained approximately 60% of alite, 20% of C, i A CaF,. 1% of belite and 5% of ferrite. Admixtures are required to control the rate of reaction of the C, 1 A CaFj and the nature of the products. One of the cements included a proprietary retarder based on citric acid, togetlier with 2"/o of CaC O, . The other contained 2.5% of hemihydrale. In each case, Na,S04 (T o) and anhydrite were also present. The specific surface areas were around 550 m kg . 

Locher (LSI) reviewed ways of decreasing the energy consumption in cement manufacture to values substantially below those characteristic of modern Portland cement production. They included the use of fluxes to lower the burning temperature, the production of cements containing more reactive forms of belite or based on belite together with highly reactive phases, replacement of alite by the chloride-containing phase, alinite, and the use of composite cements. 

Portland cement clinker is composed of fora principal phases alite, which is close to tricalcium orthosilicate Ca3[Si04]0, belite close to dicalcium orthosilicate Ca2[SiOJ, tricalcium aluminate Ca3[Al20g] and ferrite C2(A, F). Chemical composition of these phases is complicated by solid solutions, which have the decisive influence on their reactivity with water. For the elements from which chrrker phases are composed isomorphism is typical and very developed phenomenon. The highest concentration of isomorphic elements is encountered in tricalcium aluminate (about 12-13%), and then in alumino-ferrites (about 10-11%), belite (about 6%), and the lowest in alite (about 4 %). 

Also belites in clinkers are, as a rule, p phase containing different minor elements. However, on the XRD pattern some peaks are broadening and some shifted a little. The composition of these belites is unbalanced. Ca + is usually substituted by Mg +, K+, Na+, Cr3+, Mn and [SiOJ by [AlOJ -, [FeOJ lPOJ - and [SOJ - [129]. 

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