Cements belite

Belit, n., Belith, m. (Cement) belite. bellen, v.i. bark clamor, belolmen, v.t. reward, remunerate, beluften, v.t. (Aero.) ventilate, pressurize. Beluftung, /. airing, ventilation, belustigen, v.t. amuse, divert,... 

Portland cement Belite cement Sulfobelite cement Sulfoalite cement Phase composition of clinker (%)... 

Alkali aluminate (5-calcium disilicate monosulfate), phase in Portland cement clinker, 5 472t Alkali aluminate (8-calcium disodium trialuminate), phase in Portland cement clinker, 5 472t Alkali belite, phase in Portland cement clinker, 5 472t Alkali blue toners, 14 318 Alkali borate glasses, 12 572, 573, 584 Alkali catalysed pad-dry-bake procedure, 9 485... 

Rapid cooling of the clinker is preferred for many reasons, notably to prevent the reversion of alite to belite and lime in the 1100 1250 °C regime and also the crystallization of periclase (MgO) at temperatures just below 1450 °C. The magnesium content of the cement should not exceed about 5% MgO equivalent because most of the Mg will be in the form of periclase, which has the NaCl structure, and this hydrates slowly to Mg(OH)2 (brucite), which has the Cdl2 layer structure (Section 4.6). Incorporation of further water between the OH- layers in the Mg(OH)2 causes an expansion that can break up the cement. Accordingly, only limestone of low Mg content can be used in cement making dolomite, for example, cannot be used. Excessive amounts of alkali metal ions, sulfates (whether from components of the cement or from percolating solutions), and indeed of free lime itself should also be avoided for similar reasons. 

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. 

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. 

Table 2.3 lists some phases containing MgO that are in varying degrees relevant to cement chemistry. It is not a complete list of phases with essential MgO in the CaO-MgO-AljOj-SiOj system. As seen in Chapter 1, some MgO is also taken up by all four of the major clinker phases, typical contents being 0.5-2.0% for alite, 0.5% for belite, 1.4% for the aluminate phase, and 3.0% for the ferrite phase. Magnesium oxide (periclase), like calcium oxide, has the sodium chloride structure it is cubic, with a = 0.4213 nm, space group Fm3m, Z = 4, = 3581 kgm (S5) and refrac-... 

The definition of LSF is theoretically based (Section 2.3.3), and in the form given above applies to clinkers if corrected by subtracting O.7SO3 from CaO, it may be applied to cements. It largely governs the ratio of alite to belite and also shows whether the clinker is likely to contain an unacceptable proportion of free lime, a value of 1.0 or above indicating that the latter will be present at equilibrium at the clinkering temperature and thus liable to persist in the product. In practice, values up to 1.02 may be acceptable typical values for modern clinkers are 0.92-0.98. Other parameters similar in... 

For normal cements, the effects of reducing conditions are all undesirable, but for white cements, which contain very little iron, reducing conditions are preferred because they yield a whiter product. Locher (LI2) concluded that the bad effects of reducing conditions were avoided so long as the clinker left the kiln at a temperature of at least 1250 C and thereafter cooled rapidly in air however, reoxidation of Fe in alite below 1300°C has been observed to cause the formation of exsolution lamellae consisting of CjF and belite (Lll). 

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. 

Fig. 4.2 Reflected light micrograph of a polished and etched section of a Portland cement clinker, showing crystals of alite (dark, angular) and belite (less dark, rounded) embedded in a matrix of interstitial material, itself composed mainly of dendritic ferrite (light) and aluminate (dark). Courtesy Materials Science Department, British Cement Association.

Fig. 4.3 Backscattered electron images of polished sections of (A) a Portland cement clinker and (B) grains of a Portland cement in a fresh paste. In both sections, alite is the predominant clinker phase. In (A), the relatively large, darker areas are of belite, and the interstitial material consists of dendritic ferrite (light) in a matrix of aluminate (dark) cracks and pores (black) are also visible. In (B), the belite forms well-defined regions, which are rounded, striated and darker than the alite the interstitial material, present, for example, in a vertical band left of centre within the larger grain, consists mainly of ferrite (light) and aluminate (dark). Scrivener and Pratt (S28).

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. 

Unless otherwise stated, this chapter relates to ordinary Portland cements hydrated in pastes at 15-25°C and w/c ratios of 0.45-0.65. XRD powder studies on such pastes have been reported by many investigators (e.g. C38,M67). The rates of disappearance of the phases present in the unreacted cement are considered more fully in Section 7.2.1. Gypsum and other calcium sulphate phases are no longer detectable after, at most, 24 h, and tbe clinker phases are consumed at differing rates, alite and aluminate phase reacting more quickly than belite and ferrite. The ratio of belite to alite thus increases steadily, and after about 90 days at most, little or no alite or aluminate phase is normally detectable. 

For pastes of typical ordinary Portland cements cured for 3-12 months, the CH content found by thermal methods or QXDA is typically 15-25%, referred to the ignited weight (P29,R14,M37,H37,T17,D12). Pressler et al. (P29) found that for pastes of various ages of ordinary (US Type I) Portland cements, it was linearly related to the content of non-evaporable water, but that for cements high in belite (US Type IV), it tended to a maximum while the latter continued to increase. This is readily explained, since belite yields only a little CH on hydration. The author has noticed similar behaviour even with modern cements high in alite, and that the CH content can possibly even decrease slightly after 28-91 days (T5). il... 

Table 7.1 Results of X-ray microanalyses by EPMA or SEM of the gel formed in situ from alite or belite in Portland cement pastes"... 

The rates of reaction of the clinker phases are greatly influenced by the RH of the atmosphere in which curing occurs. For a typical Portland cement paste of w/c ratio 0.59 cured at 20°C and 100% RH, Patel el al. (P28) found the fractions of the alite, belite, aluminate and ferrite phases hydrated after 90 days to be respectively 0.94, 0.85, 1.00 and 0.51. If the RH was lowered to 80%, the corresponding values were 0.77, 0.19, 0.83 and 0.32. The hydration rate of the belite thus appears to be especially sensitive to RH. On the basis of earlier data from the literature, Parrott and Killoh (P30) concluded that the effect of RH on the hydration rate (da/d/) of each of the phases could be represented by a factor (RH — 0.55)/0.45. ... 

Temperature has a large effect, especially in the earlier stages of hydration for example, from QXDA, Copeland and Kantro (C39) found that in a Portland cement paste of w/c = 0.57, the fraction of the alite hydrated at 2 days was 0.28 at 5°C, 0.63 at 25°C and 0.81 at 50°C. Apparent energies of activation calculated from such data were 41 kJ moC at a = 0.6 and 26 kJ mol " at a = 0.7 for belite, a value of 56 kJ mol at a = 0.4 was obtained. The decrease in the apparent energy of activation in the case of alite was attributed to a gradual change in rate control from a chemical process to diffusion. 

Parrott and co-workers (P30,P32,P35,P33) described a more sophisticated method for modelling the hydration process. The fraction of the total water porosity that was below 4nm was calculated by multiplying the volume fraction of C-S- H by an appropriate factor, which depended on whether the C-S-H was formed from alite or belite, the temperature and the amount of space available. The constants assumed were based on experimental data obtained using a procedure based on methanol sorption (Section 8.3.4). The effect of drying was allowed for (P35) by introducing a factor of 0.7 - -1.2(RH — 0.5) for 0.5 < RH < 1, or of 0.7 for RH 0.5. These refinements allow some deviation from the Powers-Brownyard postulate of a fixed volume ratio of gel porosity to product. Typical results for the volume fractions of pores larger than 4 nm in mature pastes of a cement with an alite content of 56% were approximately 0.26, 0.16 and 0.07 for w/c ratios of 0.65, 0.50 and 0.35, respectively (P32). For the two higher w/c ratios, these results are near the capillary porosities of Powers and Brownyard, but for w/c 0.35 the latter value is zero. 

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. 

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