Hydration ferrite

Other reactions taking place throughout the hardening period are substitution and addition reactions (29). Ferrite and sulfoferrite analogues of calcium monosulfoaluminate and ettringite form soHd solutions in which iron oxide substitutes continuously for the alumina. Reactions with the calcium sihcate hydrate result in the formation of additional substituted C—S—H gel at the expense of the crystalline aluminate, sulfate, and ferrite hydrate phases. 

The reactivity of ferrites toward water changes consecutively C2F CgAFj CgA2p [150]. The calcium aluminate and ferrite hydrates form the unlimited solid solutions. However, in hydrates generally is higher A/F ratio than in the anhydrous phase therefore some amount of Fe(OH)3 is formed [149], which can be described schematically ... 

Other Reactions. Dry hydrated lime adsorbs halogen gases, eg, CI2 and F2, to form hypochlorites and fluorides. It reacts with hydrogen peroxide to form calcium peroxide, a rather unstable compound. At sintering temperatures, quicklime combines with iron to form dicalcium ferrite. 

The hydration of the ferrite phase (C AF) is of greatest interest in mixtures containing lime and other cement compounds because of the strong tendency to form soHd solutions. When the sulfate in solution is very low, soHd solutions are formed between the cubic C AH and analogous iron hydrate C FHg. In the presence of water and siUca, soHd solutions such as C3 ASH4-C3FSH4 may be formed (33). Table 7 Hsts some of the important phases formed in the hydration of mixtures of pure compounds. 

In the cement industry, the term hydration is used to describe a range of reactions between cement and water to produce a hardened product. A cement clinker particle is a multiphase solid having massive calcium silicate grains (50-100 pm) in a matrix of interstitial aluminate and ferrite. This is described as analogous to a distorted clay sequence, which traps regions of porosity-pore size distribution from nanometer to micrometer. 

Mixed oxides have a widespread application as magnets, catalysts, and ceramics. Often, nonstoichiometric mixtures with unusual properties can be prepared for example, Fe203 and ZnO have been milled for the production of zinc ferrite [40], while mixed oxides of Ca(OH)2 and Si02 were described by Kosova et al. [77]. Piezoceramic material such as BaTi03 from BaO and anatase Ti02 has been prepared [78], while ZnO and Cr203 have been treated by Marinkovic et al. [79] and calcium silicate hydrates from calcium hydroxide and silica gel by Saito et al. [80]. The thermal dehy-droxylation of Ni(OH)2 to NiO or NiO-Ni(OH)2 nanocomposites has also been investigated [81]. 

Other than in their mean compositions. Slow cooling produces relatively large crystals of each phase, while fast cooling produces close intergrowths textures are discussed further in Section 4.2.1. Zoning occurs readily in the ferrite (Section 2.3.1), and may also occur in the aluminate. The distribution of atoms between octahedral and tetrahedral sites in the ferrite depends on the temperature at which internal equilibrium within the crystal has been achieved (Section 1.5.1). The degree of crystallinity of both phases appears to vary with cooling rate (V3). All these effects, and perhaps others, may affect the behaviour of the interstitial material on hydration. 

Table 6.7 Standard enthalpies of formation (A// kj mol" ) for some compounds relevant to hydration of the aluminate and ferrite phases (25 C except where otherwise stated)...

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. 

Transmission electron microscopy of ion-thinned sections provides data at higher resolution than can be obtained with polished sections. Rodger and Groves (R24) described regions which had probably formed in situ from the ferrite phase, and which consisted of C-S-H, a hydrotalcite-type phase and a poorly crystalline phase containing iron that could have been the precursor of a hydrogarnet. The particles of this last constituent were almost spherical and some 200 nm in diameter. The same investigation also showed that much of the product formed in situ from alite or belite was essentially pure calcium silicate hydrate. 

In an ordinary Portland cement, only some two-thirds of the Fe occurs in the ferrite, the rest being contained largely in the alite and aluminate (Table 4.3). On hydration, the Fe " in these other phases probably does not enter a hydrogarnet, but goes into AFm phases or layers formed in situ. This would account for the observation by analytical electron microscopy that small amounts of Fe are present in the AFm phases. 

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. ... 

In Ciment Fondu, the ferrite phase seems to play no significant part in early hydration at 20 C, but at 30-38 C over 80% was found to have reacted by 2 months (C47). The melilite and pleochroite seem to be unreactive. When belite is present, silicate ions can be detected in the solution within a few minutes, but then disappear it seems that precipitation occurs and further dissolution is inhibited. Among the minor oxide components. TiO, and MgO mainly occur in the unreactive phases. Na,0 and K,0 scarcely affect the solution equilibria at early ages, as their concentrations are very low (M88). 

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