Clinker hydration

Uchikawa (UI7) reviewed the hydration chemistry of pfa and other composite cements. Pfa cements differ from pure Portland cements notably in (i) the hydration rates of the clinker phases, (ii) CH contents, which are lowered both by the dilution of the clinker by pfa and by the pozzolanic reaction, (iii) the compositions of the clinker hydration products and (iv) formation of hydration products from the pfa. The two last aspects cannot be wholly separated. 

Hydration of fly ash cement differs from pure cement in terms of the hydration rates of the clinker phases, amount of calcium hydroxide formed, composition of the clinker hydration products, and additional hydration products from the reaction of the fly ash.I l Lower amounts of lime are formed in the presence of fly ash because ofthe pozzolanic reaction between the fly ash and lime formed in cement hydration. Fly ash generally retards the reaction of alite in the early stages and accelerates the middle stage reaction. The accelerated reaction is attributed to the existence of nucleation sites on fly ash particles. The aluminate and ferrite phases hydrate more rapidly in the presence of fly ash, and also there is a significant difference in the hydration rate of the belite phase up to 28 days. Table 1 gives the relative hydration rates of cement compounds in the presence of fly ash as derived from conduction calorimetry. [" 1 It can be seen that the earlier rates of hydration are generally retarded, and the later stage hydration rates are accelerated. 

Tetracalcium aluminoferrite acts as a processing aid by reducing the clinkering temperature. It hydrates rapidly but does Htde for any performance property of the cured concrete. It does, however, cause most of the color effects in the cured concrete. 

ASTM C845 Type E-I (K) expansive cement manufactured ia the United States usually depends on aluminate and sulfate phases that result ia more ettriagite formation duriag hydration than ia normal Portland cements. Type K contains an anhydrous calcium sulfoaluminate, C A SI. This cement can be made either by iategraHy burning to produce the desired phase composition, or by intergrinding a special component with ordinary Portland cement clinkers and calcium sulfate. 

Calcium aluminate chloride, phase in Portland cement clinker, 5 472t Calcium aluminate fluoride, phase in Portland cement clinker, 5 472t Calcium aluminoferrite, phase in Portland cement clinker, 5 472t Calcium aluminoferrite hydrate, 5 477t Calcium—aluminum alloys, 4 530 Calcium amalgam, 22 773 Calcium ammonium nitrate, 2 724 Calcium analysis, of water, 26 37 Calcium A zeolite, separation of hydrocarbons by, 16 823 Calcium—barium—silicon alloy, 22 519 Calcium-bearing manganese silicon,... 

See also Iron entries hydration, 5 477-478 in Portland cement, 5 467 in Portland cement clinker, 5 473t classification of, 11 55-58 crystal chemistry of, 11 59-71 defined, 11 55 energy losses in, 11 64-66 physical properties of, 11 59-71 processing of, 11 71-75 properties of spinel and M-type,... 

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. 

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. 

Supercritical C02 treatment affects the microstructure of the cement paste. In the first stage of the sc C02 treatment, free water in the cement pores is extracted. As a consequence of this dehydration process, channels of about 50-pm diameter develop. Dissolved calcium in the free water reacts with the C02 and crystallizes with the C02 as calcite along the channel walls. In the second stage, the structural water of the hydrated cement phases is extracted. The carbonation of the portlandite to form more calcite takes place. Water, bound to the CSH surrounding the partially hydrated cement clinker particles, is partially replaced by a carbonate formation. The short fibers of the CSH-cement framework, which are responsible for the physical properties of the cement, are not affected (Hartmann et al., 1999). 

The relative reactivity of the different mineral phases of cement with water is usually given as C A>C S>C S>C AF. Aluminate phases and their hydration products therefore play an important role in the early hydration process. Because of the high reactivity of calcium aluminate, the aluminate hydration reaction is carried out in the presence of sulfate ions. The latter provide control of the reaction rate through the formation of mixed aluminum sulfate products (ettringite and monosulfoaluminate) Calcium sulfate which is added to the cement clinker hence controls the properties of the aluminate hydration products. Sulfates thus play a crucial role in cement hydration and the influence of chemical admixtures on any process where sulfates are involved may be expected to be significant [127],... 

Portland cement clinker potential phase composition is presented in Table 4. It could be seen that the C3A content in the clinker was 9.46% which is important for the cement hydration rate and cement sulfate resistance. Common Portland cement is not resistant to the sulfate influence because of the significant C3A content, whose hydrates react with sulfate ions resulting in expansive compounds. Portland cement with the higher resistance to sulfates must have low C3A content. Moderate to high content of mineral alite - C3S (54.72%) is usual for the Serbian cement plants and enables the addition of higher quantities of mineral admixtures without influencing the quality of final cement. 

This chapter deals with chemical and physical properties other than ones for which the nature of the hydration products must be considered, which are treated in Chapters 5 to 8. In general, properties of the whole clinker or cement are alone considered, those of the constituent phases having been dealt with in Chapter 1, but factors affecting the reactivities of these phases are included as a link with the following chapters on hydration. 

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. 

CH can be observed as areas darker than the unreacted clinker phases but brighter than the other hydration products. As in calcium silicate pastes, these appear to have grown in regions initially occupied by water. Although the areas appear discrete on two-dimensional sections, they are not necessarily so in the three-dimensional material. They can engulf small cement grains. 

The experimental considerations applying to calcium silicate pastes (Sections 5.1 and 5.2) are equally relevant to cement pastes. Of the methods so far used in attempts to determine the degrees of reaction of the individual clinker phases as a function of time, QXDA (C39,D12,T34,P28) has proved much the most satisfactory. Procedures are essentially as for the analysis of a clinker or unreacted cement (Section 4.3.2), but it is necessary to take account of overlaps with peaks from the hydration products, and especially, with the C-S-H band at 0.27-0.31 nm. The water content of the sample must be known, so that the results can be referred to the weight of anhydrous material. If a sample of the unhydrated cement is available, and its quantitative phase composition has been determined, it may be used as the reference standard for the individual clinker phases in the paste. 

Water retained after D-drying, known as non-evaporable water, has often been wrongly identified with chemically bound water. It excludes much of the interlayer water in C-S-H, AFm and hydrotalcite-type phases and much of the water contained in the crystal structure of AFt phases. It is often used as a measure of the fraction of the cement that has reacted, but can only be approximate in this respect, because the clinker phases react at different rates and yield products containing different amounts of non-evaporable water. Fully hydrated cement pastes typically contain about 23% of non-evaporable water, referred to the ignited weight. Copeland et al. (C38) determined the non-evaporable water contents of a series of mature cement pastes and carried out regression analyses on the cement composition. For pastes of w/c ratio 0.8 and aged 6.5 years, they obtained the approximate expression ... 

The and Na" are present in the cement partly as sulphates and partly in the major clinker phases (Section 3.5.6). When the phases containing them react, the accompanying anions enter products of low solubility and equivalent quantities of OH are produced. The K, Na and OH" ions are partitioned between the pore solution and the hydration products. Early estimates of the fractions remaining in solution were too high because non-evaporable water was used as a measure of bound water and the quantity of pore solution thereby overestimated. 

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