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Chemical composition of Portland cement We have seen that the raw materials used in the manufacture of Portland cement consist mainly of lime, silica, alumina and iron oxide. These compounds interact with one another in the kiln to form a series of more complex products and, apart from a small residue of uncombined lime which has not had sufficient time to react, a state of chemical equilibrium is reached. However, equilibrium is not maintained during cooling, and the rate of cooling will affect the degree of crystallization and the amount of amorphous material present in the cooled clinker. The properties of this amorphous material, known as glass, differ considerably from those of crystalline compounds of a nominally similar chemical composition. Another complication arises from the interaction of the liquid part of the clinker with the crystalline compounds already present. Nevertheless, cement can be considered as being in frozen equilibrium, i.e. the cooled products are assumed to reproduce the equilibrium existing at the clinkering temperature. This assumption is, in fact, made in the calculation of the compound composition of commercial cements: the potential composition is calculated from the measured quantities of oxides present in the clinker as if full crystallization of equilibrium products had taken place. Four compounds are usually regarded as the major constituents of cement: they are listed in Table 1.1, together with their abbreviated symbols. This shortened notation, used by cement chemists, describes each oxide by one letter, viz.: CaO = C; SiO2 = S; Al2O3 = A; and Fe2O3 = F. Likewise, H2O in hydrated cement is denoted by H, and SO3 by . Table 1.1. Main Compounds of Portland Cement In reality, the silicates in cement are not pure compounds, but contain minor oxides in solid solution. These oxides have significant effects on the atomic arrangements, crystal form and hydraulic properties of the silicates. The calculation of the potential composition of Portland cement is based on the work of R. H. Bogue and others, and is often referred to as Bogue composition. Bogues1.2 equations for the percentages of main compounds in cement are given below. The terms in brackets represent the percentage of the given oxide in the total mass of cement. C3S = 4.07(CaO) 7. 60(SiO2) 6.72(Al2O3) 1.43(Fe2O3) 2.85(SO3) C2S = 2.87(SiO2) 0.75(3CaO.SiO2) C3A = 2.65(Al2O3) 1.69(Fe2O3) C4AF = 3. 04(Fe2O3). There are also other methods of calculating the composition,1.1 but the subject is not considered to be within the scope of this book. We should note, however, that the Bogue composition underestimates the C3S content (and overestimates C2S) because other oxides replace some of the CaO in C3S; as already stated, chemically pure C3S and C2S do not occur in Portland cement clinker. A modification of the Bogue composition which takes into account the presence of substituent ions in the nominally pure main compounds has been developed by Taylor1.84 for the rapidly cooled clinkers produced in modern cement plants. In addition to the main compounds listed in Table 1.1, there exist minor compounds, such as MgO, TiO2, Mn2O3, K2O and Na2O; they usually amount to not more than a few per cent of the mass of cement. Two of the minor compounds are of particular interest: the oxides of sodium and potassium, Na2O and K2O, known as the alkalis (although other alkalis also exist in cement). They have been found to react with some aggregates, the products of the reaction causing disintegration of the concrete, and have also been observed to affect the rate of the gain of strength of cement.1.3 It should, therefore, be pointed out that the term minor compounds refers primarily to their quantity and not necessarily to their importance. The quantity of the alkalis and of Mn2O3 can be rapidly determined using a spectrophotometer. The compound composition of cement has been established largely on the basis of studies of phase equilibria of the ternary systems CAS and CAF, and the quaternary system CC2SC5A3C4AF, and others. The course of melting or crystallization was traced and the compositions of liquid and solid phases at any temperature were computed. In addition to the methods of chemical analysis, the actual composition of clinker can be determined by a microscope examination of powder preparations and their identification by the measurement of the refractive index. Polished and etched sections can be used both in reflected and transmitted light. Other methods include the use of X-ray powder diffraction to identify the crystalline phases and also to study the crystal structure of some of the phases, and of differential thermal analysis; quantitative analysis is also possible, but complicated calibrations are involved.1.68 Modern techniques include phase analysis through a scanning electron microscope and image analysis through an optical microscope or a scanning electron microscope. Estimating the composition of cement is aided by more rapid methods of determining the elemental composition, such as X-ray fluorescence, X-ray spectrometry, atomic absorption, flame photometry, and electron probe micro-analysis. X-ray diffractometry is useful in the determination of free lime, i.e. CaO as distinct from Ca(OH)2, and this is convenient in controlling the kiln performance.1.67 C3S, which is normally present in the largest amounts, occurs as small, equidimensional colourless grains. On cooling below 1250 C, it decomposes slowly but, if cooling is not too slow, C3S remains unchanged and is relatively stable at ordinary temperatures. C2S is known to have three, or possibly even four, forms. a-C2S, which exists at high temperatures, inverts to the -form at about 1450 C. -C2S undergoes further inversion to ?-C2S at about 670 C but, at the rates of cooling of commercial cements, -C2S is preserved in the clinker. -C2S forms rounded grains, usually showing twinning. C3A forms rectangular crystals, but C3A in frozen glass forms an amorphous interstitial phase. C4AF is really a solid solution ranging from C2F to C6A2F, but the description C4AF is a convenient simplification.1.4 The actual proportions of the various compounds vary considerably from cement to cement, and indeed different types of cement are obtained by suitable proportioning of the raw materials. In the United States, an attempt was at one time made to control the properties of cements required for different purposes by specifying the limits of the four major compounds, as calculated from the oxide analysis. This procedure would cut out numerous physical tests normally performed, but unfortunately the calculated compound composition is not sufficiently accurate, nor does it take into account all the relevant properties of cement, and cannot therefore serve as a substitute for direct testing of the required properties. A general idea of the composition of cement can be obtained from Table 1.2, which gives the oxide composition limits of Portland cements. Table 1.3 gives the oxide composition of a typical cement of the 1960s and the calculated compound composition,1.5 obtained by means of Bogues equations on p. 9. Table 1.2. Usual Composition Limits of Portland Cement Table 1.3. Oxide and Compound Compositions of a Typical Portland Cement of the 1960s1.5 Two terms used in Table 1.3 require explanation. The insoluble residue, determined by treating with hydrochloric acid, is a measure of adulteration of cement, largely arising from impurities in gypsum. British Standard BS 12 : 1996 (withdrawn) limits the insoluble residue to 1.5 per cent of the mass of cement. European Standard BS EN 197-1 : 2000, which allows a 5 per cent content of a filler (see p. 88), limits the insoluble residue to 5 per cent of the mass of the cement exclusive of the filler. The loss on ignition shows the extent of carbonation and hydration of free lime and free magnesia due to the exposure of cement to the atmosphere. The maximum loss on ignition (at 1000 C) permitted by BS EN 197-1 : 2000 is 5 per cent and by ASTM C 150-09 is 3 per cent except for Type I cement (2.5 per cent); 4 per cent is acceptable for cements in the tropics. Because hydrated free lime is innocuous (see p. 51), for a given free lime content of cement, a greater loss on ignition is really advantageous. With cements containing a calcareous filler, a higher limit on the loss on ignition is necessary: 5 per cent of the mass of the cement nucleus is allowed by BS EN 197-1 : 2000. It is interesting to observe the large influence of a change in the oxide composition on the compound composition of cement. Some data of Czernins1.5 are given in Table 1.4; column (1) shows the composition of a fairly typical rapid-hardening cement. If the lime content is decreased by 3 per cent, with corresponding increases in the other oxides (column (2)), a considerable change in the C3S : C2S ratio results. Column (3) shows a change of per cent in the alumina and iron contents compared with the cement of column (1). The lime and silica contents are unaltered and yet the ratio of the two silicates, as well as the contents of C3A and C4AF, is greatly affected. It is apparent that the significance of the control of the oxide opera:209 02-12-2013 10:54:03

Properties of Concrete, Fifth Edition > Chapter 1. Portland cement > Chemical composition of Portland cement : Safari Books Online

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composition of cement cannot be over-emphasized. Within the usual range of ordinary and rapid-hardening Portland cements the sum of the contents of the two silicates varies only within narrow limits, so that the variation in composition depends largely on the ratio of CaO to SiO2 in the raw materials. Table 1.4. Influence of Change in Oxide Composition on the Compound Composition1.5 In some countries in the European Union, there is a limit on soluble hexavalent chromium usually of 2 ppm of mass dry cement. Contact with excess chromium in fresh concrete may lead to dermatitis. It may be convenient at this stage to summarize the pattern of formation and hydration of cement; this is shown schematically in Fig. 1.2. Fig. 1.2. Schematic representation of the formation and hydration of Portland cement

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