Advances in Cement Research, 2000, 12, No. 1, Jan, 19-28 Calculations of Portland cement clinkering reactions T. L. Barry* and F. P. Glassert Amethyst Systems; University of Aberdeen Calculations have been undertaken of both equilibrium and non-equilibrium chemistry of relevant parts of the CaO-Fe)0;-AlOs-SiO; system and related reactions in the gas phase. The examples provide new insights into topics of current concern in the manufacture of Portland coment, including the early stages of melting, the undesirable retention of lime, the ferrous iron content and the phases formed during non-equilibrium cooling, their proportions and composition. The proportion of the C3S (alite) phase depends exclusively on the early stages of cooling, when neither ferrite nor CzA is present. This and the fact that the phases do not have fixed compositions illuminate the limitations of the Bogue calculation for estimation of C38. Calculations involving the gas and liquid salts are used 10 investigate reactions of sodium and its build-up in the hot zone of the kiln. The scope and limitations of the database and methods for calculations on these processes are discussed. Introduction ‘The manufacture of Portland cement is chemically very complex. Moreover, because the kiln is rotary, direct observations of the conditions in the kiln and the processes taking place are difficult, Nevertheless, scientific advances, particularly in the characterization of the products, are enabling manufacturers to improve and standardize products and to decrease environmental impacts. This paper examines the potential of thermo- dynamic calculations of phase equilibria to contribute to understanding and process control. The problems are formidable. © The raw materials are locally sourced as far as possible: they include recycled materials and ash from the fuels used, especially coal. In addition to the major components CaO, Fe,03, AlzO; and SiOs, significant amounts of Na;O, KO, MgO, MnO, ZnO, TiO; and other oxides may be present. The control of alkali levels is a particular requirement both for environ- Amethyst Systems, 2 Marlingdene Close, Hampion, Migalesex TWI2 3B, UK ‘University of Aberdeen, Department of Chemistry, Meston Walk, Old Aberdeen ABD 3UE, UK. (ACR 320) Paper received 24 September 1998 November 1998 sccepted 10 ‘mental reasons and to improve long-term compatibility with certain aggregates. The fuel and raw materials contain variable amounts of sulphur and chloride, which, together with carbon dioxide and variable amounts of water, contribute to the complexity of the overall chemistry, ‘ Although the raw materials are very finely ground, compositions inevitably vary locally within the material ‘* The paths of individual particles through the preheater and kiln vary. The counter-current gas stream may cause particles to progress at different rates or even retrogress. Heating rates, residence times and cooling rates are not entirely uniform, ‘As the material is subject to rapid cooling, departure from equilibrium is inevitable and indeed may be desirable, For example, C3S (alite), which is unstable at low temperatures, is retained and C3A tends to adopt disordered, non-equilibrium structures, © The crystalline phases undergo transitions and solid solution. Moreover, this solid solution affeets both the temperatures and rate of phase transitions occurring during clinker cooling, At first sight, the presence of metastable states and inhomogeneous conditions make phase equilibrium calculations seem unpromising. On the other hand, there are many ways in which the calculations can make a contribution, 19 0951-7197 © 2000 Thomas Telfond LidBarry and Glasser # The thermodynamic models allow the phase equilibria of high-order multicomponent systems to be calcu- lated in great detail from critically assessed data for lower-order systems without further experiment. * A fiamework is provided that takes account of the chemistry both overall and in detail in a self-consistent way. + Data for metastable phases can be used in calculations. # The speed of the calculations enables the effect of variables of composition, fuel and temperature to be investigated in response to need © Calculations can reveal gaps and limitations. in experimental data and hence focus experimental research. + The driving foree for chemical change is the Gibbs energy, a knowledge of which is inherent in the data ‘Thus the calculation system can be linked to process models to provide information on kinetic as well as equilibrium processes. The thermodynamic models are described briefly and examples are presented that illustrate the potential of ‘thermodynamic methods to improve cement making, The basis of the calculations The calculations were undertaken using MTDATA,! the National Physical Laboratory (NPL) Databank for Metallurgical Thermochemistry, in association with the oxide database. Equilibrium is calculated using an algorithm that distributes the elements between the species in the gas, liquid and crystalline phases in such away as to minimize the Gibbs energy. In the normal mode of operation, the compositions of the phases are not predetermined; they result from the calculation and are limited only by the model used when the data were assessed. MTDATA incorporates a data assessment module. Critically assessed data for the species in each phase are stored in the form of parameters of expressions that relate the Gibbs energy to temperature and, where appropriate, pressure, Parameters are also stored for the concentration and temperature dependence of inter- action energies between the species of solution phases. ‘The definitions of the species in the phases and the particular models used for the interactions therefore form an important part of the data, Data are generated by critical assessment of experimental data from the literature and are consistent with SGTE (Scientific Group, Thermodata Europe) unary data for the ele- ments? The oxide database was developed at NPL with joint funding from DTI and a group of sponsors coordinated through MIRO (Mineral Industry Research Organisation). It has been used in connection with pyrometallurgical processing,” steel making, glass mak- ing, pollution control, corrosion contro,’ nuclear tech- nology” and geochemistry.” 20 In the most common type of calculation, the overall composition of the system is defined in terms of the amounts of its components. Equilibrium is achieved ‘when the components are assigned to species in such a way as to minimize the Gibbs energy (or Helmholtz energy if volume rather than pressure is fixed). It is also possible 0 calculate compositions necessary to achieve certain results and, for example, to determine the temperature that would be reached when a fuel is combusted, Individual species and phases can tempora- rily be excluded from calculations, thereby providing a means for exploring metastable phenomena. Many properties and types of diagram can be calculated The oxide liquid is modelled as 2 solution of non- ideally interacting species that include not only the components, expressed as CaO, FeOys, AlOrs, and SiOz, but also associates, e.g. CaSiOs and Ca;SiOy. Associates are included where the experimental. data indicate sharp changes in component activites. The use of fractions in the formulae, e.g. AIO, rather than AlaOs, influences the ideal entropy contribution to the Gibbs energy. Lime is modelled as (Ca**, Fe?*, Fe'*, Va)O™-, ie. as an ionic solid solution of oxides stable in or soluble in the halite structure, where Va represents # vacancy, in this case on the cation sublattice 3S (alite) is modelled in the oxide database as a single stoichiometric phase, the mineral hatrurite, although in fact there are seven known variants,"* of which only the rhombohedral form is of significance at temperatures important in the burning of cement. C3S is unstable with respect to lime and C:$_ below 1270°C, but the rate of decomposition is slow and in practice it undergoes transformations 1 other C3 variants at lower temperatures. Solid solution of AkOs and Fe,0s in the C3S phase has not been taken into account. CoS (belt): the oxide database incorporates data for three phases of this nominal formula, These are aC28, which is stable above 1440°C and is taken to be stoichiometric in the C-F-A~S system, a’C28, which is modelled as a solid solution of CaxSiQ, and Fe:SiO, (but not including ferric iron), and olivine (yC:S), Solid solution is more extensive in olivine than in a's, CsA is modelled as a solid solution of Cay-sAI05 and Cay sFe0, Ferrite, named C2F in the lists of phases on the iagrams, also known as brownmillerite and CAF, is, modelled as a solid solution of CalOn5 and CaFeOn Cindy is modelled as a solid solution of CasAl;Oy6s and CapAlsFeOyes. The model restricts replacement by Fe to one out of seven AD ions. CA is modelled as @ solution of CasAlOy2 and CasAlsFeOy2. The model restricts replacement by Fe** to one out of six Al ions In addition, the following phases were included in the calculations of Figs 1~-9: CAF CA2, CA, CR, CF: Advances in Cement Research, 2000, 12, No. 1+509 Calculations of Portland cement clinkering reactions mraosecs é E tater ose Kom aos 08 va 28+ 68 K | +300] f-caracs+os [4 iB foc +n sree +008 +m 0d . 1 4 Sor 00a 00808 8 Fraction of AO, by mass Fig. 1. Binary section through the CFAS system. Mass fractions C 069, $022, A+ PF = 09. The temperature for onset of liguid formation is calculated to be 1334°C for A = 0:04 to 0077. Phase fields which are to0 narrow to show on the scale of the diagram are also designated 09 099 og 24 Bod 3 os} : tiie oo — oy a er aces od Sa a ne waoy Fig. 2. The masses ofthe phases in chemical equilibrium as «a function of temperature for a composition C 0°69, F 0-036, A 0054, 50:22. The liquid disappears completely at temperatures below 133C and rankinite (C;S;), most of which were modelled as solid solutions The oxide database also includes data for many other phases in the C-F-A-S system, including the SiOz polymorphs, melilite, pyroxenes and wollasto- nites, The oxide database presently also includes data for ferrous iron and the addition to the liquid of MgO, Advances in Cement Research, 2000, 12, No. 1 Fig. 3. Mass of liquid formation as a function of proportions Of lsOs and Fe;0s at temperatures fram 1334°C to 1450°C ZnO, NasO, KO and some other components of Pyrometallurgical interest, but data for the solution of these components in some of the solid phases of Portland cement are currently more restricted. There are also current limitations on the mixing of sulphates and carbonates in the liquid and solid phases in the oxide database. 21Barry and Glasser oe os B TO E os| 2 o6 3 od 2 : Ho ane $ 3 AD y i : i & og] 02] Ferrite On § Fete fos} # 3 o1 Line 2 80, Po oor Oa Oa oor 00S os Oar O08 a Te Ti80 70 WAL) re Fig, 4. Equilibrium phases at 1350°C as a function of mass fraction of AlzOs for compositions C 0-68, S022, A+F 009 Gao gos 3 fod g Fes Boa 3 Kio, § of] £ a 3 o4 30, a oF 008005 004 G05 908 OUT oF wiA.o) Fig 5. Equilibrium composition of the liquid at 1450°C as a Junction of mass fraction of Al:Os for compositions C 0-68, $022, A+F 0.09 The salt liquid is treated as an ionic solution with the anions and cations on different sublattices. Effect of varying the ratio of ALO; to Fe203 on liquid formation The solid-state reaction of siliceous materials and lime to give C3$ and C2S is slow, but material transport is greatly facilitated by the presence of liquid. Thus the volume of liquid formed at the low-temperature end of processing is an important variable for efficient clinker- ization. Lea and Parker" have determined that the lowest 2 Fig. 6. The composition of the liquid phase resulting from Scheil cooling of the liquid phase in a clinker of overall composition C 0°69, F 04036, 4 0054, S022. The starting composition of the liguid ar 1450°C is C 0°552, F 0-147, A 022, S 0081 oof Tague “ota of esta increments 300 7350 Ta00 7a ne Fig, 7. The amounts of erystaltine phases formed during ‘each step in Scheil cooling of the liquid phase in a clinker ‘of overall composition C (+69, F 04036, A 0-054, S$ 0-22. The starting composition of the liguid at 14S0°C is C 0°332, F 0147, A 0-22, $ 008). Each step corresponds to —I°C temperature at which a significant volume of liquid is generated is 1338°C. Herath-Banda and Glasser"® and Glasser® have related the amount of liquid to the Al;O3 amd Fe05 contents and the A/F ratio. relevant calculated phase diagram is shown in Fig. 1 ‘The phases normally found in Portland cement, C38, C28, CsA and ferrite, are stable in the composition range A/F = 08-5 at temperatures between 1266°C and 1334°C. The lowest emperatue for liquid tobe present is calculated to be 1334°C and the composition at which liquid formation is maximum has A/F ~ 1-34. Both of Advances in Cement Research, 2000, 12, No. {ST -——————___] o7 oa 4 i E og 3 3 og] iis 0 ena ee eos 20,8 00] =| Tae 13 Ta Taso ne Fig 8. The accumulated mass of each of the individual Phases formed during Schell cooling of a clinker of overall ‘composition C 0°69, F 0036, A 0034, S 0-22 from 1450°C, including the C38 and C;S that were unmelted at 1450°C. The mass of aC3S has been transferred to a'C3S at 1438°C. A comparison with Fig. 2 reveals important differences in the fraction of CxS at temperatures Below 1340°C and the Continuation of liguid below 1334°C. The proportions of errte, CoS and CsA are also different oo o od 20, 128012601300 1310 1a a0 1340 Tas me Fig. 9. The composition of successive increments in the ferrite phase from Fig. 7 these values are close to the experimental determinations of Lea and Parker.” Figure 2 shows the equilibrium masses of phases calculated for a composition C 69%, F 3:6%, A 5: S 22%, at temperatures between 1270°C and 1450°C. The sudden onset of melting at 1334°C is a notable feature of the diagram. The fall in the amount of CsS ‘on cooling between 1340°C and 1330°C and the com- positions of the C;A and ferrite phases will be consid- Advances in Cement Research, 2000, 12, No. 1 Calculations of Portland cement clinkering reactions cred in relation to phase transformations occurring on cooling, Figure 3 shows that equilibrium fraction of the liquid as a function of A/F ratio for temperatures between 1334°C and 1450°C. Perhaps surprisingly, the amount of liquid formed is rather insensitive to temperature The mass fraction of SiO. in the melt is low and vaties only from 5% to 8% between 1350°C and 1450°C. However, the range of A/F ratios over which melting ‘occurs is very sensitive to temperature. At 1360°C, the A/F ratios over which melting is greater than 20% by ‘mass expands to cover the range 0-4~2-0 and includes the compositions with high A/F ratios that are used to achieve white cements. Figure 4 shows the calculated phase distribution at 1350°C for clinkers containing 69% CaO, 22% SiO, and 9% AlOs + Fe,0s. It is useful to note that low A/F ratios maximize the formation of C38 but this increases the tendency to lime retention (discussed further below). On the other hand, high A/F ratios cause the formation of CsA and C;$ and lower proportions of C:S. Of course, it is unlikely that these reactions would approach global equilibrium after short periods at this temperature, and higher temperatures are needed to spread the liquid to regions with locally different compositions. The type of calculations on which Figs 2-5 are based also provide information on many other aspects of the phase equilibria, including ‘the compositions of the phases, enthalpies and activities of components. Phase transformations on cooling The cooling of Porttand cement clinker is deliber- ately rapid and commences while itis still in the kiln. Under these conditions, the phase assemblage is not in overall thermodynamic equilibrium. A physical model is therefore needed to take account of the relative rates of various processes. A simple example is the Scheil model, reviewed by Cahn and Hassen,"" in which, at each successive stage of cooling, the erystalline phases formed in the previous stage are deemed not to take any further part in reaction with the liquid and a new equilibrium is determined between the liquid and freshly formed solids. It is, of course, possible to take account in separate calculations of phase transforma- tions in the solids, e.g. the rapid transformation, be- tween aCyS and a’C,S at ~1438°C. The composition of the remaining liquid changes progressively until a eutectic is reached, at which point the remaining liquid stallizes Figure 6 shows how the composition of a liquid changes as a function of temperature during cooling from 1450°C in small steps using the Scheil model. It will be seen that the final composition, C 50%, A 37%, F 9%, S 4%, is very different from that expected for the initial liquid formed on melting. Moreover, the 23Barry and Glasser lowest temperature at which liquid is retained, 1284°C, is substantially lower than the temperature for the onset ‘of melting in the starting composition as a whole. Figure 7 identifies the masses of the solid phases formed at each decrement in temperature, and Fig. 8 shows the accumulated amounts of the phases, includ- ing the amounts of C3S and C.S present before cooling commenced. At temperatures greater than 1360°C, the crystallization of C3S and C2S follows close to the equilibrium line, but below this temperature, formation of C3S ceases and CsA starts to form. This causes the concentration of Fez03 in the melt to rise but, below 1333°C, it falls again when ferrite starts to form, initially very rapidly, and the rates of formation of both CsA and C2S decline. Finally, at the eutectic, the calculated phases in equilibrium with the small amount of remaining liquid are CizAr, ferrite, a’CyS and CA. OF these phases, neither CjzA7 nor CA is normally found in Portland cement. However, the predicted amounts are very small and might be undetectable by X-ray diffraction. Solid solution of AlOs in the C;S phase would also potentially reduce the amount of Al available for the formation of CA and possibly Ci2Ax. It is also unlikely that the Scheil model is wholly appropriate: processes ‘may continue in the solid state after crystallization and the newly formed phases may not be in perfect equilibrium with the melt, For example, the crystal- lization of CsA tends to occur with undercooling and the formation of disordered solid solutions that extend beyond the usual composition range." ‘The amounts of phases calculated for Scheil cooling from 1450°C to 1280°C and those for equilibration at 1327°C are compared in Table 1 with results of the Bogue calculation. For the Bogue calculation, the compositions of the ferrite and CsA phases were taken to be CasAlsFe:0io and CasAl;Og respectively. The origin of the difference between the amount of C3S predicted by the Scheil and equilibrium calculations is seen most clearly by a comparison of Fig. 8 with Fig 2. The decrease in Fig. 2 of 0-035 in the fraction of CS does not occur in Fig. 8 because, if the assump- tions of Scheil apply, the C3S once formed would not react further. ‘Comparisons of the composition differences of the individual phases between the equilibrium and Scheil- cooled calculations are complicated by the fact that in Scheil cooling the compositions of both ferrite and CsA change with temperature, as illustrated for ferrite in Fig. 9. Under equilibrium conditions, the composi- tions of the phases listed in Table 2 are calculated to be nearly constant between 1334°C and 1266°C and not very different from the first ferrite and CsA to form uring Scheil cooling. The Bogue calculation of proportions of phases As originally presented, the Bogue calculation, which is based on a straightforward mass balance, appeared to give an unequivocal method for calculation of the phase compositions of Portland cements. Furthermore, it could be justified theoretically and was simple to apply. The original calculation did not include correc- tion factors for solid solution of the clinker components in the phases, but subsequent investigations using electron microprobe data on actual materials have improved the correspondence between assumptions and reality."* Guttridge!® measured Cy quantitatively by X-ray diffraction and generally found that, although the summed phase content was close to 100%, X-ray diffraction gave higher CsS concentrations than Bogue, although discrepancies were somewhat reduced by using a modified Bogue formulation. In critically reviewing this, Taylor concludes: ‘There is wide agreement that the Bogue calculation gives seriously incorrect results, especially for C3S. It has offen been stated that the errors arise because equilibrium is not maintained during cooling but this is only partly correct. ... The calculation gives incorrect results mainly because the phases do not have the composi- tions assumed for them, and the absence of equilibrium conditions from cooling merely alters the errors that The authors of the current paper agree that the Table 2. Equilibrium at 132°C. Calculated compositions of the CsA and ferrite phases expressed as mass fractions of the components Phase x0 F20; E Ga ‘6103 90549 0368 Ferite 0.4678 02958 02364 Table 1. The fractional amounts of phases calculated t0 form as a result of Scheil cooling of a clinker (CaO 69, Fes0s 36, AlzOs 5-4, SiO; 22) from 1450°C 10 128°C compared with those calculated for equilibration at 1327°C and with the Bogue calculation Phase os os GA | Fornte cA Equilibria | o7206 0871 0867 01056 Scheil cooled | o7sse 0-0606 0-048 011266 60003 0.0087 Bogue calculation ones | _oosas 0.0854 011056 24 Advances in Cement Research, 2000, 12, No, 1proportions of all the phases in the clinker are directly related to their compositions and the overall composi- tion, However, the Scheil calculations show in a very direct way how lack of equilibrium allows more C$ to be retained than would be predicted by either Bogue ot modified Bogue. All the C3S is produced before any CsA or ferrite crystallize, and thus their compositions are more a consequence than a cause of the proportion of C38. Moreover, because the compositions of the phases are not single valued, the information on which the Bogue calculation should be based is incomplete. ‘The magnitude of the extra Cs that is calculated with the Scheil model, a few weights per cent, corresponds closely to the extent of disagreement between, on the cone hand, calculation schemes, and on the other, actual measurements. Thus non-equilibrium effects of cooling do not ‘merely alter the errors that arise” but directly control the amount of Cs$ in the clinker. An important goal, therefore, is for manufacturers of high-C;S cement to validate and use the methods presented here as a means for enhancing product properties. As part of validation, it would be desirable to undertake a careful study of the composition of the phases, paying particular attention to individual grains that, from their microstruc- ture, could be identified as forming during the early and late stages of crystallization. It would be essential to avoid any interference from intergrowing crystals. Once validation had been completed and the basic, pattern of cooling behaviour established, it would not be necessary to undertake multistep Scheil-type calcu- lations for each overall composition. If the primary concern lay with the proportion of C3S, only a single calculation would be necessary, to be undertaken at a selected temperature above but close to that where further formation of C3S ceased during cooling. In this way it would be possible rapidly to make plots of the amount of C$ formation under cooling conditions as a function of composition. It would clearly be desirable to extend the data to include solution of additional components, at least for the liquid, CsS and CS phases. The proportion of ferrous oxide Most of the calculations undertaken for this paper exclude oxygen as a component and therefore do not allow for reduction of some of the ferric oxide to ferrous oxide, This is a reasonable approach, because cement kilns are normally run with a small excess of air, suificient to keep the oxygen partial pressure at about 0:01 atm and to avoid the presence of more than a trace of CO. A few calculations have been undertaken as a check, and these show that, in this atmosphere at 1450°C, 3.7% of the total iron would be present as Fe* in a clinker of composition C 69%, F 36%, A. 54%, S 22%, equivalent to only 0-12% FeO in the overall composition. However, because Fe* would tend Advances in Cement Research, 2000, 12, No. 1 Calculations of Portland cement clinkering reactions to substitute for calcium rather than aluminium, there may be circumstances, particularly under more redu- cing conditions, in which the presence of Fe? might modify the partition of iron between phases sufficiently to change the proportions of product phases and affect the colour of the clinker. Sodium transport In recent years, the proportion of alkalis in cement has been reduced to improve the long-term perform- ance of the hydrated cement in contact with alkali- susceptible aggregates. The following calculation of the partion of sodium between the gas and condensed phases is illustrative only. It assumes that sodium is the only alkali present and that itis exclusively present as various gaseous species and salts, including a molten salt containing sulphate, carbonate, chloride and hydrox- ide. The partition of sodium into the cement clinker phases, which will certainly occur, is neglected, With these assumptions, the calculation ean be restricted to the Na-C-H,-O;-N;-S-Cly system, mote conveni- ently expressed for purposes of mass balance as the Na,O0-CO;~H;0-0;—Nz-SO;-HC1 system. In a modem coal-fired kiln, every 100+ of clinker requires about 13+ of fuel," of which about 11 t are carbon and 0:6 t hydrogen (ie. CO; 40 and H0 51), If 69% of the clinker is CaO, originally present as CaCOs, this implies a further 54 t of CO. The amounts of NazO and KO in clinker are assumed to be 015% and 07%, Finally, the amounts of HzO, SO; and HCL would vary very much with the type of raw material but are assumed to be 5, I and 0-2 t respectively. The stoichiometric total of oxygen that needs to be supplied to bum the fuel is 335t, which implies 117¢ of nitrogen. A further 2¢ of oxygen is needed to give a residual partial pressure for Oz close to O01 atm. The calculations of equilibria took into account 64 phases and 246 gaseous species, though for routine calcula tions the great majority of the phases and species could have been omitted. On the other hand, adding in CaO, FeO, Fe0s, AlOs, SiOz and Kz0 would have greatly increased the complexity and would have needed addi- tional data It is recognized that volatilization of sodium in the hhot zone causes the sodium to be cartied by the counter-current gas flow back to cooler zones, where it condenses and sometimes undesirably accumulates in a deposit. More normally, the sodium condenses into the incoming solids and a cycle develops’ that reaches a steady state when the amount of sodium leaving the hot zone in the clinker is equal to that in the input stream, For this to occur, the total sodium in the hot zone (condensed phases plus gas) must be greater than in the input and output streams. Calculations based on the above assumptions indicate tha, in a temperature cycle to 1450°C, the steady-state 25Barry and Glasser concentration of sodium, expressed as NazO, is likely to increase to 1-6t, ie. by about 10-fold. In practice, the total sodium would not be constant over the temperature range of the recycle loop, and we have arbitrarily selected 2 as the basis for the calculations. Fig. 10 shows the composition of the major species in the gas phase, and Fig. 11 the composition of species (on a molar scale in the liquid phase. It will be seen that q x we fo o & ; vce & wc a Z 7 ™ a a ee as ts re Fig. 10, Mlustrasive calculation of gaseous species in a cement kiln as a function of temperature. The gas is in equilibrium with 2 molten salt mixture; ef Fig. 11. The ‘overall composition in kg units is Na;O 2, CO; 94, H:0 10, Oz 2, Nz IIT, SO» 1, HCL 02 19) Fa,S0, 06 Na,co, 02 a NaOH a TCT 1205 7205 TAG 1300 re Fig. 11, Mlustrative calculation of the composition of a ‘molten salt mixture that would form in equilibrium with the gaseous atmosphere of Fig. 10. The overall composition in ‘kg units is Na;O 2, CO: 94, H:0 10, Oz 2, Nz 117, 80: 1, HCL 02. The amount of sodium in the kiln builds up until the amount present in the hottest zone is equal to the amount in the raw materials 26 the liquid is mainly sodium sulphate at all temperatures bt carbonate is substantial at the lower temperatures, while NaOH and NaCI make smaller contributions. In the gas phase, the major carrier of sodium is gaseous NaOH, with smaller proportions of NaCl, Na and NaySOs. The carrier for sulphur is SO> Clearly, the proportions of sulphur, water and chlor- ine in the fuel and meal will have a significant effect (on sodium recycling. Indeed, the proportions of sulphur and chlorine in the hot zone will also be modified by recycling, as discussed qualitatively by Glasser.” For the calculations to be quantitatively useful, the presence of K,O must be properly modelled, because the presence of both Na and K in the melt would reduce the activity and volatilization of both, Salt solid solutions also exist, Furthermore, the partition of the alkalis to the solid and liquid oxide phases and mixing of sulphate and halides in the oxide melt would reduce the amount of recycling and so must be taken into account. Under some conditions, the molten salt may not form, and this may well be the preferred outcome For quantitative purposes, the phase equilibrium calcu- lations need to be linked to a counter-current reactor model. Discussion Each calculation with MTDATA determines not only the phases, their speciation and compositions but also many other properties, including chemical potentials, component activities, enthalpy, entropy and heat capa- city. In principle, densities and phase volumes can be calculated but the data for pressure dependence are incomplete. A few examples of the types of problem that could be tackled with the aid of this information are briefly discussed. The rate of crystallization as a function of falling temperature is initially low and fairly constant, but at 1334°C over 10% of the melt crystallizes over a very narrow temperature range. In practice, the release of heat will cause the rate of temperature fall to decrease. ‘The enthalpy changes calculated by MTDATA can be presented in the form of a DSC (differential scanning calorimetry) plot, which could be compared directly ‘with experimental studies to investigate this behaviour and its possible consequences. The retention of lime in the clinker impairs the properties of the cement, The most significant tempera- ture for lime retention is the maximum reached by the clinker because, provided the composition has been properly chosen, once the lime has reacted it should not reform unless the rate of cooling is unusually slow ‘and C3S disproportionates. At 1450°C, for the composi- tion range C 69%, $ 22%, A+ F = 9%, the activity of CaO is nearly constant at 0:93 over the range of A/F ratios for which C3S and C,S coexist, but for lower A/F ratios it rises rapidly to 0:99, at which point Advances in Coment Research, 2000, 12, No. |impure lime becomes stable. Cement makers use various expressions known as ‘lime saturation factors? to choose compositions that avoid lime retention. By this means, if, for example, the A/F ratio were in- creased, other changes would be made to maintain the proportion of C3S while avoiding lime saturation. In view of this, it would be of obvious interest to determine the activity of CaO along composition lines of constant lime saturation factor. In practice, no matter how finely the raw materials are ground and mixed, composition variations will occur and a higher than ‘theoretical proportion of SiO2 is needed to avoid lime retention, Rates of reaction depend on the driving force for chemical change, implicit in the Gibbs energy and the activity gradients of the components, as well as factors related to the mobility of components. In the four- component system C-F—AS, the path of the reaction, between, for example, a particle of silica and the melt, is unlikely to follow a straight line with respect to composition. For this ease, the kinetics of equilibration have been studied experimentally and related to the shape and disposition of the field of stability of C3$ at liquidus temperatures.""*° These studies illustrate the feasibility in principle of modelling the overall process of dissolution. Processes of crystallization on cooling could also be modelled that would allow improvements over Scheil-type calculations. However, the prospects for advances in this area are more distant than other possibilities discussed above. This paper has shown that calculations based on thermodynamic data can make significant contributions to the chemistry and manufacture of cement. For max mum benefit, calculations should be set up to relate as closely as possible to practical problems. Moreover, the interpretation of results should take account of existing scientific knowledge and know-how. Further experi- mental research is needed both to check the calcula- tions and to provide data for additional components. The calculation methods depend on and increase the value of experimental research; they should not be seen as an alternative to it. Conclusions Thermodynamic calculations of phase equilibria have been demonstrated that can provide useful information about many aspects of the manufacture of Portland cement © The onset of melting and the effect of temperature on the fraction melted, the composition of the melt and the activities of components can be quantified, ‘* Conditions for partial reduction and the effect of ferrous iron on the phase composition can be pre- dicted ‘ Calculations on incomplete equilibrium during ery- Advances in Cement Research, 2000, 12, No. | Calculations of Portland cement clinkering reactions stallization on cooling have been demonstrated using the Scheil model. These predict proportions of C3S greater than those estimated by the Bogue calculation and indicate that the Bogue calculation does not provide a fundamental basis for estimation of the amount of CS. * Calculations are made of the composition of the gas and of the liquid salt phase that can develop as a result of sodium recycling. The effect of hot zone tempera- ture and the amounts of water, sulphur and chlorine in the feedstock can be determined ‘The calculations yield much detailed inter-consistent information, Many points of possible comparison with limited experimental observations are available, thus expanding the utility of these observations. Overgeneralization of conclusions based on a few results should be avoided. Calculations should be undertaken that relate to specific compositions and conditions. Practical experience should always be taken into account when setting up the calculations and interpreting the results. © Further critically assessed thermodynamic date are needed for fuller investigation of additional compo- nents and the recycling of alkalis. Acknowledgements ‘Thanks are due to Dr G. K, Moir for a discussion of current issues in the manufacture of Portland cement, ‘The oxide database was used with the agreement of NPL and MIRO. References 1 Daviss R. H,, DINSDALE A. T, GisbY J. A., HODSON S. M. and BALL R. G. J. Thermodynamic modeling using MT DATA: a description showing applications involving oxides, alloys and aqueous solutions. In Applications of Thermody- namie Databases in the Symhesis and Processing of Materials (eds P. Nash and B. Sundman). ASM, Rosemount, 1995, pp 371-384, 2. DinsoaLe A. T. SGTE dats for the pure elements. CALPHLAD, 1991, 15, 317-425 3. Barry TL, DINSDALE A. T. and Gisty J. A. 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