' , SUB-THEME I-1 Influence of the nature and preparation of raw materials on the reactivity of raw mix R. BUCCHI, Italcementi spa, ITALIA 1-1/3HORRERERER ERE? 1-1/4 1, INTRODUCTION. Itis said that a cement factory arises where a mar~ ket of such a product exists and where deposits of maw materials suitable for preduction are available. In the practice the first condition alvays (er almost always) keeps its strictnass whereas the second, one is often compromised by other needs till to be peduced to the banal requisite to merely give the four fundamental oxides in the proportions deman ~ ded. However experience shows that nazare and charac - teristics of rocks and, generally, of the materials tused for the raw mesl involve important consequen - fees on investments, operating costs and quality of the cement produced - I seems therefore reasonable that the cement indu- sury devotes grater attention to the study of raw ma terials and the methods used for their preparation. 2, REACTIVITY AND BURNABILITY. 1 Definitions. The raw mix is @ system consis ~ ing of several components in finely dispersed pha ~ ses. It transforms ito clinker through a series of Teictions between about 400° and 1450°C. Tis reac livity 1s defined by the overall rate of these reac ~ ons at the temperetures completing them in practi~ cally suitable times. So as is defined with refered Ce 10 a given tix, the reactivity prescinds from eve Fy quality atteibate of the obtained clinker. On the contrary it has a considerable influence on the enez fy consumption of the process and the capacity of the plant. The concept of reactivity differs from that of bur ability, as the derivative of ¢ function differs from the function itself (or from the value which the lat- ter wkes for given values of the variables). 2.2 Expression of CaO in the mix during burhing. Since the fundamentel constituents of climker are all caleium compounds, the transformed CaO gives a suitable measure of the advancement of the over- fll process. The amount [of CaO, in a givenform Of combination present at any moment and temperaty Fe, can be expressed in different terms (he formu Ins without mark represent concentrations of the cor responding chemical apecias in the raw meal, in homogeneous unities of mass 0: between about 400°C and 1000°C, as de - wee Saccaeboneuon pC ot SE Satin. b where CO} is the mass % of COp i the tan ( Actually, in practice, these planes result not strictly t = con: storming mix; between about 700°C and 1460°C, as free C20: Ca0;, im the L.o.t,-free mix, mass %5 Fcady fraction of CaO, with respect to 12 tal CaO, CFeqoy ~ C20r/ CAO), Scaog fraction of CaO; with respect 0 the "saturation CaO ealeulated accor ~ ding to Lea and Parker (see TAB. 1D, undim.5 Hcaoys Sraction Of CaO; with respect 10 the hydraulle factors Hcaoe = CaOy/ SiOp+A1203¢¥ e705)» Uadim, between about 400°C and 1450°C, as burning dearee @ (2): 12105 £09034 C804, sain [2] el here CO} ani $0} aré the mass % of COz hd S03 in the tamaforming mix, in unites Romopeteous with those of CaOp nd CaO,. Ghe term 0.7 504 mat be neglected when $036K,0 + NazO, in molar concentrations Only, 9 and Fogo, versus the processing time and temperature cofrecily express a measure of the burnability of the mix. Their derivatives ver sus time (or, om the average, the ratio of the finite variations of functions to the ime intervals when these variations occur) measure the reactivity, for given constant temperatures. The quantities 5 cay and Hego, considered by Longuet # Courtault 3) land Plrunder and Wickert (4) respectively, concern fn some way the burnability of the components of the mix rather than that of the mix itself 2.3 Course of the CaO wansformation. 2.9.1 a= 2,0) describes the CO transforma ton versus the temperature tand the reaction tl ~ me. itis represented, inthe space (+; +t; +0), by a curved surface whose intersections by planes ‘almost parallel to (@j@) for t= const. and 10 (as0) for 0; = const.(peendotsotherms and pseudo-isochro nes of reaction respectively (*) are experimentally deterained 2.3.2 The teend deductble from the Uterature data G, 6) of a psewdo-tsochrone 1s schematically repre sented in FIG. 1. The reaction velocity increases in two temperature ranges: Detween ti and 12 (about 850°C and 950°C) when Ky of the CaCO3 dissociation sharply increases (7). The first free CaO appears «or Q~ const., but more or less ineli - fed with respect (aj 0 Jor (ar; 0 because of the vaniabiisy (with 1) of the tine and the temperatures rea ched to bring a sample to the test temperature tj. SLULLLLLLL LLL LLL LLU LL Lbbkltn this interval-whereas CaCO has already disappeared at t2 ©) + Detween ty and ty (about 1250%C and 1300%C) whore theCgS iSrmation ours The values 1, 12, ponding ordinates are typical of the reactive pre - parties of the mix. 3 and ty and those of the corre- 2.3.3. The portion of pseudo-isochrone 9 (1) for i mconst, between about 400°C and tz is called vonation function (9). FIG. 2 shows some derived trom Vogel's (2) and Ritzman's (9) papers. he decar bonation and the first reactions in the solid phase, are greatly important in the study of the calcining esses outside the kiln (10). mn of paeudo-isechrone between ) expressed by CaQp=! (1,8) for a0; Meopacons, masse — [3] suai ns 0 ferent ont ire ples of © Therefore this quantity expre: reluctance to burning (13). I-1/5 show the funetions of four typical mixes of which the literature (11, 12) and other sources (13, the necessary number of couples of values ( summarizes the values of a, b and t3+ +5 The portion of 1 1450" seudo-isotherm between t2 expressed by CaOp=f (8, 0 for const 4.8 logartomie anenon G6, 19" CaOpek eh nO (ye const, ma [-] (with constant k and h), at least in the 0'€ @ € 30" range for tj » 1380°C (@). PIG. ples (12, 13). 2h Me ity. [eis expres of the following quantities @etermined under tly reproducible conditions): 1 of CaOy of a pseudo-isachrone at gi- + Examples: 30! and 1300°C or 1400) and 1450°C (16); 42" and 1450" (13): 15' and 1450°C (3); 15! and 1370°C 5! and 1400°C (17); a.s.0. Increasing va ~ of CaOp correspond to decreasing react 08 Got + measure of 8; of a pseudo-isotherm, necessa- ry #0 a8 CaO; becomes equal to o lower than faxed value, Example: 8, for CaOr ¢ 2% at 1350°C (18). Increasing values of @y corre - spond to decressing reactivities (ws1-1/6 factor Kyu.’ Sultkowski (11) characterizes the burnability as the ratio of CaQr to the maxi - rum of CaOy=f (0 in the 700°C 4 r <1400°C range, 0 being of few seconds: cay vin, [5] The mansore ybsed on ete dat he ma reddy of Gn, Rico tras he SOR A Kou * CaO pmax factor AC, Blaise et Al. (12) rightly think that the evaluation of the burnability demands wef} pp FIG. © FUNCTIONS CaO} 2 «®t vve function for fixed 0 in the aforesaid tempe- ature range: Bena ose Be cea lero-a) °9 a quantitative expression related to the Ci or 1,0) trend in the overall 1000* et 1450 Sport oF5igf 2410} range. This requirement is satisfied by the ae Foal ratio of a constant (+600) reference surface 134) Sn 22459} (CaOt; 0 area to the one egal) of the abo- ony) Tatas] sel - fo tay | 00041 0.174, 9 | Hoag Paap aoe actos AC in paragraph 2s GH Suitably enlarged for the highest temperamres. Gs) The times necessary to pass from each level of temperature to the next higher one are added to these ti- mes. Consequently 2 CaOy~f (¢,0) quite different from both the isochrones and the isotherms is obviously wel. HEHRERE ERT LULL LL Lb bab FEREEREEREEEROEET CULLbility of the measure ts ensured by strictly controlled working modes. The inadequancy of the first three methods, expres- sing the measure of the burnability by means of the co-ordinates of an only point of CaOp= f(t, @) is ob vious. On the contrary, the factor AC seems to be ‘eresting in this connection. It has the ad ~ ‘vantage of considering the overall course of the CaO combination in the presence of liguid, the trend of the reactions in the solid phase as well as (by the ‘value Co) the extreme portion of the decarbonarion Fimetion- It is also clear that the examined measures of buraa, bility give results whose significance, methed by ms, thod, does not exceed that of the relative compart - son, since the technological process develops under quite different conditions from the laboratory ones nd different from one another depending on the ty ~ pe of plant. 2.5 Evaluations of the burnability by calculation. ‘At least three methods allow the burnability of the tical” means ‘experimental 1-1/7 mix to be calculated (in the absence of mineralizers fand other specific additions), by its chemical, min relogical and physical parameters. These proc tres are important since they explain, to some ex ~ tent, the influence of the different chemical and phy, } parameters on the burning process. 2.5.1 Ludwig and uckensteiner (18, 19, 20) sho ~ ‘wed that the practical burnsbility (+) Bpy of ¢ mix, time of Feaction at 1350% needed to ov Sports vam [] coincides (correlation coefficient r=0.985 for 12 mixes) with the value of the theoretical burnability, Bihy 0 called since 1t can be calculated from: Byh=55-5411 9H got 58 (I lI-90)?-0.43 (SA)? min. [8] This equation 1s obviously valid for Kg, Ill 290, It n extended to the temperatures of 13 3. icances of the symbols are: *30" bas ‘and 1400°C in a fotlowing paper C terogencity > 904m", measured as the amount of raw meal retained on 90 ym sie ve lessened of the quantity of multimineral aggregations of elewents < 90 ym present in this oversize, mase % of the mixs SA, amount of liguid phase at 1950°C after Dahl (22), mass of the Lowi -free mixs Kgilll, Katkstandard after Spohn et Al. (23) undim. ‘The hypothesis on which the determination of Hoo is based - namely that the ratio of CaO to hydraulic factors in the multimineval aggregations > 90 um 13 ‘equal to the one in the mix - may not oceur imall cases. 2.5.2 Kock et Al. (17) determined the correlation between burnsbility (CaO; for t~1400°C and 0, = 15)) of 168 sndustrial mixes (raw materials of 15 dif fervent deposite) and 20 parmaers resulted signifi - cant out of 15 examined. From a 3™ order-regres sion it results (correlation coefficient r=0.949): 15! _0,022y-1.N(0,022y-1)%s 0.01882 400° ~ 0.008 5 mse [9] cao} without any veference to the technological process.VUUEELLLLLL LL 1-1/8 caveat -5 Yeel." "JG0L CaO pop, S210, ODA CAO pgp SLATS Cage, «value of reference Gap, obtained by Solsig aay miret ue fuse nay weenie gbOtc nod 1 pee defied Umit Xi = differences between the value of each. paramiers and the value of the same for the reference mix} 2; = Constant) coefficients of x, defining the regression. ‘Oc |n65e1.65A00.35F | = eombienble CeO BSL 65AO.O5F |e: Garomaan ena Ctle| OO max. combinable CoO Ther Spot sax. combinable CoO sp |2.8501.1400.70F &s) up |2.8501.18600.65F & Bo [REDO GA “poreanal componttion™ (GaP ant GAAP | shee Bopoe J Rese [aa A [otrugaa ryt [PR oe can “aheres often | SM [Sa | wilca wodata wy a ne on modulus a om ons. caleare sodalue oo soy] 30.85% _[uignese madatne | 62) NOTES. 3,A,F,C Bund Ware mass Hof S102, AYD3, Fey SOs aos Eo ES Ste erect Jos mass of CaO im the Lovtenfree new meal (win cline The limits of the variables within which the corre- lation Is valid are siated [9] 2.5.3 Christensen (2) reports an empiric relation nating C2070" 05... t0 be calculated versus the che nating CaO30' ggg to be calculated he che, mical composition, as well as the content in parti - cles of caleite >125 ym and quartz and flint > dda This relation is consistent with Ludwig and Ruckensteiner's. 3, CHEMICAL COMPOSITION. 3:1 Composition in raw materials, ‘The mass guan- tities of n rew materials, having independent che- rmical composition (+), necessary for the mass unit of raw meal are solutions of linear systems of 1 si multaneous equations expressing the n-1 conditions of chemical composition nesigned to the mix. The methods of algebraic solution, among which (25, 26, 27,28, 29) and the graphic procedures, out of which Fenaroli's (20, 31, 32) end Glauser's (38) ones are reminded, are based on this principle. A methed of optimized solution (for the minimum consumption of uel for burning) was developed by Xirokostas and Zoppas (34). 3.2 Composition in oxides. The chemical compost: Uowef the mt is defined by assigned values of one or more characteristic parameters (TAB. 11) suita. bly chosen on the basis of the composition of the av lable raw materials. 3.2.1 In the system C-A-5~F, the compositions of the plane C38-C3A = CgAF (the latter expressed numerically as C3A%CF), contain GG mass % of CaO. GG is fully combinabie only under conditions of equilibrium cooling ensuring a complete reaction between free CaO and liquid during the cooling it - self, Therefore GG isa limit practically unat - tainable in any case. ‘An identical situation occurs for all the BO composi ons without C25. According to Spohn (36) SP is the maxinum amount (Guage 9) of CaO combinable in the clinker cooled not sn equilibrium. The straight line 2.85+1.1-C-0 joins C38 with (CoA) in the plane C-A~S and it te called Wetzel line 3) ++). In the apace C= A= 3 F, the plane 2.85+1.1A+0.7F-C=0 contains C38, (CoA) and CgAF Uhie tine expressed numeri - cally as GoA¥C9#). Kil G4, 45) defined Kalketan- dard, qd, as the CaO: SP ratio Gf a elitker oF @ rav moa). "LP 1a the maximum quantity of CaO com Dinable in the clinker cooled not in equilibria, ae- cording to Lea and Parker (37). In the apace C-A~ () The independence of chemical composition of any raw material (with respect to the compositions of any muy ber of othess)is verified by the non-identity condition between suitable ratios of of oxides expressing the cha ‘mical analysis and the homologous ratios of all the other raw mterials, including those olxainable by addition or subtraction from one another. (@*) This line is near (but does not coincide with) the line joining CgS to point Z (Z = invariant at 1470°C famong liquid, CaO, Cg$ and CyA, having composition 54.8% CaO, 22,7%A1203, 6% S102, 16.5 %Fe303)- SELL LULLLL Loo OULU LLS-F, the plane 2,854 1-184 +0.65F -C-0 tains CgS, invariant Z at 1470°C and CgAF (CaO combined with F is 4Ca0- 1,18Al,03). “The compos Mons containing CaO « LP are deprived of equili brium free CaO. The CaO: LP ratio is called lime gaturation factor (LSE) or also modified Kalksian gard (Kyu. Spohn et Al, (23) showed that MgO combines in clin ker up to the limit of about 2 mass % (of clinker) by releasing 0.75 mass % CaO for each I mass © MgO, tule. Inmost cases the mount exceeding 2% oes not affect the CaO combinations. For s reason these Authors proposed KqAIll as (Ca0-0, MgO): LP ratio, or (CaO-1.5): LB when MgO € 2% or MgO ® 22 reapectivel Christensen) stained avery sma expression SPUSK eoercted by the presence of Sg9 ot ence vusain. [2] Ca0-0.77 MgO “ZUS+ 1.18A+0.00F 3.2.2 The sulphate modulus, recently introduced by Osbaeck G2), determines the fraction of solub alkalis with reapect to the tote! alltalis ia clinker fcconding to the sesults of Pollit and Brown's re - search G7). 3.2.3 The reason why the potential compound com- ‘position according to Begua (38) does net cor: ‘spond to the mineralogical composition of clinker de termined by microscope and/or X-ray diffraction is well-known. Above all the calculated amounts of 98 and C75 deviate, being the former higher than that of alite and the latter lower than that of Delite (23, 48, 49, 50). Nevertheless Bogue's model is a simple and clear reference of unnegligible pratt ~ cal utility. Therefore Hansen (51) proposed its re~ vision by calculating the aluminate ac C3A9,9F9.1 and the alumino-ferrite a8 CoAg,64F 9,42 53, Ea 240.54F0.46' Ls: The interpretation of SM, TM and CM in terms of the potential compound composition was given by Buecht and Buzzetti (5). 3.3. Chemical composition and reactivity. The ef - Teets due to the minor compounds are discussed in Chaps. 6 and 7. 3.3.1 As the lime saturation of the mix i the number of CaCO3 particles sterically (4) Dabi's (22) equations are bas: of 1.23 (or 1.63 under MgO saturation conditions). (8) Mussanug (15) showed that the function CaOp with KS, for constant 4 and 8, Test anction is multiplied by tie valué 29 1-1/9 nated” by each particle of acidic oxides increases and therefore the mass fraction of CaO (of the total fone present), diffusing into these oxides in the time tunit for each tamperaiire below about 130°C, de ~ creases. All the values of the functions = #(t, 0) and a= f(t, 0), expressing burnability and reacuvi nirary, as the liquid phase appears (abo - "C), the Kinetic# of the dissolution proces Ses in the liquid is affected only to a slight extent = any other condition unchanged by the mass of the: Sent solid CaO. The graphs of the functions a= (8) and CaOp= F(t, @ of mixes differing galy in the lime saturation, between about 1300* and 140°C, fare roughly parallel and distant from one snether of an ontinate value equal (case of CaO) o proportional (case of ) to the difference of free CaO present at temperature and time (jj, B,) when the Ligaid appears. This trend seems to be confir~ med by the data derived and calculated from Heil ~ man's (58), Toropov and Luzinina's (57), Pfrun ~ der and Wickert's (4), Blaise et 4l,'s (12) papers Also Mussgnug (15), Ludwig and Ruckensteiner (9), Kock et Al-'s (17) equations - even if with different dependence - express the increase in CaOy (for gi ven tiy @er in 0; for CaOy 22%, when the lime Therefore above 1300°C, the increase in this pa = rameter determines a decfease in burnabi lity whe reas it does not practically affect the reactivity: 3.3.2 The processes occurring in the presence of quid phase are clearly affected by the amount com position and properties of the lntser. The liquia pearing at 1338°C in the system C-A:- SF (301°C, under MgO saturation conditions) has A: F= 1.23 (1,63 under MgO saturation conditions) (58). The- refore AlzO3 and Fey03 act as agents of first mel- Sing for raw meals having TM <1-23 (61.63) oF TM>1.23 (>1.63) respectively. At the same 5M, liquid 15 maximum at TM =1.23 1.83; atthe same TM, the amount of liquid increases (22) as SM decreases viscosity of the liquid phase decreases as A: F re- duces (60) vith consequent inereace in the rate of the dissolution processes. the amouns of At constant temperature, the These circumstences, and other exemined in Chap. 6, explain why the increasing silica modulus-mixes show worse and worse reactivities et Kg, TM and. a= ny aber conttion uncharged @, 1560 (*"). On the contra~ on a composition of the Hquid, at 1938°C, having A : F=1.38(69) instead “This difference does not change the kind of reasening (KSSH S24, Capa f(SM) coincides with CaOr=f(KS), when the angular feselsairemodul) linearly inerea: coefficient of theCOLLEGE 1-1/10 zy the deductions on the influence of the TM varia - tions badly agree with the results of Mussgnug's 45) and Lehemann et Al.'s (@) works. Neverthe - Tess it ig observed in this connection that raw meals having IM between 1.3 and 1.6 are almost univer ~ sally judged as the easiest to burn, at any other con, dition unchanged. 4. PARTICLE SIZE. 4.1 Demolition of the structure of she clayey mine Fale; _CaCO3 decarbonation. 4uls1 Both processes proceed according to first onler-reactions and they are governed by the rates fof this type of reactions. The research of many Au thors (62, 63, 64, 65, 66, 67) shows that the time for the dissociation of & CaCO3 particle 1s a linear fun tion of the particle diameter, in the range of the lusuall sizes that they have in the raw meal. 4.1.2 The time O'xg demanded for the isothermal demolition of the muss unit of clayey minersl, di ~ (buted in quasi- spherical pardcles having nar- row grading interval, 1s approximatively proportis, nal to the reciprocal of the specific surface 3'y4 of these particles: es Oyen se fe] where k! is constant (s-cm2-g-1) at constant tempe- Tone and activation eneray 4.1.3 Similarly, the time demanded for the decar- ‘Donation of the wass unit of uasi-epherical CaCO3 particles having narrow grading interval is expres- ea by « [13] type function (except for the diffe ~ Pent nungrigel value of kD in that stage of the pro- Geos when ine dissociation sate ts higher than the diffusion rate of CaO in the acidic oxides. TAS 0 cars starting from the first appesrance-tenperats fe of free CaO ag far at the temperature of comple te disappearance of CaCO3 (212). Below the for = mer temperature, the early decarbonation supplies GeO to the reactions with SiOp, AlgO3 and Fey sence of free CaO); in this stage of the process the dissociation times are controlled by the aif ~ Sion rate of CaO in the acidic solid phases. 4.2 Reactions between solid phases. 4.2.1 In the simple processes of binary diffusion between the fundamental oxides, the direction of transfer of matter follows De Keyser's rule (68): 20 0.70) S102 (2.39) C20 0.70)» A1D3 (1-66) A1Q3 1.66)» Si02 (2.39) (9) Only formally the dimensions of k are the same as D. TULLE ULL he affinity values of oxygen after Katelaar are wi- thin brackets) according to which the oxide having, less affinity for the oxygen diffuses on and inside the oxide having a greater affinity (acceptor oxide). The diffusion proceeds by three ways (65): (@) transfer of matter gn the external surface of the particle of acceptor oxide (surface iffusion); () twansfer of matter along the surfaces joining the grains of the particles of the acceptor oxide (@iffusion at the joints); (©) tronsfer of matter inside the grains of the acceptor oxide (lattice or volume diffusion). ‘The weaker bonds of the atoms and/or ions at the surface and the greater disorder existing at the joints of the grains determing, in these sites, a hl- cher level of free energy than that present inside the lattice. Consequently the activation energies of the process at the surface Qs, at the joints Q; and inside the lattice Q,, increase according to the fol- lowing order under tsothermal conditions (70): Q5=Q td where Q (cal*moles-1) represents the activation energy of the type of diffusional procass considered, T (°K) ie the temperature at which this process oc~ care, and D, (en?-e"1) ea Gquasi-) constant, cal~ {THE THICKNESS OF THE MATTER TRANSFORMED led pre-exponential factor or frequency factor (of the atomic oscillations) formally equal to D when Tae, 4.2.3. From [14] the roactvigy in the solid phase ‘isly contelied ty the size ofthe grains of CxO SCeeplores that is te ecldie oxides, 31Op, ANOS ont ez03- The tine Oy denaned forthe isothermal reaction afte nassMint of acceptor oxide Cserted ta Ghset-spherical grane having narvow grading intez GP Bamyantse’ 1-W/u val) is approxitmtively proportional to the recipro- cg) of the square of the specific where k" (s-em4- 9" is constant at constant tempe- ature and activation eneray Qr. wo remarks on the quantity 5", are necessary: 5'hq measures the surface of the mass untt of portions of single-phase mavter (acceptor oxi- des) delimized by ceystal joints where the dif. aston coef than Dp. Brie~ ‘represents the specific = Its value can be represented by 3 tained from the usual measure of specific sur= Jace of powdered matter only when te parti - cles consist of a single grain of a single ming ralogical species. Ladwig and Ruckenstei = ner's (18) concept of heterogeneity > 90 ym, Hygo, already seen in 2.5.1, takes into ac - count this eriterion. S'ly refers to the fineness thet the acceptor oxides have when the reactions develop, stant by instant during the process (and ot ne cessarily to the Aneness thet they have in the ‘raw meal before the thermal process). From what considered in 4.2.1, the surface of the fres particles, consisting of single ~ oF multi-phase grains, (that is the one referable to the usual meas Fes of specific surface) affects the kinetes of the overall diffusion process in that it is an extent of the by-pase of the lattice process. 4.3 Reactions of clinkerization. 4.3.1. Clinkerization is controlled by the diffusion process in the liquid phase (71, 72). 4.3.2 Rumyantsev (73) and Kondo ana Chot (74) sho, wed that the isothermal dissolution of Cp5 and CaO Inthe iguid phase at the temperasure of cliskeriza tion ig described by equations of the same type as 5). Be), 07) E8jent [8] governing te laren duthusfon G). 5 equation (78) does not differ from Kondo's and Choi's (74) and both of them do not differ from {i6] when, in the former, the due size (oven ia ansgiel so t and tn the later is expressed as the diomn- favcovered iy the dilfsoton with regard fo the radi ofthe grsin or petieles1-1/12 Nevertheless, in the isothermal dissolution, 5'hy represents the surface of the mass unit of the C75 fant CaO grains wetted by the Kiguid phase, wheress dc :dy is the gradient of concentration in the con ~ tact solution. 4.3.3 Therefore the process rate is controlled by: + fhe grain size of the phases produced in the previous reactions between solid phases; + the size of the CaO grains resulting from de~ carbonation; (@ifferently from what occurs for the latter process, the time for the disso~ lution of CaO {s proportional to the fourth po- wer of the grain diameter); he wetting power (surface tension) of the li- quid phase. 4.4 Technological considerations, ‘The described iodal is an approach that, as such, has only a be~ inning-value. Nevertheless it ellows some deduc- tons useful for the practice to be drawn. fohel. Tha diameter of the grains of the acidte ox- ides - at the fourth power in [19] - would have a decisive effect, acconding 1 this model, on the Ki- netics of the reactions both in the solid phase and Inthe presence of liquid. Thus the considers ~ ble importance, for the reactivity of @ mix, of the size of quarts here contained is explained. On the Contrary in the reactions in the solid phase, the Giameter of the pure CaCO particles would have a reduced influence, merely proportioned to the °9ua ze of ste size (see equation [1]. During the dis Solution process inthe liquid, the dlameter of the CaO grains from the decazbonation of CaCO3 would have the same importance ¢8 that of the acidle oxi- des. ‘These deductions are directly or indiré med by several data of the literature G6, 76, 77, 78, 79, 80, 81), but not by others (82, 8). 4s. The particles consisting of coarser single- Phase grains in the industrial raw mesls, are the ast to complete the reactions. It becomes obvious that the reactivity 1s inereased by the reduced gra~ ding imterval, at the same specific surface. In this connection, therefore, methods and equipment to ~ day used for grinding the raw meal in the technolo- bbleal practice do not seem the most suitable to pro- duce the moat reactive grading at the lovest energy consumption. Clearly this inadequacy must be at- tributed to the poor separation precision of the equipment "cutting" the feed produced in the closed Circuit mills. It 4s also due to the indifferentiated application of the mechanteal grinding energy to ma, terials having different grindsbility which, because of this, are differently distributed into the differax igmiding intervals (63). This problem can be solvad by separately grinding the component the most difficult to grind (for ex quartz) (76, 84), according to a method already used in some modern cement factories (85, 26. 5. MINERALOGICAL SPECIES AND THEIR. REACTIVITY. Sul Activity state of solids. 5.1 The ense or hardness of an industrial raw Imeal to burn must be referred to the petrographic characteristics of the rocks composing it, the pre - gent mineralogical species and their state of activi- ty just before being attributed to the different tech nological parameters, such as chemical compositor, fineness of grinding, homogeneity 2-8-0. The two expressions of the previous chapter: pede vents? fi] Qs KO > 505 > Na >P2Dg > SO > FI Cl 20 > TOy > MnOs> > Cr035 the frequency distribution is of normal-logerithm type (except for that of T!O2, approsching the nor mal one): (® Also culled: minor components, minor constitie! production of cements having better quality Modifiers of the properties of the liquid phase. ‘are the minor compounds called fluxes and 2 The mineralizers acting in the liquid and/or liquid-so ~ Fluxes are substances which lower the rst appearance-temperature of the liquid phase (131). Mineralizers are substances which, throuh any mechaniem, accelerate the rate of the process or reaction between solid phates, or in the liquid phase oF at the liquid solid interface (131). ‘Attributing (64) both properties to fluxes ~ that is the lowering of the first-melting point and the re ~ Guetion in the viscosity of the liquid-must be avoi- ded because not always the same substance produ- ces the two effects simultaneously. Ir does not id phase. ints, minor elements, impurities, traces.LULL 1-1/16 even seam suitable to assign (132) the role of mine- ralizers only to fluxes, since many of these act just {in the solid phase. TAB. 1V. COMPOSITION OF THE-LiQUDS OF wien BUET AND. TIMASHEV-C3? > STUDIED THE VARIATIONS OF oat 7. Tapa ua? a a sez | so oo 6.2.1 The important role that fluxes play on the tansformation of the raw mix must be referred: + first of all, to the necessity of the presence of a liquid phase for the rapid CS formation (peritectic reaction); ow MN thas already been mentioned (paragraph 3.3.2) that this. temperacare is 138°C tn the most basic part of the system C-S-A-F (59); 1501°C in the sa, mo in the presence of 5% MgO (58); 1280°C in the sy. stem C-S-A-F-M- N (133), All the minor com ~ pounds dissolving tn the liquid phase decrease its Hiret appearance-temperatre, Nevertheless, sin- ce Cg8 does not form below 1250%C, this tomperata re mist be considered the lowest (also theoretical) limit for clinkerization. 6.2.2 The substances able to modily the kinetics of the C78 and CaO dissolution and the rate of ionic diffusion in the same, affect the rate of the peritec- tie reaction (134, 195, 13€, 73). Butt and Timashev + | i “ta ecana |e ee FIG, .POLYENERMS OF OF THE QUID PHASES ‘AND? OF TAB.IV..APTER BUTT.ANDTIAASHEV 37 + afterwards, to the need to avoid the “ageing” of the CaO and C28 crystals before dissoluing {in the liquid; + finally, to the energy saving of the process, ‘which results to be the higher the lower the first appearance-temperature of the liquid. PULL LLLLLE LLL LLG Fig. 9 .ISOTHERMS (1450%C) OF OF THE LOUD PHASE ?OF AB. FOR INCREASING ‘CONTENTS INDIFFERENT MINOR COMPOUNDS. AFTER QUTT AND TIMASHEY (397 ) (137) have exhaustively reported on the mechanism of formation of clinker. ‘The mineralizers act, at the solid-liquid interface, by increasing the wettng power of the liquid phase ~ that is by reducing its Surface tension ~ and they increase the fraction of exposed surfice of the solid phase which discolve. On the contrary, the mineralizers in the liguid pha- se accelerate the fonte diffusion by reducing the vi- seosity. ‘The surface tension 0 of the Liquid phitse of clinker {s of the order of hundreds of dynes-em"1, betwe - fen 1300°C and 1450°C (138); the viscosity 7 is of the order of potses (60). According to Butt and Ti- nashev (137): » ronio ora-2 maim. [x] te valid between 1400" © ot 104C fr the quar DULL LLL LL CULLzy liquids having the composition given in TAB.IV, The values of the constant a and b are also shown in the same TAB. IV, oa S25 oe {AND 2 0 TAB IV. AFTER BUTT AND TMASHEV7 The variation of @ versus the temperature is shown in FIG. 6, whereas FIG, 9 gives the isotherms pop | “TEE TT OT TT Fig.t1 ISOTHERM (1450 ) OFA OF THE AFTER BUTT. AND. TURASHEY (137) of liquid 2 at 1450°C for increasing concentrations 1-1/17 in different minor compounds. The viscosity is caused by the mobility of the ions S107" In the presence of minor compounds the values of 7) depend on the equilibrium displacement between the co-ordinative stractures of the amphoteric dements mofsene ech [al FIGS. 10 and 11 show the variations of 9] versus the temperature and the concentration of different minor compounds. It must be pointed out that ineren, sing KO and NazO reduce Obut increase 7), at the safectivensss| x Be 5 5 Ma? 2 20 se © 1.65 ous | ost os | 013 | 0.88 3.0 5 NOTES, Values of Caer Pealing (AD for sons {a octahedral co-ordination with O24 O,7 4 Ose seis sum of teypsion radius and O2- Ja? = cetionte RV after Whittaker and Munmas 1423 5.2.3 ‘The ability ofan ion to modify the characte Siocies ofthe liquid is a property of the electron Configuration of the jon itsel. The effectiveness By which the viscosity is reduced, atthe same tem- jeruiuve, increases as the electronegetivityX, oF fhe eld force Z/ad, or the ionic porential Z/e of the ton increte (137, 199, 140,00 drown by the ves of TAB.V. fons Hee K* ard Nal hang large radius and Tov change do not reduce but increase (37). Ale tothe mineratising effctivences, meamtred by the Aegnee of combination of CaO terough the quid pha Ser incteases asd, Z/eZ and Z/a tneresce (143,1-1/18 144, 145, 146, 147, 148) (FIG. 12); in fact ons he - ‘ving small radius and high charge (Cr, V, Ti, Mn, a.s:0.) are the most effective mineralizers. ‘This behaviour towards the liquid phase of clinker must be considered as a particular case of a more general rule, valid for all the «ilicatic magmas 049. 6.3 Equltbrium modifiers between phase and struc- lure modifiers of the clinker minerals. 6.3.1 The minor compounds distribute differently: Anjo the clinker phases at high temperature and they determine displacements of the equilibria among the Phases. New solid solutions and new compounds of- ten form. In any case the evaluation of the effects Levees iy eget Tia» ca te pers (137, 138, 153, 154, 155, 198, 49, 157, 158) pu- Dlished on thisaibpct allow two types of model of ac vation to be designed: + the presence of an isomorphogeneous substi = tute ina lattice causes disorder and often in- creases the concentration of defective struc ~ tures of any kind (punctual, Linear and super- ficial). This rise ean increase the free ener ay of the structure by reducing its stability fond by activating its hydraulicity (#9. There are, however, some exceptions: for instance the impurities do not increase the concentra - tion of the imperfections inside the lattice of C28 (160). Foreign ions, depending on their tonie potential, can make the structure of B= ~C25 more stable (and decrease its hydraulic activity) AGL; + when ions having high value of Z/a vary the surface tension, the ionic mobility and the concentration gradients in the ligiid, they mo, ify the conditions of formation and growth of the crystals at the same time. In thie way the microstructure of clinker varies with possible increase in the relative hydraulic activity asa. 6.4 Mineralizers between solid phases and through formation of atypical liquid phase Gx), These are F1G.12 . MINERALIZING EFFECTWENESS OF BFERENT ‘BURNT AT 1350 UNDER LOAD OF g1OOWITH ADDITION (OF 0,01g~9% EQUIV. OF F>. AFTER TEOREANU AnD TRAN VAW HUYNH (948) of one or more minor compounds presume the know- edge of the resulting phase relations, out of which ‘the most important are reported in Chap. 7. 6.3.2 These minor compounds that, in adequate con centration, increase the hydraulic properties of an ker and/or its minerals, are called activators (of hydraulicity) (150, 15, 152). The fundamental pa - (+) The stability of a structure corresponds to a minimum of the free energy F at temperavures > 0°K ( for {sothermal and isochorel systems). Disorder and imperfections increase bot the minor compounds which increase, at the same temperature, the dissociation tension of CaCO, the rate of the diffusion processes in the solid phase and/or give intermediate compounds favouring oF ac celerating the C35 formation. ‘The mineralizers of this type (NaCl, CaCl2, BOs, NagBQ07, NaNO3, phosphates, fluorides, sulpha — tes, &.840-), which gave interesting Inboratory re. sults, are mmerous. Nevertheless most of them have the disadvantage of yielding technological con- ditions unfavourable for other aspects, or they in ~ wove costs not repaid by the advantages obtained . For this reason, today, the cement industry utili - zes only fluorite and gypsum (or anhydrite), in par- teular cases and for specific purposes. 6:5, Minor volatile compounds. 6.5.1 The minor chemical species, vhose vapor tension is unnegligible at the burning temperatures and, at the same time, not high enough at the tempe ranire of the exhaust gases, volatilize in the hotter Zones of the kiln and condense in the cooler ones (on the raw mix, on the walls, on the recuperators, TS, the internal energy U and the entropy S. The stability decreases when AU >TAS (159). Gm) Liquid phase different from the typical liquid phase of clinkerization as for composition and properties (i. e+ liquid phases of chlorides, sulphates, nitrates, a,s.0.).a.s.0.). Thus, a cycle of these compounds is asta lished (163, 164, 165, 165, 167, 168, 169, 170, 171 172, 173, 174).1t increases the Concentration in th processed material up to the (maximum) level X; ne- eded to balance the entering and the coming out With respect to the concentrations Ay and Ay of the chemical species 1, in the fresh raw meal and in the fuel respectively, X, expresses the intensity of the cycle of that chemical species by the recycling fac- or Ky G67): with Kj, Aj ond Ag, in homogeneous units of mass K; depends on the type of process (171) and other different paremeters, among whick the coefficients of primary volatility €); and cycle wolaulity €, of the considered spacies (167); €14 = mass fraction, with respect to the toxal fone, of the species i volatilized from the fresh raw meal_ having concentration Ay Genaim.) 2, = mass fraction, with respect to the total fone, of the species 1 volatilized from the burning al having concentration X Gndim The two coetficie 1s are referred to given tempers Ritzman (172) published the quantisative relations from whlch X; and the concentration of { in clinker, at steady conition, are caleulated versus Aj, Ags 17 €21 and other variables of the process. From Locher et Al.'s (170) equations, i 15 possible to culate Xj versus the time of recycle, as well as the time necessary to attain the equilibrism concentra ~ tion X; in the burning material. 6.5.2 Cll, Bri-, JI, atkalts, sulphates, Muor des and zine compounds produce cycles. Kj of the two latter species are vary low. There is little in- Formation on the cycles of Bri- and J!” even if the- re is evidence of the aggressiveness of these halo~ gens on the electrofilters and their ducts. Kj (and therefore X,) of chlorides, sulphates and alkalis are high and Unble for the direct or indirect formation of most coatings and rings which jeopardize the re- gularity and the operation continuity of Kilns+ Im the technological practice, three methods allow the coming out emounts of volatile compounds to be increased in order to reduce X, shut off of the cycle generally by total elimi - ration of the dust of electrofilter (and somett- mes of grate in the lepol kilns) when the vol tle compound concentrates in the dust (170, 175). The latter condition, and the necessity to reutilize the recovered dust, limit the prac 1-1/19 ticability of the method only to the kil ducing very reduced anounts of dust (0.04 + #.0,08 kg/kgeli.), that is to the lepol aiet odule-fed Kins. (In order to reduce the pro- duction of dust the characteristics of the nod, les can be improved by eveiding the presence, in the raw meal, of compounds hydrolyzablein Cat*, by adding Na003, a.s.0. shut off of the cycle by (partial or toxal) bypass of the exit gases in the suspension preheater kilns (165, 165), especially when they are equipped with precateiner(176, 177,178, 10); reduction in the volatili the chemical species which recycles by addition of suitable compounds to the raw meal (see paragraphs 7-314 and 7.6.3) and by adopting the meas - es which ensble the burning at lower tempe - natures. Obviously, in thts way, clinker be- smpound, This me- the semi-dry process sin- ce the nodules release fever compounds than the raw meal, at any other condition unchan - ged G64, 171). 7. BEHAVIOUR OF SOME MINOR COMPOUNDS: Zl Sulphate 7.1.1, Sulphates (gypsum, anhydrite, celestine, ba risine), and exceptionally elementary sulphur, are often present in the evaporitic limestones. On the contrary the ancient limestones can be mineralized by sulphides (prevailingly blende and galena). Clayey sediments, marls, detrital rocks contain both sulphides (pyrites and marcassite) and sulpha- tes. Gypsum and enhydrite are sometimes added to the raw six aa mineralizers and modifiers of the re cycle of alkalis (170). Sulphides and sulphur of the raw meal and the fuel ave oxidized to sulphates and combined, as such, in the solid phases during bur - ring (179, 169). 7.1.2 Fundamental ken taining systems: wledge of the sulphate-con S03 preferably combines as (Ky Na)g5Oy- At ordinary temperature; the solid solution con- tains the two sulphates in the same ratio o: the present oxides if (in moles) S03 9 KO + NazO} on the contrany it corresponds to abou 3K2S0,4"NazS0, in the opposite case (180); 2C450,*Ky80, ts stable up to 101°C in the system CaS0,"K290,. The compound can form during the cooling of high potassium and sulphate clinkers (18135 + SCA+Ca50, (182, 183) is stable up to about 140°C. Kestov (18%) explains how to caleu - late st8 amount, eventually together with Ca, in the clinkers rich in CaSOj.. Alkalis (165) and low A: F ratios (40.64) (186) prevent Its formation;1-1/20 2C28+CaSO, (187) forms from the oxides al- ready at 900%C. Above 1298°C it decomposes in @-CaSO, and a! ~C7S containing 1.1 mole %Ca5O43 + C35 coexists with CaSO, in the system CaO- C28-CaSO, (188), The saturated solid solu tion of CaSO, in CyS contains about 2.92503 (ar 1310°C) (£69). “Sulphatic C38 has lower hhydraulicity (189) and decreasing mechanical strengths a9 the S03 content increases (190); + the compatibility (coexistence at the equili - Drium) among CaSO, 2C75-Ca80, and ICA CaS0g and SCA*CaSOz with CaO, "C28,C; ahy land Ca ~ in the 950°/1150°C range and in the y fet | | | | | lover alkali content than $03 (including the one of, fuel, im the absence of Cli-, allows the alkalis to be "fixed" in clinker as sulphates and therefore it reduces the internal cycle of the kilns (FIG. 13). Generally the quality (early mechanical strengths) of clinker is favoured by the cordition (in motes) 503 >K,0 + NazO - at least for limited amounts of S03 in excess (200, 201, 202, 203, 204). The most effective action of CaSO, is cbrained on raw meals having low A: F ratio (1-2 ¢ 1.5) and moderate lime saturation (~0.8), for contents of 2.34 2.5% SOgin clinker (185). Alkali sulphates are less active mineralizers than CaSO,. On the other hand they promote-similarly | + FIG.13. FORMATION OF ALKALI SULPHATES IN CEMENT KILNS. AFTER LOCMER ET AL. (170 ) absence of Kp80, and C3 - was established by Pliego Cuervo et Al. (191). Te aya, aso ae ches Sree pene a me a 710.14. 802 EMISSIONS WITH THE GASES OF AFTER LOCHER ET AL.(170) to Fl-and Cl!> - the formation of CgS (181). 7.1.6 Nevertheless the use of calcium sulphate must be cautious. One mst consider the lower hy= draulicity of sulphatic alite, as well as the fact that the simultaneous presence of AlS* and SOZ", in the absence of MgO, ‘mpoverishes the clinker in'C38, ‘Whose formation can even be prevented (189). Sul in the absence of suitable concentration in MgO, al- 30 Naz5O, and high contents in K750j can avotd the C35 fermation (181). , The unfaypurable effect ofthe combined action of AIS* and Of” is eliminated, or Strongly weakened, by the presénce of a sufficientquantity of bigO. These phenomena are likely to be related to the particular "wetting and penetrating" properties of the liquid phases containing high amounts of alkali sulphates which,in this way, would be able to “mineralize" a very rapid decomposition of CaS at 1250°C, during the elinker cooling (205). Finally one must remember the role of sulphates in the formation of rings and coatings (205, 207) which, fn the upper parts of kilns, prevailingly consist of sulphosilicats, 2CaSO,°K,S0, and NapSOy 7.1.5 The S02 emissions with the Kiln gases which process, under normal condition, raw meals and fuels containing sulphur compounds are poor (179, 170, 208, 209), The grazhof FIG. 14 shows the 80, concentrations in the gases, calculated by Lo- cher et Al. (170) versus the overall amounts of sul- hur entering the kiln. 1.2 Fluoride! 7.2.1 The vicariance between F1* and O1l~ makes: Aluorine the most important halogen of the sedimen tary rocks. It is contained in earbonatic rocks (100 + 600 pm F), combined as fluorite and flucr-a- patite; in marls, clays, shales (300 + 2500 ppm F); tn sandstones, calcareous sands, loess (60 + 360 ppm). The thinerals of the most rich clays are il lite (0.1 20.3%F), micas @-1+0.2F), montmoril- lonite (~ 0.03%), Fluorine is always present in the cement raw mx and it is often added to imp: ve tte reactivity 7.2.2 Some aspects of the equilibria in the CaF containing-systems are interesting for the practi- cal implications: in the system C-5-CaFn, (C2S)p-CaFy forms @ 950°C and decomposes at 1040°C in C28 and CaF (210).. The compound 11Ca0-45109-CaFy (211), or more precise - ly 19Ca0-7 $109 2CaF 2 (212), also called N(CgS)grCaFo" it stable beween 1110°C and 185°C. its incongruent melting gives trigonal C38, @”-CyS and liquid, at 1185°C; + im CypA7, O% is replaced by F1~ gt 1900°C tne eeatiuous series of slit solutions 3), Cy why (Calpe (Oe x €1), vhose extreme term Coduine 2.7E. ‘The singular term, ‘when x=0.8, contains 2.3¢F. In the most basic part of the system C- A Cap, the so lid solutions of the interval 0.8 2x 211.0 are in equilibria with CaO at 1300°C; those of the interval 04 0.8, with CgA (214). In the most basic and F-poorest part of the sy- Stem C-A-S = CaF (21S) the colutions of the interval 0.84 x2 1,0 ere compatible, tach time, with €28 and C35 at 1500°C, or wth Cy8 and CaO, but not with CgA. On the costrary, the later ia tm equilibrium wich the solutions of the sntorval 04 x € 0.8, CoS and gS (FIG. 15). leis therefore wrong to tak chat, in every ease, CaF decompo: 7.2.3 Bven small amounts (<0,3% CaF) of fluo Ges in the raw meal increase the values of (of the carbonatic phase 1-1/21 S08 C3A in CaO and a solid aiusnd Fin City (216) }) really this occurs only for higher con- tents in CaF than thove of the plane C28-C35 -C14,287"(CaF2)p,g. In the practice the flug idized clinkers coniain CgA or C12. ,A7* (Ca¥ 9), oF doth, depending on the F content and the cooling conditions (217)s the system C--A~ F= Cag at 1250°C (218), in ts most basic part, has not quaternary com = pounds but only solid solutions containing @ Small amount of fluorides in the system C- CS - CaS0g -CaF between 1000°C and 1150°C (212), an only quaternary compound 3625+3CaS04+CaF 2 (Huorellestadi- FIG.18. MOST BASIC PART OF THE SYSTEMC-AS-CaFy (WoT TO SCALE). AFTER MASSAZZAAND PEZZUOLI5 te) is presant. It is incompatible with both CS not saturated with CaSO, (1000*C) and (C38)3"CaF} (1150°C). The two silico-Fluo- rides (@28)9*CaF2 and "(C35)2°CaF 2" would only form in the raw meals containing F : SO3 Gaass 30 > 0.158, they modify C2 the Kinetics of all the burning reactions deeply (2, 219, 82,3, 220, 221, 222). The amount of -C2S, which forms as from 750°C, increases and a liquid ‘phase, which favours the diffusion processes among the encting solid phases, appears already S00 (223) Therefore, at 850°C Cp of CaF 2 determines the? ‘CacOg wh poses by separating COz, C2 = Lam), the presence ne°2 formation of (Cp5)o By at 360°C (PEG, = L atm); decom C28 and Cad, the two latter in a parsicularly active state to be combined in CgS: in this way, spurrive would play: fa role of intevmediate phase which accelerates the formation of alite. These phenomena are evidenced, in the DTA graphs, by the variations in height or area of the thermal effects of the transformations versus the content in CaF (82) (FIG, 16). The de-1-1/22 creases in the specific effectiveness of fluoride as ‘also clear, as alrea- its concentration 1 A——|Sipecacosr 7 Fia.16 DTA EFFECTS OF THE RAW MEAL VERSUS Cae CONTENT. AFTER COURTAULT( 821) dy pointed out by Vogel (2) and recently reconfir med by Johansen et Al. (224). Similarly w spurrite, also (C25)g-CaF 2 and 957 -2CaF 9 would. giver, teen 95Dand 1200°C appro. , to a mechaniam of formation of alite through incon ~ grient melting of Cj957-2CaF 9, acconding toa sche the proposed by Gutt (220). The higher rate of for= mation of C8 in the presence of CaF is also attri- buted (224) to the larger extention of he primary phase Meld of C38 Inthe C- 5 -CaFy and C-S~A Systems. Inany case the C38 formation begins st Jower temperatures by at least 150° + 200°C than those in te absence of fluorides. On the contrary the existence of C1987+2CaF 2 in = volves = during the clinker cooling = the attack of lite and belite by the liquid, with separation of =1987"2CaF because of the peripheral reaction at 1185°C (225), In the practice the rate of cooling is always fast enough 30 that the reaction does not oc car} nevertheless the case of fluoridized clinkers containing C1957-2Ca¥ 9 (as @ costing of alte) is not rare. The poor hydraulicity of C3S fluoridized (226) would explain the low mechanleal strengths of clinkers containing more than 0.5 40.6% F (227), 7.2.4 The mineralizing action of fluorine com - pounds is attributed to their influence on the stabi- ty of the rhombohedral structure of CaCO3 and on the mobility of the (SiO,!V groups of silicates (2) This influence increases as the lattice energy ef fluoride increases and thevefore, in first approach, DOO O UL LLLLLLELLL ELLE LLU LLL bea a the radius of the cation decreases.. For this rea son, at the same concentration in F, MgFg and LiF have higher effectivenesses and (in decreasing or ~ der) NaF, CaF, SrFz the lower ones. BaF and KF are the lesa sctive (82, 147). The uosilicat having the same ionle species and equal content in F, have equal (62) or slightly lower (228) affective- ness than that of fluorides. 7.2.5 Fluorite is generally used in the technologi- cal practice for its lower cost and its easy handling. Im the last few years its use has extented not only. to the manufacture of waite clinkers but also of nox nal ones because of the fuel saving and the increa~ se in the Kila capacity that this mineralizer and flux often enables. The advantages obtanable, at the sa me amount added, are not equal for all the raw meals and all the types of kiln: asa rule, the har — der raw meals to burn, containing macrocrystalline rocks, and the short processing-kilns, above all, the lepol ones, sake the most advantage. The int nal cycle of fluorine in the burning plants is weak and such that only traces are found in the gases (229). The losses correspond to the eventual shut off of the cycle by extraction of the electrofilier dust which generally has higher (10+ 208) concentra tion in fluoride then that of the raw meal (values rg ferred to the calcined matter). Experience suggest to limit the additions of fluorite not above 0.5 + 0,0%F of clinker, in onler to avoid the dangerous decrease in mechanical strengths. Within this Limit the hyéraulicity and the strengths of clinker are quite normal if it still contains 1+ 2% ‘ree CaO or anyhow it is intended for the produc - tion of high fineness cement. 1.3 Phosphates. 7.3.1 The organogen sedimentary rocks (fossilife- rouo limestones, marls and clay of shore-sea fa cies, 2.8.0.) contain verying and sometimes consi Gefable amounts of phosphates. These minerals are flso present in sandstones, sands, and prevailin = fly detrital clays. Phosphoras compounds are con tained in the by-products of the siderurgical indu ~ sury blastfurnace slags, slags from electric furna- ces, from converters, avs.0+) often used in the ce ment raw meal. 7.3.2 The fundamental knowledge on the phospha- te clinkers 1s mainly due to the Researchers (230, 231, 232, 227, 233, 220) of the Building Research Station of Garston (United Kingdom). Schlauat (234), V'ikov and Tabakova (235), Fix et Al. (236), Salge and Thorman (237) gave further contribu ~ POs preferably concentrates in belite to the det ment of alite and the interstal phase (237): the concentrations inthe three phases areinthe ratio 4: 21 1 approximatively. In the system CaO- Si09- PDs, a series of solld solutions of CaO and P20 in C38 (233) appears asa primary phase of erystallization. The compost tions given in TAB, VI have been assigned to the saturated term (called C38") (233, 234, 237). C35" HONS G1ASS 4) OF Cys" AFTER DIFFERENT AUTHORS (2,20, jases| “sass aro | a4 1-1/23 on between C25 and PSS! increases as the % of PAs tncrenges: an experimental confirmation was obtained by Saige and Thorman (237). The opporty hily of using very high values of ime samuration (or ;persaturation) for the phosphatic raw meals, Consistently with the present content in POs, ts clear. The hydraullcity of the phosphatic clinkers shows a TAB. Vil. APPROXIMATE COMPOSITIONS (MASS%) OF THE Lbtrine SOLD SOLUTION Pes” AT ssore a]as| a5 AETER DIFFERENT AUTHORS (230,230,254, 277) anos ae T Saige] as er eee lee G58)” | ade | Gaan" [emma o> | s| 26] 20 a, eee |e aa) way as tha prosence oF A ws |ws| ne] 0 70 [es] a | wa ee | sa fosa] 9 | ue has trigonal strictures with respect to C38, 1¢ eo jLeo Ikea 4 Ika shows distorted elementary cell having reduced i mensions (227). The hydraulic activity ought to be slightly higher than that of C38. Phosphatic belite {s a solid solution of F-CyP in B C25 (lor contents « 2 Ps) and inaranda~CyS Gor higher contents in P2053 227). Since the se Hee of solid solutions C25 ~C3P shows e lack of tubsolid miscibility, a liming composition called PSS" is in equilibrium with C35" at 1500°C. The - re are still considerable uncerialmes for the practi~ Gal consequences on the composition of PSS! CAB. VID. Temast not even excladed chat tt falls outside the line joining C25 to CaP, towards higher Time contents, because of the marked aptitude of this solution io tke hyperstocchiometric CaO (236, 237), The composition of PSS! found by Nurse (230) confirms ts hypothesis. 7.3.3. The portion of the system CaO - CpS - C3} near C25 and C35, at 1500°C, is shown in FIG. 17, the compositions dedueible from the paper ‘gned to C33" and PSS! ‘The phases in equilibrium are: (C38 and solid solution C2$ - PSS, for lower content in P25 than the line C38 PSS"; solid solution C35 -CyS" and PSS', for con - tent in PgOs between the line C35 ~ PSS" and the line C35"- PSS"; CaO, solid solution C35- C35" and PSS! for higher content in POs than the line C38" - PSs! £48" disappears, as an equilibrium solid phase,for Higher coments in PgOs than che lina CaO- PSS. in the C35-C5-P3S'- C35” field, the amounts of C8 and/or C48" decrease and that of solid solu - 3 3 (© imleatad a PSS. Te he prasence of ALD; Feg03y MgO and ale, at 100°C. (Bia Hic. eet G5). In he Fez05, MgO dnd alt APs, slight increase for low contents in POs (0.5 + 1.0%) (235, 237, 238, 239), probably due to the peculiar structure of CS"; afterwards (t considerably de ~ creases as the content in P2Os increases. This drop must be related to the decrease in the C35/C2S / F1G.17 MOST BASIC PART OF THE SYSTEM ©20-,5-C4P AT 1500 % (NOT TOSCALELT-1/24 ratio, as well as to the progressive increase in the amount of the structures @andaC9S, to the detri = ment of the B-form. 7.3.4 Wis recognized (235, 240, 241, 242) thar pho, sphates have a strong accelerating action on all the Feactionsoccurring during thé burning of clinker. ‘The process of combination of CaO in the solid pha- se is facilitated; conditions favourable for a rapid crystallization of the clinker mierels occur in the presence of liquid phase. The presence of hydroxyapatite in raw meals con ~ taining chlorides ought to reduce their intensity of internal recycle in the kilns and in this way it should avoid (or minimize) the formation of spurrite coa ‘ui CONTENTS = Guas8 6, IN APTER VILKOV ET AL. Gis). 0.74 20 | a5 0.8% tema eco) 0.96 10 | os \g5 (207). Therefore the correction of raw meals with suitable amounts of phosphatic additions can be fan effective means to improve some technological conditions of the clinker burning. ‘The uncertainty of the compositions of C35" and, above all, of PSS* does not allow the calculation of the maximum content in POs, practically allowable ina raw meal. V'ikoy and Tabakova (235) suggest the limits ehowa in TAB. VIL. 5 The favourable influence of CaF2 on the raw meals containing P205 was examined by several Au thors among whom Simonovekaya and Ved zinska (243) and Gurt (220). Tymasher et Al. (244) studied the effects of concentrations of 0.8 41.5% POs, on the raw meals containing high amounts of alkalis. Leh Tiransum compound: 7.4.1 Titanium is present in the clayey sediments and in the detrital ones as both hydrolysis product cooprecipitated with Al, Fe, Be and Zr (bauxites, laterites, a-s-0.) and combined im less altereble re sidual minerals, cuch as ilmenite, rutile and titani= 7.4.2 Owing to the great proximity of the jonte rays and the strong energy of the bond Ti-0, Tis vi- cariant of Fe” in the tetrahedra (FeO, of cal cium alumno-ferrive (245, 246, 247, 248). Tt alco me, places AIS* in the came alunino-ferrite and the alu= minate (orthorhombic, cubic and tetragonal forms) RATIOS OF MASS TN TiOy INTHE ‘CLINEER PHASES AFTER DIFFERENT AUTHORS « Midgley | Horaain | 283°] insret eos [S| Re [sone bale mo fa far | 2 stant oe | aa | a soedps | 2/88 THT amerpanou] oe || Te TOTES. () Artima neat af be dteaons oa CSET Tee, Ccyiae fsdeericaions ono inert ser (158, 249), In alite, the vicariance between (TiO)! and GOD i lanted WSOC at 13 mole Myequa BA S3 nas % TiO of C3 (S, T). The form My and. the form R remain stabilized up to 7 mole & (2.45 mass % TiO.) and for higher contents respectively (250)- The limit of the solid solution in belite corresponds 10 0.76 mass Ti02 (51). -The limits of vicariance of Ti4t instead of 514+, A13+ and Fes in the mine- rls of pure clinker result from a recent research sa: 18.540.5 The distribution in the different phages of clinker appears to be varying (253, 49, 254, 158); neverthe- less the tendency to the entichment in alumino-fern te is clear (TAB, Tx). It-was reported (254) that increasing amounts (up to 4 of TiOz ina clinker having K,,~90, SM~2, TM-=1_~ aoe im equivalent replacement of SiO, - determing a sharp reduction in the alite content with cequel gain in belite without, however, appreciable ‘variations in the amounts of the other phases (FIGS, Variations of the same type are mich more restrat- ned when TiQp is added in place of equivalent _a = mounts of S103. Itts assined that either the solid solution of TiO in belite contains hyperstoechiome, ic CaO (as is assumed for phosphatic belite) oF the presence of TiOz displaces the compositions of the invariants at 139B°C and 1341°C of the sy - stem C-5-A-F. In any case, in the practice, it seems suitable to calculate the saturation of the raw meals containing TiO (not exceeding ~ 2.59 by summing the Sof SiO to the % of TiO (in equivalent amounts), ‘oy tents eater 7.4.3 1% Gf clinker) of THO is enough to reduce the temperature of incipient melting of the rew meal by 30° 100°C (254). 140 reduces the surface ten sion of the Liquid phase (138) and causes a drop in the viscosity proportional to ite concentration (at least within 4% 1102) (255). These conditions faci ~ Ttate the CaO combination and the alite formation, which are however considerably favoured also by the intermediate formation of CaO TiO and solid solutions of CaO in the same. The effectiveness of the mechanism of CS production would even exceed the one occurring in the presence of CaF 2 (256). The presence of Tip gives clinker a darker colour than the weual one. 7.4. TiQp retards the initial rate of the clinker hydration (250, 49, 254, 257) with slower setting ti- res and lower early etvengths (1 and 2 days). Ne~ Vertheless Kondo (250) showed that alite containing TiO has a higher hydraulic activity than ordinary alite for ages over three days. The TiO clinkers ‘examined by Kaétel (254, 252) confirm higher (ap to 20%) strengths between 3 and 90 days, for TiO con tents of about 1%. ‘The highest increases occur in linkers having very high lime saturation and high SM (252), 7:5 Chrome compounds 7.5.1 Generally limestones contain only traces of chrome, Since Cr is an isomorphogenous substitute 1-1/25 in the femic silicates, sts found in the sediments rom basic and altrabasic rocks and in the sedimen- tary products of hydrolysis (aterites, bauxites, a. -0.). Chrome is sometimes present in the raw meals containing siderurgical slags. The wear of the grinding media and the linings of the raw mix mills a2 well as the one of the refractory inside the kilns produce only traces. +502 Although there is a certain disagreement (258, 259, 155, 260) about whether chrome replaces Ca or Sit in C35, or both, the latest research G1, 262) sgeme t indicate that tetrahedra (CrQDM and (CrOp)!¥ replace (SiO, IV according to: asitre2crSt + cam? [23] sie cht [x] (Car? = lattice vacancy of Ca), with mean state of Sxidetion of Crr.6 G53)._ Different Author® fix the lmtt of solubility et 0.9 C283), 14 (256), 2-5 (285, 265), 1.7 05, 2.0 059) of Crg0g mass kot solid solution. The Crz03 earuration increas solubility of Aiz03 (2.1 t6 1.3%) in C9S and creases that of Fa203 (0.9 to 0.7% (155) in excess with respect © saturation decomposes C38 in C28 and CaO (155, 265, 138) ‘avai et AL. (155) the forms Ty and Ty Gor Cr03 1.28 and Cr703 > 1.4%, respectively) re- main stabilized at ondinary temperature; according to Hornain (4), on the contrary, the hexagonal forms and Mjgdo. Cr5+ replaces Sift in Cy at 1100°C + 1250°C, by stabilizing the form Bat ordinary temperature the limit of solubility attains at least 8.5 of CrgOy% solid solution (257, 261). cx replaces AI in CyA G9, 150. InC6AgE tp (04 pe 0.7625" occupies ocuhe dric sites instead of Fe? and A19* (247). Peters ond Hamel (258) studied the relations of subsold phase in the systems, CaO-ALD3 - $C40.3A1303- CaC1O, -ALgOg. at _1300%C S10 Alg03- 3510 "A104 Sx, AIDS uua0ee. Ina typical clinker containing 0.55% CrO3 , 76.3% C35, 9.1% Cz8, 5.3% C3A and BSCAF, Hornain (9) found the following “distribution of chrome into the different phases (ratios among Inass concentrations of Cr03 in the phases): alite belite : aluminate : alumino-ferste 1 2 2 on 16 The limit of solubility. of Cr03 in clinker is about 2% (under oxidizing conditions): consideraPPREARAGUEE TEENY 1-1/26 ble amounts of free CaO appear above this concen tration (241). 7.5.3 The viscosity of the liquid decreases, at the same temperature, for concentrations up to 2% Crg03 of liquid (138). Increasing contents of Crg03 up 1 4mass% cause also & reduction im the surface tension; this eduction is the greater the higher the A: F ra - io (259). ‘Therefore the lime combinations is favoured in the raw meals which are difficult to burn and ave high A: F ratio (210). ‘Alte forms more rapidly and its crystals become larger (9). However, also as regards the kinetics of the clinker formation, it is suitable that the Cr03 content does not exceed 0.5 + 1.0% of clinker case, 137). 7.5.4 The solid solution of chrome in C35 con tains, in the lattice, punctual defects due to va eles and linear faults which, during the reas tion with water, favour the detachment of Ca?" from the latyice sites. Although the data of the Lterature are discor” dant on the minimum amount of Cr0 needed, ne- vertheless it is accertsined that the presence 25 + 0.50 % CrzO3 incresse the iniual by- Graulic activity of clinker (155, 260,138, 29, 21, 2, 152). ‘The effect mainly concerns the mechenical strenghs at very short ages (270) of clinkers ha- vying high lime saturation (154) and high A; F ratio G70). Strengths at longer ages are not affected or are negatively influenced (270) ‘The presence of small amounts of fluorine and manganese favours the action of chrome (272). 7.6 Potasstum and sodium. 7.6.1. The misin carriers of alkalis into clayey rocks and clastic sediments are orthoclase, l= bite and plagioclase of magmatic rocks. K and Na are also contained in the structure of some phyllesilieates, above all the three layer - sialites such as micas, illite, montmorillonite, All the sediments, including the carbonatic ones sometimes contain soluble alkali salts which are residues of the deposit environnement. KO and NaZO in the raw meals of European ce- mant factories (170) range between 0.5 and. 2.0% and between 0.05 and 0.6% respectively (ratio. of the mass concentrations between 3 end 10). Jawed and Skalny (273) have recently revised the ULLAL ULLAL LR Ro knowledge about alkalis in clinker. 7.6.2 Because of their marked voladlity, alka - Ass give rise to a cycle, inside the kilns, which increases their concentration in the processed material with possible danger to the regular cour, se of the process (164, 167, 169, 170, 274). The intensity of the recycle more concerns the potassium compounds than the sodium ones, being the former more volatile than the latter, et the same temperatures (FIG. 19) (164, 275, 276). Moreover this intensity depends on the mature of the present alkali minerals and anionic species, fon the chemical composition of he raw meal, on the characteristies of the process as well a on: the type of kiln (173). Under normal conditions, the alkalt voladlity of the raw meals increases, in the onder, for feld- spars, micas, illite and montmorillonite, that is a5 the bond energy of the considered silicate de~ creases (164). Sulphates determine leas intense cycles than car bonates, and these than chlorides (164) (FIG.19). The noddle-fed kilns (lepol and long with snterna Fecuperators) have poorer recycles than the dry meel-fed ones (both with suspension preheater fand long with internal recuperators) and than the wet Kilns (171). 7.6.3 Although they act as fluxes, alkalis are the technologically less desiderable compounds among the minor ones. They can be eliminated from the in- termaleyele through the three systems already menig, FIG.19 VAPOR PRESSURE OF SODIUM AND POTASSIUM SULPHATES aND CHLORIDES (642752761, Oened in the paragraph 6.5.2 through ahut off of the cycle by (total 0 partial) elimination of the electrofilter Gast. This technique is not practicable with the suspension preheater kilns; through shut off of the cycle by (partial or total). bypass of the external recuperaror. Unfortunately the method involves the wasting of an amount of energy which is proportional to the amount of bypass; this ose can cubstantially be reduced by the technique of the calcination outside the kktln 10). Today the total bypass of the kiln gases with a nearly full precalcination, enables Iow alkalt clinkers to be chem produced also from maw meals rich in aikalis (277), eventually by using addition of calcium chlo ride (278, 279, 280, 28195 through clinker. The method can be used nant ins and denante te cont ee eptitalts w sulphates 79, 295. ieihsehvesttey high nouns of reaping those tn the Dunning material ee pro BiG ot cunters ving al te alas contained inte rev neal tnd fuels The - ‘Store icio not procticable wih raw mesls Tench elias (hfs Neyo > abou Ok SP ealeind mater becsuse of he shentng coatings nl singer, Moeover [ec oren pcre oth nar mele nox very poor in alla C2 0.80 Nag # THiS euivs afte called mnteia dhefave mnied fos low ala ckers. TE eC o30 pp of thecal ed eateries te ayo ineloct= 7.604 The alkalis present in clinker as sulpha - tes, particularly K2S0,, favourably affect its strengths at early ages (up to 3 days) whereas they lower those at 28 days and over (42, 283). 2:7. Magnesium 7.7.1 In the practice there are not calcareous rocks deprived of magnesium, vhich replaces Ga2", also at random: Generally limestones of the oldest formation are richer. Magnesium is also present in clayey and detrital sediments @s ‘a carbonate, as a silicate of primary rocks and finally as an isomorphogenous substitute in some phyllosilicates. 7.7.2 MgO distributes, in the solid solution, into the clinker minerals as far as saturation; the ex- cess remains uncombined as periclase. In alite, the solid solution is of substimtive type 1-1/27 Mg2*—eCa2* (284, 158). Its content in MgO is ‘constant fraction of MgO of clinker, within the 04M, ¢ 3% ranger thie fraction 1s 0.74 conding to Yamaguchi and Takagi (285) and 0.63 according to Kristna: 0). Asa rule, the ri - chest alites are monoclinic (286); the poorest ones fare trigonl (158, 50). The MgO content in belt ~ p30 is 0.25 40.35 MgO of clinker, within the Oe Magy, ¢ 2 range ( ). The presence of high concentrations in MgO would reduce the activation energy of the conversion a -C28—» a'-C2S, with consequent stabilization, during cooling, of ‘the hydraulically less a: ave form B (287). " Although the liquid phase can contain up to BY MgO (AF = = 1,3), (288), the replacement of Ce2* and by Mg2*, in CJA ond C2Az erally jello. metres containing 3, some cases, concentrations of 6% and over “pO p €0.7) 98 hg 3.5% MeO. ‘In been found (50). The presence of magnesia favours compositions of C2A,F yp having higher values of Dy with decrease Bok Peas ce ending in Erease in C35, 10 the detriment of C75 (285, 289, 290, 48, 291). Poriclase appears as an independent pha: fn clin- (23, 50}: depending ZMK 4a y—p te RELL | sce F1G.20 . AUTOCLAVE EXPANSION FOR INCREASING MgO CoNTENT|2m-236 290)1-1/28 fon its excess and the rate of cooling, it appears in large roundish crystals arranged in clusters a well as in dendritic shape, finely dispersed and ‘well-distributed into the mass (292, 293, 294). 7.7.3. The reactivity of raw meais is favoured by the presence of gO only in the range of the higher temperanines (about 1300°C) (228). At any other variable unchanged, the first appearance-tempen ture of the liquid drops by some tens of °C; visco- sity and surface tension of the liquid reduce whe ~ Yeas the mobility of all the present ionic structs ~ res increases (137). Under these conditions, the Aissolutions in the liquid of C25 and CaO are mo - re rapid and C35 forms more quickly (228). Unfor tunately - as known - the presence of periclase Gespecially the one in the form of large erystals in clusters) makes the coment unstable. Therefore the standards of several countries (295) limit ite content and/or prescribe a test of unsoundness in autoclave (296). ‘The results achievable by this test with regard to the # of MgO in clinker, reported by different Au- thors (297, 298, 299) are shown in FIG. 20. Nevertheless it 1s recognized that the test is not probative with every type of cement (288, 298). Moreover the decrease in the mechanical strengths atmediun ages, that some cements containing @ Ki- mited amount of MgO (« 4 + 58) show, also with quite normal volume stability, ts worrying C1, ‘Br, BBB). Recording to Soda et Al. CBN) this phe nomenon would be limited only fo clinkers very ich in C23, containing over 2% MgO, and it would be attributed to the convertion of @-C2S to B -C28. 1-94 Saye dco Sopee ae crehy te etal econ of weg MeO OS eer Mat Satie we ners ot eee omy al rou aureheoes ee samt a asoj-oeramo-2 [a] when 24 1M gO 6 about. 7:8. Strontium, 7-8.1 Asa nile, strontium is present sm minimum amounts in ancient limestones (and mazls), attriby table to sediments of skeletons and shells of orgi= nisms. On the contrary, even Important contents Gap to 10% SrO and over) are sometimes found in recent limestones (and marls), especially of eva~ poritic and chemical origin. The more frequent mineral is celestine (SrS0;), This (together with other evaporitic minevals) 1 also present, asa cement, in the calcareous and siliceous detrital se- diments (sandstones, grauwackes, a.8-0.). Stron- tianite is relatively rare; itis generally found in. veins of limestones and marie. 7.8.2 The phase equilibria of the system CaO-SrO ~'SiO vere reexamined and completed by Brist and Appendino (200) at 120°C and, in the most basic part, at 1350°C. In CagSiO,, Sr is vicariant of Ce? in all che proportions (with stabilization of the form @"), whe- reas in CagSiOg the vieariance is limited tol + 2 atomic % Sr, roughly corresponding t© (Capo. Sr9,05) 5105 (point N of FIG. 21). The strudtines F1G.21 MOST BASIC PART OF THE SYSTEM 20-510 si0g\NOT NO SCALELAFYER BRIS! AND APPENDINO (200), Ty and Ty remain stabilized, at room temperatu- re, up t0 letomie % Sr and at the limiting concen — pation respectively (G01). In the two-phase field 2S -M-=N-CgS, the solid solutions of SrO in C28 and SiO in C38 coexist, whereas in the three-phase field CM-N, (Ca. 95 5r9,95)5i05 4s in equilibrium with the solid solution (Cay g8rQ.2) 5104 (point MA) and free CaO... 1s deduced that the mites of Cg5++C25 can carry not more than 2.25 + 11,40% 510 CGegment NM) in the solid solu- ‘ion, depending on the Cg5 1C25 mtio; for conterts exceeding these limits, free CaO of equilibrium (oexisting with Nand M) always appears. When 'Sr0 exceads a value between 11.40% (point M) and 8.71% (point W) depending on the gS :C25 ratio, the solid solution of 35:0-5iO2 im CgS disappears and only (Ca, S1)25i0, and (Ca, $190 remain in equilibrium Gin the ease concerning the composition of portland cement clinker, (Ca, $10 is practical- ly pure CaO). 7.8.3 Giliolt, Massazza and Pezzuoti (302, 303) studied the equilibria of the systems CaO-Sr0-S0) =S03 and CaQ-Sr0-A1g03-503 at 130°C, They UU ELLELLLLLCEEERLLLLL LL LLL LiL aafound in the former, on the segment CaSQ4-SrSOg, three series of solid solutions separated by two lacks of miscibility, and the compound CaSO,+ +25r80, G04) as a singular zerm (lor x = 0.08 f the series (Cay ,Sr)5O, with 0,04 x 40.7. ‘The saturated solution N in the presence of 503 is fm equilibrium with M, CaO and a solid solution S50, - CaSOj: for this reason, the limits 2.25 + 11.40% 5x0 become higher in the presence of $03 Gn fact, as FIG. 22 shows, a part of S10 forms a solid solution with CaS0,). The equilibria of the systems CaO - 5x0 - A1,03- 503 (FIG. 23) evidenced incompatibilities between solid solutions CgA- 350-AlzO, and all the sulpha, FIG.22 .MOST BASIC PART OF THE SYSTEM (0:510-8i0p.50), AFTER GIIOU ET AL (802), tic phases, except for the extreme term 3510-03, with $804: therefore the solid solutions CaO, 5r0):AL04 decompose in the presence of S03 10 orn free CaO and a solid solstion of the series 4{Ca0, $10)-3A105+S03, having the compound SCA-CaS0, (205, 183, 305, 307) and the compound 3Sr0+A103)- SxS, GOB) ae extremes The direct measurements (electron microanalysis) carried out by Massazza and Pezzuoli (909) on in- dustrial and laboratory clinker confirmed that, for contents of 4 + 5% SO, this element preferably Atstributes into delite and, to a lesser extent, into alite. Free CaO is just contaminated. 7.8.4 Although celestine (and probably strontani- 1s) have an accelerating action on the combination reactions of CaO in the solid phase (310) and they lower the appearance-temperature of he liquid (G02), their presence in the raw meals is not desi~ rable since they are liable for the release of free CaO of equilibrium and - over coreain limite - for 1-1/29 the distruction of elite, From this standpoint, SeCO3 is more dangerous than SrSQ, and the clin- kers having high degree of lime saturation are mo ~ inerable than the prevailingly belitic ones. 16.29 MOST BASIC PART OF THE SYSTEM On the other hand SrSO, - at least in the abserice of alkalis - decomposes the solid solutions XCa0, SrO)+A10g by releasing CaO in this case too. The limits of acceptability of the SrO concentration rn two typical raw meals are given in TAB. X. It would seem that higher concentrations can be allo = ‘wed in the presence of CaF G10). Butt et Al, (G11) found that hydvaulieity and vengths developed by strontium alites are conside 2: Teoma comics | O75] F055] canis Gop] 5 3 srromanite S109 | _§ a vably lower than those of the ordinary ones: they attributed this fact to the lower number and the smaller sizes of the lattice voids in strontium ali - 2.9 Barium, 1 Limestones contain varying, amounts of ba1-1/30 rium (104 600 ppm Ba), essentially as barite poritie limestones are rich (up t0 1000 ppm) o: ceptionally, very rich. Barium can concentrate tm the hydrolysis minerals of clayey sediments al - 50 in appreciable amounts. It is found in the de ~ trital rocks, besides as a sulphate, also asa re - sidual femic mineral (amphiboles and pyroxenes). 7.9.2 Ba? replaces Ca”* in all the minerals of linker, except for alumino-ferrite (152). FIG. 24 shows (312) the portion richest in lime of the system CaO = BeO ~ SiQy. Te results that FiG.24 .MOST BASIC PART OF THE sysTEM 0-820.S:0,{NOT NOSCALELAFTER BRIN%2) + im the two-phase field C3S-CpS -Q- Rs 99 Tid solution (C,B)S and solid sclsons (BBS: + tn the two-phase field CgS-R-CaOr solid solutions (C, 8)38 and CaO; + inthe three-phase field CaO -Q-R: solid solution (C, 8225 having composition Q, sanurated solid solution (C, B)33 having composition 2, and Cas + on the right of the Q= CaO Iine:solid solu~ tons (C, Bz S and CaO; coexist in equilibrium, in each of these times. The limiting solta solution R of BaO in C8 con ~ tains 1.5 mole % BaO (2.96 mass 10 G13), or 1,0 mole % BoO (2.99 mass %) 01), at 1600°C and 1450°C respectively. LUE LLLLLLL LEAL EEL LLL LL lob ldb ddd bb The stabilized form is Ty (in the presence of MgO 2 2% moles, Myiny,) (G01). The solid solution Q of BaO in C2S, in equilibrium with Rand CaO, con tains 7 mole % BaO (11.55 mass %) at 1350°C (312). ‘The form a! remains stabilized (314, 315). The l= nniting sold solution of BaO in CA contains about 1.5 mole % BaO (about 2.5 mass 9) (152. 7.9.3 In disagreement with other Authors (316, 317), Suleimenoy et Al. (318) and Kurdowski (152) Delieve that the presence of Ba ~ also in limited amount - affects neither the characteristics of the Liquid phase nor the rate of the lime combina On the contrary, barium appears t0 be one of the most effective "activators" of the hydraulicity and strengths of clinker; the latter are higher by 10 + 4+ 20% at any age, all the other conditions unchan ~ ged (152, 271, 150, 319, 320). The optimum concentration is between 0.3 and 0.5 mass % BaO and the clinkers containing few fluxes (SM *3.0) (152) and having high content in C26 50) are more favoured by this concentration: Barium cements demand suitable additions of gy ~ psum and eventually of Ky80z ($20). This behaviour of clinker is Strangely different from that of the solid solution of Ba in CaS} for this solusion, im fact ~ because of she larger ionic radius of Ba2* with respect to Ca” - Butt et AL. (B11) theorized and experimentally confirmed a ve~ duced hydraulie activity. ‘The action of BaClz on CA, between 900°C and 1000°C, was studied by Muminov and Akhmedov. oa. . L10_ Zine. 7.10.1. The content sa zine i the sedimentary rocks doce not exceed the tens of ppm, @2 e rule Its mainly contained in the detrital and clayey rocks (magnetite and chlorite vectors). Sprung and Rechenberg (322) found amounts ranging bet - ween 25 and 62,10°% ZnO in 23 raw meals. from German coment factories. Nevertheless higher concentrations must be expecied in raw meals con {ining limestones mineralized by sulphides or cor: rected with pyrite cinders rich in blende. 7.20.2. During the burning process, 80 + 90% 2x0 Gr 2n9) in the raw meal te combined in clinker (G22, 323). Therefore cliskers contain between 30 fa 100-10-% 210, depending onthe content in the raw met end the ancunt of electroflver dust rejected out of the cycler Roughly half zine distributes into silicates Geith sharp preference for alita, 10 the detriment of ba- lite) and the other half doe’ into the matrix Geith preference for the ferritie phase) (323, 293). The, efore, for a normal composition of clinker, slum) Tyno-ferrite and aluminage, alite and belite should re sult less rich in the decreasing order two by two. jornain (49) found concentrations (Zn0 mass of phase) resulting in the ratios: elite : aluminate : alte : alumino-ferrite 1 4: BG 7 According to Kndfel (323, the saturation atinins 5.1 6& ZnO in alumino-fervite, £2 5% in alaninate, about 1b in alite, 0.3% im belie ‘Recording to Ono et Al. (324) and Tsuboi et AL. GSD), trigonal C5 would be stabilized; acconding to Enbiel (823) yoy, and B -CyS, and accor ding to Hornain @B) C38 My, and B -CoS would Im the clinkers studied by Kndfel (323) - also con- taining only ZnO - @ new phase probably con sting of free ZnO (aineite) appears together with zine containing-minerals ‘The presence of ZnO reduces the amount of alumi - nate in favour of alumino -fervite (323, 293, 325) each 1% ZnO reduces the former and increases the latter by little less than 2. Strangely, an inerease in alite does not correspond co this variation (323). 10.3 Zine is a very effective flux and mineralt zor (23, 293): it lowers the clinkerization tempe- Tature and accelerates the lime absorption Nevertheless the effect on the properties of clin ~ ker (except for a darker colour) are not quite clear According to Aktsu (825) just 0.3% ZnO would ne ~ atively affect the hydraulicity. On the contrary, Knbfel's (323) research show that Umited contents in Zn (< 1 + 28) ima typical inker having Kg, ~ 95, SM~= 2.2 and IM = 2.5 Getermine an improvement in its mechanical strengths by ap to 20% and over (especially at shortages). 8, CONCLUSIONS. 8.1 It is important to distinguish reactivity from Dumabiliry of a raw moe. In the present paper, the concept of reactivity hus been associated to that of rate of reaction, or of a set of reactions, for given conditions of temperetyre. On the contrary, burnability expresses an amount of matter transformed or still to transform, at any instant and temperature of the process. This distinction seams particularly useful to compa~ re raw meals having different lime saturation. 1-1/31 Reactivity and burnability are fundamental pro- perties having important effects on the capacity of ants and the energy needs of the process. The choice of the ype of kiln and its dimensions, the proportioning of the raw meal, the more suita- ble admixtares cannot prescind from a right evalua tion of such properties ~ Nevertheless the knowledge on this matter is not Gatistnciory, above all for want of a sultable methe dology of measurement, universally adopted The methods entrusting the eval tation of burabilt- ty to the value of CaO; that the function CaOp = F(t, 6) assumes for only a couple (643 9), oF to the va ues and 8{, for which the quantixy of Cay be ~ comes equal to or lower than an established amount, prove to be insufficient On the contrary, Blaise et Al.'s method seems ‘0 be rational. 1 ‘evaluates buraability on the ba sis of the course of the reactions in the overall range between 100°C and 1450°C. 1 practicel purposes, the characterization of the raw mix by three values of average reactivity rele- ‘vant to three significant temperature intervals instance, 500°C » 1000°C, 1000°C + 1300°C, 1300°C + 1450°C), under standard conditions of temperature and time gradients, could result even more useful 8.3. Reactivity and Lime saturation affect the value of the burnability. In its turn, reactivity is @ function of SMa, TM, fi neness, present mineralogicsl species and activity state of such species. The laws governing the diffusion processes among solids and between solid# and liquid well explain the influence that these variables have on the reae~ peuy Particularly, the dependence of the diffusion coef- ficients on the activation energy; and the dependon cce'of the valve of the latter on the concentrations of defective structures in the solid matter, con: ute the basis for a satisfactory model of interpre tation of the phenomena. This model also explains the interesting possibiLities offered by the so called, mechanical, thermal, and chemical activations of the raw meal. 8.4 It seems right to expect that the chemical activa tion (er however one prefers to call, or must inter pret, the action of the minor compounds acting as minetalizers and/or fluxes) constitute the mo: promising field for the development of new technolo Gicel methods. The knowledge on the mechanism of ‘ction of these compounds, and on the phase rela tions that they yield, more and more frequently al low higher capacities of the equipment and energy savings to be obtained. Thanks to this knowledge, also the limits of exploivability of raw materials as well as of yastes, which are sometines Introduced into the raw mal for ecological decontamination pur poses, are enlarging.1-1/32 REFERENCES 1. VOGEL, E. (1953) "Untersuchungen liber den Enteluerungsgrad der Granalien auf dem Le - polrost”, Silikattechnik 4, 469. 2.- VOGEL, B. (1959) "Die Wisiang von Flvsepat und Kietabbrand auf den Reakwonsverlauf Yon Zementrohmehlen watersalb 1100" techntk 10, 415. LONGUBT, P. et COURTAULT, B. (1964) *Apuinude 8 a elinkérisation des eras de ci - menterie", Rev. Mater. Constr, N* 585, 174 4.- PFRUNDER, VR, ot WICKERT, H. (1970) "einige Versuche liber den Finfluss der chemi schen Zusammensetzung und der Mahling auf die Sintering von Zement-Rohmetlen", Ze ~ ment-Kalk-Gipe 23, 147, QUITTKAT, W.(1965) "Die Phasenumbildung- Svorginge beim Zenent-Klinkerbrennen us Rohmehlen mit Branntkalk-, Kelkhydras- nd Kalksteinkonponente und ihre Bedeurung don technischen Brennprozess", Tonind. 21g 29, 351. PHILIPP, 0. et SCHRADER, B. (1974) “Ap plication of thermal, chemscsl and mechanical Activation in clinker burning”, 6t In Congr Chem. Cement, Moscow. LEHMANN, H, et THORMANN, P. (1963) "Uber den Einfluss der Kalksteinkoragrisse auf die Klinkermineratbildung", Tanind. Ztg. 8], 389. LEHMANN, H., LOCHER, F.W. at THOR ~ MANN, P. (4964) "Der Einfluss der kalksteip korngrbase suf die Klinkermineralbildung ith Temperarurbereich von 850°C bis 1450°C", Tonind. Zig. 88, 409 et 537. RITZMANN, H. (1976) "MBglichkaiten und Grenzen der Vorkalzination bei verschiedenen Drehrohrofenverlahren", Zement-Kalk-Cips 29, 7. 10.- BUCCHI, B, (1978) "Caleining systems outsi- de the suspension preheater cement kilns", UL Cemento 75, 411. 11. SULIKOWSXI, mixes", Proc. Tokyo P.1, 106, 12.- BLAISE, R.,MUSIKAS, N, et TIEDREZ, Hl. (1971) "Nouvelle méthode de décermination ci nétigue de aptitude & la euisson d'un cru de cimenterie", Rev. Mater. Constr. N* 674 ~ 675, 287. ANCARDI, M.T. (1962) "Relazione interna Laboratorio Centrale Haleementi", 18 juin. lé.- 8. TE DES CIMENTS FRANCAIS (1975) "Px vate communication", Paris. P. (1968) "Burnability of raw th int. Symp. Chem. Cement, MUSSGNUG, 6. (1983) "Sinterfilnigkett vom Rehmeblen. Tagunsber. der Zementingustrie H 7, Dusseldort 14 +17 Mei 1952 p. 33° Zement-Kalk-Gips 6, 45. 16.- Dyckerhoff, K. (1958) "Untersuchungen an Ze mentrohmischungen mit sehr hohem Siliketm dul", Zement-Kalk-Gips 11, 198. KOCK, H., REY, G. et BECKER, F. (1974) ‘A statistical model for determining the burns, bility of cement raw mixes", 6th Int. Congr. Chem. Cement, Moscow. 16.- LUDWIG, U. et RUCKENSTEINER, G. (2973) “Binflass der Phasengrenzen bei der Klinke bildung", Proc. 11th Conf, Silicate Ind. Bu pest Pel, p. 355. LUDWIG, U. et RUCKENSTEINER, 6. (1973) Einflisse auf das Srenaverhalien von Zement rohmehlen und die Klinkerqualitit", Tonind 21g 91, 313. 20.- LUDWIG, U. et RUCKENSTEINER, G. (1974) “Uber die Brennbarkeit von Zementrohinehlen Cem. Concr. Res. 4 239. 2l.- LUDWIG, U. ot DARR, G.M. (1975) "Wer de Brennbarkeit von Zementrohmehl", Zement - Kalk-Gips 28, 421. 22.+ DAHL, L.A. (1998) "Estimation of phase com- position of clinker inthe aystem C38-C25- ‘gA-C,AF at clinkering temperatures"; Rock Pleas fy 4b 46,62, 0k oe ad 3B tS, 5D 23.- SPOHN, E., WOERMANN, E. et KNOFEL, D, G4968) "A relsnement of the lime standard for mula", Proc. 5! Int, Symp. Chem. Cenent, Tokyo Pa, 172, (1969) "Zine vorfetnerte Kalkstandandformel”, Zement-Kalk-Gips 22, 55. CHRISTENSEN, NH. (1979) "Burnabiliy of cement rew mixes at 140°C, I The effect of the chemical composition”, Cem. Concr. Res. 9, 219. 25. LEGRAND, J. (1961) "Relations entre les ca ractéristiques d'un clinker et celles des. ses matiéres premieres", Rev. Mater. Constr. NP 554, 469; N* 555, 505; N° 556, 25; N* 557, 50; N*'588, 83. 26.~ BUCCHI, R. (1965) "Legantt tdraulici", Enei- clopedia Scienze e Tecniche SADEA Firenze 19.- 27.» GLAUSER, A. (1966) "Berechmingen von Por, tlandzement - Robxischungen mittels der Ae = quivalentiorm von Niggliund Kills Kelkeandara! I Teil : Zement-Kalk-Gips 19, 238, 1 Teil Zemant-Kalk-Gips 2, 102. Tit Teil: Zement- Kalk-Cips 20, 287. GLAUSER, A. (1970) "Die Auswerting des ihl'schen’Silikatmoduls in aequivalentnorma- 28,-ae 32. 3. a. 38. 3. 0. a 42. 43. wven Berechmungen von Portlandzement-Rok - rmischingen", Zemeat-Kelk-Gips 23, 312. GLAUSER, A, (1972) "Der Tonerdemodul in equivolentnormativen Berechnungen von Roh- mnischingen", Zement-Kalk=Gips 25, 202. FENAROLI, €. (1929) "Rappresentaziont ara fiche e calcolo dei Tegan idraulics", Ind. kale Con. 28, 85. SESTIM, Q. (1961) "I sistema quaternario CaO $iGp~AlZO5- Fez e Te sue applica ~ Toni", Chin. Inds (sian 23, 163. BUCCILL, R. (1952) "Procedimente 4 appros~ simizione successiva per il caleolo di misce — ia de cemento mediante il metodo arafico di Fe naroli", ind. Ital. Cem. 22, 292. GLAUSER, A. (1974) "Sher Methoden der phischen Darstellung in der Zementchemie ine fer Bercksichtzing der Aequivalentnoma", Zewent-Kalk-Gips 2, 610. XIROKOSTAS, D.A. et ZOPPAS, C.F. 17) problem of cement blending optim mm. Conc. Res. 7, 503. GUTIMANN, A. et GLE, F. Mangan im Zementklinker,zugleich ein Betrag zur Konsitdondrage des Zenentes", Zament= Kalk-Gips 18, 500, 537 et 570. SPOHN, E, (1932) "Die Kalkgrenze des Por- Mlandzements™, Zenent 21, 702, 717 et 731. LEA, F.M. ot PARKER, T.W (1936) "The quatemazy system CaO A1j03 - Si02- FezO3 {hn relation o cement technology”, Blig. Re Pap. N16. BOGUE, R.H. (1929) "Calculation of the com- pounds in portland cement", Ind. Eng. Chem. Anal. Ea. 2, 192 HERATH BANDA, RM. ot GLASSER, F.P. (1978) "Role of iron aod aluminium oxides as flanes during the burning of portland cement", Cem. Concrs Res. 8; 319. KUHL, H., (1913), Zement-Protokoll des V.D. P.Z.F. G5. KUHL, H, (1925) "Der junge Zenenchemiker", Zement 15, 636. OSBAECK, B, (979) "Der Einfluss von Alka lien auf die. Festigkeitseigenschaften von POE dandzement”, Zement-Kalk-Cips 32, 72. WETZEL, E. (0911), Zement-Protekoll des V.D.P.Z.F, 281.3 (1912) 217; C813) 347 et ana 145. KOHL, H. (1929) "Die Berechnung der besten Zementroimiachung", Zement 18, 833 et 868. KOHL, H, (1993) "Der Kalkstandard der Por Bie 54 56. 58. , 1-1/33 tlandzemente",Tonind. Ztg. 57, 460- CHRISTENSEN, N.H. (1978) "The effects of magnesia on lime combination in clinker World Com. Technol. 8, 223. POLLITT, H.W.W. et BROWN, A.W. (1968) “The distribution of allalis in Portland cemert clinker", Proc, 5é* Int, Symp. Chem. Cenen, Tokyo Pl, 322. KNOFEL, D. et SPOHN, B, (1965) "Der quan tative Phasengehalt in ‘Portlandzementklin = ern’, Zement-Kalk-Gips 22, £71. HORNAIN, H. (1971) "Sur la répartition des lénents de transition et leur influence 7 quelques propristés du clinker ot du ciment", Rev. Mater. Constr. N® 671-672, 23 KRISTMANN, M, (1977) "Portland cement clinker, Mineralogical and chemical investt- gations P.tet P. 1", Cem. Coner. Res. J, 649 0t 8, 93. HANSEN, W.C. (1968) "Potential compound composition of portland cament clinker", J-Ma ter. 3, 100, MAJUMDAR, A.J. (1966) "The ferrite phase n cement", Trans. Brit. Ceram. Soe. 6&y 105 TARTE, P. (1966) "Study of interaction bet- ween tricalcium aluminate and diealcium alu- inoferrite", Silieates Ind. 31, 243. SCHLAUDT, C.M. et ROY, D.M, (1965) ‘Crystalline solutions in 3CaOAL309 inthe join CagA1g03 - CagFe,03", Navare 207, 819, BUCCHL, B. et BUZZBTTI, F, (1975) "inter~ pretation of modules as a function of potentia! Composition of portlend cement clinker", Cem. Technol. 6, 72 HEILMANN, T. (1952) "The influence of the fineness of cement raw mixes on their barnabi, sy", Proc 384 Int. Symp Chem Cement, London, 711 TOROPOV, NA. et LUGININA, 1.G. (953) "Effect of the grain size on assinitation of CaO during burning of portland cenent", Tse sent 19, N° 2,17 SWAYZE, M.A. (1946) "A report on studies of: 1 the ternary system CaO = CsA3-C2F; Tine gunternary system CaO CgA3- C2F ~ CpSillltte quatermary system as modified by SKiagnesie”, Amer. J. Set 264, 1 ot 65 LEA, F.M. et PARKER, T.W. (1934) "Inve ‘tigation of « portion of the gus ternary sysem Ca0- A103 Sip ~ Fey the quaternar systen GO Cy8~C5A3-C,AF", Pal Trans. Br Soc. 234, N° 731; Ie SYCHEV, M.M, (1962) "The tectinologieat1-1/34 properties of cement raw mixes", Gosstroy - feat 131 61, JOHANSEN, V. (1977) "Coceibn de clinker de cenento portland en hornos rotatorios", Mat. de Constr. N° 165 - 167, 85. 62,- VOSTEEN, B. (1971) "Physikalische und che nnische Kinetik endethermer topochemischer Gtelchigewichtareaksionen", Chem. Ing. Tech. 2.43, 478. 63.- ZACHAROV, G.V. (1973) "Das Brennen von genahlenem Kallsiein in. schwebendem Zus ~ tani", Streit, Mater. 19, 11. 6é.- VOSTEEN, B, (1974) "Vorwirming und voll- omnens Kalzination von Zementrohehl ia einem Schwebegeasystem, Zement-Kalk-Gips 21, 443. 65.- OHME, K., SCHRADER, R. et MULLER, A (1975) hKsseuik dor thermischen Dissosiation ‘yon Kalkstein und Zemenrohimehl im Flugetas- Breaktor”, Silikattechnik 26, 403. 66.- MULLER, A, (0977 "Zum Einfluss verfahren stechatacher uad stofMicher Parameter auf die Kinaukder thermischen Zersetzung von Kalatunkarbonat", Proc. 12% Conf. silicate Ind. Budapest P.1, p. 565. MULLER, A., DAHM, B, e¢ STARK, J. (1979) "Beterag 2ur Kine der Calciumearbe natzersetzang", Zement-Kelk-Gipe 32, 78. 66,- DE KEYSER, W.L, (1965) "Studies'on the solid state reactions between 5103, A103, MgO, Cad, Fe705, 2109", Proc. 6h Cont. Silicate Ind. Budapest p. 138. HEDVALL, J.A, (1952) "Binfthrung im die Fe suxdrperchemie', Vieweg u. Sohn, Braun - sehweig. 70. ADDA, ¥. et PHYLIBERT, J, (1965) "La aif fasion dans les eolides", Tome Il, chap. XIL et Xlll pp. 667 et 751. Presses Univ. Paris. 7L.- CHRISTENSEN, N.H. et SIMONSEN, K.A. G970) "Diffusion in portland cement clinke?", J. Amer. Ceram. Soc. 53, 361- JOHANSEN V. et JEPSEN, 0.1. (1972) "Burnabiliy of raw mix: Theoretical appro- ch to the particle size of C&O in clinker" Tat Ana. Mest. Am. Ceram. Soc, Wha shington. RUMYANTSEV, P-F, (1966) "On kinetics of formation of yortland cement clinker", Proc: Stine, Symape Chem. Cement, Tokyo P-L, in. Th. KONDO, RB. et CHOL, nisms and Kinetics of portland cement clinker formation for an example of the solid state reaction in the presence of «liquid phase”, Proc. sit lat. Symp. Chem. Cement, Tokyo 7 .- & a. 8 TULL LLCO EERRLLLLLL Luli Pal, 163, SYCHEV, M.M. et ASTAKHOVA,M.A. (1962) Influence of the limestone fineness on the bar, nability of the cement mixes", Tsement 28, N° 3, 12. ~ THORMANN, P. (1968) "ber die Bedeumng der getrennten Vermahlung von Kalkmergel und Sand fir die Klinkernineralbildung beim Zementbrennen", Tonind. Z1g- 92, 7. KAWAMURA, S. et MIZUKAMI, K. (1969) "The influence of quar and feldspsr om the burning process of cement clinker”, Rev. 200 Gen. Meet. Cem. Assoc. Japan, Tokyo p. 50 KANTSEPOL'SKUL, 1.S., TEREKHOVICH,S, V. et DROZHZHIN, A. Kh, 0971) "Optimize tion of the fineness of the grinding of a mixture of raw materials", Tsement 37, N* 9, 16. CEBRIAN ZALAMA, J.L. (1973) "La sfitce bre en los crudos de cemento portland”, Cam. Hermigon 44, 295. CEBRIAN ZALAMA, J,L, (1973) "Quinicada ensayo de aptinid © cocctén de crudos de ce = mento portland", Cen. Hormigon 44, 693. FOREST, J. (1973) "Erade de certains ming raux du clinker et de la réactivité des erusde clmenterie", Silieates Ind. 38, 121,149 et 175. COURTAULT, B. (1963) "Ende des réactiont 2 Vétat solide jusqu'a 1600°C eu moyen de I's nalyse thermique différentielie", Rev. Mater Constr. N° 569, 37; N® 570, 67; N° 571, 110; N° 572, 143; N* 573, 190. RICHARTZ,, W. (1971) "Ausschalten von Feh- Terquellen bei der Roentgenflucreszenzanaly ~ se", Zement-Kalk-Gips 24, 72. LOCHER, F.W. (1975) "Einfluss der Kiinker hersteliung auf die Eigenschaften des Zeman", Zement-Kalk-Gips 28, 265. BUCCHL, R., VALOTI, S, et GIOVANETTI, G. (1975) "Visita delis cementeria di Bathd Jn Ciments Canada Lafarge. Rapporto Ttalee= Mt S.p/As; Bergamo", june BUCCHI R. et GIOVANETTI, G. (1978) "Vist ta della comenteria di Bussac della 8.16 des Ciments Francais. Rapporto Ttaleementi Sp. A., Bergamo", octobre. BECKER, F. (1970) "Einfluss verschieden - langer Mahldauern auf die Eigenschaften des Rohmehls", Vertrag bet 8. Chemikersitzung der Gruppe Holderbank. Reference (4) de V- R, Plrunder et H. Wickert in Zement-Kalk- Gips 23, 147. SCHRADER, R., HOFFMANN, B., PLANUZ, H. et HENNEBERGER, J. (1970) “Uber aksi- ‘ertes Caleiamoxya", Zément-Kelk-Gipe 23194,89. a. 96. 95; 96. 97. 98. 100. 101. 102, MCHEDLOV-PETROSYAN, O.P., SHCHE- TKINA, T.YU. et FATALIBV, 8.8, (975) "Die Rolle metastabiler Phasen bei Silikatbil dungeprozessen", Silikattachnik 26, 258. MCHEDLOV-PETROSYAN, 0.P., SAPOS- HINIKOVA, N.1., SKRYNNIK, LW. et SH CHETKINA, T. YU. (977) "Untersuchung des Bisflussesder Kalkstruktur auf die chemi- sche Aktivitdt bet der Klinkerbildung", Sili- kattechnik 28, 234. AKATSU, K. ot IKEDA, T. (1971) "An expe~ dient method for determining reactivity of 3 liceous raw materials", Rev- 25th Gen. Meee Cam. Assoc. Japan, Tokyo P» 47- BECKER, F. et SCHRAMLI, W. (1960) "WE tandzement imLichte neverer Anschawungen der Festkixperchemie", Zement-Kalx-Cips 43, 222, SCHRAMLI, W. et BECKER, F. (1969) "Die Reaktionen zwischen Kak und KieselsSure verschiedener Axtivitit im Temperaturberei- Chiuncer 100°C", Zement-Kalk-Cips 13,265 SCHWIETE, H.E. et HECHLER, B.W.196 Olid state reactions of silicate systems", Proc. 8" Conf. Silicate Ind. Budapest p-93. HEDVALL, J.A. (1966) "Solid state chemi - stry", Elsevier Publ. Co Amsterdam. MAKASHEV, 9.D. (1970) "Burnability of eg, ment raw mises", Tsement 36 N° 1, 14. MAKASHEV, 3.D. (1974) "Effect of maw m terial physico-chemicsl properties on reae~ tivity of raw mix and on clinker minerogenci- ‘ processes",Proc. 6 Int. Congr. Chem Cement, Moscow. DASGUPTA, A. (1975) "Burasbility of ce -w materials and clinker formation netics", Chem. Era 11, 7 RENNEN, H. ot SCHWIETE, H.E, (1963) "Reactions dfkaolinite and enfcium oxide be ‘tween 450° and 800°C", Proc. 7% Conf. Si- Tcate Ind, Budapest p< 171 SCHNEIDER, F.U. (976) "Untersuchungen Dar Daratelling and Anaiyse aktiver Feetetof fevstinde ale Folge intensiver Mahbesnapm Chung" Aufbereit. Techs 19, 452. WOLFE, J.A. (1955) "What to look for in se ecting cement raw materials", Rock Prod. 5B, aug. 132. KIEFER, CH. (1950) "Stabilité et classifica- tion des minéraux phylllteux. Application aux argiles de cimenterie", Rev. Mater Constr. N° 422, 3353 N* 423, 358; N* 424, 19; N* 425, 535 N° 426, 843 N* 427, 109; N° 428, 141; N° 429, 191; N° 430, 225; N° 431/32, 58. 103. 108.- 108.- 109, 110. 13. 114. 15. 116. un. 118.- 1-1/35 UTELSPACKER, H, et VAN DER MA’ - REL, H.W. (1968) "Atlas of electron micro- scopy of clay minerals and their admixm ~ ree", Elsevier Publ. Co., Amsterdam. LEROUX, A, (1975) "Les differentes textu- res et leur influence sur le comportementdes sols argileux et marneux”, Geologia applica- me idrogeologia Vol. X, P. Il, 67. SCHWIETE, H.E. (1956) "Der Einfluss der Tonminerele auf die Staubbildung beim Kl kerbrand" Zement-Kalk-Gips 9, 351. LEHMANN, #., WUHRER, J. et LAHN, W. (1958) "Das Brennverhalten von Kalksveinen aus verschiedenen geologischen Formatio - nen", Tonind. Ztg. 82, 434, 486, 542. SCHWIETE, H.B. et ZIEGLER, G. (1956) "Bettmag aur Thermochemie des Kalkes" Tonind. Zig. 80, 97- ora GRIM, R.E. (1968) "Clay mineralogy’ Edt, McGraw-Hill Book Co., New York. GRIM, R.E. (1962) "Applied clay minerale ~ gy", McGraw-Hill Book Co., New York. MILLOT, G. (1964) "Géologie des argiles", Masson et Cie, Eat. Paris GOERG, W. (1956) "Reaktionen zwischen Kalk und Tenminevalien", Tonind. 2tg. 60, 219. HILL, G. ot SCHWIETE, HE. (1958) "Der Einfluss des Mineralbestandes und dar Ver- forming ¢af das Brennverhalten von Grana ~ tien aus Zenent-Rohmeblen", Zement-Kalk- Gips 1, 181. LUDWIG, U., MULLER-HESSE, H. SCHWIETE, 1.£. (1960) "Uber die Konsti- tution und das Eriufrten tydraullscher Hake’ Zement-Kallk-Gips 13, 443, BERECZKY, A. (1961)"Die Besrebun gen zur Erzeugung nochweriger Zenento", Tontnd Zig. 85, 37. MCHEDLOV-PETROSYAN, 0.., SAPOS- HNIKOVA, N.1. ot SHCHETEINA, T. YU. (1975) "Theredinamte methods for studying the reactivity of raw material mixtures and cenents", Tsement 41 N° 10, 17 BUTT, YU. M., TIMASHEV, V.V, et VOL- KOV, V.V. (964) "Effect of mineralogical composition and structure of initial compo ~ nents on the reaction eapscity of initial mi- xes", Tr. Gos. Vses, Nauch, ~ losled. I Teen. Prom. N* 20, 82, TALABER, J. (1968) "Solid phase diffusion of CaO in ihineral substances", Proc. 9% Conf. Silicate Ind. Budapest p. 171 RAUSCHENFELS, E, (1976) "Die Sinterbar1-1/36 119. 1a. 126. 125. 128. 17. 123, 130 131 132. kkeit von Zement-Rohmehl”, Zement-Kalk- Gips 29, 78. ASANO, T, (1965) "Onoda cement company's lime esleinition process in cement manufact re", Pat Quarry 58, (1), 184. FATALIEV, 3.A, (1963) "Effect of limesto- ne microstructure on the petrographic cha - acteristics of pordand cement clinker and the strength of concrete”, Dokl. Akad. Nak, Azerd. SSR 190), 4. FATALIEV, 5.A. (1965) "Special festures of mineral formation sx fring of chongee vib limestones of various microstructures", Tas, nent 32 Ne 3,5. PHILIPP, ©, 1973) "Einfluss des Afhezver Inltons auf den Gazbrend von Zementkliner Silikatechnik 24, 265. IMLACH, J.A. et HOFMANNER, F. (974) investightion of linker forwation by DTA and optical microscopy”, 6! Int. Congr. Chem, Cement, Moscow: MARSCHNER. H. (1968) "Relationship bet- ween carbonate grain size and non-carbon~ qe content in carbonate sedimentary rocks From: "Recent developments in carbonate sg dimentology in Central Europe" ", by G. ME ler and GoM. Friedman, Springer-Verlag, New York p. 55 BLAINE, R.L., BEAN, L. et HUBBARD, E. K- C961) “Occurrence of iainor and trace © Tements in portland coment", Pare 1, Dail = Ging Science Series 2, National Bureau, of Standerde, Auge De 3Se BLAINE, 1. (1968) "A starietionl snidy of the effects of trace elements on te proper = ties of portlané cement", Proc, 5! Int Symp. Chem: Cement, Tokyo Plt, 86. DYCKERHOFF ZEMENTWERKE .<., WIESBADEN (1979) "Private communication 39.03.1979". HOLDERDANK “MANAGEMENT UND BERA~ TUNG A.G., TECHNISCHE STELLE, HOL- DERBA.K (1978) "Pri ate commasieaton 20, 12,1878". LAFARGE CONSEILS et ETUDES, PARIS 979) "Private commrtenton 23.07.1979". S.TE DES CIMENTS FRANCAIS, PARIS 979) "Private conmanication 25.06.197 KLEMM, W.A. et SKALNY, 1.01976) "Mine nd flones in the clinkering pre Sees", Com: Ress Progre Chap. 14, 59. TEOREANU, 1. (1974) "The chemtatry of White and coloured cements", 6t Ine. Congr Chem. Cement, Moscow ralizers STO UULLLLLCUCEEERLLL LL LLL LL 133.- HANSEN, W.C, (1930) "Influence of magne- 104.- TOROPOV, N.A. et RUMYANTSEV, P.F .135.- TOROPOV, N. sla, ferric oxid and soda upon the temperaty, 72 of liquid formation in certain portland ca, ment mixtures", J. Res. NBS 4, 55. (1965) "Formation of portland cement clinker, Zh. Prikl. Khim. (Leningrad) 38: 1, Factors controlling the rate of clinker Formation. (3), 660; Tl, A method for the study of the kinetics of solution of clinker minerals in the liqud phase of portland cement clinker. (), 1123; UL. Ksnetice of dissolution of ealesum oxide in the liquid phase of cement clinker. , 1614; IV. Kinetics of dissolution of dicaletum sili- ete in the liquid phase of cement clin ker. (8), 1858; V. Kinetics of dissolution of tricaleium stl, este in the liquid phase of cement clin er. (B), 1860 © 1558. Av, RUMYANTSEV, P.. et FILIPOVICH, VR. (1964)"Kinetics of disso lation of CaO,CJ5,C2S and S10 in a molten cement clinker”, J: Phy- Chem. 38, 528. 136,- TOROPOV, N.A. et RUMYANTSEV, P.F 137. 138. 139.- SHMIDT, TU, uo. ia. 1967)" Over die Bildungskinewk vow Zament Slinker", Silikattechnik 18, 322 et 49. BUTT, Y.M., TIMASHE, V.V., et 050- KIN, A.P. C374) "The mechanism of clin - ker formation processes nnd the modification ofits structure”, Gt Int. Congr. Chem. Ce- ment, Moscow. SYCHEV, M.M. (1968) "Problem of admixty res", Proc. St Int, Symp. Chem. Cement. Tokyo Pol 157. A, (1959) "Effect of compost tion on properties of alka silicate glasses Structure Glass, Proc. All-Union Conf. Glassy State, 3% (Leningrad) 274 GRACHIAN, A.N., ZUBEKHIN, A.P. ot LEONOV, VM. (1971) "Dependence of the liquid phase viscosity of a cement clinker on the characteristics cations end anions of ineralizers", 2h. Prikl, Khim. (Lenin - sea) 44, 189. PAULING, 1, (1960) "The nature of cheint. cal bond", Cornell, Univ.Press. New York, P- 6s 142.- WHITTAKER, E.J.W. et MUNTUS, R. 0970) Jonie radi for use in geochemistry", Geo - chim. Cosmochim. Acta 34, 945. 143.- OKOROKOV,, §.D_,GOLINKO-VOL'FSON, 5. Wt145.- war. 153.- L., SHEVELEVA, B.1, et YARKINA, T.N. (1957) "Comparison of salts group as poten - tial mineralizers in firing portland cement clinker”, Tsement 23, N? 3,5. PYACHEV, V. et TIKHONENKOVA, Z 2966) "Assimilation of lime during synthesis of clinker minerals and calcination of clin - ker in the presence of addition of Cr03, BZO3, Py0s and V205", lav. Vyssh. Ucheb. Zaved.. Xtim. Khim. Tekhnol. 9, 802. PONOMAREV, 1.F., GRACHIAN, A.N. 2% ZUBEKHIN, 4.P. (1966) "Influence of mine rralizing additives on the process of cement clinker formation as a function of the electro hogetivity of the mineralizer cation and axtor Dokl. Akad. Nauk SSSR 165, 410. TEOREANU, I. et TRAN VAN HUYNHC970 "Wechssbeziehingen zwischen der minerelt = sierenden Wirkung der Stoffe auf die Por - ‘landzementklinkerbildung und dem periedi - schen System der Elemente", Silicates Ind TEOREANY, L. et TRAN VAN HUYNH) "Lunfluence des composés fuorés surles pro cossus de eristallisat et sur la compost tion des constimants minéralogiques des clin kers de cimenportland", Rev. Mater. Con= str. N° 656, 73. SHUBIN, V.1, (1974) "Investigation into eon solidation of portland cement clinker", 62 Int. Congr. Chem. Cement, Moscow. HESS, P.C, (1971) "Polymer model of sili- cate melts", Geochim. Cosmochim. Acta 35, 289. KURDOWSKI, W. et SZUMMZR, A. (1968) "Linfluence des composants mineurs sur les propristés hydrauliques au clinker portland" Silicates Ind. 33, 183. TEORENAU, I, et ENCULESCU, M. (1973) "Influence des microadditions d'exydes des mésnux de transition sur lee propriétés des silicates du clinker de ciment p Mater. Constr. N° 684, 31. KURDOWSK1, W, (1974) "Influence of minor components on hydequlic activity of portland coment clinker”, 6t" Int, Congr. Chem. Ce~ ment, Moscow. ONO, Y.et SODA, ¥. (1965) "Effect of theexl stallographic propersies of alite and belite on the strength of coment", Semento Gijutsu Nempo 19, 93. BUTT, Y.M., TIMASHEV, V.V. et MALO- ZOUN, Lil, (968) "The erystallization of compounds in the presence of Cr703, P25, or $03 and the properties of the resultant Cement", Proc. 5® Int. Symp. Chem. Ce ~ 1-1/37 ment, Tokyo P. 340. 155.- SAKURAL, T., SATO, T. et YOSHINAGA, A. (1968) "The effect of minor component fon the early hydraulic activity of the major nd cement clinker", Proc. ~ Symp. Cham. Cement, Tokyo 156,- BOIKOVA, A.1. (1968) "Ordered and disor dered strictures of wricaletum silicate solid solutions", Proc. 90 Conf, Silicate Ind. Bu dapest p. 41. FIERENS, P. et VERHATCEN, J.P. (972 "Senactare end reactivity of cheomiim-doped tricalcium silicate", J. Amer. Ceram. Soc. 55, 09. REGOURD, M. et GUINIER, A. (1974) "The erystel chemistry of the constituents of por~ rnd cement clinker", thint. Congr-Chem. Cement, Moscow. 159.- CAROBBI, G. (1971) "Travato ai minerslo ~ sia", Vol. I page. 347 et sega. USES - Bai- Zion! Scientifiche Fixenze. 160.- MAYCOCK, J.N, et MC CARTHY, M Jr. (1973) "Crysat latice defects in dicalcium silicate", Proc. 11% Conf, Silicate Ind. Bu dapestP.1, 385. 161,- PRITTS, I.M., et DAUGHERTY, K.E. (2976) "The effect of stabilizing agents on the hydration rata of B-C25", Com. Con Res. §, 783. 162,- GRZYMEK, J. (1959) "Die Beatnflussung der Alitbildung im Porlandzementklinker", Silt- kettechnk 10, 81. 163.- VOGEL, E. (1960) "Heterogene Reaktionen an Zemantdvehofen", T-l, T. IL, et T. TL Silikattechnik L1, 476, 512, 572. 164.- GOES, C, et KEIL, F, (1960) "Wher das Verhalten dev Alkslien beim Zementbreanen’s Tonind. Ztg+ 84, 125. 165.- WEBER, P. (1960) "Wirmeilbergang im Dre- hofen unter Bericksichfgane der Kreislaufva rginge und Phasenneubildung", Zement-Kalk Gipe Sonderau 166.- MUSSGNUG , G. lifrage in Schwebegaswlrmeiausels Zewent-Kalk-Gips 15, 197. = WEBER, P. (1964) "Alkaliprobleme und Al- kalibescitigung bei virmesparenden Trocken jSfen", Zement-Kalk-Gips 17, 335. 168. - VIKTORENKOV, V.J. et VOLKONSKIL, B. V, 965) "Circulation of alkalies in furna ces with cyclone exchangers", Tsement 31, N° 6,12. 169.- RITZMANN, H. (1971) "Kretslufe in Dre-1-1/38 170. an. 176. 175. 176. 17. 178. 190, 11. 182. hofensystemen", Zement-Kalk-Gips 24, 338. LOCHER, F.W., SPRUNG, S. et OPITZ,D. 4972) "Reaktionen im Bereich der Ofengase. Krelsliufe flidtiger Stoffe, Ansiize, Besei- igen von Ringen”, Zement-Kalk-Gips 25,1. BUCCHI, B. et GANDINE, P.A. (1972) "A contribution to the knowledge of the cycles of some volatile compounds in coment kilns. I- Theoretical considerations. Il ~ Experimen= tal results and their interpretation. Ill - Wet process", Chim. Ind. (Milan) 53, 819,825,354 1097. RITZMANN, H. (1972) "Raw meal peohester and alkali problems", Rock Prod. 8! Ins. Cement. Ind. Seminar Chicago, dee. 3-6 pe 39. TEOREANU, I., PURI, A. at GEORGESCU, M. 975) "Volatility of alkalis from raw me - terials and raw mixes for portland cement a, kers", Mater. Constr. (Bucharest) 5@2), 55- LOCHER, F.W. (2978) "Verfahrenstechnike und Zementeigenschaften", Zement-Kalk-Gips 31, 269. CARLSEN,H.S, (1966) "Behavior of elkelies during the burning process", Rock Prod. 69 ©), 87. BIBGE, N. et PEARSON, L. (1977) "The theory and devalopment of bypass systems for preheater and flash ealeinerkiin system", IEEE 197 Cement Ind. Techn, Confer. Oms= ha (U-S.) may 16-19. SVENDSEN, J. (1978) "Alkaliarmer Zement aus HochalkaliRohatoffen mit energiewires- chaftlich gllastiger Verfahrenstechnik", Ze- mont-Kalk-Gips 31, 281. WARSHAWSKY, J. ot PORTER, E.8.(1978) "Werminderang des Alkalt und Sehwefelgeh- alts im Kisnker durch einen Ofen-By pase im Vorealeiniersystem", Zement-Kalk-Gips 31, 284. SPRUNG, S. (1965) "Das Verhalten des von Zementklinker™ NEWKIRK, T.F. (1951) "Effect of $03 on the alkali compounds of portelnd cement clin ker", RP 2261, 1, Res. N.B.S. 47, 349. GUTT, W. ot SMITH, M.A, (971) "Studies of sulphates in portland cement clinker", Com. Technol. 2, 143. FUKUDA, N. (1961) "Effect of calcium sul- phate on the compound composition of por ~ ‘land cement clinker", Semento Gijusts Nem- pol, 25. FUKUDA, N, (1961) "Constitution of sulpho- aluminows clinker”, Bull, Chem. Soc. Ja ~ 185. 186. 187. 188. 189. 190. a1. 192. 193. 194. 195. 196. pan 24, 138. KOSTOV, B. (1965) "Mineral formation du ~ ring firing of sulphatized porddand cement raw materiel mixtires", Compt. Rend. Acad. Bulgare Sei. 18, 335. BUDNIKOV, P.P. (2967) "Effect of alkalies and calcium sulphate on the synthesis of cal cium aluminates and of portland clinker", Cemens-Wapno Gips 22, T.A. et AKHMEDOV, M.A, Influence of calcsum sulphate on the mineralization processes during the fringof cement mixtures", Proc. 9 Conf, Silicate Ind. Budapest p. 253. GUTT, W, et SMITH, M.A. (1965) "A new calcium silicosulphate", Namure 210, 408, GUTT, W. ex SMITH, M.A. (1967) "Studies of the sub-system Ca0-Ca0- Si09-CaSO,", Trans. Brit. Ceram. Soc. 66, 557. GUTT, W. et SMITH, M.A, (1968) "Studies fof the role of eslcium sulphate in the manulas ture of portland cenent clinker", Trans. Brit. Ceram. Soc. 67, 487. SMITH, M.A, et GUTT, W. @970) "The ef- fect of imagnesium and sulphate ions on the hydraulletty of triealesum silicate", Cem. Technol. 1, 187. PLIEGO.CUERVO, Y.B. et GLASSER, P. 1979) "The role of sulphates im cement clinkering: subsolidue phase rela system CaO-A1g03-Si0z-SO3", Cem. Res. 9, 51 OKOROKOV, 5.D., GOLYNKO-VOL'FSON, S.L. et KUKUSHKINA, B.S. (1960) "The mi neralizing action of sulphates in the synthe ~ sis of separate minerals of portland cement clinker", Tr, Leningr. Tekhnol. Inst. im. Lensoveta (55), 84. OKOROKOV, 5.D., GOLYNKO-VOL'FSON, S.L. et KORNEEV, V.L. (1960) "Change in the strength of dicaletin silicate depending on the nature of the stabilszing admierare’", Tr. Leningr. Tekhnol. Inst, im. Lensovers 6), 93. AKHMEDOV, M.A. et RAGOZINA, T.A. (961) "The effect of calcium sulphate on the sintering point of the portland cement clin ~ ker", Vop. Ispot'z. Miner. Rast. Syr'ya Sredno: Azti, BUDNIKOV, P.P. et KUSNETSOWA, LP. (1962) "The effect of gypsum on the formation of the minerals of the portland clinker", Zh. Prikl. Khim. (Leningrad) 35, 939. RAGOZINA, TA, et AKHMEDOV, M.A. (4962) "The effect oF CaSO, on the phase com,199. DL 202. 206. 208. - BUDMIKOV, P. ~ ABBASSL, GH. (1974) += AMAPUTL, M. = HATANO, H. G9 position of calelum silicates and aluminates at caleination", Uzb. Khim. Zh. - POD'YACHEVA, 1.B, (1964) "Gypsum as mi- neralizer ta clinker", T=. ‘tring of portland cement - BUDNIKOV, P.P. et AZELITSKAYA, B.D. (1964) "A praxcatinent of raw materials and its effect on the properties of cement", Ce ~ ment-Wapno Gips 11, 235. XUSNETSOWA, L.P. ex SAWELJEW, W.G. (1965) "Eigenschafven yon 3Ca0-3A103-CaSO, und sein Einfhss auf die Festigkeit von Klinketmineralien und Ze- ment”, Silikattachnik 16, 414 (Sonderheft). = TANDILOVA, K.B, ot DZHADZHANASHVI ~ 11, 0.5. (1968) "Mineralizeraccelerator of the clinker burning process", Sb. Tr.‘ lis. Gos. Neuch. - lesled. Inst. Stroit. Ma- ter. N°3, 150. = AZELITSEAYA, 8.D., PONOMAREV, LF BLONSKAJA, V.M., KARBIKEV, M.G., LO KOT A.A. et STEFANOV, V.M, (1969) "The effect of gypsum on the phase composition of alkali containing clinker", Tsement 35 N* 2 ~ VOLKONSKH, B.V. et SHTEYERT, N.P. (1970) "The relationship between cement pro, perties and alkali content of clinker", Tse tment 36 N* 10,6 YU. M., KAUSHANSKH, VE. TU KIL, A.M. et PANINA, N.S. 971) "The infiience of gypsum on the properties of coment containing alkalis", Tsement 37 N° 4,16. ‘Contras de de Vinflxence des méwux ale: composition et sur Vhydratation des Guclinker", Rev, Mater. Constr. N° 631, 315. .- PLIEGO-CUERVO, Y.B. et GLASSER, F. P. (977) "The role of sulphates in cement cliniering reactions: phase formation and melting sn the system Ca0-CaSi0,-CaSO,- K280,", Cem. Coner- Res. 7, 477. . et TSUMAGARL, A. (1968) "Formation of double salt in coment burning Proc. 5! Int. Symp. Chem. Cement, Tokyo 1, 135. y7.- SYLLA, HM. (1974) "Untersuchungen zur Bildung von Ansatzringen in Zementdrehoten! Zement-Kalk-Gips 27, 499. 2) "Uber das Verhaleen des Schwofels im Wirmetauscherofen", Ze~ ment-Kalk-Gips 25, 18. LLL 0 em a2, 213 24. a7. 2B. a9 220. 221 222. 1-1/39 ETOC, P. (1976) "Le four de cimenterie: pidge & soufre efficace", Rev. Mater. N* 701, 210. GUTT, W. et OSBORNE, G.J. (1965) "The system 2Cx0vS10y:CaF 2", Trans. Brit Coram, Sec. 65, 521 - AKALWA, 8., SUDOH, G. et TANAKA, M (1966) "Sadie on mineraitzing effect of CaF 2 and ternary compound in the eysten Ca0=Si02-CaFQ", Semento Gijutsu Nempo D, B. = GILIOL, C., MASSAZZA, F. et PEZZUO- LI, M. (979) "Studies on clinker oaleiam a, Ueates bearing CaF and CaSO,", Cem. Coner, Res. 9, 2! ASSAZZA, F. et PEZZUOLI, M. (1970) "Ricerche sti 12Ca0-7A1203 ¢ sul statema 12Ca0-7A1,03 -11Ca0-7A103-CaF 2", TL Cemento 67, it BRIS, C. et ROLANDO, P. (1966) "Sul meg, canismo di decomposizione dell'atluminato triceleico in presenza at fluoruro @ clorire ai ealeio", Annals di chimica, 56, 224. MASSAZZA, F. et PEZZUOLI, M. (1969) “Equilibres & état solide dane le © guaternaire CaO-A1z03-Si02-CaF)", Rev. Mater. Constr. N° 643, 81 ‘DSHMIDT, E.M., KRUGLYAK, S.L., LOVA, N1A. et SYRKIN, YA.M. 975) "On the mineralogical composition of clinker containing fluorine", Tsement Zaneayay. ~ IMLACH, J.A, (1974) "The influence of hea ‘ing conditions on the production of fluorine Containing Portland cement clinker", Cem. Technol. 5, 403. MASSAZZA, F., PEZZUOLI, M. et GILIO LL, C, (4970) "Relations d’équilibre & 'ézat solide dans le systime quate; A103 - Fey03 - CaF 2", Be N*683, 357. |. LUGININA, 1.6.(1961) "Influence of minere- lizers on the eliaker formation by rapid ft ~ ring", Teoment 27 N* 4, 20. = GUTT, W. (1968) "Manufacture of portland cement from phosphatic raw materials", Pro, Strint. Symp. Chem. Cement, Tokyo P.1, 93. = SCHLEGEL, E. (1968) "Die Einvirkung von Pluspat auf die Entsuerung von Magnesit, Caleit und Dolomit", Zement-Kelk-Gips 21, 386 - KLEMM, W.A., HOLUB, K.J. et SKALNY, J. 0977) "The effects of fluxes and mineral zers in lowering cement kiln temperatures",1-1/40 223,- COURTAULT, B. (1962) " 224. 225. 228. 227. 228. 229. 232. 233. 235. 236. -- NURSE, 8, .- SCHLAUDT, C.M. (1964) "Phase eq! Nea Progress Report N* 1, Jaly 1977 (Prepared for Div. Adv. Energy ant Resources, — Re~ search and Tecknotogy National Sctence Foundation Washington - Sactvité des ens de cimenterie”, Silicates Ind. 27, 141 - JOAHNSEN, V, et CHRISTENSEN, N.#t (4979) "Rate of formation of C38 im the sy - stem CaO-SiOy-A1z03-Fe703-MgO wath ad dition of CaF", Cem, Coner. Res. 9, 1 - TANAKA, M., SUDOH, G. et AKAIWA, 5, (1968) "New compound Cay 2i,019F2 in the system Ca0-510-CaF2 and the role of CaF: fm the buening of cement clinker", Proc. 5% tee Symp. Chom. Comsat, Tolgs Pte 12, - NURSE, R.W., MIDGLEY, H.G., GUTT, WW, et FLETCHER, K. (1966) "Bifect of poly morphism of tricaletum silicate on ite reacti= vity"+ Symp. on structure of portland ce - ment paste and concrete , Highway Research Board, 8.8.90, Washington, - WELCH, J.H. et GUTT, W. (1960) "The ef- fect of minor components on the hydraulic, of the calcium eilieates”, Proc. * Int. Symp. Chem» Cement, Washington, 1, 59. - SKALNY, J., HOLUB, K.J, et KLEMM, W. A, (1978) "Influence of potential insera‘stisl phase composition on clinkering react fCemento 75, 352+ = SPRUNG, S. et von SEEBACH, H.M. (1968) "Blugrhadshalt und Fluoremission von Ze = mentéfen", Zement-Kalk-Gips 21, 1 = NURSE, R.W. (1952) "The effect of phospha, te on the constitution and hardening of por and cement", J. Apple Chem- 2, 708. W., WELCH, J.H. ex GUTT, W. (1958) “A new form of tricileium phosphee", Nasure 192, 1230. - NURSE, R.W., WELCH, J.M. et GUTT, W. (1959) "High somperatare phase equilibria in the system dicaleium silicate-tricaleium pho- sfate”, J. Chem. Soe. N® 220, 1077. = GUTT, W. (1953) "High temperature phase equilibria in the system 2Ca0, 5:02-3Ca0, P205-CaO", Nature 197, 142. Libeia and cristal chemistry of coment and refracto- ay phases in the system CaO-MgO-A1203 - Fe703-CaFy-Pj05-5i02", Ph.D. Thesis, Pennsylvania State University = WILKOV, V, et TABAKOVA, N. (1967) "The effect of P2D5 on clinker formation and i quality of cement", Strois, Mat. Silk. Prom 2,6. - FIX, W., TROMEL, G.et HEINKE, R. (196 “Untersuchung zur Gleichgewichtee: der festen Phasen im System Ca- S10p-3Ca0, P05", Arch. Elsenhuetteny. 2, 979. 237.- SALGE, H. et THORMANN, P. (973) "her den Einfluss von P20s auf die Konstisation von Portlandzementklinker", Zement-Kalk- Gips 26, 532. 238.- GUYE, F. (1954) "Influence du phosphore ser Te ciment ourtland”, Rev. Mater- Constr. Na, 299.- ARAPOVA, A.S., PAKHOMOVA, V.1., et DEMKINA, L.iM. (1908) "Phosphorives in ~ crease the strength of portland cement", Teg, rent 35 N° 1, 10+ BUI VAN TIEN, BUTT, YU. M. et VO ~ ROBIEVA, M.A, (1969) "Action of apatite du, ring the firing of cement clinker", Tr. Mosk Teckhnol. Inst. N* 63, 165, AKATSU, K., MAEDA, K. et IKEDA, I. (1970) "The effect of Cry03 and POs on the Strengh and color of portland cement clinker", Rev. 24th Gen. Meet. Cem. Aasoc- Japan, Tokyo, 20. TEOREANY, 1, et TRAN VAN HUYNH (1970) "Minerallzing influence of apatite on the for~ mation of portland cement clinker", Rev. Roam. Chim. 15, 229. 243.- SIMANOVSKAYA, R.E. et VODZINSKAYA, Z.,, (1955) "Effect of fisor on the reaction of clinker minerals cristallization and forma~ tion in presence of phosphates", Teement 21 NP 5,12. 26.- TIMASHEV, V.V., GALPERINA, T.YA., BYKOVA, S.N., SEVOSTIANOVA, L.1. ex YANKOV, N,F. (1979) "Effect of phosphorus on phase composition and properties of ce ment produced of high-allali raw materials", Tsement 45 N* 3, 6. MOORE, A.E. (1965) "Examination of « po: ‘and cenent clinker by electron probe micro- analysis", Silicates Ind. 30, 445+ PONOMAREV, 1.F,, GRACHIAN, A.N. et ROTYTSCH, N.W, (1968) "Binfluss von Kom, binationan der Oxide von Obergengselementen aul die Etgenschafien des Weissen Portland zements”, Silskattechntk 28, 69. 247.~ SAKURAL, T. et SATO, T. (1968) "Written, discussion on "Analysis of portland cement ma. clinker" Yamaguchi G, et Takagi 5.) 5% Int. Symp. Chem. Cement, Tokyo P-L, 2a 248.- SYCHEV, M.M., KOPINA, G.1. at ZHUR - BENCO, V.B. (1969) "Phase distribution of alloying additives and the modification of clin ker microstructure", Tsement 35 N° 4, 3.Ble 3. 256. 257. 261 FIERENS, P., THAUVOYE, M. ot VERHA\ GEN, J.P.0974) "Bifects of tvon (Il) and i= tanivin QV) on the tricaleium aluminate struc~ ture and reactivity", Il Cemento 71, 3. KONDO, B. et YOSHIDA, K, (1968) "Misct- bilities of special elements ih tealcium sii~ cate and alite and the hydration properties of C38 solid solutions", 5! Int. Symp- Chan. Cement, Tokyo P.1. 252, EREMIN, N.J., EGEREVA, A.J, DIMITRIE VA, A. et FIRFAROVA, J.B. (1570) "Solid solutions of 2C20-Si02'with some metal oxi- des", Zh. Prikl. Kim. (Leningrad) 43, 18. KNSFEL, D. (1979) "Der Einbau von TiOp {a die Piasea des Portlandzemenihlnkers”, Zement-Kalk-Gips 32, 35. MIDGLEY, H.G. (1968) "The minor elements fn allte((rionlelum silicate) and belite leal chum silicate) from some portland cement lia ers as determined hy slectron probe X- my microanalysis", S® Int- Symp: Chem Cement, Tokye Pet, 225. ANSFEL, D. (1977) "Becinflussung einiger Eigenschaften des Portlandzementslinkers und des Portlandzements durch TIO2", Ze 2 mmont-Kalk-Gips 30, 191, SYCHEV, M.M. et Z0ZULIA, P.V. (1967) "Clinker liquid Wacostey and sintering pro- cesses", Tr. Gos. Vses. Prockt. Nauch.- fled: Inat. Taens Prom. 33, 3+ ROYAK, S:M,, ASTREYEVA, O.M. et LU KINA, MN. (955) "Effect of Heansum dtoxi- de on elisker formation processes", Taement 2N'3,12, FIERENS, P., THAUVOYE, M. et VERHAE GEN, J.P: (1972) "The influence of tron GU) and tiantum GV) on the structure and reacti- ity of tricalcium silicate”, Il Cemento, 93, au BOIKOVA, A.L. (1964) "Stotchiometry and polymorphiem of tricalcium silicate”, Dokl. Chem» Fechnol- 156 6), 90. SYCHEV, M.M. et KORNEEV, V.1. (1965) "Cromalice of portland cement clinker", Zh. Prikl. Khim. Cheningred) 38, 2642. FIERENS, P. et VERHAEGEN, J.P. (1972) "Sumicture and reactivity of chromium-doped twicaletum silicate”, J- Amer. Ceram. 50 BB, 309. JOHANSEN, V. (1972) "Sold solution of on in CagBiO5", Com. Coner Res. JOHANSEN, V. €978) "Absorption spectra of CrOf” in Cag5i0g and CagAlz05", Cem- Sone" Res: 8, 245° 253. 2h. 266. 268. 269. 270. mn. 273. 21h. 275. 1-1/41 BUTT, YU.M., TIMASHEV, V.V. et MA - LOZHON L.1. (1968) "Cristallization of mi nevals in clinker containing chromiun oxide" Inorganic Materials 4 (3), 431. WOERMANN, E., HAHN, TH. et EYSEL, W. (1963) "Chemische und strukturelle Unter suchungen der Mischeristalibildung von Tri caleiumsilzkat", Zement-Kalk-Gips 16, 370. BOIKOVA, A.1. (1968) "The effect of chro- rium oxide oa the structural tragsformations in tricalcium silicate", Proc. 5! Int. Symp- Chem. Cement, Tokyo P.1, 234. BOIKOVA, A.1., TOROPOV, M.A., PUI KO, M.M: et GRUM.GRZHIMAILO, C.V. 1966) "Effect of Cr oxide on structural tren sformotion of tricalcium silicate", ley. Akai: Nauk. SSSR, Neorg. Mater. 2, 1796. GLASSER, F.P. et OSBORN, E.F. (1958) Phase equilibrium studies in the sysiem Ca0-Cry03-5i03", J. Amer. Ceram. Soc. 4% PETERS, D. et HUMMEL, F.A. (1979) "Pha se studies in the systems CaQ.AIz03-CaCro, ee $10-A1jO3-SrCr04", Cem. Concr- Re.) 253. ZOZULIA, P.V. et SYCHEV, M.M. 1972) "Surface tension of portland cement clinker iguid phase", Inzh.-Fiz. lasled. Stroit, Mater. p. 55+ IMLACH, J.A, (1975) "Assessment of the 7 le of chromium in portland cement maniacs, re", Amer. Ceram: Soc- Bull. 54, 519. UTT, YU-M, et TIMASHEV, V.V. (1968) "Technological and physical-chemical cha ~ pagertstics of the minifacrare of rapid har = ening and high strength cements", Proc. tH Conf. Silicate Ind. Budapest p- 217. TERAMOTO, H. et KOLE, 5. (1975) "Phasen zusnmmensetzung und Hydratation eines ho ~ chstwertigen Portlandzamentklinkers mit Fremdbestandteilen”, Zement-Kalk-Gips 28, 370. JAWED, I. et SKALNY, J. (1977) "Alkelterin cement: a review", Cem. Couer. Res. 7, 719 et 8, 37. DANOWSKL, W. et STROBEL, U. (1976) "Alkalibela stharkeiteuncersichangen in Troe Kenbrennanlagen", Zenent-Kalk-Gips 29, 458. HALSTEAD, W.D. (1970) " Saturated vapor pressure of potssium sulphate", Trans. Fa, Faday Soe. 66, 1966. CUBICIOTTI, I et KENESHEA, F.J. 1972) "Thermodinamies of vaporisation of sodium sulphate", High Temp. Set. 4, 32.1-1/42 278. 279. 280. 281. 8 286. 287. 230. CHRISTIANSEN, 5, et MADSEN, G.M. (1974) "Precalciners for cement kilns: deve- opment and applications", Rock Prod. 10% Int. Cement. Ind. Seminar Chicago, dic. 8 11 p. 100. DAHL, L.A, (1941), Meet. of Portl. Cem. Assoc. St, Louis, Mo. may 15. WOODS, H,(1942) “Removing alkalies by heating with admixtures", Rock Prod. 4, febr. 66 HOLDEN, E.R. (1950) “Reduction of alka - lies in portland cement", Ind Eng. Chem. 357 BOHMAN, B, (978) "Einfiues von Cal thlorid-Zugabe zum Ofermetl uf den Atk = {i-Haushalt and die Klinkerqualidt von Was mretauscherSien®, Zement-alk-Gips 31,278 SYLLA, Hud. (1977) "AndatzDildung dusen Saleschnelzen", Zement-Kalk-Cipe 99,487. GEBAUER, J. ot KRISTMANN, M. (1979) "The influence of the composition of ins ~ strial clinker on cement and concrete proper 1 World, Cem: Technol. 10, 45. RW, (1968) "Phase equilibria and formtice of portland cement minerals", Proc. 5' Int. Symp. Chem. Cement, Tokyo Pal, 77. YAMAGUCHI, G. et TAKAGI, $. (1966) "The analysis of portland cement clinker", Proc. Sint. Symp. Chen. Cement, Tokyo Pl tat. MAKI, I. et CHROMY, 5. (1978) "Characte- ization of the alite phase in pordland cement clinker by microscopy", Il Cemmnto 75, 247. SODA, ¥,, MIZUKAML, K. ex SHIRASAKA, M, (49693 "On the dacline in the develop = ment of the strength of pertland cement by the inevease of magnesia", Rev. 22% Gen. Meet. Com. Assoe. Japan, Tokyo p. 48. NIKIFOROV, YU. V., ZOZULYA, R.A, et IVANOVA, N.M. (1974) "Role played by ma- gggess linker and cement technology", Gth Int. Congr. Chem. Cement, Moscow. CIRILLI, V. et BRISI, C. (1955) "Influenzs del modulo caleareo aula composizione della fase ferrica del clinker ai portland”, Ind. kal. Com. 25, 5+ KRAMER, H. et ZUR STRASSEN, H. (1960) “Discussion. Phase equlibria ond onstitusion of porta! cement clinker

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