Studies on the influence of different fly ashes and Portland cement on early hydration of calcium aluminate cement

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1 J Therm Anl Clorim (0) 06: DOI 0.007/s Studies on the influence of different fly shes nd Portlnd cement on erly hydrtion of clcium luminte cement Brr Pcewsk Iwon Wilińsk Mriol Nowck Received: Septemer 00 / Accepted: 7 April 0 / Pulished online: My 0 Ó The Author(s) 0. This rticle is pulished with open ccess t Springerlink.com Astrct The influence of three minerl dditives, i.e. fly shes from pulverized comustion nd from fluidized comustion of hrd col s well s Portlnd cement, on erly hydrtion (up to 8th dy) of clcium luminte cement ws investigted. Cement pstes contining 0, 5 nd 5 wt% of dditives were studied y the use of clorimetry, therml nlysis nd infrred spectroscopy methods. It ws confirmed tht hydrtion of clcium luminte cement is closely dependent on the type of ddition nd its mount. The influence of dditives of different properties on cement hydrtion ws discussed sing on received results nd other literture reports. Keywords Clcium luminte cement Fly sh Portlnd cement Het of hydrtion TG DTA IR Introduction Clcium luminte cements re hydrulic inders of specil properties nd pplictions. They re minly pplied in production of fire-resistnt mterils ut this kind of cement is lso useful in cses when concreting in tempertures elow zero, higher resistnce for sulphte ggression or fst increse of strength re required. Moreover clcium luminte cement my e component of redy for use mixtures for specil pplictions in uilding works, for exmple, quick hrdening or expnsive inders. B. Pcewsk (&) I. Wilińsk M. Nowck Fculty of Civil Engineering, Mechnics nd Petrochemistry, Institute of Chemistry, Wrsw University of Technology, Luksiewicz 7 St., Plock, Polnd e-mil: pcewsk@pw.plock.pl Clcium luminte cements re expensive mterils, especilly in comprison with Portlnd cement. Tht is why, it is imed t reduction of mount of clcium luminte cement in composite or its prtil sustitution y other, cheper mterils. Despite high price of clcium luminte cements, their ppliction might e potentilly greter if one succeed in eliminting dnger of strength reduction eing consequence of conversion of luminte. Clcium luminte cements re especilly sensitive to chnges of conditions of hrdening. It cuses tht their properties, such s rte of hrdening, strength, etc., chnge inter li in presence of dditives. Reserch works concerning mixing of clcium luminte cement with different fine-grined dditives such s wste mterils (e.g. silic fume [, ], fly sh [ ], slg [], spent luminosilicte [5]) s well s other types of cements (e.g. Portlnd cement [6, 7]) hve een undertken. In this wy one my otin new inder of improved nd/or chnged properties. It is the effect of ction of ctive dditives tht influence physicl nd chemicl processes nd rising products of hydrtion. The min products of hydrtion of clcium luminte cement t mient temperture (0 5 C) re hydrted hexgonl clcium lumintes type of CAH 0 nd C AH 8 s well s luminium hydroxide AH (revitions used in cement chemistry nd therey in this work: C-CO, A-Al O,H-H O, S-SiO, c-co ). The hexgonl hydrtes, CAH 0 nd C AH 8, re metstle products. They inevitly convert with time or t higher temperture nd in presence of humidity into cuic product C AH 6 nd AH. Strength of hrdened cement mteril decreses s the effect of this conversion [8]. Some dditives of pozzolnic or hydrulic properties, replcing prt of cement in the mteril, re proposed to reduce hydrte conversion nd its negtive effects. In cement pste, rective silic is relesed from these

2 860 B. Pcewsk et l. mterils nd then it rects with components of the system. Phse C ASH 8 rises in this process. Some other C A S H phses my lso e formed, s it ws oserved y uthors of work [9]. Arising of C A S H type phses my e n lterntive rection wy for C AH 6 forming during conversion. One of mechnism of dditive ction is proposed s follow []: silic relesed from the dditive rects initilly with clcium lumintes to produce C ASH 8.In this wy the formtion of C AH 8 nd susequently its conversion to C AH 6 re voided. However, in literture reports one my find tht some reserchers do not gree whether the totl prevention of conversion in this wy is possile. Mechnism of ction of pozzolnic nd hydrulic dditives in luminte cement system nd their role in conversion process is not fully explined yet. Thus, such investigtions should e continued. A lot of reserch works hve een devoted to introduction of fly sh into hydrting luminte cement system [ ]. These works minly relte to the influence of different fly shes coming from conventionl technologies of comustion on hydrtion of cement nd properties of the composite. In literture there re no reserch works found devoted to introduction of fly sh from fluidized comustion of col into hydrting luminte cement system. This type of fly sh exhiits different properties in comprison with the shes coming from conventionl methods of comustion. It is n effect of lower temperture of comustion (on verge out 850 C). Fluidized fly sh is chrcterized y porous grins nd, in contrst to conventionl fly sh, it usully does not include glss or sphericl grins. In composition of fluidized fly sh one my find: minly dehydrted luminosilictes, qurtz, clcium compounds in the form of CO, C(OH) nd CCO s well s nhydrite or gypsum from flue-gs desulphuriztion, nd lso non-comusted col [0]. In the presence of C? ions, fluidized fly sh exhiits higher pozzolnic ctivity thn conventionl fly sh []. One my expect tht, for the ske of its chemicl composition, fluidized fly sh will rect in hydrting luminte cement system in similr wy s Portlnd cement. Therey, fluidized fly sh my e considered s potentil dditive limiting the luminte conversion (like conventionl fly sh) s well s sustitute of Portlnd cement in quickly hrdening or expnsive inder. The im of this work ws investigtion of erly hydrtion (up to 8th dy) of clcium luminte cement in the presence of different dditives. The ction of fly sh from fluidized comustion of hrd col, s new type of dditive, in luminte cement pste ws studied in comprison with fly sh from pulverized comustion nd Portlnd cement. The results presented in this work concern voidnce of conversion of lumintes nd possiilities of usge of industril wste in inders for specil pplictions. Experimentl Grey clcium luminte cement Górkl 0, produced y Górk Cement Sp. z o.o (Polnd), ws used s min component of the smples. For this cement the content of components reclculted into oxides is (mss%): Al O [ 0%, CO [ 6%, SiO \ %, Fe O pproximtely % nd minerlogicl composition is: CA s sic phse nd C AF, C A 7 nd C AS s ccompnying phses (ccording to product description given y producer []). Three types of inorgnic dditives were used: two kinds of fly shes from different technology of comustion of hrd col nd Portlnd cement type of CEM I.5 R. Fly sh from fluidized comustion (men temperture of comustion out 850 C, clcium sorent dded for fluegs desulphuriztion) of hrd col ws further signified in short s fluidized fly sh. Fly sh from conventionl, pulverized comustion (temperture ove 000 C) ws signified s pulverized fly sh. Approximtely, the shes oxide chemicl composition (the min components) ws the following: for fluidized fly sh 55% SiO, 6% Al O, 5% Fe O, 0% CO, 5% SO nd for pulverized fly sh 50% SiO, 0% Al O, 7% Fe O, 5% CO, % SO (mss% in ll cses). The studied smples were cement pstes with the dditions (0, 5 nd 5 mss% of dditive in the mss of dry inder). The wter/(cement? dditive) rtio ws 0.5. Erly hydrtion ws studied during first 8 h (externl temperture ws 5 C) y mens of differentil BMR clorimeter constructed t the Institute of Physicl Chemistry of Polish Acdemy of Science. The results were clculted using computer softwre []. Therml nlysis nd infrred sorption mesurements were crried out for the cement pstes fter nd nd 8th dy of hydrtion. Smples for these mesurements were hydrted in seled gs t temperture C during first weeks nd then t 5 0 C. At the ppointed time, hydrtion ws stopped y the use of cetone. SDT 960 Thermonlyser, produced y TInstruments (heting rte 0 C/min, mss of smple: 9 mg, nitrogen tmosphere) nd FTIR spectrophotometer Genesis II, produced y Mttson ( cm -, smple preprtion pelletizing with KBr) were used. Results nd discussion Clorimetric mesurements Clorimetry is good method for studies on cement hydrtion during its first hours of ction when chemicl nd physicl processes occur most intensively. This technique ses on continuous mesurements of het relesed in time, strting from the ddition of wter into the dry inder.

3 Studies on the influence of different fly shes nd Portlnd cement 86 Results of these mesurements for clcium luminte cement pste contining different dditives re presented in Fig.. Min effects of het relesing re oserved up to h, tht is why this period ws only presented in the figure. The course of clorimetric curves is closely relted to the chemicl nd physicl processes occurring in the system. During first minutes fter ddition of wter quick relese of reltively smll mount of het is oserved. This effect cn e ttriuted to the wetting of inder grins, their superficil dissolving nd the eginning of hydrtion processes. C? nd Al(OH) - ions re trnsferred into the solution, which quickly ecomes sturted. The next stge is so clled induction period, in which the relese of het is inhiited nd the hydrtion nuclei pper nd grow. After completion of this period mssive precipittion of hydrtes occurs which is ccompnied y significnt het relese [5]. Introduction of 5% of dditives into cement system cuses ccelertion of hydrtion processes which is mnifested in shortening of induction period. Addition of pulverized fly sh is the exception. In cse of higher mount of dditives (5%), their influence is more diverse. The ccelerting ction is displyed y oth of fly shes nd lso y Portlnd cement. It my e influence of nucletion ction of dditive fine grins, ut lso relesing of ions securing high ph of environment (ph of wter extrct of the dditives is ove ). N? nd K? ions lierted from the shes s well s C? from Portlnd cement nd fluidized fly sh my ccelerte hydrtion of clcium luminte cement. Generlly, cting of lklis, coming, e.g. from ggregte, depends on their concentrtion nd temperture, especilly when rising products re considered. For exmple, smll concentrtion of K? ions my ccelerte hydrtion of cement nd chnge minerlogicl composition of cement mteril []. In the presence of 5% of dditives, the intensity of het relesing fter induction period is smller compred to the result for reference smple. It my suggest tht, in first hours of hydrtion, the mount of rising products is lower in the presence of dditives despite their ccelerte ction ( dilution of cement y mteril of smller ctivity). It is especilly visile in the cse of pulverized fly sh tht suggests its reltively low chemicl ctivity in the initil stges fter ddition of wter into cement. Activity of silicte dditives is determined y the rte of penetrtion of silic into solution. In the cse of conventionl fly sh its initil low ctivity is confirmed y lot of reserch works devoted to studies on this mteril s pozzolnic dditive into Portlnd cement composites (e.g. [5]). Grins of pulverized fly sh need some time for dissolving nd tking prt in chemicl rections. The fluidized fly sh, in contrst to pulverized one, exhiit higher ctivity []. In the cse of ddition of Portlnd cement, tht is n ctive hydrulic mteril, into luminte cement pste the products of hydrtion of these two types of cements my rise, i.e. hydrted luminte phses, C S H or C A S H phses nd ettringite. Bsing on presented results one my constter tht the course of initil hydrtion of clcium luminte cement in the presence of dditives is dependent on oth their qulity nd quntity. In the cse of ddition of Portlnd cement the ove sttements re lso confirmed y work of other uthors [6]. Erly hydrtion of inder composed of clcium luminte cement nd Portlnd cement depends on quntity proportion of oth components. Thus, different products my rise during hydrtion of these systems nd it my e oserved using clorimetry mesurements. When the content of clcium luminte cement is not less thn 80%, het relesing is minly cused y hydrtion of this cement. Portlnd cement lso undergoes hydrtion in this time ut this process does not cuse seprted het effect on clorimetric curve [8]. It is visile on presented results for cement pste contining 5% of Portlnd cement (see Fig. ). In cse of mixtures rich in Portlnd cement (not studied in this work) clorimetric curves re similr to result for Portlnd cement, especilly in cses when content of luminte cement does not exceed 0% [6]. Fig. Het evolution curves for cement pstes with 5 nd 5% cement sustitution y different mterils; 5% of dditive, 5% of dditive, reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement dq/dt/j g h dq/dt/j g h Time/h Time/h

4 86 B. Pcewsk et l. Presented results show tht introduction of lredy 5% of Portlnd cement into clcium luminte cement my chnge physicl nd chemicl processes. During first minutes of hydrtion of cement pste contining 5% of Portlnd cement, the het evolution is more intensive thn in the cse of smple with only 5% of this dditive s well s of reference smple. It my e n effect of relese of SO - ions to solution nd then formtion of ettringite. Moreover C? ions coming from Portlnd cement tke prt in forming of hydrted luminte phses. As result the induction period decreses. However, mechnism consisting in ccelertion of hydrtion of oth cements should e lso tken into considertion, e.g. ccelertion the hydrtion processes of Portlnd cement s the result of het relesed y recting luminte cement [6]. In the next period of hydrtion the reppernce of fst increse of het evolving, with two mximums on clorimetric curve t out 7.5 nd 0 h, is oserved. Such shpe of clorimetric curve hs no confirmtion in literture. In the cse of inders of similr components proportion s in this report, the uthors of works [6, 7, 6] conclude tht generl shpe of het relese curve is similr to this one otined for reference smple (i.e. for only clcium luminte cement, one pek fter induction period). Moreover uthors of works [6, 7] do not indentify ettringite in such smples. The sence of ettringite my e explined y nonsufficient vilility of SO - ions. It is possile, tht oserved some differences etween literture dt nd results presented in this work my e effect of using of different types of cements nd conditions of hrdening (e.g. different wter/cement rtio, temperture, the wy of wter ddition etc.). The ction similr to Portlnd cement (especilly when its higher mount ws considered) my e lso shown y fluidized fly sh due to the presence of gypsum nd luminosilictes in its composition. In this sitution, however, n dditionl effect of het relese is not oserved. One my expect tht complex products of rections etween components of fly sh nd lumintes rise, s it ws oserved y uthors of work [], in which cement pstes mde of luminte cement, fly sh nd gypsum were studied. Therml nlysis Detiled interprettion of results otined for clcium luminte cement pstes is difficult ecuse of complexity of composition of studied smples. The processes of dehydrtion of individul compounds overlp. Multistge decomposition of some hydrtes my cuse rising of compounds tht lso my e expected in hydrtion products of the cement. Moreover tempertures of decompositions for prticulr hydrtes, like in the cse of other compounds, depend on their degree of crystllinity, mss of smple, conditions of mesurements, gs tmosphere, etc. It explins different temperture rnges tht re found in literture nd scried to presence of specific phses. Thus, therml nlysis results should e discussed only s estimted nlysis of composition of luminte cement pstes. However, it does not chnge the fct, tht therml nlysis is often pplied y lot of reserches nd otined results my e helpful especilly in comprtive nlysis of influence of dditives on hydrtion process. The results of therml nlysis received in this work re presented in Figs., nd. The min mss loss of dehydrtion of different hydrtes occurs up to 500 C. Tht it why, this region ws only presented for more cler disply of the differences in shpes of TG, DTG nd DTA curves. Totl mss loss occurring up to 500 C ws ssumed s the mount of wter ound in hydrtes. Tking into considertion the ove mentioned limits, following interprettion of therml nlysis results for smples fter dys of hydrtion ws ccepted (minly sing on []): up to 0 C (the min mximum on DTG curve t out 80 C) dehydrtion of AH xh O gel, 0 0 C (mximums on DTG for reference smple t out 5 nd 00 C) overlpping effect of dehydrtion of CAH 0 nd C AH 8 phses, 0 70 C (DTG mximum t out 0 C) decomposition of AH (gisite), C dehydrtion of C AH 6 (very smll effect), lterntively C AS -x H x, ove 700 C decomposition of crontes (not presented in the figures). Aove processes re ccompnied y endothermic effects on DTA curves. Summrizing, one my conclude, tht following compounds re identified in -dy-old smples of cement pstes: AH xh O, CAH 0 nd C AH 8 s well s gisite AH. The presence of C AH 6 is lmost not oserved. Reltively low tempertures of mximums of dehydrtion effects on DTG curves result on the one hnd from smll smple mss, nd on the other hnd they my indicte low degree of crystllinity of products rising in initil periods of hydrtion. Introduction of dditives into cement pste cuses quntity nd qulity differences in hydrtion products, depending on properties nd mounts of the dditive. Smller differences in shpes of registered curves re oserved in cse of 5% of dditive (Fig. ). The DTG results registered for smples contining 5% of oth of fly shes re similr to the findings for the reference pste, however, in cse of fluidized fly sh slightly greter content

5 Studies on the influence of different fly shes nd Portlnd cement 86 Fig. TG, DTG nd DTA curves for cement pstes with 5 nd 5% cement sustitution y different mterils (nd dy of hydrtion); 5% of dditive, 5% of dditive, reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement Mss/% Mss/% DTG DTG DTA DTA Endo Endo Temperture/ C Temperture/ C Fig. TG, DTG nd DTA curves for cement pstes with 5 nd 5% cement sustitution y different mterils (8th dy of hydrtion); 5% of dditive, 5% of dditive, reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement Mss/% Mss/% DTG DTG DTA DTA Endo Endo Temperture/ C Temperture/ C of AH xh O gel is oserved. Introduction of very ctive hydrulic mteril such s Portlnd cement cuses more differences in rising products. In this cse eside mximums on DTG t out 80, 00 nd 0 C lso dditionl effects t out 05 nd 80 C re visile. Moreover effect registered for the other smples t 5 C ppers in the form of two peks t out 5 nd 0 C. In cse of 5% of dditives loss of mss up to temperture 500 C (Fig. ), corresponding to the mount of wter ound in hydrtes, is close to vlue for reference smple in cse of fluidized fly sh nd lower for pulverized fly sh nd Portlnd cement ddition.

6 86 B. Pcewsk et l. Mss loss/% (0%) (5%) (5%) (5%) (5%) (5%) Type of cement pste dys 8 dys (5%) Fig. Mss loss up to temperture 500 C for cement pstes with 5 nd 5% cement sustitution y different mterils (fter nd nd 8th dy of hydrtion); reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement Introduction of higher mounts of dditives, i.e. 5% (Fig. ), cuses greter differences in quntity nd qulity of hydrtion products thn in situtions when only 5% is present. In the cse of 5% of pulverized fly sh the shpes of registered curves indicte tht hydrtion products re similr to these, tht rise in reference pste nd some differences re only in their quntity. Lower mss loss to 500 C for the smple contining this fly sh indictes lso lower mount of ound wter in comprison with reference. It lso my confirm low initil ctivity of this type of dditive (see Fig. ). The gretest qulity chnges in hydrting systems is cused y ddition of 5% of Portlnd cement s well s fluidized fly sh. In the cse of Portlnd cement the first effect on DTG is slightly shifted to 90 C. Then, during the increse of temperture, cler peks re visile t out 0, 0 nd 75 C, respectively. It is proly effect of overlpping of dehydrtion processes of products of hydrtion for two cements existing in the system. Like in the cse of other smples, the effect of dehydrtion of gisite t out 0 C on DTG is oserved, nd then, from the side of higher tempertures, dehydrtion of C AH 6 strts to e visile. It my e n effect of ccelerte of luminte conversion to C AH 6 s result of higher content of C? nd lklis. According to informtion given in [] smll mount of gypsum lso my influence on C AH 6 formtion in this wy, tht production of ettringite nd inding of lumintes in this process is preferred. However, too low mount of gypsum in investigted systems my e insufficient to destiliztion of C AH 6 phse. It is chrcteristic tht the mss loss t out 80 C relting to C(OH) decomposition is not oserved even when 5% of dditive is introduced. It confirms tht rising C(OH) s product of hydrtion of Portlnd cement quickly undergoes further rections with luminte phses. Similr shpes of DTG nd DTA curves to these registered for smples contining Portlnd cement re lso oserved for the cement pstes with fluidized fly sh ddition. It confirms erly presumptions out similr influence of these types of mterils on luminte cement hydrtion. In the cse of 5% of fluidized fly sh eside extreme t out 80 C, the second effect t out 90 C followed y two peks t out 0 nd 5 C re lso visile on the DTG curve. Proly first products of rections tking prt with components of fluidized fly sh were lredy produced. Lower mss losses up to 500 C for smples contining 5% of Portlnd cement or fluidized fly sh indicte, however, lower mounts of wter ound in hydrted phses s compred to reference without the dditions. After 8th dy of hydrtion the therml nlysis results exhiit more differences in compositions of the studied cement pstes (Fig. ). For lmost ll smples ppernce of effect with extreme t out 80 C (00 C for the reference) ws reveled, tht my e relted to presence of phse C AH 6. Simultneously the intensity of effect t out 5 C corresponding to dehydrtion of AH increses. Also in the cse of 8th dy old smples the greter differences in the results, s compred with the reference, re displyed y the smples contining 5% of Portlnd cement nd fluidized fly sh. The TG, DTG nd DTA curves for these smples indicte rising new hydrtion products in the systems, different from those tht re produced in the reference pste. On the contrry, pulverized fly sh does not cuse significnt differences in qulity composition of cement pste. However, in the presence of Portlnd cement nd fluidized fly sh compound silicte luminte phses s well s luminte sulphte phses re formed. Proly C S H phse tht is formed in initil stges of hydrtion undergoes further trnsformtions with prticiption of hydrted lumintes nd AH. As result phses type of C A S H, e.g. C ASH 8 re formed. In the cse of 5% of Portlnd cement it is confirmed y reltively low content of AH compred to incresed mount of C AH 6. It suggests tht AH relesed during conversion, tht is ccelerted in the presence of Portlnd cement, undergoes further chemicl rections. Moreover silicte ions my incorportion into structure of lumintes. The products, tht re formed in the presence of fluidized fly sh during 8 dys of hydrtion, re in some degree different thn in the presence of Portlnd cement, tht is confirmed y the shpes of registered curves. The effect relted to C AH 6 is not clerly visile. It my suggest tht in the presence of fluidized fly sh conversion is not ccelerted s in the cse of Portlnd cement, ut it is inhiited.

7 Studies on the influence of different fly shes nd Portlnd cement 865 Infrred spectroscopy IR spectr of cement pstes for selected wve numers regions re presented in Figs. 5 nd 6. Additionlly in Fig. 7 spectr for dry components re lso presented for comprison. Compring the results for the reference cement pste nd for dry clcium luminte cement, one my oserve distinct differences resulting from occurring of chemicl processes. The nds chrcteristic for dry cement, i.e. intensive complex nd with extreme t out 805 cm - corresponding to virtions of AlO groups s well s nds of AlO 6 virtions t out 680 nd 60 cm - [], grdully chnge. The nd oserved in spectr of cement t out 5 cm - shifts to slightly higher vlues of wve numers in spectr for cement pstes. For cement pstes contining the dditives there re lso not oserved ny nds tht my e unequivoclly comined with their presence in the smples. The shpes of ll spectr for cement pstes re similr. The following groups of nds my e specified []: Fig. 5 IR spectr for cement pstes with 5 nd 5% cement sustitution y different mterils (nd dy of hydrtion); 5% of dditive, 5% of dditive, reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement Wvenumers/cm Wvenumers/cm Wvenumers/cm Wvenumers/cm

8 866 B. Pcewsk et l. Fig. 6 IR spectr for cement pstes with 5 nd 5% cement sustitution y different mterils (8th dy of hydrtion); 5% of dditive, 5% of dditive, reference smple (0% of dditive), ddition of pulverized fly sh, ddition of fluidized fly sh, ddition of Portlnd cement Wvenumers/cm Wvenumers/cm Wvenumers/cm Wvenumers/cm rod, intensive nd in the region of wve numers of cm -, with the extreme t out 80 cm - overlpping nds of OH virtion in hydrtes, the nd of middle intensity t out 60 cm - nds of ending virtions of OH in HOH, nd of middle intensity t out 5 cm - the stretching virtions of CO - in crontes type of clcite (5 cm - ), rgonite? vterite (the nd form the side of higher wve numers), overlpping intensive nds:. t out 00, 965, 800 cm - the nds of ending virtions of OH in gisite, ut the nd t out 0 cm - my e lso relted to Si O, while the nd t out 800 cm - to virtions of Al O. out 565 cm - nds of virtions of Al O. The rod intensive nd of OH virtions in region of cm - with the extreme t 500 cm - indictes the presence of CAH 0 [] tht proly is the min hydrtion product. It is confirmed y sence of other nds tht could identify individul groups of the

9 Studies on the influence of different fly shes nd Portlnd cement Wvenumers/cm 00 Fig. 7 IR spectr for components of cement pstes; clcium luminte cement, Portlnd cement, pulverized fly sh, fluidized fly sh Moreover in cse of smples contining fluidized fly sh nd Portlnd cement shoulder of nd t out 00 cm - is oserved. The sorption nds t out 7 nd 875 cm - with connection of distinct nd t out 0 cm - my e relted to virtions in clcite [8]. In discussed wve numers region, the result for reference cement pste fter 8th dy is not significntly different from this one registered fter nd dy. When 5% of fluidized fly sh is dded some shoulder t 07 cm - is visile oth in nd nd 8th dy of hydrtion. It my suggest the presence of non-rected sh in the system (the min nd for fluidized fly sh is t out 080 cm - the virtions of Si(Al) O in tetrhedrl groups [], see Fig. 7). However, loction of this nd my lso indicte formtion of ettringite with the shre of SO - ions introduced with the fly sh. Also in cse of 5% of Portlnd cement similr nd is oserved. In the second cse discussed nd ppers t out 0 cm - fter nd dy nd fter 8 dys it shifts to out 0 cm - nd increses its intensity. The nd chrcteristic for virtions of SO in ettringite my e expected t out 0 cm - [] thus otined results my suggest smll mount of this compound formed in presence of higher mount of fluidized fly sh nd Portlnd cement. However, complexity of investigted systems cuses tht unequivocl identifiction is not possile. compounds, e.g. there is not distinct nds of stretching virtions of OH in gisite or in phses type of C AcH. In cse of 5% of fluidized fly sh nd Portlnd cement one my oserve some shoulders y the side of higher wve numers tht my indicte ccelertion of chemicl processes nd therey more mount of AH (gisite) formed during hydrtion. This effect is most of ll visile in the spectr for the smples fter 8 dys of hydrtion. In this cse two extremes t out 70 nd 55 cm - nd some shoulder t out 60 cm - seprte. Distinct nd t out 665 cm -, tht my confirm the presence of C AH 6 [, ], is not visile. In the region of wve numers of cm - in IR spectr for ll cement pstes the nds t out: 00, 970 nd 550 cm - re visile. It should e noticed tht in cse of smples with dditives the nd t out 970 cm - my e lso connected with C S H phse. When 5% of dditives re considered, the spectr fter nd dy of hydrtion re similr to the reference. Greter differences chrcterize the IR spectr for smples contining higher mount of dditives. Following sorption nds re visile for smples contining 5% of dditives: for cement pste with pulverized fly sh t out 855, 785 nd 7 cm -, with fluidized fly sh out 90, 785, 7 nd 670 cm -, nd with Portlnd cement 855, 785, 7 cm -, respectively. Conclusions Received results of hydrtion of clcium luminte cement in the presence of different dditives llow to drw following conclusions:. Hydrtion of clcium luminte cement is closely dependent on the type of ddition nd its mount.. Introduction of 5% of fluidized fly sh or Portlnd cement cuses ccelertion of hydrtion processes (shortening of induction period). Conventionl fly sh used in the sme mount does not influence significntly kinetics of cement hydrtion.. After introduction of 5% of studied dditions, shortening of induction period ensues independently of their types. Forming of new products is lso oserved.. In the presence of fluidized fly sh nd Portlnd cement in cement pste mde of clcium luminte cement, compound products type of C A S H eside of typicl products of cement hydrtion rise. The presence of conventionl fly sh cuses minly quntity differences in hydrtion products compred with reference smple. 5. In the cse of presence of fluidized fly sh nd especilly of Portlnd cement initil ctivity is dependent on

10 868 B. Pcewsk et l. trnsfer of C? s well s SO - into the solution nd proly formtion of ettringite. In cse of conventionl fly sh dissolving of the grins nd going of ions into pore solution need more time. Proly this process is fster in cse of porous grins of fluidized fly sh. Moreover in cse of ll used dditives other ions, eside of clcium nd sulphte ions, relesing into wter nd lso fine grins of these mterils influence hydrtion of cement. 6. Replcement of Portlnd cement y fluidized fly sh in specil inders mde of clcium luminte cement my e lterntive for development of fst-setting inders. However, the mount of fly sh nd its properties should e optimized. It is possile tht for otining optiml properties of the inders some dditionl mount of gypsum should e introduced. 7. Fluidized fly sh used in mount of 5% of inder mss my effectively reduce the conversion of luminte. Aove conclusions resulting from initil studies need to e confirmed. It is necessry to perform further investigtions of hydrtion of clcium luminte cement in the presence of dditives (XRD, SEM nd others) nd of composites otined on the sis of such two-component inder. Open Access This rticle is distriuted under the terms of the Cretive Commons Attriution Noncommercil License which permits ny noncommercil use, distriution, nd reproduction in ny medium, provided the originl uthor(s) nd source re credited. References. Hidlgo A, Grcí JL, Cruz Alonso M, Fernández L, Andrde C. Microstructure development in mixes of clcium luminte cement with silic fume or fly sh. J Therm Anl Clorim. 009;96:5 5.. Hidlgo López A, Grcí Clvo JL, Grcí Olmo J, Petit S, Cruz Alonso M. Microstructurl evolution of clcium luminte cements hydrtion with silic fume nd fly sh dditions y scnning electron microscopy, nd mid nd ner-infrred spectroscopy. J Am Cerm Soc. 008;9: Fernández-Crrsco L, Vázquez E. Rections of fly sh with clcium luminte cement nd clcium sulphte. Fuel. 009;88:5 8.. Quillin K, Osorne G, Mjumdr A, Singh B. Effects of w/c rtio nd curing conditions on strength development in BRECEM concretes. Cem Concr Res. 00;: Pcewsk B, Wilińsk I, Bukowsk M. Clorimetric investigtions of the influence of wste luminosilicte on the hydrtion of different cements. J Therm Anl Clorim. 009;97: Ping Gu, Beudoin JJ. A conduction clorimetric study of erly hydrtion of ordinry Portlnd cement/high lumin cement pstes. J Mter Sci. 997;: Gwlicki M, Nocuń-Wczelik W, Bąk Ł. Clorimetry in the studies of cement hydrtion. Setting nd hrdening of Portlnd cement clcium luminte cement mixtures. J Therm Anl Clorim. 00;00: Hewlett PC, editor. Le s chemistry of cement nd concrete. th ed. London: Arnold; Rivs Mercury JM, Turrills X, de Az AH, Pen P. Clcium lumintes hydrtion in presence of morphous SiO t tempertures elow 90 C. J Solid Stte Chem. 006;79: Giergiczny Z. Popioły lotne z du_zą zwrtością wpni (in Polish). Cement Wpno Beton. 005;55:7 8.. Pcewsk B, Blonkowski G, Wilińsk I. Studies on the pozzolnic nd hydrulic properties of fly shes in model systems. J Therm Anl Clorim. 008;9: Informtion of Górkl cement producer. Product description clcium luminte cement Górkl Accessed Sept 00.. Poznński J. Computer softwre for processing of dt otined from clorimeter Fernández-Crrsco L, Blnco-Vrel MT, Puerts F, Vázquez T, Glsser FP, Lchowski E. Hydrtion of high lumin cement in the presence of lklis. Adv Cem Res. 000;: Rhhl V, Tlero R. Influence of two different fly shes on the hydrtion of Portlnd cements. J Therm Anl Clorim. 00;78: Ping Gu, Beudoin JJ, Quinn EG, Myers RE. Erly strength development nd hydrtion of ordinry Portlnd cement/clcium luminte cement pstes. Adv Cem Bs Mter. 997;6: Grcés P, Grci Alcocel E, Grci Andreu C. Hydrtion chrcteristics of high lumin cement/portlnd cement mixtures. ZKG Int. 998;: Blnco-Vrel MT, Mrtínez-Rmírez S, Vázquez T, Sánchez- Morl S. Role of lklis of ggregte origin in the deteriortion of CAC concrete. Cem Concr Res. 005;5: