SPECIFIC HEAT CAPACITY OF CEMENTITIOUS COMPOSITES IN HIGH-TEMPERATURE RANGE

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1 SPECIFIC HEAT CAPACITY OF CEMENTITIOUS COMPOSITES IN HIGH-TEMPERATURE RANGE Jitka Poděbradská 1, Jaroslav Pavlík 1, Jan Toman 2, Robrt Črný 1 1 Czch Tchnical Univrsity, Faculty of Civil Enginring, Dpartmnt of Structural Mchanics, Thákurova 7, Praha 6, Czch Rpublic 2 Czch Tchnical Univrsity, Faculty of Civil Enginring, Dpartmnt of Physics, Thákurova 7, Praha 6, Czch Rpublic Abstract Spcific hat capacity c of svral cmntitious matrials, namly cmnt mortar, thr typs of glass fibr rinforcd composits and two typs of carbon fibr rinforcd composits, is dtrmind in th tmpratur rang of 25 0 C to C. Two basic typs of c(t) functional rlationships ar idntifid. Th first charactristic for matrials with silicous aggrgats is an incrasing function up to about C, which thn bgins to dcras. Th scond is a dcrasing function in th whol studid tmpratur rang. Ky words: cmnttitious composits, spcific hat capacity, high tmpraturs 1 Introduction Fibr rinforcd cmnt composits ar producd by incorporating a small amount of fibrs in cmnt mortar to ovrcom th traditional waknss of inorganic cmnts, namly poor tnsil strngth and brittlnss. Th lngth and contnt of th fibr rinforcmnt can b chosn to mt th strngth and toughnss rquirmnts of th product. Also, th typ of aggrgats can b varid in ordr to control thrmal proprtis. Glass fibr rinforcd cmnt composits (GFRCC) hav found thir plac as vrsatil and commrcially viabl matrials for us in construction industry in th bginning of 1970s [1]. Currntly, thy ar frquntly applid in wall systms, utilizd in form work, pipwork, usd for surfac bonding and rndring, tc. Thy can also rplac asbstos cmnt products as fir protction matrials. Mor dtaild survy of GFRCC applications can b found.g. in [1]-[3]. Carbon fibr rinforcmnt has found its application first in polymric matrics for automotiv and aircraft industry. It partially rplacd prviously usd glass fibrs in such situations whr suprior strngth proprtis, vry low tnsil strains and mass savings wr ncssary. Th initial phass of utilization of carbon fibrs in th production of composit matrials wr affctd by its high pric. Carbon fibr is producd by th controlld oxidation, carbonization and graphitization of carbon-rich organic prcursors, which ar alrady in fibr form. In th bginnings of carbon fibr production th most oftn usd prcursor was PAN (polyacrylonitril) that gav 18

2 suprior carbon fibr proprtis but was quit xpnsiv. Th apparanc of low cost pitch basd carbon fibrs in 1980s has ld to a significant incras of various applications of carbon fibrs. In th construction industry it rsultd in an incrasing us of carbon fibr rinforcd cmnt composits (s,.g., [4] for dtails). A comprhnsiv survy of both proprtis and procssing of carbon fibrs and of th various typs of carbon fibr rinforcd composits can b found in [5]. In th currnt rsarch practic, th mchanical proprtis of fibr rinforcd cmnt composits (FRCC) ar in th cntr of intrst of most rsarchrs working on thos matrials. This is quit logical taking into account why thy wr dvlopd, i.. to improv th tnsil and flxural strngth of cmnt basd composits. Howvr, thr ar numrous applications of fibr rinforcd composits that rquir a good knowldg of thrmal paramtrs. For instanc, lightwight FRCC can b usd as thrmal insulation matrials, othr FRCC can b mployd as fir protction matrials, tc. Thrfor, th knowldg of thrmal proprtis of FRCC particularly in high tmpratur rang is vry important. In this papr, spcific hat capacity of svral carbon and glass fibr rinforcd cmnt composits is dtrmind in a wid tmpratur rang and compard with cmnt mortar. 2 Mthod for th dtrmination of spcific hat capacity As th adiabatic mthods ar not vry suitabl for masuring high-tmpratur spcific hat capacity of building matrials, mainly bcaus of th ncssity to us rlativly larg sampls, a nonadiabatic mthod by Toman and Črný (s [6] for dtails) was mployd for th dtrmination of tmpratur-dpndnt spcific hat capacity. W will prsnt th main ida of th mthod in what follows. Th nonadiabatic calorimtr that w usd has a mixing vssl with a volum of 2,5 litrs. Th volum of th masuring fluid (watr in this cas) is about 1 litr. Th maximum volum of th masurd sampls is 1 litr. Th amount of hat loss of th nonadiabatic systm is dtrmind using a calibration. Th calorimtr is filld with watr, whos tmpratur is diffrnt from th ambint air. Thn, th rlation of watr tmpratur to tim, T c (t), is masurd. Th tsts show that th calibration curv T c (t) is narly xponntial; small diffrncs in masuring conditions caus only small changs in th calibration curv. Th xprimnts hav a rplicability bttr than 1%. Th masuring mthod itslf is basd on wll-known principls. Th sampl is hatd to a prdtrmind tmpratur T s in a muffl furnac and thn put into th calorimtr with watr. Thn, th rlation of watr tmpratur to tim T w (t) is masurd, th watr bing slowly stirrd all th tim, until th tmpraturs of th masurd sampl and th calorimtr ar qual. Th duration of tmpratur quilibration achivs typically svral hours, dpnding on th thrmal conductivity and siz of th matrial bing masurd. 19

3 Th hat balanc of th sampl-calorimtr systm can b writtn in th form: mc( T T ) = ( K + m c )( T T ) + m L Q, (1) s w w wo r whr m is th mass of th sampl, T s th tmpratur of th sampl prior to bing put into th calorimtr, c th spcific hat capacity of th sampl in th tmpratur intrval [T,T s ], K th hat capacity of th calorimtr, m w th mass of th watr, c w th spcific hat capacity of watr, T wo th initial watr tmpratur, L th latnt hat of vaporation of watr, Q r th raction hat of a possibl hydrolysis, m th mass of vaporatd watr. Dtrmining th spcific hat capacity c dirctly from quation (1) w would obtain a man valu of spcific hat capacity, c man, in th intrval [T,T s ] by c man ( K + mwcw )( T Two ) + m L Qr =. (2) m( T T ) s Howvr, from th physical point of viw, it is mor corrct to dtrmin th valu of th spcific hat capacity "pointwis", in accordanc with th basic physical dfinition of th spcific hat capacity, h( T ) c( T ) =. (3) T Using rlation (3) to dtrmin th spcific hat capacity, w hav to spcify th zro-point of th nthalpy scal, i.., w hav to nsur that all th nthalpy calculations ar rlatd to a crtain constant tmpratur. This rfrnc tmpratur can b, for xampl, T k = 0 0 C. Upon adding Q = mc T T ), (4) o ( k whr c o is th man spcific hat capacity of th sampl in th tmpratur intrval [0,T ], to both sids of quation (1), and dividing by m, w obtain h ( K + mwcw )( T Two ) + m L Qr ) = + co ( T T ). (5) m ( Ts k Th valu of c o is considrd to b constant, taking into account th condition T s T >> T T (6) k and it can b masurd, for xampl, using th classical adiabatic mixing mthod. Prforming a st of masurmnts for various sampl tmpraturs T i, w obtain a st of points [T i, h(t i )]. A rgrssion analysis of this pointwis givn function rsults in a functional rlationship for h = h(t) and, using rlation (3), also in th function c = c(t) as th first drivativ of h with rspct to T. 20

4 3 Matrials and sampls Th xprimnts wr don with svral diffrnt typs of cmntitious matrials, cmnt mortar, thr typs of glass fibr rinforcd composits and two typs of carbon fibr rinforcd composits. Th sampls of cmnt mortar had th following composition (i.. th mixtur for on charg): Portland cmnt ENV CEM I 42.5 R (Králův Dvůr, CZ) 450 g, natural quartz sand with continuous granulomtry I, II, III (th total scrn rsidu on 1.6 mm 2%, on 1.0 mm 35%, on 0.50 mm 66%, on 0.16 mm 85%, on 0.08 mm 99.3%) g, watr 225 g. Th sampls of glass fibr rinforcd cmnt composits dnotd as GC I, GC II, GC III wr plat matrials with Portland cmnt matrix (cmnt CEM I 52.5 Mokrá), which was rinforcd by alkali-rsistant glass fibrs (CEM-FIL 2 250/5B Tx mm for GC I, CEM-FIL 70/30 6 mm for GC II and GC III), th matrials GC II and III containd vrmiculit and wollastonit. Th basic composition of GC I, II, III is shown in Tabl 1 (th prcntag is calculatd among th dry substancs only, watr corrsponding to th watr to cmnt ratio of 0.8 is to b addd to th mixtur). Tabl 1 Composition of glass fibr rinforcd cmnt composits in %. Cmnt Sand Plasticizr GC I Glass fibr Wollastonit Vrmiculit Microsilica GC II GC III Th carbon fibr rinforcd cmnt composit spcimns (dnotd as CC I and CC III) had th composition shown in Tabl 2 (again calculatd among th dry substancs only). Portland cmnt CEM I 52.5 Mokrá was usd for CC I, aluminous cmnt Alcoa CA-14M for CC III, carbon fibr was pitch basd with 10 mm lngth. Watr in th amount corrsponding to th w/c ratio of 0.8 was addd to th mixtur for CC I, 0.73 for CC III. Tabl 2 Composition of carbon fibr rinforcd cmnt composits in %. Cmnt Microdorsilit Plasticizr Carbon fibr Wollastonit Mthylcllulos Dfoamr Microsilica CC I CC III Th dimnsions of th spcimns wr 71x71x71 mm. 21

5 4 Exprimntal rsults and discussion Th rsults of spcific hat capacity masurmnts carrid out using th nonadiabatic mthod dscribd in Sction 2 ar shown in Fig. 1. Two basic typs of c(t) functional rlationships can b idntifid. Th first is charactristic for cmnt mortar, GC I and CC III. Hr c(t) is an incrasing function up to about C, and thn it bgins to dcras. For GC II, GC III and CC I c(t) is a dcrasing function in th whol studid tmpratur rang Spcific hat capacity (J/kgK) GC I GC II GC III CC I CC III Cmnt mortar Tmpratur ( C) Fig. 1 Spcific hat capacity of studid cmntitious composits Th rlativly fast incras of spcific hat capacity of cmnt mortar in th tmpratur rang of C can b attributd probably to th ffct of silicous aggrgats. Silicon dioxid has at 25 0 C th spcific hat capacity of 730 J/kgK whil at C it is 1380 J/kgK [7]. This is in basic accordanc with our rsults bcaus th cmnt to sand ratio for th cmnt mortar was 1:3 so that th ffct of aggrgats on th spcific hat capacity (which is an additiv quantity in th sns of th thory of mixturs) was vry pronouncd. Similarly w can xplain th dcras of th spcific hat capacity of cmnt mortar abov C. Silicon dioxid undrgos at C th α β transition [7], and th nwly formd β form has th spcific hat capacity of only 1125 J/kgK [7]. Similar ffcts to thos on cmnt mortar can b obsrvd on GC I which has a similar composition xcpt for th cmnt to sand ratio that is 1:1. This might b th rason of th slowr incras of th c(t) function in th tmpratur rang of C. As for th rmaining matrials, thir c(t) function bhavior cannot b xplaind vn in a similar rough and simpl way lik with cmnt mortar and GC I bcaus of th lack 22

6 of rliabl data for th spcific hat capacitis of thir particular compounds. Anothr factor making any statmnt in this sns vn mor complicatd ar th chmical ractions in cmnt gl aftr hating that rsult in fact in our cas in a dtrmination of spcific hat capacity for a st of diffrnt matrials. 5 Conclusions Th spcific hat capacity of th studid cmntitious composits xhibitd various tmpratur dpndncs for diffrnt matrials. Th incrasing charactr of th c(t) functions that is typical for most crystallin solids (s,.g., [7]) was obsrvd for th matrials with silicous aggrgats, and only up to C. For th othr matrials th spcific hat capacity dcrasd with tmpratur. Although this typ of c(t) function is not vry common, it might b xplaind in gnral by th complicity of th studid systms whr quit a fw chmical ractions and phas transitions occur aftr th tmpratur incras. Acknowldgmnt This rsarch has bn supportd by th Ministry of Education of Czch Rpublic, undr grant No. MSM: Rfrncs [1] Majumdar A.J., Laws V., 1991 Glass Fibr Rinforcd Cmnt. BSP, Oxford. [2] Tru G., 1986 GRC Production and Uss. Palladian Publications Ltd., London. [3] Young J., 1978 Dsigning with GRC. Architctural Prss, London. [4] Ohama Y, 1989 Carbon-cmnt composits. Carbon 27, [5] Chung DDL, 1994 Carbon Fibr Composits (London, Buttrworth-Hinmann). [6] Toman J., Črný R., 1995 Calorimtry of Building Matrials. Journal of Thrmal Analysis 43, [7] CRC Handbook of Chmistry and Physics, 1991, ditd by D.R. Lid. 72nd Edition, CRC Prss, Boca Raton, pp. 4-83,

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