Aditivos e sua influência no comportamento de secagem e resistência à tração de concretos refratários.

INTRODUÇÃO

Os refratários são produtos fundamentais para uma vasta gama de indústrias. De modo geral, qualquer processo que envolva altas temperaturas depende do desempenho de refratários. A necessidade de melhorias de processos, aumento GD H¿FLrQFLD H GD SURGXWLYLGDGH UHVXOWDP HP FRQWtQXRV LQYHVWLPHQWRV SDUD LQFUHPHQWDU R QtYHO GH TXDOLGDGH GHVVHV SURGXWRV 'HQWUH HOHV RV UHIUDWiULRV PRQROtWLFRV RX QmR SUp PROGDGRV FRPR RV FRQFUHWRV WrP VH GHVWDFDGR HP UHODomR

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Departamento de Engenharia de Materiais - DEMa, Universidade Federal de S. Carlos - UFSCar

Rod. Washington Luiz, km 235, C.P. 676, S. Carlos, SP 13565-905

ivone@iris.ufscar.br, vicpando@power.ufscar.br

Resumo

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3DODYUDVFKDYH: concretos refratários, aditivos, secagem, hidratos.

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surface. The hydration of calcium aluminate cement is also responsible for the castables permeability reduction. This process is

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favored the dispersion of castable and decreased water consumption resulting in the main formation of hydrates C₃AH₆ and AH₃. The formation of AH₃ is particularly favored by precipitation of C₃AH₆ due to alumina content available to its formation to be larger.

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development. On the other hand, in the presence of additive AC it was observed reduction in relation the formation these hydrates due his retarder effect which occurred by calcium ions consumption. Moreover, the presence of bigger water content contributed for increase of porosity and decrease of traction strength of castable.

.H\ZRUGV: Refractory castables, drying, mechanical strength, hydration, cement.

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MATERIAIS E MÉTODOS

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RESULTADOS E DISCUSSÃO

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do ligante. Esse elevado estado de dispersão resultou em XPPHQRUFRQVXPRGHiJXDSDUDDSUHSDUDomRGRFRQFUHWR TXDQGRFRPSDUDGRDRVGHPDLVDGLWLYRV7DEHOD,

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3AH6 pRKLGUDWRIRUPDGRPDMRULWDULDPHQWHHPWHPSHUDWXUDVDFLPD GHo_{&RXQDSUHVHQoDGHWHRUHVUHGX]LGRVGHiJXD2KLGUDWR} AH₃$OO₃.3H2IRUPDVHHPWRGDDIDL[DGHWHPSHUDWXUDH WHRUHVGHiJXDHPERUDRDXPHQWRGDWHPSHUDWXUDHRSDVVDUGR WHPSRSRVVDPRGL¿FDUVXDHVWUXWXUDGHDPRUIDSDUDFULVWDOLQD Entre as diferentes fases de aluminato de cálcio hidratado, o C₃AH₆pRPDLVHVWiYHOHR&$+RPHQRVHVWiYHOMiSDUDR AH₃ D HVWDELOLGDGH DXPHQWD TXDQGR HVWH FRPSRVWR SDVVD GH DPRUIRSDUDFULVWDOLQR>@(VWDVXSRVLomRHVWiGHDFRUGRFRP RIDWRGHTXHHPFRQFUHWRVFXUDGRVHPFRQGLo}HVRQGHDVIDVHV CAH e AH₃ na forma de gel são favorecidas, o tempo ou o DXPHQWRGDWHPSHUDWXUDID]HPFRPTXHHVWHVPDWHULDLVSDVVHP JUDGDWLYDPHQWHDVHUHPFRQVWLWXtGRVSHODIDVH&₃AH₆ e pelo AH₃ cristalino.

)LJXUD5HVLVWrQFLDjWUDomRD~PLGRRXDSyVVHFDJHPDo_{&HPIXQomRGRWHPSRGHFXUDSDUDFRQFUHWRVSUHSDUDGRV}

FRP&$0RX6HFDUQDSUHVHQoDGHGLIHUHQWHVDGLWLYRVGLVSHUVDQWHV

>)LJXUH7UDFWLRQVWUHQJWKZHWRUGULHGDWo_{&DVDIXQFWLRQRIFXULQJWLPHIRUFDVWDEOHVSUHSDUHGZLWK&$0}

or Secar 71 cement containing different dispersant additives.]

)LJXUD 3RURVLGDGH DSDUHQWH SDUD FRQFUHWRV SUHSDUDGRV FRP &$0RX6HFDUQDSUHVHQoDGHGLIHUHQWHVDGLWLYRVGLVSHUVDQWHV

FXUDGRVGXUDQWHKDo_C.

>)LJXUH$SSDUHQWSRURVLW\IRUFDVWDEOHVSUHSDUHGZLWK&$0

or Secar 71 in the presence of different additives, cured at 50 o_C

for 72 h.]

tempo de cura (h)

'HVVDIRUPDpSRVVtYHOREVHUYDUSRUPHLRGRVHQVDLRVGH VHFDJHP)LJXUDDH[LVWrQFLDGHDOJXQVSLFRVGHGHVLGUDWDomR DEDL[RGHo_{&RVTXDLVQmRVHDSUHVHQWDPEHPGH¿QLGRV} (VWH IDWR p DLQGD PDLV FUtWLFR TXDQGR XWLOL]DGR R DGLWLYR &6 $ ¿P GH VH YLVXDOL]DU PHOKRU D RFRUUrQFLD GRV SLFRV GH GHVLGUDWDomR HVWHV HQVDLRV IRUDP UHSHWLGRV XWLOL]DQGRVH DPRVWUDVVHFDVDo_{&)LJ'HIDWRSRGHVHUREVHUYDGD} PDLVQLWLGDPHQWHDH[LVWrQFLDGHSLFRVRVTXDLVSRGHPVHU UHODFLRQDGRVjSUHVHQoDGRKLGUDWR&AH₈o_&$+

3 o&&

3AH6

o&H$+SRUYROWDGHo_C.

7RPDQGR FRPR EDVH D RFRUUrQFLD GD IRUPDomR GHVVHV tipos de hidratos, quando comparamos as curvas de secagem DSUHVHQWDGDV QD )LJ SRGHVH REVHUYDU TXH RV WLSRV GH KLGUDWRV IRUPDGRV VRIUHUDP LQÀXrQFLD GR WHRU GH iJXD GLVSRQtYHOFRQIRUPHSUHYLVWRSHOD)LJ¬PHGLGDTXHIRL FRQVXPLGRXPPDLRUWHRUGHiJXDQDSUHSDUDomRGRFRQFUHWR

)LJXUD9HORFLGDGHGHVHFDJHPHPIXQomRGDWHPSHUDWXUDGDDPRVWUDSDUDFRQFUHWRVSUHSDUDGRVFRP&$0RX6HFDU

QDSUHVHQoDGHGLIHUHQWHVDGLWLYRVSDUDRVWHPSRVGHFXUDDo_&GHHK

>)LJXUH'U\LQJUDWHDVDIXQFWLRQRIWKHVDPSOHWHPSHUDWXUHIRUFDVWDEOHVSUHSDUHGZLWK&$0RU6HFDUFRQWDLQLQJ

different additives, for curing time at 50 o&RIDQGK@

)LJXUD (VTXHPD UHSUHVHQWDQGR DV UHDo}HV GH KLGUDWDomR PDLV

comuns para CAC.

>)LJXUH*HQHUDOGLDJUDPIRUK\GUDWLRQUHDFWLRQRI&$&@

Temperatura (ºC)

V

$&!&'!&6RFRUUHXDIRUPDomRSUHIHUHQFLDOGRKLGUDWR CAH₈GDGRDRSLFRGHGHVLGUDWDomRFDUDFWHUtVWLFRHPWRUQR GHo_{&3RURXWURODGRDXWLOL]DomRGRDGLWLYR&6FRPR} GLVSHUVDQWHQDSUHSDUDomRGRVFRQFUHWRVUHIUDWiULRVOHYRXj REWHQomRGHFRQFUHWRVPDLVÀXLGRVFRPUHGX]LGDSRURVLGDGH consumindo um menor teor de água quando comparado DRVGHPDLVDGLWLYRV$SUHVHQoDGHVVHPHQRUWHRUGHiJXD SRGHMXVWL¿FDUDIRUPDomRSUHIHUHQFLDOGRKLGUDWR&

3AH6 na WHPSHUDWXUD GH FXUD XWLOL]DGD o_{& -i TXDQGR XWLOL]DGR} $& DOpP GR WHRU GH iJXD GLVSRQtYHO SDUD D IRUPDomR GH CAH₈ ser o maior entre os aditivos testados outro fator pode WHUFRQWULEXtGRSDUDDUHGXomRTXDQWRDIRUPDomRGH&₃AH₆ quando comparado a CD. De acordo com estudos anteriores >@ HVVH DGLWLYR DSUHVHQWD XP H¿FLHQWH HIHLWR UHWDUGDGRU GRPHFDQLVPRGHKLGUDWDomRGRFLPHQWR(OHVHTHVWUDRV tRQV &D _{GL¿FXOWDQGR D IRUPDomR GH KLGUDWRV PDLV ULFRV}

em cálcio como C₃AH₆,VVRSRGHMXVWL¿FDUDHYROXomRGD DOWXUDGRSLFRFDUDFWHUtVWLFRGDGHVLGUDWDomRGR&₃AH₆ com RWHPSRLQGLFDQGRTXHQDSUHVHQoDGHVVHDGLWLYRDIRUPDomR GHVVHKLGUDWRIRLUHWDUGDGD)LJ$VVLPDOpPGRPHQRU FRQVXPRGHiJXDQDSUHSDUDomRGRFRQFUHWRXPDVHJXQGD YDQWDJHP FRP UHODomR DR XVR GR DGLWLYR &6 SRGH VHU DWULEXtGDDRIDWRGHTXHMiFRPKRPDWHULDOQmRDSUHVHQWD QHQKXPDHYROXomRGDVIDVHVFRQWULEXLQGRSDUDDUHGXomRGR WHPSRGHGHVPROGDJHPGHFRQFUHWRV3RGHVHREVHUYDUQD

)LJTXHSUDWLFDPHQWHWRGDiJXDDGLFLRQDGDpFRQVXPLGD QDIRUPDomRGDIDVH&₃AH₆-iFRPiFLGRFtWULFRjPHGLGD TXH VH DXPHQWD R WHPSR GH FXUD GH SDUD K SRGH VHUYHUL¿FDGDDIRUPDomRGHXPDPDLRUTXDQWLGDGHGDIDVH C₃AH₆UHGX]LQGRRWHRUGHiJXDOLYUHREVHUYDGRSRUPHLRGR SLFRHPWRUQRo_C.

$LQÀXrQFLDGRDGLWLYRTXDQWRDRWLSRGHKLGUDWRDVHU IRUPDGRSRGHVHUPHOKRUYLVXDOL]DGDTXDQGRFRPSDUDPRV DVFXUYDVGHVHFDJHPSDUDXPWHPSR¿[RGHFXUDHPIXQomR GD SUHVHQoD GRV GLIHUHQWHV DGLWLYRV GLVSHUVDQWHV )LJ 3RGHPVH LGHQWL¿FDU WUrV UHJL}HV EHP GH¿QLGDV VHQGR UHJLmR$ DEDL[R GH o_{& FRUUHVSRQGHQWH D SUHVHQoD GH} iJXDOLYUHHDIRUPDomRGHKLGUDWRVFRPPDLRUWHRUGHiJXD &AH₈UHJLmR%o_{&FRUUHODFLRQDGDDIRUPDomR} dos hidratos C

3AH6 e AH3HUHJLmR&

o&GHYLGR DIRUPDomRGRKLGUDWR$+

&RPRGLVFXWLGRDQWHULRUPHQWHQDSUHVHQoDGRVDGLWLYRV $& H &' D RFRUUrQFLD GH GHVLGUDWDomR QD UHJLmR $ p predominante sendo os picos na região C menos notados SULQFLSDOPHQWH QD SUHVHQoD GH $& SDUD K GH FXUD 3RU RXWUR ODGR TXDQGR R DGLWLYR &6 p XWLOL]DGR RFRUUH D IRUPDomRSUHIHUHQFLDOGHKLGUDWRVQDUHJLmR%(QWUHWDQWR QDSUHVHQoDGHVVHDGLWLYRVHGHVWDFDDIRUPDomRGHKLGUDWRV na região C.

$ IRUPDomR GH IDVHV FRPR $+₃ p SDUWLFXODUPHQWH IDYRUHFLGDSHODSUHFLSLWDomRGR&₃AH₆XPDYH]TXHKiPDLV DOXPLQD GLVSRQtYHO SDUD D IRUPDomR GR KLGUDWR$+₃ >@ Essa fase aparece freqüentemente como um gel e devido a sua DOWDFDSDFLGDGHGHSUHHQFKHUYD]LRVLQWHUSDUWLFXODVSRGHVHU FRUUHODFLRQDGDDRGHVHQYROYLPHQWRGHUHVLVWrQFLDPHFkQLFD $IRUPDomRSUHIHUHQFLDOGR&₃AH₆TXDQGRQDSUHVHQoDGH&6 SRGHMXVWL¿FDUDPDLRUIRUPDomRGH$+₃ e consequentemente RJDQKRGHUHVLVWrQFLDjWUDomR$GHVLGUDWDomRGHXPDPDLRU quantidade de AH₃ o_{& SRGH MXVWL¿FDU D VXSHULRU} IRUPDomRGH$+YHUL¿FDQGRVHXPDXPHQWRGRSLFRUHODWLYR a região C. Dessa forma, a medida que o aditivo permitiu a IRUPDomRGHXPPDLRUWHRUGH&₃AH₆IRLREVHUYDGRXPPDLRU SLFRUHODWLYRDUHJLmR%&₃AH₆$+₃HFRQVHTXHQWHPHQWH QDUHJLmR&$+

(QVDLRV UHDOL]DGRV SDUD FRQFUHWRV QD DXVrQFLD GH OLJDQWH XWLOL]DQGRVH FRPR GLVSHUVDQWHV RV DGLWLYRV &6 H $&PRVWUDUDPTXHQmRKiRFRUUrQFLDGHXPSLFRDFLPDGH o&,VVRFRQ¿UPDTXHWDOSLFRQmRVHGHYHDKLGUy[LGR GHDOXPtQLRIRUPDGRDSDUWLUGDVDOXPLQDVGDPDWUL])LJ PDVVLPGHXPGHVEDODQFHDPHQWRHQWUHDVFRQFHQWUDo}HV de CaO e AlO₃ provenientes do cimento.

&DEH UHVVDOWDU TXH DGLWLYRV QRUPDOPHQWH HPSUHJDGRV QDFRPSRVLomRGHFRQFUHWRVUHIUDWiULRVQmRDWXDPVRPHQWH QDGLVSHUVmRGDVSDUWtFXODVGDPDWUL]HOLJDQWHPDVRHIHLWR GDVXDDWXDomRSRGHLQÀXHQFLDUQRWLSRGHKLGUDWRIRUPDGR &RQVHTHQWHPHQWH D LQÀXrQFLD GRV DGLWLYRV IRL YHUL¿FDGD QDUHVLVWrQFLDjWUDomRHQRFRPSRUWDPHQWRGHVHFDJHPGRV FRQFUHWRVVHPDQWHQGRDWpPHVPRHPSURSULHGDGHVHPDOWD WHPSHUDWXUDFXMRHVWXGRHVWDVHQGRUHDOL]DGR

$ ¿P GH HQWHQGHU PHOKRU D LQÀXrQFLD GRV DGLWLYRV RV HQVDLRV GH VHFDJHP WDPEpP IRUDP UHDOL]DGRV SDUD FRPSRVLo}HVQDDXVrQFLDGHVWHV3RGHVHUREVHUYDGRQD)LJ

)LJXUD 9HORFLGDGH GH VHFDJHP HP IXQomR GD WHPSHUDWXUD GD DPRVWUD SDUD FRQFUHWRV SUHSDUDGRV FRP S GH &$0 QD SUHVHQoDGRDGLWLYR&6~PLGRVRXVHFRVDo_{C, para os tempos}

GHFXUDDo&GHHK

[Figure 5: Drying rate as a function of the sample temperature for

FDVWDEOHV SUHSDUHG ZLWK ZW &$0 DQG DGGLWLYH &6 ZHW RU

R OLJDQWH XVDGR p R 6HFDU )LJ 'H IDWR TXDQGR VH FRPSDUDP RV UHVXOWDGRV GH UHVLVWrQFLD j WUDomR REWLGRV QDSUHVHQoDGRVGLVWLQWRVOLJDQWHVDSyVVHFDJHPDo_C )LJRFRUUHXXPDPDLRUGLIHUHQoDQDSUHVHQoDGH&' ,VVRFRPSURYDTXHRIDYRUHFLPHQWRTXDQWRDIRUPDomRGH AH₃HFRQVHTHQWHPHQWH$+QDSUHVHQoDGH6HFDU&' FRQWULEXLXSDUDRDXPHQWRGDUHVLVWrQFLDjWUDomR(QWUHWDQWR RVUHVXOWDGRVPRVWUDPTXHQDSUHVHQoDGH&6DUHVLVWrQFLD j WUDomR REWLGD FRP R VLVWHPD 6HFDU &' p VXSHUDGD LQGHSHQGHQWHGROLJDQWHXVDGR'HVVDIRUPDDFRPSRVLomR IRUPDGDQDSUHVHQoDGROLJDQWH6HFDUHRDGLWLYR&6SRGH VHU DSRQWDGD FRPR D PDLV H¿FLHQWH SDUD D SUHSDUDomR GH FRQFUHWRVHQWUHDVGLIHUHQWHVFRPSRVLo}HVDYDOLDGDV3RGH VHDOLDUXPDH¿FLHQWHGLVSHUVmRGRFRQFUHWRHHOHYDGDÀXLGH] FRPDXPHQWRGHUHVLVWrQFLDjWUDomR(QWUHWDQWRRIDWRGH JHUDUXPDHVWUXWXUDPDLVGHQVDSRGHGL¿FXOWDUDVHFDJHPGR PDWHULDODFDUUHWDQGRHPSUHMXt]RVFRPRDH[SORVmRGRFRUSR GHSHQGHQGRGDWD[DGHDTXHFLPHQWRXVDGD

CONCLUSÕES

2VDGLWLYRVQRUPDOPHQWHHPSUHJDGRVQDFRPSRVLomRGH concretos refratários não atuam somente na dispersão das que o teor de água livre a ser eliminada durante o aquecimento

p VLJQL¿FDWLYDPHQWH DXPHQWDGR SLFR SUy[LPR o& ,VVRPRVWUDTXHSDUWHGDiJXDDGLFLRQDGDQDSUHSDUDomRGR FRQFUHWRQmRHVWiVHQGRXWLOL]DGDQDIRUPDomRGHKLGUDWRV 1DDXVrQFLDGHDGLWLYRDGLVSHUVmRGROLJDQWH¿FDSUHMXGLFDGD ID]HQGRFRPTXHPHQRVSDUWtFXODViUHDVXSHU¿FLDOVHMDP H[SRVWDV D KLGUDWDomR UHGX]LQGR R FRQVXPR GH iJXD OLYUH SDUDDIRUPDomRGHKLGUDWRV-iTXDQWRPHOKRUIRUDGLVSHUVmR GDVSDUWtFXODVGROLJDQWHPDLRUDKLGUDWDomRHRFRQVXPRGH iJXDSDUDDIRUPDomRGDVIDVHVKLGUDWDGDVUHVWDQGRPHQRV iJXD OLYUH D VHU HOLPLQDGD GXUDQWH D VHFDJHP ,VVR UHGX] RV ULVFRV GH H[SORVmR GR FRQFUHWR GXUDQWH HVWD HWDSD GR SURFHVVDPHQWR7DPEpPpREVHUYDGRXPSLFREHPPHOKRU GH¿QLGRUHODWLYRDIRUPDomRGH&₃AH₆ quando comparado ao PHVPRSLFRQDSUHVHQoDGHDGLWLYRV(VVDGLIHUHQoDSDUHFH HVWDUDVVRFLDGDDRGHFUpVFLPRQDIRUPDomRGRKLGUDWR$+₃ HFRQVHTXHQWHPHQWHGH$+3RUWDQWRVRPHQWHDIRUPDomR preferencial de C₃AH₆QmRJDUDQWHDIRUPDomRGH$+₃.

2VFRUSRVPROGDGRVQDDXVrQFLDGHDGLWLYRVDSUHVHQWDUDP muitos defeitos, resultando numa estrutura muito mais porosa TXDQGR FRPSDUDGD j HVWUXWXUD GH FRUSRV REWLGRV D SDUWLU GH FRQFUHWRVEHPGLVSHUVRV(VVDFDUDFWHUtVWLFDHVWUXWXUDOSDUHFH LQÀXHQFLDU QD IRUPDomR GH KLGUDWRV GH DOXPLQD VHQGR TXH TXDQWR PDLV GHQVD D HVWUXWXUD PDLV SURSLFLD D IRUPDomR GH AH₃FRPRRFRUUHQDSUHVHQoDGH&68PRXWURIDWRUTXHSRGH SURSLFLDUDIRUPDomRGH$+₃pRDXPHQWRGHWHPSHUDWXUD,VVR SRGHULDMXVWL¿FDURVLJQL¿FDWLYRDXPHQWRGHUHVLVWrQFLDjWUDomR YHUL¿FDGRSDUDRVFRUSRVTXDQGRQDSUHVHQoDGH&6VHFRVD o_{C quando comparado aos corpos úmidos.}

&RPSDUDQGRVH DV FXUYDV GH VHFDJHP REWLGDV QD SUHVHQoD GRV GLVWLQWRV OLJDQWHV HVWXGDGRV &$0 H 6HFDU QmR p REVHUYDGD GLIHUHQoD TXDQWR D IRUPDomR GH IDVHV TXDQGR QD SUHVHQoD GH &6 3RU RXWUR ODGR QD SUHVHQoDGH&'DIRUPDomRGDIDVH$+VHGHVWDFDTXDQGR

)LJXUD 9HORFLGDGH GH VHFDJHP HP IXQomR GD WHPSHUDWXUD GD DPRVWUDSDUDFRQFUHWRVSUHSDUDGRVQDDXVrQFLDGHOLJDQWH S GH iJXD XWLOL]DQGRVH FRPR GLVSHUVDQWH RV DGLWLYRV &6 H$& FXUDGRVGXUDQWHK

[Figure 6: Drying rate as a function of the sample temperature for castables prepared without binder but containing CS and AC

DGGLWLYHVFXULQJDWo_&IRUK@

)LJXUD 9HORFLGDGH GH VHFDJHP HP IXQomR GD WHPSHUDWXUD GD DPRVWUDSDUDFRQFUHWRVSUHSDUDGRVFRP&$0RX6HFDUVHP

DGLWLYRVSDUDRVWHPSRVGHFXUDDo_&GHHK

[Figure 7: Drying rate as a function of the sample temperature for

FDVWDEOHVSUHSDUHGZLWK&$0RU6HFDUZLWKRXWDGGLWLYHVIRU

SDUWtFXODVGDPDWUL]HOLJDQWHPDVRHIHLWRGDVXDDWXDomR SRGHLQÀXHQFLDUQRWLSRGHKLGUDWRIRUPDGR

2DGLWLYR&6VHGHVWDFDFRPRXPH¿FLHQWHGLVSHUVDQWH SURPRYHQGRDUHGXomRQRFRQVXPRGHiJXD,VVRDFDUUHWDQD IRUPDomRSUHIHUHQFLDOGRVKLGUDWRV&

3AH6GLVSRQLELOL]DQGR PDLV DOXPLQD SDUD D IRUPDomR GH $+₃. Esses tipos de KLGUDWRVFRQWULEXHPSDUDDXPHQWDUDUHVLVWrQFLDjWUDomRGR material.

3RURXWURODGRRDGLWLYR$&GHVIDYRUHFHDIRUPDomRGR hidrato C₃AH₆XPDYH]TXHDWXDSRUPHLRGRFRQVXPRGH tRQVFiOFLR7DPEpPDSUHVHQoDGHXPPDLRUWHRUGHiJXD QRVFRQFUHWRVSUHSDUDGRVFRP$&FRQWULEXLSDUDDIRUPDomR do hidrato CAH

8.

$ IRUPDomR GR KLGUDWR $+₃ p DLQGD PDLV IDYRUHFLGD TXDQGR R OLJDQWH XWLOL]DGR p R 6HFDU UHVXOWDQGR HP VXSHULRU UHVLVWrQFLDj WUDomR TXDQGR FRPSDUDGR DR XVR GH &$0

AGRADECIMENTOS

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