橡胶的老化与寿命估算_续_第十章橡胶贮存期或性能变化

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394,,,,TWDakin19841960,,,1DakinP,tT,Dakin1948,Pt:f1(p)=kt(1),k,T,Arrhenius:k=A0e-E/RT(2)(1)(2):logt=logf1(p)A0+ET-12.303R(3)PPet,logt=logf1(pe)A0+ET-12.303R=a+bT-1(4),tT,Dakin68Dakin(4)f1(P)=log(P/P0),Pt,(4)f1(P),(4)(4),,,P,,(4):logt=logt1=b(T-1-T-11)(5)(a),(b)tT-168Dakin(logt1,T-11),b,,,,T,,,,,2,Pt,,,k,(2)k,,,P2t,:y=e-kt(6)(6),92©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(6),,:y=Ae-kt(7)y=Ni-1Aie-ktN=23,Ai=1(8)y=Be-kt(9)(6)(9),y=f(P),f(P)=P/P0;,f(P)=1-PB,kA(7),,,(8),,,X2(9)(6)(7),,,Maxwell,(9)69(a);(b);(c)logkT-1693,2,PtT,P=f(tT),,P,P(T1,t)=P(T2,t/aT)(10),,,,(10):P(T1,t)1T1=P(T2,t/aT)2T2(11),1,2T1T2,WLF:logaT=-C1(T-T0)C2+T-T0(12),T0,C1C2,,:,,(10)T0P(T0,t0),TP(T,t),P=(T0,t0)=P(T,t)(13)(10)(13)t0=t/aT(14)(4)logaT=logt-logt0=b(T-1-T-10)(15)aTT0T,(13)(15)TPt,7070Pt4P2t2T,03©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.=f(t,T)P=f(t),kArrhenius,P=f(t,T),(2)(9),:log[-log(y/B)]=B0+B1x1+2x2(16),y=f(P),B0=log(A0/2.303),B1=E/2.303R,B2=a,x1=T-1,x2=logt,,Arrhenius,(16)(9),(16),55.1,P,:P=Ae-k,PLL0;;(1-),;,d;k,d-1;AlnP,P:P=Ae-k,kT-1Arrhenius:k=Ze-E/RT,T,K;E,Jmol-1;Z,d-1;R,JK-1mol-15.2,nP:12,jP1,P2,Pjj=1,2,n5.2.1P=Ae-kkx=;y=lnP;b=-k,P=Ae-ky=a+bxa,brb=Lyy/Lxxa=…y-bŠxr=LxyLxxLyy,Lxx=nj=1(xj-Šx)2Lyy=nj=1(yj-…y)2Lxy=nj=1(xj-Šx)(yj-…y)Šx=nj=1xjn…y=nj=1yjn(A),99%,f=n-2rr,|r|r,xy,y=a+bx,b|r|r,xykT,T1,T2,Tik1,k2,,kii=1,2,mx1=T-1,T=273Qy1=lnK,ai=lnZbi=-E/Rk=Ze-E/RTy1=ai+bix1,ai,bir1bi=Ly1y1/Lx1x1,ai=…y1-biŠx1r1=Lx1y1Lx1x1Ly1y1,Lx1x1=mi=1(x1i-Šx1)2Ly1y1=mi=1(y1i-…y1)213©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.=mi=1(x1i-Šx1)(y1i-…y1)Šx=mi=1x1im…y=mi=1y1im(A),95%,f=m-2rr1,r1r,,y1=a1+b1x1;r1r,y1=ai+bix1(Qs,)…ksxs=1/TsTs=273+QsLn…ks=ai+bi1/Ts…ks=e(a1+b11/Ts)y1=a+bx1y1Sy=S1+1m+(xs-Šx1)2Lx1x1S=(1-r21)Ly1y1m-2,y1=aitsy+bix1lnk=aitsy+bi1Ttt(A)t(Qs,)kslnks=ai+tsy+bi1Tsks=e(ai+tsy+bi1Ts)(Qs,),P=Ae-kAQ,:AQ95%AQr2,,Qs,As=a2+b2Qs:AQ,A,1As1mAA=mi=1AimŠPsPsŠPsQs,,Ps…ksksAsP=Ae-k:ŠPs=Ase-…ksc,Ps=Ase-ksc2.2P=Ae-k,,,II=mi=1mj=1(Pij-ŠPij)2,Pijij^PijijI,,P=Ae-klnP=lnA-ky=a+bxab,mkk=|b|AeA=mi=1Aimk=Ze-E/RTy1=a1+b1x1,a1,b1m^kiŠP=e(a1+b1x1)I=mi=1mj=1(pij-Špij)2=mi=1mj=1(Pij-^Ae-^kiij)2:01,=0.500.51,I,=0.50I,0015,01510.10,0.050.01I,Aky1=a1+b1x1:,Qs(Ts=273+Q)ks,ŠPsPsA…ksks,P=Ae-kŠPs=Ae-…ks,Ps=Ae-ks23©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.()r95%99%10.9971.00020.9500.99030.8780.95940.8110.91750.7540.8746-0.8347-0.7988-0.7659-0.73510-0.70811-0.68412-0.66113-0.64114-0.62315-0.60616-0.59017-0.57518-0.56119-0.54920-0.537t95%16.34022.92032.35342.13152.015B()P=Ae-kzP=Ae-kk=Ze-E/RTA=a2+b2QXylnplnpalnAlnAb-k-krx1lnky1T-1ailnZbi-ERr1r2Q,Qs,T,KXs1/(273+Q)SSyS1+1m+(xs-Šx1)2Lx1x1t95%,f=m-2t()…ksks(95%)ŠPsks(95%)66.1-dcdt=kc,c;t;kdtc,,c0t=0,:c0/c=ektPP0ct=0c0,:P0/P=ekt:lnP0/P=ktlne=ktk,Arrhenius:k=Ae-B/RT,A;e2.718;R,8.314J/(molK);T,KklnP0/P=kt,t:lgt=lglgP0/PA+ElgeR1T(6)a=lglgP0/PA,b=ElgeR33©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.=a+b1T(7),,lgt1/T,a,bb,E:E=Rblge(8),bTTt,a,(lgt,1T),,,6.2,(),(71),,,Tt,(71),t1t2t3tn,,7126.3(6)(7),,,y=lgt,x=1T(6):y=a+bx(9),ab,,,6161T,K333343353363373383ty=lgt1.971.6301.2000.8500.5100.180,x=1T10-33.0030032.915452.8328612.7548212.6809652.610966:n=6,t:dab:y=6.340x=16.798006810-3…y=1.05667Šx=2.79967810-3y2=8.9928x2=47.13674310-6(y)2/n=6.69927(x)2=47.0291810-6(y-…y)2=y2-(y)2/n=2.293533(x-Šx)2=x2-(x)2/n=0.10756210-6xy=18.24640010-3(x)(y)/n=17.74995910-3(x-Šx)(y-…y)=xy-(x)(y)/n=0.49644110-3b=(x-Šx)(y-…y)(x-Šx)2=4615.4a=…y-bŠx=11.865ab(9)(7),,:^y=11.865+4615.4x(10)43©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.=y1+y2+y3+y4+y5+y6=1.970+1.630+1.200+0.850+0.510+0.180=6.340y…y=yn=6.3406=1.056667xŠxlgt=-11.865+4615.41T(11)(10)(11)62,271,25(298K):t=4179.59d=11.50a,()2,ab62TK()x=1T…y=lgtt,d298(25)3.35570510-33.6234197313(40)3.19488810-32.881760.33333(60)3.00300810-31.99598343(70)2.9154510-31.59138.99353(80)2.8328610-31.21016.22363(90)2.75482110-30.85007.03373(100)2.68096510-30.5093.23383(110)2.61096610-30.1861.536.461xy,,,,xyrr=(x-Šx)(y-Šx)(x-Šx)2(y-…y)2(12)(12):r=0.49644110-30.10756210-62.293533=0.9995n-2=6-2=4a0.05,,0.811r0.99950.811,xy,6.5,,,,2,,,2,:PP0=aekt(13),P;P0;a;e;k;t;()1,,,,,72,,,A;,B,,A,B,72253©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(12%22%,15%40%),,,7.1,,,,;7.2:(GB/T3512-2001),(GB/T528-1998),(GB/T1685-1989):5,4,10K:NRCR383K;NBRSBRIIRBR383363K;EPDM430383K,:,53,,;,50%,50%10,,,,20%,80%,90%,,15010080mm3,,,,,,,,,:(GB/T3512-2001),(GB/T1685-1989),3d,,3d,,3h,,,(GB/T1683),,1d,,1d,,,1d,,,1d,,1d,,,(GB/T528-1998)10,57.3y,:y=Bek(1)yff0;LL0;1;B;k,d-1;,d;kT:k=Ae-E/RT(2)63©1994-2013ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.:,(1),,,II=Pi=1nj=1(yij-^yij)2(3),yiji,j;^yijijI,,(1):y=a+bx(

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