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2/3()(6-1)CVK TT温度TC时表面张力为零。2/3(6)(6-2)CVK TT对于液态聚合物,与T的关系?1190=1 (6-3)cTT 20911(1)(6-4)9ccdTdTTT常数dTdn0AnloglogV1dTdndTdndTdnn010 (6-6)dnTpTVV)/(1n0cmG (6-7)cmGGc m,(G)0TPcm,G()0 (6-8)cmT PcmT PT PGGAAA20 (6-9)TTcmcmPPPGA T gr,(G)0 (6-11)T PgrG (6-10)grGGgr,G()0 (6-12)T PgrA 2grG()0 (6-13)TTgrPPPA T g:玻璃态的表面张力;:玻璃态的表面张力;r:橡胶态的表面张力,:橡胶态的表面张力,在玻璃化转变中,表面张力不发生突变。在玻璃化转变中,表面张力不发生突变。nbbbMKXX/表面张力与分子量?表面张力与分子量?2/3=/(6-15)bnKM 1/41/4/(6-16)snKM4=(P/V)(6-17)n=(P/V)(6-18)iiP=P (6-19)例:求聚甲基丙烯酸甲酯的表面张力例:求聚甲基丙烯酸甲酯的表面张力 CH3结构单元:结构单元:CH2C COOCH32个个CH3 56.12=112.2一个酯键一个酯键 64.8一个一个-CH2-39.0一个一个 C 4.8 Pi加和加和220.8(P/V)4=(220.8/86.5)4=42.810-3N/m cohE (6-20)UHRTcoh(CED)=E/(6-21)V1/21/2coh=(CED)(E/)(6-22)V21/3 0.86=16.8(/V)(6-23)0.430.14c (6-24)KV1.521.85c,0.327()/(6-25)sssm sFnnV1122=(6-26)1221 (6-27)1221 (6-28)1212a-W (6-29)1/2c12Wa=(W)(6-30)cWc 1122W22cW1/2121212-2()(6-32)V=(6-33)A 1/31/312V1/31/3 2124 (6-34)()VVVV22221 2111 21 22 112A1/2442222121 11 12 22232243 (6-35)3232224343IIIIKTIIKTKT V:相互作用单元的摩尔体积 1/212A122()(6-36)I III1/2SLV2()(3-39)SVLVSLV 2SV2(1 cos)(6-40)4LV1/2SVcos=21 (6-41)LV1/2121212-2()(6-42)21/21/21212 (6-43)(6-44)dpdp1/21/212121212-2()-2()(6-45)dp 221/21/21/21/2121212()()()()(6-46)ddpp1/21/21/21/2()()()()1+cos=2 (6-47)ddppSLSLLL1/21/21/21/21/21/21/21/2()(21.8)()(51.0)1+0.052=272.872.8()(49.5)()(1.3)1 0.809=250.850.8dpSSdpSS340.0,1.540.0 1.541.5(10/)dpssdpsssN m1221a21a-W =-W (6-48)dpaW1212121222 ddppdpccccaaddppccccW WW WWWWWWW12121212121244-(6-50)ddppddpp 1212121244 (6-49)ddppdpaaddppWW L44(1cos)(6-51)ddppSLSLddppLSSLc0SVsSLlim =(6-52)=LVSLe1/2C,cos=2(/)1 (6-57)LV2C,11 cos (6-58)4LV状态方程:状态方程:2SV2(1 cos)(6-40)4LV1/21/21/21/2()()()()1+cos=2 (6-47)ddppSLSLLLL44(1cos)(6-51)ddppSLSLddppLSSL2C,11cos (6-58)4LV
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