第一章 4 固体松弛2011.ppt

?I松弛 Y Men, J Rieger, H-F Endeler, D Lilge, Macromolecules 2003, 36, 4689-4691 支化聚乙烯的?松弛 支化度不同对?I基本无影响，因为所有样品都有近似的结晶度、熔点、片晶厚度和界面滑移。 363K UHMWPE的MAS 2D谱 1、2C原子对应无定形信号； 9、10C原子对应结晶信号 在MAS条件下，PE晶区T构象的化学位移与无定形区G构象相差2ppm 交叉峰(ca)对应结晶区向无定形区的磁化信号的交换，约为结晶峰信号(c)强度的20% 晶区-无定形区间(界面区)CH2发生相互交换 ? 180?翻转+平移1个CH2单元 翻转速率符合Arrhenius关系 Ea = 105 kJ/mol K Schmidt-Rohr, HW Spiess, Macromolecules 1991,24, 5288 MAS: magic angle spinning 魔角旋转，样品高速旋转，旋转轴与磁场夹角54.7?，消除核自旋间的磁相互作用 结晶-非晶转变 DD/MAS 2D-13C NMR 78 ?C LDPE：1%结晶单元参与180?翻转运动?分子链扩散 PE单晶：非晶组分中45%参与扩散 MLLDPE(10bu/1000C)：非晶组分中7~13%参与扩散 K Kuwabara, H Kaji, M Tsuji, F Horii, Macromolecules 2000, 33, 7093 结晶-非晶转变 PE单晶链扩散的1D随机行走模型 结晶stem含84个CH2，界面链含20个CH2 180?翻转运动导致CH2沿结晶stem前行或后退，概率均为1/2 在链扩散中，stem长度保持不变 每个stem均可发生180?翻转运动 无限制扩散 扩散发生在 ±(2Mi+Mc) 扩散发生在±Mi K Kuwabara, H Kaji, M Tsuji, F Horii, Macromolecules 2000, 33, 7093 结晶-非晶转变 PE单晶, 0.05 wt% p-xylene, 78?C 13C NMR 无尖锐折叠信号 Noncrystalline 20 CH2 loose loop vc＝0.81 K Kuwabara, H Kaji, M Tsuji, F Horii, Macromolecules 2000, 33, 7093 结晶-非晶转变 斜方 单斜 100?C、N2热处理7d PE单晶 20 CH2 loose loop 处于热力学准平衡态 K Kuwabara, H Kaji, M Tsuji, F Horii, Macromolecules 2000, 33, 7093 结晶-非晶转变 Interfacial component unannealed K Kuwabara, H Kaji, F Horii, Macromolecules 2000, 33, 4453 MLLDPE (10bu/1000C) 结晶-非晶转变 metallocene-catalyzed a high conductivity at low frequency that masks the normal mode and (2) a relatively high molecular weight that increases considerably the relaxation time of the normalmode. * Polarity, symmetry, and steric hindrance to rotation appear to play strong roles in the determination of both Tg and n. DD:dipolar decoupling 偶极去耦 * Even in the presence of the chain diffusion, no remarkable change has been observed in the structure of the noncrystalline overlayer by annealing at 100 °C for 7 days. Therefore, the loose loops seem to be the quasi-equilibrium structure for the noncrystalline overlayer of polyethylene single crystals. * The interfacial region is defined as