Cooper-White Justin J, Hill David J T
Center for Research and Development of Isotopes and Radiation Technology, National Nuclear Energy Agency, Jakarta, Indonesia.
J Biomater Sci Polym Ed. 2002;13(9):1007-20. doi: 10.1163/156856202760319153.
The dynamic rheological behaviour of gamma-irradiated 12.8 wt% poly(vinyl alcohol) (PVA), 12.8 wt% poly(vinyl pyrrolidone) (PVP), and a blend of 8 wt% PVA and 4.8 wt% PVP aqueous solutions have been studied pre- and post-gelation. The non-irradiated solutions displayed rheological behaviour typical of dilute to semi-dilute polymer solutions, with the complex viscosity being independent of the frequency and shear rate (i.e. Newtonian behaviour) over the range of frequencies tested and the loss modulus G"(omega) and storage modulus G'(omega) being nearly proportional to omega and omega2, respectively. After a set of doses of gamma-radiation, the magnitudes of the dynamic moduli G'(omega) and G"(omega) increased as the absorbed dose increased, with notable differences between the two homopolymers and the blend. The stages of gelation were effectively monitored by means of dynamic rheological measurements, allowing the possible mechanisms of network formation to be elucidated. The doses required for gelation of the PVA, PVP, and blend samples, determined on the basis of the Winter and Chambon criteria for gelation, were found to be 12 kGy for the 12.8 wt% PVA, 4 kGy for the 12.8 wt% PVP, and 5 kGy for the 8 wt% PVA/4.8 wt% PVP solutions. The unexpected lower gelation dose demonstrated by the blend sample, compared with predictions based on the blend composition, and the associated gelation mechanism are also discussed.
研究了经γ辐照的12.8 wt%聚乙烯醇(PVA)、12.8 wt%聚乙烯吡咯烷酮(PVP)以及8 wt% PVA与4.8 wt% PVP混合水溶液在凝胶化前后的动态流变行为。未辐照的溶液表现出稀溶液到半稀溶液典型的流变行为,在所测试的频率范围内,复数粘度与频率和剪切速率无关(即牛顿行为),损耗模量G''(ω)和储能模量G'(ω)分别与ω和ω²近似成正比。经过一组γ辐射剂量后,动态模量G'(ω)和G''(ω)的大小随着吸收剂量的增加而增大,两种均聚物和混合物之间存在显著差异。通过动态流变测量有效地监测了凝胶化阶段,从而阐明了网络形成的可能机制。根据Winter和Chambon凝胶化标准确定的PVA、PVP和混合样品凝胶化所需的剂量,对于12.8 wt% PVA为12 kGy,对于12.8 wt% PVP为4 kGy,对于8 wt% PVA/4.8 wt% PVP溶液为5 kGy。还讨论了混合样品与基于混合组成的预测相比所表现出的意外较低凝胶化剂量以及相关的凝胶化机制。