کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
---|---|---|---|---|
5186863 | 1381115 | 2005 | 11 صفحه PDF | دانلود رایگان |
Thermal-induced simultaneous phase separation and liquid-solid transition (gelation) in waterborne polyurethane dispersions has been detected morphologically and rheologically. The viscoelastic material functions, such as dynamic shear moduli, Gâ² and Gâ³ complex shear viscosity, η* and loss tangent, tan δ were found to be very sensitive to the structure evolution during the gelation process and the subsequent formation of a fractal polymer gel. At the onset temperature of the gelation process, an abrupt increase in Gâ², Gâ³ and η* (several orders of magnitude) was observed during the dynamic temperature ramps (2 °C/min heating-rate) over a wide range of angular frequency. The temperature dependencies of Gâ², Gâ³ and tan δ were found to be frequency independent at the gel-point, Tgel, providing a fingerprint for determining Tgel of the dispersions. Furthermore, a dramatic increase in zero-shear viscosity, η0 (v-shape) was observed at T=Tgel and found to be in good agreement with the value obtained from the tan δ versus T data. As expected, the time-temperature-superposition principle was found to be only valid for temperatures lower than the Tgel; the principle failed at Tâ¥70 °C. The morphology of the dispersions at 70 °C for 2 h showed for 36, 38 and 40 wt% formation of a network structure having a unique periodicity and phase connectivity. A lower critical solution temperature (LCST) phase diagram was estimated based on the different morphologies of the dispersions. The coexistence of liquid-liquid and liquid-solid transitions at the same temperature range confirmed the complex behavior of the polyurethane dispersions, pointing to the need for a new theory that explicitly takes this special behavior into account.
Journal: Polymer - Volume 46, Issue 24, 21 November 2005, Pages 10897-10907