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Chemorheology of thermosetting resins. I. The chemorheology and curing kinetics of unsaturated polyester resin

机译:热固性树脂的化学流变学。一、不饱和聚酯树脂的化学流变学和固化动力学

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AbstractThe rheological properties and curing kinetics of a general‐purpose polyester resin have been determined during isothermal cure. Both steady and oscillatory shearing flow properties were determined using a cone‐and‐plate rheometer, and the curing kinetics were determined using a differential scanning calorimeter (DSC). It was found that, as cure progresses, the steady shear viscosity increases very rapidly with cure time at all shear rates investigated, and normal forces shownegativevalues at low shear rates andpositivevalues at high shear rates. The observednegativenormal forces are believed to result from material shrinkage during cure, andpositivenormal forces from the deformation of large molecules, formed by crosslinking reactions during cure. Note that, in a cone‐and‐plate rheometer, the shrinkage force acts in the directionoppositeto that of normal forces. It is, therefore, concluded that extreme caution is needed in the interpretation of normal force measurements with thermosetting resins, subjected to steady shearing flow. Dynamic measurements seem to offer some insight on the onset of gel formation. More specifically, we have found that, when the unsaturated polyester resin was cured at a fast rate, the time at which a maximum in the loss modulusG”occurs coincides reasonably well with the timetη∞at which the steady shear viscosityηapproaches infinity. However, at a slow rate of cure, the time at which tanδequals unity agrees fairly well withtη∞. DSC measurement has permitted us to determine the degree of cure as a function of cure time and the kinetic parameters in an empirical expression for the curing kinetics advanced by Kamal and co‐workers. By combining the rheological and DSC measurements, we have constructed plots describing how the viscosity increases with the degree of cure, at various values of isotherm
机译:摘要 在等温固化过程中测定了一种通用聚酯树脂的流变性能和固化动力学。使用锥板流变仪测定稳态和振荡剪切流特性,并使用差示扫描量热仪 (DSC) 测定固化动力学。结果发现,随着固化过程的进行,在所有所研究的剪切速率下,稳定的剪切粘度随着固化时间的增加而迅速增加,并且法向力在低剪切速率下显示负值,在高剪切速率下显示正值。观察到的负正向力被认为是由固化过程中的材料收缩引起的,而正法向力是由固化过程中交联反应形成的大分子变形引起的。请注意,在锥板流变仪中,收缩力的作用方向与法向力相反。因此,得出的结论是,在解释热固性树脂在稳定剪切流下测量法向力时需要格外小心。动态测量似乎为凝胶形成的开始提供了一些见解。更具体地说,我们发现,当不饱和聚酯树脂以快速固化时,损耗模量G“中最大值出现的时间与稳态剪切粘度η趋近无穷大的时间η∞相当吻合。然而,在缓慢的固化速度下,tanδ等于统一的时间与η∞相当吻合。DSC测量使我们能够确定固化程度与固化时间的函数关系,以及Kamal及其同事提出的固化动力学的经验表达式的动力学参数。通过结合流变学和 DSC 测量,我们构建了描述粘度如何随着固化程度的增加而增加的曲线图,在不同的等温线值下

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