【摘要】 动态自催化固化反应动力学研究中的机理函数基于SB公式,动力学模型需要拟合4个参数:指前因子A、活化能Ea、反应阶数m、n.本文中采用非线性最小二乘回归方法,拟合结果表明4个参数的非线性回归结果不稳定,尤其表现在参数A与m的估计结果上.笔者对造成上述结果的原因进行了分析,指出由于模型参数效应曲率相当大,增加了模型的非线性强度,使得最小二乘回归分析结果不可靠.根据实验数据特征,本文中在不确定机理函数形式前提下,运用Model-free方法,先获得活化能平均意义下的估计值,再进行参数A、m、n的非线性最小二乘回归分析.结果表明减少回归函数参数个数,可极大程度降低模型的非线性强度,从而获得有效的动力学参数估计.更多还原

【Abstract】 In chemical kinetic analysis of non-isothermal cure reaction,autocatalytic reaction mechanism function was based on estk-Berggren equation,parameters of regression were pre-exponential factor A, activation energy Ea,reaction order mand n.In this article,we fit rate equation with four parameters by nonlinear regression based on the least squares estimation,regression result was unreliable,especially the estimator of Aand m.This article pointed that nonlinearity of model with large parameter-effects curvature was responsible for the terrible regression result.In the next section,according to characters of experiment data,we estimated Eafirstly with model-free methods,rate equation would only have three parameters, parameter-effects curvature of model was cut short,and with this solution we could get effective estimation of kinetic parameters.更多还原