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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.
Based on the SB formula, the kinetic model needs to fit four parameters: pre-exponential factor A, activation energy Ea, reaction order m, n.In this paper, the non-linear least squares The fitting results show that the nonlinear regression results of the four parameters are unstable, especially on the estimation results of the parameters A and M. The author analyzes the causes of the above results and points out that because the curvature of the model parameters is quite large, Which increases the nonlinear strength of the model and makes the result of the least square regression analysis unreliable.According to the characteristics of the experimental data, under the premise of uncertain mechanism function form, using Model-free method, the average value of activation energy is obtained first , Then the nonlinear least squares regression analysis of the parameters A, m, n was carried out.The results showed that reducing the number of regression function parameters could greatly reduce the nonlinear strength of the model and obtain an effective dynamic parameter estimation.