Estimation of kinetic parameters associated with the curing of thermoset resins. Part I: Theoretical investigation

Abstract

This is a two-part theoretical and experimental study on the estimation of kinetic parameters associated with the curing of a thermoset epoxy resin. In Part I, the estimation procedure is presented. This estimation procedure is based on a method referred to as the Box-Kanemasu method, which involves the minimization of a least squares function, and it represents a new application of this method. The kinetic parameters under consideration were the Arrhenius constants associated with two rate constants in a kinetic model used to describe the curing rate of an amine epoxy resin. The use of differential scanning calorimetry (DSC) and dielectric data assuming isothermal and dynamic experimental conditions was first investigated in a sensitivity study. It was determined that the degree of cure should be treated as the dependent variable and that data from isothermal experiments should be used. The estimation procedure was then used to estimate the Arrhenius constants from simulated degree of cure data with added errors. These results compared favorably with those found using a linear regression method.

Kinetic parameter estimation using an adiabatic reaction, with validation using NIR spectroscopy, 1 Application to a macrodiol / isocyanate polyurethane formulation

“…A methodology based on the calculation of sensitivity coefficients [16,17] determined the most accurate variable to use. This methodology is not the purpose of the present work and will not be described in this article, but the reader can find all details in ref.…”

A Method of Estimating Kinetic Parameters of Thermoset Cures: Application to a Dicyanate Ester Resin

“…The minimization of the objective function can be done by any optimization technique, nevertheless, most published studies use gradient based techniques that can be quite sophisticated. [7,21,22] The basic idea of such techniques consists of differentiating the objective function with respect to the parameters to be estimated, setting the resulting equation equal to zero and then solving iteratively to find each parameter using the Taylor series approach to linearize the equation (for more details, one can refer to Beck and Arnold [13] ).…”

“…[19,21,23] Scott and Saad, [21,22] have made sensitivity studies for both isothermal and nonisothermal DSC experiments and shown that the problem of correlation between Arrhenius parameters is minimized for isothermal experiments when using the conversion degree as the modeled variable. They successfully identified the four parameters A 1 , E 1 , A 2 and E 2 of a Kamal & Sourour model (assuming exponents n = 2 and m = 1), applied to an epoxy amine thermoset system from a set of isothermal experiments.…”

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone). I. DSC characterization of curing reaction

“…Eventually this advantage results in performance liquid chromatography (HPLC), 5,6 reduced manufacturing costs, shorter lead time, torsional braid analysis (TBA), [4][5][6][7] and DSC. 6,8,9 and improved control and prediction of the properOne of the simple and fast methods to characterties of the finished products. It is also of benefit ize the curing reaction kinetics is DSC, which is to realize in situ control of composite quality.…”