Optimal Choice of the Regularization Parameter for Direct Identification of Polymers Relaxation Time and Frequency Spectra.

Recovering the relaxation spectrum, a fundamental rheological characteristic of polymers, from experiment data requires special identification methods since it is a difficult ill-posed inverse problem. Recently, a new approach relating the identification index directly with a completely unknown real relaxation spectrum has been proposed. The integral square error of the relaxation spectrum model was applied. This paper concerns regularization aspects of the linear-quadratic optimization task that arise from applying Tikhonov regularization to relaxation spectra direct identification problem. An influence of the regularization parameter on the norms of the optimal relaxation spectra models and on the fit of the related relaxation modulus model to the experimental data was investigated. The trade-off between the integral square norms of the spectra models and the mean square error of the relaxation modulus model, parameterized by varying regularization parameter, motivated the definition of two new multiplicative indices for choosing the appropriate regularization parameter. Two new problems of the regularization parameter optimal selection were formulated and solved. The first and second order optimality conditions were derived and expressed in the matrix-vector form and, alternatively, in finite series terms. A complete identification algorithm is presented. The usefulness of the new regularization parameter selection rules is demonstrated by three examples concerning the Kohlrausch-Williams-Watts spectrum with short relaxation times and uni- and double-mode Gauss-like spectra with middle and short relaxation times.