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The relaxation spectrum is a fundamental viscoelastic characteristic from which other material functions used to describe the rheological properties of polymers can be determined. The spectrum is recovered from relaxation stress or oscillatory shear data. Since the problem of the relaxation spectrum identification is ill-posed, in the known methods, different mechanisms are built-in to obtain a smooth enough and noise-robust relaxation spectrum model. The regularization of the original problem and/or limit of the set of admissible solutions are the most commonly used remedies. Here, the problem of determining an optimally smoothed continuous relaxation time spectrum is directly stated and solved for the first time, assuming that discrete-time noise-corrupted measurements of a relaxation modulus obtained in the stress relaxation experiment are available for identification. The relaxation time spectrum model that reproduces the relaxation modulus measurements and is the best smoothed in the class of continuous square-integrable functions is sought. Based on the Hilbert projection theorem, the best-smoothed relaxation spectrum model is found to be described by a finite sum of specific exponential-hyperbolic basis functions. For noise-corrupted measurements, a quadratic with respect to the Lagrange multipliers term is introduced into the Lagrangian functional of the model's best smoothing problem. As a result, a small model error of the relaxation modulus model is obtained, which increases the model's robustness. The necessary and sufficient optimality conditions are derived whose unique solution yields a direct analytical formula of the best-smoothed relaxation spectrum model. The related model of the relaxation modulus is given. A computational identification algorithm using the singular value decomposition is presented, which can be easily implemented in any computing environment. The approximation error, model smoothness, noise robustness, and identifiability of the polymer real spectrum are studied analytically. It is demonstrated by numerical studies that the algorithm proposed can be successfully applied for the identification of one- and two-mode Gaussian-like relaxation spectra. The applicability of this approach to determining the Baumgaertel, Schausberger, and Winter spectrum is also examined, and it is shown that it is well approximated for higher frequencies and, in particular, in the neighborhood of the local maximum. However, the comparison of the asymptotic properties of the best-smoothed spectrum model and the BSW model a priori excludes a good approximation of the spectrum in the close neighborhood of zero-relaxation time.

Different viscoelastic models and characteristics are commonly used to describe, analyze, compare and improve the mechanical properties of polymers. A time-dependent linear relaxation modulus next to frequency-domain storage and loss moduli are the basic rheological material functions of polymers. The exponential Maxwell model and the exponential stretched Kohlrausch-Williams-Watts model are, probably, the most known linear rheological models of polymers. There are different identification methods for such models, some of which are dedicated to specific models, while others are general in nature. However, the identification result, i.e., the best model, always depends on the specific experimental data on the basis of which it was determined. When the rheological stress relaxation test is performed, the data are composed of the sampling instants used in the test and on the measurements of the relaxation modulus of the real material. To build a relaxation modulus model that does not depend on sampling instants is a fundamental concern. The problem of weighted least-squares approximation of the real relaxation modulus is discussed when only the noise-corrupted time-measurements of the relaxation modulus are accessible for identification. A wide class of models, that are continuous, differentiable and Lipschitz with respect to parameters, is considered for the relaxation modulus approximation. The main results concern the models that are selected asymptotically as the number of measurements tends to infinity. It is shown that even when the true relaxation modulus description is completely unknown, the approximate optimal model parameters can be derived from the measurement data that are obtained for sampling instants that are selected randomly due to the appropriate randomization introduced whenever certain conditions regarding the adopted class of models are satisfied. It is shown that the most commonly used stress relaxation models, the Maxwell and Kohlrausch-Williams-Watts models, satisfy these conditions. Since the practical problems of the identification of relaxation modulus models are usually ill posed, Tikhonov regularization is applied to guarantee the stability of the regularized solutions. The approximate optimal model is a strongly consistent estimate of the regularized model that is optimal in the sense of the deterministic integral weighted square error. An identification algorithm leading to the best regularized model is presented. The stochastic-type convergence analysis is conducted for noise-corrupted relaxation modulus measurements, and the exponential convergence rate is proved. Numerical studies for different models of the relaxation modulus used in the polymer rheology are presented for the material described by a bimodal Gauss-like relaxation spectrum. Numerical studies have shown that if appropriate randomization is introduced in the selection of sampling instants, then optimal regularized models of the relaxation modulus being asymptotically independent of these time instants can be recovered from the stress relaxation experiment data. The robustness of the identification algorithm to measurement noises was demonstrated both by analytical and numerical analyses.