Derivative spectroscopy and the continuous relaxation spectrum

Abstract

Derivative spectroscopy is conventionally understood to be a collection of techniques for extracting fine structure from spectroscopic data by means of numerical differentiation. In this paper we extend the conventional interpretation of derivative spectroscopy with a view to recovering the continuous relaxation spectrum of a viscoelastic material from oscillatory shear data. To achieve this, the term “spectroscopic data” is allowed to include spectral data which have been severely broadened by the action of a strong low-pass filter. Consequently, a higher order of differentiation than is usually encountered in conventional derivative spectroscopy is required. However, by establishing a link between derivative spectroscopy and wavelet decomposition, high-order differentiation of oscillatory shear data can be achieved using specially constructed wavelet smoothing. This method of recovery is justified when the reciprocal of the Fourier transform of the filter function (convolution kernel) is an entire function, and is particularly powerful when the associated Maclaurin series converges rapidly. All derivatives are expressed algebraically in terms of scaling functions and wavelets of different scales, and the recovered relaxation spectrum is expressible in analytic form. An important feature of the method is that it facilitates local recovery of the spectrum, and is therefore appropriate for real scenarios where the oscillatory shear data is only available for a finite range of frequencies. We validate the method using synthetic data, but also demonstrate its use on real experimental data.