Rheological Spectroscopy

A rapidly expanding field of study is that concerned with the time response of colloidal systems to a mechanical disturbance. The importance of this was hinted at at the beginning of the chapter (page 110), and recent major developments in instrumentation have opened up new areas of research. 

Further discussion of rheological spectrometry would lead to a somewhat more involved treatment of response theory, which is beyond the scope of this book. 

The great variety of rheological phenomena exhibited by colloidal dispersions, only a few of which have been dealt with above, not only provide a major theoretical challenge but also present many opportunities for exploitation in industrial applications, some of which will be mentioned in Chapter 14. 

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Foam rheology has been a challenging area of research of interest for the yield behavior and stick-slip flow behavior (see the review by Kraynik [229]). Recent studies by Durian and co-workers combine simulations [230] and a dynamic light scattering technique suited to turbid systems [231], diffusing wave spectroscopy (DWS), to characterize coarsening and shear-induced rearrangements in foams. The dynamics follow stick-slip behavior similar to that found in earthquake faults and friction (see Section XU-2D). 

Raman measurements [INFRARED TECHNOLOGY AND RAMAN SPECTROSCOPY - RAMAN SPECTROSCOPY] (Vol 14) -rheological measurements [RHEOLOGICALMEASUREMENTS] (Vol21)... 

Keywords Biofluids Chemosensors Emission spectroscopy Mechanosensors Optical properties Polarity Rheology Twisted intramolecular charge transfer Viscosity... 

For the continuous mode, we utilized a dynamic rheological technique, Fourier transform mechanical spectroscopy (FTMS) (77,75), which provided a powerful method for monitoring, simultaneously, the evolving dynamic moduli at several frequencies during the course of photo-cross-linking. In this technique, an oscillatory strain, y, was applied to the sample, such that... 

In this section we deal with perhaps the most conceptually difficult of all the responses observed in linear viscoelastic materials. This is the response of a material to an oscillating stress or strain. This is an area that illustrates why rheological techniques can be considered as mechanical spectroscopy. When a sample is constrained in, say, a cone and plate assembly, an oscillating strain at a given frequency can be applied to the sample. After an initial start-up period, a stress develops in direct response to the applied strain due to transient sample and instrumental responses. If the strain has an oscillating value with time the stress must also be oscillating with time. We can represent these two wave-forms as in Figure 4.6. 

Rossi et al. [30] evaluated rheologically mucins of different origin with polyacrylic acid and sodium carboxymethyl cellulose. The same group also reported a novel rheological approach based on a stationary viscoelastic test (creep test) to describe the interaction between mucoadhesive polymers and mucins [31,32]. Jabbari et al. [33] used attenuated total-reflection infrared spectroscopy to investigate the ehain interpenetration of polyaciylic acid in the mucin interface. 

Fig. 1.3 Relaxation map of polyisoprene results from dielectric spectroscopy (inverse of maximum loss frequency/w// symbols), rheological shift factors (solid line) [7], and neutron scattering pair correlation ((r(Q=1.44 A )) empty square) [8] and self correlation ((t(Q=0.88 A" )) empty circle) [9],methyl group rotation (empty triangle) [10]. The shadowed area indicates the time scales corresponding to the so-called fast dynamics [11]...

Fig. 4.20 Temperature dependence of the average relaxation times of PIB results from rheological measurements [34] dashed-dotted line), the structural relaxation as measured by NSE at Qmax (empty circle [125] and empty square), the collective time at 0.4 A empty triangle), the time corresponding to the self-motion at Q ax empty diamond),NMR dotted line [136]), and the application of the Allegra and Ganazzoli model to the single chain dynamic structure factor in the bulk (filled triangle) and in solution (filled diamond) [186]. Solid lines show Arrhenius fitting curves. Dashed line is the extrapolation of the Arrhenius-like dependence of the -relaxation as observed by dielectric spectroscopy [125]. (Reprinted with permission from [187]. Copyright 2003 Elsevier)...

Colloid chemists do not only rely on optical methods and rheology to obtain information about the structure of their samples. Spectroscopy, in which... 

The effect of aging and of process variables on the rheological properties of solid proplnts has been the subject of mechanical shear relaxation spectroscopy (Ref 4). The technique is of interest to such filled polymer systems generally in that anisotropy in the viscoelastic properties can be readily observed... 

It is not possible to discuss all the methods available for characterizing foods critically and systematically in a single volume. Methods pertaining to interfaces (food emulsions, foams, and dispersions), fluorescence, ultrasonics, nuclear magnetic resonance, electron spin resonance, Fourier-transform infrared and near infrared spectroscopy, small-angle neutron scattering, dielectrics, microscopy, rheology, sensors, antibodies, flavor and aroma analysis are included. 

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