Dynamic-mechanical relaxation spectroscopy

Of particular importance for detection of chemical or physical change in polymer materials are mobility filters, which are sensitive to differences in the numbers of molecules within a given window of correlation times. Within reasonable approximation such filters are relaxation filters. Here, Tj filters are sensitive to differences in the fast motion regime while T2 and Tip filters are sensitive to the slow motion regime. Which time window is of importance can be seen from Fig. 5.7 [101]. It shows a double-logarithmic plot of the mechanical relaxation strengths Hi(t) for two carbon-black filled styrene-butadiene rubber (SBR) samples as a function of the mechanical relaxation time T. They have been measured by dynamic mechanical relaxation spectroscopy. In terms of NMR, the curves correspond to spectral densities of motion. But the spectral densities relevant to NMR are mainly those referring... 

Fig. 6.13 Illustration of the whole-frequency spectroscopy for the dynamic mechanical relaxation of the typical non-crystalline high-molecular-weight linear polymers...

As with PIB, cited above, the nuclear resonance studies on PMMA can be closely correlated with other kinds of measurements of molecular motion. Fig. 9 shows a graph of the variation of the correlation frequency with reciprocal temperature for this polymer, with results from NMR spectroscopy, dielectric studies, and measurements of dynamic mechanical relaxation [22]. The curve at the highest temperatures reflects the motion of the main chains and is associated with the glass transition. The next curve at lower temperatures is prominent in dielectric measurements and is ascribed to motion of the electrically polar portion of the ester group. The relaxations at lower temperatures are ascribed to the rotation of methyl groups attached to the main chain. The relaxation seen by NMR at the lowest temperatures are attributed, as noted previously, to the rotation of methyl groups belonging to the ester substituents. 

When the ball is set in motion by a force, F, it oscillates under the Hooke s Law extension and compression of the spring, but its motion is retarded by the viscous drag of the surrounding medium. In infrared vibrational spectroscopy, the ball is an atom set in excited motion by the irradiation and there is no surrounding viscous medium. In dynamic mechanical relaxation, the ball is part of a molecule set in motion by an applied stress and other chains form the surrounding medium. 

The molecular origin of observed deformation mechanisms have been elucidated by various spectroscopic methods — including mechanical relaxation spectroscopy — and by the previously listed tools which characterize the morphology. They are supplemented by dynamic scattering and diffraction techniques [52, 53]. 

Roudaut et al. (1999a) used low-frequency pulsed-proton NMR and dielectric dynamic mechanical spectroscopies to study molecular mobility in glassy bread (<9%) as a function of temperature. Based on NMR results, they reported that some (if not all) of the water molecules were much more mobile than the polymer matrix whose relaxation time could not be measured within the 20-p,s dead time of the RF probe. 

DMAIC improvement process, 22 174 DM AM hydrogels, 13 738 Dma relaxation spectroscopy, 19 586. See also Dynamic mechanical analysis (DMA)... 

During the last two decades, studies on ion solvation and electrolyte solutions have made remarkable progress by the interplay of experiments and theories. Experimentally, X-ray and neutron diffraction methods and sophisticated EXAFS, IR, Raman, NMR and dielectric relaxation spectroscopies have been used successfully to obtain structural and/or dynamic information about ion-solvent and ion-ion interactions. Theoretically, microscopic or molecular approaches to the study of ion solvation and electrolyte solutions were made by Monte Carlo and molecular dynamics calculations/simulations, as well as by improved statistical mechanics treatments. Some topics that are essential to this book, are included in this chapter. For more details of recent progress, see Ref. [1]. 

The first data on polymer systems were collected via (laser-) light-scattering techniques [1] and turbidity measurements, further developed by Derham et al. [2,3]. Techniques based on the glass-transition of the polymer-blend constituents were also tested, such as DSC, Dynamic Mechanical Spectroscopy, and Dielectric relaxation [4]. Films made from solutions of... 

DSC measurements showed that the crystallization ability of this interphase region was reduced by the silane modification of the glass beads. Despite an increase in the amount of amorphous material with increasing number of silane layers, a decrease in the intensity of the fourth lifetime was observed. This decrease in the free volume is in accordance with the earlier observed reduced mobility in the interphase region measured by dynamic-mechanical spectroscopy in the melt state [9,10] and creep and stress relaxation measurements in the solid state [12]. 

Tonami et al.179) studied atactic-PMAA (at-PMAA)-PEO complex membranes by means of infrared spectroscopy, stress relaxation measurement and torsional analysis of dynamic-mechanical properties. They pointed out that the polymer complex was formed through hydrogen bonds between the ether... 

The characterization of the elastomer-filler interactions at a molecular level may be cairied out by spectroscopic techniques such as IR and NMR spectroscopy. X-ray and neutron scattering, dynamic mechanical and dielectric spectroscopy, and molecular dynamics simulations [6]. Up to now, the most comprehensive studies of silica filled PDMS [4, 7-22] and carbon black filled conventional rubbers [23] have been carried out by H [4, 7—20, 23], [21], and C NMR relaxation experiments [22],... 

The relaxation properties as probed by dynamic mechanical spectroscopy (DMS) for a series of ESI are shown in Figure 26.2. In accordance with the DSC results, the tan S loss maximum or Tg for the semicrystalline ESI appears to be fairly independent of styrene content. For the essentially amorphous ESI (>45wt% S), Tg increases with increasing styrene content. When compared with the amorphous ESI, the amplitude and width of the Tg loss peak are lower in amplitude and broader, respectively, for the lower styrene ESI, as is characteristic of a semicrystalline material. The amorphous ESI exhibit an intense loss process associated with the amorphous phase Tg(ESI). The width of this loss... 

This chapter discusses the dynamic mechanical properties of polystyrene, styrene copolymers, rubber-modified polystyrene and rubber-modified styrene copolymers. In polystyrene, the experimental relaxation spectrum and its probable molecular origins are reviewed further the effects on the relaxations caused by polymer structure (e.g. tacticity, molecular weight, substituents and crosslinking) and additives (e.g. plasticizers, antioxidants, UV stabilizers, flame retardants and colorants) are assessed. The main relaxation behaviour of styrene copolymers is presented and some of the effects of random copolymerization on secondary mechanical relaxation processes are illustrated on styrene-co-acrylonitrile and styrene-co-methacrylic acid. Finally, in rubber-modified polystyrene and styrene copolymers, it is shown how dynamic mechanical spectroscopy can help in the characterization of rubber phase morphology through the analysis of its main relaxation loss peak. 

Another possibility of determining the gel point with the help of rheological methods is dynamical mechanical spectroscopy. Analysis of change of dynamic mechanical properties of reactive systems shows that the gel point time may be reached when tan S or loss modulus G" pass a miximum [3,4,13], Some authors proposed to correlate the gel point with the intersection point of the curves of storage and loss moduli, i.e., with the moment at which tan 5 = 1 [14-16], However, theoretical calculations have shown that the intersection point of storage modulus and loss modulus meets the gelation conditions only for a certain law of relaxation behavior of the material and the coincidence erf the moment of equality G = G" with the gel point is a particular case [17]. The variation of the viscosity... 

Landry and Henrichs [63] applied dynamic mechanical spectroscopy and H NMR to investigate sub-T motion in polycarbonate(PC)/PMMA and PC/poly(cyclohexylene dimethylene terephthalate)(PCHDMT). Examination of H NMR spectra and relaxation times led them to conclude that local... 

The rates of change (slopes of the curves) of many important properties (such as the refractive index, surface tension, and gas permeabilities) as a function of temperature, the value of the dielectric constant, and many other optical and electrical properties, often change considerably at Tg. These changes enable the measurement of Tg by using techniques such as refractometry and dielectric relaxation spectroscopy. Refractometry provides results which are similar to those obtained from dilatometry, because of the correlation between the rates of change of the specific volume and of the refractive index with temperature. Dielectric relaxation spectroscopy is based on general physical principles which are similar to those in dynamic mechanical spectroscopy, the main difference being in its use of an electrical rather than a mechanical stimulus. 

Secondary relaxations are usually measured either by mechanical methods such as dynamic mechanical spectroscopy or (somewhat less often) by electrical methods such as dielectric relaxation spectroscopy [159], The existence of Tp is generally ascribed to the onset of a significant amount of some kind of motion of the polymer chains and/or the side groups attached to them, on a much smaller and more localized scale than the large-scale cooperative motions of chain segments associated with Ta. These motions are usually inferred from the results of measurements using methods such as nuclear magnetic resonance spectroscopy. See... 

Effects of addition of a compatibilizing block copolymer, poly(styrene-b-methyl methacrylate), P(S-b-MMA) on the rheological behavior of an immiscible blend of PS with SAN were studied by dynamic mechanical spectroscopy [Gleisner et al., 1994]. Upon addition of the compatibilizer, the average diameter of PS particles decreased from d = 400 to 120 nm. The data were analyzed using weighted relaxation-time spectra. A modified emulsion model, originally proposed by Choi and Schowalter [1975], made it possible to correlate the particle size and the interfacial tension coefficient with the compatibilizer concentration. It was reported that the particle size reduction and the reduction of occur at different block-copolymer concentrations. 

---