Spectroscopy, mechanical

The use of infra-red or ultraviolet spectroscopy to examine the molecular groups present in a chemical compound is familiar to any chemist. One of the main uses of this technique is to apply a range of electromagnetic frequencies to a sample and thus identify the frequency at which a process occurs. This can be characteristic of, say, the stretch of a carbonyl group or an electronic transition in a metal complex. The frequency, wavelength or wavenumber at which an absorption occurs is of most interest to an analytical chemist. In order to use this information quantitatively, for example to establish the concentration of a molecule present in a sample, the Beer-Lambert law is used  

Here the relative intensity 7rei of radiation being transmitted, travelling a distance / through a sample, has an exponential dependence on two properties, the concentration of the material c and ex, the extinction coefficient or absorption coefficient of the material. The value of ex 

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The excellent low temperature properties of FZ have been iadicated ia Table 1. Modulus curves were obtained usiag dynamic mechanical spectroscopy to compare several elastomer types at a constant 75 durometer hardness. These curves iadicate the low temperature flexibiUty of FZ is similar to fluorosihcone and ia great contrast to that of a fluorocarbon elastomer (vinyUdene fluoride copolymer) (Fig. 3) (15). 

Since pc 1/2, we observe that Me 2Mg, as commonly observed. Mg is determined from the onset of the rubbery plateau by dynamic mechanical spectroscopy and Me is determined at the onset of the highly entangled zero-shear viscosity law, T) M. This provides a new interpretation of the critical entanglement molecular weight Mg, as the molecular weight at which entanglement percolation occurs while the dynamics changes from Rouse to reptation. It also represents the... 

A Relaxation time measurement in the solid (Al) in solution (A2). B Mechanical spectroscopy. C Variable-temperature NMR spectroscopy (coalescence temperature measurement). D Variable-temperature EPR spectroscopy... 

Additives in Highly Filled Composites by Mechanical Spectroscopy , XApplPolmSci 18,1295-... 

Elasticity measurements can serve as a measure of the degree of interconnection in gels. Covalently cross-linked networks can be distinguished from physically cross-linked networks by the use of a technique termed mechanical spectroscopy [333]. Compression of gels has also been used to assess the physical structure [28,168,303]. 

From the dynamic mechanical spectroscopy, an increase of PTMO molecular weight from 650 to 2000 results in a decrease in both the modulus and the glass transition temperature of the final product. The SAXS results indicate that a correlation distance exists in the samples, and this distance increases as PTMO molecular weight increases. A cluster model is thus suggested to account for the experimental results. 

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... 

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. 

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. 

Molecular mixing via dynamic mechanical spectroscopy. While electron microscopy yields the phase size, shape, etc., as delineated above, dynamic mechanical spectroscopy (DMS) yields the composition within each phase. The DMS measurements employed a Rheovibron direct reading viscoelastometer model DDV-II (manufactured by Toyo Measuring Instruments Co., Ltd., Tokyo, Japan). The measurements were taken over a temperature range from -120°C to 140°C using a frequency of 110 Hz and a heating rate of about 1°C/ min. Sample dimensions were about 0.03 x 0.15 x 2 cms. 

Dynamical mechanical spectroscopy and Izod impact results suggest that the glass transition temperature of the elastomer phase constitutes the most critical parameter in achieving impact resistance in these materials. 

Other in vitro methods include the determination of the weight needed to break the adhesion [41], the fluorescent probe [35], the flow channel [42], mechanical spectroscopy [43], the falling film [44], colloidal gold staining [45], viscometiy [46], the thumb test [47], the adhesion number [47], and electrical conductance [47]. 

R Musto, M. Abbate, G. Ragosta and G. Scarinzi, A smdy by Raman, near-infrared and dynamic-mechanical spectroscopies on the curing behaviour, molecular structure and viscoelastic properties of epoxy/anhydride networks, Polymer, 48, 3703-3716 (2007). 

Solution phase chemists have developed a tremendous variety of tools to elucidate mechanisms. Spectroscopy, kinetics, isotopic labeling, and many more are all in the chemical mechanic s tool kit, for use in mapping out reaction pathways. In contrast, the tool kit for the gas phase reaction mechanic is far more limited. The low concentration and short lifetime of gas phase reaction intermediates and products severely limits the use of many of the conventional tools. Gas phase ion-molecule chemists have therefore both adapted solution phase tools to their unique needs and developed many new ones. 

While several experimental techniques provide Information relating to dual phase continuity, the two most important methods Involve scanning electron microscopy and dynamic mechanical spectroscopy [16,22-2A]. Donatelll, et al [1 ] performed the first mechanical study on PB/PS IPN s. Figure 5 [ 6] illustrates the fit provided by the Davies equation [22] and the Budlansky equation [25,26], both of these equations derived on the assumption of dual phase continuity. 

Oulevey, F., Gremaud, G., Semoroz, A., Kulik, A. J., Burnham, N. A., Dupas, E., and Gourdon, D. (1998). Local mechanical spectroscopy with nanometer-scale lateral resolution. Rev. Sri. Instrum. 69,2085-94. [319]... 

D. Mari and R. Schaller, Mechanical spectroscopy in carbon nanotube reinforced ABS, Mater. Sci. Eng., A, 521-522 255-258, September 2009. 

The usefulness of spectral densities in nonequilibrium statistical mechanics, spectroscopy, and quantum mechanics is indicated in Section I. In Section II we discuss a number of known properties of spectral densities, which follow from only the form of their definitions, the equations of motion, and equilibrium properties of the system of interest. These properties, particularly the moments of spectral density, do not require an actual solution to the equations of motion, in order to be evaluated. Section III introduces methods which allow one to determine optimum error bounds for certain well-defined averages over spectral densities using only the equilibrium properties discussed in Section II. These averages have certain physical interpretations, such as the response to a damped harmonic perturbation, and the second-order perturbation energy. Finally, Section IV discusses extrapolation methods for estimating spectral densities themselves, from the equilibrium properties, combined with qualitative estimates of the way the spectral densities fall off at high frequencies. 

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... 

This chapter provides an introduction to integral calculus, together with examples set in a chemical context. However, as we shall see in the following chapter, we need integral calculus to solve the differential equations which appear in chemical kinetics, quantum mechanics, spectroscopy and other areas of chemistry. The key points discussed in this chapter include ... 

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]. 

The latexes were cleaned by ion exchange and serum replacement, and the number and type of surface groups were determined by conductometric titration. The molecular weight distributions of the polymers were determined by gel permeation chromatography. The stability of the latexes to added electrolyte was determined by spectrophotometry. The compositional distribution was determined by dynamic mechanical spectroscopy (Rheovibron) and differential scanning calorimetry, and the sequence distribution by C13 nuclear magnetic resonance. 

Abbreviations y x AFM AIBN BuMA Ca DCP DMA DMS DSC EGDMA EMA EPDM FT-IR HDPE HTV IPN LDPE LLDPE MA MAA MDI MMA PA PAC PB PBT PBuMA PDMS PDMS-NH2 interfacial tension viscosity ratio atomic force microscopy 2,2 -azobis(isobutyronitrile) butyl methacrylate capillary number dicumyl peroxide dynamic mechanical analysis dynamic mechanical spectroscopy differential scanning calorimetry ethylene glycol dimethacrylate ethyl methacrylate ethylene-propylene-diene rubber Fourier transform-infra-red high density polyethylene high temperature vulcanization interpenetrating polymer network low density polyethylene linear low density polyethylene maleic anhydride methacrylic acid 4,4 -diphenylmethanediisocyanate methyl methacrylate poly( amide) poly( acrylate) poly(butadiene) poly(butylene terephtalate) poly(butyl methacrylate) poly(dimethylsiloxane) amino-terminated poly(dimethylsiloxane)... 

Marie et al. [49] also studied the in-situ block copolymer formation via reactive blending of functionalized homopolymers. In their work, blends were characterized by SEM, DSC and dynamic mechanical spectroscopy (DMS). It should be noted that their blends (PA-6/PDMS and PS/PDMS) were composed totally using functionalized homopolymers. The different reactions under investigation were amine(NH2)/anhydride(An), amine(NH2)/epoxy(E) and carboxylic acid(COOH)/epoxy(E) (Fig. 5). 

The interest in the rotation of cyclopentadienyl rings (or aromatic organic rings in general) attached to metals (15) originated with the discovery of ferrocene itself (3b). Many methods have been employed to study the phenomenon, among them solid-state and solution NMR (187), dipole moment measurements (188), electron and X-ray diffraction techniques (189,190), mechanical spectroscopy (117), and last but not least molecular orbital calculations (191). 

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