Structural relaxation time basic properties

The identification of both short chain and long chain branches in polyethylene at concentrations of 1 per 10,000 carbon atoms has become feasible with the availability of improved probes and improved computer hardware/ software capabilities. Reviewed in this chapter are the methods and computations as well as the basic requirements for sound quantitative analyses namely, correct choice of solvent, a consideration of concentration effect on line widths and satisfying nuclear Overhauser effects and spin lattice relaxation time requirements. Finally, the NMR generated structural information is put to use in correlations with polyethylene physical properties and measurements of number average molecular weight. 

In the last three decades, nuclear magnetic resonance has become a powerful tool for investigating the structural and physical properties of matter. Today, nuclear magnetic resonance is the physical method most widely used in analytical chemistry. For special applications, e.g. relaxation time measurements, there is available a variety of modifications of the basic nuclear magnetic resonance experiments such as pulse and spin-echo methods. In the course of this development and when electronic computers were provided at a reasonable price, Fourier transform spectroscopy was applied to nuclear magnetic resonance in the middle of the sixties. At that time, Fourier methods were already used to a large extent in far infrared spectroscopy (see Refs. and references cited therein). 

Dispersed systems, i.e. suspensions, emulsions and foams, are ubiquitous in industry and daily life. Their mechanical properties are often tested using oscillatory rheological experiments in the linear regime as a function of temperature and frequency [29]. The complex response function is described in terms of its real part (G ) and imaginary part (G"). Physical properties like relaxation times or phase transitions of the non-perturbated samples can be evaluated. The linear rheology is characterized by the measurement of the viscoelastic moduli G and G" as a function of angular frequency at a small strain amplitude. The basics of linear rheology are described in detail in several textbooks [8, 29] and will not be repeated here. The relations between structure and linear viscoelastic properties of dispersed systems are well known [4,7, 26]. 

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