Infrared spectroscopy molecular microstructure

In earlier literature reports, x-ray data of a-based ceramics, the /3-like phase observed in certain silica minerals was explained by a structural model based on disordered Q -tridymite. However, others have suggested that the structure of the stabilized jS-cristobalite-like ceramics is closer to that of a-cristobalite than that of Q -tridymite, based on the 29Si nuclear magnetic resonance (NMR) chemical shifts (Perrota et al 1989). Therefore, in the absence of ED data it is impossible to determine the microstructure of the stabilized jS-cristobalite-like phase. ED and HRTEM have provided details of the ceramic microstructure and NMR has provided information about the environments of silicon atoms in the structure. Infrared spectroscopy views the structure on a molecular level. 

Copolymers with sites for association in aqueous solutions were pre-pared by copolymerizing acrylamide with N-alkylacrylamides or with the ampholytic monomer pairs sodium 2-acrylamido 2 methylpro-panesulfonate (NaAMPS) and 2-acrylamido-2-methylpropane-dimethylammonium chloride (AMPDAC). The copolymers were characterized by elemental analysis, NMR and Fourier transform infrared spectroscopy, and lowhangle laser and quasielastic lightscattering measurements. Rheological properties were studied as a function of microstructure, molecular weight, polymer concentration, electrolyte concentration, and shear rate. On the basis of those results, a conceptual model that is based on microheterogeneous domain formation in aqueous solutions is proposed. 

Infrared spectroscopy also provides information on molecular microstructure, e.g. the repeat units resulting from addition polymerization of dienes. For example, polyisoprenes (Fig. 2.9) can be distinguished, based on differences in absorption between C-H out-of-plane bending vibrations. The infrared spectra of stereoregular polymers are also distinct from those of their less regular counterparts, but these differences do not arise directly from tacticity but indirectly due to its effect on chain conformation. 

If you have been working your way through this epic in a more or less linear fashion, then you might have started to ask yourself some fundamental questions such as, How do you know if a vinyl polymer is isotactic, or atactic, or whatever How do you know the composition and sequence distribution of monomers in a copolymer How do you know the molecular weight distribution of a sample This last question will have to wait until we discuss solution properties, but now is a good point to discuss the determination of chain microstructure by spectroscopic methods. The techniques we will discuss, infrared and nuclear magnetic resonance spectroscopy, can do a lot more than probe microstructure, but that would be another book and here we will focus on the basics. 

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