Spectroscopy and scattering of polymers

This chapter deals with two rather separate topics spectroscopic methods involving vibrational spectroscopy, i.e. infrared (IR) and Raman spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and a few other spectroscopic techniques and methods using scattering of various waves including X-rays, light and neutrons. 

The polymer-related problems which can be solved by spectroscopy are many and varied. They may concern chemical aspects and chain structure, e.g. tacticity, mer sequence distribution, chain branching or structure of radicals. They may concern physical aspects, e.g. chain orientation, crystallinity, crystal thickness, miscibility of polymers, chain conformation or chain dynamics. 

Scattering is a phenomenon noted in everyday life. We can see a light beam in a black room from all angles. The light is scattered. The sky is blue due to 

This chapter will present the different techniques separately. The basic elements of the methods are only briefly presented. The application of the methods in polymer physics is our main concern. 

The atoms in molecules vibrate. This may be accomplished by changes in bond length, bond angle or torsion angle. The molecule consists of a set of harmonic oscillators. The disturbance of a molecule from its equilibrium causes a motion which is a combination of a number of simple harmonic vibrations. The latter are referred to as normal modes. The frequency of the motion of the atoms in each of the normal modes is the same and all atoms will pass the zero position simultaneously. 

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The architecture of macromolecules is another important synthetic variable. New materials with controlled branching sequences or stereoregularity provide tremendous opportunity for development. New polymerization catalysts and initiators for controlled free-radical polymerization are driving many new materials design, synthesis, and production capabilities. Combined with state-of-the-art characterization by probe microscopy, radiation scattering, and spectroscopy, the field of polymer science is poised for explosive development of novel and important materials. New classes of nonlinear structured polymeric materials have been invented, such as dendrimers. These structures have regularly spaced branch points beginning from a central point—like branches from a tree trunk. New struc-... 

Another polymer symposia was organised by IUPAC in 1947 in Liege. At this conference, the discussion included synthesis and technology of polymers like polyethylene, nylon, polyester. New characterisation methods such as x-ray scattering, x-rays, electron microscope, osmometry, nmr, IR, Raman spectroscopy, etc. were now available for characterisation of polymers. These methods become essential because of increasing complexity of new polymers. 

Further details of the theory and application of Raman spectroscopy in polymer studies can be found elsewhere (1. 9). However, vibrational frequencies of functional groups in polymers can be characterized from the spacing of the Raman lines and thus information complementary to IR absorption spectroscopy can be obtained. In addition, since visible radiation is used the technique can be applied to aqueous media in contrast to IR spectroscopy, allowing studies of synthetic polyelectrolytes and biopolymers to be undertaken. Conformation and crystallinity of polymers have also been shown to influence the Raman spectra Q.) while the possibility of studying scattering from small sample volumes in the focussed laser beam (-100 pm diameter) can provide information on localized changes in chemical structure. 

The different methods - potentiometry conductometry turbidimetry vis-cometry " calorimetry , kinetira, sedimentation , dynamic flow birefringence, light scattering , high resolution H-NMR spectrometry , chromatography, spectroscopy , electron microscopy , and others have been used for the investigation of the formation and composition of polymer-polymer complex. ... 

The effect of dissolved CO2 on the miscibility of polymer blends and on phase transitions of block copolymers has been measured with spectroscopy and scattering (40). The shifts in phase diagrams with CO2 pressure can be pronounced. Polymer blends may be trapped kinetically in metastable states before they have time to phase separate. Metastable polymer blends of polycarbonate (PC) and poly(styrene-cn-acrylonitiile) were formed with liquid and supercritical fluid CO2 in the PCA process, without the need for a surfactant. Because of the rapid mass transfer between the CO2 phase and the solution phase, the blends were trapped in a metastable state before they... 

Spectroscopy and scattering/diffraction methods play a central role in polymer science and physics. The enormous development of new techniques in the past decades, leading to improved sensitivity, has been a major force in the creation of new knowledge and new ideas in almost all the fields covered by this book. 

A fibre of a semicrystalline polymer is highly stressed. How can the deformation be recorded by spectroscopy and scattering techniques ... 

The polymer concentration profile has been measured by small-angle neutron scattering from polymers adsorbed onto colloidal particles [70,71] or porous media [72] and from flat surfaces with neutron reflectivity [73] and optical reflectometry [74]. The fraction of segments bound to the solid surface is nicely revealed in NMR studies [75], infrared spectroscopy [76], and electron spin resonance [77]. An example of the concentration profile obtained by inverting neutron scattering measurements appears in Fig. XI-7, showing a typical surface volume fraction of 0.25 and layer thickness of 10-15 nm. The profile decays rapidly and monotonically but does not exhibit power-law scaling [70]. 

The ease of sample handling makes Raman spectroscopy increasingly preferred. Like infrared spectroscopy, Raman scattering can be used to identify functional groups commonly found in polymers, including aromaticity, double bonds, and C bond H stretches. More commonly, the Raman spectmm is used to characterize the degree of crystallinity or the orientation of the polymer chains in such stmctures as tubes, fibers (qv), sheets, powders, and films... 

When the spectral characteristics of the source itself are of primary interest, dispersive or ftir spectrometers are readily adapted to emission spectroscopy. Commercial instmments usually have a port that can accept an input beam without disturbing the usual source optics. Infrared emission spectroscopy at ambient or only moderately elevated temperatures has the advantage that no sample preparation is necessary. It is particularly appHcable to opaque and highly scattering samples, anodized and painted surfaces, polymer films, and atmospheric species (135). The interferometric... 

The main experimental techniques used to study the failure processes at the scale of a chain have involved the use of deuterated polymers, particularly copolymers, at the interface and the measurement of the amounts of the deuterated copolymers at each of the fracture surfaces. The presence and quantity of the deuterated copolymer has typically been measured using forward recoil ion scattering (FRES) or secondary ion mass spectroscopy (SIMS). The technique was originally used in a study of the effects of placing polystyrene-polymethyl methacrylate (PS-PMMA) block copolymers of total molecular weight of 200,000 Da at an interface between polyphenylene ether (PPE or PPO) and PMMA copolymers [1]. The PS block is miscible in the PPE. The use of copolymers where just the PS block was deuterated and copolymers where just the PMMA block was deuterated showed that, when the interface was fractured, the copolymer molecules all broke close to their junction points The basic idea of this technique is shown in Fig, I. 

We report here the results of our recent studies of poly(alkyl/arylphosphazenes) with particular emphasis on the following areas (1) the overall scope of, and recent improvements in, the condensation polymerization method (2) the characterization of a representative series of these polymers by dilute solution techniques (viscosity, membrane osmometry, light scattering, and size exclusion chromatography), thermal analysis (TGA and DSC), NMR spectroscopy, and X-ray diffraction (3) the preparation and preliminary thermolysis reactions of new, functionalized phosphoranimine monomers and (4) the mechanism of the polymerization reaction. 

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