Orientation Raman spectroscopy

Blown film extrusion, online orientation, Raman spectroscopy, low-density polyethylene... 

The varying actual orientation of molecules adsorbed at an aqueous solution-CCU interface with decreasing A has been followed by resonance Raman spectroscopy using polarized light [130]. The effect of pressure has been studied for fatty alcohols at the water-hexane [131] and water-paraffin oil [132] interfaces. 

Lesieur P, Vandevyver M, Ruaudel-Teixier A and Barraud A Orientational studies of Langmuir-Blodgett films of porphyrins with polarized resonant Raman spectroscopy Thin Soiid Fiims 159 315-22... 

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... 

Polarization effects are another feature of Raman spectroscopy that improves the assignment of bands and enables the determination of molecular orientation. Analysis of the polarized and non-polarized bands of isotropic phases enables determination of the symmetry of the respective vibrations. For aligned molecules in crystals or at surfaces it is possible to measure the dependence of up to six independent Raman spectra on the polarization and direction of propagation of incident and scattered light relative to the molecular or crystal axes. 

The diffusion, location and interactions of guests in zeolite frameworks has been studied by in-situ Raman spectroscopy and Raman microscopy. For example, the location and orientation of crown ethers used as templates in the synthesis of faujasite polymorphs has been studied in the framework they helped to form [4.297]. Polarized Raman spectra of p-nitroaniline molecules adsorbed in the channels of AIPO4-5 molecular sieves revealed their physical state and orientation - molecules within the channels formed either a phase of head-to-tail chains similar to that in the solid crystalline substance, with a characteristic 0J3 band at 1282 cm , or a second phase, which is characterized by a similarly strong band around 1295 cm . This second phase consisted of weakly interacting molecules in a pseudo-quinonoid state similar to that of molten p-nitroaniline [4.298]. 

As a prelude to the discussion it is necessary to consider the definition of orientation in terms of the Euler angles, and the definition ofan orientation distribution function in terms ofan expansion ofLegendre functions. These definitions set the scene for examining the information which can be obtained from different spectroscopic techniques. In this review, infra-red and Raman spectroscopy and nuclear magnetic resonance, will be considered. 

In this review the definition of orientation and orientation functions or orientation averages will be considered in detail. This will be followed by a comprehensive account of the information which can be obtained by three spectroscopic techniques, infra-red and Raman spectroscopy and broad line nuclear magnetic resonance. The use of polarized fluorescence will not be discussed here, but is the subject of a contemporary review article by the author and J. H. Nobbs 1. The present review will be completed by consideration of the information which has been obtained on the development of molecular orientation in polyethylene terephthalate and poly(tetramethylene terephthalate) where there are also clearly defined changes in the conformation of the molecule. In this paper, particular attention will be given to the characterization of biaxially oriented films. Previous reviews of this subject have been given by the author and his colleagues, but have been concerned with discussion of results for uniaxially oriented systems only2,3). 

In this review recent theoretical developments which enable quantitative measures of molecular orientation in polymers to be obtained from infra-red and Raman spectroscopy and nuclear magnetic resonance have been discussed in some detail. Although this is clearly a subject of some complexity, it has been possible to show that the systematic application of these techniques to polyethylene terephthalate and polytetramethylene terephthalate can provide unique information of considerable value. This information can be used on the one hand to gain an understanding of the mechanisms of deformation, and on the other to provide a structural understanding of physical properties, especially mechanical properties. 

Interfacial water molecules play important roles in many physical, chemical and biological processes. A molecular-level understanding of the structural arrangement of water molecules at electrode/electrolyte solution interfaces is one of the most important issues in electrochemistry. The presence of oriented water molecules, induced by interactions between water dipoles and electrode and by the strong electric field within the double layer has been proposed [39-41]. It has also been proposed that water molecules are present at electrode surfaces in the form of clusters [42, 43]. Despite the numerous studies on the structure of water at metal electrode surfaces using various techniques such as surface enhanced Raman spectroscopy [44, 45], surface infrared spectroscopy [46, 47[, surface enhanced infrared spectroscopy [7, 8] and X-ray diffraction [48, 49[, the exact nature of the structure of water at an electrode/solution interface is still not fully understood. 

A considerable amount of work has been directed towards the study of detailed molecular orientations and motions of guest molecules in urea canal inclusion compounds and structural changes such as those described above. Methods used include infrared s2) and Raman spectroscopy 52,53, esr 54 56). nqr S0,57), and nmr ( H, 2D,... 

In recent years,3 4 however, there has been renewed interest in the study of the electrode/solution interface due in part to the development of new spectroscopic techniques such as surface-enhanced Raman spectroscopy,5-7 electrochemically modulated infrared reflectance spectroscopy and related techniques,8,9 second-harmonic generation,10-12 and others which give information about the identity and orientation of molecular species in the interfacial... 

Normal transmission IRLD can also be used to characterize polymeric fibers, although scattering can induce sloping baselines. Raman spectroscopy then becomes a convenient alternative. Rutledge et al. have recently probed the orientation in electrospun nanofibers composed of a core of Bombyx mori fibroin and an outer shell of poly (ethylene oxide) [24], The orientation values were low, less than 0.1, as is often the case in electrospun fibers. 

Raman spectroscopy is an inelastic light scattering experiment for which the intensity depends on the amplitude of the polarizability variation associated with the molecular vibration under consideration. The polarizability variation is represented by a second-rank tensor, oiXyZ, the Raman tensor. Information about orientation arises because the intensity of the scattered light depends on the orientation of the Raman tensor with respect to the polarization directions of the electric fields of the incident and scattered light. Like IR spectroscopy, Raman... 

The theory of orientation measurements by linearly polarized Raman spectroscopy has been developed in detail by Bower in 1972 [44]. The Raman intensity, I, is given by... 

Because the determination of the order parameters by Raman spectroscopy is not straightforward, some works have focused on using intensity ratios to evaluate the molecular orientation (see above). Frisk et al. [56], in particular, have shown that the simple parameter R = 1 — Ixx/Izz — 1 — (axx)/(azz) can efficiently, although qualitatively, characterize orientation in polymers. 

Some characteristics of, and comparisons between, surface-enhanced Raman spectroscopy (SERS) and infrared reflection-absorption spectroscopy (IRRAS) for examining reactive as well as stable electrochemical adsorbates are illustrated by means of selected recent results from our laboratory. The differences in vibrational selection rules for surface Raman and infrared spectroscopy are discussed for the case of azide adsorbed on silver, and used to distinguish between "flat" and "end-on" surface orientations. Vibrational band intensity-coverage relationships are briefly considered for some other systems that are unlikely to involve coverage-induced reorientation. 

Surface-enhanced Raman spectroscopy (SERS) has been widely used to study the interaction of solvent molecules with the electrode surface, including orientation at the interface. The first observation of the Raman... 

Raman spectroscopy is a powerful tool for probing orientation, stress, and strain. Galiotis et al. have written a review on the determination of stress and strain in composites and fibers using Raman spectroscopy [179]. Young et al. discuss the complexities of correct interpretation of molecular orientation information encoded in Raman spectra of polymers [180]. Caution and a suitable number of control studies are necessary to prevent faulty conclusions. 

R.R Paradkar, S.S. Sakhalkar, X. He and M.S. Ellison, On-line estimation of molecular orientation in polypropylene fibers using polarized Raman spectroscopy, Appl. Spectrosc., 55, 534-539 (2001). 

M. Tanaka and R.J. Young, Molecular orientation distributions in uniaxiaUy oriented poly(L-lactic acid) films determined by polarized Raman spectroscopy. Macromolecules, 39, 3312-3321 (2006). 

M. Tanaka and R.J. Yoimg, Review Polarised Raman spectroscopy for the smdy of molecular orientation distributions in polymers, J. Mater. Sci, 41, 963-991 (2006). 

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