Polymers Raman spectroscopy

For conducting polymers, Raman spectroscopy has been specially examined as a way to determine the value of the conjugation length and different methods have been proposed ... 

The utility of the technique is illustrated by the Raman spectrum of PAN/MWCNT composite nanofibers shown in Fig. 6.5 (Hou et al. 2005). Strong Raman scattering (disorder-induced scatter) by MWCNTs in the matrix gives rise to D, G, and D signals. The peak at about 2300cm is due to the -CN group of the polymer. Raman spectroscopy also has been used to study CNTs in composite nanofibers of sUk (Ayutsede et al. 2005, 2006), carbon fibers (Chung et al. 2005), and PAN (Hou et al. 2005). 

Yoshino and Shinomiya [20] have published Raman spectra of solutions of various polymers. Raman spectroscopy has many applications in the identification of polymers in which additives obscure the polymer peaks obtained in the IR spectrnm. 

For polymers, Raman spectroscopy is particularly useful for characterizing the unsaturation in the monomers and polymers. The general nature of the polymerization... 

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... 

More recently, Raman spectroscopy has been used to investigate the vibrational spectroscopy of polymer Hquid crystals (46) (see Liquid crystalline materials), the kinetics of polymerization (47) (see Kinetic measurements), synthetic polymers and mbbers (48), and stress and strain in fibers and composites (49) (see Composite materials). The relationship between Raman spectra and the stmcture of conjugated and conducting polymers has been reviewed (50,51). In addition, a general review of ft-Raman studies of polymers has been pubUshed (52). 

H. W. Seisler and K. HoUand-Morit2, Infra Red and Raman Spectroscopy of Polymers Marcel Dekker, Inc., New York, 1980. 

The methods used to characterise polymers are partly familiar ones like X-ray diffraction, Raman spectroscopy and electron microscopy, partly less familiar but widespread ones like neutron scattering and nuclear magnetic resonance, and partly... 

Among the techniques mentioned previously, XPS has the greatest impact on polymer surface analysis. A major additional source of chemical information from polymers comes from IR and Raman spectroscopy methods, These vibrational data can be obtained from the bulk and the surface region, although the information depth is much greater than with AES, XPS, or ISS. 

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. 

Advanced techniques like molecularly imprinted polymers (MIPs), infrared/near infrared spectroscopy (FT-IR/NIR), high resolution mass spectrometry, nuclear magnetic resonance (NMR), Raman spectroscopy, and biosensors will increasingly be applied for controlling food quality and safety. 

Raman spectroscopy has enjoyed a dramatic improvement during the last few years the interference by fluorescence of impurities is virtually eliminated. Up-to-date near-infrared Raman spectrometers now meet most demands for a modern analytical instrument concerning applicability, analytical information and convenience. In spite of its potential abilities, Raman spectroscopy has until recently not been extensively used for real-life polymer/additive-related problem solving, but does hold promise. Resonance Raman spectroscopy exhibits very high selectivity. Further improvements in spectropho-tometric measurement detection limits are also closely related to advances in laser technology. Apart from Raman spectroscopy, areas in which the laser is proving indispensable include molecular and fluorescence spectroscopy. The major use of lasers in analytical atomic... 

Various techniques have been introduced which still lack specific applications in polymer/additive analysis, but which may reasonably be expected to lead to significant contributions in the future. Examples are LC-QToFMS, LC-multi-API-MS, GC-ToFMS, Raman spectroscopy (to a minor extent), etc. Expectations for DIP-ToFMS [132], PTV-GC-ToFMS [133] and ASE are high. The advantages of SFC [134,135], on-line multidimensional chromatographic techniques [136,137] and laser-based methods for polymer/additive analysis appear to be more distant. Table 10.33 lists some innovative polymer/additive analysis protocols. As in all endeavours, the introduction of new technology needs a champion. 

The vibrational spectrum of a metal complex is one of the most convenient and unambigious methods of characterization. However, it has not been possible to study the interactions of metal ions and biological polymers in this way since the number of vibrational bands from the polymer obscure the metal spectrum. The use of laser techniques for Raman spectroscopy now make it very likely that the Raman spectra of metals in the presence of large amounts of biological material will be measured (34). The intensity of Raman lines from metal-ligand vibrations can be... 

Whereas several techniques may thus be used to study a certain characteristic of a polymer sample, for instance IR and Raman spectroscopy and X-ray diffraction as well as NMR may be used to determine or infer the crystallinity level of a sample, different techniques work differently and therefore usually do not measure the same. What this means is that crystallinity levels obtained from the same sample may differ when a different technique is applied, see, for example, ref. [23] and chapter 7 and references therein. However, these differences do not necessarily imply one technique being better than another. In fact these differences may contain useful information on the sample (see, for example, ref. [25]). 

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. 

N. Everall, Chapter 4, Raman spectroscopy of synthetic polymers. In M.J. Pelletier (Ed.), Analytical Applications of Raman Spectroscopy, Blackwell Science, Oxford, 1999, pp. 127-192. 

The use of organic polymers as conductors and semiconductors in the electronics industry has led to a huge research effort in poly(thiophenes), with a focus on the modification of their electronic properties so that they can behave as both hole and electron conductors. Casado and co-workers [60] have performed combined experimental and theoretical research using Raman spectroscopy on a variety of fluorinated molecules based on oligomers of thiophene, an example of one is shown in Figure 7. 

Vanduyne R.P., Hulteen J.C., Treichel D.A., Atomic-force microscopy and surface-enhanced Raman-spectroscopy. 1. Ag island films and Ag film over polymer nanosphere surfaces supported on glass, J. Chem. Phys. 1993 99 2101-211. 

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