Polymers oriented samples

SIMS, and SNMS in rare cases, such as for HgCdJTei samples or some polymers, the sample structure can be modified by the incident ion beam. These effects can often be eliminated or minimized by limitii the total number of particles incident on the sample, increasing the analytical area, or by cooling the sample. Also, if channeling of the ion beam occurs in a crystal sample, this must be included in the data analysis or serious inaccuracies can result. To avoid unwanted channelii, samples are often manipulated during the analysis to present an average or random crystal orientation. 

Anisotropic behaviour is also exhibited in optical properties and orientation effects can be observed and to some extent measured by birefringence methods. In such oriented materials the molecules are in effect frozen in an unstable state and they will normally endeavour to take up a more coiled conformation due to rotation about the single bonds. If an oriented sample is heated up the molecules will start to coil as soon as they possess sufficient energy and the mass will often distort. Because of this oriented materials usually have a lower heat distortion temperature than non-oriented polymers. 

Hence, the extension of an isotropic unoriented partially crystalline polymer leads to the formation of a highly organized material with a characteristic fibrillar structure. The anisotropy of the sample as a whole is expressed by a higher modulus, tenacity and optical anisotropy. It would seem that the increase in strength in the drawing direction suggests that the oriented samples consist of completely extended chains. However, while the strength of such perfect structure for polyethylene has been evaluated as 13000 MPas), the observed values for an oriented sample are 50 to 30 MPa. 

Fig. 3a. P200 and P400 as a function of draw ration for the pseudo-affine deformation scheme (uniaxially oriented sample) b P20o and P400 as a function of draw ratio X for the rubber network affine deformation scheme (N = 6, uniaxially oriented sample). Reproduced from Journal of Polymer Science by permission of the publishers, John Wiley Sons Incs (C)...

Molecular orientation and the testing direction strongly influence the observed modulus of a polymer sample. Fibers are typically highly oriented and exhibit much higher modulus values than non-oriented samples prepared from the same polymer. In the case of films, we typically observe anisotropy a film exhibits a range of modulus values depending upon the testing direction. 

A more complex but faster and more sensitive approach is polarization modulation (PM) IRLD. For such experiments, a photoelastic modulator is used to modulate the polarization state of the incident radiation at about 100 kHz. The detected signal is the sum of the low-frequency intensity modulation with a high-frequency modulation that depends on the orientation of the sample. After appropriate signal filtering, demodulation, and calibration [41], a dichroic difference spectrum can be directly obtained in a single scan. This improves the time resolution to 400 ms, prevents artifacts due to relaxation between measurements, and improves sensitivity for weakly oriented samples. However, structural information can be lost since individual polarized spectra are not recorded. Pezolet and coworkers have used this approach to study the deformation and relaxation in various homopolymers, copolymers, and polymer blends [15,42,43]. For instance, Figure 7 shows the relaxation curves determined in situ for miscible blends of PS and PVME [42]. The (P2) values were determined... 

X-ray studies of oriented samples of LC polymers are therefore the main method for the structural study of smectic mesophase, as well as for any other structural type of LC polymers. 

Similarly with low-molecular nematics is manifested in that the nematic polymers may form equally well schlieren texture, typical for low-molecular nematics (Fig. 18a) (polymers B.3.3-B.3.4, Table 9). The enthalpy of transition from LC state to isotropic melt is also close to that for low-molecular nematics. At the same time, there also exist definite structural differences. X-ray patterns of the same polymers, even in unoriented state, display certain elements of structural ordering in the arrangement of side branches (a weak diffuse halo at small angles), which could indicate a sibotactic nematic type of ordering. These differences are most distinct for oriented polymer films. As an example Fig. 18b, c, present X-ray patterns of unoriented and oriented samples of one and the same nematic polymer 121 l24. In fact two sharp small angle... 

In analyzing the spectrum of a polymer we do not, of course, limit ourselves to the study of a single specimen. We have already noted the significant information which can be obtained by studying oriented samples as well as deuterated polymers, when possible. In this section we will consider briefly how the study of other kinds of specimens adds to our knowledge of the origin of bands. 

Since many of the aromatic polymers studied [e.g., poly(n-hexylphenylsilane)] are also quite rigid in solution and optical microscopy studies on concentrated solutions often show signs of long range order, a partially oriented sample of this material was prepared by shear flow extension. Third harmonic measurements at 1.064 /im on partially oriented films prepared in this... 

Typical values of electrical properties of the homopolymer without additives and treatments are in the Table 3.8. The values can be substantially changed by the type of cooling and post-treatments, which determine the morphological state of the polymer. Dielectric constants as high as 17 have been measured on oriented samples that have been subjected to high electrical fields (poled) under various conditions to orient polar crystalline form.74... 

Another way to disentangle linear polyethylenes, and thus control the interphase without using a solvent, is to anneal the polymer in the hexagonal phase. Bassett has discussed the role of the hexagonal phase in the crystallization of polyethylene extensively in an earlier chapter in this book Briefly, polyethylene exhibits a number of different crystal structures, with the hexagonal phase being observed in linear polyethylenes at elevated pres-sure/temperature in isotropic samples or at ambient pressure in oriented samples. For this reason, we have to distinguish between these two situations, namely isotropic and oriented polyethylene. However, we will focus only on isotropic polyethylene and will refer readers to reference [18,19] for an overview of oriented polyethylene. 

Up to now we have considered the CP film as an amorphous, homogeneous and isotropic medium. However, CPs are intrinsically anisotropic since the 7r-electrons are delocalized along the macromolecule backbone. An anisotropic optical response, typical of oriented samples, is extremely important both for fundamental science (e.g., comparison with theoretical predictions) and for technological reasons (polarized emission is recommended in displays [55,56]). The orientation process for conjugated polymers is very difficult and several approaches have been used to remove the typical random-coil conformation of CP and to induce the extended aligned conformation. It is not the aim of this article to review all orientational techniques used with CPs. However, it should be mentioned that very high degrees of orientation have been achieved... 

Most research effort, therefore, concentrated on those polymers where it is possible to control morphology, to obtain chemically pure materials and to manipulate them to provide forms, e.g. chain oriented samples and thin films, suitable for basic research and applications. The development of synthetic routes that provide clean, reproducible samples has been critical in the progress achieved in understanding the physics of conjugated polymers. This in turn underpinned the rapid development of technological applications, which appeared on a much shorter timescale than for other, comparable technologies. The level of scientific and technical interest in polymers, such as PAc, PAni, PPy, PThs, PPVs and polyfluorenes, has resulted in the commercial production of them and their precursors. 

The next major improvement in sample quality was the result of developments in direct synthesis. Oriented samples were obtained by the polymerisation of acetylene with the conventional titanium catalyst on a single crystal substrate and in nematic liquid crystals, see Tsukamoto (1992). Heat-treating the catalyst was found to produce polymer that could be stretched to give oriented samples. This resulted in a higher electrical conductivity along the orientation direction, up to 2xl05 fl-lm-1 being obtained. Naarman and co-workers heat treated the catalyst at 393 K and carried out the reaction in silicone oil at room temperature (Theophilou et al., 1986). Silicone oil was chosen as it has the same viscosity at room temperature as the usual solvents... 

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