Polymer films, molecular orientation

The use of a fibre-coupled confocal Raman microscope and an infrared microscope for both point mapping and global imaging in the study of spatial variations in polymer chemistry and morphology is illustrated by studies of the curing of the UV-cured acrylate coatings, crystallinity in drawn polyethylene terephthalate (PET) film, molecular orientation in PET bottles, and the analysis of a PES/PEES copolymer blended with epoxy resin and cured at elevated temperature. 8 refs. 

The molecular orientation of the polymer in a fabricated specimen can significantly alter the stress—strain data as compared with the data obtained for an isotropic specimen, eg, one obtained by compression mol ding. For example, tensile strengths as high as 120 MPa (18,000 psi) have been reported for PS films and fibers (8). PS tensile strengths below 14 MPa (2000 psi) have been obtained in the direction perpendicular to the flow. 

While thin polymer films may be very smooth and homogeneous, the chain conformation may be largely distorted due to the influence of the interfaces. Since the size of the polymer molecules is comparable to the film thickness those effects may play a significant role with ultra-thin polymer films. Several recent theoretical treatments are available [136-144,127,128] based on Monte Carlo [137-141,127, 128], molecular dynamics [142], variable density [143], cooperative motion [144], and bond fluctuation [136] model calculations. The distortion of the chain conformation near the interface, the segment orientation distribution, end distribution etc. are calculated as a function of film thickness and distance from the surface. In the limit of two-dimensional systems chains segregate and specific power laws are predicted [136, 137]. In 2D-blends of polymers a particular microdomain morphology may be expected [139]. Experiments on polymers in this area are presently, however, not available on a molecular level. Indications of order on an... 

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. 

Sometimes the hazy optical properties of polypropylene are a detriment to its use in thin films. To address this problem, as well as to improve physical properties and reduce material costs, we can orient the molecular chains by stretching the polymer film after it has left the extrusion die. There are two methods of orienting films, film blowing, shown in Fig. 11.6, and tentering, shown in Fig, 19.6. 

Having said this, it was felt therefore that there is a need for a book addressing analysis and characterisation of polymers from the point of view of what we wish to call the primary analytical question. Many excellent textbooks and reference works exist which address one or more individual analytical techniques, see, for example, references [1-10]. These books form the basis of the knowledge of the technique expert. They also contain many excellent and varied examples on successful applications of analytical techniques to polymer analysis and characterisation. There are also books which address the multitude of analytical techniques applied in polymer analysis, see, for example, references [11-24], However, a synthetic chemist may wish to know the constitution of his/her polymer chain, a material scientist may want to find out the reasons why a fabricated sample had failed. What technique is best or optimal to study chain constitution will depend on the situation. Polymer failure may result from morphological features, which needs to be avoided, a contaminant, a surface property degradation, etc. When a sample has been processed, e.g., a film blown, molecular orientation may be the key parameter to be studied. A formulation scientist may wish to know why an additive from a different supplier performs differently. It is from such points of view that polymer analysis and characterisation is addressed in this book. 

A second type of anisotropic system is the biaxially oriented or planar random anisotropic system. This type of material is illustrated schematically in Figure 2A. Four of the five independent elastic moduli are illustrated in Figure 2B in addition there are two Poisson s ratios. Typical biaxially oriented materials are films that have been stretched in two directions by either blowing or tentering operations, rolled materials, and fiber-filled composites in which the fibers are randomly oriented in a plane. The mechanical properties of anisotropic materials arc discussed in detail in following chapters on composite materials and in sections on molecularly oriented polymers. 

Polymer films were produced by surface catalysis on clean Ni(100) and Ni(lll) single crystals in a standard UHV vacuum system H2.131. The surfaces were atomically clean as determined from low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). Monomer was adsorbed on the nickel surfaces circa 150 K and reaction was induced by raising the temperature. Surface species were characterized by temperature programmed reaction (TPR), reflection infrared spectroscopy, and AES. Molecular orientations were inferred from the surface dipole selection rule of reflection infrared spectroscopy. The selection rule indicates that only molecular vibrations with a dynamic dipole normal to the surface will be infrared active [14.], thus for aromatic molecules the absence of a C=C stretch or a ring vibration mode indicates the ring must be parallel the surface. 

Aromatic molecules can be polymerized catalytically on clean metal surfaces, or electrochemically to produce oriented polymer films. Initial adsorption of aromatic molecules occurs by electron donation from the aromatic molecule to the surface. This electron donation creates radical cations that can polymerize. Molecular orientation in the films depends on the stable bonding configuration of the radical cation. Thiophene, pyridines, and pyrrole all polymerize with the ring substantially perpendicular to the surface, whereas aniline polymerizes with the phenyl rings parallel to the surface. The catalytically... 

Even at their best, the models are able to predict only macroscopic properties of the films, yielding no information on microscopic parameters that may affect resist performance. It is highly probable that spin casting induces some structure or preferential chain orientation into the films, or causes secondary effects such as the aggregation observed by Law. These effects are barely addressed in the currently available literature. However, some earlier works (3.17-191 on solvent (static) cast films have investigated the molecular orientation of polymer chains as well as chain relaxation due to thermal annealing. 

The diffusion and the permeability are inversely related to the density, degree of crystallinity, orientation, filler concentration, and crosslink density of a polymeric film. As a general rule, the presence of plasticisers or residual solvents increases the rate of diffusion in polymers. Films cast from poor solvents have high permeability. The rate of diffusion or permeability is independent of the molecular weight of the polymer, providing the polymer has a moderately high molecular weight. 

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... 

Figure 6. Schematic representation of molecular orientation in a polymer film with respect to die poling field in the z direction.

In the limit of the oriented gas model with a one-dimensional dipolar molecule and a two state model for the polarizability (30). the second order susceptibility X33(2) of a polymer film poled with field E is given by Equation 4 where N/V is the number density of dye molecules, the fs are the appropriate local field factors, i is the dipole moment, p is the molecular second order hyperpolarizability, and L3 is the third-order Langevin function describing the electric field induced polar order at poling temperature Tp - Tg. 

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