Orientation of chain molecules

Figure 8-2. Parallel orientation of chain molecules in drawn fibre.

Later, J. J. Trillat demonstrated, by detailed experiments on the orientation of chain molecules on metal surfaces, and in phase boundaries, that the parallel arrangement of chain molecules can be detected similarly in the liquid or adsorbed state and that it plays a determining role for the physicochemical and technical properties of such films. 

Fluorochemicals repel both water and oU because they produce an extremely low energy surface (18—26). The effectiveness of the fluorochemicals depends upon uniform surface coverage and orientation of the molecules on the fiber surface so that the perfluoroalkyl chains are directed away from the surface. The result is a GST as low as 5—10 mN /m (dyne/cm). Fluorochemical finishes are often formulated with nonfluorinated resin-based water-repeUent extenders. These water repeUents not only reduce the cost of the finish but may also improve durabUity (27,28). 

Usually, the transition of polymer systems into the oriented state occurs as a result of deformation e.g. upon exposure to external stress. When the polymers undergo deformation both the macromolecule as a whole and its parts (segments) can undergo orientation. The rates of these orientation processes are very different and, hence, the orienting forces affect first of all the orientation of chain segments and subsequently that of a chain molecule as a whole. However, by varying the extension velocity and the temperature, only the overall orientation process may predominate, thus extension of all chains occurs in a single act. 

Besides crystalline order and structure, the chain conformation and segment orientation of polymer molecules in the vicinity of the surface are also expected to be modified due to the specific interaction and boundary condition at the surface between polymers and air (Fig. 1 a). According to detailed computer simulations [127, 128], the chain conformation at the free polymer surface is disturbed over a distance corresponding approximately to the radius of gyration of one chain. The chain segments in the outermost layers are expected to be oriented parallel to the surface and chain ends will be enriched at the surface. Experiments on the chain conformation in this region are not available, but might be feasible with evanescent wave techniques described previously. Surface structure on a micrometer scale is observed with IR-ATR techniques [129],... 

The lattice gas model of Bell et al. [33] neither gave any detailed mechanism of the orientational ordering nor separated the contributions of the headgroup and the acyl chain. Lavis et al. [34] discussed Ref. 33 critically and concluded that the sharp kink point in the isotherm at transition was an artifact of the mean field approximation used. An improved correspondence to experimental data was claimed by the use of the real-space renormalization group method [35]. The same authors returned to the problem [35] and concluded that in addition to the orientation of the molecules, chain melting had to be included in a model which could interpret the phase transitions. 

Many conformations were sampled by the usual MC procedure. The result is of course that there is no preferred orientation of the molecule. Each conformation can, however, be characterised by an instantaneous main axis this is the average direction of the chain. Then this axis is defined as a director . This director is used to subsequently determine the orientational order parameter along the chain. The order is obviously low at the chain ends, and relatively high in the middle of the chain. It was found that the order profile going from the centre of the molecules towards the tails fell off very similarly to corresponding chains (with half the chain length) in the bilayer membrane. As an example, we reproduce here the results for saturated acyl chains, in Figure 10. The conclusion is that the order of the chains found for acyl tails in the bilayer is dominated by intramolecular interactions. The intermolecular interactions due to the presence of other chains that are densely packed around such a chain,... 

The fluorescence polarization technique is a very powerful tool for studying the fluidity and orientational order of organized assemblies (see Chapter 8) aqueous micelles, reverse micelles and microemulsions, lipid bilayers, synthetic non-ionic vesicles, liquid crystals. This technique is also very useful for probing the segmental mobility of polymers and antibody molecules. Information on the orientation of chains in solid polymers can also be obtained. 

Introduction. Today nitrocellulose is one of most important derivatives of cellulose used in industry and commerce, and a major product of the chemical industry. Its wide and manifold applications are due mainly to its extraordinary physical properties. Thus a protective coating of nitrocellulose varnish, a nitrocellulose film or a tube of smokeless powder — all are characterized by relatively high elasticity and mechanical strength. These properties are a direct consequence of the microstructure of cellulose, which is composed of highly oriented long-chain molecules of polysaccharide. Not only nitrocellulose, but also other derivatives of cellulose, such as other esters and ethers, demonstrate similar characteristics. 

Fig. 3. Stereodiagrams of a-carbon atom chains of RNase-A and RNase-S from the studies by X-ray diffraction on the crystalline enzymes (a) RNase-A from the work of Kartha et al. (60). (b) RNase-S from the work of Wyckoff et al. (62). The orientation of the molecules has been made as similar as possible to simplify comparison. The figures are reproduced with the kind permission of Dickerson and Geis (63).

In an interesting application, the long-chain substituted 4- -hexoxybenzylidene-4 -iodoaniline (HBIA), 5 has been incorporated in the liquid-crystal phase of 4- -hexoxy-benzylidene-4 -propylaniline (HBPA, 6)13. The intensity pattern of the Mossbauer spectrum allowed the orientation of the molecule to be estimated, showing that the smectic tilt angle was 50°. 

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