Amorphous polymer features

Figure 3.16a shows the storage and loss components of the compliance of crystalline polytetrafluoroethylene at 22.6°C. While not identical to the theoretical curve based on a single Voigt element, the general features are readily recognizable. Note that the range of frequencies over which the feature in Fig. 3.16a develops is much narrower than suggested by the scale in Fig. 3.13. This is because the sample under investigation is crystalline. For amorphous polymers, the observed loss peaks are actually broader than predicted by a...

Lubricity of crystalline polymers is usually higher than that of amorphous polymers. Excellent machinery parts are made from crystalline nylon-6,6 resins, eg, gears, cams, wedges, and other components not requiring lubrication. Gears made of amorphous polyimide resin, on the other hand, do not exhibit this feature. 

Amorphous stereotactic polymers can crystallise, in which condition neighbouring chains are parallel. Because of the unavoidable chain entanglement in the amorphous state, only modest alignment of amorphous polymer chains is usually feasible, and moreover complete crystallisation is impossible under most circumstances, and thus many polymers are semi-crystalline. It is this feature, semicrystallinity, which distinguished polymers most sharply from other kinds of materials. Crystallisation can be from solution or from the melt, to form spherulites, or alternatively (as in a rubber or in high-strength fibres) it can be induced by mechanical means. This last is another crucial difference between polymers and other materials. Unit cells in crystals are much smaller than polymer chain lengths, which leads to a unique structural feature which is further discussed below. 

Miscibility or compatibility provided by the compatibilizer or TLCP itself can affect the dimensional stability of in situ composites. The feature of ultra-high modulus and low viscosity melt of a nematic liquid crystalline polymer is suitable to induce greater dimensional stability in the composites. For drawn amorphous polymers, if the formed articles are exposed to sufficiently high temperatures, the extended chains are retracted by the entropic driving force of the stretched backbone, similar to the contraction of the stretched rubber network [61,62]. The presence of filler in the extruded articles significantly reduces the total extent of recoil. This can be attributed to the orientation of the fibers in the direction of drawing, which may act as a constraint for a certain amount of polymeric material surrounding them. 

In general, there are three kinds of moduli Young s moduli E, shear moduli G, and bulk moduli K. The simplest of all materials are isotropic and homogeneous. The distinguishing feature about isotropic elastic materials is that their properties are the same in all directions. Unoriented amorphous polymers and annealed glasses are examples of such materials. They have only one of each of the three kinds of moduli, and since the moduli are interrelated, only two moduli are enough to describe the elastic behavior of isotropic substances. For isotropic materials... 

The challenges involved in the material properties of PPC relate to its thermal features, i.e., its thermal decomposition, and the glass transition temperature (Tg) of about body temperature of the otherwise amorphous polymer. These have implications for processing and application of the material. This review will discuss consecutively the thermal, viscoelastic, and mechanical properties of PPC and the experiences in processing PPC and its composites. The properties of solutions of PPC will also be presented, and the biodegradabUity and biocompatibility discussed. Spectroscopic properties will not be discussed. Further information on NMR data can be found in the following references [2, 10-12]. A t3 pical spectrum is shown in Fig. 2 [13]. 

If crystallization is carried out from concentrated solutions, multilamellar aggregates are formed. In particular, melt crystallization of polyethylene gives bunched-up lamellae with an overall spherical symmetry. The space between the lamellae contains uncrystallized amorphous polymer. These objects are called spherulites, and their radii grow linearly with time, in spite of their intricate morphological features [9]. Another remarkable feature of spheruhtes formed by linear polyethylene is that they are gigantically chiral, although the molecules are achiral. 

Local structural features have been postulated for amorphous polymer systems, based on the asymmetry of chain-like molecules. Flory (56) has shown that molecular asymmetry in itself is no barrier to a dense random packing of the chains are sufficiently flexible. Robertson (57) suggests, however, that some degree of local alignment is required simply to accomodate linearly connected sequences in the rather limited space available. Unfortunately, Calculations of local cooperative effects are extremely difficult and sensitive to specific assumptions about available packing arrangements. 

We have a specific interest in the self-assembled structures formed by poly(ferrocenylsilane) block copolymers, such as poly(ferrocenyldimethylsilane-Z -dimethyl-siloxane) (PFS-PDMS) and (ferrocenyldimethylsilane-Z>-isoprene) (PFS-PI). The PFS block contains an iron atom in the main chain repeat unit. These polymers are particularly promising for novel applications, since they can be used as charge-transport materials and, by pyrolysis, as precursors to ferromagnetic ceramics [4-6], Moreover, they can by synthesized with a very narrow molar mass distribution, with excellent control over chain length and composition [7], An important feature of PFS is that the polymers bearing two methyl groups on the silane unit are crystalline, whereas polymers with two different substituents on each silane (methyl, ethyl methyl, phenyl) are atactic and remain amorphous. This feature of the polymer composition has a strong influence on the type of self assembled structures that these poly-... 

The general features of the D vs. Cj relations for amorphous polymer-solvent systems slightly above or below Tg° are not fully elucidated. This is mainly due to the fact that, as will be explained in the next section, the sorption processes in glassy polymers are not Fickian and hence the methods for the determination of D (cj) presented in the previous section can no longer be applied. In principle, D values of such systems could be determined from steady-state permeation measurements, but Kishimoto (unpublished) has shown that the analysis of permeation data on glassy systems is complicated by factors which are not yet fully resolved. 

The character of the polymethyl methacrylate data is essentially similar to that found for systems atactic polystyrene-benzene at 25°, 35°, and 50° C. [Kishimoto, Fujita, Odani, Kurata and Tamura (1960) Odani, Kida, Kurata and Tamura (1961)] and also atactic polystyrene-methyl ethyl ketone at 25° C. [Odani, Hayashi and Tamura (1961)], and appears to be fairly general for amorphous polymer-solvent systems in the glassy state. On the other hand, the cellulose nitrate data shown in Fig. 8 appear to manifest features characteristic of crystalline polymer-solvent systems. For example, the earlier data of Newns (1956) on the system regenerated cellulose-water (in this case, water is not the solvent but merely a swelling-agent) and recent studies for several crystalline polymers all show essentially similar characters [see Kishimoto, Fujita, Odani, Kurata and Tamura (I960)]. To arrive at a more definite conclusion, however, more extensive experimental data are needed. 

Hopfenberg and Frisch (1969) succeeded in describing all observed behavioural features for a given polymer-penetrant system in a diagram of temperature versus penetrant activity, which seems to be of general significance for amorphous polymers. It is reproduced in Fig. 18.13. 

Cowie, J.M.G. (1975). Some general features of Tg-M relations for oligomers and amorphous polymers. Eur. Polym. J. 297-300. 

X-ray diffraction measurements and structural calculations on murein [22-25] and pseudomurein [26-28] have revealed several common structural features in both polymers. Murein and pseudomurein sacculi possess a density of p= 1. 39-1.46g/cm which is characteristic of highly ordered material. A much lower density, in the range of p= 1.24-1.32g/cm is to be expected for amorphous polymers [26]. X-ray diffraction showed diffuse Debye-Scherer rings with Bragg periodicities of about 0.45 nm and 0.94 nm in the planes and of 4.3-4.5nm vertically to the planes of both types of cell walls. These data have been interpreted in two different ways ... 

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