Polymer, amorphous microcrystalline

Similar behavior has been observed for noncrystallizing polymers. For example, the diffusivity of water in poly(vinylpyrrolidone) (PVP) (Oksanen and Zografi, 1993) has been shown to increase at water contents beyond the hydration limit. Additional reports have shovm that the hydration limit has physical significance for other polymer excipients. Microcrystalline cellulose and lactose for compression, for example, lose their direct compaction properties at water contents just below (Huettenrauch and Jacob, 1977), and gelatin capsules become brittle as the water content is reduced below Wm (Kontny and Mulski, 1989). Recently, the chemical stability of a model peptide in PVP matrices was shown to improve when the amorphous dispersion was stored below the polymer s hydration limit (Lai et al., 1999a Lai et al., 1999b Lechuga-Ballesteros et al., 2002). 

Polymers are difficult to model due to the large size of microcrystalline domains and the difficulties of simulating nonequilibrium systems. One approach to handling such systems is the use of mesoscale techniques as described in Chapter 35. This has been a successful approach to predicting the formation and structure of microscopic crystalline and amorphous regions. 

Applications. Among the P—O- and P—N-substituted polymers, the fluoroalkoxy- and aryloxy-substituted polymers have so far shown the greatest commercial promise (14—16). Both poly[bis(2,2,2-trifluoroethoxy)phosphazene] [27290-40-0] and poly(diphenoxyphosphazene) [28212-48-8] are microcrystalline, thermoplastic polymers. However, when the substituent symmetry is dismpted with a randomly placed second substituent of different length, the polymers become amorphous and serve as good elastomers. Following initial development of the fluorophosphazene elastomers by the Firestone Tire and Rubber Co., both the fluoroalkoxy (EYPEL-F) and aryloxy (EYPEL-A) elastomers were manufactured by the Ethyl Corp. in the United States from the mid-1980s until 1993 (see ELASTOLffiRS,SYNTHETic-PHOSPHAZENEs). 

As mentioned in Chapter 1 and earlier in this chapter, the presence of microcrystalline domains in an amorphous (random coil) polymer matrix has the effect of stiffening the material, generating opalescence rather than transparency, and raising the temperature at which the material can be used before it undergoes liquid-like flow. 

Amorphous carbon refers to charcoal, soot, coal, and carbon black. These materials are mostly microcrystalline forms of graphite. They are characterized by small particle sizes and large surface areas with partially saturated valences. These small particles readily absorb gases and solutes from solution, and they form strong, stable dispersions in polymers, such as the dispersion of carbon black in tires. 

For a crystalline/crystalline blend, Yoshie et al. [151] studied blends of PVA and poly(3-hydroxybutyrate) (PHB). They found that PVA/PHB is compatible only when the blend contains a larger amount of PVA, and Model C was found with amorphous and crystalline PHB. Kwak et al. [94] studied poly(ether-ester)/PVC to find a common Ti, but double-exponential Tip decays. Model B was proposed with a mixed amorphous phase and two microcrystalline phases for component polymers. Note that Guo [95] reexamined this blend and pointed out that these assignments have to be reconsidered. 

Linear Polymers Long chains are necessary to confer the mechanical properties of fibers, plastics, and elastomers that make polymers so valuable. Fibers such as cellulose and polyester arc semicrystalline materials in which the same chemical stmeture exists in both rigid microcrystalline and flexible amorphous phases. Plastics may be either semicrystalline, such as poly(ethylene terephthalate) (the same polyester of fibers is also the PET of beverage bottles), or completely amorphous and glassy, such as polystyrene or poly(methyl methacrylate) (PMMA, Plexiglas or Lucite ). Elastomers are completely amorphous and flexible and would flow as a viscous mbbery liquid except that the polymer chains are cross-hnked to prevent macroscopic flow but allow reversible stretching. As an example, poly(dimethylsiloxane)... 

IBM-X polyimide is the proprietary polymer used in IBM s flat panel displays. This polyimide is disordered/amorphous, while the BPDA-PDA polyimide film discussed before (Fig. 6.7) has microcrystalline domains. We note that rubbing introduces in both film surfaces the same charge anisotropy, independently of the presence/absence of locally ordered domains. 

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