Pure polymer systems

In fires, the polymeric materials are consumed by the flaming combustion which is a gas-phase process. Thus, the polymer must degrade to yield volatile combustible species to fuel the conflagration. To begin, this chapter first considers the various processes by which pure polymer systems degrade. 

This chapter deals exclusively with thermotropics (pure polymer systems). This review deals with longitudinal one-comb and network PLCs and blends of longitudinal PLCs and conventional flexible chain polymers (Figure 10.2). An excellent introduction to the subject including a presentation of definitions and classifications is given by Brostow [10]. It is important to emphasize that a given PLC at a given... 

The chemical potential per repeating unit of the x-mer, ptx, for the pure polymer system, i.e. when V2= 1, is given by... 

It is found that when compared with the corresponding pure polymer system, the melt viscosity of the filled polymer system at a high shear stress range reaches a stable value. 

Equations (18) and (19) represent the dependence of the equilibrium melting temperature on chain length for a pure polymer system which adheres to the crystallite model of Figure 14. Here dg represents the interfacial free energy associated with the basal plane of the equilibrium crystallite. Tjn g is the equilibrium melting temperature of a crystallite of size Ce which is comprised of chains of x units. It should not be identified a priori with the melting temperature of a molecular crystal formed by chains of the same size. Equation (18) can be rewritten in more compact form as... 

With appropriately substituted oxetanes, aluminum-based initiators (321) impose a degree of microstmctural control on the substituted polyoxetane stmcture that is not obtainable with a pure cationic system. A polymer having largely the stmcture of poly(3-hydroxyoxetane) has been obtained from an anionic rearrangement polymerisation of glycidol or its trimethylsilyl ether, both oxirane monomers (322). Polymerisation-induced epitaxy can produce ultrathin films of highly oriented POX molecules on, for instance, graphite (323). Theoretical studies on the cationic polymerisation mechanism of oxetanes have been made (324—326). 

The terminal R groups can be aromatic or aliphatic. Typically, they are derivatives of monohydric phenoHc compounds including phenol and alkylated phenols, eg, /-butylphenol. In iaterfacial polymerization, bisphenol A and a monofunctional terminator are dissolved in aqueous caustic. Methylene chloride containing a phase-transfer catalyst is added. The two-phase system is stirred and phosgene is added. The bisphenol A salt reacts with the phosgene at the interface of the two solutions and the polymer "grows" into the methylene chloride. The sodium chloride by-product enters the aqueous phase. Chain length is controlled by the amount of monohydric terminator. The methylene chloride—polymer solution is separated from the aqueous brine-laden by-products. The facile separation of a pure polymer solution is the key to the interfacial process. The methylene chloride solvent is removed, and the polymer is isolated in the form of pellets, powder, or slurries. 

The polymer, like many fluorine-containing polymers has very good weathering resistance and may also be used continuously up to 150°C. Outside of the electrical field it finds use in fluid handling, in hot water piping systems, in packaging and in chemical plant. A widely used specific application for PVDF is in ultra-pure water systems for the semiconductor industry. 

OCV conditions, by a newly formed SEI is expected to be a slow process. The SEI is necessary in PE systems in order to prevent the entry of solvated electrons to the electrolyte and to minimize the direct reaction between the lithium anode and the electrolyte. SEI-free Li/PE batteries are not practical. The SEI cannot be a pure polymer, but must consist of thermodynamically stable inorganic reduction products of... 

Figure 5. (a) The ( A, SO,) anion symmetric streching mode of polypropylene glycol)- LiCF,SO, for 0 M ratios of 2000 1 and 6 1. Solid symbols represent experimental data after subtraction of the spectrum corre-ponding to the pure polymer. Solid curves represent a three-component fit. Broken curves represent the individual fitted components, (b) Relative Raman intensities of the fitted profiles for the ( Aj, SO,) anion mode for this system, plotted against square root of the salt concentration, solvated ions ion pairs , triple ions, (c) The molar conductivity of the same system at 293 K. Adapted from A. Ferry, P. Jacobsson, L. M. Torell, Electrnchim. Acta 1995, 40, 2369 and F. M. Gray, Solid State Ionics 1990, 40/41, 637. 

Heat treatment at 400 °C of pure polymer specimens and composites containing 0.16 and 0.34 of calcite has shown [221] that the base polymer was sublimated without residue the specimen with Vf = 0.16 left a powder, and the specimen with Vf = 0.34 a brittle skeleton. Electron microscopy confirms that the latter consists of large crystalline inclusions interconnected by systems of small particles. 

FT rheometry is a powerful technique to document the nonlinear viscoelastic behavior of pure polymers as observed when performing large amplitude oscillatory strain (LAOS) experiments. When implemented on appropriate instmments, this test technique can readUy be applied on complex polymer systems, for instance, filled mbber compounds, in order to yield significant and reliable information. Any simple polymer can exhibit nonlinear viscoelastic properties when submitted to sufficiently large strain in such a case the observed behavior is so-called extrinsic... 

The mechanisms of photochemical degradation of a polymer are rather difficult to study as the observed degradation is typically a result of the effect of light on the contaminants in the polymer rather than the pure polymer. Studies typically look for the degradation products, either low molecular weight volatiles or radicals, or work to identify the wavelength of light absorbed by the system via spectroscopic methods. 

In a pure homopolymer system, the free-energy density only depends on Ec (the quantity that determines the chain rigidity) and Ep (the quantity that determines the tendency of backbone chains to form parallel, close-packed structures). Let us first consider the relative stability of the pure polymer melt and the polymer solid in the limit of infinitely long chains. In that case, we... 

As in PP-based nanocomposite systems, the extended Trouton rule, 3r 0 (y t) = r E (so t), also does not hold for PLANC melts, in contrast to the melt of pure polymers. These results indicate that in the case of P LANC, the flow induced internal structural changes also occur in elongation flow [48], but the changes are quite different in shear flow. The strong rheopexy observed in the shear measurements for the PLA-based nanocomposite at very slow shear rate reflects the fact that the shear-induced structural change involved a process with an extremely long relaxation time. 

Commercial plastics HDPE, PP, PS and PVC in granulate form have been used as model feed. The degradation of pure polymers was followed using either at thermoanaly-tical method (MOM Derivatograph Q) or in a laboratory batch reactor system with gaschromatographic product analysis. 

The chemical potential of the polymer is affected by "impurities" such as solvents or copolymerized units. For an equilibrium condition in the presence of water as the diluent, the melting temperature of starch (Tm) would be lower because p in the presence of diluent is less than pi). For the starch-water system at equilibrium, the difference between the chemical potentials of the crystalline phase and the phase in the standard state (pure polymer at the same temperature and pressure) must be equal to the decrease in chemical potential of the polymer unit in solution relative to the same standard state (Flory, 1953). By considering the free energy of fusion per repeating unit and volume fraction of water (diluent), the... 

Miyata and Nakashio [77] studied the effect of frequency and intensity on the thermally initiated (AIBN) bulk polymerisation of styrene and found that whilst the mechanism of polymerisation was not affected by the presence of ultrasound, the overall rate constant, k, decreased linearly with increase in the intensity whilst the average R.M.M. increased slightly. The decrease in the overall value of k they interpreted as being caused by either an increase in the termination reaction, specifically the termination rate constant, k, or a decrease in the initiator efficiency. The increase in kj(= kj /ri is the more reasonable in that ultrasound is known to reduce the viscosity of polymer solutions. This reduction in viscosity and consequent increase in Iq could account for our observed reductions [78] in initial rate of polymerisation of N-vinyl-pyrrolidone in water. However this explanation does not account for the large rate increase observed for the pure monomer system. 

Compared to the DSC diagram of pure PNIPAAm, we noticed that the LCST transitions detected in the IPNs samples were in the range of 31-32°C. There was no significant deviation from the LCST of the pure PNIPAAm, which was the major difference between a PNIPAAm-based IPN and a PNIPAAm copolymer in which the LCST will be greatly influenced by the comonomers. Thus, the formation of IPN gave a relatively independent polymer system in which each network may retain its own property. 

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