Polymer cold flow

In Fig. 6.4 the dependence, corresponding to the Eq. (6.6) for PC and PAr is adduced. This dependence linearity is one more confirmation of amorphous polymers cold flow turbulence. Thus, glassy polymers high-elasticity process can be considered as motion of objects with length characteristic scale which occurs in turbulent regime. 

The considered model of amorphous glassy polymers cold flow allows to make two main conclusions [7]. 

The authors of Ref [19] used the stated above treatment of polymers cold flow with application of Witten-Sander model of diffusion-limited aggregation [20] on the example of PC. As it has been shown in Refs. [21, 22], PC structure can be simulated as totality of Witten-Sander clusters (WS clusters) large number. These clusters have compact central part, which in the model [18, 23] is associated with notion cluster. Further to prevent misunderstandings the term cluster will be understood exactly as a compact local order region. At translational motion of such compact region in viscous medium molecular friction coefficient of each cluster, a particle, having radius a, is determined as follows [24] ... 

Membrane Limitations Chemical attack, fouling, and compaction are prominent problems with RO and NF membranes. Compaction is the most straightforward. It is the result of creep, slow cold flow of the polymer resulting in a loss of water permeability. It is measured by the slope of log flux versus log time in seconds. It is independent of the flux units used and is reported as a slope, sometimes with the minus sign omitted. A slope of—0.001, typical for noncelhilosic membranes, means that for every threefold increase in log(time), 10 seconds, a membrane looses 10 percent of its flux. Since membranes are rated assuming that the dramatic early decline in permeability has already occurred, the further decline after the first few weeks is veiy slow. Compaction is specific to pressure, temperature, and envi-... 

Whilst polyisobutene is a non-rubbery polymer exhibiting high cold flow (see Section 11.3), the copolymer containing about 2% isoprene can be vulcanised with a powerful accelerated sulphur system to give moderately rubbery polymers. The copolymers were first developed in 1940 by Esso and are known as butyl rubbers and designated as HR. As they are almost saturated they have many properties broadly similar to the EPDM terpolymers. They do, however, have two properties that should be particularly noted ... 

Poly(vinyl acetate) is too soft and shows excessive cold flow for use in moulded plastics. This is no doubt associated with the fact that the glass transition temperature of 28°C is little above the usual ambient temperatures and in fact in many places at various times the glass temperature may be the lower. It has a density of 1.19 g/cm and a refractive index of 1.47. Commercial polymers are atactic and, since they do not crystallise, transparent (if free from emulsifier). They are successfully used in emulsion paints, as adhesives for textiles, paper and wood, as a sizing material and as a permanent starch . A number of grades are supplied by manufacturers which differ in molecular weight and in the nature of comonomers (e.g. vinyl maleate) which are commonly used (see Section 14.4.4)... 

By incorporation of some trihalide to give a branched polymer such as Thiokol ST (about 2% of 1,2,3-trichloropropane is used in this instance). The resultant vulcanisates have lower cold flow and compression set than obtained with Thiokol A. 

Despite these early successes in the commercialization of acrylic polymers, no acrylic PSAs were manufactured on a larger scale until many years later. One of the primary reasons for the initial commercial failure of the acrylic PSAs was their lack of cohesive strength. Unlike the higher Tg, plastic-like polymers obtained from monomers like methylmethacrylate, polymers synthesized from alkyl acrylates typically formed sticky, cold-flowing materials with little if any utility. 

In practice, the phenomenon of creeping flow at x < Y can usually be neglected. Thus, certainly, it is insignificant in the treatment of filled polymers, though it may be important, for example, in the discussion of the cold flow of filled elastomers. However, we cannot forget the existence of this effect, to say nothing of the particular interest of the physist in this phenomenon, which is probably similar to the mechanism of flow of plastic crystals. 

Chemically universally stabile is poly-tetrafluoroethylene (PTFE, Teflon ), but it is relatively expensive. A problem is the cold flow , that is, the polymer is slowly deformed under the mechanical stress of the pressure on the gaskets and a leakage of the cell can occur (PTFE compounds, e.g. with glass powder or graphite, show a better behavior.)... 

The durability of the particle network structure imder the action of a stress may also be time-dependent. In addition, even at stresses below the apparent yield stress, flow may also take place, although the viscosity is several orders of magnitude higher than the viscosity of the disperse medium. This so-called creeping flow is depicted in Fig. 11 where r (. is the creep viscosity. In practice this phenomenon is insignificant in the treatment of filled polymer melts, but may be relevant, for example, in consideration of cold flow of filled elastomers. 

The Tg of elastomers must be below the use temperature. The high degree of cold flow which is characteristic of polymers at temperatures above the Tg is reduced by the incorporation of a few crosslinks to produce a network polymer with a low crosslink density. 

Cured polymers of butadiene with low cross-link density do not tend to cold flow and are useful elastomers. These vulcanized elastomers crystallize when stretched, but when the stress is removed, the restoring force is largely entropy and most of the crystals melt and the chains return to the random conformation.The tensile strength is increased dramatically when large amounts of carbon black or amorphous silica are added. 

These highly amorphous elastomers have relatively low Tt values (—73 C) and tend to crystallize when stretched. The cold flow of these thermoplastic polymers is reduced when they are crosslinked (vulcanized) with a small amount (2%) of sulfur. Since these polymers of isoprene have a solubility parameter of 8.0 H, they are resistant to polar solvents but are soluble in many aliphatic and aromatic hydrocarbon solvents. The cross-linked derivatives swell but do not dissolve in these solvents. 

Cold flow can be most effectively decreased and performance of the final product improved by branching the polymer molecule. 

Radiation-Induced Crosslinking. In the absence of oxygen, the predominant effect of ionizing radiation on UHMWPE is crosslinking (27). Crosslinking of UHMWPE forms covalent bonds between the polymer chains, which inhibit cold flow or creep of the individual polymer chains. 

However, a method to improve the flow properties of such fuel oils of animal or vegetable origin, has been developed (26). This consists in adding a EVA copolymer or a comb polymer based on methyl acrylate and a-olefins. In addition, terpolymers of ethylene, vinyl acetate and isobutylene have been found to be useful as cold flow improvers (29). 

Cold flow -m PVAc [VINYL POLYMERS - VINYL ACETATE POLYMERS] (Vol 24)... 

The thermoset component in polyurethanes gives them better compression set than most thermoplastic polymers. They also have better cold flow properties. Polyurethanes are tough and more resilient than a large number of other plastics. 

FEP, a copolymer of tetrafluoroethylene ( IFF) and hexafluoropropylene (HFP), is essentially PTFE with an occasional methyl side group attached. The methyl groups have effect as defects in crystallites and therefore reduce the melting point. These side groups also impede the slipping of the polymer chains past each other, thus reducing the cold flow. 

PCTFE has better mechanical properties than PTFE because the presence of the chlorine atom in the molecule promotes the attractive forces between molecular chains. It also exhibits greater hardness, tensile strength, and considerably higher resistance to cold flow than PTFE. Since the chlorine atom has a greater atomic radius than fluorine, it hinders the close packing possible in PTFE, which results in a lower melting point and reduced propensity of the polymer to crystallize.7 The chlorine atom present in ECTFE, a copolymer of ethylene and CTFE, has a similar effect on the properties of the polymer. 

Bucknall and Smith s theory has been further confirmed by recent work. Matsuo (42) published electron micrographs of stress-crazed rubber-reinforced polymers and found his results to be in good agreement with those of Bucknall and Smith. Recently, Arends (3) related the cold-flow of thermoplastics to Eyring s theory of viscous flow and enlarged the scope of their theory. 

Permeation can be a problem with these materials and can cause corrosion of the substrate. Some of these plastics are significantly less permeable than others. Permeation is especially a problem with Teflon when used with many liquids, including liquids as different as styrene and bromine. Kynar is generally more resistant to permeation than Teflon, but may be more brittle. Cold flow may also be a problem with some of these polymers. The use of glass filled polymers can help overcome cold flow. 

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