Polyethylene diffusivity

The resolution of infra-red densitometry (IR-D) is on the other hand more in the region of some micrometers even with the use of IR-microscopes. The interface is also viewed from the side (Fig. 4d) and the density profile is obtained mostly between deuterated and protonated polymers. The strength of specific IR-bands is monitored during a scan across the interface to yield a concentration profile of species. While in the initial experiments on polyethylene diffusion the resolution was of the order of 60 pm [69] it has been improved e.g. in polystyrene diffusion experiments [70] to 10 pm by the application of a Fourier transform-IR-microscope. This technique is nicely suited to measure profiles on a micrometer scale as well as interdiffusion coefficients of polymers but it is far from reaching molecular resolution. 

Another option is to use polyethylene diffusers, and/or stainless steel or monel metal screen diffusors. There are many viable approaches. If the pores are too fine, more pressure will be needed and the diffuser will clog more easily. Our system has a regular fiberglass hardware screen, which makes a larger size bubble and thus scrubs less surface but it does not require much pressure to push the gas through. 

Figure 13.20 The variation of D with for deuterated polyethylene diffusing in a protonated polyethylene matrix, at a diffusion temperature of 176.0 0.3°C. Each point represents a separate experiment and is the mean of 10 separate profiles. The lengths of experimental runs (< ,) vary by a factor of 3 within each pair of experiments for a given DPE fiaction. The least-squares best fit to the data is the relation D = 0.2 and is...

Electrical trees consist of visible permanent hoUow channels, resulting from decomposition of the material, and show up clearly in polyethylene and other translucent soHd dielectrics when examined with an optical microscope. Eresh, unstained water trees appear diffuse and temporary. Water trees consist of very fine paths along which moisture has penetrated under the action of a voltage gradient. Considerable force is required to effect this... 

When the voltage force and source of water are removed, most of the injected water diffuses away and evaporates, and the tree disappears. This disappearance indicates that channels or paths close up, because if they did not, their appearance would be enhanced rather than diminished when the water is replaced by air which has a greater refractive index difference with respect to polyethylene. 

Figures 4 and 5 show how the diffusion coefficient and solubility coefficient vary for a series of linear esters in low density polyethylene film. The trends are generally tme for other permeants in other films. As the size of the permeant increases, the diffusion coefficient decreases and the solubility coefficient increases. Since the increase in solubility coefficient is larger than the decrease in the diffusion coefficient, the permeability actually increases as the permeant size increases.

Fig. 4. Diffusion coefficient at 30°C of esters in a low density polyethylene film (18).

There are several approaches to the preparation of multicomponent materials, and the method utilized depends largely on the nature of the conductor used. In the case of polyacetylene blends, in situ polymerization of acetylene into a polymeric matrix has been a successful technique. A film of the matrix polymer is initially swelled in a solution of a typical Ziegler-Natta type initiator and, after washing, the impregnated swollen matrix is exposed to acetylene gas. Polymerization occurs as acetylene diffuses into the membrane. The composite material is then oxidatively doped to form a conductor. Low density polyethylene (136,137) and polybutadiene (138) have both been used in this manner. 

Fig. 7 gives an example of such a comparison between a number of different polymer simulations and an experiment. The data contain a variety of Monte Carlo simulations employing different models, molecular dynamics simulations, as well as experimental results for polyethylene. Within the error bars this universal analysis of the diffusion constant is independent of the chemical species, be they simple computer models or real chemical materials. Thus, on this level, the simplified models are the most suitable models for investigating polymer materials. (For polymers with side branches or more complicated monomers, the situation is not that clear cut.) It also shows that the so-called entanglement length or entanglement molecular mass Mg is the universal scaling variable which allows one to compare different polymeric melts in order to interpret their viscoelastic behavior. 

Here Ceq is the ethylene concentration equilibrium to the concentration in a gaseous phase, Kp the propagation rate constant, N the concentration of the propagation centers on the catalyst surface, Dpe the diffusion coefficient of ethylene through the polymer film, G the yield of polymer weight unit per unit of the catalyst and y0at, ype are the specific gravity of the catalyst and polyethylene. 

In semi-cristalline polymers, rate-enhancement under stress has been frequently observed, e.g. in UV-photooxidation of Kapron, natural silk [80], polycaprolactam and polyethylene terephthalate [81]. Quantitative interpretation is, however, difficult in these systems although the overall rate is determined by the level of applied stress, other stress-dependent factors like the rate of oxygen diffusion or change in polymer morphology could occur concurrently and supersede the elementary molecular steps [82, 83], Similar experiments in the fluid state showed unequivocally that flow-induced stresses can accelerate several types of reactions, the best studied being the hydrolysis of DNA [84] and of polyacrylamide [85]. In these examples, hydrolysis involves breaking of the ester O —PO and the amide N —CO bonds. The tensile stress stretches the chain, and therefore, facilitates the... 

The simplest way to prepare a biocatalyst for use in organic solvents and, at the same time, to adjust key parameters, such as pH, is its lyophilization or precipitation from aqueous solutions. These preparations, however, can undergo substrate diffusion limitations or prevent enzyme-substrate interaction because of protein-protein stacking. Enzyme lyophilization in the presence of lyoprotectants (polyethylene glycol, various sugars), ligands, and salts have often yielded preparations that are markedly more active than those obtained in the absence of additives [19]. Besides that, the addition of these ligands can also affect enzyme selectivity as follows. 

Adsorption on solid matrices, which improves (at optimal protein/support ratios) enzyme dispersion, reduces diffusion limitations and favors substrate access to individual enzyme molecules. Immobilized lipases with excellent activity and stability were obtained by entrapping the enzymes in hydrophobic sol-gel materials [20]. Finally, in order to minimize substrate diffusion limitations and maximize enzyme dispersion, various approaches have been attempted to solubilize the biocatalysts in organic solvents. The most widespread method is the one based on the covalent linking of the amphiphilic polymer polyethylene glycol (PEG) to enzyme molecules [21]. 

Other microporous materials have been synthesized using the porogen polyethylene glycol in polyethylene oxide-urethane gels [27]. Micropores were formed in the gel, and it was found that the diffusion of larger species, vitamin B12, was enhanced relatively more than that of a smaller species, proxyphylline. This result is in qualitative agreement with that found for electrophoretic transport by RiU et al. [322] discussed earher, where the mobility of larger species was preferentially enhanced in the templated media. 

So the handling of hydrocarbons presents serious fire hazards. There are many accidents linked to this in the industrial sector. For instance, a serious accident happened when polyethylene was stored. It appeared to be caused by the diffusion of monomer through the mass of polymer, which created an inflammable atmosphere in the storage container. Incorporating a mixture of oxygen and styrene in a reactor cause spontaneous ignition. 

Ozone diffuses readily into amorphous region of the polyethylene (32) and oxidation probably occurs much deeper in the solid sample. Ozone also attacks the crystalline part of polyethylene but it has a slow initiation stage followed by more rapid oxidation (13). Because ozone does not diffuse into the crystalline regions (13.32). oxidation is restricted to the surface. The resulting oxidized functional groups on the crystalline regions will remain at the surface, whereas those formed in the amorphous region can diffuse into the bulk. 

A PP sample after ozonization in the presence of UV-irradiation becomes brittle after 8 hrs of exposure, whereas the same effect in ozone is noticeable after 50-60 hours.Degradation of polymer chain occurs as a result of decomposition of peroxy radicals. The oxidation rapidly reaches saturation, suggesting the surface nature of ozone and atomic oxygen against of PP as a consequence of limited diffusion of both oxygen species into the polymer. Ozone reacts with PP mainly on the surface since the reaction rate and the concentration of intermediate peroxy radicals are proportional to the surface area and not the weight of the polymer. It has been found that polyethylene is attacked only to a depth of 5-7 microns (45). 

Ethylene vinyl acetate has also found major applications in drug delivery. These copolymers used in drug release normally contain 30-50 wt% of vinyl acetate. They have been commercialized by the Alza Corporation for the delivery of pilocarpine over a one-week period (Ocusert) and the delivery of progesterone for over one year in the form of an intrauterine device (Progestasert). Ethylene vinyl acetate has also been evaluated for the release of macromolecules such as proteins. The release of proteins form these polymers is by a porous diffusion and the pore structure can be used to control the rate of release (3). Similar nonbiodegradable polymers such as the polyurethanes, polyethylenes, polytetrafluoroethylene and poly(methyl methacrylate) have also been used to deliver a variety of different pharmaceutical agents usually as implants or removal devices. 

Polyethylene-based membranes are manufactured for use in hazardous waste landfills, lagoons, and similar applications. Two of these products have been tested to determine their effectiveness as barriers against radon diffusion. (In most cases, diffusive flow is considered of little or no significance as a mechanism of radon entry compared with convective flow). A 20-mil high-density polyethylene tested 99.9% effective in blocking radon diffusion under neutral pressure conditions. A 30-mil low-density polyethylene tested 98% effective in blocking radon diffusion under neutral pressure conditions. 

The side-by-side diffusion cell has also been calibrated for drug delivery mass transport studies using polymeric membranes [12], The mass transport coefficient, D/h, was evaluated with diffusion data for benzoic acid in aqueous solutions of polyethylene glycol 400 at 37°C. By varying the polyethylene glycol 400 content incrementally from 0 to 40%, the kinematic viscosity of the diffusion medium, saturation solubility for benzoic acid, and diffusivity of benzoic acid could be varied. The resulting mass transport coefficients, D/h, were correlated with the Sherwood number (Sh), Reynolds number (Re), and Schmidt number (Sc) according to the relationships... 

JS Vrentas, JL Duda, MK Lau. Solvent diffusion in molten polyethylene. J Appl Polym Sci 27 3987-3997, 1982. 

Many polymers are used in barrier applications, either to keep contents in or contaminants out. Food packaging is an excellent example of such usage. Plastic films and containers of many types are used to package food. Blow moldedbottles often contain numerous layers, each of which provides specific benefits. Polyethylene layers are excellent water barriers, polyvinyl alcohol is a good oxygen barrier, and polyethylene terephthalate impedes the diffusion of carbon dioxide from carbonated drinks. Other barrier applications include toothpaste tubes, diaper backsheets, tarpaulins, and geomembranes, which are used to line containment ponds and landfill pits. 

Figures 8 and 9 show the dependence of the self-diffusion constant and the viscosity of polyethylene melts on molecular weight [47,48]. For small molecular weights the diffusion constant is inversely proportional to the chain length - the number of frictional monomers grows linearly with the molecular weight. This behavior changes into a 1/M2 law with increasing M. The diffusion...

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