Diffusion of polymer

C, k progressively increases because the formation rate of the smallest seed crystaUites is also increasing. However, at lower temperatures, the rapid crystallisa tion process is impeded by slow diffusion of polymer molecules from the overcooled melt to crystallisa tion sites. 

One of the most common rubber adhesives are the contact adhesives. These adhesives are bonded by a diffusion process in which the adhesive is applied to both surfaces to be joined. To achieve optimum diffusion of polymer chains, two requirements are necessary (1) a high wettability of the adhesive by the smooth or rough substrate surfaces (2) adequate viscosity (in general rheological properties) of the adhesive to penetrate into the voids and roughness of the substrate surfaces. Both requirements can be easily achieved in liquid adhesives. Once the adhesive solution is applied on the surface of the substrate, spontaneous or forced evaporation of the solvent or water must be produced to obtain a dry adhesive film. In most cases, the dry-contact adhesive film contains residual solvent (about 5-10 wt%), which usually acts as a plasticizer. The time necessary... 

The dry adhesive films on the two substrates to be joined must be placed in contact to develop adequate autoadhesion, i.e. diffusion of polymer rubber chains must be achieved across the interface between the two films to produce intimate adhesion at molecular level. The application of pressure and/or temperature for a given time allows the desired level of intimate contact (coalescence) between the two adhesive film surfaces. Obviously, the rheological and mechanical properties of the rubber adhesives will determine the degree of intimacy at the interface. These properties can be optimized by selecting the adequate rubber grade, the nature and amount of tackifier and the amount of filler, among other factors. 

In the extensive literature on polymer drag reduction, it has occasionally been reported that a continuous thread of a high-concentration polymer solution injected into the axis of a pipe produces a drag-reduction effect on the water flow in the pipe [856]. The thread seems to persist through the length of the pipe and little, if any, diffusion of polymer to the walls of the pipe is apparent. 

The bond fluctuation model not only provides a good description of the diffusion of polymer chains as a whole, but also the internal dynamics of chains on length scales in between the coil size and the length of effective bonds. This is seen from an analysis of the normalized intermediate coherent scattering function S(q,t)/S(q,0) of single chains ... 

L Haggerty, JH Sugarman, RK Prud homme. Diffusion of polymers through polyacrylamide gels. Polymer 29 1058-1063, 1988. 

The intercept Vo and slopes B in log V against 1/AT of FCSCs were plotted against Mn in Fig. 24. This showed that Vo significantly decreased with an increase of Mn, whereas B did not, as was shown by Hoffman et al. [28] Vo and B of ECSCs showed similar Mn dependence to those of FCSCs. As Vo is related to self diffusion of polymer chains and B is related to the activation free en-... 

The overall rate of crystallization is determined by both the rate of nuclei formation and by the crystal growth rate. The maximum crystal growth rate lies at temperatures of between 170 and 190 °C [71, 72], as does the overall crystallization rate [51, 61, 75], The former is measured using hot stage optical microscopy while the latter is quantified by the half-time of crystallization. Both are influenced by the rate of nucleation on the crystal surface and the rate of diffusion of polymer chains to this surface. It has been shown that the spherulite growth rate decreases with increasing molecular weight due to the decrease in the rate of diffusion of molecules to this surface [46, 50, 55, 71, 74],... 

Another unique attribute of polymerizations of multifunctional monomers is the dominance of reaction diffusion as a termination mechanism [134,136, 143-146]. Reaction diffusion involves the mobility of radicals by propagation through unreacted functional groups. This termination mechanism is physically different from translation and segmental diffusion termination mechanisms which involve the diffusion of polymer macroradicals and chain segments to bring radicals within a reaction zone before terminating. Whereas normal termination mechanisms are related to the diffusion coefficient of the polymer, reaction diffusion must be considered differently. In essence, reaction diffusion is... 

More rigorons treatments include hydrodynamic interaction effects and relate the diffusivity directly to the molecular weight of the polymer chain. The general result is that the diffusivity of polymer chains in solntion is related to the molecular weight of the polymer, M ... 

The rapid transport of the linear, flexible polymer was found to be markedly dependent on the concentration of the second polymer. While no systematic studies were performed on these ternary systems, it was argued that the rapid rates of transport could be understood in terms of the dominance of strong thermodynamic interactions between polymer components overcoming the effect of frictional interactions this would give rise to increasing apparent diffusion coefficients with concentration 28-45i. This is analogous to the resulting interplay of these parameters associated with binary diffusion of polymers. 

The mere fact that a density inversion occurs through coupled diffusion of polymer components is not a sufficient condition for the generation of instability associated with fluid motion. For example, the system may be stabilised by either fluctuations in the movements of the solute leading to dissipation of the density inversion or local viscosity gradients. 

As the thickness of the laminate increases, the strength of this thermal spike and the degree of thermal lag during heat-up increases. Figure 8.8 shows the results for a 62.5-mm (500 ply) laminate of the same material. Now the center-line temperature never reaches the autoclave temperature during the first dwell, and the thermal spike during the second dwell is nearly 135°C. The thermal spike is directly related to the release of internal heat during cure. The thermal lag is a manifestation of the low thermal diffusivity of polymer matrix composites. 

In polymers, the field-gradient spin-echo methods of measuring self-diffusion have been useful in three more or less distinct areas, the diffusion of polymers in their own melt and in concentrated solutions, in dilute and semidilute solutions, and the diffusion of penetrants and diluents in polymer hosts. A fourth category, the diffusion of bulky or flexible molecules in polymer hosts, is useful for subject matter not closely associated with the first and third category. It should be noted that the work reviewed here represents only a small fraction of the diffusion studies in polymers, including those using other NMR methods. 

The effect of curing on the diffusion of polymer and the curing agent is studied for the system of hydroxyl-terminated polybutadiene (R-45-M)/isophorone disso-cyanate (IPDI). Both components contribute to the echo intensity and the plot of In P(x)/I(0)] vs (G5)2 (A — 5/3) consists of two exponentials (Eq. (22)) the fast component (the steep intial slope) is attributed to the IPDI, and the long component to the R-45-M. The dependence of both diffusion constants on the curing time is shown in Fig. 19. The accuracy for Dfast data is less pronounced than for the polymer D(Mn), because only the first few data points are relevant for its determination. Furthermore, the low tail of the R-45-M molecular weight distribution nearly coin-... 

Although the above work was serendipitous, the study of concentration fluctuations in bulk polymers should be a fruitful area of research. Intentional polymer mixtures could be prepared which would allow the mutual diffusion of polymers in polymers to be obtained. Although the molecular weights might need to be kept low, the measurement of polymer motions in the bulk state would be very valuable. 

The diffusion of polymer chain radicals has no influence on the termination rate. This is because the frequency of encounter decreases—by decreasing diffusion constant—to the same extent as the lifetime of the permeation state increases. 

More recently, a spaghetti model for a swollen matrix was developed to provide mechanistic understanding of the complex release process (Fig. 4.4). This model treats polymer erosion as diffusion of polymer across a diffusion layer adjacent to the gel layer.19,20 Thus two competitive diffusional processes contribute to overall drug release diffusion of polymer across the diffusion layer and diffusion of drug across the gel layer. Two parameters have been identified to characterize their relative contributions. Polymer disentanglement concentration Cp>dis gauges the... 

Most important macroscopic transport properties (i.e., permeabilities, solubilities, constants of diffusion) of polymer-based membranes have their foundation in microscopic features (e.g., free-volume distribution, segmental dynamics, distribution of polar groups, etc.) which are not sufficiently accessible to experimental characterization. Here, the simulation of reasonably equilibrated and validated atomistic models provides great opportunities to gain a deeper insight into these microscopic features that in turn will help to develop more knowledge-based approaches in membrane development. 

Leonov AI (1994) On a self-consistent molecular modelling of linear relaxation phenomena in polymer melts and concentrated solutions. J Rheol 38( 1) 1—11 Liu B, Diinweg B (2003) Translational diffusion of polymer chains with excluded volume and hydrodynamic interactions by Brownian dynamics simulation. J Chem Phys 118(17) 8061-8072... 

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