Polymers boundary condition

Industrial scale polymer forming operations are usually based on the combination of various types of individual processes. Therefore in the computer-aided design of these operations a section-by-section approach can be adopted, in which each section of a larger process is modelled separately. An important requirement in this approach is the imposition of realistic boundary conditions at the limits of the sub-sections of a complicated process. The division of a complex operation into simpler sections should therefore be based on a systematic procedure that can provide the necessary boundary conditions at the limits of its sub-processes. A rational method for the identification of the subprocesses of common types of polymer forming operations is described by Tadmor and Gogos (1979). 

IMPOSITION OF BOUNDARY CONDITIONS IN POLYMER PROCESSING MODELS... 

Soil, S.K. and Chang, C. J., 1986. Boundary conditions in the modeling of injection mold-filling of thin cavities. Polym. Eng. Sci. 26, 393-399. 

The tests in the two previous paragraphs are often used because they are easy to perform. They are, however, limited due to their neglect of intermolecular interactions. Testing the effect of intennolecular interactions requires much more intensive simulations. These would be simulations of the bulk materials, which include many polymer strands and often periodic boundary conditions. Such a bulk system can then be simulated with molecular dynamics, Monte Carlo, or simulated annealing methods to examine the tendency to form crystalline phases. 

The boundary conditions are given by specifying the panicle currents at the boundaries. Holes can be injected into the polymer by thermionic emission and tunneling [32]. Holes in the polymer at the contact interface can also fall bach into the metal, a process usually called interlace recombination. Interface recombination is the time-reversed process of thermionic emission. At thermodynamic equilibrium the rates for these two time-reversed processes are the same by detailed balance. Thus, there are three current components to the hole current at a contact thermionic emission, a backflowing interface recombination current that is the time-reversed process of thermionic emission, and tunneling. Specifically, lake the contact at Jt=0 as the hole injecting contact and consider the hole current density at this contact. 

Besides crystalline order and structure, the chain conformation and segment orientation of polymer molecules in the vicinity of the surface are also expected to be modified due to the specific interaction and boundary condition at the surface between polymers and air (Fig. 1 a). According to detailed computer simulations [127, 128], the chain conformation at the free polymer surface is disturbed over a distance corresponding approximately to the radius of gyration of one chain. The chain segments in the outermost layers are expected to be oriented parallel to the surface and chain ends will be enriched at the surface. Experiments on the chain conformation in this region are not available, but might be feasible with evanescent wave techniques described previously. Surface structure on a micrometer scale is observed with IR-ATR techniques [129],... 

This velocity profile is commonly called drag flow. It is used to model the flow of lubricant between sliding metal surfaces or the flow of polymer in extruders. A pressure-driven flow—typically in the opposite direction—is sometimes superimposed on the drag flow, but we will avoid this complication. Equation (8.51) also represents a limiting case of Couette flow (which is flow between coaxial cylinders, one of which is rotating) when the gap width is small. Equation (8.38) continues to govern convective diffusion in the flat-plate geometry, but the boundary conditions are different. The zero-flux condition applies at both walls, but there is no line of symmetry. Calculations must be made over the entire channel width and not just the half-width. 

The heat transfer model, energy and material balance equations plus boundary condition and initial conditions are shown in Figure 4. The energy balance partial differential equation (PDE) (Equation 10) assumes two dimensional axial conduction. Figure 5 illustrates the rectangular cross-section of the composite part. Convective boundary conditions are implemented at the interface between the walls and the polymer matrix. 

A polymer coil does not only possess a structure on the atomistic scale of a few A, corresponding to the length of covalent bonds and interatomic distances characteristic of macromolecules are coils that more or less, obey Gaussian statistics and have a diameter of the order of hundreds of A (Fig. 1.2) [17]. Structures of intermediate length scales also occur e. g., characterized by the persistence length. For a simulation of a polymer melt, one should consider a box that contains many such chains that interpenetrate each other, i. e., a box with a linear dimension of several hundred A or more, in order to ensure that no artefacts occur attributable to the finite size of the simulation box or the periodic boundary conditions at the surfaces of the box. This ne-... 

As an example of such applications, consider the dynamics of a hexible polymer under a shear how [88]. A shear how may be imposed by using Lees-Edwards boundary conditions to produce a steady shear how y = u/Ly, where Ly is the length of the system along v and u is the magnitude of the velocities of the boundary planes along the x-direction. An important parameter in these studies is the Weissenberg number, Wi = Ti y, the product of the longest... 

This relative importance of relaxation and diffusion has been quantified with the Deborah number, De [119,130-132], De is defined as the ratio of a characteristic relaxation time A. to a characteristic diffusion time 0 (0 = L2/D, where D is the diffusion coefficient over the characteristic length L) De = X/Q. Thus rubbers will have values of De less than 1 and glasses will have values of De greater than 1. If the value of De is either much greater or much less than 1, swelling kinetics can usually be correlated by Fick s law with the appropriate initial and boundary conditions. Such transport is variously referred to as diffusion-controlled, Fickian, or case I sorption. In the case of rubbery polymers well above Tg (De < c 1), substantial swelling may occur and... 

Many other interesting examples of spontaneous reflection symmetry breaking in macroscopic domains, driven by boundary conditions, have been described in LC systems. For example, it is well known that in polymer disperse LCs, where the LC sample is confined in small spherical droplets, chiral director structures are often observed, driven by minimization of surface and bulk elastic free energies.24 We have reported chiral domain structures, and indeed chiral electro-optic behavior, in cylindrical nematic domains surrounded by isotropic liquid (the molecules were achiral).25... 

The dynamics of the solvent and polymer are coupled in a polymer solution. Although this coupling is expressed partly through the friction and noise terms in Eq. (28), a complete description requires a boundary condition. The most common choice of this boundary condition is the no-slip condition... 

Using this boundary condition as a constraint, the equations of motion for the combined system of polymer and solvent can be derived to be [55-59]... 

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