Density polymer melts

Yethira] A and Woodward C E 1995 Monte Carlo density functional theory of nonuniform polymer melts J Chem. Phys. 102 5499... 

Polymer Melting poiut, °C Crystal type Helix type Crystalline density, g/cm ... 

With the availability of the higher density polymers the value of the melt flow index as a measure of molecular weight diminishes. For example, it has been found that with two polymers of the same weight average molecular weight (4.2 X 10 ), the branched polymer (density = 0.92 g/cm ) had only 1/50 the viscosity of the more or less unbranched polymer (density = 0.96 g/cm ). This is due to long chain branches as explained above. 

Since polyethylene is a crystalline hydrocarbon polymer incapable of specific interaction and with a melting point of about 100°C, there are no solvents at room temperature. Low-density polymers will dissolve in benzene at about 60°C but the more crystalline high-density polymers only dissolve at temperatures some 20-30°C higher. Materials of similar solubility parameter and low molecular weight will, however, cause swelling, the more so in low-density polymers Table 10.5). 

Polymer Melting point range °C Density g/cm Degree of crystallinity % Stiffness modules psi X 10 ... 

It is precisely the loosening of a portion of polymer to which the authors of [47] attribute the observed decrease of viscosity when small quantities of filler are added. In their opinion, the filler particles added to the polymer melt tend to form a double shell (the inner one characterized by high density and a looser outer one) around themselves. The viscosity diminishes until so much filler is added that the entire polymer gets involved in the boundary layer. On further increase of filler content, the boundary layers on the new particles will be formed on account of the already loosened regions of the polymeric matrix. Finally, the layers on all particles become dense and the viscosity rises sharply after that the particle with adsorbed polymer will exhibit the usual hydrodynamic drag. 

This closeness of 0 to zero explains the existence of a gas-oversaturated solution area in the polymer melt, when P < Pg, but the entire volume of gas remains in the solution. The degree of oversaturation, particularly upon free foaming (not in flow) can be 2- to 3-fold. In real polymer compositions, there are always solid admixtures, which have poor wetting areas. This reduces the degree of oversaturation at the interface melt-molding tool. Moreover, bubble nuclei can result from fragmentation of gas bubbles in the polymer [16]. Another factor that promotes the formation of bubble nuclei is the presence of localized hot points in the polymer melt they act as nuc-leation centres. Hot points appear either after a chemical reaction in the melt polymer [17], or in overheated areas on the surface of metal equipment [18]. Density of nucleation can be improved via introduction of various agents that reduce tension of the polymer [19]. 

A rather crude, but nevertheless efficient and successful, approach is the bond fluctuation model with potentials constructed from atomistic input (Sect. 5). Despite the lattice structure, it has been demonstrated that a rather reasonable description of many static and dynamic properties of dense polymer melts (polyethylene, polycarbonate) can be obtained. If the effective potentials are known, the implementation of the simulation method is rather straightforward, and also the simulation data analysis presents no particular problems. Indeed, a wealth of results has already been obtained, as briefly reviewed in this section. However, even this conceptually rather simple approach of coarse-graining (which historically was also the first to be tried out among the methods described in this article) suffers from severe bottlenecks - the construction of the effective potential is neither unique nor easy, and still suffers from the important defect that it lacks an intermolecular part, thus allowing only simulations at a given constant density. 

The MRI technique has also been used with systems of more practical importance, such as a polymer melt [19]. Here a low density polyethylene melt was... 

Stereodefects reduce the overall regularity of an isotactic polymer chain and hinder its ability to crystallize. As the concentration of defects increases, the degree of crystallinity falls, resulting in reduced density, reduced melting temperatures, lower heat distortion temperatures, reduced modulus, and reduced yield stress. 

Finally, a further unsolved problem should be mentioned. If we compare the plateau moduli of different polymer melts and relate them to the Kuhn length and to the density, this relation can also be adequately described with the scaling model, if an exponent a near 3 is chosen [73]. It is not known why this exponent is different if the contour length density is varied by dilution in concentrated solution or by selecting polymer chains of different volume. 

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... 

The structures of the solid-melt interface and the melt confined within a narrow gap are of great significance in diverse areas of research such as lubrication, adhesion, or in future nanometer science. It is well recognized that the melt of n-alkanes, and other simple molecules show anomalous oscillations in density, viscosity, etc. vs. depth from the surface showing the presence of marked layer structures in the melt [40]. Even in polymer melts similar layering phenomena were suggested near the solid surface [41], but no pronounced ordering or the onset of crystallization were reported. 

Fig. 30 Generic temperature-density diagram for a polymer melt proposed by Olmsted et al. [4]. The horizontal axis indicates the normalized density pw, which is defined as the average mass density of the melt multiplied by the specific volume w of the monomer... 

The integral equation theory is a simple means of studying the density profiles of dense polymer melts at surfaces where the structure is dominated by... 

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