Rheology of polymer melts. Viscoelastic parameters and their influence on flow under static conditions
Rheology of polymer melts - Viscoelastic parameters and their influence on flow under static conditions
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Rheology of polymer melts - Viscoelastic parameters and their influence on flow under static conditions
The application of finite element computer analyses to polymer flows of the type encountered in melt processing operations is described. A code capable of predicting values of fluid veleocity, pressure, shear stress, and temperature at any point within the flow field was developed. As such, is is of value in diagnosing such processing problems as regions of fluid stagnation at which thermal degradation may occur, or regions of excessive shear deformation which lead to thermomechanical damage. It is further able to generate predictions of the forces which must be applied to the melt to achieve the desired flow, and this information is of value in designing processing equipment of optimal efficiency and minimum energy consumption.
Shear rate at which transition from Newtonian to non-Newtonian flow occurs for polystyrene, polyethylene and polydimethylsiloxane
We analyze the onset of "necking" and subsequent filament failure during the transient uniaxial elongation of viscoelastic fluid samples in extensional rheometers. In the limit of rapid elongation (such that no molecular relaxation occurs), the external work applied is all stored elastically and the Considere criterion originally developed in solid mechanics can be used to quantitatively predict the critical Hencky strain to failure. By comparing the predictions of the Doi-Edwards model for linear homopolymer melts with those of the "Pom-Pom" model for prototypical branched melts we show that the critical strain to failure in rapid elongation of a rubbery material is intimately linked to the molecular topology of the chain, especially the degree of chain branching. The onset of necking instability is monotonically shifted to larger Hencky strains as the number of branches is increased. Numerical computations at finite Deborah numbers also show that there is an optimal range of deformation rates over which homogeneous extensions can be maintained to large strain. We also consider other rapid homogeneous stretching deformations, such as biaxial and planar stretching, and show that the degree of stabilization afforded by inclusion of material with long-chain branching is a sensitive function of the imposed mode of deformation.
High-performance polymers that have improved processing characteristics, and a method of making them, have been invented. One of the improved characteristics is low (relative to corresponding prior polymers) melt viscosities at given temperatures. This characteristic makes it possible to utilize such processes as resin-transfer molding and resin-film infusion and to perform autoclave processing at lower temperatures and/or pressures. Another improved characteristic is larger processing windows that is, longer times at low viscosities. Other improved characteristics include increased solubility of uncured polymer precursors that contain reactive groups, greater densities of cross-links in cured polymers, improved mechanical properties of the cured polymers, and greater resistance of the cured polymers to chemical attack. The invention is particularly applicable to poly(arylene ether)s [PAEs] and polyimides [PIs] that are useful as adhesives, matrices of composite materials, moldings, films, and coatings. PAEs and PIs synthesized according to the invention comprise mixtures of branched, linear, and star-shaped molecules. The monomers of these polymers can be capped with either reactive end groups to obtain thermosets or nonreactive end groups to obtain thermoplastics. The synthesis of a polymeric mixture according to the invention involves the use of a small amount of a trifunctional monomer. In the case of a PAE, the trifunctional monomer is a trihydroxy- containing compound for example, 1,3,5-trihydroxybenzene (THB). In the case of a PI, the trifunctional monomer is a triamine for example, triamino pyrimidine or melamine. In addition to the aforementioned trifunctional monomer, one uses the difunctional monomers of the conventional formulation of the polymer in question (see figure). In cases of nonreactive end caps, the polymeric mixtures of the invention have melt viscosities and melting temperatures lower than those of the corresponding linear polymers of equal molecular weights. The lower melting temperatures and melt viscosities provide larger processing windows. In cases of reactive end caps, the polymeric mixtures of the invention have lower melt viscosities before curing and the higher cross-link densities after curing (where branching in the uncured systems would become cross-links in the cured systems), relative to the corresponding linear polymers of equal molecular weights. The greater cross-link densities afford increased resistance to chemical attack and improved mechanical properties.
Melt-flow instability of extruded polymers - failure criterion and equations of state, and linearized stability analysis in Newtonian fluid, power-law fluid, and elastic fluids
Linear aromatic polyphenylene ether sulfideimide (BDSDA/APB) polymer molded, used as resin, and cast into thin films. In effort to improve further both use properties and amenability to process BDSDA/APB, molecular weight of polymer varied by variations in percentage of end capping. Effect of end capping BDSDA/APB determined by measurement of polymer melt viscosity and fracture-energy values for different number average synthesized molecular weights.
Discussion of a problem encountered in the processing of viscoelastic materials that is caused by the presence of a hydrodynamic instability in the extrusion of polymer melts. The importance of the so-called Weissenberg number in determining the onset of the melt fracture is examined using classical linearized hydrodynamic stability analysis. It is shown that the simple shearing flow of a viscoelastic fluid becomes unstable at a critical value of the Weissenberg number. Implications for the extrusion processing of polymers are reviewed.
The feasibility of applying the in situ fiberization process to the fabrication of strain isolation pads (SIP) for the Space Shuttle and to the fabrication of graphite-epoxy composites was evaluated. The ISF process involves the formation of interconnected polymer fiber networks by agitation of dilute polymer solutions under controlled conditions. High temperature polymers suitable for SIP use were fiberized and a successful fiberization of polychloro trifluoroethylene, a relatively high melting polymer, was achieved. Attempts to fiberize polymers with greater thermal stability were unsuccessful, apparently due to characteristics caused by the presence of aromaticity in the backbone of such materials. Graphite-epoxy composites were fabricated by interconnecting two dimensional arrays of graphite fiber with polypropylene IS fibers with subsequent epoxy resin impregnation. Mechanical property tests were performed on laminated panels of this material to evaluate intralaminar and interlaminar shear strength, and thus fracture toughness. Test results were generally unpromising.
A method is described for studying the influence of a temperature gradient on the crystallization of quiescent polymer melts. The apparatus used consists of two brass plates with embedded electrical resistance heaters and cooling coils. The crystallizations experiments were conducted by placing polymer specimens between the paltes, and manually adjusting heaters and cooling fluids for temperature control. Linear polyethylene, isotactic polyprophylene, and a high density polyethylene were used. It is concluded that the role of a temperature gradient in producing oriented crystallization is in producing conditions which lead the spherulitic growth pattern to proceed primarily in one direction. Steep gradients diminish the penetration of supercooling and favors oriented growth.
A finite element formulation for the analysis of polymer processing is presented and its use in some typical situation including entry flow, transient Couette flow, and the Graetz (forced convection) problem is illustrated. The element formulations are constructed on the premise that momentum convection can be neglected (polymer melt flows typically have very low Reynolds' numbers), but that convective heat transfer may be significant (high Peclet numbers). Nonisothermal effects are considered important in polymer processing, due in part to the significant heating which may occur due to viscous dissipation, and also to the very strong influence of temperature on fluid viscosity. The flow is treated as Newtonian with the flow field being coupled to the heat transfer equation only through the viscous heat generation.
The instant invention involves a process for use in preparing tapes or rovings, which are formed from a thermoplastic material used to impregnate longitudinally extended bundles of carbon fibers. The process involves the steps of (a) gas spreading a tow of carbon fibers; (b) feeding the spread tow into a crosshead die; (c) impregnating the tow in the die with a thermoplastic polymer; (d) withdrawing the impregnated tow from the die; and (e) gas cooling the impregnated tow with a jet of air. The crosshead die useful in the instant invention includes a horizontally extended, carbon fiber bundle inlet channel, means for providing melted polymer under pressure to the die, means for dividing the polymeric material flowing into the die into an upper flow channel and a lower flow channel disposed above and below the moving carbon fiber bundle, means for applying the thermoplastic material from both the upper and lower channels to the fiber bundle, and means for withdrawing the resulting tape from the die.
The work has been done according to the US/Russian Joint Project "Experimental Evaluation of the Material Flammability in Microgravity" a continued combustion study in the SKOROST test apparatus on the OS Mir. The objective of the project was to evaluate the flammability and flame-spread rate for the selected polymer materials in low velocity flow in microgravity. Lately, the issue of nonmetal material combustion in microgravity has become of great importance, based on the necessity to develop the fire safety system for the new International Space Station (ISS). Lack of buoyant flow in microgravity reduces oxygen transfer into the combustion zone, which leads to flame extinction when the flow velocity is less than the limiting flow velocity V(sub lim) for the material. The ISS FGB fire-safety system was developed based on this phenomenon. The existence of minimum flow velocity V(sub lim) to sustain fire for the selected materials was determined both theoretically and experimentally. In the latter, it is shown that, even for thermally thin nonmetal materials with a very low oxygen index C(sub lim) of 12.5% (paper sheets with the thickness of 0.1 mm), a limiting flow velocity V(sub lim) exists at oxygen concentration Co(sub OX) = 17-21%, and is about 1.0 - 0.1 cm/sec. This might be explained by the relative increase in thermal losses due to radiation from the surface and from the gaseous phase. In the second series of experiments in Skorost apparatus on Orbital Station Mir the existence of the limiting flow velocity V(sub lim) for combustion was confirmed for PMMA and glass-epoxy composite strip samples 2 mm thick at oxygen concentration C(sub OX) = 21.5%. It was concluded that V(sub lim) depends on C(sub OX) for the PMMA sample with a low oxygen index of 15.5%, the limiting flow velocity V(sub lim) was less than 0.5 cm/sec, and for the glass-epoxy composite sample with a high oxygen index of 19%, the limiting flow velocity V(sub lim) was higher than 15 cm/sec. As of now only those materials that maintain their integrity during combustion were investigated. The materials that disintegrate when burning present more danger for fire safety because the flame can spread farther with the parts of the structure, ejected melt drops, et cetera. Materials such as polyethylene are of great interest since they form a lengthy melt zone during the combustion in normal gravity. This melt zone generates drops of liquids that promote faster flame spread compared to usual combustion. The preliminary results of polyethylene insulation flammability evaluation in microgravity are shown in the NASA Wire Insulation Flammability (WIF) experiment during Space Shuttle flight STS-50. A lot of interesting data was collected during the WIF test program. However, one of the most important results was that, in microgravity, the extinction of the polyethylene occurred almost immediately when the flow of relatively low oxygen concentration (C(sub OX)=21%) was stopped. The purpose of the work reported here is to expand the existing data base on material flammability in microgravity and to conduct the third series of the space experiment using Skorost apparatus on Orbiatl Station Mir with melting polymers, which might increase the probability of fire and its propagation in ventilated microgravity environment of orbiting spacecraft.
Network rupture hypothesis and molecular structure considerations used in obtaining constitutive equations for flow of polymer melts and solutions
Network rupture hypothesis and molecular structure considerations used in obtaining constitutive equations for flow of polymer melts and solutions
A finite element formulation designed to simulate polymer melt flows in which both conductive and convective heat transfer are important is described, and the numerical model is illustrated by means of computer experiments using extruder drag flow and entry flow as trial problems. Fluid incompressibility is enforced by a penalty treatment of the element pressures, and the thermal convective transport is modeled by conventional Galerkin and optimal upwind treatments.
Computer simulation studies were conducted to investigate materials properties. All the calculations were carried out using atomic level simulation techniques which are based on semiempirical or model functions. During this project, functions with varying degrees of complexity were derived and employed in simulations. Investigations include covalently bonded materials as well as systems involving metal atoms. For small clusters calculated results provided information on various energy- and structure-related properties along with vibrational characteristics. Also, energy barriers for configurational transitions were calculated for selected cases. Simulation calculations for surfaces produced new results in areas related to surface energies, reconstructions and relaxations, surface defects, surface stresses as well as adsorption and nucleation processes. Simulations were also performed on bulk materials. Calculated results provided an atomic level understanding on energetics and structures of point defects, crystal stability, elastic properties, and materials strength for various systems. Calculations involving polymeric materials include studies of polar polymer melts and polymer/solid interfaces. Simulations employing specially developed codes provided significant information about energetics and conformational characteristics of different polymeric chains.