Flow of polymer melts through a well-lubricated,conical die

The concept of gross melt fracture of polymer melts as a tensile failure in the die entry region was supported in this work by the observation of a dramatic increase in the melt fracture of poly-ethylene extrudates upon lubricating thoroughly a conical, converging extrusion die. This flow, according to an analysis using a Fromm viscoelastic model, was found capable of producing axial tensile stresses in the extrudate in excess of 10⁶ dynes/cm² at the very moderate exit shear rate (no lubricant) of 100 sec^?1. A calculated stress level of about 5 × 10⁶ dynes/cm² caused sharp, deep transverse cuts to appear in the extrudate. The ability of tensile stresses of this magnitude to fracture melts was demonstrated by separate experiments run in simple tension on molten rods, using similar rates and total deformations. A large qualitative difference between high and low-density polyethylene in both these experiments was noted.     

Die drawing: Solid phase drawing of polymers through a converging die

Die drawing, a new process for the production of oriented thermoplastic rods with an ultrahigh modulus of elasticity, involves drawing an isotropic workpiece through a converging die at temperatures below the polymer melting point. Die drawing of polypropylene is described, but the process is applicable to any polymer which can be drawn by conventional means. The considerable advantages of die drawing compared with conventional tensile drawing and hydrostatic or ram extrusion are discussed.     

Analytical and experimental study of the die drawing of circular rods through conical dies

An analysis is presented of the process of die drawing isotropic polymers, in the form of circular rods, to produce highly oriented materials with enhanced mechanical properties. The stresses in a small element of material undergoing the drawing process have been analyzed using a force-equilibrium approach and the initial yield and flow stresses in the material have been predicted from the von-Mises yield criterion. The stress-strain-strain rate characteristics of the polymer used in the analysis were deduced from uniaxial tensile test data obtained at the same temperature at which the die drawing occurred. Experimental results are presented of the stress in polypropylene GSE-108 rods when die drawn at 90°C in a purpose-built die drawing facility. Novel techniques were used to determine the stress and strain distributions along the die. A comparison of the experimental results and the analytical predictions shows good agreement.     

The production and properties of poly(aryletherketone) (PEEK) rods oriented by drawing through a conical die

Oriented poly(aryletherketone) (PEEK) rods have been produced by drawing isotropic polymer through a conical die. Room temperature Young's moduli were measured by three-point bending and ranged from 5 GPa at a draw ratio of about 2 to 11 GPa at a draw ratio of about 4. Dynamic mechanical properties were explored in the range ?150 to 200°C; two loss peaks were observed, with the higher corresponding to T_g.     

Gas transmission through polymers

Little data is available on gas transmission through thick polymer samples. There is, therefore, a temptation to assume an inverse relationship between gas transmission rate and thickness and to calculate flow through thick samples using permeability data obtained on thin films. This is incorrect, as the calculation assumes steady flow, and with thick samples this state may not be reached for months or even years. Thus both diffusivity and permeability are needed to calculate the gas flow and the calculations are more complex than simple permeability calculations. Because of the long time scale, the effects of varying the thickness are difficult to demonstrate experimentally. We describe a computer simulation of the manometric method which compares the behavior of two materials with similar permeabilities but different diffusivities. Although thin samples behave identically, they differ increasingly with thickness. The pitfalls in using the gradient and time lag of the pressure curve to calculate permeability and diffusivity are also discussed.     

Drawing behavior of polyblend fibers from polypropylene and liquid crystal polymers

Polyblend fibers were made from mixtures of polypropylene (PP) and thermotropic liquid crystal polymers (LCPs). The as-spun fibers were drawn to produce the oriented structure for the PP matrix. The LCPs were found to exist in thin and long fibrils in the as-spun fibers; after drawing, they were split into short fragments. From a simplified model whereby a single LCP fibril is embedded in a PP matrix fiber, it was calculated out that the length of the LCP fibril in the drawn fiber is directly proportional to the fibril diameter and tenacity, and is reversely proportional to the compressional stress on the fibril and the friction coefficient between the fibril and the surrounding matrix. With regard to the drawing conditions, it was found that a long length of the LCP fibrils can be preserved by increasing the drawing temperature, or by reducing the draw rate. The effect of two-stage drawing on the LCP phase morphology was also studied in the present work. © 1994 John Wiley & Sons, Inc.     

Diffusion of gases through polyurethane block polymers

The diffusivities of simple gases through a series of polyurethane block copolymers of differing aromatic urethane content and type of soft segment were measured using a quadrapole mass spectrometer as a detecting device. Although an Arrhenius expression generally described the temperature dependence of diffusion in this system, a discontinuity was observed in the Arrhenius plots for some materials, and the discontinuity was found to be related to the onset of the glass transition in the hard domains. Increasing the hard segment content of the materials decreased the diffusivity due to the increase in the activation energy of diffusion. Increasing the soft segment length brought about a decrease in the activation energy with an increase in diffusivity. Polyster urethanes had lower activation energies for diffusion than polyether urethanes of similar hard segment composition. Finally, as the penetrant diameter was increased, a decrease in the diffusivity and an increase in the activation energy was noted.     

Oxygen transmission through highly crosslinked polymers

Highly crosslinked polymers of varying structure were produced by the reaction of poly(glycidyl acrylate) (PGA) and methacrylate (PGM) with a variety of anhydride crosslinking agents: chlorendic (CA), glutaric (GA), maleic (MeA), succinic (SA), and polyrnalonic (pMnA) anhydrides. Topology was also varied by the use of a diluent and a comonomer in the backbone chain. Oxygen permeation measurements were made on these polymers coated onto a polypropylene film substrate before crosslinking. The crosslinking process greatly reduced the O₂ permeability which, however, was dependent not only on the degree of crosslinking (yield of the crosslinking reaction), but also on the crosslink density, the chemical nature of the structural elements, and the topology of the polymer network. Thus the most impermeable coating (XPGA/CA) was made not from the stiffest and bulkiest components (PGM and CA), but by the reaction of the bulkiest anhydride (CA) with the more flexible polymer backbone chain (PGA). This is explained in terms of the need for chain flexibility to produce a crosslinked structure of optimum space filling character and network tightness.     

An extrusion die with rollers for foaming polymers

Operation of a flat slot die with rollers for the extrusion foaming of polymers, which has been originally designed by Benkreira et al. (Int. Polym. Proc., 19, 111 (2004)), is considered. The rotation of rollers makes it possible to independently control shear rate inside the die, in the bubble nucleation zone, thus influencing the cell density. In experimental studies of low‐density polyethylene foaming, the influence of the roller rotation speed on the cell density at variable isobutane and talc concentrations and die outlet area has been determined. Based on the fluctuational nucleation theory, a simple model is proposed for estimating the number density of supercritical nuclei formed at the nucleation stage and evaluating the cell density in the foam with allowance for bubble coalescence effects. POLYM. ENG. SCI., 54:96–109, 2014. © 2013 Society of Plastics Engineers     

Pressure drop through a tapered die with optimized flow characteristics

The flow of power-law liquids through tapered dies has been analyzed in an earlier paper.¹ We now consider a taper which is additionally streamlined so as to make the transition from a broad and sluggish flow to a flow which is narrow and fast and as smooth as possible. This involves (1) the rational selection of an appropriate taper function within the relevant flow geometry and (2) the integration, between limits, of that function.     

Development of an extrusion die with rollers for foaming polymers

Ideas concerning the use of a flat slot die with rollers in the technology of extrusion foaming of polymers are developed. Based on the experimental study of low‐density polyethylene foaming with isobutane, dependences of the cell density and foam density on the polymer solution viscosity, gap width between rollers, die temperature, and talc concentration have been analyzed. A model is formulated for estimating the intensity of coalescence of supercritical bubbles in an inhomogeneous field of flow velocities. The number density of supercritical nuclei formed in a polymer–gas solution in the limiting case of high pressure drop rate is estimated. The obtained simple estimations allow the results of experiments to be justified on a qualitative level. POLYM. ENG. SCI., 55:2256–2269, 2015. © 2015 Society of Plastics Engineers     

多孔高吸水性树脂孔结构的图像分析法

本文探索了一种对多孔高吸水性树脂的孔结构进行定量表征的研究方法。采用Image J图象处理软件,将多孔高吸水性树脂的SEM照片转换为二值图后,利用软件的图形处理与计算功能,结合体视学的原理,得到多孔高吸水性树脂的孔结构参数。根据差分盒维数的思想,结合MATLAB编程计算,对二值图处理后得到图象的分形维数,用以表征结构复杂的多孔高吸水性树脂孔结构的规整性。通过所建立的表征方法,对不同预溶胀时间下通过冷冻诱导相分离法制备的多孔高吸水性树脂的结构的变化规律进行了讨论。     

Designing triple-shape memory polymers from a miscible polymer pair through dual-electrospinning technique

Recently, multiple-shape memory polymers (SMPs) have attracted a great deal of attention in biomedical applications. Therefore, a series of triple-SMPs were developed by simply blending of two immiscible SMPs exhibiting two distinct transition temperatures, which is required for triple-shape memory (SM) effect. However, fabrication of triple-SMPs from completely miscible polymer pairs using the conventional blending approach is a challenging problem. Because this type of blends consists of one homogeneous phase and thereby exhibit only one transition temperature and dual-SM behavior. To overcome this problem, herein, a novel and versatile strategy is introduced for preparation of phase separated blends from a completely miscible polymer pair, exhibiting triple-SM behavior. Dual-electrospinning technique was utilized to simultaneously electrospin poly(lactic acid) (PLA) and poly(vinyl acetate) (PVAc), as a model miscible polymer pair, to obtain an interwoven polymer composite with two well-separated thermal transitions, as revealed by dynamic mechanical analyze. Consequently, the SM experiments revealed that the electrospun PLA/PVAc composites have triple-SM behavior. Furthermore, incorporation of graphene nanoplatelets into the composite fibers significantly improved the triple-SM properties of samples. Additionally, excellent adherence and spreading of the osteoblasts on the fibrous scaffolds containing graphene were observed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47471.     

Spherical agglomeration in a conical drum

The spherical agglomeration process is a means of size enlargement in which agitated particles, suspended in a liquid, are bonded together by a second liquid, which will wet the solid surfaces and be immiscible with the suspending medium. A process is described in which agglomeration takes place in a cone shaped vessel, rotating horizontally about its symmetric axis. The cone configuration of the agglomerator imparts a longitudinal impulse to the charge, which is most effective on the largest particles. This causes a size classification within the cone, with the largest agglomerates congregating at the base. The result is the continuous production of uniformly sized, highly spherical pellets. The factors affecting agglomerate growth and size are outlined and discussed.     

Heat transfer to molten polymers flowing through tubes

A theoretical and experimental study of heat transfer to polymer melts flowing through circular tubes is presented. The mathematical model provides for shear heating and expansion cooling effects, and also heat of reaction during flow for various wall boundary conditions. Experimental results, obtained using low density polyethylene, show reproducible temperature and velocity profiles. The measured inlet melt temperature profile and the axial wall temperature profile provide the boundary conditions for the calculations. The experimental data confirm the predictions of the magnitude of the shear heating and expansion cooling effects during tube flow.     

Permeation and diffusion of environmental pollutants through flexible polymers

Permeation and diffusion characteristics of high density polyethylene (HDPE), elasticized polyolefin, and polychloroprene membranes have been determined for various organic pollutants at 22 and 50°C. A standard ASTM permeation cell method was used to measure the permeation rate while an immersion/weight gain method was used to obtain the diffusion coefficient. Thickness-dependent permeation rates were determined for HDPE membranes. An equimolar mixture of various permeants was also used to see the possibility of synergistic effects by combination of permeants. The experimental results are discussed in relation to the suitability of HDPE membranes in severe environments.     

Monitoring the chemical crosslinking of propylene polymers through rheology

The chemical crosslinking of propylene polymers is described; the reaction has been performed under dynamic conditions, using a peroxide and a furan or bis-maleimide-based coagent as crosslinking promoter; the reaction mechanisms have been investigated through FT-IR spectrometry. Crosslinking experiments have been carried out while keeping constant the amount and the nature of peroxide and increasing the coagent concentration; four different coagents have been used. The samples have been studied, in the molten state, by measuring the melt flow rates (MFR) and the values of G′ (storage modulus), G″ (loss modulus), Tg(δ) (ratio G″/G′), and η^∗ (complex viscosity), in the frequency range 10⁻²-10² rad s⁻¹. Another set of measurements has been performed on the same materials, collecting for each sample the values of η⁰ (zero shear viscosity) and J_e⁰ (steady state creep compliance) by creep-creep recovery experiments. The effects of crosslinking degree estimated by gel content and through rheological measurements allows one to evaluate the efficiency of the coagent both in terms of prevention of β-scission and promotion of the crosslinking reactions. These results are discussed with reference to the selection of proper conditions of the crosslinking process in order to achieve a material having desired MFR, rheological behavior and melt elasticity for selected application.