The Structure of High Molecular Weight Linear Polyethylene Injection Moulded at High Pressures

Abstract

High density polyethylene with a low melt flow index (0.1 g/10 min) was injection moulded at pressures ranging from 100 to 500 MPa. The tensile modulus and strength in the flow direction increased substantially with the injection pressure. Three regions are characteristic of the specimens produced; a thin layer near the surface, a transition layer beneath the skin, and a core. DSC, wide angle X-ray scattering (WAXS), scanning and transmission electron microscopy were used to study the structure of the different layers. It was concluded that the skin was slightly oriented containing primarily chain-folded lamellae; the transition layer had a fibre texture and was oriented in the flow direction; the orientation of the core was similar to that of the transition layer but contained extended chain-morphologies similar to those found by Porter et al. in capillary extruded specimens. The composite structure gives rise to the improvement of mechanical properties and the increase in modulus is due to the core material. A monoclinic phase in the core was found by X-ray diffraction.     

Structure of poly (p-phenylenebenzobisoxazole) (PBZO) and poly (p-phenylenebenzobisthiazole) (PBZT) for proton exchange membranes (PEMs) in fuel cells

The structures of membranes of PBZO and PBZT extruded with counter rotating dies (CRD) were studied by wide angle X-ray diffraction (WAXD), small angle X-ray scattering (SAXS), atomic force, scanning electron and transmission electron microscopy (AFM, SEM, and TEM). The structure of CRD-extruded PBZO was compared with that of a solution-cast membrane. The extruded membranes have sheet structures typical of rigid-rod polymers. The heterocyclic rings of the extruded membranes are oriented approximately parallel to the membrane surface, while those of the cast membrane are oriented perpendicular to the surface. The parallel orientation of the rings of the extruded membranes may be due to the normal force exerted during extrusion. The polymer molecules near the surfaces of the extruded membranes are oriented along the shear directions of the extruder, while those in the middle are oriented randomly. There is little cholesteric nature. These materials have potential as microporous PEMs holding ion conducting polymers (ICPs).     

Formation and peculiarities of heterogeneity in polyethylene samples obtained by extrusion

Three-layer structure was observed in the polyethylene strips obtained under definite conditions of extrusion, with the high degree of orientation of the core layer being most remarkable. The wide-and small-angle X-ray investigation of the different layers of the strips and the pole figures analysis were performed. In the outer layers a texture is formed. Crystalline structure formed in the core is characterized by almost regular cylindrical arrangement of a and b axes around the extrusion direction. The c axes direction almost coincides with the extrusion direction. In the core of the extruded strand, lamellae are arranged in parallel stacks. The angle value between the normal to the lamellae surface direction and the extrusion direction is about 30°.     

Structural,rheological, and mechanical properties of ternary blends of PEN,PET, and liquid crystalline polymer

Structural, rheological, and mechanical properties of ternary blends of a liquid crystalline copolyester (LCP) composed of p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, poly(ehtylene naphthalate)(PEN), and poly(ethylene terephtalate) (PET) were investigated using capillary rheometry, tensile testing, scanning electron microscopy, and X-ray diffraction. Viscosity-shear rate behavior of the ternary blends is very similar to that of pure polymers and their binary blends. The activation energy of flows of the ternary blends was smaller than those of PEN and PET. Tensile modulus and strength of extruded strands of the blends increased with increasing LCP content. The extruded strands of the blends consist of a crystalline and oriented LCP phase and an amorphous and unoriented PEN/PET blended phase. Tensile mechanical properties and structures of the ternary blends were discussed.     

新型PVC片材的力学性能和阻隔性能的研究

采用微层挤出技术制备了微层PVC片材,采用涂覆法制备了多层PVC/PVA复合片材,对其力学性能和阻隔性能进行了研究。结果表明:①多层结构有利于提高PVC/PVA复合片材的阻隔性能,涂覆PVA溶液增大了片材的拉伸强度。②微层PVC片材的分子链发生取向,沿挤出方向的拉伸强度明显高于垂直挤出方向;微层PVC片材的层数越多,取向作用越强,越有利于阻隔性能的提高。     

Morphology of extruded high-density polyethylene pipes studied by atomic force microscopy

Atomic force microscopy (AFM) was used to study the structure of extruded polyethylene (PE) pipe. During extrusion, the outer surface of the pipe was cooled with water. Two cross sections, parallel and transverse to the extrusion direction, were examined in order to spatially follow the structural development during extrusion. The morphology revealed was spherulitic, and the spherulites had a mostly banded appearance when viewed under the AFM. We were not able to distinguish an oriented skin layer at the surface of the pipe, either by AFM or polarizing microscopy. The changes in the pipe's structure resulting from the cooling conditions were found to be rather gradual, and no clearly defined zones were observed. A slight orientation towards the extrusion direction was detected only in the area of the pipe crystallized under the lowest degree of undercooling. Measured spherulitic size, band period, and lamellae thickness showed a gradual increase in their values from the cooled to the noncooled surface of the pipe. Transmission electron microscopy (TEM) was used to verify the band period and lamellae thickness measurements done by AFM. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 515–523, 1997     

Sheet extrusion of microcomposites based on thermotropic liquid crystalline polymers and polypropylene

This work is concerned with the extrusion of sheets from pellets of polypropylene (PP) containing pregenerated microfibrils of thermotropic liquid crystal polymers (TLCPs), referred to as microcomposites. The TLCPs used were HX6000 and Vectra A950. The microcomposites are produced by drawing strands of PP and TLCPs generated by means of a novel mixing technique and pelletizing the strands. The work was undertaken in an effort to improve on the properties for in situ composites in which the TLCP fibrils are generated in contractions in the die and the subsequent drawing step. In situ composites usually exhibit highly anisotropic mechanical properties and the properties do not reflect the full reinforcing potential of the TLCP fibers. Factors affecting the mechanical properties of the composite sheets considered include the effect of in situ composite strand properties and TLCP concentration. In addition, the properties of the extruded sheets are compared to those of microcomposites processed by means of injection molding. It is shown that the sheets produced using microcomposites have a good balance between the machine and transverse direction properties (ratios of these properties ranging from 0.8 to 1.2) and those properties compare well to those obtained by processing microcomposites in injection molding. The tensile modulus of the composite sheets increases with increasing in situ composite strand modulus. The moduli of the 20 wt% Vectra A950 and HX6000 composites are about equal to the modulus of 20 wt% glass reinforced PP (about 2.1 GPa), while the tensile strength of the TLCP reinforced composites is 28% lower than that of the glass reinforced PP. Furthermore, it is shown that the tensile modulus of the 10 wt% TLCP composites approach the predictions of composite theory, while at 20 and 30 wt% TLCP negative deviations from the predictions of composite theory are seen. Finally, it is concluded that the properties of the sheets produced through the extrusion of microcomposites may be further improved by improving the modulus of in situ composite strands and reducing the TLCP fiber diameter.     

Oriented structure formation during polymer film extrusion

An experimental technique is described for producing fiberreinforced polymer films by inserting needle-like obstructions in a film-extrusion die. The, needles act as nucleation sites, generating a highly extensional local flow field, which causes sufficient orientation to induce the formation of oriented fibrillar crystallites embedded in a much less oriented matrix. To study the effectiveness of the above technique, linear low density polyethylene (LLDPE) and blends of linear low density with high density polyethylene (HDPE) were extruded through a film die with converging walls, with one or five needles inserted parallel to the extrusion direction, Microscopy observations, birefringence, and differential scanning calorimetry (DSC) measurements performed on the produced films showed in all cases that the presence of the needle induced the formation of a more oriented phase, which in most cases had a birefringence at least an order of magnitude higher than the film matrix. The best results were obtained in the case when blends of HDPE and LLDPE were extruded. The oriented structures obtained in this case consisted of HDPE and exhibited not only high birefringence but melting point elevation as well, indicating their fibrous nature.     

Structures and tensile properties of a magnetically and mechanically oriented liquid crystalline copolyester,Xydar

A wholly aromatic thermotropic liquid crystalline copolyester consisting of p-hydroxybenzoic acid, terephthalic acid, and p,p′-biphenol, one from the Xydar series, was aligned by means of magnetic fields and mechanical methods. The tensile properties of these samples were different depending on the orientation degree and the means used for the orientation. Magnetically oriented films exhibited lower elastic modulus and ultimate tensile strength than mechanically oriented films of the same orientation degree, but the elastic modulus of magnetically oriented films was comparable to that of the mechanically stretched films of lower orientation degrees. This suggests that magnetic fields could be used as an additional means of controlling the orientation of thermotropic liquid crystalline copolyesters during molding or film fabrication. The difference in tensile properties was discussed in relation to the oriented structures examined by scanning electron microscopy, polarizing microscopy, and wide angle X-ray measurement.     

Stress‐induced crystallization of biaxially oriented polypropylene

The hot stretching of thick, extruded sheets at high temperatures is a very important process in the production of finished biaxially oriented polypropylene (BOPP) films with special inner structures. Through a simulation of hot stretching in the machine direction (MD) of the processing of BOPP films, it was found that at high temperatures, the stretching ratio greatly influenced the obtained crystalline structure, as observed by differential scanning calorimetry (DSC). Also, in MD hot stretching, the crystallinity increased by an average of 20%. Wide‐angle X‐ray diffraction patterns of extruded sheet samples with and without stretching confirmed the structural changes shown by DSC, and the results proved that β‐crystal modification did not occur during the MD hot‐stretching process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 686–690, 2003     

Antimicrobial PLA/TPS/gelatin sheets with enzymatically crosslinked surface containing silver nanoparticles

In the present work, poly (lactic acid)/thermoplastic starch/gelatin sheets were produced by calendering–extrusion process and silver nanoparticles (AgNPs, synthesized by chemical reduction with d ‐glucose), were incorporated at sheet surfaces to promote antimicrobial activity. A gelatin solution containing AgNPs was enzymatically crosslinked as a layer at sheets surface using transglutaminase. AgNPs presented 63 nm (z average size) and spherical shape (scanning electron microscopy, SEM) while morphology analysis showed that sheets presented internal porosity. Mechanical properties (Young modulus, elongation at break, and tensile strength) and water vapor permeability presented significant difference in function of gelatin amount added to sheets formulation due to increased internal porosity. Antimicrobial activity was demonstrated against Bacillus cereus, Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa for the AGNPs solution as well as for the surface treated films. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43039.     

A level set method for simulating wrinkling of extruded viscoelastic sheets

When a polymer is extruded freely from a rectangular die of large cross-sectional aspect ratio, wrinkles are observed. While not present in extruded Newtonian materials, such wrinkles develop in extruded viscoelastic sheets and are understood as an elastic stress-driven instability. The present study is devoted in developing a transient finite element method, which combines the matrix-logarithm-based formulation of the conformation tensor and the single-phase level set method, for simulating wrinkles that form during sheet extrusion of viscoelastic fluids. Numerical analyses of sheet extrusion were conducted over a wide range of flow rate and width-to-thickness ratio of the die exit cross section, χ, to determine critical conditions for the onset of wrinkling of extruded sheets. For large aspect ratios, that is, χ >> 1 , wrinkles develop at moderate extrusion flow rate, corresponding to a Weissenberg number of about 29. Calculations based on Rayleigh's energy method show that the critical compressive stress, σ_c, for the onset of wrinkling of an elastic sheet scales like σ_c~1/χ² , with a significant drop for χ >> 1 . As next to the die exit lip, compressive normal stresses are induced in the extruded sheet, wrinkling will take place for large χ (σ_c being small), in accordance with numerical predictions.     

A multi‐stream flow technique to obtain isotropic texture in extruded thermotropic liquid crystalline polymer melts

In this article, we present a simple method toward achieving global orientation isotropy in a capillary‐extruded thermotropic liquid crystal polymer (TLCP), that is, a random copolyester of 73 mol% hydroxybenzoic acid (HBA) and 27 mol% hydroxynaphthoic acid (HNA), by passing it through porous, flow altering metal foam inserts placed in the pathway of extrusion. TLCP melt flow through foam metal inserts causes a rapid creation of large number of small streams of varying cross‐section that subjects all regions of the flowing body to intense shearing leading to high orientation in individual streams. These individual streams of varying velocity and direction interact to form a structure similar to a woven rope. As a direct result of this randomization effect of these small streams, the extruded liquid crystal polymer tends toward isotropic macro properties. The degree of orientation anisotropy is evidenced by scanning electron microscopy (SEM) and micro beam wide angle x‐ray diffraction (WAXD) techniques and contrasted in samples extruded with and without the presence metal foam inserts. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

Processing–morphology–property relationships of polypropylene–graphene nanoplatelets nanocomposites

Polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs) were prepared via melt extrusion. A special sheet die containing with two shunt plates was designed. The relationships among the flow field of the special die, exfoliation, and dispersion morphology of the GNPs in PP and the macroscopic properties of the nanocomposites were analyzed. Flow field simulation results show that the die with shunt plates provided a high shear stress, high pressure, and high velocity. The differential scanning calorimetry, X‐ray scattering, and electron microscopy results reveal that the nanocomposites prepared by the die with the shunt plates had higher crystallinity values and higher exfoliation degrees of GNPs. The orientation of the GNPs parallel with the extrusion direction was also observed. The nanocomposites prepared by the die with shunt plates showed a higher electrical volume conductivity, thermal conductivity, and tensile properties. This indicated that the high shear stress exfoliated the GNPs effectively to a thinner layer and then enhanced the electrical, thermal, and mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44486.     

Effect of a separator in a sheet die on the anisotropy of tear strength of extruded medium density polyethylene

Sheets of medium density polyethylene (MDPE) were extruded through a slit die containing an internal separator. Thus, the melt stream was momentarily split before emerging from the die. A line of separation was evident in the extruded sheets. It is attributed to incomplete welding or healing. Measurements of tear energy G_c revealed that the extruded sheets were anisotropic and that the weld line was extremely weak after extrusion start-up, only about 1/5 of the strength elsewhere. As extrusion continued, the strength of the weld line increased to reach that of the bulk material after about 10 min. This is attributed to an increasing temperature of the melt in the die region, aiding interdiffusion. A sample containing 30% by weight of short glass fibers showed less initial weld-line weakness but the weld line remained weak in this case, even after long extrusion times.     

Thermoforming of liquid crystalline polymer sheets

Liquid crystalline polymer (LCP) extruded sheets were further processed by the conventional thermoforming method. The available processing temperature range was defined through the structural, thermal, and elevated temperature mechanical characterization of the extruded sheet. This temperature range was found for LCP to be quite narrow, in the proximity of the crystal-mesophase transition. The structural changes imposed on the LCP sheet during forming and its thermal stability were investigated using wide angle X-ray diffraction, mainly for the determination of the chain orientation distribution, DSC, and dynamic mechanical analysis. Thermoforming onto a symmetrical male mold was found to enhance the orientation in the extrusion machine direction and even change the preferred orientation in the extrusion transverse direction to orientation along the thermoforming direction. Annealing at the thermoforming temperature range results in a more ordered and thermally stable structure accompanied by just a slight orientation loss.     

Thermal properties and morphology of hydrostatically extruded polypropylene

The melting point, specific heat, and morphology and hydrostatically extruded polypropylene (PP) were studied to clarify the plastic deformation of three different parts of the extrudates (periphery, intermediate, and core) parallel to the direction of hydrostatic extrusion. Differential scanning calorimeter (DSC) measurements showed that, for all the parts studied, the peak and the end-of-transition, temperatures had a minimum value at a percentage reduction in area, R, of 50% Similar behavior was observed for the specific heat evaluated at several temperatures below the melting point. The morphological structure observed by use of a polarizing microscope indicated that the shape- of spherulites above R = 50% changed from spherulitic to elliptic. It is suggested that the pronounced changes taking place around R = 50% are closely related to the marked bend in the extrusion pressure versus extrusion ratio curve which takes place at the same R value. The molecular chains in the coarse spherulites appear to be deformed below R = 50% in such a way that finer spherulites are formed; but at R values above 50% the presence of elliptic spherulites implies that non-uniform deformation is present under higher hydrostatic pressure of extrusion.     

Poly(p-phenylene terephthalamide) films formed from extrusion and coagulation of liquid crystalline sulphuric acid solutions: Characterization of orientation and void structure,annealing, and upgrading of film mechanical properties

Poly(p-phenylene terephthalamide) (PPD-T) films have been prepared by continuous extrusion of liquid crystalline 17 percent PPD-T/sulphuric acid solutions through an annular die followed by coagulation, Films extruded without drawdown exhibit some polymer chain orientation in the machine direction. This is increased by uniaxially drawing down films. Films produced with a lubricated conical mandrel sitting between the die and the coagulation bath exhibit an equal biaxial orientation. The uniaxially oriented films exhibit highly anisotropic mechanical properties, while the mandrel-produced film exhibits balanced properties. Heat treatment at 350°C results in significant enhancement of the tensile strength of the mandrel film. Void structures in the films have been investigated by mass density, scanning electron microscopy (SEM), and small-angle X-ray scattering (SAXS). Density measurement indicate a void content decreasing with decreasing film thickness and heat treatment. SEM locates micron-size voids in the thickest films, apparently caused by rapid coagulation. SAXS indicates much smaller void sixes which are roughly prolate ellipsoids (long axis in machine direction) for uniaxial films and oblate ellipsoids (short axis in thickness direction) for the mandrel produced films. Various techniques are used to estimate mean void size.     

Fracture behavior of die‐drawn toughened polypropylenes

The Leeds die‐drawing process has been used to make oriented sheets of toughened polypropylenes. Die‐drawn oriented sheets were produced by drawing at 110°C to draw ratios of 4, 6, and 10. Comparative measurements have been undertaken of the plane stress fracture toughness at room temperature using the essential work of fracture method for isotropic and oriented polypropylene homopolymer and the two polypropylene blends containing 10 and 25% of a polyethylene‐based elastomer. In the isotropic state, the blend containing 25% elastomer exhibited higher fracture toughness than the homopolymer and the 10% blend. The oriented sheets were tested both parallel (cracks perpendicular to the draw direction) and perpendicular (cracks parallel to the draw direction). For the latter case of cracks parallel to the draw direction, the fracture toughness of all the materials decreased with increasing draw ratio and up to a draw ratio of 4 the 25% blend exhibited higher fracture toughness than the other two materials. At higher draw ratios, however, the unfilled polypropylene was tougher than the blends. When tested parallel to the draw direction, all three materials failed with the cracks growing slowly initially followed by sudden rupture. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1336–1345, 2003     

Deformation velocity dependence on tensile fracture characteristics of polypropylene injection molding parts

To clarify the mechanism of the deformation and fracture in a low‐velocity impact test on the isotactic polypropylene (i‐PP) sheet made by injection molding, the change of the style of fracture and the form of deformation was examined while changing the speed of the striker in a low‐velocity impact test. In the injection molding sheet, an oriented skin layer of some thickness is formed on the surface of the sample sheet. By the stress perpendicular to the orientation direction of the skin layer, crazes were formed easily in parallel with the orientation direction in this layer, and cracks were formed from there. Because these cracks bring the sample sheet a strong restraint of strain, a high stress concentration occurs at the end of this crack even if the formation of the oriented layer is limited on the surface of the sample sheet only, and the low‐velocity impact test leads the sample sheet to a brittle fracture. As a result, the injection molding sheet that forms oriented structure on its surface causes the ductility‐brittleness transform at a lower velocity of deformation compared with the nonoriented sheet. POLYM. ENG. SCI., 53:2659–2665, 2013. © 2013 Society of Plastics Engineers