Change of morphology in high molecular weight polyethylene during die drawing

Deformed high molecular weight polyethylene (HMWPE) rod, produced by die drawing at 115°C, was cleaved longitudinally at liquid nitrogen temperature and the cleaved surface was etched using a permanganic etching technique. A series of etched surfaces of HMWPE sections with different draw ratios (from 1 to 13) were analyzed employing scanning electron microscopy (SEM). The change of crystalline structure in HMWPE during die drawing was observed. In undrawn HMWPE. the spherulites were made up of sheaflike lamellae and scattered within the amorphous phase. During die drawing in the first instance, the microscopically inhomogeneous deformation occurred and the spherulites aligned along the drawing direction. At a draw ratio of about 7, local melting occurred, the spherulites disintegrated, and the sheaflike lamellae oriented, followed by straininduced recrystallization and the growth of the lamellae. Finally, at a draw ratio of about 12, the plastic deformation of the lamellae occurred and microfibrils were formed. © 1993 John Wiley & Sons, Inc.     

Production and properties of highly oriented polyoxymethylene by die‐drawing

Highly oriented monofilaments were produced by a high‐temperature die‐drawing process followed by tensile drawing. It was shown that a successful high‐speed process required high‐quality melt‐extruded rod. The mechanical properties and structure of the die‐drawn products were investigated by means of tensile and bending tests, dynamic mechanical measurements, DSC, and X‐ray diffraction. The bending modulus and the tensile strength increased with increasing draw ratio. It was also observed that at high draw ratios the γ‐dispersion peak in the dynamic mechanical tan δ curve, which is associated with main chain micro‐Brownian motion in the amorphous regions, diminishes, implying that these chains become taut. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1268–1278, 2003     

Influence of mold design on the mechanical properties of high-pressure injection—molded polyethylene

High-pressure injection molding (nominal pressure 500 MPa) is known to substantially improve the mechanical properties of high-density polyethylene of a high molecular weight (HMWPE). This work shows that if the mold is equipped with an exit cavity, the tensile modulus and strength of HMWPE-bars molded is further improved at high pressure levels. The maximum values of the stiffness and strength (thin bars, 1 mm) obtained with the exit chamber is about 12 GPa and 260 MPa, respectively. The improvement due to the exit cavity is of the order of 30 percent for the tensile strength for thicknesses lower than 4mm, while the modulus increases about 1 to 1.5 GPa for bars with thicknesses between 1 and 6 mm. The orientation of the melt during the filling of the mold was also found to have an influence on the mechanical properties of the HMWPE bars.     

The Effect of Processing Parameters on the Crystalline,Orientation, and Mechanical Properties of Two‐Stage Die‐Drawn Polypropylene

An investigation specifically focusing on the relationship among processing parameters, structure, and mechanical properties of solid two‐stage die‐drawn polypropylene (PP) has been done in this study, which aimed at providing a reliable reference in the choose of appropriate conditions that can be able to meet a specific processing requirement. PP sheets were drawn through a self‐design solid two‐stage die‐drawing apparatus to various drawing ratios (DRs) at different speeds and with different die‐exit thicknesses. The results showed that tensile strength, modulus, and the degree of orientation significantly increased with the nominal DR and could be further improved by increasing the drawing speed. While the crystallinity increased prior and decreased to near a constant value when the drawing speed was over 150 mm/min in the researched scope. Larger the die‐exit thickness was, lower the orientation degree was but higher the crystallinity could be obtained. Compared with crystallinity, orientation degree plays a leading role in the final product properties during a two‐stage solid die‐drawing process. POLYM. ENG. SCI., 59:2347–2355, 2019. © 2019 Society of Plastics Engineers     

Damage in large scale solid state deformation of thermoplastic polymers at elevated temperatures and varying strain rates

Abstract

A key factor which limits the production speed of the polymer die drawing process is the premature fracture of the material on exit from the die. In this paper, the growth of damage in the material during the die drawing process has been studied using a combination of thermoplastic finite element analysis and structural characterisation by means of scanning electron microscopy and small angle X-ray scattering for the specific case of die drawing of polyoxymethylene. It is demonstrated that special profiled dies offer a more beneficial strain rate distribution than the conventional conical dies and allow higher production speeds to be obtained. Voids grow in the material as a result of the tensile stresses pertaining near the die exit and then, crazes appear from within the material at a critical stress level leading ultimately to final fracture. The results suggest that although the crazes initiate at a critical stress, the extent of crazing at the maximum draw ratio obtained (～13) is independent of the type of die and hence the stress level. Fracture of the drawn product occurs at different stresses for different die profiles but always at the maximum draw ratio of 13, suggesting that this relates to the limiting extensibility of a molecular network.     

高相对分子质量PE的增塑熔融纺丝 Ⅰ.纺丝工艺

采用石蜡增塑高相对分子质量ＰＥ后纺丝并经高倍拉伸制备高强高模纤维。此法比凝胶纺丝法工艺简单，产率高，成本低。该文研究了高相对分子质量ＰＥ和石蜡共混物的热性能、流变性、可纺性和纺丝工艺。     

Mechanical and physical properties of ultraoriented polyoxymethylene produced by microwave heating drawing

The properties of ultra-oriented polyoxymethylene tubes produced by drawing under microwave heating have been assessed by mechanical testing, optical microscopy, scanning electron microscopy, X-ray analysis, birefringence and differential scanning calorimetry. The highest Young's modulus of 58 GPa was obtained at room temperature (77 GPa at ?150°C) at a draw ratio of 33. The maximum tensile strength was 1.7 GPa at a draw ratio of 26. The nonuniformity of Young's modulus in a radial direction has been compared with the nonuniformity of the birefringence and heat of fusion.     

Improvement of Flexural Strengths of Poly(L‐lactic acid) by Solid‐State Extrusion, 2. Extrusion Through Rectangular Die

Solid‐state extrusion of poly (L ‐lactic acid) (PLLA) through rectangular die was performed to produce high flexural strength plates that can be used as internal fixation devices. A single‐angle wedge‐shaped rectangular die was utilized having the die exit dimension of 4 mm × 1 mm. Billets were machined out from vacuum compression molded PLLA having different crystallinities to have various thicknesses and thus various imposed draw ratios. Solid‐state extrusion of billets was performed at various drawing rates at 130 °C, above glass transition and below melting temperature. Extruded plates had the width and thickness smaller than the die due to the further drawing outside the die. The decrease in width was larger than the decrease in thickness, and this became more prominent with increasing draw ratio and drawing rate, resulting in a significantly smaller aspect ratio. Contributions of die drawing and further drawing outside the die were estimated from the extruded plate dimensions, by which the drawing rate effect was attributed to the further drawing outside the die. As actual draw ratio increased, crystallinity, melting temperature, crystalline orientation factor, and birefringence increased. Throughout the whole process the decrease in molecular weight was largely suppressed to be about 10%. As billet crystallinity, draw ratio, and drawing rate increased, both flexural strength and flexural modulus increased up to the maxima of 202 MPa and 9.7 GPa, respectively. This enhancement in mechanical properties was correlated with structural developments.

Changes in flexural strength of solid‐state extruded PLLA plates as a function of draw ratio (the effect of drawing rate is co‐plotted by hollow symbols at corresponding draw ratio.).     

Mechanical properties and microstructure of poly(ethylene terephthalate) microfiber prepared by carbon dioxide laser heating

We determined that a poly(ethylene terephthalate) microfiber was easily obtained by irradiating a carbon dioxide laser to an annealed fiber. The annealed fiber was prepared by zone drawing and zone annealing. First, an original fiber was zone drawn at a drawing temperature of 90°C under an applied tension of 4.9 MPa, and the zone‐drawn fiber was subsequently zone annealed at 150°C under 50.9 MPa. The zone‐annealed fiber had a degree of crystallinity of 48%, a birefringence of 218.9 × 10^?3, tensile modulus of 18.8 GPa, and tensile strength of 0.88 GPa. The microfiber prepared by laser heating the zone‐annealed fiber had a diameter of 1.5 μm, birefringence of 172.8 × 10^?3, tensile modulus of 17.6 GPa, and tensile strength of 1.01 GPa. The draw ratio estimated from the diameter was 9165 times; such a high draw ratio has thus far not been achievable by any conventional drawing method. Microfibers may be made more easily by laser heating than by conventional technologies such as conjugate spinning. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1955–1958, 2003     

Effect of drawing on structure and properties of a liquid crystalline polymer and polycarbonate in-situ composite

Fibers (strands) with various draw ratios were spun from the liquid crystalline state of a pure aromatic liquid crystalline copoly(ester amide) and the melts of its blend with polycarbonate. Scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), and differential scanning calorimetry (DSC) were employed to investigate the structure and properties of the resulting fibers. Mechanical properties of the fibers were also evaluated. It was found that both the crystallite size and heat of fusion of the liquid crystalline polymer (LCP) increase steadily with draw ratio. However, the crystal-nematic transition temperature of the LCP is virtually unaffected by drawing. Moreover, heat of fusion of LCP is much smaller than that of isotropic condensation polymers despite the presence of very sharp diffraction peaks in WAXS measurements. These results are ascribed to the (semi)rigid rod nature of the LCP chains and the persistence of an ordered structure in the LCP melt, i.e., entropy effect. It was further observed that tensile modulus and tensile strength along fiber axis rise with draw ratio for the composite fibers. The elastic modulus of the composite fibers were found to be as high as 19 GPa and tensile strength reached 146 MPa with draw ratios below 40 and an LCP content of 30 wt%. Compared with the thermoplastic matrix, the elastic modulus and tensile strength of the in-situ composite have increased by 7.3 times and 1.4 times, respectively, with the addition of only 30 wt% LCP. This improvement in mechanical properties is attributed to fibrillation of the LCP phase in the blend and the increasing orientation of the LCP chains along the fiber axis during drawing.     

Structure evolution and orientation mechanism of isotactic polypropylene during the two‐stage solid die drawing process

High oriented isotactic polypropylene prepared by self‐designed two‐stage die drawing apparatus was explored through kinds of methods, including differential scanning calorimetry, two‐dimensional wide‐angle X‐ray diffraction, polarized light microscope, and tensile test. The results showed that there was a great difference between the orientation mechanism and structure evolution of two‐stage solid die drawing process and single‐stage solid die drawing process. All samples would undergo free drawing process after die drawing process. Die drawing and free drawing process were of equal importance to single‐stage die drawing process while die drawing process showed an prominent contribution to the two‐stage die drawing process. Drawing speed showed beneficial influence on die drawing process for both single‐ and two‐stage die drawing process routes. Under the same processing condition, tensile strength and modulus of samples prepared by two‐stage die drawing process were higher than those prepared by single‐stage die drawing process and the maximum value could reach 241.93 MPa and 3.57 GPa, respectively. Moreover, two‐stage die drawing samples showed better dimensional stability than single‐stage die drawing samples especially under low draw rate. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46581.     

Production of ultrahigh modulus polyoxymethylene by drawing under dielectric heating

A tensile drawing process under dielectric heating has been developed for polyoxymethylene. The influence of ambient temperature, electric field strength, and strain rate on the maximum draw ratio and the tensile modulus has been examined. Tubes possessing tensile moduli up to 63GPa were produced by the new drawing technique. It is speculated that the achievement of such ultrahigh moduli is due to the fact that the stress by drawing is used effectively to orient the molecular chains in the noncrystalline regions and at defect regions within the crystal lamellae. This is because these regions are heated to higher temperatures than the crystalline regions during dielectric heating.     

高相对分子质量PE的增塑熔融纺丝 Ⅱ.拉伸工艺和纤维的结构性能

采用石蜡增塑高相对分子质量ＰＥ后纺丝并经高倍拉伸制备高强高模纤维。此法比凝胶纺丝法工艺简单,产率高、成本低。该法研究了高相对分子质量ＰＥ和石蜡共混初生纤维的萃取拉伸工艺和拉伸纤维的结构性能。     

Orientation of amorphous poly(ethylene terephthalate) by tensile drawing,roll-drawing,and die-drawing

Orientation of initially amorphous poly(ethylene terephthalate) films and sheets was carried out by means of tensile drawing in a tensile tester, roll-drawing using a series of four rolling stations, and by die-drawing. The drawing temperature was 80 and 90°C and drawing rate ranged from 2 to 20 cm/min in the different processes. Crystallinity was observed to increase with draw ratio for all these processes. The onset of crystallinity development depends on the drawing rate. The glass transition temperature was essentially constant and crystallization temperature decreased with increasing draw ratio. The trans conformers content was observed to increase with draw ratio at the expense of the gauche conformers for the three processes. The orientation of the trans conformers increases readily from the beginning of draw and saturates rapidly. The orientation of the gauche conformers was negligible. Some differences are observed for the behavior of the 1020 and 730 cm^?1 benzene ring bands, which may be due to differences in the benzene ring configuration at the surface as a result of different deformation mechanisms for the die and roll-drawing. However, further investigations to elucidate this hypothesis are needed. The mechanical properties obtained in the longitudinal direction increased for all the processes. In the transverse direction, the roll and die-drawing processes induced a decrease in modulus and strength with increasing draw ratio, similar to that observed for uniaxial orientation. This indicates that these processes are mainly uniaxial, despite the plane strain nature of the deformation.     

干-喷湿纺聚丙烯腈纤维拉伸工艺研究

研究了干 -喷湿纺聚丙烯腈 (PAN)初生纤维的喷丝头拉伸比和三级拉伸 (空气拉伸、DMF浴拉伸、热水和沸水拉伸、干热拉伸 )工艺中各拉伸比对纤维性能的影响。结果表明 :提高喷丝头拉伸比可明显地降低初生纤维的线密度 ,提高强度 ;三级拉伸工艺中各拉伸比的提高均有利于PAN纤维线密度的减小及其强度、声速取向度和抗张模量的提高 ;合理调配三级拉伸中各拉伸比可制得强度超过 7.0cN/dtex的PAN纤维     

Effects of processing parameters and molecular weight distribution on the tensile properties of polypropylene fibers

The tensile properties of polypropylene fibers, produced in a short-spin line, are correlated with the parameters of the three processing stages (spinning, drawing, and annealing), and with the molecular weight distribution. In general, tensile stiffness and strength increase with increasing molecular orientation, while the elongation at break decreases. The degree of orientation is determined by the deformation ratios and temperatures of the first two stages. Tensil modulus and strength also increase with increasing annealing stage shrinkage ratio. All the tensile properties, including the elongation at break, increase with increasing average molecular weight. The mechanisms of crystallization and deformation are related to the molecular weight distribution in different ways. Hence, the tensile modulus is highest for broad distributions when the draw ratio is low, and for narrow distributions when the draw ratio is high. The tensile strength increases and the elongation at break decreases as the width of the molecular weight distribution decreases, for all combinations of processing parameters. The distribution of tensile strength, for fibers with high draw ratios, broadens as the molecular weight distribution narrows. The total draw ratio of fibers, as experienced during processing and testing, and the true stress at break, are discussed in terms of deformation rates and relaxation times. © 1994 John Wiley & Sons, Inc.     

Two-stage drawing of poly(ethylene 2,6-naphthalate)

Initially amorphous and semicrystalline films of poly(ethylene 2,6-naphthalate) with different molecular weights were drawn by two-stage drawing, that is, coextrusion at low temperatures (25–160°C) followed by tensile drawing at high temperatures (200–245°C). Both films could be drawn up to a draw ratio of 8–10 by this method under controlled conditions. The tensile modulus and strength of drawn samples were greatly affected by the draw temperature for the first stage, predrawn morphology, and molecular weight. The remarkable effects of these variables on the tensile properties are closely related to the difference in the resultant amorphous chain orientation of the samples, reflecting the disentanglements and chain slippage during drawing, and the dissipation of chain orientation after processing.     

Push–pull extrusion: A new approach for the solid-state deformation illustrated with high density polyethylene

The crystalline state deformation of high density polyethylene has been examined at an extrusion draw ratio of 30 over a range of temperatures and pressures. The experiments involve combined pushing (extrusion) and pulling through a conical die. The pressure dependence of the extrusion rate through conical dies is given by a logarithmic relation and the temperature dependence by an activation energy of ～95 kcal/mole. An equation established for the total applied force linearly relates the pulling and extrusion pressure components and represents a force balance at the die entrance and exit. Steady-state extrusion, with or without pulling, was feasible in a pressure range beyond which fractures occurred owing to strain rate and shear or tensile failure. Under some circumstances the extrusion rate was increased by ten times. The mechanical properties and mode of deformation were not affected by pull load and fibers with a tensile modulus of 55 GPa were produced at T < 110°C.     

Roller drawing of polyoxymethylene

The roller drawing of polyoxymethylene (POM) sheets was carried out in the temperature range of 140–157°C. The mechanical properties, the molecular orientation, and the microstructure of the roller-drawn POM sheets were investigated by means of tensile test, dynamic viscoelasticity, wide-angle X-ray diffraction, small-angle X-ray scattering, visible dichroic spectrum, electron microscopy, and so on. The Young's modulus and the tensile strength increased with increasing draw ratio up to draw ratio, λ of 14–15. The improvement of the mechanical properties is concerned with structural changes, such as the increase in orientation function in the crystalline and amorphous regions and the formation of taut tie molecules and crystalline bridges in the intercrystallite and interfibrillar regions. In the higher draw ratio range (λ > 15), the increase in Young's modulus and tensile strength was restricted by the formation of interfibrillar microvoids.     

Transparent,Lightweight, and High Strength Polyethylene Films by a Scalable Continuous Extrusion and Solid‐State Drawing Process

The continuous production of transparent high strength ultra‐drawn high‐density polyethylene films or tapes is explored using a cast film extrusion and solid‐state drawing line. Two methodologies are explored to achieve such high strength transparent polyethylene films; i) the use of suitable additives like 2‐(2H‐benzotriazol‐2‐yl)‐4,6‐ditertpentylphenol (BZT) and ii) solid‐state drawing at an optimal temperature of 105 °C (without additives). Both methodologies result in highly oriented films of high transparency (≈91%) in the far field. Maximum attainable modulus (≈33 GPa) and tensile strength (≈900 MPa) of both types of solid‐state drawn films are similar and are an order of magnitude higher than traditional transparent plastics such as polycarbonate (PC) and poly(methyl methacrylate). Special emphasis is devoted to the effect of draw down and pre‐orientation in the as‐extruded films prior to solid‐state drawing. It is shown that pre‐orientation is beneficial in improving mechanical properties of the films at equal draw ratios. However, pre‐orientation lowers the maximum attainable draw ratio and as such the ultimate modulus and tensile strength of the films. Potential applications of these high strength transparent flexible films lie in composite laminates, automotive or aircraft glazing, high impact windows, safety glass, and displays.