Ultrasonic measurements of the elastic stiffness constants of oriented polyethylene

High density polyethylene (Rigidex 9), a high density copolymer of polyethylene and poly(butene-1) (Rigidex 2000), and low density polyethylene (Alkathene WJG 11) were oriented by hot drawing. The crystalline texture, as determined by wide- and low-angle X-ray diffraction, was a highly oriented chain axis in the draw direction with random orientation transversely and with lamellae surfaces perpendicular to the draw direction. Elastic stiffness constants were measured by a contact-probe ultrasonic pulse technique at 2.5 MHz both before and after annealing in a temperature range which did not significantly alter the crystalline texture. Assuming orthorhombic symmetry the nine stiffness constants of Rigidex 2000 and the three longitudinal and three shear stiffness constants of Rigidex 9 were measured after drawing and after subsequent annealing. Only the longitudinal constants of Alkathene were measured, as shear waves could not be transmitted. The longitudinal stiffness in the draw direction was markedly affected by drawing and by annealing, while the crystalline texture remained substantially unchanged; by comparison the other stiffness constants showed little change. Drawn Rigidex 9 reached a tensile modulus in the draw direction of 69 GPa. The results are compared with ‘static’ and low frequency measurements reported in the literature.     

Tensile creep and recovery in ultra-high modulus linear polyethylenes

The tensile creep and recovery of oriented linear polyethylene (LPE) monofilaments have been studied for a range of samples of different structure. Starting with a comparison of samples of different draw ratio prepared from one grade of polymer, the measurements were extended to examine the effects of molecular weight. Although the viscoelastic behaviour is markedly non-linear it was found valuable to model the creep and recovery at each level of stress by a simple linear solid representation. This representation enabled a clear distinction to be made between recoverable and irrecoverable creep, both of which are affected by draw ratio and molecular weight. When the irrecoverable creep was examined further in terms of an activated Eyring process, a clear distinction between the two molecular weight grades could be made. In particular, the high molecular weight grade displayed a critical stress below which irrecoverable creep fell to a negligible level. This finding could be of considerable importance with regard to the application of ultra-high modulus LPE fibres in reinforcement.     

口模拉伸高取向聚乙烯材料的研究

研究了不同拉伸比的高取向聚乙烯材料的拉伸行为,并用X射线衍射及广角X射线衍射研究了共聚聚乙烯材料的取向度及结晶度。随着拉伸比和口模温度的升高,取向聚乙烯的结晶度明显提高,证实了高取向材料在制备过程中存在应力诱导的结晶过程,同时还存在温度作用的二次重结晶过程。     

Shear and tensile relaxation behaviour in oriented linear polyethylene

The dynamic shear behaviour of oriented linear polyethylene has been studied with particular reference to previous studies of the dynamic tensile modulus. First, it has been shown that the increase in the ?50°C plateau shear modulus with draw ratio can be understood on a Takayanagi-type model in terms of an increase in crystal continuity. The crystal continuity is estimated from the longitudinal crystal thickness and the long period on the basis of the random crystalline bridge model. At a similar level of sophistication it is also possible to explain the cross-over in the ranking of samples of increasing draw ratio with change of temperature. The dynamic mechanical behaviour is then considered in terms of a simple extension of this Takayanagi model in which crystalline sequences which span two or more adjacent lamellae are regarded as the fibre phase in a short fibre composite. It can be shown that this model gives a satisfactory prediction of the changes in dynamic tensile modulus and loss with temperature, for a range of samples with different degrees of crystal continuity.     

Thermal conductivity of highly oriented polyethylene

We have measured the thermal conductivity of oriented polyethylene both along and perpendicular to the draw direction for draw ratio λ between 1–25 and in the temperature range of 120 to 320K. The results for λ ? 5 have been analysed in terms of the modified Maxwell model while the further increase of thermal conductivity along the draw direction at higher λ has been explained by the Takayanagi model. The Young's modulus and thermal conductivity along the draw direction for the sample with λ = 25 were found to be 64 GN/m² (at 220K) and 140 mW/cm K (at 300K), respectively, which are extremely high values for polymers. This material, which is a good electrical insulator and yet has a high thermal conductivity, may be useful in electrical applications requiring large dissipation of heat.     

Ultradrawing of thermoplastics by solid state coextrusion illustrated with high density polyethylene

Ultra-thin films of high density polyethylene of high orientation have been produced by the recently developed technique of solid state coextrusion. The films were prepared under moderate conditions, without lubricant in continuous lengths by extruding through conical dies of extrusion draw ratio up to 36. This is a draw ratio higher than achievable by conventional solid state extrusion at comparable processing conditions through slit dies. The ultra-thin films of high orientation were transparent and exhibited dead bend. The physical and mechanical properties were evaluated and compared with the properties of the same high density polyethylene extruded through a slit die. The increase in the melt point, crystallinity, tensile modulus, and birefringence indicates that the method is very efficient for the production of ultra-thin and highly oriented films. An experimental technique is also presented for preparing billets of controlled and uniform initial morphology and free of voids.     

固态挤出HDPE性能与结构研究

采用4个不同拉伸比的口模，在较低速度下对高密度聚乙烯(HDPE)成功地实现了固态挤出。结果表明，试样的拉伸强度最大提高到250MPa。采用SEM测试分析其微观结构表明，试样中生成了大量高度取向的微纤结构；DSC分析表明，试样的结晶度增加，晶片增厚，晶体的尺寸更加均匀。     

Effect of gamma radiation on low density polyethylene

Low density monofilaments of polyethylene with varying draw ratios were subjected to high energy radiation using Co⁶⁰ gamma radiation source. It was found that the tensile strength is sharply improved with the increasing dose up to 20 Mrd beyond which a sharp decrease in tenacity and initial modulus was observed. The swelling behaviour also decreased with the increased in dose of irradiation. However, density showed an increasing trend. The shrinkage behaviour of all the filaments was found to increase with increasing dose and draw ratios. The results have been explained in terms of continuous increase in crosslink density with the increasing dose of irradiation along with loss of crystallinity, which appears to be more severe in the latter stages of exposure. The samples exhibited memory effect after redrawing at 100°C and cooling under tension followed by further heating at 110°C under relaxed condition. The shrinkage was still much higher but independent of draw ratio.     

Relaxation Behavior of Polyethylene Oriented by Various Techniques

Abstract

Stress relaxation of high-density polyethylene extrudates and those crystallized from highly deformed melt (PE-1) have been investigated in a wide range of temperatures (?50 to +120°C) and draw ratios from 5.5 up to 12.2 at the different constant tensile strains from 1 up to 20%. The experimental data obtained have been summarized by the time-temperature superposition principle. Relative intensity of stress relaxation (the stress drop in 10³ s divided by the initial stress) has been observed to increase together with the growth of draw ratio despite the enhancement of the short-term properties. The radiation cross-linking of the PE-1 samples may only decrease the stress relaxation intensity by 30%. The relaxation properties of a number of oriented polyethylene samples produced by various techniques were compared. It has been established that all the investigated materials are characterized by similar values and high relative drops in stress, whereas the short-term properties are essentially different. It points out to the relaxation processes being intensive both in the oriented and unoriented PE.     

Roll-drawing and die-drawing of toughened poly(ethylene terephthalate). Part 2. Fracture behaviour

Orientation of polymers in the solid-state has been used for a long time in enhancing the properties of the products and the die-drawing process at Leeds University (UK) and the roll-drawing process at IMI (Canada) have been used to produce oriented polymer products in a wide variety of shape and sizes. In this work, we explore the fracture behaviour of isotropic and oriented toughened poly(ethylene terephthalate) (PET) in order to improve the toughness of the oriented products in a direction other than the principal draw direction.The fracture behaviour of isotropic and oriented PET homopolymer and the two PET blends (containing 10% polyethylene elastomer and 10% compatibilized elastomer) was studied using the multi-specimen J-integral approach. In the isotropic case, the compatibilized blend had higher toughness than the homopolymer and the non-compatibilized blend. The oriented sheets from the die-drawing and roll-drawing process, drawn to a draw ratio of 3.2 at 170 °C were tested with the initial notch both parallel and perpendicular to the draw direction. For the former case, the compatibilized blend was tougher and in the other direction the drawn homopolymer was tougher than the blends. At similar draw ratios, the fracture behaviour and the toughness of the oriented sheets from the die-drawing and roll-drawing processes were identical.     

Preparation of ultra-high modulus linear polyethylenes; effect of molecular weight and molecular weight distribution on drawing behaviour and mechanical properties

A systematic investigation of the effect of molecular weight and molecular weight distribution on the cold drawing behaviour of linear polyethylene has been undertaken. In the molecular weight range studied, the natural draw ratio was very sensitive to the morphology of the initial material; spectacular effects on the natural draw ratio were observed provided that an optimum initial morphology was achieved. These effects can be related to both molecular weight and molecular weight distribution.The extensional modulus and melting behaviour of the drawn material was also examined. To a first approximation the extensional modulus related to the natural draw ratio, and at very high draw ratios (～30) extremely high extensional moduli (～700kbar) were obtained. The structure and properties of the drawn material did, however, also depend on the molecular weight and molecular weight distribution. In particular, when certain molecular weight requirements were satisfied, the oriented samples showed the presence of extended chain material. It does, however, appear that although differences in molecular weight and molecular weight distribution give rise to differences in extensional moduli, the presence of extended chain crystallization per se is not a necessary requirement for the production of high modulus material.     

Uniaxial deformation of overstretched polyethylene: In-situ synchrotron small angle X-ray scattering study

Synchrotron small angle X-ray scattering was used to study the deformation mechanism of high-density polyethylene that was stretched beyond the natural draw ratio. New insight into the cooperative deformational behavior being mediated via slippage of micro-fibrils was gained. The scattering data confirm on the one hand the model proposed by Peterlin on the static structure of oriented polyethylene being composed of oriented fibrils, which are built by bundles of micro-fibrils. On the other hand it was found that deformation is mediated by the slippage of the micro-fibrils and not the slippage of the fibrils. In the micro-fibrils, the polymer chains are highly oriented both in the crystalline and in the amorphous regions. When stretching beyond the natural draw ratio mainly slippage of micro-fibrils past each other takes place. The thickness of the interlamellar amorphous layers increases only slightly. The coupling force between micro-fibrils increases during stretching due to inter-microfibrillar polymer segments being stretched taut thus increasingly impeding further sliding of the micro-fibrils leading finally to slippage of the fibrils.     

A DSC study of oriented samples of a blend of linear and branched polyethylene

Summary Differential scanning calorimetry (DSC) of cold-drawn samples of a blend of linear (LPE) and branched polyethylene (BPE) shows that the melting point of the high temperature peak decreases monotonically with increasing draw ratio. This is in apparent contradiction to the data obtained for pure LPE, for which quite unanimously the melting point has been shown to increase with increasing draw ratio. An explanation of this deviation in behaviour between the blend of LPE and BPE and the pure LPE is proposed based on the idea that the transformation of the lamellar structure to a fibrillar structure involves several kinds of rearrangement including a mixing on a supermolecular level of the originally segregated LPE and BPE components. The crystal rearrangements occurring on heating (in the DSC) in oriented pure LPE that are responsible for the high melting point of this system are thereby hindered.     

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.     

The effect of orientation on radiation-induced degradation in high density polyethylene

The oxidative degradation of cold drawn highly oriented high density polyethylene is studied by IR spectroscopy. Both gamma and ultraviolet radiation sources are used. It is found that under gamma radiation the oxidative degradation, as determined from carbonyl formation, is reduced very significantly but that the trans-vinylene unsaturation in the polymer increases with draw ratio. Similar results are obtained for samples irradiated in vacuum or when the polymer is stabilized with a radical quencher. Annealing (with free-ends) of the samples restores the rate of carbonyl formation over and above that of the undrawn polymer although restoration after annealing with fixed-ends is not complete. There, is further increase in trans-vinylene development after annealing. In stabilized samples, the effect of annealing on carbonyl and trans-vinylene development appears to depend on draw ratio. Under ultra-violet radiation, the oxidative degradation of drawn and unannealed samples is also reduced with increasing draw ratio. The same effect is observed in stabilized samples. Annealing, once again, restores the rate of oxidative degradation to that of the undrawn polymer. The main unsaturation product during ultraviolet irradiation is the vinyl end group and its development is suppressed with drawing. During ultraviolet irradiation of unannealed drawn samples, cracks, generally perpendicular to the draw direction (intrafibrillar cracks) appear on the sample and with further irradiation they penetrate into the sample. In the case of stabilized and unannealed drawn samples, cracks parallel to the draw direction (interfibrillar cracks) appear first and continued irradiation results in the appearance of intrafibrillar cracks. These observations may have significance in modelling the fibrous structures obtained by drawing semicrystalline polymers.     

Effect of molecular weight on the morphology and drawing behaviour of melt crystallized linear polyethylene

The effect of molecular weight on the cold drawing behaviour of melt crystallized linear polyethylene has been studied. It is shown that the draw ratio achieved under comparable conditions rises with decreasing $\text{M}\text{?}{}_{\mathrm{w}}$, very high draw ratios (～36) being possible for optimum morphology of the undrawn polymer. The yield behaviour was also examined, and it is shown that the yield stress is affected in a complex fashion by both crystallization conditions and molecular weight. These results are discussed in terms of the crystallization and morphology of the melt crystallized polymer.     

Structure-property relationships on uniaxially oriented carbon nanotube/polyethylene composites

Multi walled carbon nanotubes have been incorporated into a linear low density polyethylene matrix through high energy ball milling technique at room temperature, without any chemical modification or physical treatment of the nanotubes. Highly oriented samples, with different draw ratios, were obtained by drawing at 80 °C the composite films. SEM and FTIR results on the drawn PE films demonstrate that the molecular chains in both crystalline and amorphous phases are well oriented along the drawing direction. The effect of different weight percent loadings of nanotubes and draw ratio on the morphology, thermal, mechanical and electrical properties of the composite fibers have been investigated.     

The influence of the draw ratio of melt-spun polyethylene fibres on γ-irradiation induced effects as observed by ESR

The influence of draw ratio on free radical behaviour in melt-spun polyethylene fibres has been examined using ESR spectroscopy. The stability of free radicals produced by γ-irradiation is greatest some where between draw ratio 1 and 10. The general trend of radical stability has been found to correlate with the trend of gel content with draw ratio. The possible link between the extent of crosslinking and the production of stable radicals has been discussed in terms of morphological aspects.     

Functionalization of high density polyethylene in melt state through ultrasonic initiation and its effect on mechanical properties of glass fiber reinforced composites

Summary Functionalization reaction of high density polyethylene (HDPE) with γ-methacryloxy-propyltrimethoxysilane (MAS) or with MAS and MAH performed in melt state through ultrasonic initiation by a laboratory-scale ultrasonic extruding reactor was studied in this paper. The effect of ultrasonic intensity on the percentage of grafting and melt flow rate of the functionalized products was investigated. The results show that by imposing ultrasonic vibration during melt-extruding process, the scission of HDPE chain bonds can be caused to form macroradicals, the functionalization reaction of HDPE with MAS or with MAS and MAH can be realized. The percentage of grafting and the melt flow rate of the functionalized products depend upon the ultrasonic intensity and reaction temperature. The fuctionalization reaction of HDPE with MAS can be promoted by adding a second grafting monomer MAH. The ultrasonic-induced products have a higher reactivity with the coupling agents coated on the surface of glass fibers, the mechanical properties of the composite improved by the ultrasonic induced product are higher than that of by peroxide initiated product and the mechanical properties of HDPE/GF composite modified by HDPE-g-MAH-MAS are higher than that of by HDPE-g-MAH. The SEM experimental results indicate that an oriented crystal layer exists between the interface of glass fiber and the HDPE matrix, the interfacial bonding strength is the determining factor of the formation of the oriented crystal layer.