The influence of drawing,twisting, heat setting and untwisting on the structure and mechanical properties of melt spun polypropylene filament

The changes in structure and mechanical properties of melt spun polypropylene filaments were determined as the filaments were successively (i) drawn, (ii) twisted, (iii) annealed, and (iv) untwisted. Filaments spun to two different melt draw down levels were studied. The effects of draw temperature and draw ratio, extent of twist, annealing temperature, and the extent of untwisting were examined. Melt spun and twisted filaments (draw ratio of 1) were also considered. Structural characterization techniques used in this study include wide angle (WAXS) and small angle (SAXS) diffraction, scanning electron microscopy (SEM), birefringence and density measurement. Drawing increased crystalline orientation and at low temperatures disrupted the monoclinic unit. cell existing in the melt spun fibers. The drawing produced considerable fibrillation under all conditions even when carried out at 120°C. The fibrillation quid void formation due to low temperature drawing was more pronounced. The variation of WAXS patterns and mechanical properties of twisted drawn filaments was interpreted by presuming that the fibrils act in a manner analogous to that of the filaments in a continuous filament twisted yarn. In the case of incompletely drawn filaments the effect of additional drawing occurring during twistin must be considered. Twisted fibers annealed at 150°C sowed a drastic reduction in tensile properties, while those annealed at 125°C did not set the twist and caused the fibers to tend to untwist. Annealing at 140°C appeared to give satisfactory heat setting. Annealing of cold drawn and cold drawn and twisted fibers increased the density, removed many defects and reformed a well defined monoclinic crystal structure and a lamellar morphology. Untwisting of heat set filaments tended to give back the properties of hot drawn fibers. In some cases, however, the opening of cracks was noted.     

Interaction of melt spinning and drawing variables on the crystalline morphology and mechanical properties of high-density and low-density polyethylene fiber

An experimental study of the spinnability and the variation in crystallinity and orientation in high-density and low-density polyethylene fibers with melt spinning and drawing conditions has been carried out. Three polymers (two high-density and one low-density) and eicosane (C₂₀H₄₂) were studied. The maximum spinnability was in the lower molecular weight high-density polyethylene. Hermans-Stein a, b, and c crystallographic axis orientation factors were computed from wide-angle x-ray scattering patterns. In the spun fiber, small take-up velocities cause the b axis to become perpendicular to the fiber axis in each fiber. The c axis increasingly orients itself parallel to the fiber axis as take-up velocity increases. The a axis orientation is different for each polymer. The results are interpreted in terms of modern theories of crystalline morphology, specifically the development of row structures. In the drawing experiments, the two high-density polyethylenes necked. A phenomenological theory of necking is discussed. The a, b, and c axis orientation factors were determined for different stages of drawing. In the necked regions and in completely drawn fibers, the c axis was parallel to the fiber axis and the a and b axes are perpendicular to the fiber axis. The tangent Young's modulus and tensile strength of the spun fibers increased with take-up velocity and in the drawn fibers were an order of magnitude higher than in the spun fiber. The mechanical properties of spun fiber may be correlated with the c axis (Hermans) orientation factor. The drawn fiber shows significant variations in Young's modulus and tensile strength at constant unit cell orientation.     

拉伸热定型对PET-PA/PA6共混纤维结构与性能的影响

以聚酯-聚酰胺共聚物/聚酰胺6(PET-PA/PA6)共混物为原料,采用熔融纺丝法制备了PET-PA/PA6共混纤维,讨论了拉伸热定型工艺对PET-PA/PA6共混纤维结构与性能的影响。结果表明:随拉伸倍数的增大,PET-PA/PA6共混纤维的断裂强度、取向度、结晶度以及沸水收缩率均明显增大;拉伸温度和热定型温度对PET-PA/PA6共混纤维的断裂强度和取向度的影响相对较小;随拉伸温度的升高,PET-PA/PA6共混纤维的断裂强度、取向度和结晶度呈现先增大后减小的趋势,并在拉伸温度为85℃时出现最大值;随热定型温度的升高,PET-PA/PA6共混纤维的结晶度增大、沸水收缩率减小;较佳的工艺条件为拉伸倍数1.6,拉伸温度85℃,热定型温度150℃。     

熔纺UHMWPE纤维结构和力学性能初探

采用超高相对分子质量聚乙烯(UHMWPE)切片进行熔融纺丝,拉伸倍数为22～25,对制得的熔纺UHMWPE纤维的力学性能进行测试,用扫描电镜(SEM)和X射线衍射(XRD)仪对熔纺及凝胶纺UHMWPE纤维的表面形貌和结晶性进行了表征。结果表明:熔纺UHMWPE纤维的断裂强度为17.02 cN/dtex;相比凝胶纺纤维,熔纺纤维线密度大,纵向沟壑多;熔纺UHMWPE纤维结晶度为64.76%,比凝胶纺纤维的稍低,但其取向因子为0.993,大于凝胶纺纤维的。     

Effect of mechanical recycling on crystallization,mechanical, and rheological properties of recycled high-density polyethylene and reinforcement based on virgin high-density polyethylene

This study investigated the effects of mechanical recycling on the crystallization, mechanical, thermal, and rheological properties of recycled high-density polyethylene (rHDPE), as well as vHDPE/rHDPE pellets and films made by different compositions. The results confirmed the presence of contaminants in rHDPEs, and the crystalline diameter of rHDPE is smaller than that of virgin high-density polyethylene (vHDPE), with diameters ranging from 0.60 to 0.72 μm. The content of 75 wt% vHDPE in rHDPE film could repair the defects of crystalline morphology to approximate that of vHDPE films and significantly improve the elongation at break. The temperature required for the transition from crystalline to amorphous state of rHDPE film was 2°C lower than that of vHDPE, and the crystallization time and crystallinity declined compared to that of vHDPE. For rheological performance, the apparent shear viscosity and melt fluidity of rHDPE were worse than those of vHDPE. The blending of low rHDPE with vHDPE is a feasible option not only to reduce plastic waste but also to maintain acceptable properties of the blend composition.     

The enhancement of the mechanical properties of a high-density polyethylene

This paper describes the process optimization in injection molding of high-density polyethylene (HDPE). Both conventional injection molding and shear controlled orientation (SCORIM) were employed in processing. The process optimization was based on design of experiments and complemented with analysis of variance. Mechanical characterization was carried out by tensile testing. Wide-angle X-ray diffraction and differential scanning calorimetry were used for the structural characterization of the moldings. High-density polyethylene exhibits 7.2 GPa Young's modulus and 155 MPa of ultimate tensile strength following the application of SCORIM processing. These results account for a fourfold increase in Young's modulus and a fivefold increase in ultimate tensile strength compared to conventional injection molding. The maintenance of toughness while enhancing stiffness and strength of the SCORIM moldings is attributable to an oriented morphology developed during shear flow, i.e., shish-kebab structure. The frequency of shearing action has the strongest influence on the morphology development. It is also demonstrated that the studied parameters are very much interdependent. It is possible to achieve substantial gains in mechanical properties of HDPE in SCORIM processing without causing a substantial increase in cycle time. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2473–2483, 1999     

Photooxidative effects on properties and structure of high-density polyethylene

The environmental degradation of high-density polyethylene (HDPE) has been studied, in addition to that of HDPE blends, containing various concentrations of ethylene carbon monoxide copolymer. Extruded sheets of each material were exposed to natural Arizona sunlight for times up to 6 months. Exposed samples were then analyzed with respect to molecular weight, density, thermal behavior, mechanical properties, and infrared absorption. Additional samples were exposed to laboratory weathering conditions, evaluated in terms of property changes, melted, reformed, and then reevaluated without further weathering exposure. Results indicate that sunlight exposure causes decreased elongation to break, increased embrittlement, decreased molecular weight, and increased crystallinity. Environmental oxidative degradation is elucidated by the measurement of specific infrared bands, sensitive to the formation of carbonyl and vinyl end groups. As environmental degradation causes reductions of molecular weight, polymer chain mobility increases, leading to a higher degree of crystallinity. This increased crystallinity, along with the decreased molecular weight, accounts for the loss of ductility, indicated by a sharp decrease in ultimate elongation. The presence of carbon monoxide copolymer in the blended samples accelerates the process of environmental degradation, however, the degradation mechanisms appear to be similar to those observed for nonblended HDPE. © 1994 John Wiley & Sons, Inc.     

The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. III. Anelastic properties and their dependence on structure

Viscoelastic parameters for poly(ethylene terephthalate) (PET) fibers heat set under different conditions were determined at 110 Hz between room temperature and about 200°C. The correlation of dynamic mechanical properties with structure and their dependence on the temperature of the measurement are discussed. It was found that in addition to the structural parameters such as degree of crystallinity, crystallite and amorphous orientation, etc., morphological factors such as size and distribution of crystallites also influence the dynamic mechanical properties. The activation energy of the α-transition is reported, and the effect of the distribution of relaxation times on the activation energy is discussed.     

拉伸与热定型对聚苯硫醚长丝结构性能的影响

以国产聚苯硫醚(PPS)树脂为原料,用熔融法纺丝制得PPS长丝。采用差示扫描量热仪、热重分析仪研究了后处理对纤维结晶和热性能的影响;利用声速取向测量仪研究了拉伸对纤维取向的影响;用单纱电子强力仪测量了纤维力学性能。结果表明:热拉伸倍数增大,PPS纤维取向度、结晶度增加,纤维的断裂强度增加,断裂伸长减小;拉伸倍数大于5,会出现较多毛丝和断头;控制热拉伸温度85～105℃,热定型温度100℃以上;纤维的结晶主要在热拉伸过程中基本完成,热定型进一步完善结晶结构;高温下氧气的存在,会使PPS纤维发生严重的氧化降解。     

Morphological considerations on the mechanical properties of blown high-density polyethylene films

Blown films having a broad range of morphologies were prepared from high-density polyethylenes (HDPE) with unimodal and bimodal molecular weight distribution under several processing conditions, and the effect of their morphological features on the dart drop impact resistance, Elmendorf tear strength, and tensile properties of the films has been studied. The organization of lamellar stacks seems to play a critical role on the mechanical properties of the blown HDPE films. The dart drop impact resistance of the blown HDPE films is highly dependent on the presence of the network structure of lamellar stacks and the level of the intraconnectivity and interconnectivity of lamellar stacks. The coherent orientation of lamellar stacks leads to significant anisotropy of tear and tensile properties. © 1997 John Wiley & Sons, Inc.     

拉伸对聚芳砜酰胺(PSA)纤维力学性能的影响

研究了聚芳砜酰胺(PSA)纤维制备过程中各阶段拉伸倍数对纤维最终力学性能的影响,并制备出最高断裂强度达到3.62 cN/dtex的PSA纤维。要得到综合力学性能较高的PSA纤维,合适的表观喷头拉伸倍数为-50%～30%、塑化拉伸倍数为2、热拉伸倍数为2。PSA为较难结晶的高聚物,不论是聚合物粉末还是拉伸纤维,其结晶度都较低。PSA纤维的大分子取向与纤维的断裂强度关系十分密切,大分子取向因子与纤维的断裂强度呈线性关系,提高大分子取向程度是提高PSA纤维强度的重要途径。     

The influence of drawing temperature on mechanical properties and organization of melt spun polyethylene solid-state drawn in the pseudo-affine regime

Mechanical properties of high density polyethylene (HDPE) solid-state drawn with fixed draw ratio at different temperatures in a fiber/tape spin line were investigated. All drawing experiments were performed in the pseudo-affine regime, i.e. no effective relaxation of the molecules occurs during drawing. For such conditions, the Young's modulus is uniquely determined by the applied draw ratio. The general appearance of the stress-strain behavior of drawn HDPE, and in particular its yield strength, however, is strongly influenced by the stretching temperature applied. For a fixed draw ratio, a significant drop in yield stress can be observed with decreasing drawing temperature. Characterization of structure and organization of the solid-state drawn HDPE was performed using various analytical techniques, such as wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). It is proposed that solid-state drawing at temperatures above the α-relaxation temperature results in relative large crystals so that corresponding tapes show a high yield point. Drawing at low temperatures below the α-relaxation temperature of PE, however, causes formation of small or imperfect crystals that can be destructed at low stress (low yield point), which is a preferable start situation for a second solid-state drawing step in a multiple drawing process.     

超高相对分子质量聚乙烯纤维热牵伸性能研究

就超高相对分子质量聚乙烯纤维热牵伸过程的拉伸比和牵伸温度对纤维力学性能的影响进行了试验.研究结果表明,拉伸比4.5～6.0和牵伸温度144～150℃是最适合超高相对分子质量聚乙烯纤维热牵伸的关键参数,纤维力学性能可以达到拉伸强度35 cN/dtex和拉伸模量1 100 cN/dtex以上.     

The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. I. Structural changes

We report structural changes in commercial multifilament poly(ethylene terephthalate) (PET) yarn when it is heat set in silicone oil over a range of temperatures between 100 and 220°C for times ranging from 1 min to 1 hr, while the yarn was (1) free to relax, and (2) held taut at constant length. In one case, viz., a sample heat treated for 1 hr, the cooling time was also varied to study the effect of rate of cooling. The free-annealed and taut-annealed samples showed considerable differences. The predominant role of the temperature of heat setting on structure is discussed in detail. There are considerable changes in the amount and orientation of the amorphous phase, and these will be shown to have important influence on mechanical properties in subsequent reports.     

Thermal and mechanical properties of aluminum powder-filled high-density polyethylene composites

Thermal conductivity and mechanical properties such as tensile strength, elongation at break, and modulus of elasticity of aluminum powder-filled high-density polyethylene composites are investigated experimentally in the range of filler content 0–33% by volume for thermal conductivity and 0–50% by volume for mechanical properties. Experimental results from thermal conductivity measurements show a region of low particle content, 0–12% by volume, where the particles are distributed homogeneously in the polymer matrix and are not interacting with each other; in this region most of the thermal conductivity models for two-phase systems are applicable. At higher particle content, the filler tends to form ag-glomerates and conductive chains resulting in a rapid increase in thermal conductivity. The model developed by Agari and Uno estimates the thermal conductivity in this region. Tensile strength and elongation at break decreased with increasing aluminum particles content, which is attributed to the introduction of discontinuities in the structure. Modulus of elasticity increased up to around 12% volume content of aluminum particles. Einstein's equation, which assumes perfect adhesion between the filler particles and the matrix, explains the experimental results in this region quite well. For particle content higher than 30%, a decrease in the modulus of elasticity is observed which may be attributed to the formation of cavities around filler particles during stretching in tensile tests. © 1996 John Wiley & Sons, Inc.     

Influence of soapstone waste on the mechanical and rheological properties of high-density polyethylene

Soapstone is an abundant mineral in Ouro Preto - Minas Gerais, Brazil and its main destination is in the production of craftsmanship. Rock recovery in those activities is low and the waste disposal is done with little control, which can be hazardous to the environment. This work proposes an alternative use of such potentially harmful waste as reinforcement in a novel polymer matrix composite, which can be particularly attractive to the automotive industry and of which very little information is available elsewhere in the literature. Firstly, the characterization of the waste was performed. Particle size and shape parameters were determined by automated image analysis and the mineralogical composition was determined by X-ray diffraction, infrared, and Raman spectroscopy. High-density polyethylene was used as matrix and the composites were made in three matrix/filler ratios: 90/10, 80/20, and 70/30 by weight. Tensile and rheological properties were measured in order to determine the influence of the particles on the polymer mechanical behavior and processing conditions. The materials showed a pseudoplastic behavior and the filler's influence was more pronounced in the 70/30 composites, which showed higher viscosities than the neat polymer. The addition of particles resulted in more brittle and rigid composites, with higher values of tensile strength.     

The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. II. The elastic modulus and its dependence on structure

The effects of temperature, time of heat setting, and rate of cooling on the elastic modulus of free-and taut-annealed poly(ethylene terephthalate) (PET) fibers were determined at different time scales using Instron, Rheovibron, and pulse propagation meter. The correlation of the elastic modulus with structure is critically examined in terms of the widely used simple one-phase and two-phase models for fiber modulus. It is concluded that these simple models are not universally applicable.     

高密度聚乙烯/聚酰胺6复合纤维的制备及性能

以高密度聚乙烯(HDPE)为皮,以聚酰胺6(PA 6)为芯,采用皮芯复合纺丝方法制备了HDPE/PA 6复合纤维及复合色丝;对HDPE/PA 6复合纤维制备过程中的组分配比、纺丝与拉伸工艺进行了探讨,对复合纤维的截面形貌、力学性能及其织物的凉感性能进行了表征。结果表明:实验范围内,HDPE与PA 6切片的质量比为40:60时,可纺性良好,HDPE/PA 6复合纤维的初生纤维横截面皮芯结构清晰;当PA 6组分的螺杆挤出温度为260℃时,可纺性较好,在HDPE组分中添加质量分数1%～2%的专用改性母粒,可获得更好的纺丝效果;拉伸倍数为2.6～2.8时,制备的HDPE/PA 6复合纤维断裂强度达3.57～3.82 cN/dtex,且复合纤维面料的接触凉感系数达0.23 J/(cm~2·s),具有良好的接触瞬间凉感性能;制备的棕色HDPE/PA 6复合色丝的表观染色深度达5.437,复合色丝具有较好的染色性能。     

The effect of heat setting on the structure and mechanical properties of poly(ethylene terephthalate) fiber. IV. Tensile properties other than modulus and their dependence on structure

The stress-strain characteristics of poly(ethylene terephthalate) fibers, heat set under different conditions have been studied under tension, and mechanical properties such as tenacity, yield point, elongation at break, and work of rupture are presented and discussed. An attempt has been made to correlate these mechanical properties with structural parameters. The orientation of the molecules in the fiber and the size and distribution of the crystallites emerge as important factors controlling the tensile properties.     

Effects of mechanical drawing on the structure and properties of peek

This study examines the effects of crystallinity and temperature on the mechanical properties of PEEK. Crystallinity in PEEK Increases with annealing temperature up to a maximum of 28 percent with a melting point at 335°C. A minor melting peak also occurs about 10°C above the annealing temperature. In cold drawing the samples exhibited a yield stress and necking followed by homogeneous drawing. The yield stress increases with crystallinity, but there is no change in the modulus. The extension in the necking process also increases with crystallinity, however there is only a slight increase in extension-to-break since necking is compensated by the final amount of homogeneous drawing. The yield stress of PEEK when drawn at T_g (145°C) is significantly lower than at room temperature indicating a reduction in mechanical properties at temperatures approaching T_g. After mechanical drawing the minor melting peak disappears and on heating the material undergoes cold crystallization near the onset of T_g. There is evidence that this minor crystalline component might contribute to the yield stress changes with annealing history. Cold drawing induces crystallization of amorphous PEEK but decreases crystallinity and generates microscopic voids in crystalline PEEK, The various effects of crystallinity on mechanical properties could be important in determining the stress response of PEEK as the matrix in composites.