The influence of drawing,twisting, heat setting,and untwisting on the structure and mechanical properties of melt-spun high-density polyethylene fiber

The variation of crystalline morphology and mechanical properties of polyethylene fibers was studied as they were sequentially melt spun, drawn, twisted, heat set, and untwisted. Twisting of as-melt spun fibers was also investigated. The morphology was characterized using wideangle x-ray diffraction, small-angle x-ray diffraction, and scanning electron microscopy techniques. Drawing results in high crystalline orientation, fibrillation, and large increases in modulus and tensile strength. Effects due to variation of spinning conditions were noted. Twisting either as-spun or drawn fibers decreased the axial orientation, modulus, tensile strength, and usually also the elongation to break. The changes in these properties increased with twist angle. Twisting also caused transformation of a small fraction of the sample to the monoclinic form of polyethylene. Heat setting caused healing of voids generated during drawing and increased the perfection and periodicity of the stacking of lamellar crystals along the fiber axis. Heat setting also caused the monoclinic polyethylene to transform back to the orthorhombic form, and it increased the modulus and tensile strength. Untwisting returned the orientation in the fiber to essentially that which it would have if it had not been twisted, but untwisting also resulted in the formation of kink bands.     

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.     

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。     

Oriented crystallization in fiber formation: Inferences from the structure and properties of melt spun syndiotactic polypropylene filaments

In processes, such as melt spinning, the crystallization behavior of syndiotactic polypropylene (sPP) is found to be substantially different from that of most other linear polymers. The anisotropic stress field in such processes leads invariably to extension as well as alignment (orientation) of the chains in the melt, both of which contribute usually to dramatic enhancement in the rate of crystallization. However, since the primary structure of the sPP chain in its most preferred crystal form is comprised of a “coiled helical,” ? (T₂G₂)₂? , sequence, stress‐induced chain extension can lead to conformational sequences that are not favorable for crystallization in this form. As a consequence, process conditions that generate higher stress levels can cause a diminution in the rate of crystallization of this polymer. Such conformation‐related aspects of oriented crystallization of sPP have been addressed through an analysis of the structure and properties of melt‐spun fibers, produced over a range of spinning speeds. The results serve to identify a refinement that is needed in current models of oriented crystallization and also a mechanism to promote the nucleation of crystallization of sPP. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2305–2317, 2001     

Improving the mechanical properties of polypropylene via melt vibration

The effect of melt vibration on the mechanical properties of polypropylene prepared by low-frequency vibration-assisted injection molding (VAIM) has been investigated. With the application of melt vibration technology, the mechanical properties of polypropylene are improved. The yield strength increases with the increment of the vibration frequency, and a peak stands at a special frequency for VAIM; the elongation at break decreases first and then increases with increasing vibration frequency, and a valley stands at a special frequency. The tensile properties increase sharply at an enlarged vibration pressure amplitude with sharply decreased elongation at break. The Young's modulus and impact strength also increase with the vibration frequency and pressure vibration amplitude. When it is prepared at 59.4 MPa and 0.7 Hz, the maximal yield strength is approximately 40 MPa versus 33.7 MPa for a conventional sample; an 18.7% increase in the tensile strength is produced. Self-reinforcing and self-toughening polypropylene molded parts have been found to be prepared at a high vibration frequency or at a large pressure vibration amplitude. Scanning electron micrographs have shown that, in the vibration field, the enhancement of the mechanical properties is attributable to more pronounced spherulite orientation and increased crystallinity in comparison with conventional injection moldings. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and structural properties of melt spun polypropylene/nylon 6 alloy filaments

Investigated in the present study are the physical properties, morphology, and structure of PP/N6 alloy filaments (10, 20 wt % N6) made with or without PP‐g‐MAH as compatibilizer. The alloy filaments produced at the take‐up speeds of 300 and 800 m/min were drawn with draw ratio of 3.5 and 2, respectively. Stress–strain curves of PP and alloy filaments show ductile and brittle behavior, respectively. It is suggested that the brittle behavior of alloy filaments is due to the presence of microvoids or micropores at the interface of PP and N6; these lead to stress concentration and thus to a decrease in tenacity, modulus, and elongation at break. Effects of the blending of N6 with PP on birefringence and crystalline and amorphous orientation factors of the composite filaments are studied. The amorphous orientation factor, f_am, of PP was found to increase with an increase in the amount of N6. The alloy filaments behaved like isostrain materials and most of the force in spinning and drawing was born by the PP phase. The presence of N6 fibrils helped to orient PP chain molecules in amorphous regions. However, the crystalline factor, f_c, of PP decreased with the increase in nylon fraction. This means the presence of the crystals of N6 caused a decrease in the orientation of the PP crystals. LSCM micrographs of the filament showed the presence of matrix–fibril morphology with the N6 fibrils oriented along the axis. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 532–544, 2005     

The influence of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers

An investigation was carried out on the effects of annealing treatment on the molecular structure and the mechanical properties of isotactic polypropylene fibers annealed in an air heated environment at temperatures ranging from 60 to 140°C. Analysis of the equatorial X‐ray diffraction traces showed the presence of a three phase system of amorphous‐smectic‐monoclinic forms and revealed the transformation of the metastable smectic form to the highly stable monoclinic form as the annealing temperature is increased, resulting in an enhanced degree of crystallinity and the crystallite size. The improvements in the degree of crystallinity and the crystallite size became more remarkable above 120°C. Evaluation of the crystallinity was carried out using an analysis of density, infrared spectroscopy, and X‐ray diffraction methods whereas the state of the molecular orientation was evaluated using polarized infrared spectroscopy measurements only. Polarized infra‐red spectroscopy measurements after the curve fitting procedure showed a slight increase of the molecular orientation of the helical chain segments present in the crystalline phase represented by the IR bands at 841 and 998 cm^?1 whereas the amorphous structure represented by the IR band at 974 cm^?1 showed no significant change with increasing annealing temperature. The improvement in the molecular orientation of the crystalline phase became more remarkable above 120°C. Tensile strength of the annealed fibers increased with increasing annealing temperature but the elongation at break and the initial modulus were not affected as much as the tensile strength. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

The influence of processing parameters on the properties of melt‐spun polypropylene hollow fibers

Isotactic polypropylene hollow fibers were produced by melt spinning. Spinning speeds up to 1880 m/min were used, and sample hollowness (percentage void in cross section) ranged from 0 to 69%. The fiber samples were characterized using dynamic mechanical analysis, birefringence, tensile testing, and differential scanning calorimetry. The hollow fibers were found to have higher crystallinity, orientation, and strength than the analogous solid fibers. In general, the polymer orientation in a hollow fiber was larger than the orientation in a solid fiber, even when the spinning speed for the latter was much larger. For a fixed outer diameter, increasing the hollowness improved fiber properties. However, as hollowness was further increased, fiber properties declined slightly. At a given percentage hollowness, increased spinning speed increased modulus and tenacity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1759–1772, 2002     

The influence of structure and processing conditions on engineering mechanical properties in bulk crystallized isotactic polypropylene

A study of the influence of processing conditions and structure on engineering mechanical properties was conducted in bulk isotactic polypropylene. The influence of one processing parameter, undercooling, defined so as to account for both pressure and temperature effects, was particularly studied. Improved mechanical properties were found with increased undercooling. At low undercoolings, brittle failure without yield occurred, presumably the result of a sparsity of intercrystalline links under these conditions. As undercooling was increased, failure occurred after yielding as failure stress elevated dramatically, apparently because of greater link density. A modest improvement in yield stress with increased undercooling was attributed to the increasingly crosshatched lamellar structure produced at higher undercoolings, a structural trend confirmed by electron microscopy. Spherulite size, varied by altering melt history (melt temperature and time at melt temperature) at constant undercooling, was found to have no effect on engineering yield stress. This result indicates that apparent yield stress–spherulite size effects found by several earlier investigators were probably caused by structural variations other than spherulite size.     

Effect of cryo-ground rubber on melt flow and mechanical properties of polypropylene

The influence of cryo-ground rubber (CGR) on melt flow and mechanical properties of polypropylene has been investigated. Cryo-ground rubber was incorporated in the polypropylene matrix (a) in powder form and (b) as masterbatch with natural rubber. Natural rubber was found essential as a dispersing agent. The loading of cryo-ground rubber has no significant effect on viscosity at high shear rates (>61 s^?1) but at lower shear rates (>61 s^?1), viscosity functions change shape with increasing cryo-ground rubber content. The dynamic mechanical properties revealed that polypropylene is thermodynamically incompatible with natural rubber and cryo-ground rubber. Cryo-ground rubber in the powder form shows poor adhesion to polypropylene matrix and, therefore, decreases the impact strength at higher loading. Addition of masterbatch of cryo-ground rubber and natural rubber improves the impact strength of polypropylene.     

The influence of extrusion parameters on the mechanical properties of polypropylene sheet

Extruded thermoplastic sheet is widely used in the production of thin-gauge tubs and containers for the food and beverage industry using the thermoforming process. The production of high quality thermoformed parts is critically dependent on the standard of extruded sheet feedstock used. The extrusion process itself imparts a thermal history to the sheet, and this in turn partly dictates its subsequent thermoformability. This paper assesses the influence of various extrusion parameters on the mechanical and morphological properties of polypropylene sheet, with a view to defining the optimum extrusion conditions for polypropylene. The extrusion parameters under consideration are chill-roll temperature, line speed, sheet thickness and melt temperature.     

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.     

热水浴拉伸对聚丙烯腈初生纤维结构和性能的影响

研究了聚丙烯腈(PAN)初生纤维在热水浴拉伸过程中超分子结构和力学性能的变化。结果表明:PAN初生纤维中的内应力随拉伸温度的升高而减小,随拉伸速率和拉伸倍数的提高而增大;初生纤维在热水浴中的玻璃化转变温度约为80℃,当水浴温度低于和高于80℃时,纤维分别发生冷拉和高弹形变;PAN初生纤维的结晶度和晶区取向度随拉伸温度的升高先增大后减小,随拉伸速率和拉伸倍数的升高而增大。     

Structural evolution and mechanical properties of iPP melt spun fibers subjected to thermal treatment

An investigation of the structure and mechanical behavior of melt-spun isotactic polypropylene (iPP) fibers subjected to thermal treatment in an inert atmosphere is described. Two iPP formulations, Basell Pro-fax PH835 and ExxonMobil Achieve 3854, synthesized by the Ziegler-Natta and metallocene catalysts respectively, and spun at take-up velocities of 1000 to 3000 m/min are considered. The evolution of the structure is monitored with WAXS, SAXS, Raman spectroscopy and birefringence measurements. The fibers spun at 1000 m/min are predominantly mesomorphic, while those spun at 3000 m/min are semi-crystalline in the as-spun state. Thermal treatment for 20 min at 145 °C erases the processing history and increases the crystallinity of all samples. It is shown that thermal treatment leads to the formation of a secondary set of kebab lamellae which are thinner than the original ones, separated by thicker lamellae. The spatial variability of the lamellar thickness and of interlamellar spacings is estimated from the SAXS data and it is concluded that the variability is rather pronounced in all samples. Both annealed and non-annealed fibers are subjected to monotonic and cyclic mechanical testing. Large differences are seen in the behavior of non-annealed fibers processed in different conditions. The monotonic mechanical behavior of the annealed fibers is not very much different from that of the corresponding non-annealed fibers. The central difference between annealed and non-annealed samples is observed in the cyclic behavior; annealed samples containing lamellae with bimodal distribution of thickness exhibit bimodal hysteresis curves while this feature is not observed in non-annealed samples.     

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℃。     

The relationship between mechanical properties and structure in rolled polypropylene

The relationship between mechanical properties and fine structure has been studied in polypropylene rolled both unidirectionally and biaxially (cross rolled). In unidirectionally rolled samples, a complex dependence with cold work is observed with a substantial change being observed at about 50 percent cold work. At 70 percent cold work, the yield strength and tensile strength increase substantially in the roll direction as compared with the starting billet but decrease only slightly in the transverse direction. Above 50 percent cold work, Young's modulus increases rapidly in the roll direction with a smaller increase in the transverse direction. The elongation to freak decreases in the roll direction but increases in the transverse direction. A striking feature is the large increase in ductility due to a small amount of cold work (ca., 10-20 percent). Analogous property changes are observed for cross rolled samples although no significant variation with direction in the sheet was found. The complex property changes are accompanied by complex changes in the molecular orientation as observed by wide angle X-ray pole figures and by changes in the morphology as observed with small angle x-ray scattering. These changes are interpreted in terms of a model incorporating tilting both of lamellae and of chain stems within the lamellae at early stages of rolling followed by breakup of lamellae and molecular rearrangement at later stages.     

The influence of molecular weight on the melt rheology of polypropylene

Melt viscosity and melt elasticity data were obtained over a broad range of temperatures and shear rates on a series of four polypropylenes of different molecular weight but approximately the same molecular weight distribution. The superposition technique was used with both temperature and molecular weight to shift flow curves for all four materials at three temperatures each along the shear rate axis to generate a master flow curve at a given temperature and molecular weight. For polypropylenes of this type, and molecular weight distribution shift, factors which can be used to extend the useful range of experimentally obtained flow data were determined. The dependency of apparent viscosity on weight average molecular weight at shear stresses as high as 10⁶ dynes/cm² is shown. The dependency of melt elasticity on molecular weight and temperature is discussed.     

Ultra-high modulus isotactic polypropylene. I. The influence of orientation drawing and initial morphology on the structure and properties of oriented samples

The influence of a number of factors (temperature–speed regime and the quantity of draw stages, molecular weight of a polymer, etc.) on the deformability of initial isotropic IPP and on mechanical characteristics of highly-oriented samples, obtained in the process of a two-stages isothermal orientation drawing, was studied. It was shown that the maximum achievable values of elastic modulus and draw ratio depended not only on the molecular weight of a polymer and the sizes of spherulites, constituting initial IPP, but on the structural organization of inner-and interspherulite regions. Upon physical aging of initial isotropic films, irreversible structural changes take place, which result in the formation of microvoids while being drawn and in the reduction of mechanical properties of obtained material. An extremal dependence of elastic modulus and draw ratio of maximum drawn IPP samples on draw speed was discovered. A structural model, which is supposed to possesstie molecules with various degrees of tautness in amorphous layers, was proposed. Higher effectiveness of two-stage drawing in comparison with one-stage drawing was established. The optimum temperature–speed regime of orientation drawing, which permits the reception of highly oriented, ultra-high modulus IPP with maximum high mechanical characteristics (elastic modulus ～ 30–35 GPa and tensile strength ～ 1,1 GPa), was determined.