Heating of polymers during neck propagation

The heating of polyethylene terephthalate, polyamide-66, and polyamide-6 during tensile drawing at room temperature was studied theoretically and experimentally. At a low draw rate, the necking temperature was close to the temperature of the surrounding air. An increase in the rate results in the transition to the adiabatic conditions of drawing. A necking temperature of 140°C was experimentally recorded in polyethylene terephthalate at a draw rate of 1000 mm/min and during the approach to the adiabatic conditions of drawing. A formula describing the dependence of the necking temperature on the draw rate was derived. The resulting value agreed fairly well with the theoretical estimation of the temperature. The drawing (strain) ratio in the neck and the draw stress are the crucial parameters determining the temperature. The rate of the transition to the adiabatic conditions of drawing was determined. The temperatures of adiabatic heating for various polymers were calculated. The increases in the temperatures of polycarbonate and low- and high-density polyethylene are relatively low. The increases in temperature can be regarded as moderate for polypropylene and polyvinyl chloride, while they attain the highest values in polyamide-6 and polyethylene terephthalate owing to the high draw ratios in the neck and the high draw-stress values.     

Mechanical and barrier properties of ternary nanocomposite films based on polycarbonate/amorphous polyamide blends modified with a nanoclay

Ternary polycarbonate (PC)/amorphous polyamide–nanoclay (naPA) nanocomposite (PC/naPA) films were obtained by melt mixing and drawing, and the effects of the naPA content and the draw ratio (DR) on the structure, morphology and mechanical and barrier properties were studied. Despite the presence of nanoclay, the films exhibited a negligible roughness and the excellent optical properties of PC and amorphous polyamide (aPA). The dispersed naPA phase was pure and small, indicating compatibility. The naPA did not hinder the drawing ability of PC. At low DRs the dispersed phase was elongated and oriented along the machine direction (extrusion flow direction), but at high DRs, it fibrillated due to the higher non‐isothermal elongational flow induced by drawing. The laminar structure of the nanoclay allowed the films to be reinforced both in the machine and the transverse directions. The oxygen permeability of PC was reduced by 42% in the nanocomposite with 25% of naPA, and dropped further with the DR, which is attributed to the increased tortuosity of the oxygen path induced by fibrillation. Copyright © 2015 John Wiley & Sons, Ltd.     

The production and properties of poly(ethylene naphthalate-2,6-dicarboxylate) monofilaments

Experimental spinning and drawing conditions are described for poly(ethylene naphthalate-2,6-dicarboxylate), PEN, which produce good quality 0.5 mm monofilaments with high strength and uniformity. Mechanical properties were measured for a range of draw temperatures and draw ratios and an initial modulus of 22 GPa and a strength of 0.6 GPa were obtained by single stage drawing to a draw ratio of 6.6. The maximum birefringence achieved by single stage drawing was 0.33 compared with a theoretical maximum of 0.332 calculated from the bond polarizabilities and bond angles of the aligned monomer unit. Network parameters relevant to undrawn PEN and to the early stages in the drawing process were derived from simple rubber elasticity theory by making birefringence and shrinkage force measurements on films drawn homogeneously to low draw ratios. These suggest that the PEN network contains relatively stiff chains between entanglements and that the PEN network is modified much more in the drawing process than is the case with poly(ethylene terephthalate). A new method of measuring the birefringence of highly drawn thick filaments is described.     

The effect of orientation on the mechanism of deformation of polymers

The mechanical behavior of HDPE, medium-density PE, and amorphous and amorphous-crystalline PET after their preliminary orientation is studied. The polymers are oriented by rolling at room temperature on lab-scale rolls, tensile drawing at temperatures somewhat higher than their glass-transition temperatures, and extrusion at room temperature. At low degrees of rolling (below 1.5), the tensile yield stress does not actually increase. (In amorphous-crystalline PET, this parameter even decreases.) It seems that the absence of strain hardening at low draw ratios is a common feature of the behavior of polymers below their glass-transition temperatures. In contrast to the tensile yield stress, the engineering strength increases in proportion to the degree of rolling. A new procedure for construction of the dependence of true tensile yield stress on tensile strain is advanced. At low strains, the true tensile yield stress shows practically no increase. This conclusion is verified by theoretical calculations.     

Shrinkage,shrinkage force and the structure of ultra high modulus polyethylenes

Measurements of shrinkage and shrinkage force have been undertaken on drawn polyethylenes over a wide range of temperatures. The behaviour has been studied as a function of draw ratio and molecular weight for several linear polyethylenes and polyethylene copolymers. Although complete retraction is observed on heating even the most highly drawn samples above the melting range, at lower temperatures the shrinkage is less than that of low draw material. This is attributed to the formation of a substantial degree of crystal continuity during drawing, so that shrinkage requires mobility in the crystalline phase. The shrinkage forces are very high, being comparable with the drawing stresses at corresponding temperatures, and are molecular weight dependent, increasing with increasing molecular weight. It is considered that the results presented here on shrinkage and shrinkage force provide further support for the proposition that the drawing process relates to the extension of a molecular network.     

Dynamic mechanical investigations on drawn samples of isotactic polypropylene/EPM–Rubber blend

The physical behavior of isotropic and oriented samples of an isotactic polypropylene (iPP)/ethylene–propylene–copolymer (EPM) reactor blend was studied by performance of dynamic mechanical measurements over a wide temperature range (DMTA). The influence of thermal history and drawing procedure was examined. The results showed that with increasing draw ratio the uniaxial elastic modulus of the material was considerably enhanced, whereas the intensity and strength of the amorphous relaxations of both components were reduced. At a certain draw ratio, the glass transtions of iPP and EPM phenomenologically merged and appeared as a single relaxation. The crystalline relaxation of iPP emerged with increased draw ratio at higher temperatures and was better seperated and easier to detect. The effects observed were attributed to the orientation of the crystallites in a fibrillar structure and to the restricted molecular mobility in amorphous regions. Measurements by differential scanning calorimetry (DSC) and x-ray diffraction of several drawn samples were performed to determine the effects of drawing on the melting behavior and the crystal orientation in the semicrystalline polymer. For comparison, some results of analogous studies on neat isotactic PP are presented and discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1439–1448, 1997     

The change of the superstructure of semicrystalline polymers during deformation: results from small-angle scattering with synchrotron radiation

The change of the superstructure of different polyethylenes during uniaxial deformation is investigated. The method used is small-angle scattering with synchrotron radiation. For branched polyethylene (Lupolen 1840D) the whole deformation range is analyzed. Beginning with superstructure of the lamellar cluster type, the superstructure partly disappears on a time scale of a few minutes and the fibrillar structure is built up. The degree of destruction and rebuilding depends on the drawing temperature. For very high molecular weight polyethylene (GUR) a reversible change of the superstructure at higher deformation ratios and at different temperatures is observed. The superstructure of (ethylene—hexene) copolymers (TIPELIN) at high draw ratios depends on the drawing temperature and is almost independent of the side group content. Interfibrillar microcracks parallel to the draw direction are produced in samples with a low side group content for draw ratios λ ≥ 1.5.     

Drawing by solid-state coextrusion of blends of atactic and isotactic polystyrene with poly(2,6-dimethyl-1,4-phenylene oxide)

Atactic polystyrene (aPS)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) and isotactic polystyrene (iPS)/PPO compatible blends of varied composition were subjected to solid-state coextrusion. The efficiency of drawing, orientation, and crystallinity development were studied as a function of composition and draw ratio. The efficiency of drawing, as measured by elastic recovery, is high for coextrusion at temperatures ?40°C above the glass transition temperature of the particular blend. The maximum attainable draw ratio for the blends decreased with increasing PPO concentration; the highest blend draw ratio attained was 6.5 for 25 wt % PPO. The orientation on drawing, as measured by birefringence, increased with draw but decreased with increasing PPO component at the same draw ratio. When PPO was <50% in iPS/PPO blends, iPS crystallized on draw. The morphology of drawn blends was studied by electron microscopy and wide-angle x-ray scattering.     

Changes of the Molecular Mobility of Poly(<Emphasis Type="Italic">ε</Emphasis>-caprolactone) upon Drawing,Studied by Dielectric Relaxation Spectroscopy

Dielectric relaxation spectroscopy (DRS) of poly(ε-caprolactone) with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases.The activation energy of the α process,which corresponds to the dynamic glass transition,increases upon drawing.The enlarged gap between the activation energies of the αprocess and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes.At low drawing ratios the a process connects with the βprocess,while at the highest drawing ratio in our measurements,the a process is continuous with the a process.This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing.As the draw ratio increases,the α relaxation broadens and decreases its intensity,indicating an increasing heterogeneity.We observed slope changes in the α traces,when the temperature decreases below that at which τα ≈ 1 s.This may indicate the glass transition from the ‘rubbery’ state to the non-equilibrium glassy state.     

The mechanical anisotropy of stratified polyvinyl chloride

The mechanical anisotropy of a material obtained by stratification of oriented polyvinyl chloride (PVC) layers in different ways has been studied. PVC layers, uniaxially oriented by drawing each with a different draw ratio, were stratified in such a way that their draw axes were either parallel or perpendicular. The propagation velocities of ultrasonic pulses were measured in three principal planes defined by draw axes of the stratified material. With an immersion technique, measurements were performed at 2 MHz and 22°C. Experimentally, it was shown that while stratification of layers with draw axes parallel preserves hexagonal symmetry, the stratified material with layers' draw axes perpendicular possesses orthorhombic symmetry. © 1994 John Wiley & Sons, Inc.     

拉伸热历史对取向聚对苯二甲酸乙二酯膜在热处理过程中收缩和伸长的影响

弄清取向非晶态聚合物在热处理过程中的收缩和伸长的变化规律,以及所对应的结构变化,有较大的实用意义和科学意义。 对于取向聚对苯二甲酸乙二酯的热收缩和热伸长已有很多研究,但对于拉伸热历史对取向PET在热处理过程中的尺寸变化的影响尚缺乏系统的研究。在热拉伸的过程中发生分子链的取向、热弛豫和结晶三个相互竞争的过程。因此,改变拉伸条件可以得到具有各种不同取向和结晶的PET试样。当非晶态PET膜片在80-105℃以较低     

Visualization of strain-induced structural rearrangements in amorphous poly(ethylene terephthalate)

A direct microscopic observation procedure is applied to study the deformation of amorphous PET decorated with a thin metal layer when stretching is performed at different draw rates and at temperatures below and above the glass transition temperature T _g. Analysis of the formed microrelief allows stress fields responsible for the deformation of the polymer to be visualized and characterized. When tensile drawing is performed at temperatures above T _g, inhomogeneity of stress fields increases with the increasing draw rate; at high draw rates, the stress-induced crystallization of PET takes place. In the case of drawing the polymer at temperatures below T _g, direct microscopic observations make it possible to visualize the development of shear bands that appear in the unoriented part of the polymer specimen adjacent to the neck. The shear bands are oriented at an angle of about 45° with respect to the draw direction. When necking involves the unoriented part of the polymer, shear bands abruptly change their orientation and become aligned practically parallel to the draw axis.     

单轴取向PET薄膜的α松弛与力学行为的相关性

本文用动态力学方法研究了在不同温度和速度下单轴自由辐拉伸的聚对苯二甲酸乙二酯薄膜的非晶区状态,表明从熔体骤冷的非晶态试片在不同热拉伸条件下拉伸,可以得到非晶状态有显著差别的单轴取向薄膜。它们的非晶状态可以用动态力学温度谱的α峰的高度,形状和位置来表征。具有不同非晶状态的试样的储能模量E′(25℃)、屈服应力、负荷-伸长曲线与α松弛的参数以及其他结构参数间有很好的相关性。在一定的条件下热拉伸温度和速度存在Arrhenius型的速度-温度变换关系。     

Extrusion,fiber formation,and characterization of thermotropic copolyesters

The flow behavior and the effect of the spinning conditions on the fiber properties and structure of poly(ethylene terephthalate) modified with 60 mol% p-hydroxybenzoic acid (PET/60PHB) were investigated. PET and its copolyesters with 28 and 80 mol% PHB were used as control samples. The melt of PET/60PHB at temperatures above 265°C exhibited extremely low viscosity and low flow activation energy. High birefringence, indicating the presence of a mesophase, was observed between 265 and 300°C on a hot-stage polarizing light microscope. The maximum tensile strength and initial modulus, 438 MPa and 37 GPa, respectively, were obtained at 275°C for a 0.69 IV polymer. The fiber strength and modulus were significantly lowered when extrusion was conducted at temperatures below 265°C. The fiber properties could also be improved when a high extrusion rate and/or a high draw down ratio was used. Scanning electron microscopy revealed that the fibers spun at temperatures above 265°C had a well-developed, highly oriented fibrillar structure. The fibers spun at lower temperatures, however, were poorly oriented and nonfibrillar in character. The high orientation and superior mechanical performance achieved at high temperatures were attributed to the presence of the nematic mesophase in the polymer melt.     

Polymorphic transformations in poly(vinylidene fluoride) films during orientation

The effect of uniaxial orientational drawing and isometric annealing on the ratio of polymorphic modifications in the crystalline phase of poly(vinylidene fluoride) is studied. The role of drawing temperature and draw ratio in the structural rearrangements during polymer deformation is analyzed. The conditions providing the highest content of the polar crystalline phase in the polymer are determined. The mechanical properties of the films drawn at different temperatures are investigated.     

Plastic deformation of polypropylene: Effect of molecular weight on drawing behavior and structural characteristics of ultra-high-modulus products

The influence of molecular weight and temperature on the tensile drawing behavior of polypropylene has been studied, with particular reference to the production of ultra-high-modulus oriented materials. It has been shown that the optimum draw temperature is molecular weight independent to a good approximation, and that high-modulus products can be obtained for M?_w in the range 180,000–400,000, the highest modulus being achieved for polymer with M?_w = 181,000. As in the case of linear polyethylene, under optimum drawing conditions the Young's modulus relates only to the draw ratio. Low-temperature moduli as high as 25–27 GPa were recorded, which compare favorably with a previously reported value of 42 GPa for the crystal-lattice modulus. Although the drawing behaviour of the samples studied appeared comparatively insensitive to molecular weight, some of the properties of the draw materials, notably melting point and shrinkage at high temperature, showed a wide range of behavior.     

Films on amorphous polyamide nanocomposites: structure and properties

The ability of a nanoclay to improve the transport and mechanical properties of amorphous polyamide (aPA)‐based films was studied as a function of the draw ratio (DR) and the nanoclay content. The presence of nanoclay did not hinder the drawing ability as the maximum DR of the nanocomposites (NCs) and of the aPA were almost the same (51 for the aPA and from 51 to 55 for the NCs). The high degree of exfoliation and orientation along the drawing direction led to a 30% reduction in the water diffusion coefficient compared with the aPA. Moreover, the already low permeability of the aPA to oxygen was halved. The modulus of elasticity presented unusual increases both in the machine and transverse directions. Both increases of properties were attributed to the planar geometry of the oriented nanoclay sheets. The effects of the presence of nanoclay on the modulus of elasticity in the draw direction in addition to the effects caused by drawing lead to a combined modulus increase of 65% in the highly drawn 6%NC films. The nanoclay also reduced the modulus anisotropy of the films. An increase in either the nanoclay content or the DR causes a decrease in ductility due to both the stress concentrations created by the nanoclay and to the increasing number of chain segments located parallel to the drawing direction. The dimensional stability of the films greatly increased as the addition of 6% nanoclay led to a 70% decrease in creep deformation after 120 h. Copyright © 2012 John Wiley & Sons, Ltd.     

Plastic deformation of polypropylene VII. Long period as function of temperature and rate of drawing

Polypropylene fibers prepared by quenching in ice-water were drawn at 25, 80, 120, and 140°C to a draw ratio between 6 and 8 at draw rates 0.05, 0.5, 5, and 50 cm/min. The long period increases almost linearly with the draw rate for drawing at 25°C and decreases for drawing at higher temperatures. The effect in the latter cases is an annealing effect. As a consequence of the shorter exposure of the drawn fibers to the high temperature at higher draw rate, the long-period growth proceeds for a shorter time and hence results in a smaller increase of long period. At 25°C, however, the long-period growth is negligible. The increase of long period with draw rate is the consequence of higher adiabatic heating as calculated from the energy input during the plastic deformation which transforms the spherulitic into the fibrous structure. One concludes that the long period established during this transformation depends on the maximum temperature reached in the micronecking zone and not on the macroscopically observed temperature of the sample in the neck.     

Morphology of cold-drawn nylon 66

A nylon 66 composed of uniformly sized spherulites approximately 50 μ in diameter was examined before and after cold drawing by light and electron microscopy of thin sections and by low-angle x-ray diffraction. Spherulites retained their identity through drawing, but the spherulites elongated less than the bulk specimen indicating that relative motion of spherulities must have occurred. The observation of dilations (0.3 μ long) at interspherulitic boundaries support this contention. The thin-section electron micrographs indicated that the spherulites were composed of radiating lamellae approximately 95 A. thick. After drawing, the lamellae were preferentially oriented both parallel and perpendicular to the draw direction. Lamellae parallel to draw had thinned to approximately 70 A. While lamellae perpendicular to the draw had apparently thickened to 150 A. Three low-angle x-ray diffraction patterns yielded quantitative agreement with the electron-micrograph data. The pattern form the undrawn nylon was a diffuse ring corresponding to a 95 A. spacing. On the drawn specimen, with the beam parallel to draw, a ring corresponding to the 150 A. spacing was obtained, while with the beam perpendicular to draw two arcs were recorded at spacings of 70 and 150 A. The drawing was done at room temperature and proceeded by neck formation and propagation, yielding a 4:1 draw ratio.     

Drawing behavior and characteristics of laser‐drawn polypropylene fibers

Drawing behavior, flow drawing, and neck drawing, was studied for isotacticpolypropylene fibers in CO₂ laser drawing system, and the fiber structure and the mechanical properties of drawn fibers were analyzed. For a certain laser power, flow drawing of polypropylene (PP) was possible up to draw ratio (DR) 19.5. Though the drawing stress was very low, the flow‐drawn PP fiber exhibited oriented crystal structure and improved mechanical properties. On the other hand, neck‐drawing was accomplished from DR 4 to 12, with significant increase in drawing stress that enhanced the development of fiber structure and mechanical properties. Unlike PET, the drawing stress depends not only on the DR, but on irradiated laser power also. The 10–12 times neck‐drawn fibers were highly fibrillated. The fibers having tensile strength 910 MPa, initial modulus 11 GPa, and dynamic modulus 14 GPa were obtained by single‐step laser drawing system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 398–408, 2006