Ultrasonic measurements of the elastic moduli of ultradrawn polyoxymethylene

We have employed an ultrasonic method to measure from ?40 to 60°C the five independent elastic moduli C₁₁, C₁₃, C₃₃, C₄₄, and C₆₆ of polyoxymethylene with draw ratio λ from 1 to 26 prepared by continuous drawing under microwave heating. The elastic moduli are controlled by three major factors: molecular orientation in the crystalline regions, fraction of noncrystalline taut tie molecules, and void content. The steep rise in the axial extensional modulus C₃₃ and axial Young's modulus E₀ with increasing draw ratio results from the alignment of chains in the crystalline blocks and an increase in the number of disordered taut tie molecules. Below the γ relaxation (located at 0°C at our measurement frequency of 10 MHz), these two factors also give rise to a slight decrease in the transverse extensional modulus C₁₁, Young's modulus E₉₀ and shear modulus C₆₆. At high temperature where the amorphous regions have very low modulus, the stiffening effect of taut tie molecules becomes dominant, leading to an increase in all moduli as λ increases from 1 to 10. At higher λ the void fraction increases appreciably, causing small decreases in E₉₀, C₁₁, and C₆₆ at all temperatures.     

Influence of initial polymer concentration in solution and weight-average molecular weight on the drawing behavior of polyethylenes

The influence of initial polymer concentration in solution (c), weight-average molecular weight (M_ω), and drawing temperature on the solid-state drawing behavior of linear polyethylenes was investigated. Optimum conditions, with respect to maximum attainable draw ratio, are observed in isothermal drawing experiments. Moreover, it is shown that high maximum attainable draw ratios can also be obtained upon multistage drawing of UHMW-PE (ultrahigh-molecular-weight polyethylene, M_ω > 10⁶ g/mol) gel films cast from concentrated solutions. The high maximum attainable draw ratio in combination with the high molecular weight (M_ω > 10⁶ g/mol) and polymer concentration (c = 10% w/v) is of particular interest because it results in tapes or fibers with a high Young's modulus (100 GPa) and tensile strength (2.5–3.5 GPa). It is also shown that the maximum attainable draw ratio of polyethylenes scales with the Bueche parameter (c · M_ω) to the ?0.5 power. This experimental observation indicates that intermolecular interactions not only dominate the rheological properties of polyethylene melts and concentrated solutions, but also strongly influence the solid-state drawing behavior of linear polyethylenes.     

Mechanical properties and structure of the zone‐drawn poly(L‐lactic acid) fibers

The zone‐drawing (ZD) method was applied three times to the melt‐spun poly(L ‐lactic acid) (PLLA) fibers of low molecular weight (M_v = 13,100) at different temperatures under various tensions. The mechanical properties and superstructure of the ZD fibers were investigated. The resulting ZD‐3 fiber had a draw ratio of 10.5, birefringence of 37.31 × 10⁻³, and crystallinity of 37%, while an orientation factor of crystallites remarkably increased to 0.985 by the ZD‐1. The Young's modulus and tensile strength of the ZD‐3 fiber respectively attained 9.1 GPa and 275 MPa, and the dynamic storage modulus was 10.4 GPa at room temperature. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 991–996, 1999     

Zone‐Drawn Poly(p‐phenylene) Films. Effects of Molecular Orientation on Electrical and Mechanical Properties

The electrochemically synthesized poly(p‐phenylene) film could be zone drawn by a factor of 1.57, where the orientation function (f) increased with the draw ratio (λ), regardless of the heater temperature (T_h) or applied tension (σ), and reached 0.428 for the resulting film. The electrical conductivity in the drawing direction rose with f but decreased as T_h became higher due to dedoping that occurred simultaneously with drawing. Young's modulus and tensile strength significantly increased to 4.5 GPa and 155 MPa by zone drawing from 1.1 GPa and 79 MPa of the as‐synthesized film.     

Physical and mechanical properties of ultra-oriented high-density polyethylene fibers

Ultra-oriented high-density polyethylene fibers (HDPE) have been prepared by solid-state extrusion over 60–140°C range using capillary draw ratios up to 52 and extrusion pressures of 0.12 to 0.49 GPa. The properties of the fibers have been assessed by birefringence, thermal expansivity, differential scanning calorimetry, x-ray analysis, and mechanical testing. A maximum birefringence of 0.0637 ± 0.0015 was obtained, greater than the calculated value of 0.059 for the intrinsic birefringence of the orthorhombic crystal phase. The maximum modulus obtained was 70 GPa. The melting point, density, crystallinity, and negative thermal expansion coefficient parallel to the fiber axis all increase rapidly with draw ratio and at draw ratios of 20–30 attain limiting values comparable with those of a polyethylene single crystal. The properties of the fibers have been analyzed using the simple rule of mixtures, assuming a two-phase model of crystalline and noncrystalline microstructure. The orientation of the noncrystalline phase with draw ratio was determined by birefringence and x-ray measurements. Solid-state extrusion of HDPE near the ambient melting point produced a c-axis orientation of 0.996 and a noncrystalline orientation function of 0.36. Extrusion 50°C below the ambient melting point produced a decrease in crystallinity, c-axis orientation, melting point, and birefringence, but the noncrystalline orientation increased at low draw ratios and was responsible for the increased thermal shrinkage of the fibers.     

Drawing of ultrahigh-molecular-weight polyethylene single-crystal mats: The crystallinity

Single-crystal mats of ultrahigh-molecular-weight polyethylene can be drawn uniformly to high draw ratios, more than 20χ at the highest, after the necking process is completed. The dynamic mechanical modulus of the drawn mats increases markedly during the uniform drawing stage. The structural changes induced by the uniform drawing at 100°C have been followed by wide-angle and small-angle x-ray scattering, infrared absorption, differential scanning calorimetry, and birefringence. The crystallinity is estimated from the x-ray amorphous scattering intensity, the IR absorbance of gauche bands, the heat of fusion from DSC, and the density. The estimated crystallinities of the drawn mats are all very high and increase slightly and monotonically with increased drawing after necking, though the values of the crystallinity depend on the method of estimation. IR gauche bands and the SAXS peak due to the long period disappear at a draw ratio of about 80χ. All the results suggest that the uniform drawing after necking destroys the two-phase structure made up of alternately stacked crystalline and amorphous regions and then reorganizes it into a single-phase crystalline structure.     

Drawing behavior of linear polyethylene. II. Effect of draw temperature and molecular weight on draw ratio and modulus

The drawing behavior of linear polyethylene homopolymers with weight-average molecular weights (M?_w) from 101,450 to ca. 3,500,000 has been studied over the temperature range 75°C to the melting point. In all cases 1-cm gauge length samples were drawn in an Instron tensile testing machine at a constant cross-head speed of 10 cm/min. With the exception of the lowest molecular weight polymer, it was found that increasing the draw temperature led to substantial increases in the maximum draw ratio which could be achieved, and that this increased monotonically with increasing draw temperature. Measurements of the Young's modulus of the drawn materials showed, however, that the unique relationship between modulus and draw ratio previously established for drawing at 75°C was not maintained to the highest draw temperatures. The highest draw temperature at which this relation held was found to be strongly molecular weight dependent, increasing from ca. 80 to ca. 125°C when M?_w increased from 101,450 to 800,000. In all cases conditions could be found for drawing samples to draw ratios of 20 or more with correspondingly large values of the Young's modulus.     

Ultrahigh modulus polyethylene. II. Effect of drawing temperature on void formation and modulus

The maximum degree of molecular orientation and deformation obtained by ultradrawing of high-density polyethylene in air is limited by formation of internal voids (both longitudinal separation of fibrils and perpendicular cracking), and thus values of Young's moduli which are achievable by ultradrawing techniques are also limited to values much below the theoretical limit for fully extended chains. Temperature has a significant effect on the critical draw ratios at which intensive void formation begins, and also on the draw ratio at which failure occurs during the ultradrawing. The temperature effect is observed only for high-density polyethylene having a wide molecular-weight distribution, and which can be drawn at higher temperatures (30–40°C below its melting point), e.g., Dow Chemical polyethylene LP51.1. As a result of ultradrawing at higher temperatures, transparent, ultrahigh modulus samples having draw ratios of order of 40 have been obtained. The higher drawing temperatures significantly reduce fibril separation, and perpendicular cracking is shifted toward higher draw ratios. Hence, with LP51.1 the highest Young's moduli (65–70 GPa) have been exhibited by the samples which were ultradrawn at 100–105°C.     

Melt spinning and laser‐heated drawing of a new semiaromatic polyamide,PA9‐T fiber

Fibers of PA9‐T, a new semiaromatic polyamide containing a long aliphatic chain, were prepared by melt spinning. As‐spun fibers were subsequently drawn with a CO₂ laser‐heated drawing system at different draw ratios and various drawing velocities. On‐line observations of drawing points deciphered two drawing states; namely, flow drawing and neck drawing, over the entire range of drawing. Drawing stress revealed that flow drawing is induced by slight drawing stress under a low draw ratio up to 3, and neck drawing is induced by relatively high drawing stress under a higher draw ratio. The effect of drawing stress and drawing velocity on the development of the structure and properties has been characterized through analysis of birefringence, density, WAXD patterns, and tensile, thermal, and dynamic viscoelastic properties. For the neck‐drawn fibers, almost proportional enhancements of crystallinity and molecular orientation with drawing stress were observed. The flow‐drawn fibers have an essentially amorphous structure, and birefringence and density do not always have a linear relation with properties. The fibers drawn at high drawing speed exhibit improved fiber structure and superior mechanical properties. The maximum tensile strength and Young's modulus of PA9‐T drawn fibers were found to be 652 MPa and 5.3 GPa, respectively. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 433–444, 2004     

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.     

Mechanical properties of the novel organometallic polymer poly(ferrocenyldimethylsilane)

A study of the mechanical properties of poly(ferrocenyldimethylsilane) [Fe(η‐C₅H₄)₂SiMe₂]_n, 3 , a novel organometallic polymer, has been performed on thin films of this material. The Young's modulus and Poisson's ratio of film samples (15 × 1 × 1 mm) of 3 were measured in quasi‐static tension using a video extensometer. For 3 , the values of the Young's moduli (E) and Poisson's ratios (ν) were similar between axes in the plane and independent of the splicing direction used during sample preparation. The mean and standard deviation of the Young's modulus and Poisson's ratio were 0.78 ± 0.08 GPa and 0.37 ± 0.06 GPa, respectively. Thermomechanical analysis of 3 revealed a steady decrease of E from a room temperature value of approximately 0.70 GPa. Additionally, it was found that at 150 °C, 3 was unable to support even small stresses, consistent with the onset of a melt transition (ca. 135 °C). A mathematical model based on molecular geometry is developed to describe the results. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2280–2288, 2005     

A study on the orientation structure and mechanical properties of polyacrylonitrile precursors

The polyacrylonitrile precursors were made through the two‐stage drawing process. The orientation structure was examined through wide‐angle X‐ray diffraction (WAXD). The orientation factors and the modulus were measured through the sound velocity method. The mechanical properties, such as the Young's modulus, the tensile strength and the breaking elongation ratio were obtained by the single fiber tensile test. The results showed that the Young's modulus and the strength of the precursors increased with draw ratio, which is accordant with the enhancement of the micromolecular orientation degree. Therefore the orientation factors obtained from the experiments were compared with the theoretical curves which were predicted through the Crawford and Kolsky's model. The physical meaning of the parameters m and n were analyzed. A good agreement of the orientation factor between the experimental data and the theoretical curve was achieved. Copyright © 2005 John Wiley & Sons, Ltd.     

Electrical and mechanical properties of the zone-drawn polypyrrole films

The zone-drawing method (ZD) was applied to electrochemically synthesized polypyrrole films containing tosylate (PPy/TsO) and the mechanical and electrical properties of the resulting films were investigated. It was found that the electrical conductivity of the zone-drawn film reached 365 S cm⁻¹ in the drawing direction, which was 4.7 times that of the original film. The tensile properties of the zone-drawn film were improved and Young's modulus and strength at break increased to 4.32 GPa and 90.1 MPa from 0.53 GPa and 40.4 MPa of the as-synthesized film, respectively. The dynamic storage modulus (E) increased by the zone-drawing over a whole experimental temperature range and attained 7.0 GPa at room temperature and 4.0 GPa even at 200°C. © 1996 John Wiley & Sons, Inc.     

Effect of the microstructure on the dye diffusion and mechanical properties of polyamide‐6 fibers

The morphology, mechanical properties, and dye diffusion of drawn and heat‐set polyamide‐6 (PA6) yarns were examined. Correlations between the microstructure of PA6 yarns and the dye diffusion coefficients and mechanical properties were established. The crystallinity of PA6 yarns was estimated with density and Fourier transform infrared spectroscopy measurements. A decrease in the γ crystallinity and an increase in the γ‐crystallite size with the draw ratio were observed and attributed to the disappearance of small crystallites and an increase in the average γ‐crystallite size population during the deformation process. The scouring treatment increased the total crystallinity, almost entirely as a result of an increase in the α fraction. Thermally induced crystallization involved increases in both crystalline phases (α and γ) and did not involve crystal‐to‐crystal transformation, whereas drawing PA6 yarns involved both crystallization of the amorphous phase in the α form and γ→α transformation. A sharp decrease in the diffusion coefficient with an increasing draw ratio of PA6 yarns was correlated with an increasing amorphous orientation. The influence of thermally induced crystallinity on the diffusion coefficient seemed exceptionally strong. The mechanical properties of PA6 yarns were examined and correlated with structural changes. It was demonstrated that the crystallinity had a direct correlation with the terminal modulus and extension at break, whereas there was no correlation with the initial modulus. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 349–357, 2007     

Development of oriented structure and properties on drawing of poly(vinylidene fluoride) by solid‐state coextrusion

Gel films of poly(vinylidene fluoride) (PVDF) consisting of α‐form crystals were drawn uniaxially by solid‐state coextrusion to extrusion draw ratios (EDR) up to 9 at an optimum extrusion temperature of 160 °C, about 10°C below the melting temperature (T_m). The development of an oriented structure and mechanical and electrical properties on coextrusion drawing were studied as a function of EDR. Wide‐angle X‐ray diffraction patterns showed that the α crystals in the original gel films were progressively transformed into oriented β‐form crystals with increasing EDR. At the highest EDR of 9 achieved, the drawn product consisted of a highly oriented fibrous morphology with only β crystals even for the draw near the T_m. The dynamic Young's modulus along the draw direction also increased with EDR up to 10.5 GPa at the maximum EDR of 9. The electrical properties of ferroelectricity and piezoelectricity were also markedly enhanced on solid‐state coextrusion. The D–E square hysteresis loop became significantly sharper with EDR, and a remanent polarization P_r of 100 mC/m² and electromechanical coupling factor along the thickness direction k_t of 0.27 were achieved at the maximum EDR of 9. The crystallinity value of 73–80% for the EDR 9 film, estimated from these electrical properties, compares well with that calculated by the ratio of the crystallite size along the chain axis to the meridional small‐angle X‐ray scattering (SAXS) long period, showing the average thickness of the lamellae within the drawn β film. These results, as well as the appearance of a strong SAXS maximum, suggest that the oriented structure and properties of the β‐PVDF are better explained in terms of a crystal/amorphous series arrangement along the draw axis. Further, the mechanical and electrical properties obtained in this work are the highest among those ever reported for a β‐PVDF, and the latter approaches those observed for the vinylidene fluoride and trifluoroethylene copolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1371–1380, 2001     

A structural model for high-modulus polyethylene derived from entanglement concepts

Starting from the concept that the entanglement network is a controlling factor in polymer deformation, a molecularly based model has been constructed for polyethylene, drawn or extruded to high extension ratios λ. It predicts the experimentally observed form of the increase of Young's modulus E with λ: E^?1 = B + Cλ^?2. The model structure consists of imperfect crystalline microfibrils 10-30 nm in diameter and length αλ², about 1 μm at λ = 30. The microfibrils terminate at clusters of entanglements, and are embedded in a matrix of low modulus. This structure is very similar to that derived from solution-grown shish-kebab material. Available melting-point data for highly extended material fit the structural model well.     

A fiber composite model of highly oriented polyethylene

A fiber composite model of highly drawn polyethylene is presented. Quantitative predictions and calculations are made using shear-lag theory. The drawing process is shown to occur in two stages, a neck and a postneck taper. It is shown that there is an empirical linear relationship, with a high correlation, between the parameter x in shear-lag theory (which involves the aspect ratio of the reinforcing elements and the square root of the ratio of matrix shear modulus to the Young's modulus of the reinforcing elements) and the 3/2 power of the taper draw ratio. It is concluded that crystalline fibrils (the reinforcing elements) deform homogeneously during the secondary, taper drawing process. The increase in aspect ratio resulting from this homogeneous deformation is held to be responsible for the increase in tensile modulus owing to the increased efficiency of the fibrils as reinforcing elements. The model is also used to explain the self-hardening process exhibited by these fibers and, using measurements of density of hardened fibers, to predict that immediately after the neck the aspect (length to diameter) ratio of the crystalline reinforcing elements is ca. 2 and that the shear modulus of the matrix material in as-drawn fibers is ～10³N/m² and does not change significantly during the taper-drawing process.     

Studies on Macromolecular Complexing Agents. II. Effects of Polypropylene Oxide on the Copolymerization Reaction between Butadiene and Styrene

ABSTRACT

Ultra-high-molecular-weight poly[(R)-3-hydroxybutyrate](P(3HB)) was biosynthesized from glucose by a recombinant Escherichia coli XL-1 Blue (pSYL105) harboring Alcaligenes eutrophus PHB biosynthesis phbCAB genes. Six kinds of P(3HB) samples with differ-ent weight-average molecular weight (M_w ) from 1.1 × 10⁶ to 11 × 10⁶ measured by multi-angle laser light scattering were respectively produced at pH values of 7.0 to 6.5 in culture media. Solvent-cast P(3HB) films of high-molecular-weights over M_w of 3.3 × 10⁶ were stretched easily and reproducibly at 160°C to a draw ratio of 400-650%. Mechanical properties of the stretched P(3HB) films were markedly improved relative to those of solvent-cast film. The elongation to break, Young's modulus, and tensile- strength of stretched film (M_w = 11 × 10⁶) were 58%, 1.1 GPa, and 62 MPa, respectively. X-ray diffraction patterns indicated that the stretched film was highly oriented and had a high crystallinity over 80%. When the stretched film was annealed at 160°C for 2 hours, the mechanical properties were further improved (elongation to break = 67%, Young's modulus = 1.8 GPa and tensile strength = 77 MPa). The mechanical properties of the stretched-annealed film remained almost unchanged for 6 months at room temperature, suggesting that a high crystallinity of the stretched-annealed film avoids a progress of secondary crystallization.

     

Processing and properties of melt spun polylactide–multiwall carbon nanotube fiber composites

This article reports on the fabrication of oriented composite fibers between polylactide (PLA) and multiwall carbon nanotube (MWNT). The fibers were fabricated using a custom‐built melt fiber‐drawing setup. The influence of processing parameters on the final fiber diameter and on the orientation were characterized and optimized. Composite fibers were fabricated at various MWNT contents. Addition of low amounts of MWNT (0.25–1 wt %) to PLA did not have a significant effect on the diameters of the fibers. Observations of the composite morphology under STEM indicated preferential orientation of the MWNTs along the draw direction of the fibers. Increasing amounts of MWNTs was found to increase crystallization kinetics and content. The crystalline content had a direct and profound implication on the mechanical properties with 0.5‐wt % MWNT fibers having the highest crystalline content and also the highest Young's modulus. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 477–484