Structure and properties of bio‐based polyamide 109 treated with superheated water

The structure and properties of bio‐based polyamide 109 (PA109) after treatment with superheated water (140 °C ≤ T ≤ 280 °C) were investigated and characterized by Fourier transform infrared spectroscopy, differential scanning calorimetry, wide‐angle X‐ray diffraction, scanning electron microscopy and small‐angle X‐ray scattering. Below 170 °C, the hydrothermal treatment was considered to be a physical process, which exerted an annealing effect on PA109. It led to an increase in melting temperature, lamellar thickness and crystallinity, while the macromolecular structure, crystal structure and the order of crystalline regions were not affected. Above 170 °C, complete melting/dissolution of PA109 occurred with partial hydrolysis. Due to the high temperature and long reaction time, the hydrolysis reaction became more and more prominent, and the resin was completely hydrolyzed into oligomers at 280 °C. Also, above 170 °C, the hydrothermal treatment was accompanied by a chemical process and the melting temperature and molecular weight decreased progressively. Notably, the crystal structure was not altered, but the degree of perfection of crystals and the order of crystalline regions were broken, especially above 200 °C. The hydrolytic degradation reaction was significantly affected by temperature, while both time and the water to polyamide ratio were secondary factors which influenced it to a minor extent. The process could be considered as a typical nucleophilic substitution reaction which takes place step by step inducing the molecular weight to decrease gradually. Overall, this study provides a ‘green’ route for the processing, recycling and treatment of environmentally friendly polyamides based on hydrothermal treatment technology. © 2019 Society of Chemical Industry     

Synthesis and characterization of poly (hydroxyether ketone) and its copolymers

A novel semi‐crystalline polyhydroxyether, poly(hydroxyether ketone) (PHEK), was synthesized via the direct polycondensation between 4,4‐dihydroxybenzophenone and epichlorohydrin. By means of Fourier transform infrared and NMR spectroscopy and gel permeation chromatography (GPC), the structure of PHEK was characterized. Differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXRD) show that PHEK is a semi‐crystalline polymer with a high rate of crystallization. The polymer possesses a glass transition temperature of 109 °C and a melting temperature of 239 °C. When 4,4′‐isopropylidenediphenol was used as a second bisphenol and was added to copolymerize with a stoichiometric amount of epichlorohydin, a series of polyhydroxyether copolymers were obtained. The copolymers with various compositions were characterized by means of NMR, GPC, WAXRD and DSC. It was found that the crystallinity of the copolymers dramatically decreased with increasing content of 4,4′‐isopropylidenediphenol. The glass transition temperatures of the copolymers are intermediate between those of PHEK and the poly(hydroxyether of bisphenol A) and decreased with increasing content of 4,4′‐isopropylidenediphenol. Copyright © 2007 Society of Chemical Industry     

Poly(ethylene terephthalate)/polypropylene microfibrillar composites. III. Structural development of poly(ethylene terephthalate) microfibers

Poly(ethylene terephthalate) was extruded, solid‐state‐drawn, and annealed to simulate the structure of poly(ethylene terephthalate) microfibers in a poly(ethylene terephthalate)/polypropylene blend. Differential scanning calorimetry and wide‐angle X‐ray scattering analyses were conducted to study the structural development of the poly(ethylene terephthalate) extrudates at different processing stages. The as‐extruded extrudate had a low crystallinity (～ 10%) and a generally random texture. After cold drawing, the extrudate exhibited a strong molecular alignment along the drawing direction, and there was a crystallinity gain of about 25% that was generally independent of the strain rates used (0.0167–1.67 s^?1). 2θ scans showed that the strain‐induced crystals were less distinctive than those from melt crystallization. During drawing above the glass‐transition temperature, the structural development was more dependent on the strain rate. At low strain rates, the extrudate was in a state of flow drawing. The resultant crystallinity hardly changed, and the texture remained generally random. At high strain rates, strain‐induced crystallization occurred, and the crystallinity gain was similar to that in cold drawing. Thermally agitated short‐range diffusion of the oriented crystalline molecules was possible, and the resultant crystal structure became more comparable to that from melt crystallization. Annealing around 200°C further increased the crystallinity of the drawn extrudates but had little effect on the texture. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 137–146, 2007     

Structural Evolution of UHMWPE Fibers during Prestretching Far and Near Melting Temperature: An In Situ Synchrotron Radiation Small‐ and Wide‐Angle X‐Ray Scattering Study

Combining a homemade extension apparatus and the in situ synchrotron radiation small‐ and wide‐angle X‐ray scattering methods for measurement, the structural evolutions of gel‐spun ultrahigh molecular weight polyethylene (UHMWPE) fibers during prestretching at temperatures of 25 and 100 °C are investigated, respectively. Lamellar rotation toward the stretching direction occurs before strain hardening, while the folded‐chain crystal destruction and extended‐chain fibril formation processes occur in the strain hardening zone at 25 °C. While at 100 °C, stretching induced crystal melting before the stress plateau region and formation of fibrous crystals at the onset of the stress plateau are observed. Further stretching results in shear displacement of crystal blocks and, finally, destruction of the folded‐chain crystals and formation of extended‐chain fibrils. Prestretching UHMWPE fibers at 100 °C within a certain strain range can produce highly oriented fibrous crystals, which may provide an ideal precursor structure for the poststretching process.     

Phase stability and melting behavior of the α and γ phases of nylon 6

The phase stability and melting behavior of nylon 6 were studied by high‐temperature wide‐angle X‐ray diffraction and differential scanning calorimetry (DSC). The results show that most of the α phase obtained by a solution‐precipitation process [nylon 6 powder (Sol‐Ny6)] was thermodynamically stable and mainly melted at 221°C; the double melting peaks were related to the melt of α crystals with different degrees of perfection. The γ phase formed by liquid nitrogen quenching (sample LN‐Ny6) melted within the range 193–225°C. The amorphous phase converted into the γ phase below 180°C but into the high‐temperature α phase at 180–200°C. Both were stable over 220°C. α‐ and γ*‐crystalline structures were formed by annealing but were not so stable upon heating. Typical double melting peaks were shown on the DSC curve; melt recrystallization happened within the range 100–200°C. The peak at 210°C was mainly due to the melting of the less perfect crystalline structure of the γ phase and a fraction of the α phase; the one at 219°C was due to the high‐temperature α‐ and γ‐phase crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of high‐temperature annealing on the microstructure and mechanical properties of polypropylene with shish kebab or spherulite structure

Various annealing temperatures below, near, or above the melting temperature were used to anneal polypropylene with oriented shish kebab and isolated spherulite structures in this work. The results showed that a high annealing temperature decreases the time needed to achieve the ideal material property. When the annealing temperature is near or above the melting temperature, the impact strength would be 1.6 times improved by partial melting and recrystallization. The crystal structure of the oriented shish kebab or isolated spherulite structures was improved when annealed at 150 °C, whereas annealing at 165 or 170 °C recombined the crystal lamellae of the structure. Moreover, the high crystallinity and thick lamellae improved the impact and yield strength values of the spherulite structure. However, excessively high crystallinity and thick lamellae in the oriented shish kebab structure did not result in good mechanical performance. Therefore, the prediction of mechanical properties for the shish kebab structure based on crystallinity and lamellar thickness is not feasible. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46465.     

Variations in polymeric structure of ferroelectric poly(vinylidene fluoride) films during annealing at various temperatures

To clarify the thermal degradation mechanisms of uniaxially drawn poly(vinylidene fluoride) (PVDF) films, variations due to annealing in the polymeric structures of the films were investigated using the small‐angle X‐ray scattering (SAXS) and Fourier transform infrared (FTIR) spectroscopy. The films were composed of lamellar crystals that were stacked perpendicular to the stretch direction. Although the crystallinity of the films decreased during annealing in the temperature range above the preannealing temperature, the lamellar structure was maintained even after the annealing process. There are two kinds of irreversible relaxation mechanisms during the annealing process of the films, including both a decrease in crystallinity within the lamellae and also thickening of the lamellae. A significant lamella thickening effect was observed when the films were annealed above ～ 100°C. FTIR spectra suggested some disordered structures are developed during thickening of the lamellae. Furthermore, a long‐range periodic structure was formed in the films that were annealed above the melting temperature of PVDF. The polymeric structures formed during the fabrication process (including high‐order structures and disorders in molecular conformation) were clarified as having a significant influence on the annealing behavior of ferroelectric PVDF films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Hot compaction of polyoxymethylene. II. Structural characterization

The structural characterization of sintered polyoxymethylene was carried out to determine the mechanism of sintering. Thermal behavior and small‐angle X‐ray scattering (SAXS) of sintered samples reveal that an improvement in either crystal size or perfection, or both, takes place during the sintering process, in comparison with compression‐molding from the melt. The loss modulus data also give evidence of crystal reorganization during sintering that improves the continuity of the crystalline phase and enhances its mechanical contribution. These findings eliminate the occurrence of major melting during sintering. However, the high mobility of the chains in the crystalline phase in the temperature range of the melting onset suggests that short range rearrangements of the chains in the crystalline lamellae are likely to occur during the time of the process. The proposed mechanism of sintering is that of crystallographic welding of crystals from neighboring particles, as a result of the combined effect of plastic flow and temperature during the hot compaction operation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Polyurethanes from 4,4′‐diphenylmethane diisocyanate and poly(ethylene glycol)s. II. Crystallographic data,heats of melting and crystallization,thermal stability,crystallinity and density

Wide‐angle X‐ray scattering analysis, heats of melting, crystallization and re‐melting, thermogravimetric analysis and density measurements have been used to study the crystallographic data and degree of crystallinity of linear polyurethanes (PUs) prepared by the polymerization of 4,4′‐diphenylmethane diisocyanate (MDI) with poly(ethylene glycol)s (PEGs) of various number‐average molecular weights (M_ns) (106, 200, 400, 1000, 2000 and 4000 g mol^?1) in equivalent molar ratios. The crystallinities of polyurethanes PU1000 to PU4000 are shown to be due to the polyoxyethylene segments of the PEGs, while PU400 and PU200 appeared to be amorphous. However, PU106, similarly prepared from diethylene glycol (PEG106), is highly crystalline with a different crystal structure. Thermogravimetric analysis of PU106, PU400 and PU1000 exhibited high thermal stabilities up to 260 °C for these materials under the conditions of measurement (10 °C min^?1). The heat of melting for the 100 % crystalline structure of PU106 has been indirectly obtained. Copyright © 2004 Society of Chemical Industry     

Crystallization of polyamides under elevated pressure: 5.Pressure-induced crystallization from the melt and annealing of folded-chain crystals of nylon-11, poly(aminoundecaneamide) under pressure

High pressure dilatometry, differential scanning calorimetry, electron microscopy, X-ray diffraction, and infra-red spectroscopy to study how the crystallization of nylon-11 from the melt, as well as annealing of the folded-chain crystals, are affected by pressure in the range from 1 to 10 kbar (1 kbar = 100 MN/m²) and temperature in the range from 200° to 320°C. Pressures exceeding 3 kbar and temperatures higher than 230°C are sufficient for growth of the chain-extended crystals of nylon-11 either by pressure-induced crystallization from the melt or by annealing of the folded-chain crystals. Crystallization from the melt or annealing at 320°C or higher, and 10 kbar, resulted in crosslinking of the polymer. The highest melting temperature and heat of melting found for the chain-extended crystals of nylon-11 were 226°C and 35 cal/g respectively, as compared to 190°C and 13.6 cal/g for the folded-chain material. The texture of the chain-extended crystals of nylon-11 was found to be spherulitic with well developed striations forming circle patterns, and polymer chains passing through several lamellae. No sharp boundaries were found between the chain-extended lamellae. The alpha-crystalline modification, found for the folded-chain crystals of nylon-11, was preserved in the high pressure crystallization and annealing experiments. Infra-red absorption bands at 1420 and 1225 cm^?1 seem to be associated with the presence of folds in the nylon-11 crystals. It is suggested that, during the initial stage of crystallization under pressure, folded-chain crystals are formed, with a crystalline order and long spacing larger than that of the starting nylon-11.     

Nanostructure of Potato Starch,Part I: Early Stages of Retrogradation of Amorphous Starch in Humid Atmosphere as Revealed by Simultaneous SAXS and WAXS

Crystallization experiments on amorphous, injection-molded starch in a humid atmosphere are reported. The crystallization mechanisms have been studied using simultaneous SAXS and WAXS during a temperature stepwise increase. In contrast to the crystallization of linear synthetic polymers, in starch the WAXS peaks are observed at low temperature before the appearance of the SAXS maximum. The initial state of crystallization is dominated by the amylose (AM) component of the potato starch alone. After the initial formation of large (16 nm) uncoordinated individual crystallites, stacks of lamellae and finally, an insertion of thinner lamellae within the stacks are observed. Results indicate that only if all AM is converted into a semicrystalline structure and if the secondary starch network of double helices of AM and amylopectin (AP) is molten by a temperature increase above 70°C, crystallization of AP also occurs. Because the AM crystals act as nuclei for the AP component, a common superstructure is developed. Within a spherulite, alternating AM and AP lamellae develop radially from the center of the AP molecule. Results suggest that the AM is distributed inhomogeneously with respect to the AP molecules, leaving approximately one half of the AP fraction free, which means not crystallized to a spherulitic structure together with AM.     

Nanostructure development in wet amorphous amylopectin as revealed by in situ X‐ray scattering methods

Completely amorphous, transparent bars of amylopectin were prepared by injection molding of pure native semicrystalline samples (Waxy Maize). The formation of a semicrystalline morphology was studied during annealing treatment at various temperatures in a wet atmosphere, using simultaneous WAXS and SAXS. Amylopectin samples crystallized during 20 days in a humid atmosphere at room temperature and subjected to a successive melting process were also studied by X‐ray scattering. Results indicate that individual molecules crystallize independently from each other, similar to the case of native amylopectin grains. During the first stages of crystallization, the changes in the SAXS pattern suggest that uncorrelated crystal blocks are formed, which may arrange to lamellae (if a secondary network of double‐helix net‐points is hydrothermally dissociated). At the beginning of the crystallization process, only few amylopectin molecules (about 10%) are incorporated into the nanostructure. A shell‐like structure of semicrystalline layers, comparable to that of a native grain, develops. When crystallization proceeds further, the initially thin shell layers thicken. This causes the amorphous interlayers to be subjected to inner tensions, leading to a decrease in the melt temperature. After a storage time of 20 days in a humid atmosphere, amylopectin reaches a crystallinity level of 54%, only slightly lower than that of the initial native grains. Upon heating the retrograded amylopectin, immediately before complete melting, the long‐period shows a value of 15 nm with a crystal thickness, derived from WAXS, of only 4 nm. Such a structure, which has not been reported before, is due to the relaxations of the inner tensions during melting, which lead to a disappearance of inserted interlamellar crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3832‐3839, 2006     

New manganese catalyzed regiocontrolled synthesis of poly(2,5‐dialkyl‐1,4‐phenylene oxide)s

A new catalyst system is developed for regiocontrolled synthesis of poly(2,5‐dialkyl‐1,4‐phenylene oxide)s by oxidative coupling polymerization of 2,5‐dialkylphenol. The treatment of the α‐benzoin oxime with manganese chloride in methanol under basic condition led to the formation of manganese benziloxime complex in which α‐benzoin oxime was converted to benziloxime and coordinated to manganese as bidentate ligands. The polymerizations were conducted in toluene using manganese benziloxime complex and dibutylamine in a continuous flow of oxygen, and the structures, properties of the catalyst, and polymers were studied by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and gel permeation chromatography (GPC). The catalyst showed high regioselectivity and reasonably good yields to afford the poly(2,5‐dimethyl‐1,4‐phenylene oxide)s with 1,4‐C‐O linkage structure which possessed melting point higher than the poly(p‐phenylene sulfide) or type II liquid crystalline polymer. The regioselectivity was enhanced when employing molecular sieves‐supported manganese catalyst system at 90°C and the crystallinity of poly(2,5‐dimethyl‐1,4‐phenylene oxide)s was estimated by wide‐angle X‐ray scattering (WAXS) and DSC. The crystallinity was calculated about 23.7% and a heat‐reversible melting and crystallization behavior occurred at 327.8 and 306.8°C, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

On the effect of crystallinity on the elastic properties of semicrystalline polyethylene

The small strain elastic response of a semicrystalline polyethylene has been simulated with a simple finite element model comprising a composite microstructure of alternating amorphous and crystalline layers arranged in a multi‐layered spherical shell structure. The crystalline lamella is modeled as an isotropic solid having the experimentally determined modulus properties of bulk linear polyethylene and extrapolated to 100% crystallinity. The amorphous layer is modeled as an elastomeric solid with the modulus that of molten linear polyethylene extrapolated to room temperature. Assuming constancy of these phase properties, the finite element calculations of elastic modulus versus crystallinity fit quite well the experimental data of Crist for linear polyethylene above 55% crystallinity. At lower crystallinity the experimental modulus data, which are for copolymers, fall below the model calculations. Two possible causes are discussed: the loss of deformation constraint in lamellae of finite and decreasing width as crystallinity declines, and an expansion of the crystal lattice as a result of the crowding of the comonomer units excluded from the crystal lamella. Either effect would reduce both the modulus and the yield stress as is observed.     

Morphology and crystallization of poly(ethylene terephthalate)

The melting behaviour and the morphology of poly(ethylene terephthalate) crystallized from the melt are reported. In general, dual or triple melting endotherms are seen, and single endotherms are seen when the samples are crystallized above 215°C for long times. The location of the uppermost endotherm was found to be constant below T_c = 230°C, and above that temperature the location depends on T_c. Therefore, we have shown that samples of PET which are crystallized above T_c = 230°C contain perfect crystals only; below T_c = 230°C, they contain perfect and imperfect crystals. Scanning electron microscopy showed that the perfect crystals are the dominant lamellae in the spherulitic structure, while the imperfect crystals are the subsidiary lamellae in the spherulitic structure, The amorphous regions are located between individual lamellae.     

Transport properties and their correlation with the morphology of thermally conditioned polypropylene

Time-lag and static sorption experiments were employed to measure permeability, diffusivity and solubility constants of He, A, and CF₄ in polypropylene films cooled at various rates from the melt and subsequently annealed at varying temperatures near the melting point. While solubility constants in films annealed above 90°C showed the normal variation with the amorphous content of the polymer, solubility constants for all unannealed, quenched films were remarkably constant and independent of the rate of cooling. In fact, all quenched films appeared to have the same amorphous content (ca. 41%). The remaining material is believed to be a mixture of monoclinic and hexagonal crystallinity, the volume ratio of the two being a function of the rate of quenching, and changing on annealing, in favor of the more stable, monoclinic form; the transition occurring rather sharply at 90°C. X-ray diffraction provided supporting evidence for the presence of the hexagonal crystals. The diffusion behavior in crystalline polypropylene is normal and Fickian but instead of the usual decline with increasing crystallinity, diffusivities showed definite enhancement in the case of the annealed films, i.e., the expected monotonic decline of D with increasing crystallinity is not observed. This behavior is attributed to a reduction in diffusional impedance through formation of defects in existing crystallites, as the lamellae thicken, in a manner similar to that observed on annealing of polyethylene single crystals. The apparent activation energies of diffusion were essentially constant and independent of thermal history. This suggests that in a highly crystalline polymer diffusion is not so much impeded by the restricted mobility of chain segments but rather by the extremely small dimensions of the available diffusive pathways. In support of the argument that the transport properties of polypropylene are controlled at a level of microstructure well below the characteristic dimensions of spherulities, it was observed that bulk-crystallized polypropylene has a spherulitic structure whose size and texture do not change significantly on annealing.     

Preparation and structural characterization of nanocrystalline poly(vinyl chloride)

This article describes the development of novel nanocrystalline poly(vinyl chloride) (PVC) for potential applications in PVC processes and reports improvements in the mechanical properties and thermal resistance. Before the preparation of nanocrystalline PVC via jet milling, PVC was spray‐treated and heat‐treated to improve its crystallinity. The pulverization and degradation, morphology, crystalline structure, and melting‐point changes of postmodified PVC during jet milling and the relationship between the distributions of the particle size and processing temperature were investigated. X‐ray analysis and density testing indicated increased density and improved crystallinity. The crystalline region of nanocrystalline PVC was less than 80 nm, with a particle size distribution of 5–20 μm and a melting point of less than 128°C. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 563–569, 2004     

Melt spinning of poly(vinylidene fluoride) fibers and the influence of spinning parameters on β‐phase crystallinity

The effects of melt‐spinning and cold‐drawing parameters on the formation of β‐phase crystallinity in poly(vinylidene fluoride) (PVDF) fibers and ways of increasing such crystallinity were studied. Fibers were melt‐spun with four different melt draw ratios (MDRs) and were subsequently cold‐drawn at different draw ratios (λ). The maximum λ value in cold drawing was dependent on the MDR used in melt spinning. The crystalline structure of the fibers was studied mainly with differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The results showed that the degree of crystallinity in the fibers was determined by the MDR and that before cold drawing the crystalline structure of the fibers was predominantly in the α form. By cold drawing, α‐phase crystallites could be transformed into the β phase. It was established that, under certain conditions of melt spinning and cold drawing, PVDF fibers of up to 80% crystallinity, mainly in the β form, could be prepared. It was further proposed that fibers spun at a sufficiently high MDR consist to a large extent of extended‐chain crystals, and this greatly affects the melting point of PVDF. Thus, DSC melting‐point data were shown to be insufficient for determining the crystalline phase of PVDF. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparing elastomeric behavior of block and random ethylene–octene copolymers

This work compared the elastomeric properties of two low‐crystallinity ethylene–octene copolymers. One was a block copolymer with lamellar crystals and the other was a random copolymer with fringed micellar crystals. The comparison of the stress–strain behavior at 23°C revealed that the initial elastic modulus and the yield stress depended only on the crystallinity of the copolymer. When the temperature was raised above 23°C, melting of the fringed micellar crystals of the random copolymer caused a rapid decrease in the modulus. Some decrease in the modulus of the block copolymer over the same temperature range was attributed to the crystalline α‐relaxation. Both polymers exhibited strain‐hardening, ultimate fracture at high strains, and high recovery after fracture. However, in the block copolymer, the onset of strain‐hardening and the ultimate fracture occurred at higher strains. The block copolymer also showed higher recovery from high strains. The initial stretching resulted in a permanent change in the stress–strain curve. It was suggested that following the onset of crystal slippage at the yield, the crystals underwent permanent structural changes through the course of the strain‐hardening region. The transformation of the fringed micellar crystals occurred at lower strains than the transformation of the lamellar crystals. The extent of the structural transformation was described by the crosslink density and the strain‐hardening coefficient extracted from elasticity theory. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Structure and processability of iodinated poly(vinyl alcohol). IV. Drawability of the films iodinated at solution before casting

The drawability of iodinated at solution before casting (IBC) polyvinyl alcohol films prepared by casting aqueous solutions of 10 wt % PVA containing 15.2, 39.8, 83.2, 117.0, and 140.1% was examined with a tensile tester at 20–60°C. The tensile behavior of IBC films showed that the yield and breaking loads were much lower, and the breaking elongation was even higher than those of the unoriented iodinated after casting (IAC) films as well as the untreated PVA films. The maximum draw ratios of the films with the weight gain of 15.2, 39.8, 83.2, 117, and 140.1% were 4.5, 5.5, 8.5, 8.0, and 7.5, respectively, which were achieved at 20°C in all. The crystallinity of all films increased by the maximum draw, regardless of crystallinity before drawing. The crystalline structure was recovered to the original PVA crystalline lattice by deiodination. Amorphous orientation and initial moduli increased with the maximum draw ratio, while the orientation of crystals was constant. The orientation and moduli increased up to the weight gain of 83.2%, whose highest draw ratio and initial modulus were 8.5 and of 7.1 GPa, respectively, and then decreased. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008