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1.
This study examined the effect of the ultradrawing behavior of gel film specimens of ultrahigh‐molecular‐weight polyethylene (UHMWPE) and UHMWPE/low‐molecular‐weight polyethylene (LMWPE) blends on their physical properties. The concentration of a gel film approximated its critical concentration at a fixed drawing temperature; its achievable draw ratio was higher than that of other blend specimens with various concentrations. Noticeably, when about 5 wt % LMWPE was added to a UHMWPE/LMWPE gel film specimen, the achievable draw ratio of the gel film increased, and this contributed to an apparent promoting effect on its anticreeping properties and thermal stability. Therefore, when ULB?0.9 was drawn to a draw ratio of 300, the anticreeping behavior was improved to less than 0.026%/day. Moreover, with respect to the thermal stability, when the same specimen was drawn to a draw ratio of 300, the retention capability of its storage modulus could resist a high temperature of 150°C, which was obviously much higher than the temperature of an undrawn gel film specimen (70°C). To study these interesting behaviors further, this study systematically investigated the gel solution viscosities, anticreeping properties, dynamic mechanical properties, thermal properties, molecular orientations, and mechanical properties of undrawn and drawn UHMWPE/LMWPE gel film specimens. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008  相似文献   

2.
The influence of formation temperature on the ultradrawing properties of ultrahigh‐molecular‐weight polyethylene/carbon nanotube (UHMWPE/CNT) fiber specimens is investigated. Gel solutions of UHMWPE/CNT with various CNT contents were gel‐spun at the optimum concentration and temperature but were cooled at varying formation temperatures in order to improve the ultradrawing and tensile properties of the UHMWPE/CNT composite fibers. The achievable draw ratio (Dra) values of UHMWPE/CNT as‐prepared fibers reach a maximum when they are prepared with the optimum CNT content and formation temperature. The Dra value of UHMWPE/CNT as‐prepared fibers produced using the optimum CNT content and formation temperature is about 33% higher than that of UHMWPE as‐prepared fibers produced using the optimum concentration and formation temperature. The percentage crystallinity (Wc) and melting temperature (Tm) of UHMWPE/CNT as‐prepared fiber specimens increase significantly as the formation temperature increases. In contrast, Wc increases but Tm decreases significantly as the CNT content increases. Dynamic mechanical analysis of UHMWPE and UHMWPE/CNT fiber specimens exhibits particularly high α‐transition and low β‐transition, wherein the peak temperatures of α‐transition and β‐transition increase dramatically as the formation temperature increases and/or CNT content decreases. In order to understand these interesting drawing, thermal and dynamic mechanical properties of the UHMWPE and UHMWPE/CNT as‐prepared fiber specimens, birefringence, morphological and tensile studies of as‐prepared and drawn fibers were carried out. Possible mechanisms accounting for these interesting properties are proposed. Copyright © 2010 Society of Chemical Industry  相似文献   

3.
The influence of two‐stage drawing conditions on the ultradrawing behavior of the gel films of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene blends is reported in this article. The critical draw ratios (λc) of the gel films prepared near their critical concentrations were found to depend significantly on the draw ratio attained in the first drawing stage (D1r) and on the temperature utilized in the second drawing stage (Tsec). After drawing the gel films to a fixed draw ratio in the first drawing stage, each two‐stage drawn gel film was made to exhibit a maximum λccmax) by drawing the drawn gel film at its corresponding optimum Tsec. In addition, the optimum Tsec was found to increase significantly with the D1r value of the drawn gel films. It is worth noting, on the other hand, that the λcmax of two‐stage drawn gel films increased consistently with an increasing D1r until its value reached an optimum value of 160. These results clearly suggest that, as Tsec and D1r are increased to their optimum values, the λcmax of the two‐stage drawn gel films can be improved further so as to be higher than those of the corresponding one‐stage drawn gel films. These interesting phenomena were investigated in terms of reduced viscosities of the solutions and by an analysis of the thermal, birefringence, and tensile properties of the drawn gel films. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1890–1901, 2001  相似文献   

4.
An investigation of the influence of the contents of original and modified attapulgite (ATP) on the ultradrawing properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE)/ATP (FAx) and UHMWPE/modified ATP (FAmx) as‐prepared fibers is reported. Similar to what is found for the orientation factor values, the achievable draw ratios (Dra) of the FAx and FAmx as‐prepared fibers approach a maximum value as the original ATP and/or modified ATP contents reach their corresponding optimum values. The maximum Dra value obtained for FAmx as‐prepared fiber specimens is significantly higher than that for FAx as‐prepared fiber specimens prepared at the optimum original ATP content. Similar to what is found for the orientation factors and achievable drawing properties, the tensile strength (σf) and initial modulus (E) of both drawn F2Ax and F2Amx fiber series specimens with a fixed draw ratio reach maximum values as the original and/or modified ATP contents approach the optimum values, respectively. The σf and E values of the F2Amx fiber specimens are always significantly higher than those of the corresponding F2Ax fiber specimens prepared at the same draw ratios and ATP contents but without being modified. To understand the interesting ultradrawing, orientation and tensile properties of FAx and FAmx fiber specimens, Fourier transform infrared spectral, specific surface area, transmission electron microscopic and elemental analyses of the original and modified ATPs were performed. Copyright © 2012 Society of Chemical Industry  相似文献   

5.
A systematic study of the influence of the drawing temperature and rate on the ultradrawing properties of film samples prepared from gel solutions of ultrahigh molecular weight polyethylene and low molecular weight polyethylene blends is reported. At a fixed drawing rate, the achievable draw ratios reached a maximum value when each film specimen was drawn at a temperature near its optimum temperature (Top). It is interesting to note that the Top values of each film sample increased consistently with the drawing rate. The achievable draw ratio of each film sample drawn at a constant rate and a temperature near Top is referred to as the Draop, which reached another maximum value as the drawing rates approached an optimum value. Dynamic mechanical analysis of the film sample exhibited an extraordinary high transition peaked at temperature near 95°C, which is again very close to the Top value found for the film sample drawn at a relatively low rate. On the other hand, the birefringence values and tensile strengths of the film specimen were found to improve significantly with the draw ratios, although the improvement of these properties reduced significantly at high draw ratios. Moreover, both the drawing temperature and rate showed beneficial influence on the birefringence, and tensile strengths of the drawn film specimens. Possible mechanisms accounting for these interesting deformation properties are suggested.  相似文献   

6.
The ultradrawing behavior of gel films of plain ultrahigh molecular weight polyethylene (UHMWPE) and UHMWPE/low molecular weight polyethylene (LMWPE) blends was investigated using one- and two-stage drawing processes. The drawability of these gel films were found to depend significantly on the temperatures used in the one- and two-stage drawing processes. The critical draw ratio (λc) of each gel film prepared near its critical concentration was found to approach a maximum value, when the gel film was drawn at an “optimum” temperature ranging from 95 to 105°C. At each drawing temperature, the one-stage drawn gel films exhibited an abrupt change in their birefringence and thermal properties as their draw ratios reached about 40. In contrast, the critical draw ratios of the two-stage drawn gel films can be further improved to be higher than those of the corresponding single-stage drawn gel films, in which the two-stage drawn gel films were drawn at another “optimum” temperature in the second drawing stage after they had been drawn at 95°C to a draw ratio of 40 in the first drawing stage. These interesting phenomena were investigated in terms of the reduced viscosities of the solutions, thermal analysis, birefringence, and tensile properties of the drawn and undrawn gel films. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 149–159, 1998  相似文献   

7.
The drawing and ultimate tensile properties of the modified PA 6 (MPA) fiber specimens prepared at varying drawing temperature were systematically investigated, wherein the MPA resins were prepared by reactive extrusion of PA 6 with the compatibilizer precursor (CP). At any fixed drawing temperature, the achievable draw ratio (Dra) values of MPA as‐spun fiber specimens increase initially with increasing CP contents, and then approach a maximum value, as their CP contents are close to the 5 wt% optimum value. The maximum Dra values obtained for MPA as‐spun fiber specimens prepared at the optimum CP content reach another maximum as their drawing temperatures approach the optimum drawing temperature at 120°C. The tensile and birefringence values of PA 6 and MPA fiber specimens improve consistently as their draw ratios increase. Similar to those found for their achievable drawing properties, the ultimate tensile and birefringence values of MPA fiber specimens approach a maximum value, as their CP contents and drawing temperatures approach the 5 wt% and 120°C optimum values, respectively. Investigations including Fourier transform infrared, melt shear viscosity, gel content, thermal and wide angle X‐ray diffraction experiments were performed on the MPA resin and/or fiber specimens to clarify the optimum CP content and possible deformation mechanisms accounting for the interesting drawing, birefringence, and ultimate tensile properties found for the MPA fiber specimens prepared in this study. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers  相似文献   

8.
Ultra‐high‐molecular‐weight polyethylene (PE) with viscosity‐average molecular weight (Mv) of 3.1 × 106 to 5.2 × 106 was prepared with a heterogeneous Ziegler–Natta MgCl2 (ethoxide type)/TiCl4/triethylaluminum catalyst system under controlled conditions. The optimum activity of the catalyst was obtained at a [Al]/[Ti] molar ratio of 61 : 1 and a polymerization temperature of 60°C, whereas the activity of the catalyst increased with monomer pressure and decreased with hydrogen concentration. The titanium content of the catalyst was 2.4 wt %. The rate/time profile of the catalyst was a decay type with a short acceleration period. Mv of the PE obtained decreased with increasing hydrogen concentration and polymerization temperature. The effect of stirrer speeds from 100 to 400 rpm did not so much affect the catalyst activity; however, dramatic effects were observed on the morphology of the polymer particles obtained. A stirrer speed of 200 rpm produced PE with a uniform globulelike morphological growth on the polymer particles. The particle size distributions of the polymer samples were determined and were between 14 and 67 μm. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010  相似文献   

9.
The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.  相似文献   

10.
Dimensions of conical dies were found to have a significant influence on thermal, morphological, orientation, ultradrawing, and dynamic mechanical properties of the as‐prepared and/or drawn ultrahigh molecular weight polyethylene (UHMWPE) fiber specimens prepared in this study. Many demarcated “micro‐fibrils” were found paralleling to fiber direction of the as‐prepared UHMWPE fiber specimens. The percentage crystallinity, melting temperatures, orientation factor (fo) and achievable draw ratio (Dra) values of each as‐prepared UHMWPE fiber specimen prepared at a fixed length of outlet land reach a maximum value, as the entry angles of the conical die approach the optimum value at 75°. The maximum fo and Dra values obtained for each F2075‐y as‐prepared fiber series specimens prepared using the optimum entry angle reach another maximum value as their length of outlet land approach the optimum value of 6.5 mm. The ultimate tensile strengths and moduli of the drawn UHMWPE fibers prepared at the optimum entry angle and length of outlet land are significantly higher than those of fibers prepared at other conditions but stretched to the same draw ratio. Possible reasons accounting for the above interesting properties were discussed in this study. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers  相似文献   

11.
Blends of chlorinated polyethylene and an ethylene vinyl acetate copolymer of various compositions were prepared by mixing in the melt state. Dynamic rheological properties of these blends were studied at different temperatures below, near, and above the TS, the temperature of phase separation, and in a frequency range from 0.01 to 100 rad/s. It is shown that the time–temperature superposition principle is suitable in all investigated temperature ranges. G′ versus G″ representations for the blends were found to be independent of temperature and varying weakly with the composition. Changes in the relaxation spectra H(τ) were discovered which depend on the prehistory of the blend preparation and on thermal conditions in the working unit of a rheometer (increasing the temperature from 140 to 180°C or decreasing the temperature from 180 to 140°C). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1911–1918, 2003  相似文献   

12.
Multifunctional hydrogels combining the capabilities of cellular pH responsiveness and shape memory, are highly promising for the realization of smart membrane filters, controlled drug released devices, and functional tissue‐engineering scaffolds. In this study, lipase was used to catalyze the synthesis of medium‐chain‐length poly‐3‐hydroxyalkanoates‐co‐polyethylene glycol methacrylate (PHA‐PEGMA) macromer, which was used to prepare pH‐responsive and shape memory hydrogel via free radical polymerization. Increasing the PEGMA fraction from 10 to 50% (mass) resulted in increased thermal degradation temperature (Td) from 430 to 470°C. Highest lower critical solution temperature of 37°C was obtained in hydrogel with 50% PEGMA fraction. The change in PEGMA fraction was also found to highly influence the hydrogel's hydration rate (r) from 2.8 × 10?5 to 7.6 × 10?5 mL·s?1. The hydrogel's equilibrium weight swelling ratio (qe), protein release and its diffusion coefficient (Dm) were all found to be pH dependent. Increasing the phosphate buffer pH from 2.4 to 13 resulted in increased qe from 2 to 16 corresponding to the enlarging of network pore size (ξ) from 150 to 586 nm. Different types of crosslinker for the hydrogel influenced its flexibility and ductility. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41149.  相似文献   

13.
Vitamin E stabilization of radiation‐crosslinked ultrahigh‐molecular‐weight polyethylene (UHMWPE) joint implants was successfully introduced to improve long‐term oxidation resistance. Current clinically available vitamin E stabilized UHMWPE implants were prepared by the postirradiation diffusion of vitamin E into 100‐kGy‐irradiated UHMWPE by a two‐step process, which included doping in pure vitamin E at an elevated temperature below the melting point followed by an annealing step at an elevated temperature in inert gas to homogenize the antioxidant throughout components of desired thickness. We hypothesized that the diffusion of vitamin E could be enhanced with supercritical carbon dioxide (SC‐CO2) during homogenization without an increase in the surface vitamin E concentration, which would thus result in faster homogenization. Our hypothesis tested positive; crosslinked UHMWPE doped with vitamin E at 120°C and homogenized in SC‐CO2 at 10–12 MPa had a greater penetration of vitamin E than those homogenized in inert gas. We attributed the faster diffusion of vitamin E in irradiated UHMWPE in SC‐CO2 to the dissolution of vitamin E in the supercritical fluid and a rate of diffusion that was closer to that of the supercritical fluid in the polymer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012  相似文献   

14.
For the preparation of high‐molecular‐weight (HMW) poly(N‐vinylcarbazole) (PVCZ) with a narrow molecular weight distribution, N‐vinylcarbazole (VCZ) was solution‐polymerized in 1,1,2,2‐tetrachloroethane (TCE) at ?20, 0, and 20°C with photoinitiation. The effects of the polymerization temperature and the concentrations of the polymerization solvent and photoinitiator on the polymerization behavior and molecular parameters of PVCZ were investigated. A low polymerization temperature with photoirradiation was successful in obtaining HMW PVCZ with a smaller temperature rise during polymerization than that for thermal free‐radical polymerization by azobisisobutyronitrile (AIBN). The photo‐solution‐polymerization rate of VCZ in TCE was proportional to [AIBN]0.45. The molecular weight was higher and the molecular weight distribution was narrower for PVCZ made at lower temperatures. For PVCZ prepared in TCE at ?20°C with a photoinitiator concentration of 0.00003 mol/mol of VCZ, a weight‐average molecular weight of 920,000 was obtained, with a polydispersity index of 1.46, and the degree of transparency converged to about 99%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2391–2396, 2003  相似文献   

15.
Compatibilization of the blends of polydimethyl siloxane (PDMS) rubber and low‐density polyethylene (LDPE) was achieved through reactive processing during extrusion in a Monsanto Processability Tester (MPT). The chemorheological characteristics of 50 : 50 LDPE : PDMS blends with varying proportions (0–8 wt %) of ethylene comethyl acrylate (EMA) were investigated at three different temperatures (170, 190, and 210°C) and four different shear rates (61.3, 122.6, 306.6, and 613.1 s?1). It was found that EMA reacts with vinyl groups of PDMS rubber at a temperature of 190°C during extrusion through the capillary of MPT, forming EMA‐grafted‐PDMS rubber (EMA‐g‐PDMS), which acts as the compatibilizer for the blend systems. The results are based on IR spectroscopy, melt rheology, and phase morphology of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2810–2817, 2003  相似文献   

16.
The roller drawing of ultrahigh molecular weight polyethylene (UHMW-PE) sheets were carried out in the roller temperature Tr range of 100–140°C. In addition to the roller drawing in the solid state (Tr = 100°C), we attempted to crystallize the molten UHMW-PE sheet under the roller-drawing process (Tr = 100–140°C). The tensile and dynamic viscoelastic properties, the molecular orientation, and the microstructure of the roller-drawn UHMW-PE sheets were investigated. The mechanical properties of UHMW-PE sheets were much improved by crystallization during the roller drawing process at Tr = 140°C. The sheets roller-drawn at Tr = 135 and 140°C exhibited c-axis orientation to the draw direction and (100) alignment in the sheet plane. However, at Tr = 100°C the elastic motion of the amorphous chains induces the twinnings of lattice, which enhances the transition to the (110) alignment in the sheet plane. The dynamic storage modulus below γ-dispersion temperature showed good correlation with crystallinity and orientation functions, while taut tie molecules and thick crystallites play an important role in the storage modulus above γ-dipersion temperature.  相似文献   

17.
High‐strength and porous ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers have been prepared through a two‐stage drawing process. Combined with tensile testing, scanning electron microscopy, and small‐angle X‐ray scattering, the mechanical properties, porosity, and microstructural evolution of the UHMWPE fibers were investigated. The first‐stage cold drawing of the gel‐spun fibers and subsequent extraction process produced fibers with oriented lamellae stacks on the surface and plentiful voids inside but with poor mechanical properties. The second‐stage hot drawing of the extracted fibers significantly improved the mechanical properties of the porous fibers because of the formation of lamellar backbone networks on the surface and microfibrillar networks interwoven inside to support the voids. With various processing conditions, the optimized mechanical properties and porosity of the prepared UHMWPE fibers were obtained a tensile strength of 1.31 GPa, a modulus of 10.1 GPa, and a porosity of 35%. In addition, a molecular schematic diagram is proposed to describe structural development under two‐stage drawing, including void formation and lamellar evolution. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42823.  相似文献   

18.
The effects of a mixed solvent consisting of water and organic solvents such as acetone and methanol on the photografting (λ > 300 nm) of N‐isopropylacrylamide (NIPAAm) on linear low‐density polyethylene film (thickness = 30 μm) was investigated at 30°C and 60°C. Xanthone, which had been coated on the film, was used as a photoinitiator. The photografting initiated even in the system at 30°C by using a longer irradiation time. It was found that the maximum percentage of grafting was attained at a certain concentration of organic solvent in the mixed solvent, which shifted to a lower concentration of organic solvent in the system at 60°C compared with the system at 30°C. It was found that the grafted chains of the sample prepared in the system with the higher polymerization temperature and the use of mixed solvent penetrated into the center of the film compared with the sample prepared in the system with the lower polymerization temperature and use of a water solvent. Moreover, the NIPAAm‐grafted films exhibited temperature responsiveness, swelling and shrinking in water at 0°C and 50°C, respectively. The extent of this characteristic was found to be closely related to the location of the grafted chains in film substrate, which was measured by an attenuated total reflection infrared spectroscope and a scanning electron microscope. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 458–463, 2003  相似文献   

19.
The zone‐drawing method was applied to chemically synthesized polyaniline cast films of emeraldine base under various applied tensions and drawing temperatures. The changes in the microstructure and viscoelastic properties of the resulting films were investigated. It was found that the microstructure was strongly affected by the drawing temperature (Td). The crystallinity, crystallite size, and orientation factor of crystallites, respectively, attained 42%, 23 Å, and 0.975 for the film zone‐drawn at Td = 170°C, whereas a further increase in the Td brought about a decrease of these values. The viscoelastic measurements indicated that the dynamic storage modulus attained 12 GPa at room temperature and was 5 GPa at 280°C for the film zone‐drawn at Td = 210°C, which was comparable to that of the typical engineering plastics. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 566–571, 2000  相似文献   

20.
Ultrahigh molecular weight polyethylene (UHMWPE)/nanosilica (F2Sy) and UHMWPE/modified nanosilica (F2Smxy) as‐prepared fibers were prepared by spinning of F2Sy and F2Smxy gel solutions, respectively. Modified nanosilica particles were prepared by grafting maleic anhydride grafted polyethylenes onto nanosilica particles. The achievable draw ratios (Dra) of F2Sy and F2Smxy as‐prepared fibers approached a maximal value as the original and modified nanosilica contents reached corresponding optimum values; the maximal Dra value obtained for F2Smxy as‐prepared fiber specimens was significantly higher than that of the F2Sy as‐prepared fiber specimens prepared at the optimum nanosilica content. The melting temperature and evaluated lamellar thickness values of F2Sy and F2Smxy as‐prepared fiber series specimens decrease, but crystallinity values increase significantly, as their original and modified nanosilica contents respectively increase. Similar to the achievable drawing properties of the as‐prepared fibers, the orientation factor, tensile strength (σf) and initial modulus (E) values of both drawn F2Sy and F2Smxy fiber series specimens with a fixed draw ratio reach a maximal value as the original and/or modified nanosilica contents approach the optimum values; the σf and E values of the drawn F2Smxy fiber specimens are significantly higher than those of the corresponding drawn F2Sy fiber specimens prepared at the same draw ratios and nanosilica contents but without being modified. To understand the interesting ultradrawing, thermal, orientation and tensile properties of F2Sy and F2Smxy fiber specimens, Fourier transform infrared, specific surface area and transmission electron microscopy analyses of the original and modified nanosilica were performed in this study. © 2012 Society of Chemical Industry  相似文献   

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