Ultradrawing behavior of gel films of ultrahigh molecular weight polyethylene and low molecular weight polyethylene blends at varying drawing conditions

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 (T_op). It is interesting to note that the T_op 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 T_op is referred to as the D_raop, 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 T_op 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.     

Wetting of oriented and etched ultrahigh molecular weight polyethylene

Highly oriented gel‐spun ultrahigh molecular weight polyethylene (UHMWPE) fibers possess many outstanding properties desirable for composite materials but their adhesion to such matrices as epoxy is poor. This article describes the combined effects of drawing and surface modification on the bulk and surface properties of gel‐cast UHMWPE films emphasizing the effects of etching on both undrawn and drawn films. Drawing the films yields a fibrillar structural hierarchy similar to UHMWPE fibers and a significant increase in orientation, melting point, modulus, and strength. The effects of drawing on bulk properties were more significant than those of etching. The poor adhesion of epoxy to the smooth, fibrillar, and relatively nonpolar drawn film surface improves significantly with oxidization and roughening on etching. The interlaminar shear failure occurred cohesively in the UHMWPE, and thus the interlaminar shear failure strength was greater for the drawn UHMWPE with its greater tensile strength. Nitrogen plasma etching yielded the best results, both removing any low molecular weight surface layer and etching the UHMWPE beneath. Oxygen plasma etching enhanced wetting but was too harsh, causing extensive surface degradation and a significant reduction in mechanical properties. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 405–418, 1999     

Influence of two‐stage drawing conditions on ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends

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 (λ_c) of the gel films prepared near their critical concentrations were found to depend significantly on the draw ratio attained in the first drawing stage (D_1r) and on the temperature utilized in the second drawing stage (T_sec). 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 λ_c (λ_cmax) by drawing the drawn gel film at its corresponding optimum T_sec. In addition, the optimum T_sec was found to increase significantly with the D_1r value of the drawn gel films. It is worth noting, on the other hand, that the λ_cmax of two‐stage drawn gel films increased consistently with an increasing D_1r until its value reached an optimum value of 160. These results clearly suggest that, as T_sec and D_1r are increased to their optimum values, the λ_cmax 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     

Effect of the ultradrawing behavior of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends on their physical properties

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 UL_B?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     

Investigation of the ultradrawing properties of gel spun fibers of ultra‐high molecular weight polyethylene/carbon nanotube blends

The carbon nanotubes (CNTs) contents, ultrahigh‐molecular‐weight polyethylene (UHMWPE) concentrations and temperatures of UHMWPE, and CNTs added gel solutions exhibited significant influence on their rheological and spinning properties and the drawability of the corresponding UHMWPE/CNTs as‐prepared fibers. Tremendously high shear viscosities (ηs) of UHMWPE gel solutions were found as the temperatures reached 140°C, at which their ηs values approached the maximum. After adding CNTs, the ηs values of UHMWPE/CNTs gel solutions increase significantly and reach a maximum value as the CNTs contents increase up to a specific value. At each spinning temperature, the achievable draw ratios obtained for UHMWPE as‐prepared fibers prepared near the optimum concentration are significantly higher than those of UHMWPE as‐prepared fibers prepared at other concentrations. After addition of CNTs, the achievable draw ratios of UHMWPE/CNTs as‐prepared fibers prepared near the optimum concentration improve consistently and reach a maximum value as their CNTs contents increase up to an optimum value. To understand these interesting drawing properties of the UHMWPE and UHMWPE/CNTs as‐prepared fibers, the birefringence, thermal, morphological, and tensile properties of the as‐prepared and drawn fibers were investigated. Possible mechanisms accounting for these interesting properties are proposed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Ultradrawing properties of ultrahigh‐ molecular‐weight polyethylene/carbon nanotube fibers prepared at various formation temperatures

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 (D_ra) values of UHMWPE/CNT as‐prepared fibers reach a maximum when they are prepared with the optimum CNT content and formation temperature. The D_ra 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 (W_c) and melting temperature (T_m) of UHMWPE/CNT as‐prepared fiber specimens increase significantly as the formation temperature increases. In contrast, W_c increases but T_m 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     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

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.     

Rolling and roll-drawing of ultrahigh molecular weight polyethylene reactor powders

Ultrahigh molecular weight polyethylene (UHMWPE) reactor powders have been found to be processable in the solid state by the techniques of rolling and roll-drawing. Plates of compacted UHMWPE reactor powder were prepared below their melting points. These plates were then rolled at 124°C. The maximum uniaxial draw ratio (DR) obtained by multiple rolling was about 10. In additional experiments, rolled plates of a DR of 6 were further drawn by tensile stretching at a temperature of 135°C. The specimens prepared by rolling and by the two-stage draw were characterized by tensile measurements, differential scanning calorimetry (DSC), and X-ray diffraction. Results show that, on rolling alone, the tensile modulus and tensile strength achieved were 3 GPa and 42 MPa, respectively, at a DR of 9.6. The rolled plates were effectively drawn further to a total DR of 86. Such highly drawn films exhibited tensile moduli and tensile strength up to 81 and 1.3 GPa, respectively. A high crystallinity and high crystal orientation were also obtained by the two-stage draw.     

Ultradrawing of blend films of ethylene-dimethyl-aminoethyl methacrylate copolymer and ultra-high molecular weight polyethylene prepared by gelation/crystallization from solutions

Copolymer ethylene-dimethyl-aminoethyl methacrylate (EDAM) with 3.9% DAM side groups and ultra-high molecular weight polyethylene (UHMWPE) were blended in decalin solvent. The hot homogenized solution was poured into an aluminum tray to form gels and the decalin was allowed to evaporate from the resultant gels under ambient condition. Surprisingly, the resultant dry blend films could be elongated to more than 200-fold (λ=200) even for the blend film with 90% EDAM content (9/1 composition), although the maximum draw ratio of EDAM homopolymer films was 1.6-fold (λ=1.6). The mechanism of the great drawability was dependent upon the content of EDAM. The drawability for the 9/1 composite films was attributed to large crystal lamellae of UHMWPE ensuring crystal transition from a folded to a fibrous type. Accordingly, EDAM chains were independent of ultradrawing of UHMWPE and kept a random orientation under ultra-drawing process. The storage (Young's) modulus was 10 GPa at 20 °C. In contrast, EDAM chains within the 1/1 composite films were oriented drastically together with UHMWPE crystallites. The modulus of the 1/1 composition at 20 °C reached 68 GPa, which was higher than the value (40 GPa) of polypropylene films with λ=100. Such considerable difference of modulus due to EDAM content was analyzed in relation to the gelation/crystallization from solutions.     

Impact behavior of phenolphthalein poly(ether sulfone)/ultrahigh molecular weight polyethylene blends

This work presents the structure and impact properties of phenolphthalein poly(ether sulfone) blended with ultrahigh molecular weight polyethylene (PES-C/UHMWPE) at different compositions. The addition of UHMWPE can considerably improve the Charpy and Izod impact strength of the blends. The fracture surface is examined to demonstrate the toughening mechanics related to the modified PES-C resin. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 113–118, 1998     

Preparation and characterization of novel ultra‐high molecular weight polyethylene composite fibers filled with nanosilica particles

Ultrahigh molecular weight polyethylene (UHMWPE)/nanosilica (F₂S_y) and UHMWPE/modified nanosilica (F₂S_mx‐y) as‐prepared fibers were prepared by spinning of F₂S_y and F₂S_mx‐y gel solutions, respectively. Modified nanosilica particles were prepared by grafting maleic anhydride grafted polyethylenes onto nanosilica particles. The achievable draw ratios (D_ra) of F₂S_y and F₂S_mx‐y as‐prepared fibers approached a maximal value as the original and modified nanosilica contents reached corresponding optimum values; the maximal D_ra value obtained for F₂S_mx‐y as‐prepared fiber specimens was significantly higher than that of the F₂S_y as‐prepared fiber specimens prepared at the optimum nanosilica content. The melting temperature and evaluated lamellar thickness values of F₂S_y and F₂S_mx‐y 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 (σ_f) and initial modulus (E) values of both drawn F₂S_y and F₂S_mx‐y 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 σ_f and E values of the drawn F₂S_mx‐y fiber specimens are significantly higher than those of the corresponding drawn F₂S_y 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 F₂S_y and F₂S_mx‐y 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     

超高分子量聚乙烯纤维的表面处理

综述了超高分子量聚乙烯（UHMWPE）纤维复合材料界面的重要性,总结了表面改性方法对UHMWPE纤维以及UHMWPE／树脂界面的影响。     

Preparation and characterization of ultrahigh molecular weight polyethylene and polyisoprene solvent-cast blend films

This study covers the preparation of noncrosslinked and crosslinked solvent-cast blend films of ultrahigh molecular weight polyethylene (UHMWPE) and polyisoprene rubber (PIR) and their mechanical, thermal, IR spectroscopic, and morphological characterizations. Solvent-cast films of polymer blends with 0, 10, 20, 35, 50, and 65% PIR composition were prepared by vigorous stirring from a hot decalin solution. The films were crosslinked chemically by using acetophenone as a crosslinking agent under UV radiation. The mechanical properties, measured as ultimate properties and tensile modulus, were found to decrease with PIR content but crosslinking was found to enhance the ultimate strength and tensile modulus. DSC results revealed that melting point of UHMWPE remains almost constant in blends. However, upon crosslinking, the melting point of UHMWPE is depressed almost 5°C. We observed a similar trend in the enthalpy change of the melting of UHMWPE and the variation of percent crystallinity in UHMWPE. Scanning electron microscopy (SEM) studies on the fractured surfaces of the blends showed that the fibrillar texture is present in both crosslinked and noncrosslinked blends. The crosslinking appeared to be through oxygen linkages, which are preferentially conjugated to double bonds, in addition to the possible carbon–carbon crosslinks. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1619–1630, 1998     

Toughness enhancement of poly(ethylene terephthalate) with functionalized ultrahigh molecular weight polyethylene

Ultrahigh molecular weight polyethylene (UHMWPE) is available commercially in the form of powder, consisting of fine primary particles, 1–5 μm in diameter, agglomerated into secondary “free‐flowing” particles with overall dimensions in the region of 50 to 150 μm. These are normally sufficiently coherent and retain their conglomerated particulate structure when blended with other polymers because of the extremely high viscosity of UHMWPE. In this study the surface of the agglomerated primary particles was acid functionalized by reactions with aqueous solutions of acrylic acid, after being irradiated with γ‐radiation at 15–45 kGy. The acid groups were used to introduce a glycidoxyl functionality through reactions with a difunctional cycloaliphatic epoxy resin and also to a “partial” metal carboxylate functionality through reactions with zinc acetyl acetonate. When blended with polyethylene terephthalate (PET) in either a small‐batch mixer or in a twin‐screw extruder all the treated powders, except those functionalized with acrylic acid, were broken down to their primary size and were uniformly dispersed and strongly bonded to the surrounding matrix. The blends containing the deglomerated particles were found to have much greater ductility and toughness than those produced from both untreated and acid functionalized powder. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2972–2986, 2001     

Ultradrawing properties of ultrahigh‐molecular‐weight polyethylene/attapulgite fibers

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 (FA_x) and UHMWPE/modified ATP (FA_mx) as‐prepared fibers is reported. Similar to what is found for the orientation factor values, the achievable draw ratios (D_ra) of the FA_x and FA_mx as‐prepared fibers approach a maximum value as the original ATP and/or modified ATP contents reach their corresponding optimum values. The maximum D_ra value obtained for FA_mx as‐prepared fiber specimens is significantly higher than that for FA_x 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 (σ_f) and initial modulus (E) of both drawn F₂A_x and F₂A_mx 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 σ_f and E values of the F₂A_mx fiber specimens are always significantly higher than those of the corresponding F₂A_x 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 FA_x and FA_mx 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     

Ultrahigh molecular weight polyethylene fibers prepared using conical dies with varying dimensions

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 (f_o) and achievable draw ratio (D_ra) 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 f_o and D_ra values obtained for each F₂₀^75‐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     

凝胶纺丝法制备超高分子量聚乙烯/高分子量聚乙烯纤维延伸性能的研究

用凝胶纺丝法制备了超高分子量聚乙烯(UHMWPE)/高分子量聚乙烯(HDPE)纤维,探讨了添加不同种类高分子量聚乙烯对凝胶初生纤维在后续延伸过程中延伸性能的影响。结果表明在固定制备条件时,当超高分子量聚乙烯(UHMWPE)/高分子量聚乙烯(HDPE)的质量比在最适当质量比时,高分子量聚乙烯的分子量为1.5～2.0×104时,所制备的凝胶初生纤维的可延伸比达最大值。     

Ultradrawing properties of gel films of ultrahigh‐molecular‐weight polyethylene and low‐molecular‐weight polyethylene blends prepared at various formation temperatures

The ultradrawing behavior of ultrahigh‐molecular‐weight polyethylene/low‐molecular‐weight polyethylene film specimens prepared at various concentrations and formation temperatures was studied. The critical draw ratio (D_rc) of UL_?0.7 film specimens was found to depend significantly on the formation temperature used to prepare the film specimens. At any fixed drawing temperature, the D_rc values of UL_?0.7 specimens prepared at various formation temperatures increased significantly as the formation temperatures were reduced. In fact, with an optimum drawing temperature of 95°C, the D_rc values of UL_?0.7 specimens prepared at a formation temperature of 0°C reached 488, about 50% higher than that of UL_?0.7 specimens prepared at a formation temperature of 95°C. These interesting phenomena were investigated in terms of the thermal, birefringence, and tensile properties of these undrawn and drawn UL_?0.7 specimens. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3728–3738, 2003     

超高分子量聚乙烯树脂的溶胀性的检测分析

通过上海化工研究院设计的在线检测装置对超高分子量聚乙烯(UHMWPE)溶胀过程中的温度、黏度进行测试,形成了UHMWPE树脂溶胀工艺的检测方法,对黏均分子量分别为3.261×106(A),3.833×106(B),3.455×106(C)3种不同树脂的溶胀温度、溶胀时间、溶胀比等参数进行了分析。结果表明:A,B,C树脂的溶胀温度分别为121,120,119℃;对溶胀釜加热系统设定统一温度,釜内温度达120℃时,A,B,C树脂的溶胀时间分别为60,30,3 min,溶胀比分别为2.37,2.51,2.31。