Mechanical properties of surface‐modified ultra‐high molecular weight polyethylene fiber reinforced natural rubber composites

The mechanical properties of ultra‐high molecular weight polyethylene (UHMWPE) fibers reinforced natural rubber (NR) composites were determined, and the effects of fiber surface treatment and fiber mass fraction on the mechanical properties of the composites were investigated. Chromic acid was used to modify the UHMWPE fibers, and the results showed that the surface roughness and the oxygen‐containing groups on the surface of the fibers could be effectively increased. The NR matrix composites were prepared with as‐received and chromic acid treated UHMWPE fibers added 0–6 wt%. The treated UHMWPE fibers increased the elongation at break, tear strength, and hardness of the NR composites, especially the tensile stress at a given elongation, but reduced the tensile strength. The elongation at break increased markedly with increasing fiber mass fraction, attained maximum values at 3.0 wt%, and then decreased. The tear strength and hardness exhibited continuous increase with increasing the fiber content. Several microfibrillations between the fiber and NR matrix were observed from SEM images of the fractured surfaces of the treated UHMWPE fibers/NR composites, which meant that the interfacial adhesion strength was improved. POLYM. COMPOS., 38:1215–1220, 2017. © 2015 Society of Plastics Engineers     

Enzyme‐mediated grafting of acrylamide to ultrahigh molecular weight polyethylene fiber: A novel radical initiation system

The enzyme‐mediated grafting of acrylamide (AM) to ultrahigh molecular weight polyethylene (UHMWPE) fibers using horseradish peroxidase (HRP) was demonstrated. To optimize the reaction condition, the concentrations of monomer, H₂O₂, the initiator, and time were varied. The grafting results were discussed and a reaction mechanism was proposed. Function groups and structural change of the graft copolymer were determined by FTIR spectroscopic and scanning electron microscopy micrographs for proof of grafting and the results were discussed. Results show that the surface of treated fiber becomes rougher than the untreated surface. Compared to unmodified fiber, modified fiber surface had significantly increased the interfacial shear strength, and carbonyl‐stretching regions in the IR spectra. The interfacial shear strength of the UHMWPE fiber increased, clearly indicating that enzymatic‐grafted acrylamide could significantly increase the hydrophilicity of the surfaces of UHMWPE fibers. Moreover, the hydrophilicity of treated fiber depends on the monomer concentration, the initiator concentration, and oxidizing agent concentration as well as the time of the reaction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1011–1016, 2005     

化学气相沉积PPy/UHMWPE纤维的研究

采用化学气相沉积制备了聚吡咯/超高相对分子质量聚乙烯(PPy/UHMWPE)纤维,测试了不同氧化剂浓度、不同沉积时间和温度下PPy/UHMWPE纤维的表面剪切强度,用扫描电镜、动态热机械分析仪、傅立叶变换红外光谱仪分析了PPy/UHMWPE纤维的表面形态、热机械性能和复合材料官能团的变化。结果表明:PPy均匀分布在UHMWPE纤维表面,UHMWPE纤维与PPy之间无化学键作用而是分子间作用力;随着氧化剂三氯化铁浓度的增加和吡咯沉积时间的延长,PPy/UHMWPE纤维表面剪切强度先增大后减小;随着处理温度的升高,PPy/UHMWPE纤维表面剪切强度先增大,当处理温度超过85℃时,其剪切强度则减小。     

超高相对分子质量聚乙烯纤维的低温等离子体处理

利用低温等离子体技术对超高相对分子质量聚乙烯(UHMWPE)纤维进行表面改性,用单因素试验和正交试验对改性后的UHMWPE纤维的静摩擦因数和断裂强力进行测试与分析,最终确定最优的等离子体改性工艺为压强50 Pa、功率100 W、时间180 s。对处理前后的UHMWPE纤维的毛细效应、表面形貌、红外光谱进行了测试和对比,结果发现:改性后的UHMWPE纤维的吸水性能明显增强,纤维表面变得凹凸不平,粗糙度和比表面积增大,纤维表面起伏数量增多,幅度变大,且出现了新的含氧官能团,有利于提高UHMWPE纤维表面的黏结性。     

Interfacial bond property of UHMWPE composite

The ultrahigh molecular weight polyethylene (UHMWPE)/hydrocarbon (PCH) composite was prepared by selecting a PCH resin as the matrix, which has the similar structure to UHMWPE fiber. The interfacial bond property between the PCH resin and UHMWPE fiber was investigated by macromechanics, micromechanics, and contact angle. The results show that the PCH resin has good wettability with the UHMWPE fiber surface. The UHMWPE/PCH composite has excellent transverse tensile strength, interlaminar shear strength, and the pull-out strength together with the outstanding interfacial bond property.     

EVA共混改性UHMWPE纤维的表面性能

以乙烯-醋酸乙烯酯共聚物(EVA)作为共混改性剂,将其溶解在超高相对分子质量聚乙烯(UHMWPE)纺丝溶液中,制得共混改性UHMWPE冻胶纤维;对改性UHMWPE冻胶纤维进行萃取,干燥和热拉伸制得改性UHMWPE纤维;研究了改性前后纤维的结构与性能.结果表明:共混改性后UHMWPE纤维表面引入了极性基团,纤维与树脂基体...     

The relationship between zeta-potential and pull-out shear strength on modified UHMWPE fiber reinforced epoxy composites

UHMWPE fiber exhibits high performance, featuring high tensile strength and modulus, because of its extended chain structure. However, this fiber demonstrates some defects, such as low melting point, creep, and poor interfacial bonding with resin. Therefore, it is still not widely applied in composites. This research attempted to improve the performance by applying interfacial treatment to the fiber, using polypyrrole (PPy) synthesized through oxidation. The interfacial shear strength was evaluated using the results of a pull-out test and a Zeta Potential. The UHMWPE fiber was exposed to PPy treatment at various temperatures. The PPy-modified fiber was then impregnated with epoxy to generate the composites. The effects of the modification were also examined. The performance of the composites was determined by the Zeta Potentials of the fiber and resin, using an EKA electrokinetic analyzer. The interfacial shear strength was determined by the pull-out test. The morphology of fiber was observed by SEM. Results show that the shear strength of the interface between the PPy-treated UHMWPE fiber and epoxy increased 215%. The correlation between the Zeta Potential and the interfacial shear strength was also observed.     

Influence of environmental moisture on atmospheric pressure plasma jet treatment of ultrahigh-modulus polyethylene fibers

One of the main differences between low-pressure and atmospheric-pressure plasma treatments is that there is little moisture involved in the low-pressure plasma treatment, although moisture could exist at the wall of the vacuum chamber or react with the substrate after plasma treatment, while in the atmospheric-pressure plasma treatment moisture exists not only in the environment but also in any hygroscopic substrate. In order to investigate the influence of environmental moisture on the effect of atmospheric pressure plasma treatment, ultra-high-modulus polyethylene (UHMPE) fibers were treated using an atmospheric-pressure plasma jet (APPJ) with 10 l/min helium gas-flow rate, treatment nozzle temperature of 100°C and 5 W output power. The plasma treatments were carried out at three different relative humidity levels, namely 5, 59 and 100%. After the plasma treatments, the surface roughness increased while the water-contact angle decreased with increasing relative humidity. The number of oxygen containing groups increased as the environmental moisture content increased. The interfacial shear strength of the UHMPE fiber/epoxy system was significantly increased after the plasma treatments, but the moisture level in the APPJ environment did not have a significant influence on the adhesion properties. In addition, no significant difference in single fiber tensile strength was observed after the plasma treatments at all moisture levels. Therefore, it was concluded that the environmental moisture did not significantly influence the effect of atmospheric-pressure plasma treatment in improving interfacial bonding between the fiber and epoxy. The improvement of the interfacial shear strength for the plasma-treated samples at all moisture levels was mainly due to the increased surface roughness and increased surface oxygen and nitrogen contents due to the plasma etching and surface modification effect.     

Improvement of adhesion between polyethylene and regenerated cellulose fibers by surface fibrillation

Regenerated cellulose fibers spun from straw pulp using the N-methylmorpholine N-oxide (NMMO) process were evaluated as a reinforcement for low-density polyethylene (LDPE). Surface fibrillation was carried out by a mechanical treatment to improve interfacial adhesion. Surface fibrillation resulted in a gradual change in surface topography, as detected by SEM. Long and numerous twisted fibrils were observed on the surface of the treated fibers. The fiber perimeters, determined by the Wilhelmy plate method, increased with an extended degree of fibrillation, while the strength of the fiber was not affected by the surface treatment. Model composites were prepared by embedding untreated and surface-fibrillated single fibers into an LDPE matrix, and the single fiber fragmentation (SEF) test was carried out to determine the critical fiber length. The interfacial shear strength (τ) was then calculated by applying a modified form of the Kelly-Tyson equation. It was found that the interfacial shear strength increased significantly as a result of surface fibrillation. The proposed mechanism for the improvement of interfacial adhesion is a mechanical anchoring between the matrix and the fiber.     

超高相对分子质量聚乙烯纤维的表面改性研究

选择乙烯-醋酸乙烯酯共聚物作为表面改性剂,将其溶解在二甲苯中制成复合萃取液,对超高相对分子质量聚乙烯(UHMWPE)冻胶纤维进行萃取,经干燥和超倍拉伸制得表面改性UHMWPE纤维。对改性前后纤维的表面化学结构、结晶性能、表面粘接性能和力学性能进行了比较。结果表明:加入表面改性剂后,纤维表面引入了极性基团,结晶形态不变,纤维与树脂的抗界面剪切强度大大增加,纤维的力学性能变化不大。     

The role of additional silane coupling agent treatment in oxygen plasma-treated UHMPE fiber/vinylester composites

Ultra-high modulus polyethylene (UHMPE) fiber was treated with oxygen plasma and a silane coupling agent in order to improve the interfacial adhesion between the UHMPE fiber and vinylester resin. The oxygen plasma and γ-methylmethacryloxypropyltrimethoxysilane (γ-MPS)-treated UHMPE fiber/vinylester composites showed a slightly higher interlaminar shear strength than the oxygen plasma-treated UHMPE fiber/vinylester composites. The interfacial adhesion of the oxygen plasma-treated UHMPE fiber/vinylester composites in this study is mainly due to mechanical interlocking between the micropits formed by the oxygen plasma treatment and the vinylester resin. The γ-MPS molecules adsorbed onto the UHMPE fiber surface neither affected the morphology of the UHMPE fiber surface, nor reduced the extent of mechanical interlocking. The improved interfacial adhesion by the γ-MPS treatment is due to enhanced wettability and chemical interaction through the chemically adsorbed γ-MPS molecules, as detected by Fourier-transform infrared (FT-IR) spectroscopy. The γ-MPS molecules adsorbed onto the ultra-high molecular weight polyethylene (UHMWPE) plate surface also reduced the aging effect of the oxygen plasma-treated UHMWPE surface.     

Surface modification of ultra‐high molecular weight polyethylene fiber by different kinds of SiO2 nanoparticles

We successfully improved the interfacial adhesion strength between ultra‐high molecular weight polyethylene (UHMWPE) fiber and resin by the surface modification of UHMWPE fiber with two kinds of SiO₂ nanoparticles through gel spinning process. Modified effect of treated SiO₂ nanoparticles by coupling agent was superior to original SiO₂ nanoparticles. Compared with unmodified fibers, pull‐out tests of modified UHMWPE/treated SiO₂ fibers revealed that interfacial adhesion strength increased by the maximum of 10.95%, but corresponding breaking strength decreased by 8.51%. In addition, the interfacial adhesion strength and breaking strength could continue to enhance with increasing the additive amount of treated SiO₂ nanoparticles. The results of Differential Scanning Calorimetry (DSC), X‐ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron Microscopy (SEM) indicated that the crystallinity of all modified fibers decreased while crystallite dimension increased, and the surface of modified fibers by treated SiO₂ nanoparticles exhibited polar functional group (C=O). The superiority of this modified technology was that it realized the bulk industrial production and maneuverability, low cost, and no pollution. POLYM. COMPOS., 38:1928–1936, 2017. © 2015 Society of Plastics Engineers     

偶联剂改性UHMWPE纤维表面性能的研究

选用硅烷偶联剂KH-550,KH-560和钛酸酯偶联剂NDZ-201作为表面改性剂,对超高相对分子质量聚乙烯(UHMWPE)冻胶纤维在萃取阶段进行表面处理,经干燥、超拉伸制得表面改性UHMWPE纤维。采用红外光谱仪、接触角测量仪测定了纤维的表面化学结构和表面润湿性能,采用单纤维树脂包埋-拔出法测定了纤维与树脂基体的界面剪切强度,比较了改性前后纤维的力学性能变化。结果表明:改性后纤维表面引入了极性基团,硅烷偶联剂KH-550对UHMWPE纤维的表面改性效果最好。采用质量分数为1%的硅烷偶联剂KH-550溶液处理后,纤维与环氧树脂间的界面剪切强度提高了87.8%,纤维的断裂强度和模量分别提高了6.9%和32.6%。     

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     

Surface modification of ultra-high strength polyethylene fibers for enhanced adhesion to epoxy resins using intense pulsed high-power ion beam

The effects of intense pulsed high power ion beam (HPIB) treatment of ultra-high strength polyethylene (UHSPE) fibers on the fiber/epoxy resin interface strength were studied. For this study, argon ions were used to treat Spectra? 1000 (UHSPE) fibers in vacuum. Chemical and topographical changes of the fiber surfaces were characterized using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), dynamic wettability measurements, and scanning electron microscopy (SEM). The fiber/epoxy resin interfacial shear strength (IFSS) was evaluated by the single fiber pull-out test. The FTIR-ATR and XPS data indicate that oxygen was incorporated onto the fiber surface as a result of the HPIB treatment. The wettability data indicate that the fibers became more polar after HPIB treatment and also more wettable. Although the total surface energy increased only slightly after treatment, the dispersive component decreased significantly while the acid-base component increased by a similar amount. SEM photomicrographs revealed that the surface roughness of the fibers increased following the HPIB treatment. The single fiber pull-out test results indicate that HPIB treatment significantly improved the IFSS of UHSPE fibers with epoxy resin. This enhancement in IFSS is attributed to increased roughness of the fiber surface resulting in mechanical bonding and in increased interface area, increased polar nature and wettability, and an improvement in the acid-base component of the surface energy after the HPIB treatment.     

Surface modification of drawn gel-cast ultra-high molecular weight polyethylene films

Gel-spun ultra-high molecular weight polyethylene (UHMWPE) fibers have superior properties but their use in composite material applications is limited by their poor adhesion to polymer matrices. Previous studies have shown that etching improves the adhesion of epoxy to the fibers, but leads to a reduction in mechanical properties. The purpose of this research was to use uniaxially drawn gel-cast UHMWPE films as a model system since both films and fibers have a highly oriented fibrillar structural hierarchy. Etching has detrimental effects on the mechanical properties and crystallinity of these very thin films. The small amount of carbonyl and carboxyl groups added to the surface through etching raises the film's surface tension and enhances wetting by epoxy. Even though the unmodified film cannot be bonded with epoxy, the interlaminar shear strength between epoxy and the etched films approaches the cohesive strength of the epoxy. A combination of interfacial and UHMWPE cohesive failures is observed. The increase in adhesion is attributed to the slight increase in surface oxygen.     

常压等离子体改善高性能纤维粘结性的研究

以氦气为载气,氧气为反应气体,对高强度聚乙烯和Twaron 1000芳纶两种高性能纤维进行常压等离子体处理,来改善纤维的粘结性能;采用单纤维抽拔实验测定等离子体处理前后纤维与环氧树脂之间的界面剪切力;利用原子力显微镜和X射线光电子能谱仪分析等离子体处理前后纤维表面形态和化学成分的变化。结果表明:高强度聚乙烯纤维和芳纶经常压等离子体处理后,纤维表面粗糙度增加,纤维表面碳元素含量下降,羟基、羧基等含氧或氮的极性基团增加,纤维粘结性能得到提高,但其强度无明显变化。     

等离子体射流载气流量大小对玻璃纤维改性效果影响的研究

通过大气压等离子体射流在玻璃纤维（GF）表面沉积氧化硅（SiO_x）纳米颗粒的方法改善玻璃纤维增强聚丙烯（GFRP）复合材料的界面结合性能,利用扫描电子显微镜、原子力显微镜和X射线光电子能谱等表征分析了改性纤维的表面形貌、化学成分、润湿性能和复合材料的界面结合性能,并考察了等离子体射流载气流量大小对GF改性效果的影响。结果表明,当载气流量为40 mL/min时,GF的改性效果最好,且此时GF的表面能相比对照组提高了43.18 %,GFRP复合材料的层间剪切强度提高了30.79 %;经过等离子体处理后,GF的表面粗糙度增大,极性官能团增多,复合材料的界面结合性能提升。     

Interfacial evaluation of epoxy/carbon nanofiber nanocomposite reinforced with glycidyl methacrylate treated UHMWPE fiber

Interface interactions of fiber–matrix play a crucial role in final performance of polymer composites. Herein, in situ polymerization of glycidyl methacrylate (GMA) on the ultrahigh molecular weight polyethylene (UHMWPE) fibers surface was proposed for improving the surface activity and adhesion property of UHMWPE fibers towards carbon nanofibers (CNF)‐epoxy nanocomposites. Chemical treatment of UHMWPE fibers was characterized by FTIR, XPS analysis, SEM, and microdroplet tests, confirming that the grafting of poly (GMA) chains on the surface alongside a significant synergy in the interfacial properties. SEM evaluations also exhibited cohesive type of failure for the samples when both GMA‐treated UHMWPE fiber and CNF were used to reinforce epoxy matrix. Compared with unmodified composite, a ～319% increase in interfacial shear strength was observed for the samples reinforced with both 5 wt % GMA‐grafted UHMWPE and 0.5 wt % of CNF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43751.     

超高分子质量聚乙烯纤维黏结强度增强方法研究

为提高超高分子质量聚乙烯(UHMWPE)纤维复合材料中纤维与树脂基体之间的界面黏结强度,提出通过不同质量分数的硅烷偶联剂KH-570处理纳米SiO_2对UHMWPE纤维进行表面改性。对改性处理后的纤维与乙烯基酯树脂进行黏结强度试验,发现硅烷偶联剂处理纳米SiO_2能有效提高纤维的界面黏结强度,同时使纤维保持一定的断裂强度。