Effect of High-Density Polyethylene Nanocomposite Compatibilizer Type on the Interfacial Adhesion and Mechanical Properties of Polyethylene Nano-Homocomposites

In this paper, the effect of nanocomposite compatibilizer type on the interfacial adhesion and mechanical properties of new class of polyethylene (PE) homocomposites, comprising PE/clay nanocomposites as matrix and ultra high molecular weight polyethylene (UHMWPE) fibers as reinforcement, was investigated. These were manufactured by a combination of powder impregnation and film stacking methods, introduced in previous research. Three types of high-density polyethylene (HDPE) Nanocomposites were prepared based on the various compatibilizers used: (i) nanocomposites containing HDPE-grafted maleic anhydride (HDPE-g-MA) as compatibilizer of clay and HDPE matrix, (ii) linear low-density polyethylene-grafted maleic anhydride (LLDPE-g-MA) used as compatibilizer, and (iii) nanocomposites without any compatibilizer. The effects of the presence and compatibilizer type on the quality of clay dispersion, and also the interface features of HDPE-nanocomposite and UHMWPE fibers were investigated and compared with each other. The results demonstrated that the kind of compatibilizer was an important factor determining the dispersion state of clay platelets, and influenced the UHMWPE fiber–PE matrix interface adhesion and the mechanical properties of the PE nano-homocomposites.     

Surface Modification of Ultrahigh-molecular-weight Polyethylene Fibers with Coupling Agent during Extraction Process

Ultrahigh molecular weight polyethylene (UHMWPE) fibers were treated with a coupling agent following the extraction of gel fibers, resulting in modified fibers after subsequent ultra-drawing. The structure and morphology of the modified UHMWPE fibers were characterized and their surface wetting, interfacial adhesion, and mechanical properties were investigated. It was found that the coupling agent was absorbed into the UHMWPE fiber and trapped on the fiber surface. Compared with unmodified UHMWPE fibers, the modified fibers had smaller contact angle, higher crystallinity, and smaller crystal size. The interfacial adhesion and mechanical properties of UHMWPE fibers were significantly improved with increasing coupling agent concentration and gradually reached a plateau value. After treatment with 1.5 wt% solution of a silane coupling agent (γ -aminopropyl triethoxysilane, SCA-KH-550), the interfacial shear strength of the UHMWPE-fiber/epoxy composites was increased by 108% and the tensile strength and modulus of modified UHMWPE fibers were increased by 11% and 37% respectively.     

Raman characterisation of conventional and cross‐linked polyethylene in acetabular cups run on a hip joint simulator

Five sets of differently sterilised conventional ultra‐high molecular weight polyethylene (UHMWPE) and cross‐linked polyethylene (XLPE) acetabular cups were run for 5 million cycles on a hip joint simulator in order to evaluate their wear behaviour in relation to material properties (PE grade, conventional or cross‐linked) and sterilisation method (ethylene oxide (EtO) treatment or γ‐irradiation). Gravimetric measurements revealed that conventional UHMWPE wore significantly more than XLPE. The differences in wear behaviour could be partly related to the orthorhombic contents obtained by Raman spectroscopy in the unworn areas of the cups: XLPE cups showed a significantly higher crystallinity degree than the UHMWPE specimens. Raman analysis showed that wear testing did not significantly modify the orthorhombic content of any of the tested acetabular cups. However, the set of cups that showed the highest weight loss, i.e. γ‐sterilised PE GUR1020, appeared the most homogeneously polished upon wear testing; from a molecular point of view, only this set of cups showed a significant increase of the I₁₁₃₀/I₁₀₆₀ intensity ratio, suggesting the occurrence of chain orientation. On the other hand, XLPE cups, despite the lowest weight loss undergone, showed a decrease in the amorphous content upon wear testing as well as a limited orthorhombic → monoclinic transformation, which did not appear detrimental. Copyright © 2011 John Wiley & Sons, Ltd.     

Powder compaction,sintering, and rolling of ultra high molecular weight polyethylene and its composites

The applicability of powder compaction and sintering techniques to the processing of ultra high molecular weight polyethylene (UHMWPE) powder is demonstrated. With proper processing procedure and type of UHMWPE powder, the mechanical properties obtained are nearly equivalent to those obtained by conventional melt processes. The properties were optimized by selection of a sintering temperature just above the melting point and by close control of particle size and distribution. The processability of UHMWPE is dependent on the morphology of the powder. Only those powders with a fibrous morphology provided good mechanical properties after sintering. The mechanical properties of powder compacts can be improved by several techniques. Liquid sintering with added normal molecular weight polyethylene, with close control of particle size and distribution and amount of the second component, yielded improved properties. Composites of UHMWPE, with short glass and graphite fiber reinforcement, processed by powder compaction and sintering resulted in increased modulus. The properties of these composites depended upon the amount of fibers, fiber length, fiber-matrix bonding, and fiber orientation. Rolling the powder-processed UHMWPE oriented the structure and improved the mechanical properties, although it decreased the mechanical properties of the glass and graphite fiber composites because of debonding between fiber and matrix. The properties of carbon black—UHMWPE mixtures were improved by rolling because of a more uniform distribution of carbon black.     

Thermal and Mechanical Properties of Ultra High Molecular Weight Polyethylene Fiber Reinforced High-Density Polyethylene Homocomposites: Effect of Processing Condition and Nanoclay Addition

A new method to prepare single-polymer high-density (HDPE)-ultra high molecular weight polyethylene (UHMWPE) fiber (PE-PE homocomposites) composed and also PE-PE homocomposites containing HDPE organo montmorillonite clay (OMMT) nanocomposites as a matrix (PE nanohomocomposites) was used. Owing to the major importance of fiber impregnation by the matrix and its effect on the adhesion of matrix/fiber and, consequently, the mechanical properties of the composite, a combination of powder impregnation and film stacking methods, utilizing compression molding, were used for manufacturing the PE-PE homocomposites and PE nanohomocomposites. In addition, PE nanohomocomposites with the matrix containing different amounts of nanoclay were prepared to investigate the effect of the clay on the interfacial and mechanical properties of the PE-PE nanohomocomposites. Several different processing conditions were examined to determine the best conditions for manufacturing of the PE-PE homocomposite and PE nanohomocomposites and it was concluded that 40 bar and 10 min of compression molding resulted in the highest overall mechanical properties. The PE-PE homocomposites and PE-PE nanohomocomposites showed identical trends for the relationship between the effects of processing conditions and mechanical properties. Mechanical results demonstrated that clay platelets could increase the interfacial strength by improving physical entanglements between fiber and matrix through better cocrystallization.     

Glass Transition Temperatures of Epoxy Modified with Pendent Nano‐Organic Rigid‐Rod Compounds

Pendent nanoscale organic rigid‐rod compounds are molecular fiber‐like materials that can be used to reinforce the polymer matrix. In this study, 4,4′‐diphenylmethane diisocyanate (MDI) was used to covalently connect a number of organic rigid‐rod compounds [4′‐hydroxyphenyl‐4‐hydroxy‐benzoate (HPHB), phenyl 4‐hydroxybenzoate (HPB), 4,4′‐isopropylidenediphenol (BSPA), and 2‐naphthol (NPT)] to the secondary hydroxyl groups of the epoxy resin. These reactions were monitored using Fourier transform infrared (FT‐IR) spectroscopy; the products were characterized using nuclear magnetic resonance (NMR) spectroscopy. The glass transition temperatures of the organic rigid‐rod compounds modified epoxy resins were investigated through differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Thermogravimetric analysis (TGA) was used to detect the values of Td and the thermal stabilities of the polymers.     

Effect of processing temperature on the micro- and macro-interfacial properties of carbon fiber/epoxy composites

Three different temperature schemes were applied on carbon fiber/epoxy composite to elucidate the effect on interfacial shear strength (IFSS) and inter-laminar shear strength (ILSS). It showed that carbon fiber/epoxy IFSS was significantly influenced by the processing temperature, while ILSS was only slightly changed. Moreover, the mechanical properties revealed no necessary relationship between the micro- and macro-interfacial strengths with the properties of epoxy matrix. Among all the temperature schemes, Pro2 (the one-platform curing scheme with relatively rapid heating rate) produced highest IFSS and ILSS. Fourier transform infrared spectroscopy analysis demonstrated that the sizing agent can chemically react itself and also react with epoxy resin at temperature 180?°C. The resin rheological data showed that different temperature schemes can considerably impact diffusion behavior of the resin molecules. Hence, the highest interfacial strengths for Pro2 scheme were ascribed to large extent of chemical reactions and good inter-diffusion between components, at the interface region.     

Jumplike deformation of polymer materials on the micrometer and submicrometer structural levels

Jumplike creep is considered as a reflection of the structural heterogeneity of amorphous polymers on the mesoscopic and nanoscopic levels. The D-450 epoxy resin, poly(vinyl chloride), poly(vinyl butyral), and a composite consisting of the D-450 epoxy resin and diabase microparticles are studied at a temperature of 290 K. The creep rate of the specimens under compression is measured with a laser interferometer in submicrometer-scale deformation increments. Periodic variations of the creep rate with time or under deformation correspond to a jumplike (stepwise) behavior of the creep. It is shown that diabase particles (5–10 μm in size) are responsible for the appearance of micrometer-scale jumps in the creep of the composite and that the deformation jumps on the nanometer level are comparable to the sizes of the globules. The role of the resolution of the method employed in the evaluation of the scale of deformation jumps and structural units is considered.     

Effect of matrix yield properties on fragmentation behavior of single fiber composites

Experimental and theoretical investigations have been conducted to study the dependence of fiber fragmentation behavior on matrix yielding properties. The cured Epikote 828 resins with two types of curing agents have almost similar elastic moduli, but different tensile yield strengths. The interfacial chemistry between fiber and epoxy resin is unchanged due to the same constituent of the epoxy resin. The experimental results indicate that the fragmentation behavior of the fibers embedded in the matrix is significantly different for the tested glass fiber treated by γ-glycidoxypropyltrimethoxysilane. The average fragment length decreased with increasing tensile yield strength of resin, which suggests that the interfacial shear strength determined in the fragmentation test should be different depending on the tensile yield strength of resin used. The important phenomenon observed is the transition of the micro-damage mode from matrix crack to interfacial debonding. An elastoplastic shear-lag model was used to calculate the shear stress and fiber tensile stress distributions considering different plastic behaviors of the matrices. The theoretical results indicate that the plastic behavior of the matrix has a large influence on stress transfer. Based on elastic and plastic properties of the matrix, the fiber fragmentation behavior in the matrix is predicted. Experimental and theoretical results are favorably compared.     

Preparation and Properties of Nano‐SiO2/Epoxy Composites Cured by Mannich Amine

Nano‐SiO₂/epoxy composites cured by Mannich Amine (type T‐31) were prepared and studied and the results are reported in this paper. The nano‐SiO₂ was pretreated by a silane coupling agent (type KH‐550) and mixed with epoxy resin (type E‐51) using an ultrasonic processor. Amounts of filler loading ranged from 1% to 5% of the weight of the epoxy resin. Some properties of the resulting composites were characterized by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results of tensile tests and impact tests showed that the composite with 3% nano‐SiO₂ loading presented the best mechanical performances. The tribological performance and thermal stability of the materials were also improved with the addition of nano‐SiO₂.     

Preparation of Ultrahigh Molecular Weight Polyethylene/WS2 Composites for Bulletproof Materials and Study on Their Bulletproof Mechanism

Ultrahigh molecular weight polyethylene (UHMWPE)/WS₂ nanoparticle fibers were prepared by adding inorganic fullerene-like (IF) WS₂ nanoparticles treated by a coupling agent to the precursor solution of UHMWPE. The influence of WS₂ nanoparticles on the microstructure and properties of UHMWPE fibers were characterized by the scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and mechanical property measurements. The bulletproof performance of the UHMWPE/WS₂ composite was tested by a bullet-shock test, and the bulletproof mechanism of the UHMWPE/WS₂ composite was preliminarily studied. The results showed that WS₂ nanoparticles could be uniformly dispersed in the UHMWPE fiber. After incorporating of WS₂ nanoparticles, the UHMWPE fibers became stiffer and tougher than the pristine ones. In particular, the modulus of the fibers increased from 1203 to 1326 cN/dtex. The introduction of IF-WS₂ nanoparticles led to significantly improved bulletproof performance of UHMWPE fibers.     

A COMPARISON OF THE HOT-COMPACTION BEHAVIOR OF ORIENTED,HIGH-MODULUS,POLYETHYLENE FIBERS AND TAPES*

The purpose of this article is twofold. First, there is an account of the hot-compaction behavior of a new, highly oriented, high-modulus polyethylene (PE) tape with the trade name of Tensylon® (manufactured by Synthetic Industries, USA). This tape, produced by a melt spinning route, has mechanical properties comparable to those of commercially available gel-spun fibers. Unidirectional samples were produced for a range of compaction temperatures to determine the optimum compaction conditions to obtain the best mechanical properties of the resulting compacted sheets. Second, the mechanical properties of the best Tensylon sample, manufactured at a compaction temperature of 153°C, was compared with three other hot-compacted, highly oriented PE materials, based on Certran®, Dyneema®, and Spectra® commercial PE fibers. The results showed that the optimum compaction temperature was in most cases about 1°C below the point at which substantial crystalline melting occurred. At this optimum temperature, differential scanning calorimetry (DSC) melting studies showed that approximately 30% of the original oriented phase had been lost to bond the structure together. In the case of Dyneema, the properties of the fiber were not translated into the properties of a compacted sheet, and morphological studies showed that this was because melting did not occur on the fiber surfaces, but rather in the interior of the fiber due to a skin structure. The properties of the compacted Tensylon tapes were found to be exceptional, combining very high modulus and strength with interlayer bonding and good creep resistance. Moreover, the optimum temperature appeared to be about 2°C below the point at which complete melting occurred, giving a wider processing window for this material.

     

环氧树脂胶的太赫兹光谱特性研究

环氧树脂是纤维增强复合材料加工中的一种重要的胶粘剂,太赫兹时域光谱技术已成为纤维增强复合材料无损检测的有力补充手段。固化温度是环氧树脂的重要参数之一,不同的固化温度会影响环氧树脂胶的性能,因此采用太赫兹时域光谱技术分别对室温和高温下固化的环氧树脂胶的太赫兹透射光谱特性进行了系统研究,计算得到了不同温度下固化的环氧树脂胶的折射率和吸收系数,并进行了对比分析。研究表明,由于室温下固化的环氧树脂样本基本没有气泡,而高温下固化的样本存在微量气泡,气泡的存在降低了样品的密度,因此室温下固化的环氧树脂胶样品的折射率和吸收系数均大于高温下固化的样品。在同种固化条件下制备的不同样品间折射率差别较小,同时,室温下固化不同样品间的吸收系数差别亦较小,但高温下固化样品间的吸收系数在0.6～1.5 THz差别逐渐变大,这主要是因为高温下制备的不同样本间的气泡分布不均匀,即密度分布存在差异。室温和高温下固化样品的吸收系数在整体上均随着频率的增加而增加,并且没有明显的吸收峰。此外,由于法布里-珀罗干涉效应的存在,导致有些厚环氧树脂样本的能量透过率在共振峰处要远大于薄样本。该研究对纤维增强复合材料的太赫兹无损检测具有重要的研究意义。     

Plasma treatment of carbon fibers: Non-equilibrium dynamic adsorption and its effect on the mechanical properties of RTM fabricated composites

The effect of oxygen plasma treatment on the non-equilibrium dynamic adsorption of the carbon fabric reinforcements in RTM process was studied. 5-Dimethylamino-1-naphthalene-sulfonylchloride (DNS-Cl) was attached to the curing agent to study the change of curing agent content in the epoxy resin matrix. Steady state fluorescence spectroscopy (FS) analysis was used to study this changes in the epoxy resin at the inlet and outlet of the RTM mould, and XPS was used to study the chemical changes on the carbon fiber surfaces introduced by plasma treatment. The interlaminar shear strength (ILSS) and flexural strength were also measured to study the effects of this non-equilibrium dynamic adsorption progress on the mechanical properties of the end products. FS analysis shows that the curing agent adsorbed onto the fiber surface preferentially for untreated carbon fiber, the curing agent content in the resin matrix maintain unchanged after plasma treatment for 3 min and 5 min, but after oxygen plasma treatment for 7 min, the epoxy resin adsorbed onto the fiber surface preferentially. XPS analysis indicated that the oxygen plasma treatment successfully increased some polar functional groups concentration on the carbon fiber surfaces, this changes on the carbon fiber surfaces can change the adsorption ability of carbon fiber to the resin and curing agent. The mechanical properties of the composites were correlated to this results.     

Unexpected shish-kebab structure in a sheared polyethylene melt

Scanning electron micrographs of a solvent-extracted sheared polyethylene (PE) blend revealed, for the first time, an unexpected shish-kebab structure with multiple shish. The blend contained 2 wt % of crystallizing ultrahigh molecular weight polyethylene (UHMWPE) and 98 wt % of noncrystallizing PE matrix. The formation of multiple shish was attributed to the coil-stretch transition occurring in sections of UHMWPE chains. Synchrotron x-ray data provided clear evidence of the hypothesis that multiple shish originate from stretched chain sections and kebabs originate from coiled chain sections, following a diffusion-controlled crystallization process.     

Z箍缩靶用聚合物丝的弛豫特性

 聚苯乙烯（PS）,聚乙烯（PE）及其的氘代物是Z箍缩驱动惯性约束聚变（ICF）实验中的重要固体燃料容器材料,针对物理实验对其形状的特殊要求,利用高压毛细管流变仪及HAUL-OFF熔体拉伸测试单元进行熔融纺丝,制备出直径为30～100 μm的聚合物丝样品。通过对PS,PE以及氘代聚苯乙烯（DPS）丝的力学弛豫性质研究发现：在相同的恒定应力下,实验用PS丝的蠕变量明显小于PE丝,PS丝表现出更好的尺寸稳定性;当定伸长为1％时,PS丝的松弛率明显小于PE丝;DPS丝的蠕变及应力松弛行为与PS丝具有相同的变化趋势。     

氧等离子体处理对纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维拉伸性能的影响

基于艾琳方程,提出用于定量分析纤维表面和纳米涂覆层间的纳米界面结构的理论模型.实验结果表明,纤维高分子链段受力塑性变形时,纳米界面结构内纳米微粒阻碍其形貌变化产生热激活体积,该热激活体积是纳米界面结构性能的重要表征;氧等离子体处理对纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维有增韧作用.由不同处理样品的扫描电子显微镜图片和傅里叶变换红外光谱曲线对比分析可知,经氧等离子体处理纳米二氧化硅溶胶涂覆高强、高模聚乙烯纤维的纳米涂覆层纳米颗粒分布均匀,纳米颗粒还填补纤维表面微观缺陷,活性官能团被引入到纤维表面. 关键词： 激活体积 氧等离子体 高强、高模聚乙烯纤维 纳米界面结构     

DEFORMATION MODES IN ORIENTED POLYMERS

To clarify an influence of intermolecular interaction on interfibrillar slip, a comparison study of creep at room temperature in loaded films and fibers built from macromolecules with different molecular structure (flexible and rigid chain) was carried out. These were ultimately drawn melt-crystallized and gel-crystallized ultrahigh molecular weight polyethylene (UHMWPE) films and two commercial (poly)paraphenylene terephthalamide (PPTA) fibers, Kevlar 49 (DuPont) and Armos (JSC “Tverchimvolokno”). An extremely high flow creep rate inhomogeneity was observed in both UHMWPE samples, while creep in the fibers from the rigid-chain polymers developed monotonically. Real-time microscopic observations revealed generation of kink bands in loaded UHMWPE samples. No kinks were observed in Kevlar 49 and Armos. The deformation modes operating in the loaded samples are discussed.     

Crystalline Character and Microhardness of Gamma‐Irradiated and Thermally Treated UHMWPE

Relationships between Vickers microhardness, x‐ray and differential scanning calorimetry (DSC) crystallinity, x‐ray long period, and melting points were determined for ultrahigh molecular‐weight polyethylene (UHMWPE) of various histories (as‐produced, irradiated, annealed, and remelted). It was shown that the microhardness responds very sensitively to both the irradiation conditions (total radiation dose, radiation dose rate) and the thermal treatment (annealing below the melting temperature, remelting). As microhardness reflects the yield point parameters, the results show that not only the total dose, but also the irradiation dose rate has a considerable influence on mechanical properties of UHMWPE. It was demonstrated that neither x‐ray nor DSC results are so sensitive to treatment as the microhardness results. The most important differences in properties were found between remelted samples and those thermally untreated or annealed.     

Role of curing conditions and silanization of glass fibers on carbon nanotubes (CNTs) reinforced glass fiber epoxy composites

Curing behavior of amino-functionalized carbon nanotubes (ACNT) used as reinforcing agent in epoxy resin has been examined by thermal analysis. Experiments performed as per supplier’s curing conditions showed that modification of the curing schedule influences the thermo-mechanical properties of the nanocomposites. Specifically, the glass transition temperature (T_g) of ACNT-reinforced composites increased likely due to the immobility of polymer molecules, held strongly by amino carbon nanotubes. Further, a set of composites were prepared by implementing the experimentally determined optimal curing schedule to examine its effect on the mechanical properties of different GFRP compositions, while focusing primarily on reinforced ACNT and pristine nanotube (PCNT) matrix with silane-treated glass fibers. From the silane treatment of glass fibers in ACNT matrix composition it has been observed that amino silane is much better amongst all the mechanical (tensile and flexural) properties studied. This is because of strong interface between amino silane-treated glass fibers and modified epoxy resin containing uniformly dispersed amino-CNTs. On the other hand, PCNT GFRP composites with epoxy silanes demonstrated enhanced results for the mechanical properties under investigation which may be attributed to the presence of strong covalent bonding between epoxy silane of glass fiber and epoxy–amine matrix.