Radiation‐induced graft copolymerization of MMA monomer onto UHMWPE: Adhesion improvement

Graft copolymerization of methyl methacrylate monomer onto ultra high molecular weight polyethylene (UHMWPE) and acid‐etched UHMWPE was conducted using preirradiation method in air in the presence of a Mohr salt and sulfuric acid to improve adhesion to the bone cement. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, gravimetric method, goniometry, and interfacial bonding strength measurements. The FTIR results showed the presence of ether, carbonyl, and hydroxyl groups for grafted films. The gravimetric results showed that the chromic acid etching and graft copolymerization had a synergetic effect so, the irradiated, then chromic acid etched at room temperature and grafted sample (Rad etch25) had the highest grafting degree. The interfacial bonding strength between UHMWPE and poly methyl methacrylate bone cement was considerably improved by graft copolymerization and chromic acid etching. The surface morphology was studied by scanning electron microscopy. The substitution of polar groups into the backbone of UHMWPE by chromic acid etching and graft copolymerization changed its contact angles with water and methylene iodide and increased its surface energy, as evidenced by contact angle measurements. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

高锰酸钾溶液粗化环氧树脂板的研究

在不同的微蚀温度、时间条件下,研究了高锰酸钾微蚀溶液对环氧树脂层压板和3240型环氧树脂板(基板)微蚀作用的影响。通过基板表面形貌的观察和对化学镀铜层与基板间粘结强度的测定,研究和比较了高锰酸钾体系和传统的铬酐-浓硫酸体系对两种基板的微蚀效果。结果表明,经过高锰酸钾溶液处理后,环氧树脂层压板和3240型环氧板粘结强度分别可达到5.88 N/cm和2.35N/cm,远远高于传统的铬酐-浓硫酸处理后镀铜层与基板的粘结强度;同时,使用高锰酸钾溶液可以减小环境污染,且操作简单易行,它作为新型的微蚀体系有望取代传统的铬酐-浓硫酸微蚀体系。     

表面改性超高相对分子质量聚乙烯纤维的热性能研究

采用铬酸刻蚀和化学气相沉积聚吡咯处理了超高相对分子质量聚乙烯(UHMWPE)纤维。用DSC、DMA、X-射线衍射及SEM分析了纤维的热力学性能、结晶情况及纤维的表观形貌。结果表明,铬酸处理及化学气相沉积聚吡咯处理后,纤维的耐热性均有所提高,纤维表面变得更加粗糙,其中化学气相沉积聚吡咯处理的纤维变化更明显。     

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     

Prostaglandins and prostaglandin intermediates. XV. Synthesis of 4-Oxo Carboxylic Acids and γ-Lactones by oxidative cleavage of homoallyl and homopropargyl ketones or alcohols

A convenient method to convert homoallyl or homopropargyl ketones or alcohols into 4-oxo carboxylic acids or γ-lactones is the oxidative cleavage of the multiple bond with potassium permanganate in diluted sulfuric acid. This is exemplified by the preparation of intermediates for the synthesis of 8-methylprostaglandin C₂. The oxidation of the allylic compounds with permanganate is compared with the oxidative cleavage by ozone/hydrogen peroxide, ozone/chromic acid or sodium periodate/potassium permanganate.     

铬酸处理的超高分子量聚乙烯纤维粘接性研究

本文采用不同浓度和温度下的铬酸溶液对超高分子量聚乙烯纤维进行表面处理。通过DSC、DMA、X-衍射和SEM分析纤维的结构,测试了纤维接触角、断裂强度和层间剪切强度。实验结果表明,随着处理液酸浓度的增加,纤维表面刻蚀程度增加,层间剪切强度增大,而纤维表面极性不变;处理时间和溶液温度须控制在一个合适的水平。     

Surface Activation and Adhesion Properties of Wood-Fiber Reinforced Thermoplastic Composites

Four surface activation methods were evaluated on a series of wood-fiber reinforced thermoplastic composites (WPCs) as a means to improve the adhesion of a water-based acrylic coating. Treatments with chromic acid and oxygen plasma performed best, increasing the acrylic coating peel load to WPCs by 170 and 122%, respectively, and yielding adhesion levels equivalent to or higher than those obtained on wood. The benzophenone/ultraviolet and flame treatments also improved the coating adhesion by 100 and 64%, respectively, but did not reach the adhesion levels achieved on wood. For both the chromic acid and oxygen plasma treatments, the WPC formulation impacted the treatment efficacy. Profilometry and scanning electron microscopy (SEM) showed that the chromic acid treatment acted mainly by roughening WPC surfaces. While surface oxidation was not evident from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), the improved wettability of WPCs with water suggested that the oxygen plasma treatment oxidized WPCs.     

Surface Activation and Adhesion Properties of Wood-Fiber Reinforced Thermoplastic Composites

Four surface activation methods were evaluated on a series of wood-fiber reinforced thermoplastic composites (WPCs) as a means to improve the adhesion of a water-based acrylic coating. Treatments with chromic acid and oxygen plasma performed best, increasing the acrylic coating peel load to WPCs by 170 and 122%, respectively, and yielding adhesion levels equivalent to or higher than those obtained on wood. The benzophenone/ultraviolet and flame treatments also improved the coating adhesion by 100 and 64%, respectively, but did not reach the adhesion levels achieved on wood. For both the chromic acid and oxygen plasma treatments, the WPC formulation impacted the treatment efficacy. Profilometry and scanning electron microscopy (SEM) showed that the chromic acid treatment acted mainly by roughening WPC surfaces. While surface oxidation was not evident from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), the improved wettability of WPCs with water suggested that the oxygen plasma treatment oxidized WPCs.     

高锰酸钾对芳纶的表面改性研究

利用高锰酸钾在强酸性条件下具有氧化性的特性对芳纶进行表面改性,采用正交实验探讨了硫酸浓度、高锰酸钾含量、处理温度和处理时间对芳纶力学性能的影响,采用扫描电子显微镜和生物显微镜观察处理前后芳纶的表面形貌。结果表明:最优工艺为硫酸质量分数10%,高锰酸钾浓度5g/L,处理温度为30℃,处理时间35min。改性后的芳纶强度损失不大,表面产生线状刻蚀,粗糙度提高。     

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     

PE—UHMW纤维／环氧树脂复合材料研究

对超高相对分子质量聚乙烯(PE-UHMW)纤维进行了铬酸液相氧化和纳米二氧化硅溶胶表面涂覆的复合化表面处理，并对PE-UHMW纤维／环氧树脂复合材料进行了界面性能研究。结果表明，单纯的液相氧化和表面涂覆均可以提高复合材料的界面性能，但液相氧化处理时间过长会使纤维强度降低，而复合化处理则具有协同效应，可以不降低纤维强度而大幅度提高复合材料的层间剪切强度，是一种有效的表面处理方法。     

Irradiation grafting of methyl methacrylate monomer onto ultra‐high‐molecular‐weight polyethylene: An experimental design approach for improving adhesion to bone cement

The grafting of methyl methacrylate (MMA) onto ultra‐high‐molecular‐weight polyethylene (UHMWPE) and chromic acid etched UHMWPE was conducted with a preirradiation method in air in the presence of a Mohr salt and sulfuric acid. The grafted samples were characterized by Fourier transform infrared (FTIR) spectroscopy, a gravimetric method, differential scanning calorimetry, scanning electron microscopy (SEM), and interfacial bonding strength measurements. The FTIR results showed the presence of ether and carbonyl groups in the MMA‐grafted UHMWPE (MMA‐g‐UHMWPE) samples. The Taguchi experimental design method was used to find the best degree of grafting (DG) and bonding strength. The efficient levels for different variables were calculated with an analysis of variance of the results. SEM micrographs of MMA‐g‐UHMWPE samples showed that with increasing DG and chromic acid etching, the MMA‐g‐UHMWPE rich phase increased on the surface; this confirmed the high interfacial bonding strength of the grafted samples with bone cement. The grafting of the MMA units onto UHMWPE resulted in a lower crystallinity, and the crystallization process proceeded at a higher rate for the MMA‐g‐UHMWPE samples compared to the initial UHMWPE; this suggested that the MMA grafted units acted as nucleating agents for the crystallization of UHMWPE. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface modification of polyethylene by radiation-induced grafting for adhesive bonding. V. Comparison with other surface treatments

Helium gas plasma treatment of low-density polyethylene (LDPE) yields much lower peel strength than oxidative treatment using chromic acid and oxygen gas plasma. The practical adhesion, the bondability retention, and the bond durability of oxidatively treated LDPE sheets, bonded with epoxy adhesives, have been compared with those of partially hydrolyzed LDPE–methyl acrylate surface grafts. The oxidized surfaces easily lose the bondability by light rubbing with tissue paper, solvent extraction, heat aging, and artifical weathering, whereas the grafted surfaces retain the bondability. The bondability loss is due to removal of the oxidized layer, and the bondability retention is due to retention of the surface homopolymer layer. Conventional antioxidants stabilize the grafted but not the oxidized surfaces against thermal oxidative degradation. The grafted LDPE joints have much higher bond durability in humid environments than those of the oxidized LDPE joints. The dry and wet peel strengths of oxidized LDPE joints are greatly improved by application of primers consisting of a base epoxy resin and organic solvents. An adhesion mechanism involving penetration of epoxy adhesives into the oxidized layers and subsequent reinforcement of the layers by curing of the penetrated epoxy is proposed.     

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. II. Effect on the physicomechanical and tribological properties of ultra‐high‐molecular‐weight polyethylene/poly(ethylene terephthalate) composites

We performed surface modification of ultra‐high‐molecular‐weight polyethylene (UHMWPE) through chromic acid etching, with the aim of improving the performance of its composites with poly(ethylene terephthalate) (PET) fibers. In this article, we report on the morphology and physicomechanical and tribological properties of modified UHMWPE/PET composites. Composites containing chemically modified UHMWPE had higher impact properties than those based on unmodified UHMWPE because of improved interfacial bonding between the polymer matrix and the fibers and better dispersion of the fibers within the modified UHMWPE matrix. Chemical modification of UHMWPE before the introduction of PET fibers resulted in composites exhibiting improved wear resistance compared to the base material and compared to unmodified UHMWPE/PET composites. On the basis of the morphological studies of worn samples, microploughing and fatigue failure associated with microcracking were identified as the principle wear mechanisms. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

玉米淀粉氧化工艺的研究

研究了玉米淀粉的氧化工艺。通过次氯酸钠、过氧化氢、高锰酸钾二次氧化、高碘酸钠氧化的比较,优选了高锰酸钾二次氧化作正交实验。直观分析及方差分析结果表明,最佳的氧化工艺为:氢氧化钠0.6 g,硫酸3 g,淀粉乳浓度40%,高锰酸钾1.2 g。     

Interfacial adhesion study on UHMWPE fiber-reinforced composites

Ultrahigh molecular weight polyethylene (UHMWPE) fiber has many outstanding properties. However, poor interfacial adhesion of the UHMWPE fiber/polymer matrix interface limits its applications as reinforcement in high performance polymer matrix composites. Therefore, a new thermosetting resin system, named PCH, which is only composed of carbon and hydrogen elements, has been developed according to law of similar mutual solubility and the structural characteristics of UHMWPE fiber. The adhesion property was investigated by mechanical properties test, thermal performance test, and polymer solution properties test. Test results show that a strong interaction occurs between UHMWPE fiber and the PCH matrix due to the structural and polar similarity. In the case of slight difference between solubility parameters of UHMWPE fiber and cured PCH resin, it is found that the wettability of PCH resin on surface of the fiber can be improved and the difference between the coefficients of thermal expansion of the matrix and the fiber decreases with the increase of styrene added into the PCH. An optimal interfacial adhesion can be obtained as the ratio of PCH/styrene is approximately 55/45.     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

天然鳞片石墨制备可膨胀石墨的工艺研究

以攀枝花天然鳞片石墨为原料,高锰酸钾和双氧水为氧化剂,硝酸、硫酸和高氯酸作为插层剂,制备膨胀石墨。实验发现较佳的膨化温度为950 ℃,并以此温度制备膨胀石墨。结果显示,以双氧水和硫酸制备的膨胀石墨其膨胀容积为130.97~221.80 mL/g;以高锰酸钾和硝酸制备的可膨胀石墨其膨胀容积为150.65~247.19 mL/g;以高锰酸钾和高氯酸制备的膨胀石墨,在干燥温度和时间分别为50 ℃和4~5 h时膨胀容积可达300 mL/g以上。实验还采用XRD和SEM对制备的膨胀石墨结构和形貌进行分析,测试结果发现膨胀石墨的结构完整,可用于进一步制备复合相变材料。     

In-situ oxidation and annealing of hydrogenated diamond (100) surfaces studied by high resolution electron energy loss spectroscopy

Homoepitaxially grown single crystal diamond (100) surface on polished natural type 2a diamond was carefully prepared and examined for morphology and chemical composition. Atomic force microscopy (AFM) analysis showed smooth polishing scratches consisting of broad and shallow patterns also seen by electron microscope examination in the secondary electron emission detection mode. High resolution electron energy loss spectroscopy (HREELS) was used to determinate different chemical bonding configurations present on the as grown surface and their thermal stability induced by vacuum annealing and exposure to activated hydrogen. In-situ hydrogen terminated surfaces were oxidized by exposure to thermally activated oxygen. Gradual annealing leads to the removal of oxygen containing species and to regeneration of the hydrogenated diamond surface. Annealing results in desorption of peroxide and ether groups and recovers the diamond optical phonon overtones in the HREELS. There was no indication of hydroxyl groups after oxygen exposure. Possible chemical processes involving activated hydrogen and oxygen during the exposures and subsequent annealing are suggested. Activated hydrogen and oxygen possess sufficient energy to attack absorbed species in order to form new chemical bonds absorbed onto the diamond surface.