Micromachining of crosslinked PTFE by direct photo-etching using synchrotron radiation

Micromachining of crosslinked PTFE (polytetrafluoroethylene) using synchrotron radiation direct photo-etching method has been demonstrated. High aspect-ratio microfabrication was carried out. The etching rate of crosslinked PTFE was higher than that of non-crosslinked PTFE. Through the etching rate measurements of various samples, it was found that synchrotron radiation etching rate of crosslinked PTFE only depends on the degree of crosslinking, neither molecular weight nor crystallinity. The effect of molecular motion on etching process was discussed from temperature dependence data on etching rate. Furthermore, the surface region of synchrotron radiation irradiated sample was investigated by Fourier transform infrared spectroscopy and the experimental result showed that the modification induced by synchrotron radiation proceeded before desorption.     

Acetylene-sensitized radiation crosslinking of polytetrafluoroethylene

The radiation crosslinking of PTFE in the presence of acetylene was studied. The yield of crosslinking was determined from thermomechanical testing data and, on this basis, it was concluded that crosslinking follows the chain mechanism. Radiation-crosslinked PTFE possesses high wear resistance and enhanced radiation stability.     

Modification of polytetrafluoroethylene by radiation—1. Improvement in high temperature properties and radiation stability

Polytetrafluoroethylene (PTFE) has never been reported to form a network structure when subjected to high energy radiation. Results obtained in this work indicates that when irradiation is performed under 330–340°C in vacuo PTFE can be crosslinked through irradiation. Crosslinked PTFE was found to gain a great improvement in both high temperature mechanical properties and radiation stability.     

Effect of surface treatment of UHMWPE fiber on mechanical and impact fracture behavior of PTFE/POM composites

Ultra‐high‐molecular‐weight polyethylene (UHMWPE) fiber was treated to reinforce the polytetrafluoroethylene/polyoxymethylene (PTFE/POM), and the mechanical properties of surface‐treated UHMWPE were investigated. Scanning electron microscopy was utilized to study the fracture surfaces of UHMWPE/POM/PTFE composites. Experimental results showed that the surface treatment of UHMWPE fiber effectively improves the mechanical property of POM/PTFE composites. Scanning electron microscopy studies indicated that surface modification could improve the interfacial adhesion of POM/PTFE composites. And the dispersion of UHMWPE in POM/PTFE composites was also improved after the surface modification. Copyright © 2017 John Wiley & Sons, Ltd.     

Friction and Wear of Semi-Crystalline Polytetrafluoroethylene with Spherulitic Micro-Morphology

Polytetrafluoroethylene (PTFE) is an important engineering material with a low coefficient of friction but a high rate of wear. As a semi‐crystalline polymer, its wear resistance is related to its micro‐morphology. Friction and wear properties of semi‐crystalline non‐spherulitic PTFE have been widely studied, but no investigation is reported about tribological properties of spherulitic PTFE due to difficulties in finding such properties. In this paper, friction and wear properties of PTFE with spherulitic micro‐morphology are studied for the first time. The results show that, first, under the same experimental condition, when two kinds of PTFE are rubbed against the steel disc, the number and size of debris of spherulitic PTFE are much less and smaller than that of debris of PTFE without spherulitic crystals. This means that the wear resistance of spherulitic PTFE is better than that of semi‐crystalline PTFE without spherulitic micro‐morphology. Second, the friction property of spherulitic PTFE is also different from that of PTFE without spherulitic crystals. Finally, the friction and wear mechanisms of spherulitic PTFE and non‐spherulitic PTFE are compared.     

Electrochemical characteristics and interfacial contact resistance of Ni-P/TiN/PTFE coatings on Ti bipolar plates

The Ni-P/TiN/PTFE (poly tetra fluoroethylene) composite coatings were prepared by electroless plating method on Ti plate, which was used as bipolar plates of proton exchange membrane fuel cells (PEMFCs). The morphology, crystallographic texture, electrochemical corrosion, contact resistance, and hydrophobic property of the Ti bipolar plates with coatings were investigated. The results revealed that Ni-P/TiN/PTFE coating had a dense surface morphology, uniform distribution of composite particles. Ti with coating showed 0.48 μA cm² of corrosion current in the simulated solution of PEMFCs and 6 mΩ cm² of interfacial contact resistance (ICR). The hydrophobicity test showed that the coating interface was flat and the wetting angle was 112.4°. In conclusion, The Ni-P/TiN/PTFE composite coatings exhibit superior improvement in corrosion resistance, interface hydrophobicity, and conductivity to Ni-P, Ni-P/TiN, and Ni-P/PTFE coatings. The Ni-P/TiN/PTFE coating was suited for bipolar plate surface modification of bipolar plates.     

New trend of radiation application to polymer modification — irradiation in oxygen free atmosphere and at elevated temperature

Polycarbosilane (PCS) fiber as a precursor for ceramic fiber of silicon carbide was cured by electron beam (EB) irradiation under oxygen free atmosphere. Oxygen content in the cured PCS fiber was scarce and the obtained silicon carbide (SiC) fiber with low oxygen content showed high heat resistance up to 1973 K and tensile strength of 3 GPa. Also, the EB cured PCS fiber with very low oxygen content could be converted to silicon nitride (Si₃N₄) fiber by the pyrolysis in NH₃ gas atmosphere, which was the new processing to produce Si₃N₄ fiber. The process of SiC fiber synthesis was developed to the commercial plant.

The other application was the crosslinking of polytetrafluoroethylene (PTFE). PTFE, which had been recognized to be a typical chain scission polymer, could be induced to crosslinking by irradiation at the molten state in oxygen free atmosphere. The physical properties such as crystallinity, mechanical properties, etc. changed much by crosslinking, and the radiation resistance was much improved.     

Research on high temperature friction properties of PTFE/Fluorosilicone rubber/silicone rubber

Silicone rubber (MVQ) has excellent heat resistance, but poor high temperature friction stability, which limits its application in the field of high temperature sealing. Polytetrafluoroethylene (PTFE) is self-lubricating, but its compatibility with rubber is relatively weak. In order to improve the high-temperature friction property of silicone rubber, fluorosilicone rubber (FVMQ) was used as a compatibilizer, and PTFE was added to MVQ by mechanical blending. The friction and wear properties of PTFE/FVMQ/MVQ composites at different temperatures were studied. The results show that compared with MVQ, the mechanical properties of PTFE/FVMQ/MVQ composites was basically unchanged, the coefficient of friction was hardly affected by temperature, and the amount of wear decreased with increasing temperature. PTFE/FVMQ/MVQ composites showed excellent high-temperature abrasion resistance. The high-temperature wear mode was mainly changed from abrasive wear to adhesive wear. The molten layer formed by high-temperature friction can prevent air from directly contacting the surface rubber, which inhibited rubber surface oxidation reaction process.     

Effect of ionizing radiation on the chemical composition,crystalline content and structure,and flow properties of polytetrafluoroethylene

This article describes a study of ionizing radiation-induced changes in the chemical composition, crystalline content and structure, and flow properties in polytetrafluoroethylene (PTFE). Irradiatins conducted in the presence of oxygen cause acid fluoride end groups to be formed, which on exposure to water vapor hydrolyze to form carboxylic acid end groups. Analyses by infrared (IR) spectroscopy indicate that when irradiated in a vacuum PTFE exhibits defect absorption bands which have been attributed to branch and crosslink formation. The crystalline content of PTFE which increases after exposure to radiation was monitored by IR spectroscopy, density, x-ray diffraction on unoriented samples, and differential scanning calorimetry (DSC) as the measurement probes. The melt viscosity of PTFE exposed to various radiation doses in air decreases dramatically after irradiation. Between 2.5 and 5 Mrd an increase in viscosity is attributed to the formation of branches and crosslinks. The effects of preirradiation crystallinity and postirradiation heat treatment were studied. A model is presented to explain the mechanism of the observed radiation effects.     

Au nanolayers deposited on polyethyleneterephtalate and polytetrafluorethylene degraded by plasma discharge

Polyethyleneterephtalate (PET) and polytetrafluorethylene (PTFE) foils were modified by plasma discharge. The effect of plasma modification on polymer surface wettability and on properties of gold coatings were studied as a function of time from plasma exposure (aging time) and polymer substrate temperature. Thickness, sheet resistance, and surface topology of gold layers were studied. Aging of the plasma‐exposed samples is accompanied by increase in contact angle, which is explained by rearrangement of the polymer segments in the polymer surface monolayer, and a decrease in the concentration of polar groups. The aging also leads to a decline in surface roughness R_a measured by atomic force microscopy (AFM). Under deposition conditions, comparable thicknesses of deposited Au layers were prepared on pristine PET and plasma‐treated PET and PTFE samples. The thinnest Au layers were evaporated onto pristine PTFE. The sheet resistance decreases with increasing thickness of Au layer. Plasma treatment leads to an increase of PTFE surface roughness, which becomes even more pronounced after Au deposition. A higher roughness shows that the PET samples are deposited with the Au layer at temperatures above the glassy transition temperature T_g. Copyright © 2006 John Wiley & Sons, Ltd.     

Modification of polytetrafluoroethylene and polyethylene surfaces downstream from helium microwave plasmas

Films of polytetrafluoroethylene (PTFE) and polyethylene (PE) were treated downstream from a helium microwave plasma. Vacuum ultraviolet radiation induces reduction in deionized water contact angle, probably as a result of crosslinking and desaturation of these linear, saturated polymers. Photons with energies greater than the first ionization potentials of PTFE and PE were shown to be most effective for modification. Valence band X-ray photoelectron spectroscopy (XPS) was used to determine these ionization potentials. XPS analyses also revealed that simultaneous exposure to high energy (19·8 eV) He metastables and photons (12 eV to 54 eV) results in extensive defluorination of the surface of PTFE while PE surfaces display enrichment in C---O bonding. The latter is attributed to the presence of carbonyl impurities in the untreated PE and/or reaction of surface sites with oxygen upon exposure to air.     

Direct-current discharge treatment of polytetrafluoroethylene films

The effect of treatment in a low-pressure dc discharge on the surface properties of polytetrafluoroethylene (PTFE) films modified at the anode and cathode was examined. It was found that the anode treatment of the films considerably improves the adhesive properties of the polymer and makes it possible to obtain substantially lower values of the contact angle and higher values of the work of adhesion and surface energy than in the case of other PTFE surface modification techniques. By means of IR and X-ray photoelectron spectroscopy, it was shown that discharge treatment at the anode and cathode noticeably increases the amount of oxygen-containing groups on the surface of the films.     

聚四氟乙烯和聚二甲基硅烷的链尺寸和偶极矩

基于改进的旋转异构态方法,推导了对称双取代基高分子链的均方回转半径和均方偶极矩公式,用于研究聚四氟乙烯(PTFE)、聚二甲基硅烷(PDMS)和聚乙烯(PE)链构象依赖的性质.计算得到长链聚四氟乙烯PTFE4(四态模型)和PDMS的构型参数值分别为0.44·mol0.5·g-0.5和0.43·mol0.5·g-0.5,PDMS链的相应温度系数值-7.32×10-3K-1,它与PTFE和PE的值(约-1.00×10-3K-1)相差较大.得到长链PTFE和PDMS的均方电偶极矩特征比结果都很小,如PDMS链的特征比为0.27,说明虽然PTFE和PDMS的侧基键C—F和Si—CH3都有强极性,但其聚合物却是非极性的电介质,具有较好的电绝缘性能,可见高分子链的构象和结构也对聚合物极性和电学性质有很大的影响.得到短链PTFE和PDMS(重复单元x10)均方偶极矩表现出明显的端点效应,特征比随x的改变而呈现明显的波动,这与Flory等的计算结果一致.     

Stability and ageing of plasma treated poly(tetrafluoroethylene) surfaces

In this study CO₂, H₂/H₂O and H₂O low pressure plasma treatment of poly(tetrafluoroethylene) (PTFE) foils and of thin plasma deposited fluorocarbon polymer (PDFP) films with a structure close to PTFE was investigated. The properties of the plasma were analyzed by mass spectroscopy (MS) and optical emission spectroscopy (OES). The modified fluorocarbon surfaces were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), fourier transform infrared (FTIR) spectroscopy, spectroscopic ellipsometry, electrokinetic measurements and dynamic contact angle measurements in order to find optimized treatment conditions. The results of the surface modification were compared with respect to the efficiency of the plasma treatment and the stability of the modification effect at different ambient conditions. It was shown that the H₂O plasma treatment is the most effective process for the intended modification. The hydrophobic PTFE surface was converted into a more hydrophilic one. The introduced radicals after the H₂O plasma treatment can be utilized subsequently for post plasma reactions such as grafting processes.     

Polytetrafluoroethylene modification by radiation grafting of vinylidene chloride and its dehydrochlorination

A process has been designed for manufacturing a new composite material consisting of a PTFE matrix with a carbon phase implanted in the surface layer of up to 30 μm thickness. The process involves radiation graft polymerization of vinilydene chloride (VDC) from the vapor phase onto the PTFE matrix followed by dehydrochlorination of implanted PVDC. The VDC grafting kinetics, the distribution of the grafted polymer and the carbon phase, and the mechanical characteristics of the composite material have been investigated. It has been shown that unlike initial PTFE, the composite possesses good adhesive bonding properties and a small contact angle.     

Polytetrafluoroethylene: Effects of γ-radiation on fine structure

The structure of granular polytetrafluoroethylene has been studied by electron microscopy. On the basis of the texture of surfaces resulting from fracture a model of the structure is proposed which suggests that PTFE consists of extended chain crystals with both inter- and intra-lamellar noncrystalline regions. The effects of γ-radiation on the structure have been investigated by examining the texture of irradiated fracture surfaces and also the texture produced by post-irradiation fracture. The irradiations have been performed in vacuo and in oxygen. In both atmospheres PTFE undergoes degradation with a concurrent increase in crystallinity. However, the texture of the surfaces of high crystallinity PTFE, prepared by radiation, differs markedly to the texture of fracture surfaces of high crystallinity PTFE prepared by thermal annealing. It is proposed that radiation causes rupture of bonds in the interlamellar (chain fold) and intralamellar regions, resulting in the production of chain ends and interlamellar links. Due to scavenging of the free radicals, interlamellar linking is pobably a minor process with irradiation in oxygen. These chemical changes cause modifications to the extended chain lamellar crystals and consequently alterations to the physical properties of the polymer.     

Composites Based on Polytetrafluoroethylene and Detonation Nanodiamonds: Filler–Matrix Chemical Interaction and Its Effect on a Composite’s Properties

Specific properties of PTFE composites filled with ultradisperse detonation diamonds (UDDs) with different surface chemistries are studied. It is found for the first time that filler in the form of UDDs affects not only the rate of PTFE thermal decomposition in vacuum pyrolysis, but also the chemical composition of the products of degradation. The wear resistance of UDD/PTFE composites is shown to depend strongly on the UDD surface chemistry. The presence of UDDs in a PTFE composite is found to result in perfluorocarbon telomeres, released as a readily condensable fraction upon composite pyrolysis. The chemical interaction between PTFE and UDDs, characterized by an increase in the rate of gas evolution and a change in the desorbed gas’s composition, is found to occur at temperature as low as 380°C. It is shown that the intensity of this interaction depends on the concentration of oxygen-containing surface groups, the efficiency of UDDs in terms of the composite’s wear resistance being reduced due to the presence of these groups. Based on the experimental data, a conclusion is reached about the chemical interaction between UDDs and a PTFE matrix, its dependence on the nanodiamond surface chemistry, and its effect on a composite’s tribology.     

丙烯酸水溶液聚合法制备PTFE/PAA/Nafion膜及其性能

采用廉价的多孔聚四氟乙烯(PTFE)膜作为基底, 用少量的Nafion与PTFE膜复合可制备低成本的质子膜. 但疏水性的PTFE膜与亲水性的Nafion膜结合性不佳. 基于此, 本文对疏水性的PTFE膜材料表面进行设计, 先采用丙烯酸对疏水性的PTFE膜表面进行亲水性改性, 再喷涂亲水性Nafion膜, 完成低成本PTFE/PAA/Nafion膜的制备. 实验结果表明, 改性前的PTFE膜材料水接触角为150°, 改性后的膜接触角变为55.6°, 亲水性大幅上升, 膜的机械强度和尺寸稳定性(断裂强度为25.2 MPa, 80 ℃下的溶胀率为11.9%)均优于Nafion117膜, 而 Nafion用量则节省了60%. PTFE/PAA/Nafion膜具有高质子导通率(80 ℃下达到131.9 mS/cm), 接近于Nafion117膜, 最大功率密度可以达到404.2 mW/cm².     

聚乙烯醇膜耐水改性的研究进展

聚乙烯醇(PVA)作为一种广泛应用的水溶性高分子聚合物,具有较好的气体阻隔性、热稳定性、生物相容性,故以此基料的改性膜材料成为重要的研究方向。但是由于聚乙烯醇结构中含有大量的亲水性基团(—OH),导致成膜的耐水性差,这很大程度上限制了它的推广和应用。本文总结了国内外对聚乙烯醇膜耐水改性的方法,如酯化交联、羟醛缩合、复配增塑、纳米补强和共混杂化等,有利于进一步推进聚乙烯醇耐水改性的研究,为设计和制备高性能的聚乙烯醇膜提供一定的参考,并进一步拓展聚乙烯醇的应用范围。     

表面改性SiO2对SSBR/BR绿色轮胎胎面胶结构与性能的影响

采用4种含不同官能基团修饰剂改性的二氧化硅SiO₂增强溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)共混体系, 制备了SSBR/BR/SiO₂橡胶纳米复合材料, 研究了其结构与性能. 结果表明, 在混炼胶体系中, 与未改性SiO₂填充的SSBR/BR相比, 改性SiO₂填充的SSBR/BR门尼黏度及结合橡胶含量显著增大, 表明填料-橡胶相互作用显著提高; 硫化焦烧时间缩短60%, 硫化速度增大了35%~40%. 在硫化胶体系中改性SiO₂填充的SSBR/BR具有更大的交联密度, 填料分散性明显改善, 同时也表现出更为优异的物理机械性能, 100%和300%定伸模量提高47%以上, 旋转滚筒式磨耗机法(DIN)磨耗降低5%~12%, 生热降低了约7%~13%, 热空气老化性能提升4%~22%, 代表滚动阻力的tanδ在60 ℃降低8%~13%. 此外, 与SSBR/BR/1165MP硫化胶相比, 用90 mmol/kg氨基改性SiO₂填充的SSBR/BR硫化胶的抗湿滑性能提高6.9%, 表现出最优的综合性能. 填料的良好分散及填料与聚合物的相互作用增强对于提高SSBR/BR/SiO₂胎面胶综合力学性能具有重要意义.