Photoluminescence and optical properties of He ion bombarded ultra-high molecular weight polyethylene

Ion bombardment is a suitable tool to improve the physical and chemical properties of polymer surface. In this study UHMWPE samples were bombarded with 130 keV He ions to the fluences ranging from 1 × 10¹² to 1 × 10¹⁶ cm⁻². The untreated and ion beam modified samples were investigated by photoluminescence, and ultraviolet-visible (UV-vis) spectroscopy. Remarkable decrease in integrated luminescence intensity with increasing ion fluences was observed. The reduction in PL intensity with increase of ion fluence might be attributed to degradation of polymer surface and formation of defects. The effect of ion fluence on the optical properties of the bombarded surfaces was characterized. The values of the optical band gap E_g, and activation energy E_a were determined from the optical absorption. The width of the tail of the localized states in the band gap (E_a) was evaluated using the Urbach edge method. With increasing ion fluences a decrease in both the energy gap and the activation energy were observed. Increase in the numbers of carbon atoms (N) in a formed cluster with increasing the He ion fluence was observed.     

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     

The effect of gamma irradiation and shelf aging in air on the oxidation of ultra-high molecular weight polyethylene

This study has investigated the effect of shelf aging, for up to one year in air, on the properties of gamma-irradiated ultra-high molecular weight polyethylene (UHMWPE). A variety of techniques were used to characterize the properties of treated samples. Differential scanning calorimetery (DSC) was used to characterize the morphology. The extent of cross-linking in a polymer network was detected by swelling measurements. The durometer hardness test was used to measure the relative hardness of this material, and changes in density were also measured. Results from all these measurements were combined to explain the changes in the microstructure of the aged, irradiated UHMWPE. This study shows that crystallinity is increased with radiation dose and with aging due to chain scission, which leads to a reduction in the molecular weight of the material. This allows the chains to rearrange to form crystalline regions. Positron annihilation lifetime spectroscopy confirms these conclusions. Fractional free volumes have been deduced from lifetime parameters, which correlate with the data obtained by the other techniques.     

Surface modification of ultra-high molecular weight polyethylene (UHMWPE) by argon plasma

In this work, argon (Ar) plasma generated by microwave electron cyclotron resonance (MWECR) has been used to modify the UHMWPE in order to increase the wear resistance. The results showed that the wettability, anti-scratch and wear resistance of UHMWPE treated by the Ar plasma had been improved, comparing with native UHMWPE. The FTIR and XPS spectra indicated the improvement of wettability should come from the oxygen based functional groups generated on the surface of UHMWPE. The improvement of anti-scratch and wear resistance may come from the enhancement of crosslinking of UHMWPE by Ar plasma treatment.     

Effect of gamma irradiation on high temperature hardness of low-density polyethylene

Gamma irradiation can cause the change of microstructure and molecular structure of polymer, resulting in the change of mechanical properties of polymers. Using the hardness measurement, the effect of gamma irradiation on the high temperature hardness of low-density polyethylene (LDPE) was investigated. The gamma irradiation caused the increase in the melting point, the enthalpy of fusion, and the portion of crystallinity of LDPE. The Vickers hardness of the irradiated LDPE increases with increasing the irradiation dose, annealing temperature, and annealing time. The activation energy for the rate process controlling the reaction between defects linearly decreases with the irradiation dose. The process controlling the hardness evolution in LDPE is endothermic because LDPE is semi-crystalline.     

Processing of ultra-high molecular weight polyethylene/graphite composites by ultrasonic injection moulding: Taguchi optimization

Ultrasonic injection moulding was confirmed as an efficient processing technique for manufacturing ultra-high molecular weight polyethylene (UHMWPE)/graphite composites. Graphite contents of 1 wt%, 5 wt%, and 7 wt% were mechanically pre-mixed with UHMWPE powder, and each mixture was pressed at 135 °C. A precise quantity of the pre-composites mixtures cut into irregularly shaped small pieces were subjected to ultrasonic injection moulding to fabricate small tensile specimens. The Taguchi method was applied to achieve the optimal level of ultrasonic moulding parameters and to maximize the tensile strength of the composites; the results showed that mould temperature was the most significant parameter, followed by the graphite content and the plunger profile. The observed improvement in tensile strength in the specimen with 1 wt% graphite was of 8.8% and all composites showed an increase in the tensile modulus. Even though the presence of graphite produced a decrease in the crystallinity of all the samples, their thermal stability was considerably higher than that of pure UHMWPE. X-ray diffraction and scanning electron microscopy confirmed the exfoliation and dispersion of the graphite as a function of the ultrasonic processing. Fourier transform infrared spectra showed that the addition of graphite did not influence the molecular structure of the polymer matrix. Further, the ultrasonic energy led oxidative degradation and chain scission in the polymer.     

分子量对PAMS热降解等温活化能的影响

聚α-甲基苯乙烯(PAMS)是制备激光惯性约束聚变(ICF)用靶丸的重要芯轴材料之一。采用快速热解气相色谱-质谱法(Py-GC-MS)和热重分析技术(TG/DTG)分析了不同分子量PAMS的热降解产物和热降解温度,并通过Arrhenius方程计算了不同分子量PAMS的等温热降解活化能。结果表明：分子量对PAMS热降解产物的影响可忽略不计,其热降解产物均为α甲基苯乙烯单体,且产率均接近100%;热降解温度随PAMS分子量的增加而降低,其热降解温度介于240~450 ℃之间;在相同降解率下,随分子量的减小,PAMS的热降解活化能增加,且PAMS的热降解活化能随着热降解率的增加而增加。     

Dynamic-mechanical and nuclear magnetic resonance study of relaxation processes in ultra-high molecular weight polyethylene fibres

The relaxation processes (α, β, and γ) in UHMW PE fibres drawn to different draw ratios λ have been studied by dynamic-mechanical and nuclear magnetic resonance methods. The temperature dependences of tensile loss moduli E″ and spin-lattice relaxation times T ₁ have been analyzed assuming distribution of correlation times τ according to the Davidson—Cole function. The activation energies E _a and parameters ε characterizing widths of distribution, and asymptotic value τ ₀ for correlation times have been determined from experimental data for low-temperature γ-process and for high-temperature α-process. A weak β-process has been found by dynamic-mechanical method and quantitative analysis was made only for fibres with λ = 9. The temperature dependences of second moment M ₂ of the broad-line NMR spectra have been analyzed according to the Gutowsky—Pake formula, which includes only a single correlation time τ _c without distribution. In this case the activation energies E _a and values of τ ₀ have been determined.     

Polarimetric characterization of ultra-high molecular weight polyethylene (UHMWPE) for bone substitute biomaterials

In this work the UHMWPE is characterized for their optical properties with Mueller matrix polarimeter. The transmittance birefringence, retardance, polarizance, linear and circular polarization and absorbance of polarized light at different wavelengths ranging 400-800 nm are measured. The presented Mueller matrix elements along with depth resolve polarization decrease in intensity with the change in the wavelength. Linear retardance increases compared to circular through highly scattering polyethylene. High refractive index and low mean free path; and close bonding of particles of material rotates the incoming photons and circular polarization which is dominant as compared to the linear one. Therefore the average intensity increases with both the optical depth and the scattered concentration in UHMWPE, which would accordingly decrease the apparent degree of polarization.The extracted results in terms of linear and circular retardances prove that UHMWPE is compatible, strong, and compact. This research work provides an optical characterization technique for bone substitute biomaterial in the health care industry.     

Characterization of structural modifications in poly-tetra-fluoroethylene induced by electron beam irradiation

The effects of electron beam irradiation doses on the poly-tetra-fluoroethylene (PTFE) have been studied. Several techniques, such as X-ray diffraction (XRD), differential scanning calorimetry (DSC), mechanical properties and Fourier transform infrared spectroscopy (FTIR) were applied to characterize the PTFE samples and to study the radiation effects on the crystal structure of the polymer.The irradiation dose up to 150 kGy showed an increase in the crystallinity degree of PTFE, which has been observed and confirmed during the DSC and XRD measurements. The increase in crystallinity was attributed to the scissions of the chain in the amorphous region. Moreover, the number-average molecular weights were estimated from the heat of crystallization measured by DSC technique. The results indicated that the molecular weights were decreased by increasing the heat of crystallization due to irradiation with doses up to 150 kGy. Radiation resistance of the irradiated and non-irradiated PTFE was investigated during its mechanical properties at room temperature. The dose at half value of the elongation at break is about 3.10 kGy while the dose at half value of the tensile strength is about 1.70 kGy.     

Experimental study on correlation between sound velocity and solute molecular weight in polyethylene glycol solution

In this study,ultrasound grating was used to measure the sound velocity in solutions of ethylene glycol and polyethylene glycol with molecular weights of 200,600,2000,and 10000.We found Parthasarathy empirical rule,that is,sound velocity is higher in the solution of larger molecules,is invalid in the case of polyethylene glycol solution. We tried to provide a tentative explanation using the Flory-Krigbaum's chained block cloud model.     

Cu固液界面能的分子动力学计算

本文使用分子动力学方法对液相Cu中不同半径晶胚的生长和熔化行为进行了研究. 随着半径的增加, 晶胚生长的临界温度升高. 临界形核过冷度和晶胚半径倒数成正比关系, 这和经典形核理论一致. 由上述关系计算得到Cu的Gibbs-Thomson系数为1.12×10^-7 K·m, Cu的固液界面能为0.146 J/m², Cu的Turnbull系数为0.416, 这些计算值均与实验值一致. 关键词： 分子动力学 经典形核理论 固液界面能     

Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial d 111 symmetry is similar to the trigonal Zr 3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial d 100 symmetry different from the orthorhombic O m center induced by X-ray irradiation. At a fluence around 10 18 e/cm 2 , both centers are bleached out near 600 v K, like the corresponding X-ray induced defects. At a fluence around 10 19 e/cm 2 , defects are much more stable, since complete thermal bleaching occurs near 1000 v K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.     

入射电子能量对低密度聚乙烯深层充电特性的影响

高能带电粒子与航天器介质材料相互作用引起的深层带电现象, 一直是威胁航天器安全运行的重要因素之一. 考虑入射电子在介质中的电荷沉积、能量沉积分布以及介质中的非线性暗电导和辐射诱导电导, 建立了介质深层充电的单极性电荷输运物理模型. 通过求解电荷连续性方程和泊松方程, 可以得出不同能量 (0.1–0.5 MeV) 电子辐射下, 低密度聚乙烯 (厚度为1 mm) 介质中的电荷输运特性. 计算结果表明, 不同能量的电子辐射下, 介质充电达到平衡时, 最大电场随入射能量的增加而减小; 同一能量辐射下, 最大电场随束流密度的增大而增加. 入射电子能量较低时 (≤ 0.3 MeV) , 最大电场随束流密度的变化趋势基本相同. 具体表现为: 当束流密度大于3× 10^-9 A/m²时, 最大场强超过击穿阈值2×10⁷ V/m, 发生静电放电 (ESD) 的可能性较大. 随着入射电子能量的增加, 发生静电放电 (ESD) 的临界束流密度增大, 在能量为0.4 MeV时, 临界束流密度为6×10^-8 A/m². 当能量大于等于0.5 MeV时, 在束流密度为10^-9–10^-6 A/m²的范围内, 均不会发生静电放电 (ESD) . 该物理模型对于深入研究深层充放电效应、评估航天器在空间环境下 深层带电程度及防护设计具有重要的意义. 关键词： 高能电子辐射 低密度聚乙烯(LDPE) 介质深层充电 电导特性     

The effects of contact area and applied load on the morphology of in vitro worn ultra‐high molecular weight knee prostheses: a micro‐Raman and gravimetric study

Ultra‐high molecular weight polyethylene knee prostheses of two different sizes (i.e. characterised by different contact areas) were run on a knee wear simulator in two tests differing for the applied load. Gravimetric and micro‐Raman spectroscopic analyses were performed to investigate at macroscopic and molecular levels the effects of contact area and applied load on the morphology of the knee components. The larger prostheses showed a higher mass loss in both tests, while Raman spectroscopy showed a more significant polymer degradation in the smaller prostheses, suggesting that a lower contact area is responsible for a higher wear at the molecular wear, but for a lower gravimetric wear. Raman measurements showed that in the second test (using a higher applied load), the wear mechanism changed with respect to the first test: the less severe conditions used in the latter resulted in an increase in the orthorhombic content, while the more severe conditions used in the former determined an increase and rearrangement of the amorphous phase. The results here reported allow to gain more insights into the effects of contact area, applied load and contact stress on wear. Preliminary micro‐Raman analyses on in vivo worn knee prostheses confirmed the results obtained in vitro: the retrievals of smaller size were found more degraded at molecular level than those of larger size. These findings showed that the conditions used in the in vitro tests well simulate the knee kinematics of the knee joint and thus the in vivo wear. Copyright © 2014 John Wiley & Sons, Ltd.     

Coherent molecular vibrational dynamics of CH2 stretching modes in polyethylene studied by femtosecond‐CARS

We have studied the coherent molecular vibrational dynamics of CH₂ stretching modes in polyethylene by time‐resolved femtosecond coherent anti‐Stokes Raman spectroscopy. We observed that the coherent vibrational relaxation of symmetric CH₂ stretching modes in polyethylene at room temperature is much faster than that previously measured in polyvinyl alcohol. In addition, it was detected that, at low temperature, the coherent vibrational relaxation of the symmetric stretching modes evidently becomes slower compared with that at room temperature. These temperature‐dependent measurements enable us to discriminate the contribution of pure dephasing mechanism, due to phonons and two‐level systems in polymer, from the contribution of lifetime of the vibrational excited state to the coherent vibrational relaxation of CH₂ stretching modes. We conclude that the coherent vibrational relaxation of symmetric CH₂ stretching modes at room temperature consists of the contribution of lifetime and approximately 1.5 times larger contribution of pure dephasing. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of electron and proton irradiation on recombination centers in GaAsN grown by chemical beam epitaxy

Deep level transient spectroscopy (DLTS) was deployed to study the evolution, upon electron irradiation and hydrogenation of GaAsN grown by chemical beam epitaxy, of the main nitrogen-related nonradiative recombination center (E1), localized at 0.33 eV below the bottom edge of the conduction band of the alloy. On one hand, the electron irradiation was found to enhance the density of E1 depending on the fluence dose. On the other hand, the hydrogenation was found to passivate completely E1. Furthermore, two new lattice defects were only observed in hydrogenated GaAsN films and were suggested to be in relationship with the origin of E1. The first defect was an electron trap at average thermal activation energy of 0.41 eV below the CBM of GaAsN and was identified to be the EL5-type native defect in GaAs, originating from interstitial arsenic (As_i). The second energy level was a hole trap, newly observed at average thermal activation energy of 0.11 eV above the valence band maximum of the alloy and its origin was tentatively suggested to be in relationship with the monohydrogen–nitrogen (N–H) complex. As the possible origin of E1 was tentatively associated with the split interstitial formed from one N atom and one As atom in single V-site [(N–As)_As], we strongly suggested that the new hole trap took place after the dissociation of E1 and the formation of N–H complex.     

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.     

Fluorescence probes as molecular weight detectors of polymers

It is shown that the relative intensity of the twisted intramolecular charge transfer (TICT) band of ester and benzonitrile derivatives of dialkylaniline in polymethylmethacrylate polymer matrices of different molecular weights (MW) to increase with increasing MW of the polymer. Our results emphasis the role of local free volumes (mobility in the matrix cage) and focus attention on the role of the MW of the polymer on the fluorescence of various TICT probes. These observations are confirmed by the red edge effect and fluorescence decay results.