Failure analysis on retrieved ultra high molecular weight polyethylene (UHMWPE) acetabular cups

Retrievals obtained after revision surgery, provide valuable information on the rate of wear and the causes of wear that take place in vivo. The aim of this study was to perform a root cause failure analysis to determine the principle reason for mechanical failure on failed acetabular cups, retrieved during revision surgery, by making use of sound engineering failure analysis techniques. The bearing couples varied between steel on UHMWPE and ceramic on UHMWPE. The information gained during this analysis brought to the four that the principle mode of mechanical failure for acetabular cups is overheating of the UHMWPE. The resulting overheating is mainly due to a lack of good and/or sufficient lubrication.     

Synthesis and characterization of multiwalled carbon nanotube reinforced ultra high molecular weight polyethylene composite by electrostatic spraying technique

In the present work, multiwalled carbon nanotube (MWNT) reinforced UHMWPE composite films were prepared by electrostatic spraying followed by consolidation. X-ray diffraction and differential scanning calorimetry studies showed a decrease in the crystallinity of UHMWPE due to the nature of the fabrication process as well as addition of MWNT. Tensile test showed an 82% increase in the Young’s modulus, decrease in stress to failure from 14.3 to 12.4 MPa and strain to failure from 3.9% to 1.4% due to 5% addition of MWNT. Raman spectra showed the presence of compressive stresses in the nanotubes. Fracture surface showed presence of pullout like phenomena in the MWNT reinforced film.     

Treatment of functionalized graphitic nanofibers (GNFs) and the adhesion of GNFs-reinforced-epoxy with ultra high molecular weight polyethylene fiber

Though ultra high molecular weight polyethylene (UHMWPE) fiber made of carbon and hydrogen has superior mechanical properties and effective cosmic shielding properties, it shows weak composite properties due to poor interfacial adhesion between UHMWPE fibers and polymer matrix. In this study, functionalized graphitic nanofibers (GNFs) were treated further using the sonication method. High-level sonication with a series of conditions was employed for the treatment of functionalized GNFs. submicron particle size analyzer and transmission electron microscope (TEM) were used to study effects on the length and morphology of treated nanofibers by sonication conditions. The sonication conditions were optimized for preparation of a nano-epoxy matrix containing well-dispersed, reactive, functionalized graphitic nanofibers. The adhesion ability of the nano-epoxy to UHMWPE fiber was investigated. Bundle fiber pullout specimens with single and double-ends were designed and prepared for study of the adhesion property of the nano-matrix with UHMWPE fiber. Test results showed that the nano-epoxy matrix could effectively improve interfacial adhesion property with UHMWPE fiber.     

Synthesis and characterization of bioresorbable in situ crosslinkable ultra low molecular weight poly(lactide) macromer

Reactive low molecular weight poly(l-latide) (PLA) is required to produce in situ hardened scaffolds with fast rate of crosslinking, high crosslink density, and adequate mechanical strength. The objective of this work was to synthesize unsaturated ultra low moelcular weight PLA (ULMW PLA) as an injectable in situ crosslinkable macromer for biomedical applications. Low molecular weight PLA was synthesized by ring-opening polymerization of l-lactide (LA) using diethylene glycol (DEG) as the initiator. The molar ratio of the LA to DEG ranged from 5 to 20. Non-solvents methanol, ether, and hexane were used for purification and fractionation. The PLA samples that were precipitated in methanol and ether had narrow distributions (PDI = 1.2) and resulted in a powder with M_n of 4.8 and a wax with M_n of 3.6 kDa, respectively. The PLA sample in which the supernatant from ether was re-precipitated in hexane produced a viscous ULMW PLA with M_n and PDI of 1.2 kDa and 1.2, respectively. The ULMW PLA was reacted with fumaryl chloride to produce unsaturated in situ crosslinkable poly(lactide fumarate) (PLAF) macromer. Porous scaffolds were produced after injection and in situ crosslinking of the PLAF macromer with NVP crosslinker in the presence of a porogen. New bone was formed in the scaffold when it was implanted in nude mice which demonstrated that the scaffold was osteoconductive. PLAF is potentially useful as a reactive macromer in fabrication of bioresorbable injectable in situ crosslinkable scaffolds for tissue regeneration.     

超高分子量聚乙烯(UHMWPE)纤维表面处理对UHMWPE/环氧树脂复合材料界面性能的影响机制

从工程化应用角度研究了常压空气等离子体改性对超高分子量聚乙烯（UHMWPE）纤维/环氧树脂复合材料界面性能的调节机制,主要分析了不同处理时间对UHMWPE纤维表面状态变化的影响,及其对UHMWPE/环氧树脂复合材料界面黏结性能的影响规律。采用SEM及纤维吸水测试研究了等离子体处理对UHMWPE纤维表面物理形貌及纤维表面浸润性能的影响,分别以拉伸和弯曲的方式,通过纤维表面脱黏力及层合板层间剪切强度对UHMWPE/环氧树脂复合材料的界面黏结性能进行表征。结果表明,仅经过4 s的空气等离子体处理之后,UHMWPE纤维表面脱黏力的提高幅度为84.0%,UHMWPE/环氧树脂复合材料层合板的层间剪切强度由未处理的7.01 MPa提高至15.81 MPa,增幅高达125.5%。研究发现,通过常压空气等离子体处理改变了UHMWPE纤维的表面状态,可以显著高效地调节UHMWPE/环氧树脂复合材料的界面性能,为扩大该材料的后续工程化应用提供了理论基础。      

乳酸-乙醇酸共聚物的制备及降解性能研究

以L-乳酸(L-LA)和乙醇酸(GA)为原料(L-LA和GA投料摩尔比为80∶20),二水合氯化亚锡和对甲苯磺酸(TSA)为复合催化剂,采用直接熔融缩聚法制OLGA预聚物,然后在扩链剂六亚甲基二异氰酸酯(HDI)存在下进行熔融扩链,最终得到较高分子量的乳酸-乙醇酸共聚物(PLGA),其数均分子量和重均分子量分别为5.5×104和1.3×105。将溶液浇铸法制备的PLGA薄膜在37℃、pH=7.3～7.4的磷酸盐缓冲液(PBS)中进行降解实验,采用pH分析、失重率测量、GPC、SEM、FT-IR等方法研究了PLGA薄膜的降解行为,并对降解机理进行了初步探讨。结果表明,随着降解的进行,PLGA薄膜的相对分子量和质量都会逐渐下降,在降解反应进行的前21天中,相对分子量的减小较明显,21天之后质量损失较明显。结合FT-IR谱图的研究,分析可知PLGA的降解主要是通过酯键的水解实现的。     

Enhancement on interlaminar shear strength and tribological properties in water of ultra high molecular weight polyethylene/glass fabric/phenolic laminate composite by surface modification of fillers

The ternary laminate composite of ultra high molecular weight polyethylene (UHMWPE)/high strength glass fabric (S-glass fabric)/phenolic resin was prepared, in which UHMWPE microparticles were etched by chromic acid and S-glass fabrics were treated by silane coupling agent. The interlaminar shear strength (ILSS) and tribological properties of the composite in water environment were investigated, in comparison with those of the composite without any treatments on fillers and the composite with single treatment on UHMWPE. Results showed that the composite with the combined treatment exhibited the best interfacial bond, accordingly showing remarkably enhanced water repellency, ILSS and tribological properties under water lubrication. Furthermore, after experiencing 48 h water immersion, the composites with both single and combined treatment did not suffer any degradation of ILSS and water-lubricated tribological performances, showing excellent duration in water environment.     

Deformation behavior in Simple Shear Extrusion (SSE) as a new severe plastic deformation technique

A new method for severe plastic deformation is proposed herein, entitled as Simple Shear Extrusion (SSE) due to the manner in which specimen's cross-section shape changes. This method is based on pressing material through a specially designed direct extrusion die. The process was investigated experimentally on commercially pure aluminum. Additionally, simulation of the process was also carried out, using the commercial finite element code ABAQUS/Explicit. Moreover, effect of back-pressure on the results was studied. Results show that SSE method is capable of imposing high strain values via strain accumulation during repeating the process, which is of great importance in producing ultrafine-grained or nanostructured materials.     

低温常压下高分子量左旋聚乳酸的微波合成及表征

以辛酸亚锡为催化剂低温常压下引发左旋丙交酯(LLA)开环聚合,快速高效地合成了性能良好的高分子量左旋聚乳酸(PLLA).通过正交实验研究了催化剂用量、反应温度和时间对产物分子量的影响,在催化剂用量0.21%(质量分数),反应温度100℃,反应时间60min时得到产物粘均分子量高达16.21×104.通过红外光谱(FTIR)、核磁共振氢谱(1H-NMR)对产物的结构进行分析,结果证明利用微波能有效地合成左旋聚乳酸,通过差式扫描量热(DSC)、X衍射(XRD)、旋光度和力学性能对左旋聚乳酸膜的性能进行表征,结果显示产物纯净,其结晶度为85.6%,光学纯度为98%,有良好的力学性能.     

高分子量聚对苯撑苯并双(噁)唑的合成及性能研究

采用4,6-二氨基-1,3苯二酚磷酸盐(DAR·2H3PO4)和对苯二甲酸(TPA)为原料,在氮气保护下,多聚磷酸介质中经缩聚得到聚对苯撑苯并双(噁)唑(PBO).通过重结晶使4,6-二氨基-1,3苯二酚磷酸盐纯度达到99.8％.考查了不同五氧化二磷含量和最高反应温度对聚合的影响,通过实验得到的最佳工艺条件是:聚合温度为120～180℃,控制最终五氧化二磷的质量分数ω(P2O5) =83.5％～84.5％.采用红外光谱、元素分析、XRD对PBO结构进行表征,热重分析表明PBO在氮气和空气中有很好的稳定性,在甲烷磺酸(30±0.1)℃中测得PBO特性黏度为20.4dL/g.     

Prismatic hull: A new measure of shear stress amplitude in multiaxial high cycle fatigue

The largest rectangular prismatic hull enclosing the deviatoric stress history is proposed as a measure of shear stress amplitude in multiaxial high cycle fatigue. The axes of the prismatic hull represent the amplitudes of the stress history along its directions, allowing a proper characterization of non-proportional loadings. The resulting multiaxial fatigue endurance criterion, simple to implement and very cost effective from the computational point of view, provides predictions which are in sound agreement with a wide variety of available fatigue experiments involving combined normal and shear stresses, with harmonic and non-harmonic, synchronous and asynchronous waveforms.     

一种制备8-羟基喹啉铝的新方法

用一种简单、高效的方法合成了8-羟基喹啉铝.通过核磁共振谱和紫外光谱,证明了铝参与了配位和8-羟基喹啉铝的存在.对得到的晶体进行X-射线晶体结构分析,其主要晶胞参数为单胞尺寸a=1.11882nm,b=1.32614nm,c=1.6701nm,β=94.011(10)°.V=2.4718nm3,Z=4,计算密度1.358mg/m3,吸收系数0.124 mm-1.在氯仿溶液中对Alq进行了单光子荧光测试,其发射峰在520nm处,对以Alq为电子传输层的器件进行性能测试,其EL最大发射峰在516nm,起始电压为3.0V,15V时的亮度为19458cd/m2.最大流明效率和最大电流效率分别为0.70lm/W和1.32cd/A.     

A weight function technique in three-dimensional fracture mechanics: static and dynamic

The weight function technique is used to analyse both static and dynamic three-dimensional fracture mechanics problems. The weight functions are first determined, in terms of Laplace transforms, by an indirect boundary element method. The stress intensity factor in the time domain is then obtained by Durbin's inversion method. The dynamic stress intensity factors are calculated for a central square crack in a square bar and a circular or elliptical crack in a cylinder under different types of loads. An extension of the method for arbitrary dynamic loads is developed via a dynamic Green's function approach.     

Control on molecular weight reduction of poly(ε-caprolactone) during melt spinning — A way to produce high strength biodegradable fibers

Poly(ε-caprolactone) (PCL) is known for its biocompatibility and biodegradability. These features of PCL have resulted into significant academic as well as industrial research interests for use of this polymer in various areas including biomedical and tissue engineering. Three-dimensional porous scaffolds, controlled drug release systems and nerve guides are some of the forms in which this polymer has been used. Despite these forms, fibers made of PCL have not gained much attention due to PCL's low melting point (57–60 °C) and relatively inferior mechanical properties as compared to poly(L-lactide) (PLA). Also the polymer is sensitive to the process conditions of melt spinning which leads to degradation of PCL when subjected to high temperatures in the presence of air or moisture. Here we present an approach in which addition of a bilactone, bis-(ε-caprolactone-4-yl) (BCY), during melt spinning of PCL resulted into monofilament fibers having tenacity as high as 2500 MPa. The cross-linking of PCL which occurred due to BCY transesterification compensated for molecular weight reduction of the polymer under melt spinning conditions. PCL monofilament fibers thus developed have enhanced thermo-mechanical properties and therefore have high potential to be used in tissue engineering applications in the form of sutures, a mesh or a non-woven.     

A new crystal morphology of straight-stalk dendrites in blends of poly(butylene adipate) with amorphous poly(vinyl acetate)

Discontinuity in crystallization rates and a new and unusual morphology consisting of thickened straight-stalks crystal lamellae with also straight branches radiating out from a common nucleus were observed in blends of poly(vinyl acetate) (PVAc) with poly(1,4-butylene adipate) (PBA). The discontinuity in the crystal growth and mechanisms of straight-dendrite morphology of the PVAc/PBA blends were analyzed using polarized-light optical microscopy (POM), differential scanning calorimetry (DSC), and wide-angle X-ray diffraction (WAXD). The discontinuity in crystallization rate and dendritic morphology occurred only at or near PVAc/PBA 10/90 blend composition upon crystallization at high-temperature regimes of T_c = 30-33 °C. By comparison, when crystallized at the same temperatures, PVAc/PBA blends of amorphous polymer loading greater than 15% or the neat PBA (amorphous polymer loading = 0) developed no dendrites but only typical Maltese-cross spherulites. Mechanism of straight dendrites in the blends is preliminarily expounded. Detailed interpretation requires further analyses.     

Fatigue mechanisms in poly (methyl methacrylate) at threshold: effects of molecular weight and mean stress

Fatigue tests were conducted on three linear poly (methyl methacrylate) (PMMA) resins having weight average molecular weights (M _w) of 82 000, 205 000 and 390000 and on a fourth, cross-linked sample (M _c=3337 g mol^–1). Fatigue threshold test conditions included a constant load ratio (R ^c=0.1) and a constant maximum stress intensity level (K _max ^c =0.52 MPa m^1/2). TheR ^c=0.1 test results demonstrated that fatigue resistance increased with increasingM _w, and that the cross-linked sample possessed a higher fatigue threshold than the linear Iow-M_w material. However, the K _max ^c test results revealed the opposite trend, with fatigue resistance decreasing with increasingM _w and chemical crosslinking. The marked change in relative fatigue resistance of the PMMA resins investigated under high mean stress conditions is believed to be a consequence of the competition between two molecular deformation mechanisms: chain scission and chain slippage. The presumed shift in operative mechanism as a function of theR level is reflected in differences noted on the fracture surfaces of the PMMA resins studied. Discontinuous growth band formation, which is indicative of large amounts of chain slippage, is favoured by lowM _w and lowR ratios, but disappears in association with high-M _w and highR-ratio test conditions.     

Preparation and characterization of high molecular weight low bandgap polymers based on poly(2,7-carbazole)s for organic solar cells

We report the PCDTBT {Poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]}, an alternating copolymer of 2,7-carbazole and dithienyl-2,1,3-benzothiazole, has high molecular weight and narrow molecular weight distribution. Our PCDTBT can be successfully prepared as good yield by using tetrakis(triphenylphosphine)palladium [Pd(PPh3)4] catalyst instead of Pd2dba3/P(o-Tol)3 catalyst. From the UV/Vis absorption spectroscopy, we can observe that absorption bands of PCDTBT are bathochromically shifted by increasing the molecular weight, that is to say, our high molecular weight PCDTBT can absorb much longer wavelength light compare to low molecular weight PCDTBT. The best performance can be obtained from device based on the mixture of PCDTBT (polymer-30) and PC70BM {[6,6]-phenyl C71-butyric acid methyl ester} (1:4) as an active layer, which shows 4.50% of PCE with 10.1 mA/cm2 of short-circuit current density (J(SC)), 0.85 V of open-circuit voltage (V(OC)), and 52.3% of fill factor which is very similar with Leclerc's published result.     

Freeze-drying of low molecular weight poly(L-lactic acid) nanoparticles: effect of cryo- and lyoprotectants

The chemical and physical stability of polymeric nanoparticles is poor in aqueous suspensions, and the drying of these particles is often problematic. In the present study, the stability of freeze-dried low molecular weight poly(L-lactic acid) (PLA) nanoparticles was enhanced by adding glucose and/or lactose to the formulation as cryo- and lyoprotectants, respectively. Also the effect of an extra stabilizer, Tween 80, was studied. The best freeze-dried PLA nanoparticle formulations were achieved, when glucose and lactose were added in combination so that the amount of lactose was double the amount of glucose. With this combination the redispersion of high-quality nanoparticles (homogenous particle dispersion with original size and without aggregates) was achieved. The addition of Tween 80 further improved the quality of freeze-dried PLA nanoparticles by facilitating the redispersion of the lyophilized cake into optimal nanoparticles.