可降解镁植入材料表面涂层的制备及其性能

采用浸涂法制备Mg植入材料表面聚乳酸涂层，通过选择不同相对分子质量的聚乳酸并采用硅烷偶联剂对Mg植入材料表面进行预处理，提高Mg植入材料与聚乳酸的结合力。利用扫描电镜得出浸涂时间、聚合物浓度及浸涂次数对涂层厚度的影响。发现Mg植入材料表面涂覆相对分子质量为20万的聚（乳酸-羟基乙酸）能够满足降解条件和结合力的要求。经聚乳酸表面处理的试样在Hank’s溶液中浸泡10d后，计算试样质量损失，发现表面处理后的试样质量损失明显降低。实验表明，镁表面涂覆聚乳酸涂层，可以有效提高其在模拟体液中的耐蚀性。     

骨植入镁合金表面缓蚀剂覆载的微弧氧化/PLGA复合涂层的制备与表征

目的 在可降解镁合金表面制备缓蚀剂覆载的微弧氧化/聚乳酸-羟基乙酸(PLGA)复合涂层,提高其耐蚀性.方法 首先利用微弧氧化技术在镁合金表面制备出适合复合缓蚀剂涂层的微弧氧化(Micro-Arc Oxidation,MAO)涂层,之后在微弧氧化多孔涂层上浸涂PLGA-缓蚀剂涂层,得到复合涂层,缓蚀剂选择天然植物提取物姜黄素(Curcumin,Cur).利用SEM&EDS、FTIR和AFM等实验对涂层形貌、成分及结构进行分析,通过电化学测试、体外浸泡实验评价涂层的耐蚀性能.结果 FTIR结果表明Cur可成功覆载在涂层中,且不与PLGA发生反应.电化学测试和体外浸泡实验表明MAO/PLGA-Cur涂层能有效提高镁合金的耐蚀性.动电位极化曲线显示MAO/PLGA-Cur涂覆样品的腐蚀电流密度比基体下降了3个数量级,浸泡14 d的质量损失比基体下降62.04％,比未覆载的样品减少26.63％.结论 MAO时间为10 min为最合适复合缓蚀剂涂层的参数.Cur作为缓蚀剂的最佳添加量为0.12％,PLGA的最佳添加量为12％,最佳浸涂角度为0°.     

医用镁及镁合金表面可生物降解有机高分子涂层的应用

近年来,镁及镁合金由于其生物可降解性和良好的生物相容性,在医疗器械领域的应用获得了迅速的发展,然而过快的降解速率限制了其在临床上的应用。可生物降解有机高分子涂层是一种降低镁及镁合金降解速率的有效表面改性方法,同时还可赋予镁及镁合金医疗器械多种功能性。首先综述了可降解有机高分子涂层对镁及镁合金耐腐蚀性能和生物相容性的影响。可降解聚合物涂层能阻碍腐蚀性介质与基体的接触,从而延长其降解时间。而涂层对基体的保护提供了碱性较弱的环境,更利于细胞的生长增殖;同时涂层随着基体一起降解,可降低聚合物长期存在生物体内可能引发炎症反应的风险。此外,对聚合物涂层在骨科以及心血管支架领域的应用以及进展进行了综述。一方面,可降解聚合物涂层能显著延长镁及镁合金在生物体内的作用时间;另一方面,涂层可以作为载体材料通过携带具有不同功能的试剂或者药物实现医疗器械的功能化,如促进骨愈合和药物的可控释放。因此,可降解聚合物涂层在镁和镁合金器械领域必将起到无可替代的作用。     

pH响应性聚合物抗菌涂层的制备及性能研究

目的 制备一种具有pH响应性的智能聚合物抗菌涂层,能按需实现涂层从防污到杀菌功能的转换.方法 以季铵盐甲基丙烯酰氧乙基二甲基辛烷基溴化铵(DMAEMA-8C)、对-(2-甲基丙烯氧乙氧基)苯甲醛(MAEBA)和甲基丙烯酸异辛酯(EHA)作为共聚单体,通过自由基聚合制备了一种季铵盐聚合物PMQE-CHO,并将其利用浸涂技术在不锈钢316L(SS)表面制备季铵盐聚合物涂层SS-PMQE-CHO.随后,使用PEG-NH2对季铵盐涂层SS-PMQE-CHO表面进行接枝改性,得到pH响应性聚合物涂层SS-PMQE-PEG.对涂层的基本性能进行了表征.通过大肠杆菌和荧光素偶联的牛血清白蛋白(FITC-BSA)的附着力测试,评估涂层的防污和抗菌性能.利用抗菌实验表征涂层在不同pH条件下的抗菌效果.进行体外细胞毒性分析和溶血试验,评估涂层的生物相容性.结果 涂层结构致密规整、机械性能优异,具有良好的生物相容性和低溶血率,并且可以有效地防止BSA和大肠杆菌的粘附.在菌液里培养10 h后,涂层SS-PMQE-PEG-30和SS-PMQE-PEG-40表面的细菌与SS表面的细菌相比,分别减少了94％和96％.此时,PEG显示出有效的防污作用.在菌液里培养24 h后,菌液的pH值降低.涂层SS-PMQE-PEG-30和SS-PMQE-PEG-40的功能从防污转化为杀菌,杀菌效率分别为93％和92％.即使是在PBS中浸泡两周后,涂层仍呈现出良好的功能转化性能.结论 在正常条件下,涂层SS-PMQE-PEG中的PEG可以有效抵抗蛋白质和细菌的粘附.当涂层附近的微环境变为弱酸性时,席夫碱键发生断裂,此时涂层底部的杀菌层暴露出来,以杀死细菌并抑制感染的发生.     

可降解镁合金支架聚合物涂层剥离的有限元模型及实验研究(英文)

可降解镁合金支架(MAS)能够改善商用裸支架和药物洗脱支架的长期治疗效果。由于镁合金支架在人体内降解速度太快,限制了其对病变血管的支撑性能。保护性聚合物涂层为镁合金支架提供了一种降低腐蚀速度的有效方法。然而,聚合物涂层在支架扩张时出现的剥离现象是阻碍其运用的一大障碍。在本研究中,分别运用有限元方法和实验方法对一种优化设计的镁合金支架进行了聚合物涂层剥离问题的研究。首先通过90o剥离实验测试,为粘聚区有限元模型提供了临界能量释放率,以此为基础的90o剥离的模拟结果和实验结果吻合良好。运用可靠的粘聚区模型参数,支架-聚合物涂层有限元模型考察了支架在扩张过程中是否会发生涂层剥离现象。本研究为考察支架聚合物涂层剥离现象提供了一种简单可靠的方法,为改善可降解镁合金支架的聚合物涂层性能提出了相应的建议。     

Modeling and Experimental Studies of Peeling of Polymer Coating for Biodegradable Magnesium Alloy Stents

可降解镁合金支架（MAS）能够改善商用裸支架和药物洗脱支架的长期治疗效果。由于镁合金支架在人体内降解速度太快,限制了其对病变血管的支撑性能。保护性聚合物涂层为镁合金支架提供了一种降低腐蚀速度的有效方法。然而,聚合物涂层在支架扩张时出现的剥离现象是阻碍其运用的一大障碍。在本研究中,分别运用有限元方法和实验方法对一种优化设计的镁合金支架进行了聚合物涂层剥离问题的研究。首先通过90o剥离实验测试,为粘聚区有限元模型提供了临界能量释放率,以此为基础的90o剥离的模拟结果和实验结果吻合良好。运用可靠的粘聚区模型参数,支架-聚合物涂层有限元模型考察了支架在扩张过程中是否会发生涂层剥离现象。本研究为考察支架聚合物涂层剥离现象提供了一种简单可靠的方法,为改善可降解镁合金支架的聚合物涂层性能提出了相应的建议。     

镁合金AZ31表面磷酸盐涂层在人工血浆中的降解行为

采用浸涂法在镁合金AZ31表面上制备了磷酸盐涂层,采用浸泡腐蚀、电化学等方法研究了涂层在人工血浆溶液中的腐蚀速率和降解行为,利用电子探针(EPMA)测定涂层的表面形貌及化学成分。结果表明,磷酸盐涂层使镁合金AZ31在人工血浆中的腐蚀速率明显降低,受腐蚀区域缩小,腐蚀程度降低。     

镁合金表面等离子喷涂钙/磷涂层在SBF中的降解行为研究

采用大气等离子喷涂在镁合金AZ31B表面制备了可降解钙/磷涂层。利用XRD、SEM、EDS分析了涂层的相组成、结晶度及在人体模拟液(SBF)中浸泡前后的显微形貌和元素组成,根据pH值和降解速率研究了涂层的体外降解性能。研究表明:钙/磷涂层与镁合金基体紧密结合,致密度高,涂层由较难降解的HA相和较易降解的Ca3(PO4)2、Ca4P2O9和CaO组成,涂层中HA结晶度为49.3%。生物降解性能研究显示,钙/磷涂层材料在SBF溶液中的pH值和降解速率均小于镁合金基体,且较小的变化幅度使涂层材料的降解行为控制在稳定范围内。     

医用可降解镁合金应用及表面改性研究进展

镁及其合金作为新一代生物医用可降解材料,具有良好的经济性、力学性能、生物相容性、可降解性能,在骨科、心血管科、消化科等领域具有广阔的应用前景。镁合金具有较高的化学活性,因此其降解速率较快,力学性能的维持受限,植入时可能发生的细菌感染会引发炎症和腐蚀加速等问题,因此需要通过表面改性来制备多功能一体化的涂层。综述了医用可降解镁合金作为接骨板、螺钉、血管支架、胃肠吻合器、胆管支架等植入材料的应用现状及最新研究成果。讨论了医用可降解镁合金在植入生物体时面临的析氢、pH升高、腐蚀加速、力学性能衰减、稀土元素毒性及内膜增生等具体问题,在此基础上,考察了化学转化、等离子喷涂、微弧氧化、聚合物涂层等4种镁合金表面改性技术的最新研究动态。结合体内试验和体外试验,概述了表面改性对镁合金安全性、耐蚀性、抗菌性、生物相容性等方面的影响,并简要对比了几种表面改性技术的优缺点。最后展望了医用可降解镁合金表面改性技术的发展方向。     

聚合物涂层处理镁合金的耐蚀性及溶血性研究

利用浸提法在表面防护处理后的镁合金上分别制备PLGA和壳聚糖两种聚合物涂层。通过电化学实验、接触角实验、浸泡实验对镁合金表面载药聚合物涂层进行研究。结果表明,两种载药聚合物涂层除具有药物缓释作用外,还可以在一定程度上提高镁合金的耐蚀性,并保持优异的抗溶血性。     

Effects of Post-weld Heat Treatment on Microstructure,Mechanical Properties and the Role of Weld Reinforcement in 2219 Aluminum Alloy TIG-Welded Joints

In as-welded state, each region of 2219 aluminum alloy TIG-welded joint shows diff erent microstructure and microhardness due to the diff erent welding heat cycles and the resulting evolution of second phases. After the post-weld heat treatment, both the amount and the size of the eutectic structure or θ phases decreased. Correspondingly, both the Cu content in α-Al matrix and the microhardness increased to a similar level in each region of the joint, and the tensile strength of the entire joint was greatly improved. Post-weld heat treatment played the role of solid solution strengthening and aging strengthening. After the post-weld heat treatment, the weld performance became similar to other regions, but weld reinforcements lost their reinforcing eff ect on the weld and their existence was more of an adverse eff ect. The joint without weld reinforcements after the post-weld heat treatment had the optimal tensile properties, and the specimens randomly crack in the weld zone.     

The First Phase of the SRIF Industrialized Base in ＂West Area＂ Has Been Put into Operation

After nearly two years＇ tense construction, the first phase of industrialized base of Shenyang Research Institute of Foundry （SRIF）, located at the Tiexi Casting and Forging Industrial Park in the west of Tiexi District, has now been completed and formally put into operation.     

Thermodynamics Study on the Decomposition of Chromite with KOH

Institute of Process Engineering, Chinese Academy of Sciences, China, has proposed a method for oxidative leaching of chromite with potassium hydroxide. Understanding the mechanism of chromite decomposition, especially in the potassium hydroxide fusion, is important for the optimization of the operating parameters of the oxidative leaching process. A traditional thermodynamic method is proposed and the thermal decomposition and the reaction decomposition during the oxidative leaching of chromite with KOH and oxygen is discussed, which suggests that chromite is mainly destroyed by reactions with KOH and oxygen. Meanwhile, equilibrium of the main reactions of the above process was calculated at different temperatures and oxygen partial pressures. The stable zones of productions, namely, K2CrO4 and Fe2O3, increase with the decrease of temperature, which indicates that higher temperature is not beneficial to thermodynamic reactions. In addition, a comparison of the general alkali methods is carried out, and it is concluded that the KOH leaching process is thermodynamically superior to the conventional chromate production process.     

Influence of Heat Treatment on Damping Behaviour of the Magnesium Wrought Alloy AZ61

The effect of isochronal heat treatments for 1h on variation of damping, hardness and microstructural change of the magnesium wrought alloy AZ61 was investigated. Damping and hardness behaviour could be attributed to the evolution of precipitation process. The influence of precipitation on damping behaviour was explained in the framework of the dislocation string model of Granato and Lücke.     

Effect of Rare Earth Doping on Impedance,Modulus and Conductivity Properties of Multiferroic Composites:0.5(BiLa_xFe_(1-x)O_3)–0.5(PbTiO_3)

The Lanthanum-doped bismuth ferrite–lead titanate compositions of 0.5(Bi LaxFe1-xO3)–0.5(Pb Ti O3)(x = 0.05,0.10,0.15,0.20)(BLxF1-x-PT) were prepared by mixed oxide method.Structural characterization was performed by X-ray diffraction and shows a tetragonal structure at room temperature.The lattice parameter c/a ratio decreases with increasing of La(x = 0.05–0.20) concentration of the composites.The effect of charge carrier/ion hopping mechanism,conductivity,relaxation process and impedance parameters was studied using an impedance analyzer in a wide frequency range(102–106Hz) at different temperatures.The nature of Nyquist plot confirms the presence of bulk effects only,and non-Debye type of relaxation processes occurs in the composites.The electrical modulus exhibits an important role of the hopping mechanism in the electrical transport process of the materials.The ac conductivity and dc conductivity of the materials were studied,and the activation energy found to be 0.81,0.77,0.76 and 0.74 e V for all compositions of x = 0.05–0.20 at different temperatures(200–300 °C).     

Quantitative Analysis of the Crystallographic Orientation Relationship Between the Martensite and Austenite in Quenching–Partitioning–Tempering Steels

The orientation relationships(ORs)between the martensite and the retained austenite in low-and medium-carbon steels after quenching–partitioning–tempering process were studied in this work.The ORs in the studied steels are identified by selected-area electron diffraction(SAED)as either K–S or N–W ORs.Meanwhile,the ORs were also studied based on numerical fitting of electron backscatter diffraction data method suggested by Miyamoto.The simulated K–S and N–W ORs in the low-index directions generally do not well coincide with the experimental pole figure,which may be attributed to both the orientation spread from the ideal variant orientations and high symmetry of the low-index directions.However,the simulated results coincide well with experimental pole figures in the high-index directions{123}_(bcc).A modified method with simplicity based on Miyamoto’s work was proposed.The results indicate that the ORs determined by modified method are similar to those determined by Miyamoto’method,that is,the OR is near K–S OR for the low-carbon Q–P–T steel,and with the increase of carbon content,the OR is closer to N–W OR in medium-carbon Q–P–T steel.     

Growth Kinetics of Single Inclusion Particle in Molten Melts

On the basis of the single-particle framework, a new theory on inclusion growth in metallurgical melts is developed to study the kinetics of inclusion growth on account of reaction and collision. The studies show that the early growth of inclusion depends on reaction growth and Brawnian motion collision, and where the former is decisive, the late growth depends on turbulence collision and Stokes＇ collision, and where the former is dominant; collision growth is very quick during the smelting process, lessened in the refining process, but nearly negligible in the continuous casting process.     

Theoretical Analysis for the Motion and Temperature of Melt Droplets in Spray Degassing Process

The motion of melt droplets in spray degassing process was analyzed theoretically. The height of the treatment tank in spray degassing process could be determined by the results of theoretical calculation of motion of melt droplets. To know whether the melt droplets would solidify during spraying process, the balance temperature of melt droplets was also theoretically analyzed. Then proof experiments for theoretical results about temperature of melt droplets were carried. In comparison, the experimental results were nearly similar to the calculation results.     

Using Finite Element and Contour Method to Evaluate Residual Stress in Thick Ti-6Al-4V Alloy Welded by Electron Beam Welding

This work was to reveal the residual stress profile in electron beam welded Ti-6Al-4V alloy plates(50 mm thick) by using finite element and contour measurement methods.A three-dimensional finite element model of 50-mmthick titanium component was proposed,in which a column–cone combined heat source model was used to simulate the temperature field and a thermo-elastic–plastic model to analyze residual stress in a weld joint based on ABAQUS software.Considering the uncertainty of welding simulation,the computation was calibrated by experimental data of contour measurement method.Both test and simulated results show that residual stresses on the surface and inside the weld zone are significantly different and present a narrow and large gradient feature in the weld joint.The peak tensile stress exceeds the yield strength of base materials inside weld,which are distinctly different from residual stress of the thin Ti-6Al-4V alloy plates presented in references before.     

Microstructures and Tensile Properties of Ultrafine-Grained Ni–(1–3.5) wt% SiC_(NP) Composites Prepared by a Powder Metallurgy Route

Silicon carbide nanoparticle-reinforced nickel-based composites(Ni–Si CNP),with a Si CNPcontent ranged from1 to 3.5 wt%,were prepared using mechanical alloying and spark plasma sintering.In addition,unreinforced pure nickel samples were also prepared for comparative purposes.To characterize the microstructural properties of both the unreinforced pure nickel and the Ni–Si CNPcomposites transmission electron microscopy(TEM) was used,while their mechanical behavior was investigated using the Vickers pyramid method for hardness measurements and a universal tensile testing machine for tensile tests.TEM results showed an array of dislocation lines decorated in the sintered pure nickel sample,whereas,for the Ni–Si CNPcomposites,the presence of nano-dispersed Si CNPand twinning crystals was observed.These homogeneously distributed Si CNPwere found located either within the matrix,between twins or on grain boundaries.For the Ni–Si CNPcomposites,coerced coarsening of the Si CNPassembly occurred with increasing Si CNPcontent.Furthermore,the grain sizes of the Ni–Si CNPcomposites were much finer than that of the unreinforced pure nickel,which was considered to be due to the composite ball milling process.In all cases,the Ni–Si CNPcomposites showed higher strengths and hardness values than the unreinforced pure nickel,likely due to a combination of dispersion strengthening(Orowan effects) and particle strengthening(Hall–Petch effects).For the Ni–Si CNPcomposites,the strength increased initially and then decreased as a function of Si CNPcontent,whereas their elongation percentages decreased linearly.Compared to all materials tested,the Ni–Si CNPcomposite containing 1.5% Si C was found more superior considering both their strength and plastic properties.