纯钛表面载银微弧氧化陶瓷膜的制备及性能EI北大核心CSCD

将微弧氧化和水热处理相结合,在纯钛表面制备载银微弧氧化陶瓷膜,改善其润湿性及耐蚀性,并赋予抗菌性。采用扫描电子显微镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)、X射线光电子能谱分析(XPS)对微弧氧化陶瓷膜层进行表征,通过接触角测试评价膜层亲水性,采用电化学测试对膜层耐蚀性进行评价,抗菌性实验分析膜层抗菌性。结果表明:载银微弧氧化陶瓷膜的表面形貌仍为火山多孔结构,纳米级Ag颗粒均匀分布在微孔周围。载银微弧氧化陶瓷膜的表面主要为TiO2和纳米Ag颗粒。载银微弧氧化陶瓷膜的亲水性比纯钛的亲水性高77.0%,比微弧氧化陶瓷膜的高68.2%。与纯钛相比,载银微弧氧化陶瓷膜的自腐蚀电位提高了0.44 V,与微弧氧化相比增加了0.31 V。微弧氧化陶瓷膜的抗菌率为32.2%,载银微弧氧化陶瓷膜的抗菌率大于99.9%。     

纯钛表面载银微弧氧化陶瓷膜的制备及性能

将微弧氧化和水热处理相结合,在纯钛表面制备载银微弧氧化陶瓷膜,改善其润湿性及耐蚀性,并赋予抗菌性。采用扫描电子显微镜(SEM)、能谱分析(EDS)、X射线衍射(XRD)、X射线光电子能谱分析(XPS)对微弧氧化陶瓷膜层进行表征,通过接触角测试评价膜层亲水性,采用电化学测试对膜层耐蚀性进行评价,抗菌性实验分析膜层抗菌性。结果表明:载银微弧氧化陶瓷膜的表面形貌仍为火山多孔结构,纳米级Ag颗粒均匀分布在微孔周围。载银微弧氧化陶瓷膜的表面主要为TiO_2和纳米Ag颗粒。载银微弧氧化陶瓷膜的亲水性比纯钛的亲水性高77.0%,比微弧氧化陶瓷膜的高68.2%。与纯钛相比,载银微弧氧化陶瓷膜的自腐蚀电位提高了0.44 V,与微弧氧化相比增加了0.31 V。微弧氧化陶瓷膜的抗菌率为32.2%,载银微弧氧化陶瓷膜的抗菌率大于99.9%。     

微弧氧化和阳极氧化处理镁合金的耐蚀性对比

通过电化学分析测量镁合金微弧氧化陶瓷层和阳极氧化陶瓷层的交流阻抗图谱，稳态电流／电位曲线，并对得出的交流阻抗值和腐蚀电流进行比较，结果表明，与阳极氧化处理比较，镁合金经营微弧氧化处理后交流阻抗值增大，腐蚀电流降低，微弧氧化陶瓷层特有的微观结构是其耐蚀性显著提高的主要原因。     

电化学及热处理氧化对商业纯钛耐蚀性能的影响

利用电化学氧化、热处理氧化对商业纯钛进行表面处理.不同的氧化电压和时间将产生不同形貌的氧化钛膜,电压过大时会生成很多的瘤状氧化物.热处理氧化后,钛表面生成均匀金红石和锐钛矿型混合氧化物膜,并且氧化膜下会出现Ti-O固溶体构成的渗氧层.在酸性含氯溶液和碱溶液中比较不同处理后钛板的腐蚀性能,在2种腐蚀介质中所有材料均随电位升高进入钝化区.在酸性溶液中,电化学氧化处理后钛板的腐蚀电流、维钝电流密度最小;在碱性溶液中,虽然热处理氧化对应维钝电流密度最小,但其钝化电位区间比电化学氧化对应电位区间窄.扫描电镜分析表明,热处理氧化膜随电位升高局部出现破损,而未经过表面处理的钛板,局部区域发生沿晶腐蚀.     

钛合金微弧氧化-聚四氟乙烯复合自润滑膜的制备及其性能

为了提高钛合金表面微弧氧化膜的减摩耐磨性能,在硅酸盐溶液中,对Ti6Al4V钛合金进行微弧氧化处理,采用聚四氟乙烯(PTFE)对微弧氧化膜进行封孔处理后对其进行高温固化,制备了具有自润滑和高耐磨性的微弧氧化-PTFE自润滑膜。采用扫描电镜观察了自润滑膜的表面形貌;采用摩擦磨损试验机研究了其耐磨性能;采用极化曲线研究了其耐腐蚀性能。结果表明:PTFE颗粒已进入微弧氧化膜中,自润滑膜的摩擦系数低至0.15左右,自腐蚀电位较基体大幅正移,腐蚀电流密度大幅降低,自润滑膜的耐磨性能及耐蚀性能均较基体及微弧氧化膜大幅提升。     

TA4微弧氧化陶瓷膜层的结构与性能研究

利用微弧氧化法在纯钛TA4表面制备以Ti O2为主体富含钙磷的多孔陶瓷膜层。采用扫描电镜、X射线能谱仪、X射线衍射仪、拉曼光谱仪、接触角测量仪及电化学工作站观测与分析陶瓷膜层的微观形貌、元素成分及相组成,探讨微弧氧化对其润湿性及耐蚀性能的影响。结果表明,TA4微弧氧化陶瓷膜层表面粗糙多孔,为锐钛矿相与金红石相Ti O2的混晶结构,金红石相的质量分数约为74.39%。TA4经微弧氧化改性后,表面粗糙度增加了1个数量级,接触角明显下降,表面能提高了87.05%,极性力分量增加了166.07%,体现出更好的润湿性能;自腐蚀电位正移0.53 V,腐蚀电流密度与腐蚀速率均减少了3个数量级,表现出更优的耐腐蚀性能。     

ZK61S镁合金微弧氧化膜层的结构及耐腐蚀性能

为了提高ZK61S镁合金的耐腐蚀性能,采用微弧氧化方法以不同电压(300,380,450 V)在ZK61S镁合金表面制备氧化膜并进行封孔处理。利用金相显微镜、扫描电镜、X射线衍射仪分析膜层的形貌、结构和组成;通过腐蚀电位试验、中性盐雾腐蚀试验及抗剥落腐蚀试验进行耐腐蚀性能考核。结果表明:微弧氧化呈现疏松多孔形态且均匀覆盖于基材表面,主要由Mg、MgO和Al_2Si_2O_5(OH)4相组成;微弧氧化处理后试样的腐蚀电位显著提升,且380 V所得微弧氧化试板的腐蚀电位达到-881.53 m V,经过408 h的中性盐雾腐蚀试验后的腐蚀速率为0.012g/(m~2·h),耐蚀性能比未进行表面处理的基材提高了88倍;经封孔处理的微弧氧化试板经过456 h的中性盐雾腐蚀试验后腐蚀速率降低到0.003 g/(m~2·h);封孔处理使微弧氧化膜的抗剥落腐蚀性能由微弧氧化后的EB级提升到EA级。     

表面纳米化-微弧氧化复合涂层对铝合金拉伸性能影响机制研究

通过表面机械研磨处理(SMAT)在LY12CZ铝合金表面制备表面纳米化(SNC)过渡层,再采用微弧氧化(MAO)技术对纳米晶过渡层进行微结构重构,设计制备出纳米化-微弧氧化(SNC-MAO)复合涂层,并对比研究了表面纳米化、微弧氧化及纳米化-微弧氧化复合处理对基体铝合金拉伸性能的影响。结果表明,微弧氧化处理使基体铝合金的屈服强度和抗拉强度减小,而纳米化-微弧氧化复合处理则增加了基体铝合金的屈服强度和抗拉强度。在拉伸伸长率8%的条件下,相同厚度的纳米化-微弧氧化复合涂层比微弧氧化涂层具有更好的抗拉伸破坏能力,表现出更好的膜基结合性能。     

TA2纯钛微弧氧化陶瓷膜层的颜色和性能

在添加乙酸铜、乙酸镁的磷酸-氟锆酸钾电解液中对纯钛TA2基体进行微弧氧化处理,制备出颜色均匀的浅棕色陶瓷膜层。通过X射线衍射分析(XRD)、扫描电子显微分析(SEM)及附带的能谱(EDS),研究了陶瓷膜的表面和截面形貌、元素分布、相组成;用分光光度计测量了膜层的颜色,根据热震试验和三点弯曲法评价了膜层与基体的结合强度。结果表明:随着微弧氧化时间的延长,膜层中铜镁元素的含量增加,膜层的颜色随之发生变化,膜层与基体的结合强度降低。热震实验结果表明,膜层与基体有较高的结合强度。     

球墨铸铁微弧氧化陶瓷层扩散退火前后的组织状态

过去,对铸铁件热浸镀铝再微弧氧化仅有少量的研究,且还存在残留铝影响氧化层性能的问题。为此,对球墨铸铁先热浸镀铝后再微弧氧化形成陶瓷层,采用扫描电镜、能谱分析和X射线衍射分析了陶瓷层的相组成及形貌,并探讨了对陶瓷层进行扩散退火处理的可行性。结果表明:球墨铸铁浸镀铝后微弧氧化获得的陶瓷层主要由α-Al2O3相和γ-Al2O3相组成;600℃扩散退火时,因陶瓷层与纯铝层之间热膨胀系数不匹配会导致界面处产生热应力,造成陶瓷层与纯铝层的界面处出现明显孔洞;球墨铸件微弧氧化形成的陶瓷层不适合扩散退火处理;对微弧氧化后,热浸镀铝层剩下多少为佳及处理的问题,应进一步研究。     

沉积温度对多孔钛表面仿生制备羟基磷灰石的影响

为研究沉积温度对羟基磷灰石涂层生长的影响,制备了不同温度条件下成分恒定的仿生沉积液,并采用纯钛和不同孔径的多孔钛做基体,在其表面仿生沉积羟基磷灰石涂层,再将得到的涂层试样浸泡在标准模拟体液中检测其生物活性.通过X射线衍射仪(XRD)分析涂层物相结构,用金相显微镜、环境扫描电子显微镜(ESEM)表征涂层形貌,利用能谱分析仪(EDS)计算钙磷比.研究表明:基体孔径增大,有利于沉积液进入到孔隙且表面粗糙度相对增大,从而使得HA涂层变得均匀致密;沉积温度由30℃升高至37℃,会加快HA涂层致密均匀的生长,但温度升高到44℃时,HA晶粒变粗大,涂层变得疏松化;模拟体液浸泡后,Ti/HA涂层试样表面有新的HA生成,且Ca/P比接近标准的1.67,表明该Ti/HA涂层试样具有良好的生物活性.适当增大钛基体孔径,提高沉积液温度,可以得到均匀致密的HA生物活性涂层.     

Influence of zirconia on biomimetic apatite formation in pure titanium coated via plasma electrolytic oxidation

This work demonstrated the effect of zirconia incorporation on the formation of biomimetic apatite in pure titanium coated by plasma electrolytic oxidation (PEO) method. To incorporate zirconia particles into the oxide layer, electrochemical coating was carried out under AC condition in an electrolyte containing zirconia powder. After PEO coatings, zirconia particles were distributed uniformly throughout the titanium oxide layer while the size and distribution of micro-pores remained unchanged when compared to titanium coated by PEO in an electrolyte without zirconia. It was found that a number of fine zirconia particles played an important role in triggering the occurrence of biomimetic apatite on top of the PEO-coated titanium in a simulated body fluid solution. This was mainly attributed to increased surface roughness of the oxide layer as well as inherent activation of zirconia particles to form biomimetic apatite.     

ZrO2/hydroxyapatite coating on titanium by electrolytic deposition

In this study, hydroxyapatite (HA) was coated on a titanium (Ti) substrate over a ZrO(2) layer by the electrolytic deposition method, this double layer coating was then compared with a single layer coating of HA. The HA layer was used to increase the bioactivity and osteoconductivity of the Ti substrate, and the ZrO(2) layer was intended to improve the bonding strength between the HA layer and Ti substrate, and to prevent the corrosion of the Ti substrate. The electrolytic deposition formed an HA layer with a thicknesses of approximately 20 mum, which adhered tightly to the Ti substrate. The bonding strength of the HA/ZrO(2) double layer coating on Ti was markedly improved when compared to that of the HA single coating on Ti. The improvement in bonding strength with the use of a ZrO(2) base layer was attributed to the resulting increase in chemical affinity of the ZrO(2) to the HA layer and to the Ti substrate. The osteoblast-like cells cultured on the HA/ZrO(2) coating surface, proliferated in a similar manner to those on the HA single coating and on the pure Ti surfaces. At the same time, the corrosion resistance of Ti was improved by the presence of the ZrO(2) coating, as shown by a potentiodynamic polarization test.     

Corrosion behavior of friction stir welded AZ31B magnesium alloy with plasma electrolytic oxidation coating formed in silicate electrolyte

A protective ceramic coating of about 50 μm thick on a friction stir welded (FSW) joint of AZ31B magnesium alloy was prepared by plasma electrolytic oxidation (PEO) in silicate electrolyte. Electrochemical corrosion behavior of uncoated and coated FSW joints was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The equivalent circuits of EIS plots for uncoated and coated FSW magnesium alloy were suggested. The corrosion resistance of FSW magnesium alloy depended on microstructure of the FSW joint. The heat-affected zone with severe grain growth was more susceptible to corrosion than the stir zone and base metal. The PEO coating consisted of a porous outer layer and a dense inner layer. The inner layer of PEO coating played a key role on corrosion protection of the FSW joint of magnesium alloy. Meanwhile, corrosion potential, corrosion current density and impedance at different zones of coated FSW joint were almost the same. The PEO surface treatment significantly improved the corrosion resistance of FSW joints of AZ31B magnesium alloy.     

Stability of hydroxylapatite plasma-sprayed coated Ti−6AI−4V under cyclic bending in simulated physiological solutions

The aim of this research was to study the stability of plasma-sprayed eoated metal systems and to evaluate their susceptibility to the occurrence of corrosion fatigue. Hydroxylapatite plasma-sprayed coated samples of Ti–6AI–4V were studied under cyclic bending. During fatigue testing samples were immersed in a simulated physiological solution and mechanical and electrochemical degradation were monitored. Applied loads were intended to crack the ceramic coating and not the metal substrate. Electrochemical impedance spectroscopy was used to further characterize the electrochemical behaviour. No increase in tendency to corrode was detected in open-circuit corrosion fatigue testing. It appears as if the coating cracking does not increase metal substrate corrosion susceptibility. The coating integrity has been seriously affected, with marked decrease in thickness, due to the synergistic effect of load and presence of simulated body fluids environment. Impedance results, however, show a general tendency to an increase in corrosion kinetics after corrosion fatigue testing.     

In situ composite coating of titania-hydroxyapatite on titanium substrate by micro-arc oxidation coupled with electrophoretic deposition processing

In situ composite coating of hydroxyapatite (HA)/TiO₂ were produced on titanium (Ti) substrate by micro-arc oxidation coupled with electrophoretic deposition (MAO&EPD) technique with different concentrations of HA particles in the 0.2 M NaOH electrolyte solution. The surface morphology and chemical composition of the hybrid coating were effected by HA concentration. The amount of HA particles incorporated into coating layer increased with increasing HA concentration used in the electrolyte solution. The corrosion behavior of the coating layer in simulated body fluids (SBF) was evaluated using a potentiodynamic polarization test. The corrosion resistance of the coated sample was increased compared to the untreated Ti sample. The in vitro bioactivity assessment showed that the MAO&EPD treated Ti substrate possessed higher apatite-forming ability than the untreated Ti. Moreover, the apatite-forming ability had a positive correlation with HA concentration. In addition, the cell behavior was also examined using cell proliferation assay and alkaline phosphatase ability. The coating formed at HA concentration of 5 g/L exhibited the highest cell ability.     

Influence of surface modification on the apatite formation and corrosion behavior of Ti and Ti-15Mo alloy for biomedical applications

Commercially pure Ti and Ti-15Mo specimens were subjected to alkali-hydrogen peroxide and subsequent heat treatment to produce a nanoporous titanate gel layer with anatase phase. The surface morphology of the untreated, alkali-hydrogen peroxide treated and alkali-hydrogen peroxide heat treated specimens before and after 7 days of immersion in simulated body fluid was characterized using X-ray Diffractometer (XRD), Atomic Force Microscopy (AFM), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FT-IR). The formation of nanoporous titanate gel layer and the growth of apatite layer over the surface modified specimens after 7 days of immersion in simulated body fluid were confirmed. Further, the electrochemical corrosion behavior of all the specimens was examined using potentiodynamic polarization and electrochemical impedance spectroscopic techniques.     

Formation of calcium phosphates on low-modulus Ti–7.5Mo alloy by acid and alkali treatments

This study investigated the hydroxyapatite (HA) coating on metal implants in order to enhance their bioactive properties. In this study, HA coatings were formed on the surfaces of commercially pure titanium (c.p. Ti) and Ti–7.5Mo which were acid-etched and subsequently alkali-treated before samples were soaked in simulated body fluid (SBF). Specimens of c.p. Ti and Ti–7.5Mo were etched in either H₃PO₄ or HCl, and subsequently treated in NaOH. The surfaces of acid-etched c.p. Ti showed a porous structure, whereas those of acid-etched Ti–7.5Mo showed some grinding marks, but no porosity. After subsequent alkali treatment in NaOH, the surfaces of both the c.p. Ti and Ti–7.5Mo substrates exhibited microporous network structures. The specimens were then immersed in SBF at 37 °C for 28 days. Apatite began to deposit on acid-etched and NaOH-treated Ti–7.5Mo within 1 day after immersion in the SBF. After 28 days of immersion in the SBF, a dense and uniform layer was produced on the surfaces of all samples. The HA formation rate was the highest for HCl and NaOH-pretreated samples, and the results of EDS and XRD showed that much more intensive peaks of HA appear on the specimens of HCl and NaOH-treated Ti–7.5Mo than on any other sample. Thus, this method of apatite coating Ti–7.5Mo appears to be promising for artificial bone substitutes or other hard tissue replacement materials with heavy load-bearing applications due to their desirable combination of bioactivity, low elastic modulus, and low processing costs.     

In vitro cytocompatibility and corrosion resistance of zinc-doped hydroxyapatite coatings on a titanium substrate

To improve biocompatibility and corrosion resistance during the initial implantation stage, zinc-substituted hydroxyapatite (ZnHAp) coating was fabricated on pure titanium by the electrolytic deposition method. The morphology, microstructure and chemical composition of the coating were investigated by X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray analysis and Fourier transform infrared spectroscopy. The prepared ZnHAp crystals were calcium deficient and were carbonated owing to the incorporation of some Zn²⁺. This incorporation of Zn²⁺ into the HAp significantly reduced porosity and caused the coating to become noticeably denser. In addition, the Zn²⁺ ions were homogeneously distributed in the coating. The potentiodynamic polarisation test revealed that the ZnHAp-coated surface showed superior corrosion resistance over that of the HAp-coated surface and bare Ti. The in vitro bioactivity was evaluated in a simulated body fluid, which revealed that the ZnHAp coating can rapidly induce bone-like apatite formation of nuclear and growth features. In addition, the cell response tests showed that the MC3T3-E1 cells on the ZnHAp coating clearly enhanced the in vitro cytocompatibility of Ti compared with the same cells on HAp coating. ZnHAp coating was thus beneficial for improving biocompatibility.     

Titanium scaffolds for osteointegration: mechanical,in vitro and corrosion behaviour

While titanium has been successful as an orthopaedic or dental implant material, performance problems still persist concerning implant-bone interfacial strength and mechanical modulus mismatch between metal and tissue. Porous structures are an advantageous alternative because the elastic modulus can be adjusted to match that of bone, thereby preventing bone resorption. Furthermore, to achieve early and strong stabilization theses structures may be coated with bioactive deposits, as hydroxyapatite. In the present work, titanium porous scaffolds were produced from TiH₂ slurry by a replication sponge reactive sintering method, and coated with hydroxyapatite by the sol-gel process. The obtained structures were microstructurally and mechanically characterized. Their in vitro bioactivity was investigated by soaking in a simulated body fluid (SBF). Electrochemical characterization was also performed in order to evaluate the effect of coating on corrosion resistance. The scaffolds exhibit a three-dimensionally interconnected porous structure that can be mechanically and morphologically compared to trabecular bone. Their in vitro bioactivity suggests potential for osseous integration. Coating also improves corrosion resistance in physiologically saline environment.