Structure of calcium titanate/titania bioceramic composite coatings on titanium alloy and apatite deposition on their surfaces in a simulated body fluid

In this study, TiO₂-based coatings containing Ca and P ions were prepared on titanium alloy surfaces by microarc oxidation (MAO). After soaking in aqueous NaOH solution and subsequent heat treatment at 700 and 800 °C, calcium titanate/titania bioceramic composite (CTBC) coatings were obtained. The results show that the outer layers (0–1.5 μm) of the CTBC coatings are mainly composed of Ca, Ti, O and Na constituents with a uniform distributions with increasing the depth near the surfaces. The surface phase compositions of the CTBC coating formed at 700 °C are anatase, rutile and CaTi₂₁O₃₈ phases, as well as a few CaTiO₃, while those of the CTBC coating formed at 800 °C are anatase, rutile and CaTiO₃. When incubated in a simulated body fluid (SBF), apatite was deposited on the CTBC coatings probably via formation of hydroxyl functionalized surface complexes on the CTBC coating surfaces by ionic exchanges between (Ca²⁺, Na⁺) ions of the CTBC coatings and H₃O⁺ ions in the SBF. The CTBC coating formed at 800 °C seems to facilitate the deposition of Ca and P probably due to the good crystallographic match between perovskite CaTiO₃ and HA on specific crystal planes.     

微束等离子喷涂羟基磷灰石涂层的体外生物活性研究

采用微束等离子喷涂(MPS)方法在Ti6A14V基体上制备羟基磷灰石(HA)涂层.利用扫描电镜(SEM)和x射线衍射(XRD)分析技术对HA涂层的表面形貌、相组成和结晶度进行表征,并通过模拟体液进行体外生物活性试验.结果表明,微束等离子喷涂制备的HA涂层具有一定粗糙度,存在气孔以及微裂纹.涂层存在热分解现象,涂层中含有HA、α-TCP、β-TCP和非晶相,不含CaO等杂质相.模拟体液试验表明,微束等离子喷涂工艺制备的HA涂层具有较好的生物活性和稳定性.涂层表面均有较大比例的CaP沉积层,且涂层整体保持完整,没有出现明显的剥离.     

In vitro corrosion evaluation of nitrogen ion implanted titanium in simulated body fluid

Surface modification of commercially pure (CP) titanium was attempted by nitrogen ion implantation to investigate corrosion resistance in simulated body fluid. Nitrogen ion was implanted at 70 keV energy for different doses ranging from 5 × 10¹⁵ to 2.5 × 10¹⁷ ions/cm². In Vitro Open Circuit Potential (OCP-time measurements and cyclic polarization studies were carried out to evaluate the corrosion resistance of the implanted specimens with reference to the unimplanted one. Specimens implanted at 4 × 10¹⁶ and 7 × 10¹⁶ ions/cm² showed optimum corrosion resistance, and implantation beyond this dose deteriorated the corrosion resistance. Gracing Incidence X-ray diffraction (GIXD) was employed on implanted specimens to understand the phases formed with increasing doses. The results of the present investigation indicated that nitrogen ion implantation can be used as a viable method for improving corrosion resistance of titanium. Nature of the surface and reason for the variation and improvement in corrosion resistance are discussed in detail.     

TC4钛合金表面沉积CrAlSiN涂层的组织与性能

为了提高TC4钛合金表面硬度和耐磨性能,通过等离子渗氮技术和多弧离子镀技术相结合的方法对TC4钛合金进行表面改性处理。通过扫描电镜、维氏显微硬度计、三维轮廓仪、高速往复摩擦磨损试验仪和电化学工作站,对比研究了TC4钛合金、渗氮层和CrAlSiN涂层的显微组织、硬度、耐磨性能和耐腐蚀性能。结果表明,经渗氮处理后,TC4合金表面渗氮层硬度提高了约2倍,在此基础上制备的CrAlSiN涂层的平均硬度高达3222 HV0.025,涂层表面存在少许大颗粒和凹坑;CrAlSiN涂层平均摩擦因数为0.22,磨损机理主要为粘着磨损,对磨副的材料粘着到涂层表面,而涂层几乎无磨损,耐磨性能显著提高。CrAlSiN涂层的自腐蚀电位为-0.542 V,比TC4钛合金基体的自腐蚀电位-0.747 V正移了0.205 V,表明在渗氮层基础上沉积CrAlSiN涂层显著提高了合金的耐电化学腐蚀性能。     

Corrosion behaviour of nitrogen implanted titanium in simulated body fluid

Abstract

Titanium is one of the most important materials for medical applications, as a result of its uniquely high biocompatibility. The effect of nitrogen implantation on the biocompatibility and the corrosion resistance of cp titanium are reported. Grazing incidence X-ray diffraction studies showed that implantation formed a δ-TiN_x phase. Electrochemical tests in HBSS showed an optimal decrease in corrosion current density for specimens implanted with 3 × 10¹⁷ ions cm^-2 at 25 keV, compared with unimplanted titanium. Following implantation and immersion in a commercial physiological solution, phases are precipitated which are rich in calcium and phosphorus, and these hydroxyapatite precursors indicate that this implantation regime confers optimal properties of corrosion resistance and biocompatibility.     

医用钛合金的微弧氧化膜层组织及其磨损性能

采用微弧氧化方法对医用钛合金表面进行改性,利用X射线衍射分析(XRD)、扫描电镜(SEM)对微弧氧化膜层的表面形貌和化学成分进行分析,通过小振幅往复摩擦磨损试验测量膜层的耐磨损性能.结果表明:钛合金经过微弧氧化表面处理后,所得膜层存在不同尺寸的放电微孔,氧化膜内层相对外层较为致密;膜层主要由大量金红石型TiO2相、非晶相SiO2及少量锐钛矿型TiO2相组成;与基体相比,微弧氧化膜层的初期摩擦因数从0.7降低至0.1,耐磨性提高.     

TC4钛合金表面激光合金化涂层的组织与耐磨性能

采用WC(含碳量0.1wt%)、Ni、Si混合粉末为原料,利用激光合金化技术在TC4钛合金表面原位制备了含WC、Ni、Si的涂层,使用扫描电镜(SEM)、X射线衍射(XRD)与能谱分析(EDS)等方法分析了涂层的组织与成分,用HXD-1000B型维氏显微硬度计和MMW21型立式万能摩擦磨损试验机测试了涂层的显微硬度及摩擦磨损性能。结果表明:利用优化后的激光合金化参数制备出的含WC量较多的涂层,其整体均匀致密、无裂纹,且与TC4合金基材呈冶金结合;涂层物相主要由α-Ti、Ti₅Si₃、WC和TiNi组成;涂层硬度为950 HV0.2,平均摩擦因数为0.2,平均磨损量为0.308 mg,耐磨性显著提高。     

Laser cladding of titanium alloy coating on titanium aluminide alloy substrate

1　INTRODUCTIONInthedesignandmanufactureofaviationindus try ,differentpartsoftheaircraftengineshouldmeetthedifferentrequirementsonoperatingtemperatureandserviceperformance .Thesoundbondofdissimi laralloysisthekeytechniquefordevelopingnovele quipmentsandimprovingtheirintegralperformance .Lowdensityandexcellenthigh temperaturepropertiesofTiAlalloysmakethem promisinghigh temperaturestructuralmaterials .Successfuljoiningofthesematerialswillincreasetheirutilityinengineer ing[1,2 ] .Somejoinin…     

EIS study of porous NiTi biomedical alloy in simulated body fluid

The electrochemical impedance spectroscopy was used for monitoring the formation of surface film on a fixtured sintering porous NiTi biomedical alloy in simulated body fluid (SBF) media during 12 days. Effect of NiTi sintering time on the formation of surface film in SBF was investigated. The formed surface film was calcium phosphate hydrate (CPH) with a pillar particulate structure which was developed to a spongy network with increasing the sintering time. Using such electrochemical techniques, it was shown that NiTi samples obtained after 3 h sintering at 950 °C, have higher tendency for the formation of a stable CPH film during the test.     

TA15钛合金激光非晶-纳米晶增强镍基涂层的组织结构及耐磨性

在重要航空材料TA15钛合金基材表面进行激光同轴送粉熔覆Ni60A-Ni包WC-TiB₂-Y₂O₃混合粉末可生成非晶-纳米晶增强复合涂层.对涂层进行微观组织观察、显微硬度测试及室温干摩擦磨损试验.结果表明,涂层主要由γ-(Fe,Ni),WC,α-W₂C,M₁₂C,Ti-B化合物,Ti-Al金属间化合物,Mo,Zr与V元素的碳化物以及非晶相构成.整个涂层为非晶、纳米晶及其它晶化相共存.涂层较TA15钛合金表现出更好的耐磨损性,且涂层的主要磨损机制为磨粒磨损与粘着磨损.纳米晶颗粒的产生可使涂层磨损表面光滑,有利于摩擦系数与磨损量的降低.     

TC4钛合金表面激光熔覆TiC复合涂层组织和耐磨性能

采用HL-5000型横流CO2 激光加工机,在TC4钛合金表面制备了表面平整、细密、消除了裂纹与孔隙的TiC复合涂层.通过SEM、EDAX、XRD、HXD-1000TMC型显微硬度计和HT-600型高温摩擦磨损试验机,分析了熔覆层的显微组织、成分、物相,测试了激光熔覆层的显微硬度和滑动摩擦磨损性能.结果表明,激光熔覆制备的TiC复合涂层与基体呈冶金结合,涂层中有大量小块状、针状TiC颗粒和TiC树枝晶,熔覆层的显微硬度达880～ 1087 HV0.1,耐磨性能比TC4钛合金显著提高.     

Ti811合金表面TC4激光熔覆层微观组织及性能

按照CFM56系列发动机维修手册的建议,在Ti811合金表面采用同步送粉激光熔覆技术,以TC4合金粉末为原料,制备出均匀致密、无气孔和裂纹等缺陷的激光熔覆层. 分析涂层的宏观形貌、微观组织结构和组织相变过程,测试涂层的显微硬度和摩擦磨损性能. 结果表明,扫描电镜下涂层微观组织呈现魏氏体结构特征,涂层显微硬度相比基材有所提高,主要原因是涂层中的针状马氏体α'有一定的强化作用;涂层中弥散分布的纳米颗粒Ti₃Al的沉淀强化和弥散强化等作用也在一定程度上提高了涂层的显微硬度;熔覆层的磨损机制为磨粒磨损和黏着磨损的复合磨损机制.     

TC4钛合金表面激光熔覆复合涂层的组织和耐磨性

采用5 kW横流CO₂激光器,在TC4钛合金表面熔覆TiC、TiB₂与Ni的混合粉末,制备了无气孔、无裂纹、组织均匀致密的复合涂层。用SEM、EDS、XRD、显微硬度计以及立式万能摩擦磨损试验机分析了激光熔覆层的显微组织、成分和物相,测试了激光熔覆层横截面显微硬度,以及覆层耐磨性能。结果表明,激光熔覆复合涂层与基体呈冶金结合;熔覆层组织从表层到结合区呈现出由棒状、块状向树枝状、颗粒状转变的趋势,且主要由Ti、TiC、TiB、Ti₂Ni、TiNi等相组成;熔覆层显微硬度最高可达863 HV0.2,为基体的2.5倍;熔覆层耐磨性能较TC4钛合金明显提高。     

新型医用Mg-Nd-Zn-Zr镁合金在模拟体液中的降解行为

采用光学显微镜、扫描电子显微镜、析氢实验和电化学实验等研究高纯Mg、AZ91D和新开发的Mg-Nd-Zn-Zr(JDBM)合金在模拟体液中的腐蚀行为。结果表明:JDBM和高纯Mg的平均腐蚀速率远低于AZ91D的,且前二者的腐蚀表面较平整,为一种均匀腐蚀方式;而AZ91D的表面有许多贯连的腐蚀深坑,是一种典型的点蚀方式。动电位极化曲线、电化学阻抗谱和析氢实验也表明,JDBM和高纯Mg的耐蚀性比AZ91D的好,JDBM合金在模拟体液中的腐蚀性能接近于高纯镁的。力学性能测试表明,JDBM镁合金具有优良的综合力学性能,满足生物材料对力学性能的要求。     

Apatite formation on anodized Ti-6Al-4V alloy in simulated body fluid

Titania layers were successfully prepared on the surfaces of Ti-6Al-4V alloy via anodic oxidation in H₂SO₄ or Na₂SO₄ solutions at room temperature. The titania layers consisted of pure rutile or a mixture of anatase and rutile structures after the Ti-6Al-4V alloy had been anodized in 1.0 M H₂SO₄ solution at 150 V or 0.5M Na₂SO₄ solution at 100 or 130 V. Good apatite-forming ability was demonstrated in simulated body fluid. However, surface layers with mainly titanium metallic phase or a pure anatase structure did not possess the ability to induce apatite formation. Anodic oxidation is an effective method to prepare bioactive Ti-6Al-4V alloy that can be used as an artificial bone substitute under load-bearing applications.     

Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated body fluids

The mechanical characteristics of the macro-arc oxidation(MAO) coating on Mg alloy AZ91 were examined by means of nano scratch tester.The corrosion and erosion corrosion behavior of AZ91 with and without MAO coating were investigated by using potentiodynamic electrochemical technique and micro-abrasion tribometer in simulated body fluids,respectively.The influence of HCO_3~- ions on the erosion corrosion was discussed.The results show that the coating and its substrate are in a pronounced bond.The MAO co...     

钛及钛合金表面转化膜的应用及发展

对钛及钛合金的表面转化膜处理技术进行了综述,主要包括化学氧化、阳极氧化、硅烷化、磷酸盐转化等。阐述了各种处理方法的工艺过程及其作用效果,分别指出了各种方法的优缺点。同时展望了其今后的应用及发展前景。     

Effect of cold spray deposition of a titanium coating on fatigue behavior of a titanium alloy

The deposition of titanium on a titanium alloy substrate is being examined for potential use as a surface treatment for medical prostheses. A Ti6Al4V alloy was coated with pure titanium by cold gas dynamic spraying. Coatings were deposited onto samples with two different surface preparation methods (as-received and grit-blasted). The fatigue life of the as-received and grit-blasted materials, both before and after coating, was measured with a rotating-bend fatigue rig. A 15% reduction in fatigue endurance limit was observed after application of the coating to the as-received substrate, but no significant reduction was observed on its application to the grit-blasted substrate. The reduction in fatigue endurance limit has been related to the substrate-coating interface properties, the elastic modulus, and the residual stress states. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference, (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, 2006.     

铝合金表面电火花沉积层组织与性能

采用电火花沉积技术,以硅青铜作为电极,在空气中对2A12铝合金表面进行了强化.采用扫描电镜、电子能谱分析仪与X射线衍射仪等仪器对沉积层的形貌、组织、元素分布和结构进行了分析与研究;利用显微硬度计和磨损试验机对沉积层的显微硬度与耐磨性进行了测试.结果表明,沉积层连续、致密,与基体呈冶金结合,无明显界面;主要由铜铝金属间化合物组成,显微硬度可达578 HV;沉积层耐磨性较基体显著提高,表面强化效果明显.