Densification of plasma-sprayed titanium and tantalum coatings

Thermal spraying of corrosion- resistant coatings of titanium and tantalum is difficult; dense coatings are not produced, and oxidation of these metals increases coating porosity. In this study, oxidation during plasma spraying was reduced with a shrouding system. Porosity and oxide content also were minimized by optimizing the spraying parameters. After optimization, the coatings still had open porosity and thus were incapable of protecting the substrate material against corrosion in water solutions containing 3 % NaCl. Therefore, posttreatments for improvement of corrosion resistance were studied. Electron beam fusion produced corrosion resistance equal to or better than that of bulk commercial samples of titanium and tantalum.     

SLM制备径向梯度多孔钛/钽及其表征研究

利用增材制造技术制作仿天然骨的径向梯度多孔钛/钽骨科植入物具有广阔的前景。基于三周期极小曲面（triply minimal surfaces,TPMS）建模法建立了平均孔隙率为70%的圆柱型径向梯度孔隙结构,孔隙率由中轴线（90%）向圆周面（30%）逐渐降低。利用激光选区熔化(Selected Laser Melting, SLM)工艺制作径向梯度多孔钛/钽。光学显微镜,扫描电镜,Micro-CT检测结果共同显示,SLM径向梯度多孔钛/钽的孔隙结构与设计特征一致。SLM工艺制作的径向梯度多孔钛/钽的孔隙率分别为73.18%与68.18%。力学测试结果表明,梯度多孔钛/钽的弹性模量分别为3.96±0.19GPa与3.47±0.25GPa,抗压强度分别为90.83±3.35MPa与93.27±1.24MPa。梯度多孔钛/钽的弹性模量与抗压强度分别显著高于均匀多孔钛/钽（孔隙率为70.11%的均匀多孔钛弹性模量为2.34±0.48GPa,抗压强度为67.63±1.33MPa,孔隙率为65.39%的均匀多孔钽弹性模量为1.69±0.49GPa,抗压强度为68.56±0.41MPa）。体外细胞相容性实验证明,径向梯度多孔钛/钽均具有良好的生物相容性,适合间充质干细胞与肌肉细胞的粘附生长。SLM工艺制作的径向梯度多孔钛/钽比均匀多孔钛/钽具有与天然骨组织更相近的结构与性能,是理想的骨缺损修复替代物。     

钛基微纳多级结构钽涂层的构建及其表面特征研究

采用等离子喷涂技术在医用纯钛基体表面构建出微纳米多级结构钽涂层。利用SEM、EDS和XRD分析微纳米多结构钽涂层的形貌、化学组成和物相组成,并根据ASTM C633-79评价涂层与基底的结合强度;采用牛血清蛋白(BSA)对比研究了钛基钽涂层与医用纯钛对照样表面的蛋白吸附行为。结果表明,在喷涂距离为110 mm、喷涂功率为30 k W时制备的钛基钽涂层具有典型微纳米多级结构特征,且与基体结合强度好、Ta相对含量高;蛋白吸附实验表明钛基钽涂层表面蛋白吸附量均高于医用纯钛对照样,具有良好的蛋白吸附能力。     

Effect of Plasma Spraying Process on Microstructure and Microhardness of Titanium Alloy Substrate

High-temperature titanium alloys are considered as good candidate materials for many aerospace applications. In order to increase the usable temperatures and oxidation resistance of titanium alloys, plasma spraying thermal barrier coatings (TBCs) on the titanium alloys is considered as an effective method. The effect of plasma spraying process on microstructure and microhardness of the titanium alloy (Ti-6.6Al-3.61Mo-1.69Zr-0.28Si in wt.%) was investigated by scanning electron microscope, energy dispersion analytical X-ray spectroscopy (EDAX) and microhardness test. The results show that the microstructure of the titanium alloy inside the substrate keeps unchanged after plasma spraying, and no interaction and atomic diffusion happen evidently at the bond coat/substrate interface. However there exists a thin layer of plastic deformation zone in the substrate beneath the bond coat/substrate interface after plasma spraying. The residual stresses are induced inside the titanium alloy due to the thermal expansion mismatch and the temperature gradient inside the substrate during plasma spraying, and lead to generating microcracks in the surface beneath the bond coat/substrate interface and the increase of microhardness in the substrate.     

钛合金表面离子束增强沉积膜层的环境适应性和接触相容性

利用离子束增强沉积技术在钛合金表面制备CrN硬质抗磨层和CuNiln固体润滑膜层。通过电化学测试技术对比研究了膜层和钛合金基材在含Cl介质中的抗蚀性能和接触腐蚀敏感性，利用高温静态氧化方法评价了膜层的抗氧化性能。结果表明：(1)CuNiln膜层耐电化学腐蚀性能和抗氧化性能显著优于Cu，在含Cl介质中与钛合金接触相容。(2)在含Cl水溶液中，CrN膜层耐蚀性好，与钛合金接触相容；在HCl HF混合酸中，CrN膜耐蚀性能远优于钛合金；抗氧化性能优于Ti。     

The evaluation of powder processing on microstructure and mechanical properties of hydroxyapatite (HA)/yttria stabilized zirconia (YSZ) composite coatings

In clinical applications, the mechanical failure of HA-coated titanium alloy implants suffered at the interface of the HA coating and titanium alloy substrate will be a potential weakness in prosthesis. Yttria stabilized zirconia (YSZ) reinforced HA coatings have been proven to enhance the mechanical properties of the HA coating significantly and reduce the formation of calcium oxide (CaO). In this paper, HA/YSZ (30 wt.% YSZ) composite coatings were sprayed by the plasma technique. The effects of the powder processing–mechanical ball milling method and spheroidization method on the microstructure and mechanical properties of the HA/YSZ composite coatings were evaluated. The experimental results showed that the spheroidized powders melted better than the ball milled powders during plasma spraying and formed higher mechanical property coatings (1.6326±0.08 MPa m^−0.5 of fracture toughness, 58.59±2.91 GPa of elastic modulus and 43.42±2.53 MPa of tensile bond strength). HA/YSZ solid solution formed during deposition on the substrate, which played a very important role in the mechanical properties of the HA/YSZ composite coatings. Tensile bond strength tests showed that the fracture mode was cohesive and that failure occurred at the interface of HA and unmelted YSZ particles. The molten state of YSZ had a great influence on the properties of the HA/YSZ composite coatings.     

溶胶-凝胶法制备钛基生物相容性MgO膜

植入物的表面修饰对于获得生物相容性或功能性界面非常重要。本项研究中, 钛金属表面的MgO薄膜在400?C进行溶胶-凝胶化,观察其微观结构、生物活性、抗菌性能和细胞毒性。结果发现,MgO在空气中老化后转化为Mg（OH）2。扫描电镜观察薄膜无裂纹。在模拟体液试验中显示出良好的生物活性,与成骨细胞有良好的相容性,对大肠杆菌有轻微的抗菌作用。MgO薄膜在钛金属生物医学植入物表面改性中具有潜在的应用前景。     

Features of Coatings Obtained by Supersonic Laser Deposition

The three types of coatings that can be deposited by supersonic laser deposition, namely coatings built without the melting of the processed powder particles, coatings built from molten particles and coatings made from molten particles and with solid particles embedded in the coating, are discussed. For instance, with no melting of the powder material, a titanium alloy coating without transformation of the structure and with a uniform distribution of the chemical elements in the coating cross-section was obtained. Self-fluxing coatings (NiCrCBSiFe) with high hardness were achieved by melting the powder and mixing it with the substrate. The mixing of the coating metal with the substrate metal led to a significant increase in the concentration of the main alloying elements in the coating–substrate interface. X-ray diffraction analysis also showed that the mixing of the NiCrCBSiFe coating with a medium-carbon steel substrate led to the formation of new Fe_xNi phases, while their concentration decreased through coating thickness.     

Characterization of air-formed surface oxide film on Ti-29Nb-13Ta-4.6Zr alloy surface using XPS and AES

The surface oxide film on a Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) was precisely characterized using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) to understand the composition and chemical state of the surface oxide film of TNTZ. For comparison, the component metals, titanium, niobium, tantalum, and zirconium, were also characterized to consider the effect of those on the formation of the surface oxide film on their alloy. The characterization of the surface oxide films on TNTZ and its component revealed the following issues. The surface oxide film on TNTZ consists of a composite oxide that contains titanium, niobium, tantalum, and zirconium but forms continuous layer and is very thin, ca. 3.7 nm. The oxide film is not completely oxidized because it contains various valences of cations. In particular, the oxidation of tantalum is inhibited in the oxide. Tantalum is enriched in the substrate in TNTZ just under the surface oxide because of this inhibition in the oxidation. The formation of the surface oxide film in TNTZ is predominantly governed by titanium. The preferential oxidation of an element is not always dependent on the initial oxidation potential of that element, the relationship between the oxidation energy from a smaller valence to a larger valence, and the dehydration process. In other words, a complicated competition governs the resultant composition of surface oxide.     

Magnesium as a biodegradable and bioabsorbable material for medical implants

For many years, stainless steel, cobalt-chromium, and titanium alloys have been the primary biomaterials used for load-bearing applications. However, as the need for structural materials in temporary implant applications has grown, materials that provide short-term structural support and can be reabsorbed into the body after healing are being sought. Since traditional metallic biomaterials are typically biocompatible but not biodegradable, the potential for magnesium-based alloys in biomedical applications has gained more interest. This paper summarizes the history and current status of magnesium as a bioabsorbable implant material. Also discussed is the development of a magnesium-zinc-calcium alloy that demonstrates promising degradation behavior.     

Microstructure and 3D microtomographic characterization of porosity of MAO surface layers formed on aluminium and 2214-T6 alloy

A fine characterization of the microstructure of the MAO coatings formed on aluminium (purity 99,999%) and its alloy 2214-T6 was observed using field emission gun scanning electron microscopy (FEG-SEM) with energy dispersive spectrometry (EDS) and X-ray microtomography (XMT). In addition, the influence of current frequency (pure aluminium) and the precipitates of substrate were investigated (case of 2214-T6 alloy).The MAO surface layers formed on aluminium and its alloy 2214-T6 can be divided into two parts: the outer layer with high porosity (so-call porous layer) and the inner layer with low porosity (so-call dense layer). However, the porosity of the inner layer increases toward the MAO layer/substrate interface. It is found that, both the thickness and the porosity increase when the current frequency decreases. The porosity of the MAO coating can be attributed to discharges formation in the vicinity of the MAO coating/substrate interface.In the particular case of 2214-T6 aluminium alloy (3.9% Cu), with coarse non-valve metal rich precipitates aligned perpendicular to the surface of the work electrode; the transformation of precipitates under discharge effect can provoke the formation of big channels, which go through the MAO surface layer. This last one induces local formation of a layer rich electrolyte species toward the substrate.     

微弧离子沉积阻燃涂层及其性能

采用微弧离子表面改性技术在TC11合金表面制备阻燃涂层,采用扫描电镜、透射电镜、XRD等方法分析了阻燃涂层组织及物相,采用“钛火”液滴法试验平台测试了TC11钛合金在300～700 ℃之间的燃烧参数,验证了同等试验条件下带有阻燃涂层TC11钛合金试样在300～700 ℃之间的阻燃有效性. 结果表明,制备的阻燃涂层主要由TiZr非晶相组成,涂层致密,与基体为冶金结合,700 ℃以内具有一定的阻燃性能,分析阻燃涂层的阻燃机理主要为涂层吸收能量,减小基体对热量的吸收,同时阻止钛合金与氧接触机制来阻燃.     

影响Ti合金热稳定性的因素

综述了合金元素、环境气氛、相变、涂层等因素对Ti合金热稳定性的影响.     

Cyclic Oxidation and Interdiffusion Behaviour of a NiCrAlY Coated Powder Metallurgy Beta Gamma TiAl–2Nb–2Mo Alloy

A new beta-gamma TiAl–2Nb–2Mo alloy was synthesized using powder metallurgy process and coated with NiCrAlY by air plasma spray technique. The cyclic oxidation behaviour of the coated beta-gamma alloy was investigated at 1,000?°C for up to 800 cycles. During cyclic oxidation testing, titanium nitride layer was found to form at the interface between NiCrAlY and TiAl–2Nb–2Mo and the thickness of the titanium nitride layer increased with oxidation cycles. Additionally, outward diffusion of Ti from the beta-gamma substrate caused the formation of titanium oxides on the coating surface after 630 cycles. Inward diffusion of Ni from NiCrAlY led to the formation of an inner diffusion zone containing NiAlTi and mixture of NiAlTi?+?TiAl. Due to the spallation of coating scales on the circumferential surface of the button specimens, weight loss was observed after 120 cycles; however, NiCrAlY coating on both top and bottom surfaces of the specimens remained in contact with the substrate for up to 800 cycles. Due to the inward and outward diffusion of various elements, one third of the NiCrAlY coating was consumed after 800 cycles, which suggests the need for diffusion barrier coating at the interface between the NiCrAlY coating and the TiAl–2Nb–2Mo alloy.     

Corrosion Resistance of Superhydrophobic Mg-Al Layered Double Hydroxide Coatings on Aluminum Alloys

A superhydrophobic surface was successfully constructed to modify the layered double hydroxide (LDH) coatings on aluminum alloy using stearic acid. The characteristics of the coatings were investigated using SEM, XRD, FT-IR and XPS. The corrosion resistance of the prepared coatings was studied using potentiodynamic polarization and electrochemical impedance spectrum. The results revealed that the superhydrophobic surface considerably improved the corrosion-resistant performance of the LDH coatings on the aluminum alloy substrate. The formation mechanism of the superhydrophobic surface was proposed.     

Interfacial Characteristics and Mechanical Behavior of Hybrid Manufactured AlSi10Mg-Al6061 Bimetal via Selective Laser Melting and Forging

Hybrid manufacturing (HM) uses additive manufacturing (AM) techniques to prepare complex or fine structures on traditional processing parts, which can fully utilize the advantages of AM to form complex parts, and the high efficiency and low cost of conventional processing methods in manufacturing regular components. A bimetal material was produced by selective laser melting (SLM) of AlSi10Mg on the deformed Al6061 alloy substrate in this study. Firstly, the interface characteristics of the two alloys were studied. The results show that a metallurgical interface with a thickness of 100-200 μm was formed as the result of the Marangoni convection during SLM preparation. In detail, the circular flow in the melt pool at the interface led to the dilution of alloying elements and the change of microstructure. Moreover, a suitable first-layer thickness can effectively suppress the hot cracks at the interfacial region. Based on the optimized results, the hybrid manufactured samples with different SLM processed volume ratios (SLM-part) to the substrate were prepared to study the mechanical properties and the deformation behavior of hybrid parts. The results show that the volume ratio of the SLM-part to the substrate had an influence on the strength and the elasto-plastic behavior by affecting the distribution of plastic deformation.     

钛合金表面激光熔化沉积钛基复合材料涂层的组织及性能

通过激光熔化沉积TA15+30%TiC(体积分数)混合粉末,在TA15钛合金表面制备出钛基复合材料涂层,分析了涂层的组织、硬度及界面结合强度。结果表明,激光熔化沉积过程中原始TiC颗粒发生溶解,并在凝固过程中重新析出细小的TiC,TiC有等轴状及枝晶两种形态,涂层中存在部分未熔的TiC颗粒;涂层硬度达HRC 60;涂层与基体界面为完全冶金结合,涂层的界面结合强度大于310 MPa,抗剪切强度为330 MPa;经弯曲及热震试验后,涂层未出现剥落现象,表明涂层与基体具有很好的相容性     

TC4钛合金表面化学镀Ni-P合金耐磨层研究

利用化学镀方法在TC4钛合金表面成功制备结合力良好的Ni-P合金耐磨层,研究了提高镀层结合力的方法,结合SEM、XRD、EDS等现代物理分析方法分析了不同温度热处理后镀层的组织结构,从而建立不同热处理温度、镀层结构与镀层硬度和耐磨性能的关系。结果表明:二次浸锌活化方法和热处理能显著提高镀层与基体的结合强度,经600℃热处理后镀层结合力达到35N。基材的硬度HV为3780MPa,磨损量为9.6mg,镀态镀层的硬度HV为5760MPa、磨损量为7.7mg。随着热处理温度升高Ni3P相增多,该相的弥散分布使镀层硬度增加,最高硬度HV达到9790MPa,但400℃后硬度降低,这是由于Ni3P相随着热处理温度的继续升高而发生偏聚,使弥散强化程度下降;镀层的磨损量随着热处理温度的升高而减小,说明耐磨性能随着热处理温度的升高而增强,600℃热处理后,虽然镀层晶粒长大、粗化及镀层硬度降低,但此时镀层晶格的完整性最佳,镀层塑性和韧性提高,所以耐磨性能最好。     

时效温度对激光选区熔化TC21钛合金微观组织及硬度的影响

SLM成形TC21钛合金经不同温度时效处理后进行显微组织观察和硬度测试,较为系统地探究了时效温度对其组织和硬度的影响。结果表明,时效温度较低时,随着温度的升高,次生α相呈弥散针状析出,且随着温度升高弥散度增大,同时β析出相体积分数也随着温度的升高而增加。时效温度过高时,次生α相粗化,形成尺寸较大的片状α相,强化效果下降。当时效温度为450 ℃时,所得SLM成形TC21钛合金的显微组织最为弥散、均匀,硬度达到最大值575 HV5,较熔凝态硬度提高43.3%。因此,时效温度应控制在450 ℃。     

TC4钛合金表面涂层改性:CrN素多层

目的 提高TC4钛合金的硬度和耐磨损性,改善CrN硬质涂层与TC4钛合金的适应性.方法 采用等离子体增强磁控溅射系统,通过调节热丝放电电流,在TC4钛合金基体表面沉积疏密CrN单层和素多层涂层.利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、能谱仪(EDS)、纳米压痕仪、洛氏压痕仪、摩擦磨损仪以及台阶仪,表征涂层形貌、成分、物相及性能.采用动电位极化法表征涂层的耐腐蚀性.结果 当热丝放电电流为较低的4 A×4时,沉积的CrN单层涂层为具有针孔、孔洞等缺陷的疏松结构,8 A×4沉积的CrN单层涂层具有致密结构,周期性调节热丝放电电流则获得疏密交替的CrN素多层涂层.CrN涂层均由单一面心立方结构的CrN相组成,疏松CrN单层涂层的衍射晶面为(111)、(200)、(220)及(222),致密CrN单层涂层沿(111)晶面择优生长,随着疏密子层调制比的增大,CrN素多层涂层的(111)衍射峰不断增强.疏松CrN单层涂层的最小H和最大E分别为13.0 GPa和207.5 GPa,调制比为1:4的疏密CrN素多层涂层的最小H和最大E分别为17.0 GPa和257.4 GP.在1470 N载荷下洛式压痕法表明,致密CrN单层涂层的结合强度最低,等级为HF5,其余涂层均为HF1—HF4.CrN涂层的自腐蚀电位较TC4钛合金均发生了正移.结论 CrN硬质涂层可以有效提高TC4钛合金的硬度和耐磨损性,表面得到明显强化.周期性调节等离子体密度所沉积的疏密CrN素多层涂层与单层相比,涂层性能明显改善.