Titanium alloys after surface gas nitriding

Experimental studies using differential scanning calorimetry (DSC) for nitriding of four titanium-alloys near α Ti-8Al-1Mo-1V, near α Ti-6Al-2Sn-4Zr-2Mo, α + β Ti-6Al-4V and near β Ti-10V-2Fe-3Al at different temperatures and for different periods of time are presented. The X-ray diffraction (XRD) technique was used in order to study the phase transformations that occur during gas nitriding. As a result of the nitrogen interaction, a nitrided layer was formed that consists of titanium nitrides, followed by an interstitial solution of nitrogen in the hcp α titanium phase. The microstructural changes of these alloys in relation to the alloy composition and processing parameters were studied. It was found that the microstructure of alloys nitrided at temperatures below their β transus temperatures for various periods of time is uniform and homogeneous. With the increase of the temperature above their β transus temperatures the microstructure changes to irregular. Microindentation hardness testing using a Knoop indenter was conducted on the nitrided titanium alloys to analyse their hardness evolution in relation to the nitriding processing parameters and alloy composition. It was found that the microhardness increases with the increase of the temperature and time of nitriding. The surface morphology of the Ti-6Al-2Sn-4Zr-2Mo alloy in relation to the nitriding processing parameters was analysed.     

稀土含量对Ti6Al4V钛合金等离子渗氮层组织和摩擦学性能的影响

目的研究稀土含量对Ti6Al4V钛合金表面等离子体渗氮层结构和性能的影响。方法运用等离子表面改性技术对Ti6Al4V(TC4)钛合金进行等离子渗氮处理,渗氮过程中通入不同含量的稀土作为催渗剂,以获得钛合金表面强化层。利用金相显微镜和扫描电子显微镜(SEM)观察渗氮层组织,用X射线衍射仪(XRD)分析渗层相组成,用能谱仪(EDS)检测渗层的化学成分,用维氏显微硬度计测量渗层的显微硬度,用球-盘式摩擦磨损试验机和三维轮廓仪检测渗层的摩擦磨损性能。结果TC4钛合金表面等离子渗氮层结构包括表面化合物层(主要成分为δ-TiN)和扩散层(主要为N原子扩散形成的N-Ti固溶体),加入稀土可以促进N原子向基体的扩散,提高渗氮速度。渗层厚度增加,硬度和耐磨性能提高,扩散层使钛合金基体与化合物层之间的硬度梯度更加平缓。当稀土通入速率为60 mL/min时,渗层厚度可达155μm,表面硬度为1275HV0.05,摩擦系数降到0.27,磨损率明显降低。结论钛合金等离子渗氮过程中加入稀土可以有效提高渗速,改善渗氮层硬度,提高材料表面的耐磨性能。     

Effect of Fe content on microstructures and properties of Ti6Al4V alloy with combinatorial approach

A combinatorial approach was applied to investigating the influence of Fe content on the microstructures and properties of Ti6Al4V alloy. A diffusion couple was manufactured with Ti6Al4V and Ti6Al4V20Fe alloys and annealed at 1000 °C for 600 h to obtain a wide range of compositions. By combining electron probe micro-analysis (EPMA), scanning electron microscopy (SEM) and nanoindentation, the relationships between composition and microstructure as well as hardness were determined. It is found that after aging the Ti6Al4V5Fe sample contains reasonable (about 55%) volume fraction of fine α phase and shows the peak hardness among the Ti6Al4VxFe alloys. Therefore, it is a promising candidate for the development of titanium alloys. HAADF-STEM and XRD reveal that after quenching from the single β phase field, the metastable α″ lamellae form in the Ti6Al4V5Fe alloy, and on subsequent isothermal aging, the α″ lamellae become coarse and act as precursors/preferential nucleation sites for the stable α phase.     

喷丸预处理对Ti6Al4V合金低温等离子体氮化的影响

为改善钛合金表面耐磨性能,同时达到防止薄壁零部件变形和节约能源的目的,以Ti6Al4V钛合金为对象,研究了喷丸强化预处理对钛合金低温渗氮层及耐磨性的改善作用。结果表明,喷丸强化预处理能够有效促进钛合金表面低温离子渗氮过程,在500 ℃低温渗氮试验条件下,随着喷丸预处理强度的增大,钛合金渗氮效率逐步提高,渗氮层的表面硬度、承载能力和表观韧性逐步增加,使得渗氮层的耐磨性能逐步提高。当喷丸预处理强度增加到0.25 mmA时,Ti6Al4V钛合金渗氮层的表面硬度比单纯渗氮处理试样提高32.7%,磨损率降低42.3%,使钛合金基体的磨损率降低70.5%,较好地实现了喷丸预处理促进钛合金低温离子渗氮的目标。     

Characterisation of anodic oxide films formed on titanium and two ternary titanium alloys in hydrochloric acid solutions

The purpose of this paper is to characterise the anodic oxide films formed on titanium and two ternary titanium alloys, Ti‐15Mo‐5Al and Ti‐10Mo‐10Al in 1%, 10% and 20% hydrochloric acid solutions at 25, 50, and 75°C. The anodic film on titanium in hydrochloric acid is stable between + 0.6 V (SCE) and + 2.0 V (SCE). For our new ternary titanium alloys, the passive film is formed at about + 0.6 V (SCE) and is stable to + 2.0 V (SCE). The anodic polarization curves for alloys differ from the base metal curve, presenting two peaks for the critical passivation current density in the active‐passive potential range. At the first current peak (the first critical passivation potential E_cr1) a porous titanium pentaoxide (Ti₃O₅) is formed. When the potential reaches the second current peak (the second critical passivation potential E_cr2) the compact and protective titanium dioxide (TiO₂) is formed. The impedance spectra exhibit the typical behaviour for a passive film i.e. a near capacitive response illustrated by a phase angle close to − 90 ° over a wide frequency range. The oxide film on titanium and its alloys in hydrochloric acid solutions exhibits a high resistance and a low capacitance (with the increase of the potential) attributed to the surface roughness decrease as the oxide layer thickens.     

Nitriding of Ti – 6% Al – 4% V Alloy in the Plasma of an Intensified Glow Discharge

The wear resistance of titanium alloys can be increased by thermochemical treatment like nitriding. Conventional nitriding processes require high treatment temperatures for high enough diffusion of nitrogen. However, treatment at 800°C and higher temperatures decreases the fatigue resistance of the alloys. Consequently, it is necessary to find a compromise between the increase in the wear resistance and the decrease in the mechanical properties. The use of an intensified glow discharge can solve the problem. For this purpose a source of electrons with a low negative potential is installed in addition to the cathode and the anode. In the presence of additional electrons the density of the plasma and hence the glow discharge current increase substantially without growth in the discharge pressure. This increases significantly the mean energy of the ions and decreases noticeably the heating effect of the plasma. The present work is devoted to problems in the commercial use of an intensified glow discharge. Nitriding in an intensified glow discharge makes it possible to decrease the treatment temperature to 600°C. In the Ti – 6% Al – 4% V alloy diffusion layers about 200 μm thick form due to such a process in 6 h.     

Dynamic stress–strain properties of Ti–Al–V titanium alloys with various element contents

A series of Ti–Al–V titanium alloy bars with nominal composition Ti–7Al–5V ELI,Ti–5Al–3V ELI,commercial Ti–6Al–4V ELI and commercial Ti–6Al–4V were prepared.These alloys were then heat treated to obtain bimodal or equiaxed microstructures with various contents of primary a phase.Dynamic compression properties of the alloys above were studied by split Hopkinson pressure bar system at strain rates from 2,000 to 4,000 s-1.The results show that Ti–6Al–4V alloy with equiaxed primary a(ap)volume fraction of 45 vol%or 67 vol%exhibits good dynamic properties with high dynamic strength and absorbed energy,as well as an acceptable dynamic plasticity.However,all the Ti53ELI specimens and Ti64ELI specimens with ap of 65 vol%were not fractured at a strain rate of4,000 s-1.It appears that the undamaged specimens still have load-bearing capability.Dynamic strength of Ti–Al–V alloy can be improved as the contents of elements Al,V,Fe,and O increase,while dynamic strain is not sensitive to the composition in the appropriate range.The effects of primary alpha volume fraction on the dynamic properties are dependent on the compositions of Ti–Al–V alloys.     

Ti6Al4V合金渗镀Cr-Mo表面改性层组织结构及其耐磨特性研究

采用双层辉光离子渗技术在Ti6Al4V合金表面进行多元合金化,形成均匀致密的Cr-Mo合金渗层.通过GDOES、XRD等手段标定表层成分和相结构,借助显微硬度计和球盘磨损仪测试合金渗层的性能.结果表明:合金渗层中合金化元素Cr与Mo呈梯度分布,主要由化合物Cr_(1.93)Ti_(1.07)、Cr_2Ti、Cr_2Ti_4O_(11)等相构成;改性的Ti6Al4V合金表面硬度有较大程度的提高,抗磨损性能明显改善.     

High strength Mo/Ti6Al4V diffusion bonding joints: Interfacial microstructure and mechanical properties

Joining Mo to Ti6Al4V is of great interest for applications in the weaponry and aerospace fields. In this work, a diffusion bonding technique is developed to bond a MoZr alloy and Ti6Al4V using a Cr-Ni-Ti-Si composite interlayer. The formation of the interlayer ensured that crack-free bonds were obtained. The mechanical properties and microstructure of the interface were examined. The results show that as the temperature was raised, the thickness of the diffusion layer increased and Kirkendall voids formed on the Mo alloy side. At the Mo/Cr-Ni-Ti-Si interface, a diffusion layer formed as Cr, Ni, Si and Mo dissolved into Ti to form a substitutional solid solution. As a result, the lattice constant of Ti reduced. For diffusion bonding between Mo and Ti6Al4V, a maximum tensile strength of 369 MPa was attained while a processing temperature of 950 °C was used. Ductile fractures were observed at the Mo/Ti6Al4V joints, primarily in Mo adjacent to the Mo/Cr-Ni-Ti-Si interface. The findings in this study open up new possibilities for the use of Cr-Ni-Ti-Si composite interlayer to bind Mo alloys to Titanium alloys.     

Studying and modeling surface gas nitriding for titanium alloys

In this article, experimental studies for the nitriding of four titanium alloys at different temperatures and for different periods of time are summarized. The studies focused on microstructural changes in relation to the alloy composition and processing parameters; microindentation hardness testing on the nitrided titanium alloys to analyze their hardness evolution; and the corrosion behavior of titanium alloys before and after gas nitriding in response to the corrosive condition. In addition, models were developed to simulate and monitor the evolution of surface layers during the gas nitriding of titanium alloys.     

TC4钛合金表面B-Al复合渗层的组织和性能

采用固体粉末包埋渗两步法,在TC4钛合金表面先1050 ℃渗硼 4~6 h再950~1050 ℃渗铝 4 h制备出B-Al复合耐磨渗层。利用X射线衍射仪(XRD)、扫描电镜(SEM)、波谱仪(WDS)和能谱仪(EDS)、显微硬度仪和摩擦磨损试验机对复合渗层的物相组成、显微组织、微区成分、表面硬度和摩擦因数进行测试和分析。结果表明:B-Al复合渗层厚为37~115 μm,主要由TiB₂相和TiAl₃相组成,外层是弥散分布TiB₂的TiAl₃层,向内依次形成厚度较小的TiAl₂、TiAl及Ti₃Al等Ti-Al金属间化合物层。B-Al复合渗层表面硬度为1041.7~1429.4 HV0.1,约为TC4钛合金硬度的3.03~4.16倍;经1050 ℃×6 h渗B后1050 ℃×4 h渗Al,其摩擦因数约为0.3,较TC4钛合金基体下降约25%。     

不同压力对 TC4 钛合金真空脉冲渗氮的影响

目的采用不同压力对TC4钛合金进行真空脉冲渗氮处理,提高其表面硬度及耐磨性。方法通过金相显微镜、X射线衍射仪、显微硬度计及耐磨试验机分析渗氮硬化层的组织与性能。结果 TC4钛合金经过真空气体渗氮处理后,形成了由Ti N,Ti2Al N和钛铝金属间化合物Ti3Al组成的复合改性层。渗氮压力太低,表面氮化物数量较少,氮化物层较薄;随渗氮压力的增大,表面氮化物数量增多,表面硬度及耐磨性增加。压力为0.015 MPa时,氮化物层表面硬度最大,表面硬度为1100~1200HV,有效硬化层深度为50~60μm。渗氮压力继续增加,表层组织变得疏松,表面硬度及耐磨性开始降低。结论选择合适的渗氮压力和表面氮浓度进行真空脉冲渗氮,可以提高钛合金表面硬度,改善耐磨性。     

Design and characterization of selective laser-melted Ti6Al4V–5Cu alloy for dental implants

Ti6Al4V–5Cu alloys have potential biomedical applications due to their adequate antibacterial properties. However, the wear and corrosion properties of these alloys are also crucial for dental implants. In the present study, Ti6Al4V–5Cu alloys were fabricated by selective laser melting (SLM). The microstructure and composition of Ti6Al4V–5Cu alloys by SLM were evaluated. The wear properties of the alloys in the simulated saliva environment and the atmospheric environment, as well as the electrochemical properties in the simulated saliva environment, were systematically investigated. The results showed that the crystal structure of Ti6Al4V–5Cu alloys was mainly composed of α-Ti and Ti₂Cu. In the SLM process, no preferred texture was observed due to the complex direction of the heat flux. The formation of Ti₂Cu can improve the strength of the material and make the titanium copper alloy have higher microhardness. Ti6Al4V–5Cu alloy showed a satisfactory wear resistance in both wear media. The addition of Cu reduced the second-phase content of the alloy. Meanwhile, the number of microcells was reduced, which was a positive factor to improve the corrosion resistance of the alloys.     

纳米压/划痕表征激光渗氮层的弹塑性力学性能

利用脉冲式Nd：YAG激光在Ti6Al4V合金表面进行激光渗氮处理,借助纳米压痕和划痕试验表征渗氮层的弹塑性力学性能。结果表明,在钛合金表面成功制备了高硬度、高强度、枝晶状分布的渗氮层。同时,渗氮层内硬度、模量、强度以及应力-应变关系、摩擦系数等力学性能呈现出类似于激光渗氮层内氮元素扩散曲线的非均匀性空间分布规律。硬度和弹性模量之比以及纳米划痕试验结果表明,激光渗氮层的抗磨损性能随深度的增加逐渐降低,摩擦系数随着划入深度的增加,从0.2增加到0.4。     

Investigation of the effect of aluminum on the phase composition of Ti–Al–Nb–Mo gamma alloys

A quantitative analysis of the influence of aluminum concentration on the phase composition of TNM-type Ti–Al–Nb–Mo γ-alloys has been carried out using the Thermo-Calc software and experimental methods. Isothermal and polythermal sections of the corresponding phase diagram have been calculated; the critical temperatures of phase transformations in the alloys of the system, and the chemical compositions of phases formed in them (β, α, α₂, γ) have been determined. The influence of the annealing temperature on the microstructure and phase composition of the alloys containing 43 and 40% Al has been studied.     

Ti13Nb13Zr 合金离子氮化层的摩擦磨损性能研究

目的提高医用钛合金的耐磨损性能。方法应用等离子渗氮技术在Ti13Nb13Zr基材上制备改性层,并对改性层组织、成分及硬度进行测试。利用往复磨损试验机研究改性层在干摩擦条件下的摩擦磨损性能,并与未处理的基材进行对比。结果 Ti13Nb13Zr合金表面经渗氮后形成致密均匀的改性层,硬度高达1110HV0.025,改性层的磨损体积约为基材的1/23。结论等离子渗氮技术有效地改善了Ti13Nb13Zr合金的摩擦磨损性能。     

Oxidation of nitride layers formed on Ti-6Al-4V alloys by gas nitriding

Ti-6Al-4V alloys were nitrided through gas nitriding at 950 °C for 3 h in deoxygenated, atmospheric nitrogen gas. During nitriding, nitrogen reacted and diffused into the alloys to form Ti₂N and a meager amount of TiN in a Ti-N compound layer with a thickness of 20 μm to 25 μm. An α-Ti(N) diffusion layer with a thickness of 40 μm to 80 μm formed below this layer. A small amount of Al was dissolved at the top of the Ti-N compound layer because of the strong interaction of nitrogen with Ti and Al. Nitriding resulted in the dissolution of interstitial nitrogen and the formation of nitrides. Oxidation of the nitrided Ti-6Al-4V alloys initially resulted in the formation of a Ti-N-O layer, which later oxidized to TiO₂. Above 800 °C, the nitrided alloys oxidized rapidly, accompanied by microcracking of the TiO₂ surface layer.     

Effects of Duplex Nitriding and TiN Coating Treatment on Wear Resistance,Corrosion Resistance and Biocompatibility of Ti6Al4V Alloy

Ti6Al4V alloy substrates were nitrided at 900 °C. TiN coatings were then deposited on the nitrided substrates using a closed-field unbalanced magnetron sputtering system. The microstructure, hardness and adhesion properties of the TiN-N-Ti6Al4V substrates were evaluated and compared with those of an untreated Ti6Al4V sample, a nitrided Ti6Al4V sample and a TiN-coated Ti6Al4V sample, respectively. The tribological properties of the various samples were investigated by means of reciprocating sliding wear tests performed in 0.9 wt.% NaCl solution against 316L, Si₃N₄ and Ti6Al4V balls, respectively. In addition, the corrosion resistance was evaluated using potentiodynamic polarization tests. Finally, the biocompatibility of the samples was investigated by observing the attachment and growth of purified mouse leukemic monocyte/macrophage cells (Raw 264.7) on the sample surface after culturing periods of 24, 72 and 120 h, respectively. Overall, the results showed that the duplex nitriding/TiN coating treatment significantly improved the tribological, anti-corrosion and biocompatibility properties of the original Ti6Al4V alloy.     

Constitution of Ni–Al–Ti system studied by scanning electron microscopy

The Ni–Al–Ti system is one of the key model systems for technically important materials based on nickel and titanium aluminides. A recent critical literature review by Schuster stated a lack of experimental data apart from corners of the composition triangle. This work is focused on several alloys of Ni–Al–Ti system from the central part of the composition triangle, where numerous intermetallic phases coexist. The microstructure of alloys was studied and quantified after long term annealing at 1050 °C by means of scanning electron microscopy with an energy dispersive X-ray analysis and electron backscatter diffraction. Experimental results were compared with existing literature data. In order to compare experimental knowledge on phase equilibria with results of thermodynamic modelling, phase diagram was calculated using the software package ThermoCalc and two different thermodynamic databases.     

Effect of carbon and oxygen on microstructure and mechanical properties of Ti–25V–15Cr–2Al (wt%) alloys

The effect of carbon additions on microstructure and mechanical properties of alloys with different levels of oxygen was studied in β titanium alloys of the general composition Ti–25V–15Cr–2Al (all compositions are in wt% unless otherwise indicated). The microstructures were studied using optical microscopy (OM), X-ray diffractometry (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that titanium carbides with vacancy-ordered structure formed in all alloys with C additions of over 1000 w.p.p.m. Grains were refined by carbides. Wavelength-dispersive X-ray (WDX) analysis showed that oxygen was much higher in carbides than in β matrix. After long-term exposure at 550°C α precipitation was significantly reduced in samples with titanium carbides compared with those without. A significant improvement in room temperature tensile ductility was achieved by the addition of carbon to the alloys. Elongations of ∼10% were obtained in samples which were exposed at 550°C for 500 h following heat treatments at 1050 and 700°C.