Laser treatment and PVD TiN coating of Ti–6Al–4V alloy

Laser gas assisted processing can be used to modify the surface properties of Ti–6Al–4V alloy through the use of gaseous interaction with the laser melted surface. Laser surface melting of titanium and its alloys in nitrogen to form a layer of TiN embedded in a metallic matrix which is enriched in alloying elements has attracted considerable interest. The surface roughness of the laser-treated surface is poor, therefore, a secondary processing becomes essential. In the present study, duplex treatment of Ti–6Al–4V alloy was carried out. The alloy surface was melted initially under a controlled nitrogen atmosphere, which in turn resulted in a laser-induced nitrided surface. The resulting workpiece surface, then, was PVD TiN coated. In order to assess the wear properties of the resulting surface, friction tests were carried out. SEM, XRD and microhardness were carried out for microstructural analysis and material characterization. It was found that the adhesion of the TiN coating to the base alloy improved considerably in the case of laser-treated workpieces and smooth transition in plastic shearing resistance between the TiN coating and the base alloy enhanced the wear properties of the laser-treated surface.     

Characterisation of oxide films produced by plasma electrolytic oxidation of a Ti–6Al–4V alloy

The paper discusses processing and property aspects of oxide films formed on a Ti–6Al–4V alloy by AC plasma electrolytic oxidation (PEO) in aqueous solutions containing aluminate, phosphate, silicate and sulfate anions and some of their combinations. Structure, composition, mechanical tribological and corrosion resistant characteristics of the films formed are studied by SEM, XRD and microhardness analyses, and by scratch, impact, pin-on-disc friction and potentiodynamic corrosion testing. It is found that the films produced from the aluminate–phosphate electrolyte are dense and uniform and are composed mainly of Al₂TiO₅ and TiO₂ phases of the rutile form. The films possess a beneficial combination of 50–60 μm thickness, 575 kg/mm² hardness and high adhesion and provide a low wear rate (3.4×10⁻⁸ mm³/Nm) but a relatively high friction coefficient of μ=0.6–0.7 against steel, caused by material transfer from the counterface. A minimum friction coefficient of μ=0.18 is recorded during the testing of softer rutile–anatase films, 7 μm thick, produced from a phosphate electrolyte. Both of these types of film show good corrosion resistance in NaCl and physiological solutions, where the corrosion current is approximately 1.5 orders of magnitude lower than that of the uncoated substrate. SiO₂/TiO₂-based films with 70–90 μm thickness and high bulk porosity produced from silicate and silicate–aluminate electrolytes demonstrate better corrosion behaviour in H₂SO₄ solution, due to the greater chemical stability of the film phase components in this environment.     

Production of Al–Ti–B grain refining master alloys from Na2B4O7 and K2TiF6

It is very desirable to replace the KBF₄ salt in the popular “halide salt” process to reduce the volume of fluoride salts to be added to molten aluminium in the production of Al–Ti–B grain refiners. Being over 2 times richer in B, Na₂B₄O₇ is a promising replacement for KBF₄, and is used in the present work to produce Al–Ti–B grain refiner master alloys. A fraction of the aluminide particles were entrapped in the spent salt giving a relatively lower Ti recovery when KBF₄ was replaced by Na₂B₄O₇. The grain refining performance of the Al–Ti–B grain refiner alloy thus produced was nevertheless acceptable. The spent salt became too viscous with the oxides, aluminides and borides to be removed by decanting when Na₂B₄O₇·5H₂O was used to supply boron. The viscous spent salt, entrained in the grain refiner alloy, did not only impair its performance, but also hurt the fluidity of the molten alloy and made pouring difficult.     

Production of Al–Ti–B master alloys from Ti sponge and KBF4

It is of great interest to replace the K₂TiF₆ salt so as to reduce the volume of fluoride-bearing particulate material to be added to the aluminium melt in the popular “halide salt” process. Ti sponge was used in the present work as the source of Ti in the production of an Al–5Ti–1B grain refiner. Addition of Ti granules into molten aluminium, either premixed with or before KBF₄ salt, has produced Al–5Ti–1B alloys where the boride particles were relatively few and predominantly of the AlB₂ type. The grain refining efficiency of these alloys were far from satisfactory. TiB₂ was the dominant boride phase with sufficient number of blocky aluminide particles when Ti, in excess of the TiB₂ stoichiometry was supplied before hand and the balance was reserved for co-addition with KBF₄. Al₃Ti particles were generated soon after the Ti solubility limit was exceeded in the first step while the boride particles were subsequently produced by the reaction between molten aluminium, KBF₄ and K₂TiF₆. The Al–5Ti–1B master alloy thus produced provided an adequate grain refining performance while the amount of particulate material to be added to the aluminium melt was reduced by nearly 30%.     

Dry drilling of alloy Ti–6Al–4V

This work is focused on the combined study of the evolution of tool wear, quality of machined holes and surface integrity of work-piece, in the dry drilling of alloy Ti–6Al–4V. Tool wear was studied with optical microscope and SEM–EDS techniques. The quality of machined holes was estimated in terms of geometrical accuracy and burr formation. Surface integrity involves the study of surface roughness, metallurgical alterations and microhardness tests. The end of tool life was reached because of catastrophic failure of the drill, but no significant progressive wear in cutting zone was observed previously. High hole quality was observed even near tool catastrophic failure, evaluated from the point of view of dimensions, surface roughness and burr height. However, microhardness measurements and SEM–EDS analysis of work-piece showed important microstructural changes related with a loss of mechanical properties. Depending on the application of the machined component, the state of the work-piece could be more restrictive than the tool wear, and the end of tool life should be established from the point of view of controlled damage in a work-piece.     

Deposition of Ti–6Al–4V using a high power diode laser and wire, Part I: Investigation on the process characteristics

In this paper the deposition of Ti–6Al–4V wire with High Power Diode Laser was investigated by producing single tracks. The effect of the wire feeding direction and angle was firstly studied. The influence of laser power, traverse speed and wire feed rate on the weight and dimension of the deposited single tracks was then investigated. The microstructure and hardness of the single tracks were examined. Deposition with diode laser and wire was proved to provide a high deposition rate with good quality. Columnar grains were found in the deposits. Wire feeding orientation, laser power, traverse speed and wire feed rate were verified as factors which influenced the quality of the deposit. With similar energy level, different power/traverse speed produced deposits with different hardness value. Hardness values tended to increase from the deposit, via the re-melted zone till to the heat affected zone, and then decrease again when the measurements were taken in the unaffected base material.     

Ti6Al4V钛合金表面激光合金化制备Ti-Cu合金层的组织结构

采用激光合金化技术在Ti6Al4V合金基体表面制备了厚度约为120 μm均匀致密连续的Ti-Cu合金层,分析了合金层的元素分布和显微组织结构。结果表明,Ti-Cu合金层中Cu元素随着合金层深度呈梯度分布,在靠近Ti-Cu合金层表面的区域主要是柱状晶夹杂着少量的块状晶,中上部区域主要是生长取向各异且较粗的不发达枝状晶和部分胞状晶,中下部区域主要是生长取向各异的胞状晶,合金层与基材的界面处主要以细小的平面晶为主。合金化层中Cu元素和Ti元素除了形成固溶体外,还形成了Ti₂Cu、Ti₃Cu和Cu₃Al₄等金属间化合物,同时还形成了Cu₃TiO₄和Al₂TiO₅等金属陶瓷相。     

Thermo-optical modulation for improved ultrasonic fatigue crack detection in Ti–6Al–4V

Pulsed infrared laser irradiation was used to positively identify small fatigue cracks on the surface of fatigue damaged Ti–6Al–4V specimens. The resulting transient thermoelastic deformation perceptibly changes the opening of partially closed surface cracks without affecting other scatterers, such as surface grooves, corrosion pits, coarse grains, etc. that might hide the fatigue crack from ultrasonic detection. We found that this method, which was previously shown to be very effective in 2024 aluminum alloy, must be modified in order to successfully adapt it to Ti–6Al–4V titanium alloy, where significant thermo-optical modulation was found even from straight corners or open notches. This spurious modulation is caused by direct thermal modulation of the sound velocity in the intact material rather than thermal stresses via crack closure. Different methods have been developed to distinguish direct thermal modulation from crack-closure modulation due to thermoelastic stresses. It was found that the modified thermo-optical modulation method can increase the detectability of hidden fatigue cracks in Ti–6Al–4V specimens by approximately one order of magnitude.     

Corrosion behavior of Ti–6Al–4V alloy weldment in hydrochloric acid

The corrosion behavior of a thin sheet of Ti–6Al–4V alloy was investigated in hydrochloric acid solution after welding by gas tungsten arc welding. The resulting microstructure of the weld metal (WM) consisted of coarse prior β grains containing fine acicular α platelets. It was found that both base metal (BM) and WM exhibited active–passive behavior after surface activation in open circuit potential experiments. The corrosion resistance of the BM and WM was found to decrease with increasing the temperature and acid concentration. However, the WM exhibited higher corrosion rate than the BM in all examined conditions. These results were also corroborated by electrochemical impedance spectroscopy measurements. Furthermore, it was revealed that the activation energy of the corrosion process for the WM was lower as compared to the BM, which confirmed the inferior corrosion behavior of the WM.     

A comparative study of surface integrity of Ti–6Al–4V alloy machined by EDM and AECG

The electrical discharge machining (EDM) process produces the recast layer with or without cracks on the surface that requires a remedial post-treatment in the manufacture of critical or highly stressed surfaces. One of the frequently used post-treatment processes is also the abrasive electrochemical grinding (AECG) and it has been widely used in the precision machining of difficult-to-cut materials due to an enhanced surface integrity and productivity. The aim of this study is to investigate improvability of surface integrity in terms of machining voltage, electrolyte flow rate and table feed rate parameters of AECG in EDMed Ti6Al4V alloy. Scanning electron microscopy (SEM), X-ray diffraction (XRD), energy dispersive spectrograph (EDS) and surface roughness measurement were performed to study the surface characteristics of the machined samples. Experimental results indicate that the AECG process effectively improves the surface roughness and eliminates the EDM damages completely by setting suitable grinding parameters.     

Al–Ti–B grain refiners via powder metallurgy processing of Al/K2TiF6/KBF4 powder blends

The response to thermal exposure of ball-milled Al/K₂TiF₆/KBF₄ powder blends was investigated to explore the potential of PM processing for the manufacture of Al–Ti–B alloys. K₂TiF₆ starts to be reduced by aluminium as early as 220 °C when ball-milled Al/K₂TiF₆/KBF₄ powder blends are heated. The reaction of KBF₄ with aluminium follows soon after. The Ti and B thus produced are both solutionized in aluminium before precipitating out as Al₃Ti and TiB₂. All these reactions take place below the melting point of aluminium. The ball-milled Al/K₂TiF₆/KBF₄ powder blends heat treated at approximately 525 °C can be compacted to produce Al–Ti–B pellets with in situ formed Al₃Ti and TiB₂ particles. These pellets are shown to be adequate grain refiners for aluminium alloys.     

Influence of regulated modification of nitride layer by oxygen on the electrochemical behavior of Ti–6Al–4V alloy in the Ringer's solution

The corrosion behavior of oxynitrided Ti–6Al–4V alloy was investigated in the Ringer's solution (simulated body fluid) at a temperature of 37°C. The oxynitriding of the alloy was carried out by leaking controlled oxygen‐containing medium into the reaction chamber at the final stage of the nitride formation. It was determined that oxynitriding improved corrosion resistance of Ti–6Al–4V alloy as it provided lower corrosion current density by 1.3–1.5 times and higher corrosion potential. In this paper, we analyzed that the resistance of the double layer had increased with the increase of the oxygen content in titanium oxynitride. Its value was higher compared with untreated alloy, indicating higher corrosion resistance of the oxynitrided one.     

Enhancement of the corrosion properties of cold sprayed Ti–6Al–4V coatings on mild steel via silica sealer

The pore formation associated with the cold spray process requires the development of an economical sealer to enhance the corrosion resistance of Ti–6Al–4V coatings on a mild steel substrate. Herein, a sound method is developed to seal pores in the cold sprayed Ti–6Al–4V coatings with silica sealer. Potentiodynamic polarization tests in 3.5 wt% sodium chloride electrolyte were employed to investigate the corrosion resistance of cold sprayed Ti–6Al–4V coatings fabricated at two standoff distances (30 and 70 mm) before and after the sealing process. The polarization resistance of cold sprayed Ti–6Al–4V coatings significantly increased by >80% after the sealing process. The electrochemical responses of cold sprayed Ti–6Al–4V were dependant on sealing the pores with agglomerated silica nanoparticles as observed by scanning electron microscopy and energy-dispersive X-ray analysis. The increase in polarization resistance makes the sealer an effective treatment for cold sprayed Ti–6Al–4V coatings used in marine environments and other engineering applications. This sophisticated sealing process can reduce the deposition cost by reducing the thickness of Ti–6Al–4V coatings and increasing their lifetime on metal components.     

Ti6Al4V表面激光熔覆NiCrBSi+B4C涂层的组织结构

选用NiCrBSi及2％民C混粉在Ti6Al4V合金表面进行激光熔覆处理，使基体中的Ti和B4C发生化学反应原位生成TiC、TiB2硬质增强相，制备出TiC与TiB2等增强相增强钛基复合材料涂层。综合运用XRD、SEM、EPMA和TEM等分析手段研究了优化熔覆工艺条件下的NiCrBSi＋B4C激光熔覆层的组织结构与相组成，并对复合涂层进行了硬度测试，结果表明：NiCrBSi＋2％B4C熔覆层的微观组织是在γ—Ni和Ni3Ti＋Ni3B共晶的基体上均匀分布着TiB2、TiC、CrB等相的多元组织，激光熔覆层的硬度比Ti6Al4V基体硬度提高到3～4倍。     

Analysis of diamond-like carbon and Ti/MoS2 coatings on Ti–6Al–4V substrates for applicability to turbine engine applications

Ti–6Al–4V substrates have been coated by diamond-like carbon (DLC) films, with no surface pretreatment, and have been coated by Ti/MoS₂ films, with a simple surface pre-cleaning. The DLC films were deposited by planar coil r.f. inductively-coupled plasma-enhanced chemical vapor deposition (r.f. ICPECVD); the Ti/MoS₂ films were deposited by magnetron sputtering. Both the DLC and Ti/MoS₂ films were characterized by pull tests, hardness tests, scanning electron microscopy (SEM), and wear tests (pin-on-disk and block-on-ring) to compare their adhesion, hardness, surface topology, and wear properties to plasma-sprayed Cu–Ni–In coating currently used for turbine engine applications. The DLC films were easily characterized by their optical properties because they were highly transparent. We used variable-angle spectroscopic ellipsometry (VASE) to characterize thickness and to unequivocally extract real and complex index of refraction, providing a rapid assessment of film quality. Thicker coatings yielded the largest hardness values. The DLC coatings did not require abrasive pretreatment or the formation of bond-layers to ensure good adhesion to the substrate. Simple surface pre-cleaning was also adequate to form well-adhered Ti/MoS₂ on Ti–6Al–4V. The results show that the DLC and Ti/MoS₂ coatings are both much better fretting- and wear-resistant coatings than plasma-sprayed Cu–Ni–In. Both show excellent adhesion to the substrates, less surface roughness, harder surfaces, and more wear resistance than the Cu–Ni–In films.     

Corrosion inhibition of Ti‐6Al‐4V alloy in sulfuric and hydrochloric acid solutions using inorganic passivators

The effect of iodate (IO₃^?), metavanadata (VO₃^?) and molybdate (MoO₄^2?) anions on the passivation of Ti‐6Al‐4V alloy in sulfuric and hydrochloric acid solutions was studied using open‐circuit potential measurements, polarization techniques and electrochemical impedance spectroscopy (EIS). The alloy surface was examined by scanning electron microscopy (SEM). It was found that an optimum concentration of the passivator is essential for the corrosion inhibition process. Above this concentration the rate of alloy corrosion decreases as the concentration of the passivating ion increases. Scanning electron micrographs have shown that the flawed regions present in the alloy surface were repaired in the presence of the passivator anion. The optimum concentration of each anion and its corrosion inhibition efficiency for titanium and Ti‐6Al‐4V alloy have been determined. It turned out that the corrosion inhibition efficiencies of IO₃^?, VO₃^? and MoO₄^2? anions for the corrosion of Ti and Ti‐6Al‐4V in both hydrochloric and sulphuric acid solutions exceed 98%.     

Subsolidus phase relations in the ZnO–MoO3–B2O3, ZnO–MoO3–WO3 and ZnO–WO3–B2O3 ternary systems

The subsolidus phase relations in the ZnO–MoO₃–B₂O₃, ZnO–MoO₃–WO₃ and ZnO–WO₃–B₂O₃ ternary systems have been investigated by the means of X-ray powder diffraction (XRD). There is no ternary compound in all the systems. There are five binary compounds and five tie lines in the ZnO–MoO₃–B₂O₃ system. This system can be divided into six 3-phase regions. There are three binary compounds and three tie lines in the ZnO–MoO₃–WO₃ system. This system can be divided into four 3-phase regions. There are four binary compounds and four tie lines in the ZnO–WO₃–B₂O₃ system. This system can be divided into five 3-phase regions. The possible component regions for ZnO single crystal flux growth were discussed. The phase diagram of Zn₃B₂O₆–ZnWO₄ pseudo-binary system has been constructed, and the result reveals this system is eutectic system. The eutectic temperature is 1007 °C and eutectic point component is 70 mol% Zn₃B₂O₆.