Structure and tribological performance by nitrogen and oxygen plasma based ion implantation on Ti6Al4V alloy

Ti6Al4V alloy was implanted with nitrogen-oxygen mixture by using plasma based ion implantation (PBII) at pulsed voltage −10, −30 and −50 kV. The implantation was up to 6 × 10¹⁷ ions/cm² fluence. The changes in chemical composition, structure and hardness of the modified surfaces were studied by XPS and nanoindentation measurements. According to XPS, it was found that the modified layer was predominantly TiO₂, but contained small amounts of TiO, Ti₂O₃, TiN and Al₂O₃ between the outmost layer and metallic substrate. Surface hardness and wear resistance of the samples increased significantly after PBII treatment, the wear rate of the sample implanted N₂-O₂ mixture at −50 kV decreased eight times than the untreated one. The sample implanted N₂-O₂ mixture showed better wear resistance than that of the sample only implanted oxygen at − 50 kV. The wear mechanism of untreated sample was abrasive-dominated and adhesive, and the wear scar of the sample implanted at −50 kV was characterized by abrasive wear-type ploughing.     

Microstructure and tribological behaviors of Ti6Al4V alloy treated by plasma Ni alloying

Ni modified layer was prepared on surface of the Ti6Al4V substrate by plasma surface alloying technique. Surface morphology, micro-structure, composition distribution, phase structure, and microhardness of the Ni modified layer were analyzed. Tribological performance of the Ni modified layer and Ti6Al4V substrate was investigated by using pin-on-disc tribometer. The results indicate that roughness of the Ni modified layer was increased due to formation of the micro-convex on the modified surface. The concentration of Ni gradually decreased from the surface to interior. The maximum content of Ni atoms was nearly 90%. The modified layer was composed of TiNi, Ti2Ni and Ti phases. The maximum microhardness of the Ni modified layer was about 677 HV_0.025 which was increased about two-fold of microhardness of the control Ti6Al4V substrate. Wear resistance of the Ni modified layer was improved obviously, and showed micro-abrasion wearing. The strengthened mechanism of the as-treated Ti6Al4V alloy is discussed.     

Effect of micro-particles on cavitation erosion of Ti6Al4V alloy in sulfuric acid solution

The influences of micro-particles on ultrasonic cavitation erosion of Ti6Al4V alloy in 0.1 M H₂SO₄ solution were investigated using mass loss weight, scanning electron microscopy (SEM) and white light interferometer. Mass loss results revealed that the cavitation erosion damage obviously decreased with increasing particle size and mass concentration. Open circuit potential recorded during cavitation erosion shifted to positive direction with the decreased mass loss. Meanwhile, the mass loss sharply decreased with applying a positive potential during the entire ultrasonic cavitation erosion, and the relationship between the open circuit potential and the cavitation erosion resistance was discussed.     

Infrared thermography for monitoring heat generation in a linear friction welding process of Ti6Al4V alloy

The increasing use of titanium alloys in a wider range of applications requires the development of new techniques and processes capable to decrease production costs and manufacturing times. In this regard welding and other joining techniques play an important role. Today, solid state friction joining processes, such as friction stir welding, friction spot welding, inertia friction welding, continuous-drive friction welding and linear friction welding (LFW), represent promising methods for part manufacturing. They allow for joining at temperature essentially below the melting point of the base materials being joined, without the addition of filler metal.However, the knowledge of temperature is essential to understand and model the phenomena involved in metal welding. A global measured value represents only a clue of the heat generation during the process; while, a deep understanding of welding thermal aspects requires temperature field measurement. This paper is focused on the use of infrared thermography applied to the linear friction welding process of Ti6Al4V alloy. The attention is concentrated on thermal field that develops on the outer wall of the two parts to be joined (i.e. heat generated in the friction zone), and on the maximum temperature that characterizes the process before and after the flash formation.     

Influence of slight microstructural gradients on the surface properties of Ti6Al4V irradiated by UV

Ti6Al4V alloy is one of the most widely used materials for biomedical implants. Among its properties, it is remarkable the photoactivity displayed by its passive layer, which is mainly composed by titanium dioxide. However, variations in the processing conditions may yield to differences in the microstructure which can be reflected on the surface properties of the machined product. From contact angle measurements taken on different zones of samples removed from a commercial bar of Ti6Al4V, it has been shown that the modifications of the surface Gibbs energy suffered by the alloy under UV irradiation have a radial dependence. This behaviour is related to slight microstructural changes of the alloy, particularly with an increase in the volume fraction of the β-phase when moving to the interior of the sample, which alters the composition and/or microstructure of the passive layer along its radius. This study shows that gradients in the microstructure and physical properties are sample size dependent and are likely related to thermal gradients during processing.     

The cytocompatibility investigation of Ti6Al4V modified with a fluorine-contained copolymer thin film

The objective of the present study is to preliminarily explore the effect of surface chemistry modification of Ti6Al4V with a fluorine-contained copolymer thin film on the cellular behavior of osteoblasts. A fluorine-contained random copolymer thin film was fabricated on Ti6Al4V substrate, and then characterized by X-ray photoelectron spectroscopy (XPS), contact angle meter and surface profiler. The results showed that the surface modification of Ti6Al4V alloy could simultaneously transform the surface chemical constitution and reduce the surface energy evidently. However, the surface morphology and roughness of the Ti6Al4V substrate were hardly changed after the modification. By immersion process with simulated body fluid (SBF) and then by in vitro cytotoxicity test with MC3T3-E1 osteoblasts, the fluorine-contained copolymer thin film exhibited desirable stability and admirable cytocompatibility. In conclusion, the fluorine-contained copolymer thin film could be easily applied in modifying various solid surfaces, and the as-fabricated film also has potential applications in biomedical field.     

Fabrication of Zr and Zr-N surface alloying layers and hardness improvement of Ti-6Al-4V alloy by plasma surface alloying technique

Titanium alloys are very attractive materials because they have high specific strength, excellent corrosion and erosion resistance in many active environments. However, their low hardness values and poor tribological properties require improvement of their surface properties. The present study is concerned with the fabrication of Zr and Zr-N alloying layers in the surfaces of Ti-6Al-4V substrates by plasma surface alloying technique. The microstructure, chemical composition and hardness of the surface alloying layers were analyzed to understand the mechanisms of surface alloying and hardness improvement. The Zr and Zr-N surface alloying layers formed were homogeneous and compact, in which the surface alloying elements all displayed gradient distributions. The Zr and Zr-N surface alloying layers all enhanced the surface hardness of Ti-6Al-4V alloy. Zr-N surface alloying resulted in greater improvement in hardness and the maximum microhardness of (1.37 ± 0.04) × 10³ HK was obtained at the subsurface, which was much higher than that of the untreated Ti-6Al-4V alloy. The Zr-N surface alloying layer consisted of an outer nitride layer and an inner diffusion zone of Zr and N, and its very high hardness owed to the formation of the nitride layer. The mechanism of hardness improvement of Zr surface alloyed Ti-6Al-4V alloy was solid solution strengthening.     

Structure and micro-mechanical properties of helium-implanted layer on Ti by plasma-based ion implantation

The present paper concentrates on structure and micro-mechanical properties of the helium-implanted layer on titanium treated by plasma-based ion implantation with a pulsed voltage of −30 kV and doses of 3, 6, 9 and 12 × 10¹⁷ ions/cm², respectively. X-ray photoelectron spectroscopy and transmission electron microscopy are employed to characterize the structure of the implanted layer. The hardnesses at different depths of the layer were measured by nano-indentation. We found that helium ion implantation into titanium leads to the formation of bubbles with a diameter from a few to more than 10 nm and the bubble size increases with the increase of dose. The primary existing form of Ti is amorphous in the implanted layer. Helium implantation also enhances the ingress of O, C and N and stimulates the formations of TiO₂, Ti₂O₃, TiO, TiC and TiN in the near surface layer. And the amount of the ingressed oxygen is obviously higher than those of nitrogen and carbon due to its higher activity. At the near surface layer, the hardnesses of all implanted samples increases remarkably comparing with untreated one and the maximum hardness has an increase by a factor of up to 3.7. For the samples implanted with higher doses of 6, 9 and 12 × 10¹⁷ He/cm², the local displacement bursts are clearly found in the load-displacement curves. For the samples implanted with a lower dose of 3 × 10¹⁷ He/cm², there is no obvious displacement burst found. Furthermore, the burst width increases with the increase of the dose.     

Investigation of the voltage and time effects on the formation of hydroxyapatite-containing titania prepared by plasma electrolytic oxidation on Ti-6Al-4V alloy and its corrosion behavior

Producing titania and hydroxyapatite (HA) bioceramic coating on titanium alloys increases corrosion resistance and biocompatibility of these alloys. Plasma electrolytic oxidation (PEO) is one of the effective techniques for producing this type of coating. This method produces coatings with enough thickness and appropriate adhesion. In this study, titania and HA were directly produced on Ti-6Al-4V by applying PEO process in a Ca- and P-containing electrolyte by changing voltage and time parameters. Morphology and cross section, chemical composition and elements of coatings were investigated by scanning electron microscope, X-ray diffraction and energy dispersive spectroscopy, respectively. Corrosion behavior of the samples was also examined by potentiodynamic polarization and electrochemical impedance spectroscopy. The results indicated that the formation of HA phase with titania needs a minimum voltage below which HA is not formed. By increasing the operation time, the amount of the formed HA increased. Also, the sample coated at 500 V and 15 min showed the best corrosion behavior in Ringer's solution.     

Growth characteristics of plasma electrolytic oxidation ceramic coatings on Ti-6Al-4V alloy

The aim of this work is to discuss the growth characteristics of the ceramic coatings on Ti alloy by plasma electrolytic oxidation (PEO) technique. Ceramic coatings were prepared on Ti alloy by plasma electrolytic oxidation in different electrolyte solutions under different pulse modes. The composition and the structure of the coatings were investigated by X-ray diffraction and scanning electron microscopy (SEM), respectively. The amount of the dissolved titanium into the electrolytes during PEO process was measured by inductively coupled plasma-atomic emission spectrometer (ICP-AES). The structure and the composition of the coatings were related to the mode of the spark discharge during PEO process. (a) Under the pulsed single-polar mode: In Na₃PO₄ solution, the spark discharge was mainly due to the breakdown of the oxide film, and the coatings prepared were porous and mainly structured by the Ti from the substrate. In K₄ZrF₆-H₃PO₄ and NaAlO₂-Na₃PO₄ solutions, the main mode of the spark discharge was the breakdown of the oxide film at the initial stage, and then changed into the breakdown of the vapor envelope, and the coatings were rough and thick, and mainly structured by the elements from the electrolyte. (b) Under the pulsed bi-polar mode in NaAlO₂-Na₃PO₄ solution, the spark discharge may be mainly due to the breakdown of the oxide film, the coatings prepared were dense in inner layer and loose in outer layer, and structured by the elements from both the substrate and the electrolyte. Besides, the ICP-AES analyses showed that the amount of the dissolved titanium in the electrolyte during PEO process was more under the breakdown of the oxide film than under the breakdown of the vapor envelope, which was consistent with the changes of the structure of the coatings. Cathode pulse in the pulsed bi-polar mode increased the amount of the dissolved titanium in the electrolyte, compared with the pulsed single-polar one.     

强流辐照钛合金表面特征的原子力显微研究

利用原子力显微术的轻敲模式(TM-AFM),并采用形貌与相位同时成像技术对强流脉冲离子束(IPIB)辐照前后试样表面进行了系统标征,得到了试样表面的高度像及相位像的衬度.分析结果表明:在高流强密度、多次脉冲条件下,IPIB辐照可使试样表面变得光滑化,从相位像中可以定性分析出辐照后表面硬度也得到一定程度的提高.     

Prevention of biofilm re‐development on Ti‐6Al‐4V alloy by cometary discharge with a metallic grid

The influence of a non‐thermal plasma (NTP) on the gram‐negative bacteria Escherichia coli and Pseudomonas aeruginosa, the gram‐positive bacterium Staphylococcus epidermidis, and the yeast Candida albicans grown on agar or in the biofilm form was compared. NTP was produced by a DC cometary discharge. The biofilms were grown on the surface of Ti‐6Al‐4V alloy often used in the manufacture of prosthetic implants. The exposure by NTP not only inhibited the surface growth of microorganisms in agar cultures but also significantly suppressed the viability of bacteria and yeast in biofilms and prevented its re‐developed from persistent cells remaining in the lower layers of the biofilm. An almost complete prevention of biofilm re‐development was achieved in the case of S. epidermidis; other microorganisms displayed substantial lowering of biofilm biomass and its metabolic activity.     

Microstructure and wear properties of TiCN/Ti coatings on titanium alloy by laser cladding

Titanium carbide nitride (TiCN) reinforced Ti coating was fabricated on the surface of Ti–6Al–4V alloy by laser cladding method. Microstructure and wear properties at the surface of the coating in atmosphere were investigated. Three zones can be distinguished of the coating: the clad zone (CZ), the heat affected zone (HAZ) and the substrate. The clad zone is composed of TiCN dendrites, TiO₂ and Ti. A metallurgical bonding between the coating and the substrate was obtained. The microhardness and wear resistance of the TiCN/Ti coating are significantly improved. The average hardness of the coating is about 3 to 6 times of that of the substrate. The friction coefficients of the substrate and the coating are 0.48 and 0.34 respectively. The friction coefficient of the Ti–6Al–4V substrate was insensitive to the normal load, while that of the cladded TiCN/Ti coating was very sensitive to the normal load. The wear mass losses of the cladded samples are much lower than that of the substrate whatever the normal load is.     

Experimental investigation and metallographic characterization of fiber laser beam welding of Ti-6Al-4V alloy using response surface method

In the present study, experimental investigations of fiber-laser-beam-welding of 5 mm thick Ti-6Al-4V alloy are carried out based on statistical design of experiments. The relationship between the process parameters such as welding power, welding speed, and defocused position of the laser beam with the output responses such as width of the fusion zone, size of the heat affected zone, and fusion zone area are established in terms of regression models. Also, the most significant process parameters and their optimum ranges are identified and their percentage contributions on output responses are calculated. It is observed that welding power and speed plays the major role for full penetration welding. Also, welding power shows direct effect whereas welding speed shows the inverse effect on the output responses. The bead geometry is influenced by the defocused position of the laser beam due to the change in power density on the workpiece surface. However, overall fusion zone area is unaffected. Mechanical characterization of the welded samples such as microstructural analysis, hardness, and tensile tests are conducted. It is noticed that the hardness value of the FZ is higher than the HAZ and BM zone due to the difference in cooling rate during welding which promotes the formation of α′ martensitic phase in the FZ. Also, an average hardness value in the FZ is compared for two different defocusing positions (i.e. 1 and 2 mm). It is found that hardness value is higher for 1 mm defocused position than 2 mm due the decrement in grain size below a critical range at 2 mm defocused position. The ultimate tensile strength and % elongation of the welded samples are degraded as compared to BM which can be further improved by post heat treatment.     

Grain refining of Ti-6Al-4V alloy fabricated by laser and wire additive manufacturing assisted with ultrasonic vibration

The formation of the coarse columnar crystal structure of Ti-6Al-4V alloy in the process of additive manufacturing greatly reduces the mechanical performance of the additive manufactured parts, which hinders the applications of additive manufacturing techniques in the engineering fields. In order to refine the microstructure of the materials using the high intensity ultrasonic via the acoustic cavitation and acoustic flow effect in the process of metal solidification, an ultrasonic vibration technique was developed to a synchronous couple in the process of Laser and Wire Additive Manufacturing (LWAM) in this work. It is found that the introduction of high-intensity ultrasound effectively interrupts the epitaxial growth tendency of prior-β crystal and weakens the texture strength of prior-β crystal. The microstructure of Ti-6Al-4V alloy converts to fine columnar crystals from typical coarse columnar crystals. The simulation results confirm that the acoustic cavitation effect applied to the molten pool created by the high-intensity ultrasound is the key factor that affects the crystal characteristics.     

Study of nitrogen ion implantation and diffusion phenomena on thin chromium layers followed by the atomic force microscopy and secondary ion mass spectroscopy techniques characterization

This research investigates the effect of ion implantation dosage level and further thermal treatment on the physical characteristics of chromium coatings on Si(1 1 1) substrates. Chromium films had been exposed to nitrogen ion fluencies of 1 × 10¹⁷, 3 × 10¹⁷, 6 × 10¹⁷ and 10 × 10¹⁷ N⁺ cm⁻² with a 15 keV energy level. Obtained samples had been heat treated at 450 °C at a pressure of 2 × 10⁻² Torr in an argon atmosphere for 30 h. Atomic force microscopy (AFM) images showed significant increase in surface roughness as a result of nitrogen ion fluence increase. Secondary ion mass spectroscopy (SIMS) studies revealed a clear increased accumulation of Cr₂N phase near the surface as a result of higher N⁺ fluence. XRD patterns showed preferred growth of [0 0 2] and [1 1 1] planes of Cr₂N phase as a result of higher ion implantation fluence. These results had been explained based on the nucleation-growth of Cr₂N phase and nitrogen atoms diffusion history during the thermal treatment process.     

Preparation of biomedical Ag incorporated hydroxyapatite/titania coatings on Ti6Al4V alloy by plasma electrolytic oxidation

Nano-Ag incorporated hydroxyapatite/titania(HA/TiO2) coatings were deposited on Ti6Al4V substrates by the plasma electrolytic oxidation process. Compared with the substrate, the deposited coatings display attractive mechanical and biomedical properties. First, the coatings have stronger wear resistance and corrosion resistance. Second, they show a strong antibacterial ability. The mean vitality of the P. gingivalis on the coating surfaces is reduced to about 21%.Third, the coatings have good biocompatibility. The mean viability of the fibroblast cells on the coating surface is increased to about 130%. With these attractive properties, Ag incorporated HA/TiO2 coatings may be useful in the biomedical field.