PMC:2871132 / 137130-154649 JSONTXT

{"project":"2_test","denotations":[{"id":"20480036-12608425-52068818","span":{"begin":687,"end":690},"obj":"12608425"},{"id":"20480036-14580913-52068819","span":{"begin":2144,"end":2147},"obj":"14580913"},{"id":"20480036-14580913-52068820","span":{"begin":3142,"end":3145},"obj":"14580913"},{"id":"20480036-10503972-52068821","span":{"begin":5561,"end":5564},"obj":"10503972"},{"id":"20480036-8718939-52068822","span":{"begin":6747,"end":6750},"obj":"8718939"},{"id":"20480036-8718939-52068823","span":{"begin":7700,"end":7703},"obj":"8718939"},{"id":"20480036-14609674-52068824","span":{"begin":7723,"end":7726},"obj":"14609674"},{"id":"20480036-14609674-52068825","span":{"begin":9113,"end":9116},"obj":"14609674"},{"id":"20480036-1391401-52068826","span":{"begin":11277,"end":11280},"obj":"1391401"},{"id":"20480036-3427147-52068826","span":{"begin":11277,"end":11280},"obj":"3427147"},{"id":"20480036-10905408-52068827","span":{"begin":11652,"end":11655},"obj":"10905408"},{"id":"20480036-2400799-52068828","span":{"begin":15132,"end":15135},"obj":"2400799"},{"id":"20480036-2400799-52068829","span":{"begin":15702,"end":15705},"obj":"2400799"},{"id":"T74095","span":{"begin":687,"end":690},"obj":"12608425"},{"id":"T21119","span":{"begin":2144,"end":2147},"obj":"14580913"},{"id":"T84168","span":{"begin":3142,"end":3145},"obj":"14580913"},{"id":"T48066","span":{"begin":5561,"end":5564},"obj":"10503972"},{"id":"T79695","span":{"begin":6747,"end":6750},"obj":"8718939"},{"id":"T92529","span":{"begin":7700,"end":7703},"obj":"8718939"},{"id":"T4623","span":{"begin":7723,"end":7726},"obj":"14609674"},{"id":"T3465","span":{"begin":9113,"end":9116},"obj":"14609674"},{"id":"T33678","span":{"begin":11277,"end":11280},"obj":"1391401"},{"id":"T53136","span":{"begin":11277,"end":11280},"obj":"3427147"},{"id":"T53514","span":{"begin":11652,"end":11655},"obj":"10905408"},{"id":"T79240","span":{"begin":15132,"end":15135},"obj":"2400799"},{"id":"T75705","span":{"begin":15702,"end":15705},"obj":"2400799"}],"text":"3.4.5. TiN Coating\nIn spite of their high strength, low density, and good corrosion resistance, the usefulness of Ti alloys in general engineering components is frequently limited by their poor wear resistance. If the alloy surface is subjected to conditions of sliding or fretting, adhesive wear can rapidly lead to catastrophic failure unless appropriate surface engineering is carried out. In order to combat modest contact loads, several surface treatments are commercially available, such as plasma nitriding or PVD coating with TiN. Titanium nitride is known for its high surface hardness and mechanical strength. It was also reported that the dissolution of Ti ions is very low [225]. As for dental implants, they are comprised of various components. The implant abutment part (the mucosa penetration part) is exposed in the oral cavity, and so plaque and dental calculus easily adhere on it. Removal of the plaque and dental calculus is necessary to obtain a good prognosis throughout the long term maintenance of the implant. Based on this background, Kokubo et al. [226] prepared CpTi (grade 1) samples by polishing with #2000grit paper, or buff-polishing with 6 μm diamond emulsion paste, followed by a 0.1% HF acid solution for 10 s to clean the surface, then treated in N2 atmosphere of 1 atm at 850 °C for 7 h (N2 flow rate: 50 L/min). It was reported that (i) the nitrided layer about 2 μm thick composed of TiN and Ti2N was formed on Ti by a gas nitriding method, and the dissolved amount of Ti ion in SBF (simulated body fluid) was as low as the detectable limit of ICP-MS (Inductively Coupled Plasma Mass Spectroscopy), and that the 1% lactic acid showed no significant difference from Ti [226]. SBF, in genral, consists of Na+ (142.0), K+ (5.0), Mg2+ (1.5), Ca2+ (2.5), Cl−(148.8), HCO3− (4.2), HPO4− (1.0). H.P. Na (142.0), K (5.0), Mg (1.5), Ca (2.5), Cl (103.0), HCO3 (13.5), and HPO4 (1.0).\nSurface topography and chemistry have been shown to be extremely important in determining cell-substrate interactions and influencing cellular properties such as cell adhesion, cell-cell reactions, and cytoskeletal organization [227]. The cell-substrate interaction of primary hippocampal neurones with thin films of TiN was studied in vitro. TiN films of different surface chemistries and topographies were deposited by pulsed DC reactive magnetron sputtering and closed field unbalanced magnetron sputter ion plating to result in TiN thin films with similar surface chemistries, but different topographical features. It was reported that (i) primary hippocampal neurones were found to attach and spread to all of the TiN films, (ii) neuronal network morphology appeared to be more preferential on the nitrogen rich TiN films, and also reduced nanotopographical features, (iii) at early time points of one and four days in vitro primary hippocampal neurones respond to the presence of interstitial nitrogen rather than differences in nanotopography; however (iv) at seven days more preferential neutronal network morphology is formed on TiN thin films with lower roughness values and decreased size of topographical features [227]. Bull et al. [228] studied the use of thin titanium interlayers to promote the adhesion of TiN coatings on a range of substrates. For thin interlayers, an interstitially hardened titanium layer is formed at the interface, resisting the interfacial crack propagation. However, at a critical interlayer thickness, the surface contaminants are completely dissolved in the interfacial layer, and depositing any further titanium leads to an overall softer interfacial layer which offers less resistance to crack propagation, and delamination can easily take place. For this reason, failure is observed within the interlayer for thick interlayers, whereas it occurs at the interlayer/substrate interface for thinner interlayers. Another contribution to the enhanced adhesion comes from the reduction in coating stresses in the interfacial region due to the presence of a soft compliant layer, which was examined by changing the hardness of the interlayer deposited before coating deposition. It was concluded that (i) softer interlayers do not lead to improved adhesion performance in most cases, and (ii) it appears that the best adhesion results from a hard interlayer that leads to ductile failure at the coating/substrate interface, rather than the brittle failure observed due to the presence of oxide films [228].\nMechanical-electrochemical interactions accelerate corrosion in mixed-metal modular hip prostheses. These interactions can be reduced by improving the modular component machining tolerances or by improving the resistance of the components to scratch or fretting damage. Wrought Co-alloy (Co-Cr-Mo) is known to have better tribological properties compared to the Ti-6Al-4V alloy. Thus, improving the tribological properties of this mixed-metal interface should center on improving the tribological properties of Ti-6Al-4V. It was mentioned that (i) the nitrogen-diffusion-hardened Ti alloy samples had a more pronounced grain structure, more nodular surface, and significantly higher mean roughness values than the control Ti-6Al-4V, (ii) the nitrided Ti-6Al-4V samples also exhibited at least equivalent corrosion behavior and a definite increases in surface hardness compared to the control Ti-6Al-4V samples, and (iii) fretting can be reduced by decreasing micromotion or by improving the tribological properties (wear resistance and surface hardness) of the material components at this interface [229]. The corrosion behavior of the titanium nitride-coated TiNi alloy was examined in 0.9% NaCl solution by potentiodynamic polarization measurements and a polarization resistance method [230]. XPS spectra showed that the titanium nitride film consisted of three layers, a top layer of TiO2, a middle layer of TiNx (x \u003e 1), and an inner layer of TiN, which agreed very well with results obtained by Oshida et al. [231]. The passive current density for the titanium nitride-coated alloy was approximately two orders of magnitude lower than that of the polished alloy in the potential range from the free corrosion potential to +500 mV (vs. Ag/AgCl). Pitting corrosion associated with breakdown of the coated film occurred above this potential. The polarization resistance data also indicated that the corrosion rate of the titanium nitride-coated alloy at the corrosion potential (+50 to +100mV) was more than one order of magnitude lower than that for the polished alloy. It was concluded that the corrosion rate of TiNi alloy can be reduced by more than one order of magnitude by titanium nitride coating, unless the alloy is highly polarized anodically in vivo [230]. Bordji et al. [232] prepared Ti alloys treated by: (1) glow discharge nitrogen implantation (1017 atoms cm−2), (2) plasma nitriding by plasma diffusion treatment, and (3) deposition of TiN layer by plasma-assisted chemical vapour deposition additionally to plasma diffusion treatment. A considerable improvement was noticed in surface hardness, especially after the two nitriding processes. A cell culture model using human cells was chosen to study the effect of such treatments on the cytocompatibility. The results showed that Ti-5Al-2.5Fe alloy was as cytocompatible as the Ti-6Al-4V alloy, and the same surface treatment led to identical biological consequences on both alloys. It was concluded that (i) after the two nitriding treatments, cell proliferation and viability appeared to be significantly reduced and the SEM revealed somewhat irregular surface states; however (ii) osteoblast phenotype expression and protein synthesis capability were not affected [232]. Goldberg et al. [233] utilized the plasma vapor deposition technique, by which the samples were placed into a vacuum chamber and sputtered to remove the oxide film, followed by depositing a 200 nm thick interlayer of titanium to enhance the coating/substrate interface. Alternating layers of TiN and AlN were deposited until a coating thickness of approximately 5 μm was produced. The mechanical and electro-chemical behavior of the surface oxides of Co-Cr-Mo and Ti-6Al-4V alloys during fracture and repassivation play an important role in the corrosion of the taper interfaces of modular hip implants. These corrosion properties were investigated in one group of Co-Cr-Mo and Ti-6Al-4V alloy samples passivated with nitric acid and another group coated with TiN/AlN coating. It was found that (i) Co-Cr-Mo had a stronger surface oxide and higher interfacial adhesion strength, making it more resistant to fracture than Ti-6Al-4V, (ii) if undistributed, the oxide on the surface of Ti-6Al-4V significantly reduced dissolution currents at a wider range of potential than Co-Cr-Mo, making Ti-6Al-4V more resistant to corrosion, (iii) the TiN/AlN coating had higher hardness and modulus of elasticity than Co-Cr-Mo and Ti-6Al-4V. It was much less susceptible to fracture, had higher interfacial adhesion strength, and was a better barrier to ionic diffusion than the surface oxides on Co-Cr-Mo and Ti-6Al-4V [233].\nThe most of surface treatments such as plasma nitriding or PVD coating with TiN are, however, carried out in the solid state and the depth of coating or hardening is restricted by low diffusivity. The diffusion coefficient of nitrogen in Ti is more than a thousand times slower than that in steels due to different crystalline structures. The packing factor of Ti (HCP) is 74%, while that of steel (BCC) is 68%, so that steel has more spaces available for diffusing species. In order to achieve the depth of hardening necessary to withstand the subsurface Hertzian stresses induced by heavy rolling contact, it is necessary to alloy the Ti surface in the molten state. The necessary depth of surface hardening can readily be achieved in this way by laser melting the surface in the presence of interstitial alloying elements such as carbon, oxygen, and nitrogen. Of these, nitrogen has been found to provide the best balance between increased hardness and decreased ductility, and can easily be added by laser gas nitriding. The Hertzian compressive stress in the substrate was increased to 1.36 GPa [234]. Pure iron has allotropic phase transformations: the first one is 910 °C between α-BCC and γ-FCC, and the second one is 1,390 °C between γ-FCC and δ-BCC. While investigating the deformation mechanism of transformation superplastivity, Oshida observed that the transformation front behaves as if sime-liquid due to loosing a clear crystalline electorn diffraction pattern even both α-BCC and γ-FCC are still in solid state. Based on this finding, the “semi-liquid trans-formation front” model was proposed. One of various applications using transformation superplasticity is a nitridation of metallic materials if they have an allotropic phase transformation temperature. It was demonstrated that CpTi was succeesfully nitrided when CpTi was heated and cooled repeatedly passing the β-transus temperature (between 800 °C and 930 °C) for several times in nitrogen gas filled chamber [231]. Ion implantation, diffusion hardening, and coating are surface modification techniques for improving the wear resistance and surface hardness of Ti alloy surfaces [235–239]. A Ti-6Al-4V sample was diffusion-hardened in a nitrogen atmosphere for 8 h at 566 °C and argon or nitrogen quenched to room temperature. The nitrogen-diffusion-hardened Ti-6Al-4V had TiN and TiNO complexes at the immediate surface and sub-surface layers. The diffusion-hardened samples also had a deeper penetration of oxygen compared to regular Ti-6Al-4V samples [240].\nAs briefly described in the above, Oshida et al. [231,241] applied a TiN coating onto CpTi substrate prior to porcelain firing to develop a new method to control the excessive oxidation. The bonding strength of porcelain to metals depends on the oxide layer between the porcelain and the metal substrate. Oxidation of a metal surface increases the bonding strength, whereas excessive oxidation decreases it. Titanium suffers from its violent reactivity with oxygen at high temperatures that yield an excessively thick layer of TiO2, and this presents difficulties with porcelain bonding. The oxidation kinetics of titanium simulated to porcelain firing was investigated, and the surface nitridation of CpTi as a process of controlling the oxidation behavior was evaluated. Nitrided samples with the arc ion plating PVD process and un-nitrided control CpTi were subjected to oxidation simulating of Procera porcelain with 550, 700, and 800 °C firing temperatures for 10 min in both 1 and 0.1 atmospheric air. The weight difference before and after oxidation was calculated, and the parabolic rate constant, Kp (mg2/cm4/s), was plotted against inverse absolute temperature (i.e., in an Arrhenius plot). Surface layers of the samples were subjected to x-ray and electron diffraction techniques for phase identifications. Results revealed that both nitrided and un-nitrided samples obey a parabolic rate law with activation energy of 50 kcal/mol. In addition, the study shows that nitrided CpTi had a Kp about 5 times lower than the un-nitrided CpTi, and hence the former needs 2.24 times longer oxidation time to show the same degree of oxidation. Phase identification resulted in confirming the presence of TiO2 as the oxide film in both groups, but with 1–2 μm thickness for the un-nitrided CpTi and 0.3–0.5 μm thickness for nitrided samples. Therefore, it can be concluded that nitridation of titanium surfaces can be effective in controlling the surface oxide thickness that might ensure satisfactory bonding with porcelain [231]. Oshida et al. [241] evaluated CpTi substrates subjected to porcelain firing and bond strengths under three-point bending mode (span length: 15mm; crosshead speed: 0.5 mm/min). Experimental variables included surface treatments of CpTi and porcelain firing schedules. Variables for the surface treatments were: (1) sandblasting, (2) mono- and triple-layered nitridation, and (3) mono-layered chrome-doped nitridation. Variables for the porcelain firing schedule included (4) bonding agent application, (5) bonding agent plus gold bonding agent application, and (6) Procera porcelain application. Statistically, all of them exhibited no significant differences. Hence, we employed two further criteria: (i) the minimum bond strength should exceed the maximum porcelain strength per se, and (ii) the CpTi substrate should not be heated close to the beta-transus temperature. After applying these criteria, it was concluded that mono-layered nitridation and mono-layered application of chrome-doped nitridation on both (with and without) sand-blasted and non-sand-blasted surfaces were the most promising conditions for a successful titanium-porcelain system [241]. It seems that an alloy which has the properties of titanium and is relatively inexpensive would be a very good material for surgical purposes. These requirements could be met, for example, by stainless steel coated with a firmly adhering non-porous titanium film. Głuszek et al. [242] coated 316L (18Cr-8Ni-2Mo with low carbon content) stainless steel with Ti or TiN by ion plating. The galvanic effects for the galvanic couples 316L/Ti, 316L/Ti-coated 316L, 316L/TiN-coated 316L were studied in Ringer’s solution. It was concluded that (i) both Ti and TiN coatings were non-porous, (ii) Ti served as an anode in the couple 316L/Ti, whereas for the other two couples, the coatings were the cathodes; however (iii) the dissolution rate of 316L stainless steel in these couples was smaller than expected owing to a strong polarization of the coatings [242].\nFor hip prostheses, the coupling between the metallic femoral head and the polymeric acetabular cup is normally used. Biotribiological phenomena contribute principally to the clinical failure of the prosthesis. In the metal-polymer coupling, the problems consist of biotribological wear, creep of the UHMWPE (ultra high molecular weight polyethylene), and fretting corrosion of the metal femoral head. Cyclic stress exceeding the fatigue resistance of UHMWPE produces surface microcracks and particulates that can migrate into the tissue of the host implant. This fretting-wear debris causes local irritation, proliferation of fibrous tissue, and necrosis of bone. Minimizing the wear is critically important for maintaining the long life of the femoral prosthesis. On the other hand, titanium alloys are susceptible to fretting corrosion; this susceptibility can be reduced via surface treatments. UHMWPE was gamma-ray sterilized. This sterilization technique results in a cross-linking of the polymer, which enhances its wear resistance. Tribio-logical behavior of N2-implanted and nonimplanted titanium alloys coupled with UHMWPE were studied using pin-on-flat tests, according to ASTM F 732-82 in bovine serum. The results show that while the non-implanted titanium alloy and the titanium with N2 on UHMWPE resulted in high final wear values, titanium implanted with O2 generates a wear value less than that obtained for polyethylene against 316L stainless steel. Ti-6Al-4V implanted with chromium exhibited the lowest wear. Hardness values of the implanted material corresponded to the wear rates, which assist in determining optimal elements for implantation. Implantation of certain elements may increase the surface activity, resulting in more adherent oxide layers that also increase wettability [100]."}

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TiN Coating\nIn spite of their high strength, low density, and good corrosion resistance, the usefulness of Ti alloys in general engineering components is frequently limited by their poor wear resistance. If the alloy surface is subjected to conditions of sliding or fretting, adhesive wear can rapidly lead to catastrophic failure unless appropriate surface engineering is carried out. In order to combat modest contact loads, several surface treatments are commercially available, such as plasma nitriding or PVD coating with TiN. Titanium nitride is known for its high surface hardness and mechanical strength. It was also reported that the dissolution of Ti ions is very low [225]. As for dental implants, they are comprised of various components. The implant abutment part (the mucosa penetration part) is exposed in the oral cavity, and so plaque and dental calculus easily adhere on it. Removal of the plaque and dental calculus is necessary to obtain a good prognosis throughout the long term maintenance of the implant. Based on this background, Kokubo et al. [226] prepared CpTi (grade 1) samples by polishing with #2000grit paper, or buff-polishing with 6 μm diamond emulsion paste, followed by a 0.1% HF acid solution for 10 s to clean the surface, then treated in N2 atmosphere of 1 atm at 850 °C for 7 h (N2 flow rate: 50 L/min). It was reported that (i) the nitrided layer about 2 μm thick composed of TiN and Ti2N was formed on Ti by a gas nitriding method, and the dissolved amount of Ti ion in SBF (simulated body fluid) was as low as the detectable limit of ICP-MS (Inductively Coupled Plasma Mass Spectroscopy), and that the 1% lactic acid showed no significant difference from Ti [226]. SBF, in genral, consists of Na+ (142.0), K+ (5.0), Mg2+ (1.5), Ca2+ (2.5), Cl−(148.8), HCO3− (4.2), HPO4− (1.0). H.P. Na (142.0), K (5.0), Mg (1.5), Ca (2.5), Cl (103.0), HCO3 (13.5), and HPO4 (1.0).\nSurface topography and chemistry have been shown to be extremely important in determining cell-substrate interactions and influencing cellular properties such as cell adhesion, cell-cell reactions, and cytoskeletal organization [227]. The cell-substrate interaction of primary hippocampal neurones with thin films of TiN was studied in vitro. TiN films of different surface chemistries and topographies were deposited by pulsed DC reactive magnetron sputtering and closed field unbalanced magnetron sputter ion plating to result in TiN thin films with similar surface chemistries, but different topographical features. It was reported that (i) primary hippocampal neurones were found to attach and spread to all of the TiN films, (ii) neuronal network morphology appeared to be more preferential on the nitrogen rich TiN films, and also reduced nanotopographical features, (iii) at early time points of one and four days in vitro primary hippocampal neurones respond to the presence of interstitial nitrogen rather than differences in nanotopography; however (iv) at seven days more preferential neutronal network morphology is formed on TiN thin films with lower roughness values and decreased size of topographical features [227]. Bull et al. [228] studied the use of thin titanium interlayers to promote the adhesion of TiN coatings on a range of substrates. For thin interlayers, an interstitially hardened titanium layer is formed at the interface, resisting the interfacial crack propagation. However, at a critical interlayer thickness, the surface contaminants are completely dissolved in the interfacial layer, and depositing any further titanium leads to an overall softer interfacial layer which offers less resistance to crack propagation, and delamination can easily take place. For this reason, failure is observed within the interlayer for thick interlayers, whereas it occurs at the interlayer/substrate interface for thinner interlayers. Another contribution to the enhanced adhesion comes from the reduction in coating stresses in the interfacial region due to the presence of a soft compliant layer, which was examined by changing the hardness of the interlayer deposited before coating deposition. It was concluded that (i) softer interlayers do not lead to improved adhesion performance in most cases, and (ii) it appears that the best adhesion results from a hard interlayer that leads to ductile failure at the coating/substrate interface, rather than the brittle failure observed due to the presence of oxide films [228].\nMechanical-electrochemical interactions accelerate corrosion in mixed-metal modular hip prostheses. These interactions can be reduced by improving the modular component machining tolerances or by improving the resistance of the components to scratch or fretting damage. Wrought Co-alloy (Co-Cr-Mo) is known to have better tribological properties compared to the Ti-6Al-4V alloy. Thus, improving the tribological properties of this mixed-metal interface should center on improving the tribological properties of Ti-6Al-4V. It was mentioned that (i) the nitrogen-diffusion-hardened Ti alloy samples had a more pronounced grain structure, more nodular surface, and significantly higher mean roughness values than the control Ti-6Al-4V, (ii) the nitrided Ti-6Al-4V samples also exhibited at least equivalent corrosion behavior and a definite increases in surface hardness compared to the control Ti-6Al-4V samples, and (iii) fretting can be reduced by decreasing micromotion or by improving the tribological properties (wear resistance and surface hardness) of the material components at this interface [229]. The corrosion behavior of the titanium nitride-coated TiNi alloy was examined in 0.9% NaCl solution by potentiodynamic polarization measurements and a polarization resistance method [230]. XPS spectra showed that the titanium nitride film consisted of three layers, a top layer of TiO2, a middle layer of TiNx (x \u003e 1), and an inner layer of TiN, which agreed very well with results obtained by Oshida et al. [231]. The passive current density for the titanium nitride-coated alloy was approximately two orders of magnitude lower than that of the polished alloy in the potential range from the free corrosion potential to +500 mV (vs. Ag/AgCl). Pitting corrosion associated with breakdown of the coated film occurred above this potential. The polarization resistance data also indicated that the corrosion rate of the titanium nitride-coated alloy at the corrosion potential (+50 to +100mV) was more than one order of magnitude lower than that for the polished alloy. It was concluded that the corrosion rate of TiNi alloy can be reduced by more than one order of magnitude by titanium nitride coating, unless the alloy is highly polarized anodically in vivo [230]. Bordji et al. [232] prepared Ti alloys treated by: (1) glow discharge nitrogen implantation (1017 atoms cm−2), (2) plasma nitriding by plasma diffusion treatment, and (3) deposition of TiN layer by plasma-assisted chemical vapour deposition additionally to plasma diffusion treatment. A considerable improvement was noticed in surface hardness, especially after the two nitriding processes. A cell culture model using human cells was chosen to study the effect of such treatments on the cytocompatibility. The results showed that Ti-5Al-2.5Fe alloy was as cytocompatible as the Ti-6Al-4V alloy, and the same surface treatment led to identical biological consequences on both alloys. It was concluded that (i) after the two nitriding treatments, cell proliferation and viability appeared to be significantly reduced and the SEM revealed somewhat irregular surface states; however (ii) osteoblast phenotype expression and protein synthesis capability were not affected [232]. Goldberg et al. [233] utilized the plasma vapor deposition technique, by which the samples were placed into a vacuum chamber and sputtered to remove the oxide film, followed by depositing a 200 nm thick interlayer of titanium to enhance the coating/substrate interface. Alternating layers of TiN and AlN were deposited until a coating thickness of approximately 5 μm was produced. The mechanical and electro-chemical behavior of the surface oxides of Co-Cr-Mo and Ti-6Al-4V alloys during fracture and repassivation play an important role in the corrosion of the taper interfaces of modular hip implants. These corrosion properties were investigated in one group of Co-Cr-Mo and Ti-6Al-4V alloy samples passivated with nitric acid and another group coated with TiN/AlN coating. It was found that (i) Co-Cr-Mo had a stronger surface oxide and higher interfacial adhesion strength, making it more resistant to fracture than Ti-6Al-4V, (ii) if undistributed, the oxide on the surface of Ti-6Al-4V significantly reduced dissolution currents at a wider range of potential than Co-Cr-Mo, making Ti-6Al-4V more resistant to corrosion, (iii) the TiN/AlN coating had higher hardness and modulus of elasticity than Co-Cr-Mo and Ti-6Al-4V. It was much less susceptible to fracture, had higher interfacial adhesion strength, and was a better barrier to ionic diffusion than the surface oxides on Co-Cr-Mo and Ti-6Al-4V [233].\nThe most of surface treatments such as plasma nitriding or PVD coating with TiN are, however, carried out in the solid state and the depth of coating or hardening is restricted by low diffusivity. The diffusion coefficient of nitrogen in Ti is more than a thousand times slower than that in steels due to different crystalline structures. The packing factor of Ti (HCP) is 74%, while that of steel (BCC) is 68%, so that steel has more spaces available for diffusing species. In order to achieve the depth of hardening necessary to withstand the subsurface Hertzian stresses induced by heavy rolling contact, it is necessary to alloy the Ti surface in the molten state. The necessary depth of surface hardening can readily be achieved in this way by laser melting the surface in the presence of interstitial alloying elements such as carbon, oxygen, and nitrogen. Of these, nitrogen has been found to provide the best balance between increased hardness and decreased ductility, and can easily be added by laser gas nitriding. The Hertzian compressive stress in the substrate was increased to 1.36 GPa [234]. Pure iron has allotropic phase transformations: the first one is 910 °C between α-BCC and γ-FCC, and the second one is 1,390 °C between γ-FCC and δ-BCC. While investigating the deformation mechanism of transformation superplastivity, Oshida observed that the transformation front behaves as if sime-liquid due to loosing a clear crystalline electorn diffraction pattern even both α-BCC and γ-FCC are still in solid state. Based on this finding, the “semi-liquid trans-formation front” model was proposed. One of various applications using transformation superplasticity is a nitridation of metallic materials if they have an allotropic phase transformation temperature. It was demonstrated that CpTi was succeesfully nitrided when CpTi was heated and cooled repeatedly passing the β-transus temperature (between 800 °C and 930 °C) for several times in nitrogen gas filled chamber [231]. Ion implantation, diffusion hardening, and coating are surface modification techniques for improving the wear resistance and surface hardness of Ti alloy surfaces [235–239]. A Ti-6Al-4V sample was diffusion-hardened in a nitrogen atmosphere for 8 h at 566 °C and argon or nitrogen quenched to room temperature. The nitrogen-diffusion-hardened Ti-6Al-4V had TiN and TiNO complexes at the immediate surface and sub-surface layers. The diffusion-hardened samples also had a deeper penetration of oxygen compared to regular Ti-6Al-4V samples [240].\nAs briefly described in the above, Oshida et al. [231,241] applied a TiN coating onto CpTi substrate prior to porcelain firing to develop a new method to control the excessive oxidation. The bonding strength of porcelain to metals depends on the oxide layer between the porcelain and the metal substrate. Oxidation of a metal surface increases the bonding strength, whereas excessive oxidation decreases it. Titanium suffers from its violent reactivity with oxygen at high temperatures that yield an excessively thick layer of TiO2, and this presents difficulties with porcelain bonding. The oxidation kinetics of titanium simulated to porcelain firing was investigated, and the surface nitridation of CpTi as a process of controlling the oxidation behavior was evaluated. Nitrided samples with the arc ion plating PVD process and un-nitrided control CpTi were subjected to oxidation simulating of Procera porcelain with 550, 700, and 800 °C firing temperatures for 10 min in both 1 and 0.1 atmospheric air. The weight difference before and after oxidation was calculated, and the parabolic rate constant, Kp (mg2/cm4/s), was plotted against inverse absolute temperature (i.e., in an Arrhenius plot). Surface layers of the samples were subjected to x-ray and electron diffraction techniques for phase identifications. Results revealed that both nitrided and un-nitrided samples obey a parabolic rate law with activation energy of 50 kcal/mol. In addition, the study shows that nitrided CpTi had a Kp about 5 times lower than the un-nitrided CpTi, and hence the former needs 2.24 times longer oxidation time to show the same degree of oxidation. Phase identification resulted in confirming the presence of TiO2 as the oxide film in both groups, but with 1–2 μm thickness for the un-nitrided CpTi and 0.3–0.5 μm thickness for nitrided samples. Therefore, it can be concluded that nitridation of titanium surfaces can be effective in controlling the surface oxide thickness that might ensure satisfactory bonding with porcelain [231]. Oshida et al. [241] evaluated CpTi substrates subjected to porcelain firing and bond strengths under three-point bending mode (span length: 15mm; crosshead speed: 0.5 mm/min). Experimental variables included surface treatments of CpTi and porcelain firing schedules. Variables for the surface treatments were: (1) sandblasting, (2) mono- and triple-layered nitridation, and (3) mono-layered chrome-doped nitridation. Variables for the porcelain firing schedule included (4) bonding agent application, (5) bonding agent plus gold bonding agent application, and (6) Procera porcelain application. Statistically, all of them exhibited no significant differences. Hence, we employed two further criteria: (i) the minimum bond strength should exceed the maximum porcelain strength per se, and (ii) the CpTi substrate should not be heated close to the beta-transus temperature. After applying these criteria, it was concluded that mono-layered nitridation and mono-layered application of chrome-doped nitridation on both (with and without) sand-blasted and non-sand-blasted surfaces were the most promising conditions for a successful titanium-porcelain system [241]. It seems that an alloy which has the properties of titanium and is relatively inexpensive would be a very good material for surgical purposes. These requirements could be met, for example, by stainless steel coated with a firmly adhering non-porous titanium film. Głuszek et al. [242] coated 316L (18Cr-8Ni-2Mo with low carbon content) stainless steel with Ti or TiN by ion plating. The galvanic effects for the galvanic couples 316L/Ti, 316L/Ti-coated 316L, 316L/TiN-coated 316L were studied in Ringer’s solution. It was concluded that (i) both Ti and TiN coatings were non-porous, (ii) Ti served as an anode in the couple 316L/Ti, whereas for the other two couples, the coatings were the cathodes; however (iii) the dissolution rate of 316L stainless steel in these couples was smaller than expected owing to a strong polarization of the coatings [242].\nFor hip prostheses, the coupling between the metallic femoral head and the polymeric acetabular cup is normally used. Biotribiological phenomena contribute principally to the clinical failure of the prosthesis. In the metal-polymer coupling, the problems consist of biotribological wear, creep of the UHMWPE (ultra high molecular weight polyethylene), and fretting corrosion of the metal femoral head. Cyclic stress exceeding the fatigue resistance of UHMWPE produces surface microcracks and particulates that can migrate into the tissue of the host implant. This fretting-wear debris causes local irritation, proliferation of fibrous tissue, and necrosis of bone. Minimizing the wear is critically important for maintaining the long life of the femoral prosthesis. On the other hand, titanium alloys are susceptible to fretting corrosion; this susceptibility can be reduced via surface treatments. UHMWPE was gamma-ray sterilized. This sterilization technique results in a cross-linking of the polymer, which enhances its wear resistance. Tribio-logical behavior of N2-implanted and nonimplanted titanium alloys coupled with UHMWPE were studied using pin-on-flat tests, according to ASTM F 732-82 in bovine serum. The results show that while the non-implanted titanium alloy and the titanium with N2 on UHMWPE resulted in high final wear values, titanium implanted with O2 generates a wear value less than that obtained for polyethylene against 316L stainless steel. Ti-6Al-4V implanted with chromium exhibited the lowest wear. Hardness values of the implanted material corresponded to the wear rates, which assist in determining optimal elements for implantation. Implantation of certain elements may increase the surface activity, resulting in more adherent oxide layers that also increase wettability [100]."}