Influence of thermal annealing on the microstructure,hardness and corrosion behavior of TiAlSiCuN nanocomposite films

Nanocomposite TiAlSiCuN films were deposited on high speed steels by filtered magnetic arc ion plating. Detailed properties of the films annealed at various temperatures are studied. After thermal annealing at different temperatures ranging from 400 to 800 °C, changes in the film micro‐structure, chemical and phase composition, surface morphology, hardness and polarization curve properties were systematically characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, scanning electron microscopy, nano‐indenter and electrochemical workstation, respectively. It was found that the TiAlSiCuN films could be fully oxidized at 800 °C, Al and Ti atoms all diffused outwards and formed dense protective Al₂O₃ and TiO₂ layer. Simultaneously, the TiAlN phase gradually disappeared. The films annealed at 400 °C obtained the highest hardness because of the certain grain growth and little generated oxides. Besides, the certain formation of dense protective Al₂O₃ layer made the TiAlSiCuN film annealed at 600 °C present the least corrosion current density and the corrosion voltage. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of cyclic oxidation on electrochemical corrosion of type 409 stainless steel in the simulated muffler condensates

The electrochemical corrosion behavior of 409 stainless steel after cyclic oxidation below 400 °C was investigated in the simulated muffler condensates by using surface analysis and electrochemical measurement techniques. In the cyclic processes of condensate-dipping and oxidation, specimens may form defective oxide films and weak Cr depletion underlying the oxide films. Sulfate from the condensate-dipping will give rise to sulfidation during the cyclic oxidation, being detrimental to both the oxidation and corrosion properties of stainless steel. The oxidation above 300 °C deteriorates the corrosion resistance, even leading to active corrosion in the acidic condensate solutions. Comparatively, specimens oxidized cyclically without condensate-dipping show much higher condensate corrosion resistance. It is suggested that the acidic condensate corrosion is accelerated by the synergetic effect of oxidation and condensation in the mufflers, and then may result in perforation through the defects such as cracks and nodules in oxide films on the stainless steel surface.     

Investigation of Ti/CuO interface by X-ray photoelectron spectroscopy and atomic force microscopy

The Ti/CuO interface has been studied by the techniques of X-ray photoelectron spectroscopy and atomic force microscopy. Thin films of titanium were deposited on a CuO substrate at room temperature by the e-beam technique. The photoelectron spectra of titanium and copper were found to exhibit significant chemical interaction at the interface. The titanium overlayer was observed to get oxidized to TiO₂, while the CuO was observed to get reduced to elemental copper. This chemical interaction was observed to occur until a thickness of 7 nm of the titanium overlayer. For thicknesses greater than this value, the presence of unreacted titanium in the sample was detected. Barrier characteristics at the Ti/CuO interface were also carried out for substrate temperatures of 300°C, 400°C, 500°C, and 600°C as a function of the titanium overlayer thickness. A linear trend in the barrier thickness of the overlayer was observed between 400°C and 600°C substrate temperatures. The atomic force microscopy micrographs of the unannealed samples depicted layer-by-layer growth of elemental titanium on copper. At the Ti/CuO interface in such samples, the micrographs exhibited island formation of TiO₂ corresponding to the Volmer-Weber growth model. This formation has been interpreted as the relaxation in the strain energy. The percentage coverage of the underlying substrate by the TiO₂ islands showed a linear trend for the thicknesses of the titanium overlayer investigated. The average size of these islands also showed a linear trend as a function of the thickness of the overlayer.     

Characterisation and properties of magnetron sputtered nanoscale bi‐layered Ni/Ti thin films and effect of annealing

Single‐bi‐layer of Ni–Ti thin film was deposited using DC and RF magnetron sputtering technique by layer‐wise deposition of Ni and Ti on Si(100) substrate in the order of Ni as the bottom layer and Ti as the top layer. The deposition of these amorphous as‐deposited thin films was followed by annealing at 300 °C, 400 °C, 500 °C, and 600 °C temperature with 1‐h annealing time for each to achieve crystalline thin films. This paper describes the fabrication processes and the novel characterization techniques of the as‐deposited as well as the annealed thin films. Microstructures were analysed using FESEM and HRTEM. Nano‐indentation and AFM were carried out to characterize the mechanical properties and surface profiles of the films. It was found that, for the annealing temperatures of 300 °C to 600 °C, the increase in annealing temperature resulted in gradual increase in atomic‐cluster coarsening with improved ad‐atom mobility. Phase analyses, performed by GIXRD, showed the development of silicide phases and intermetallic compounds. Cross‐sectional micrographs exhibited the inter‐diffusion between the two‐layer constituents, especially at higher temperatures, which resulted either in amorphization or in crystallization after annealing at temperatures above 400 °C. Copyright © 2015 John Wiley & Sons, Ltd.     

Surface characteristics of Ti‐10Ta‐10Nb alloy modified by hydrogen peroxide treatment for dental implants

The use of titanium‐based alloys as biomaterials is becoming more common because they have a reduced elastic modulus, superior biocompatibility, specific strength, good corrosion resistance, superior strain control, and fatigue resistance compared to conventional stainless steel and Co? Cr alloys. However, when implanted into the human body these metals are problematic because they do not directly bond with living bone. Surface treatments play an important role in nucleating calcium phosphate deposition on a surgical titanium alloy implant. The purpose of this study is to examine whether the precipitation of apatite on Ti? 10Ta? 10Nb alloy is affected by surface modification in H₂O₂ solution. Specimens were chemically treated with a solution containing 30 wt% H₂O₂ at 80 °C for 1 h, and subsequently heat treated at 400 °C for 1 h. All specimens were immersed in SBF (Simulated Body Fluid) with a pH of 7.4 at 36.5 °C for seven days, and the surfaces were examined with XRD, SEM, EDX and in vitro testing. The microstructure analysis of the Ti? 10Ta? 10Nb alloy after etching with Keller's etchant showed a Widmanstatten pattern. The micro‐Vickers hardness number was 236.44 ± 4.99, and surface roughness was increased by the surface treatment. The wettability after surface treatment was better than on the nontreated surface. Resistance to cytotoxicity was decreased by the chemical surface treatment (P < 0.05). Copyright © 2011 John Wiley & Sons, Ltd.     

Sputter‐deposited Ni/Ti double‐bilayer thin film and the effect of intermetallics during annealing

In the present study, a double bilayer of a Ni/Ti thin film was investigated. A nanoscale NiTi thin film is deposited in a Ni–Ti–Ni–Ti manner to form a double‐bilayer structure on a Si(100) substrate. Ni and Ti depositions were carried out by using d.c. and r.f. power, respectively, in a magnetron sputtering chamber. Four types of bilayers are formed by varying the deposition time of each layer (i.e. 15, 20, 25, and 30 min). The as‐deposited amorphous thin films were annealed at 300, 400, 500, and 600 °C for 1 h to achieve the diffusion in between the layers. Microstructures were analyzed using field‐emission scanning electron microscope and high‐resolution transmission electron microscope. It was found that, with the increase in annealing temperature from 300 to 600 °C, the diffusion at the interface and atomic migration on the surface increase. Cross‐sectional micrographs exhibited the interdiffusion between the two‐layer constituents, especially at higher temperatures, which resulted in diffusion patches along the interface. Phase analyses, performed by grazing incidence X‐ray diffraction, showed the formation of intermetallic compounds with some silicide phases that enhance the mechanical properties. Nanoindentation and atomic force microscopy were carried out to know the mechanical properties and surface profiles of the films. The surface finish is better at higher annealing temperatures. It was found that for annealing temperatures varying from 300 to 600 °C, the increase in annealing temperature resulted in a gradual increase in atomic‐cluster coarsening with improved adatom mobility. Copyright © 2016 John Wiley & Sons, Ltd.     

A concomitant use of some radioanalytical and metallurgical methods: Application to the study of the thermal oxidation of titanium

Polycrystalline titanium samples were oxidized in pure oxygen under a 75 torr pressure, at temperatures ranging from 400°C to 500°C, and for times up to 2 hrs. A similar treatment was applied to some single crystal samples, so as to show the relationship between the crystallite orientation and the oxidation rate. The oxide films were studied by means of radioanalytical techniques, such as nuclear microanalysis, electron diffraction and ESCA, in addition to most classical techniques such as optical and electron microscopy. The complementary side of these methods is showed. They permit us to determine the contamination of the metallic surface introduced by the polishing treatments, the oxidation rate at constant temperature, and the structure of the oxides which exists in the films. These ones are especially TiO₂, Ti₃O₅, Ti₂O₃ and TiO.     

High-k titanium–aluminum oxide dielectric films prepared by inorganic–organic hybrid solution

In this paper, high-k titanium–aluminum oxide (ATO) dielectric film has been realized by using organic–inorganic hybrid precursor solution. X-ray diffraction pattern revealed that the ATO films (Ti content less than 67 at%) remain amorphous phase for annealing treatment at 400 °C. And all of the amorphous ATO films had very smooth and uniform surface with root mean square (RMS) roughness of less than 0.5 nm. Meanwhile, the results showed that the ATO film (Ti:Al = 1:8) had the best performance, including RMS roughness of 0.33 nm, relative permittivity of 15, and leakage current density of 1.41 × 10^?6 A/cm² at 1 MV/cm.     

Electropolishing of pure metallic titanium in a deep eutectic solvent

This work presents a facile and efficient electropolishing of metallic titanium (Ti) in the relatively eco-friendly electrolyte of deep eutectic solvent (DES) using a mixture of choline chloride-propylene glycol (1 mol ChCl: 2 mol PG). The electropolishing process of metallic titanium was performed under potentiostatic condition (10 V for 40 min) at room temperature. Surface topography and morphology were investigated using scanning electron microscope (SEM) and atomic force microscopy (AFM). The promising electropolishing provides a shiny and mirror-like surface with an average surface roughness (Ra) of 37.92 nm from the parent metallic Ti with a roughness of 455.60 nm. The surface passivation after electropolishing is of the most likely acceptable mechanism for removing microscope roughness. The proposed electropolishing in the present DES electrolyte is a promising strategy for making mirror-like surface (surface resistive against corrosion) of biomedical metallic titanium.     

Effect of TiO2–Ti and TiO2–TiN composite coatings on corrosion behavior of NiTi alloy

Two kinds of biocompatible coatings were produced in order to improve the corrosion resistance of nickel titanium (NiTi) alloy. A titanium oxide–titanium (TiO₂–Ti) composite was coated on NiTi alloy using electrophoretic method. After the coating process, the samples were heat‐treated at 1000 °C in two tube furnaces, the first one in argon atmosphere and the second one in nitrogen atmosphere at 1000 °C. The morphology and phase analysis of coatings were investigated using scanning electron microscopy and X‐ray diffraction analysis, respectively. The electrochemical behavior of the NiTi and coated samples was examined using polarization and electrochemical impedance spectroscopy tests. Electrochemical tests in simulated body fluid demonstrated a considerable increase in corrosion resistance of composite‐coated NiTi specimens compared to the non‐coated one. The heat‐treated composite coating sample in nitrogen atmosphere had a higher level of corrosion resistance compared to the heat‐treated sample in argon atmosphere, which is mainly due to having nitride phases. Copyright © 2014 John Wiley & Sons, Ltd.     

Synergetic effect of sol–gel silica coating and physical/chemical pre-treatment on the oxidation behavior of Ti-6Al-4V alloy

The Ti-6Al-4V alloy was treated in concentrated phosphoric acid solution and by powder blasting, respectively, subsequently coated by silica using sol–gel dip-coating technique. A barrier layer of titanium pyrophosphate (TiP₂O₇) was synthesized at the Ti-6Al-4V substrate surface after the heat treatment. XRD and SEM/EDS analysis revealed that an amorphous silica coating was formed on the alloy. The isothermal and cyclic oxidation behavior of the treated alloy with silica coating and the corresponding bare alloy was investigated at 600 °C in static air to investigate the synergetic effect of the SiO₂ coating and surface treatment on the oxidation resistance of the alloy by thermogravimetry. The average parabolic rate constants of the treated specimens with silica coating were greatly reduced. The stratified oxide layer formed on the bare alloy, while thinner oxide layer formed on the treated alloys with silica coating. The oxidation resistance of the present alloy was improved. The effect of silica coating on the microhardness of the substrate was investigated.     

Surface characteristics of titanium–silver alloys in artificial saliva

Titanium and its alloys are widely used in biomedical and dental fields because of their excellent corrosion resistance and biocompatibility. It is well known that titanium is protected from corrosion because of the stability of the passive film that controls and determines the corrosion resistance and biocompatibility of titanium and its alloys. The purpose of this study was to evaluate the electrochemical properties of titanium–silver alloys and the surface characteristics of passive film in artificial saliva. We designed titanium–silver alloys with silver contents ranging from 0 to 5 at.%, in 1% increments. These alloys were arc‐melted, homogenized, hot‐rolled to 2 mm thickness, and finally solution heat‐treated for 1 h and quenched. Potentiostatic testing was performed, and the open circuit potentials of the alloys were measured in artificial saliva, at 37 °C. The passive films of the titanium–silver alloys were analyzed via XPS. Titanium–silver alloys maintained low current density and showed stable passive region and also had high open circuit potential as compared with pure titanium. The open circuit potential of titanium–silver alloys increased as silver addition increased. With regard to the fraction of oxygen species, a component of over 80% was found to be comprised of oxide. Therefore, the titanium surface mainly consisted of titanium oxide and, on the titanium–silver alloys, this film was composed of TiO₂, Ti₂O₃, and TiO. As silver content increased, the TiO₂ fraction also increased, as did the thickness of the titanium oxide layer formed. Copyright © 2005 John Wiley & Sons, Ltd.     

Preparation of nano and microcrystals of silver using titania xerogel matrix as template

Ag-doped TiO₂ wet gels were prepared by sol?Cgel process using a mixture of titanium isopropoxide and silver nitrate as precursor solution, with Ag:Ti molar ratio of 1:6. After drying, the titanium oxide xerogels were used as template in the preparation of nano and microcrystals of metallic silver. The porous network and the structure of the titania matrix influenced the type and distribution of silver crystal produced on the composite surface. Silver nanoparticles segregated to the surface of titania xerogel during the heating step, giving rise to nanocrystals that coalesced forming microcrystals with different shapes and faceting. The microcrystals grew on the composite surface, reaching sizes between 5 and 20 microns and self-organized of different ways. The xerogel heated at 600 °C formed by anatase, rutile and silver nanoparticles exhibited considerable photocatalytic activity to degrade methylene blue.     

Photocatalytic,phosphorus-doped,anatase oxide layers applicable to titanium implant alloys

Titanium alloys provide excellent corrosion resistance and favorable mechanical properties well suited for a variety of biomaterial applications. The native oxide surface on titanium alloys has been shown to be less than ideal and surface modification is often needed. Previously, an optimized anodization process was shown to form a porous phosphorus-enhanced anatase oxide layer on commercially pure Ti grade 4. The anodized layer was shown to improve osseointegration and to reduce bacteria attachment when photocatalytically activated with UVA preillumination. The primary objective of the present study was to create a similar phosphorus-enhanced anatase oxide layer on series of titanium alloys including commercially pure Ti grade 4, Ti-6Al-7Nb, Ti-6Al-4V ELI, alpha + beta Ti-15Mo, beta Ti-15Mo, and Ti-35Nb-7Zr-5Ta. Phosphorus-enhanced anatase oxide layers were formed on each titanium substrate. Anatase formation was shown to generally increase with oxide thickness, except on substrate alloys containing niobium. Phosphorus uptake was shown to be dependent on the titanium alloy chemistry or microstructure. Anodized layers formed on beta-structured titanium alloys revealed the lowest phosphorus uptake and the most nanosized surface porosity. A methylene blue degradation assay showed anodized layers on commercially pure Ti and both Ti-15Mo alloys to exhibit the highest levels of photocatalytic activity. Given the range of mechanical properties available with the commercially pure Ti and Ti-15Mo alloys, the results of this study indicate the benefits of phosphorus-enhanced anatase oxide coatings may be applicable to a wide variety of biomaterial applications.     

Post‐oxidizing effects on surface characteristics of salt bath nitrocarburized AISI 02 tool steel type

The effect of post‐oxidizing treatment on the characteristics of modified surface layers produced by salt bath nitrocarburizing on the industrial American Iron and Steel Institute (AISI) 02 tool steel types is investigated. Nitrocarburizing treatment is performed for 6 h and 8 h at 570 °C and post‐oxidizing treatment for 30, 60 and 90 min at 520 °C, using argon–steam mixture. Formed layers are characterized by their basic properties such as thickness layer, depth, surface hardness and wear resistance. Detailed estimation of the modified metal surface quality, in terms of chemical composition, formed phases, microstructures and diffusion mechanisms are performed by metallographic techniques, EDX, X‐ray diffraction, scanning electron microscopy (SEM) and glow discharge optical electron spectroscopy (GDOES). The corrosion resistance was investigated in 0.4 M H₂SO₄ solutions, using steady‐state electrochemical polarization methods. The obtained results revealed the existence of a superficial oxide layer which consists of magnetite (Fe₃O₄) and hematite (Fe₂O₃) and the presence of an ε‐phase associated with a small amount of γ′‐phase. Important improvements in wear, microhardness and corrosion resistance occur after these treatments and it is specifically concluded that the sole application of a nitrocarburizing treatment does not significantly ameliorate the corrosion resistance of the as‐received steel. In fact, post‐oxidation treatment contributes to increase corrosion resistance by forming a dense magnetite layer and at the same time, it partially covers the compound layer pores. Copyright © 2009 John Wiley & Sons, Ltd.     

Oxidation stability of various Ti-alloys

Since titanium metal first became a commercial reality in 1950, corrosion resistance has been an important consideration in its selection as an engineering structural material. Titanium has gained acceptance in many media where its corrosion resistance and engineering properties have provided the corrosion and design engineer with a reliable and economic material. Titanium, like any other metal, is subject to corrosion in environments of air, oxygen, moisture, and so on. In this work, high-temperature stability of Ti and various Ti-alloys (by ASTM standard) was investigated. The best results showed that for Ti-Gr.5 alloy, the oxidation at 800 °C was 3.39% and at 900 °C 8.35%. For the comparison, commercial pure Ti-alloys Ti-Gr.2 and Ti-Gr.37 containing Al were used, whereas the oxidation resistance was much worse.     

Influence of hydrothermal exposure on surface characteristics and corrosion behaviors of anodized titanium

Titanium surface was modified by anodization in phosphoric acid solution at the voltages of 100 and 250 V, respectively. Surface characteristics and corrosion behaviors of anodized titanium were investigated before and after hydrothermal exposure in 3.5 wt.% NaCl solution at 160 °C for 24 h. It was found that anodization at 100 and 250 V resulted in the formation of a dense and a porous TiO₂ layer, respectively. The existence of anatase in the oxide layers of the 250‐V samples was confirmed by X‐ray diffraction analysis but not in the oxide layers of the 100‐V samples. After the hydrothermal exposure, the surface morphology of the 100‐V sample changed significantly, and discrete nanorods were formed on the surface. In contrast, the 250‐V sample basically preserved their original surface structures after the exposure except that numerous closely packed nanoparticles emerged on the surface. X‐ray diffraction analysis indicated that the exposure transformed the amorphous oxides into crystalline anatase. The corrosion behavior investigation of anodized titanium showed that the hydrothermal exposure had slight influence on the corrosion resistance of the 100‐V samples but decreased the corrosion resistance of the 250‐V samples significantly. Copyright © 2014 John Wiley & Sons, Ltd.     

Photoelectrochemical Properties of Sol-Gel Processed Ag-TiO2 Nanocomposite Thin Films

Ag-TiO₂ thin films were prepared with a sol-gel route, using titanium isopropoxide and silver nitrate as precursors, at 0, 0.03 and 0.06 Ag/Ti nominal atomic ratios. After drying at 80°C, the films were fired at 300°C, 500°C, and 600°C for 30 min and 5 h. Glancing angle X-ray diffraction (XRD) analysis and X-ray photoelectron spectroscopy (XPS), with depth profiling of the concentration, were used to study the films. XPS analysis showed the presence of C and N as impurities in the nanocomposite films. Their concentration decreased with increasing the firing temperature. Chemical state analysis showed that Ag was present in metallic state, except for the outer layer where it was present as Ag⁺. For the films prepared with a Agt/Ti concentration of 0.06, depth profiling measurements of the film fired at 300°C showed a strong Ag enrichment at the outer surface, while composition remained almost constant within the rest of the film, at Ag/Ti atomic ratio of 0.02. Two layers were found for the films heated to 500°C, where the Ag/Ti ratios were 0.015 near the surface and 0.03 near the substrate. The photoelectrochemical properties of Ag-TiO₂ were studied for thin films deposited on ITO substrates. Photocurrents of Ag-TiO₂ nanocomposite electrodes fired at 300°C were observed even at visible light, for wavelengths longer than 400 nm.     

Nitrogen uptake of nickel free austenitic stainless steel powder during heat treatment—an XPS study

In austenitic stainless steel nitrogen stabilizes the austenitic phase, improves the mechanical properties and increases the corrosion resistance. Nitrogen alloying enables to produce austenitic steels without the element nickel which is high priced and classified as allergy inducing. A novel production route is nitrogen alloying of CrMn‐prealloyed steel powder via the gas phase. This is beneficial as the nitrogen content can be adjusted above the amount that is reached during conventional casting. A problem which has to be overcome is the oxide layer present on the powder surface which impedes both the sintering process and the uptake of nitrogen. This study focuses on whether heat treatment under pure nitrogen is an appropriate procedure to enable sintering and nitrogen uptake by reduction of surface oxides. X‐ray photoelectron spectroscopy (XPS) in combination with scanning electron microscopy (SEM) and energy dispersive X‐ray spectrometry (EDS) are used to investigate the surface of powdered FeMn19Cr17C0.4N heat treated under nitrogen atmosphere. The analyses showed reduction of iron oxides already at 500 °C leading to oxide‐free metallic surface zones. Mn and Cr oxides are reduced at higher temperatures. Distinct nitrogen uptake was registered, and successful subsequent sintering was reached. Copyright © 2014 John Wiley & Sons, Ltd.     

Study of formation and thermal stability of the Fe/ZnO(000‐1) interface

Formation and thermal stability of the Fe/ZnO(000‐1) interface have been studied by means of X‐ray photoelectron spectroscopy and low energy electron diffraction. The results indicated a pseudo 2D growth mode for iron on ZnO. In addition, it could be shown that under ultra high vacuum conditions deposited Fe⁰ on a ZnO(000‐1) single crystal was partially oxidized by a small fraction of residual ? OH‐groups and ZnO to FeO. A strong temperature dependence of the interface reactivity was found upon annealing at temperatures up to 600 °C. Starting from 200 °C iron was first oxidized to bivalent iron oxide. After complete oxidation of Fe⁰ to Fe²⁺ at 375 °C, Fe²⁺ reacted to Fe³⁺. Above temperatures of 500 °C the deposited metallic iron was completely oxidized to trivalent iron. Further experiments with FeO on ZnO showed the oxidation state and the oxide film thickness of the deposited iron to be mainly dependent on the annealing temperature. Copyright © 2008 John Wiley & Sons, Ltd.