Surface improvement and biocompatibility of TiAl24Nb10 intermetallic alloy using rf plasma nitriding

The present work describes the surface improvement and biocompatibility of TiAl₂₄Nb₁₀ intermetallic alloy using rf plasma nitriding. The nitriding process was carried out at different plasma power from 400 W to 650 W where the other plasma conditions were fixed. Grazing incidence X-ray diffractometry (GIXRD), Auger electron spectroscopy (AES), tribometer and a nanohardness tester were employed to characterize the nitrided layer. Further potentiodynamic polarization method was used to describe the corrosion behavior of the un-nitrided and nitrided alloy. It has been found that the Vickers hardness (HV) and corrosion resistance values of the nitrided layers increase with increasing plasma power while the wear rates of the nitrided layers reduce by two orders of magnitude as compared to those of the un-nitrided layer. This improvement in surface properties of the intermetallic alloy is due to formation of a thin modified layer which is composed of titanium nitride in the alloy surface. Moreover, all modified layers were tested for their sustainability as a biocompatible material. Concerning the application area of biocompatibility, the present treated alloy show good surface properties especially for the nitrided alloy at low plasma power of 400 W.     

Improvement of erosion and erosion-corrosion resistance of AISI420 stainless steel by low temperature plasma nitriding

Plasma nitriding experiments were carried out with DC-pulsed plasma in 25% N₂ + 75% H₂ atmosphere at low temperature (350 °C) and normal temperature (550 °C) for 15 h. The composition, microstructure, microhardness profiles, residual stress profiles and electrochemical impedance spectrum analyses of the nitrided samples were examined. The influence of plasma nitriding on the erosion and erosion-corrosion resistance of AISI 420 martensitic stainless steel was investigated using a jet solid particle erosion tester and a slurry erosion-corrosion tester.Results showed that the 350 °C nitriding layer was dominated by ?-Fe₃N and α_N phase, a supersaturated nitrogen solid solution. However, nitrogen would react with Cr in the steel to form CrN precipitates directly during 550 °C nitriding, which would lead to the depletion of Cr in the solid solution phase of the nitrided layer. Both 350 and 550 °C plasma nitriding could improve the erosion resistance of AISI420 stainless steel under dry erosion, but the former showed better results. In both neutral and acid environment, while the erosion-corrosion resistance of AISI 420 was improved by means of 350 °C nitriding, it was decreased through 550 °C nitriding.     

Ultrasonic cavitation erosion of gas nitrided Ti–6Al–4V alloys

Ultrasonic cavitation erosion experiments were performed on Ti–6Al–4V alloys samples in annealed, nitrided and nitrided and subsequently heat treated state. The protective oxide layer formed as a result of annealing and heat treatment after nitriding is eliminated after less than 30 min cavitation time, while the nitride layer lasts up to 90 min cavitation time. Once the protective layer is removed, the cavitation process develops by grain boundary erosion, leading to the expulsion of grains from the surface. The gas nitrided Ti–6Al–4V alloy, forming a Ti_xN surface layer, proved to be a better solution to improve the cavitation erosion resistance, compared to the annealed and nitrided and heat treated state, respectively. The analysis of the mean depth of erosion rate at 165 min cavitation time showed an improvement of the cavitation erosion resistance of the nitrided samples of up to 77% higher compared to the one of the annealed samples.     

The effect of surface nanocrystallization on plasma nitriding behaviour of AISI 4140 steel

A plastic deformation surface layer with nanocrystalline grains was produced on AISI 4140 steel by means of surface mechanical attrition treatment (SMAT). Plasma nitriding of SMAT and un-SMAT AISI 4140 steel was carried out by a low-frequency pulse excited plasma unit. A series of nitriding experiments has been conducted at temperatures ranging from 380 to 500 °C for 8 h in an NH₃ gas. The samples were characterized using X-ray diffraction, scanning electron microscopy, optical microscopy and Vickers microhardness tester. The results showed that a much thicker compound layer with higher hardness was obtained for the SMAT samples when compared with un-SMAT samples after nitriding at the low temperature. In particular, plasma nitriding SMAT AISI 4140 steel at 380 °C for 8 h can produced a compound layer of 2.5 μm thickness with very high hardness on the surface, which is similar to un-SMAT samples were plasma nitrided at approximately 430 °C within the same time.     

Microstructure and antibacterial properties of microwave plasma nitrided layers on biomedical stainless steels

Nitriding of AISI 303 austenitic stainless steel using microwave plasma system at various temperatures was conducted in the present study. The nitrided layers were characterized via scanning electron microscopy, glancing angle X-ray diffraction, transmission electron microscopy and Vickers microhardness tester. The antibacterial properties of this nitrided layer were evaluated. During nitriding treatment between 350 °C and 550 °C, the phase transformation sequence on the nitrided layers of the alloys was found to be γ → (γ + γ_N) → (γ + α + CrN). The analytical results revealed that the surface hardness of AISI 303 stainless steel could be enhanced with the formation of γ_N phase in nitriding process. Antibacterial test also demonstrated the nitrided layer processed the excellent antibacterial properties. The enhanced surface hardness and antibacterial properties make the nitrided AISI 303 austenitic stainless steel to be one of the essential materials in the biomedical applications.     

First stages of surface steel nitriding: X-ray photoelectron spectroscopy and electrical measurements

Quantitative and qualitative analysis techniques were employed to study the first stages of ultra-high vacuum plasma nitriding of the 42CrMo4 steel. At constant treatment temperature, maintained for all samples at about 360 °C, we have established the influence of treatment time on the chemical composition, thickness and electrical properties of the nitrided layer.In this purpose it was used a stacking atomic layer model describing the sample surface, which takes into account the attenuation depth of photoelectrons by the atomic monolayers. So, we have found that after 2 h of nitriding in laboratory conditions, 70% of the nitrided layer was composed of iron oxide. Also, I–V measurements indicate an influence of the nitride overlayer with increasing treatment time.     

MicroRaman study of the effect of oxide layer on nitriding of Ti-6Al-4V

Ti-6Al-4V samples were subjected to nitrogen ion implantation and low pressure RF plasma nitriding in a PIII equipment after chemical etching in Kroll's reagent. The samples were characterized by optical microscopy, AFM, microRaman, XRD and micro hardness measurements. From microRaman, oxides of titanium were found in the inter-granular β region whereas the oxide on the α region was extremely thin. The oxide on the β region was found to be amorphous and from intensity dependent Raman spectra, it was found to have a layered structure. The top layer was rutile and the inner layer anastase. Presence of Ti₂O₃ was also found. After PIII treatment at 600 °C, microRaman showed the presence of nitride in both the regions and the oxide was absent in the β regions. Also, from intensity dependent Raman spectra, it was found that in-take of nitrogen by β regions was higher. The oxide layer remained unaffected after plasma nitriding. Nitride presence in the α was established by microRaman. Even though Raman spectra from β regions were nearly the same as that of oxide, presence of nitrogen was indicated by the spectra. XRD studies of implanted and nitrided samples showed the prsence of TiN and Ti₂N in implanted sample and presence of Ti₂N in the nitrided sample. The β regions were found to have higher microhardness values after PIII and nitriding treatments. This is attributed to the deeper diffusion of nitrogen in these regions.     

Laser diffusion nitriding of Ti-6Al-4V for improving hardness and wear resistance

Owing to poor tribological properties, titanium (Ti) alloys are usually surface-treated to enhance their surface properties. Laser surface nitriding, among others, is a common method employed to increase hardness and wear resistance for Ti alloys. Conventional laser nitriding involves surface melting of Ti alloys in a nitrogen atmosphere. This inevitably results in a roughened surface and post-treatment might be required. The present study aims at laser diffusion nitriding Ti alloys without surface melting via carefully selecting the laser processing parameters. The nitrided surface was characterized by X-ray diffractometry (XRD), optical microscopy (OM), scanning-electron microscopy (SEM), and profilometry. The nitride layer formed was about 1.62 μm upon repeated passes. The change in surface roughness resulting from laser diffusion nitriding was only minimal. Nanoindentation measurements revealed that the hardness of the nitride layer was around 11.3 GPa, being about 2.3 times that of Ti-6Al-4V. Ball-on-slab sliding wear test recorded a reduction in wear volume by about 8 times. The results of the present work thus demonstrate the feasibility of diffusion nitriding of Ti-6Al-4V by laser treatment for enhancing its surface properties and performance.     

Normal and excess nitrogen uptake by iron-based Fe–Cr–Al alloys: the role of the Cr/Al atomic ratio

Upon nitriding ferritic iron-based Fe–Cr–Al alloys, containing a total of 1.50 at. % (Cr?+?Al) alloying elements with varying Cr/Al atomic ratio (0.21–2.00), excess nitrogen uptake occurred, i.e. more nitrogen was incorporated in the specimens than compatible with only inner nitride formation and equilibrium nitrogen solubility of the unstrained ferrite matrix. The amount of excess nitrogen increased with decreasing Cr/Al atomic ratio. The microstructure of the nitrided zone was investigated by X-ray diffraction, electron probe microanalysis, transmission electron microscopy and electron energy loss spectroscopy. Metastable, fine platelet-type, mixed Cr_{1? x} Al _x N nitride precipitates developed in the nitrided zone for all of the investigated specimens. The degree of coherency of the nitride precipitates with the surrounding ferrite matrix is discussed in view of the anisotropy of the misfit. Analysis of nitrogen-absorption isotherms, recorded after subsequent pre- and de-nitriding treatments, allowed quantitative differentiation of different types of nitrogen taken up. The amounts of the different types of excess nitrogen as function of the Cr/Al atomic ratio are discussed in terms of the nitride/matrix misfit and the different chemical affinities of Cr and Al for N. The strikingly different nitriding behaviors of Fe–Cr–Al and Fe–Cr–Ti alloys could be explained on this basis.     

Improvement of corrosion resistance of nitrided low alloy steel by plasma post-oxidation

Post-oxidizing treatments can be performed to improve the corrosion resistance of nitrided steel samples. In this paper, plasma nitriding treatments were performed at 540 °C for 4 h using ammonia as the working gas, and plasma post-oxidizing treatments were carried out at temperatures ranging from 350 °C to 500 °C for 2 h in oxygen gas. The treated samples were characterized by using optical microscopy, SEM, XRD, and electrochemical polarization. The X-ray analysis revealed the formation of iron-nitride phases of ?-Fe_2-3N and γ′-Fe₄N during plasma nitriding and iron oxide phases of hematite (Fe₂O₃) and magnetite (Fe₃O₄) through the post-oxidizing treatment. In particular, it was found that the very thin magnetite layer 0.8-1.5 μm in thickness on top of the compound layer was obtained by plasma post-oxidized at 400 °C and 450 °C. It was also demonstrated that the corrosion characteristics of the nitrided compound layer were further improved by post-oxidation treatment.     

Microstructure and corrosion resistance of the layers formed on the surface of precipitation hardenable plastic mold steel by plasma-nitriding

Plasma-nitriding is used to improve the wear resistance and corrosion resistance of plastic mold steels by modifying the surface layers of these steels. In this study, a precipitation hardenable plastic mold steel (NAK80) was plasma-nitrided at 470, 500, and 530 °C for 4, 8, and 12 h under 25% N₂ + 75% H₂ atmosphere in an industrial nitriding facility. The microstructures of the base material and nitrided layers as well as the core hardness were examined, and various phases present were determined by X-ray diffraction. The corrosion behaviors were evaluated using anodic polarization tests and salt fog spray tests in 3.5% NaCl solution.The results had shown that plasma-nitriding does not cause the core to soften by overaging. Nitriding and aging could be achieved simultaneously in the same treatment cycle. Plasma-nitriding of NAK80 mold steel produced a nitrided layer composed of an outer compound layer constituting a mixture of ?-nitride and γ′-nitride and an adjacent nitrogen diffusion layer on the steel surface. The amount of ?-nitride and total nitrides increased with an increase in nitriding temperature and nitriding time. Corrosion study revealed that plasma-nitriding significantly improved the corrosion resistance in terms of corrosion potential, corrosion and pitting current density, and corrosion rate. This improvement was found to be directly related to the increase in the amount of ?-nitride at the surface, indicating the amount of ?-nitride controlling the corrosion resistance.     

Structural properties of GaAs surfaces nitrided in hydrazine-sulfide solutions

The surface structure of GaAs(1 0 0), (1 1 1)A, and (1 1 1)B substrates nitrided through the wet chemical treatment in hydrazine-sulfide solution have been studied by scanning tunneling microscopy (STM) under annealing in UHV. Such treatment has earlier been shown to produce a monolayer of gallium nitride on the (1 0 0)GaAs surface. The as-nitrided substrates of all surface orientations were found to be covered by an overfilm, which contains thioarsenic compounds and has a smooth relief. Thermal desorption of the overlfilm at about 530 °C opens the own relief of the nitrided surfaces. For the (1 0 0) orientation such relief is not microscopically planar and consists of nano-scale vicinal hillocks. These hillocks occur due to surface microetching which proceeds simultaneously with the formation of the surface nitride layer. We have shown that the wet nitridation procedure forms a monolayer of surface nitride on the (1 1 1)B surface. During nitridation the (1 1 1)B surface, as well as the (1 0 0) one, is affected by the microetching in the hydrazine-sulfide solution. Therefore, it exhibits a characteristic relief formed by triangular vicinal pyramids. At the same time the nitride film is not formed on the (1 1 1)A surface, which is more chemically inert, and where the surface etching is almost absent.     

Thermal stability of titanium nitride coatings prepared by the mixing technology with laser and plasma

Titanium samples were treated by the mixing technology with laser and plasma (LPN) using different laser power densities. These nitrided samples were then annealed at 473 K, 673 K, 873 K, and 1073 K for 2 h in vacuum, respectively. The samples before and after annealing were characterized at room temperature and compared in terms of microstructure. X-ray diffraction and cross-sectional optical microscopy studies showed that the layer structure of the titanium nitride coating is preserved after annealing at 1073 K when the coating is formed using a laser power density of 8.0 × 10⁵ W/cm². Therefore, titanium nitride coatings produced by LPN demonstrate excellent thermal stability and are potential candidates for high temperature tribological applications.     

Relevant, systematic variation of morphology and magnetism according to annealing in InMnP:Zn

InMnP:Zn epilayers doped with Mn (0.290 at.%) were annealed at 723-873 K for 60 s and 473-573 K for 30 min. Using Auger electron spectroscopy, the changes in concentration profiles of the epilayers correlated to the ferromagnetic origin as a function of the annealing conditions. The epilayers annealed at 723-873 K for 60 s exhibited InMn₃ persisting up to 583 K. For InMnP:Zn epilayers annealed at 523-573 K for 30 min, the concentration depth profiles remained flat so that the stoichiometry was well maintained without precipitates such as InMn₃ and MnP comparable to the as-grown InP:Zn before doping Mn. These samples showed clear ferromagnetic hysteresis loops. Curie temperature was about 150 K. A ferromagnetic hysteresis loop was obtained even at very lower annealing temperature of 473 K.     

Unusual nucleation and growth of γ′ iron nitride upon nitriding Fe–4.75 at.% Al alloy

The influence of substitutionally dissolved Al in ferritic Fe–4.75 at.% Al alloy on the nucleation and growth of γ′ iron nitride (Fe₄N_{1? x} ) was investigated upon nitriding in NH₃/H₂ gas mixtures. The nitrided specimens were characterised employing optical microscopy, scanning electron microscopy, transmission electron microscopy, electron probe microanalysis and X-ray diffraction. As compared to the nitriding of pure ferrite (α-Fe), where a layer of γ′ develops at the surface, upon nitriding ferritic Fe–4.75 at.% Al an unusual morphology of γ′ plates develops at the surface, which plates deeply penetrate the substrate. In the diffusion zone, nano-sized precipitates of γ′ and of metastable, cubic (NaCl-type) AlN occur, having, with the ferrite matrix, a Nishiyama–Wassermann orientation relationship and a Bain orientation relationship, respectively. The γ′ plates contain a high density of stacking faults and fine ε iron nitride (Fe₂N_{1? z} ) precipitates, although the formation of ε iron nitride is not expected for the employed nitriding parameters. On the basis of dedicated nitriding experiments it is shown that the unusual microstructural development is a consequence of the negligible solubility of Al in γ′ and the obstructed precipitation of the thermodynamically stable, hexagonal (wurtzite-type) AlN in ferrite.     

Structural and photoluminescence properties of Si nanoclusters obtained by ion implantation into Si3N4 films

In the present paper we report structural and photoluminescence (PL) results from samples obtained by Si implantation into stoichiometric silicon nitride (Si₃N₄) films. The Si excess was introduced in the matrix by 170 keV Si implantation performed at different temperatures with a fluence of Φ=1×10¹⁷ Si/cm². The annealing temperature was varied between 350 and 900 °C in order to form the Si precipitates. PL measurements, with a 488 nm Ar laser as an excitation source, show two superimposed broad PL bands centered around 760 and 900 nm. The maximum PL yield is achieved for the samples annealed at 475 °C. Transmission electron microscopy (TEM) measurements show the formation of amorphous nanoclusters and their evolution with the annealing temperature.     

Correlation between impurities in Fe-Si amorphous layers synthesized by Fe implantation and photoluminescence property of β-FeSi2 precipitates in Si

Completely amorphous Fe-Si layers are formed by Fe implantation into Si substrate at a dosage of 5×10¹⁵ cm⁻² using a metal vapor vacuum arc (MEVVA) ion source under 80 kV extraction voltage and cryogenic temperature. After thermal annealing, β-FeSi₂ precipitates are formed in Si matrix. The influence of impurities in these amorphous Fe-Si layers on the photoluminescence (PL) from β-FeSi₂ precipitates is investigated. PL is found to be significantly enhanced by optimizing the impurity concentration and annealing scheme. After 60 s of rapid thermal annealing (RTA) at 900 °C, β-FeSi₂ precipitates in medium boron-doped Si substrate give the strongest PL intensity without boron out-diffusion from them.     

Structural characterization of SiGe nanoclusters formed by rapid thermal annealing

This work presents the structural characterization of nanoclusters formed from a-Si:H/Ge heterostructures processed by rapid thermal annealing (RTA) at 1000 °C for annealing times varying between 30 s and 70 s. The a-Si:H layers were grown on electron cyclotron resonance (ECR) using SiH₄ and Ar precursor gases. The Ge layer was grown in an e-beam evaporation system. The structural characterizations were performed by high-resolution X-ray diffractometer (HRXRD) on grazing incidence X-ray reflection mode (GIXRR) and micro-Raman measurements. The average grain size, Ge concentration (x_Ge) and strain were estimated from Lorentzian GIXRR peak fit. The average grain size varied from 3 nm to 7.5 nm and decreased with annealing time. The x_Ge increase with annealing time and varied from 8% to 19%, approximately. The strain calculated for (1 1 1), (2 2 0) and (3 1 1) peaks at 40 s, 50 s, 60 s and 70 s annealing time suggest the geometrical changes in nanoclusters according to process time.     

Magnetic characterization of dual phase FeZrB soft magnetic alloy

The magnetic properties and the annealing process of Fe₇₈Zr₇B₁₅ amorphous ribbons are investigated by X-ray diffraction (XRD), differential scanning calorimetry, and vibrating sample magnetometer. The fully amorphous structure of the as-quenched ribbons is confirmed by the XRD pattern. The Curie temperature and the saturation magnetization M_s of the ribbons are 305 °C and 124.3 emu/g, respectively. Annealing at 550 °C can result in an increase in M_s with annealing time due to the increasing crystallized volume fraction of α-Fe phase. The optimized annealing process is established at 550 °C for 20-30 min with maximum M_s of 146.6 emu/g. The morphology of the ribbons annealed at 550 °C is observed by scanning electron microscopy, showing that nanocrystalline α-Fe grains are dispersed in an amorphous matrix.     

Microstructures and magnetic properties of CoPt-TiO2 nanocomposite films prepared by annealing CoPt/TiO2 multilayers

CoPt-TiO₂ nanocomposite films were synthesized by rapid thermal annealing of CoPt/TiO₂ multilayers. The effects of annealing temperature, annealing time, Ag addition and TiO₂ volume fraction on the microstructures and magnetic properties of the CoPt-TiO₂ nanocomposite films were studied. Results showed that the ordering degree of CoPt and coercivity of CoPt-TiO₂ nanocomposites increased with annealing temperature. Increasing annealing time and Ag addition were able to increase the ordering degree and coercivity of CoPt. However, complete L1₀-ordering of CoPt at 550 °C annealing was not realized by increasing annealing time up to 30 min and Ag addition up to 30 vol.%. Increasing TiO₂ volume fraction at 700 °C annealing did not lead to the change of ordering of CoPt. However, the grain structure of the films changed slightly when TiO₂ volume fraction was larger than 56%. The coercivity of the film decreased slightly with the addition of TiO₂.