AISI-304 austenitic stainless steel has been nitrocarburized in N2 and C2H2 ambient using high-voltage plasma immersion ion implantation (PIII) technology. The use of different PIII treatment times revealed important hints with respect to the microstructural, mechanical and corrosion properties of the nitrocarburized layer. Grazing incidence X-ray diffraction (GIXRD) shows the presence of nitride (γN and CrN) and carbide (γC and Fe3C) phases. Glow discharge optical spectroscopy (GDOS) has been used to characterize the elemental depth profiles in which the thickness of the modified layers is derived. Dynamic microindentation method is used for the study of mechanical performance of the nitrocarburized layer as well as the untreated material. The microhardness has been increased to a maximum value of more than nine times compared to that of the untreated one. The corrosion performance is characterized by potentiodynamic polarization technique and was found to be treatment time dependent.

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 400W to 650W 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 400W.

It is known that phase transformations into austenite can take place in the surface layer of steels irradiated with intense pulses of laser, ion or plasma beams. Due to the presence of nitrogen and carbon expanded austenite in stainless steel, good corrosion resistance is maintained while the wear resistance is increased. A series of carbon steels with various carbon contents was irradiated with high intensity (5-6 J/cm(2)), short (mu s range) nitrogen and argon plasma pulses. The pulsed energy was high enough to melt the surface region of the samples. This paper reports the results of investigations of structural and tribological properties of the near surface layer of carbon steels induced by such treatment. The identified phases and wear resistance of the modified layer are presented. (c) 2007 Elsevier B.V. All rights reserved.

We investigate the effects of room-temperature irradiation of Au and Ge nanoislands grown on Si. Our studies show the formation of Au-Ge alloy phase within the islands and wetting of the substrate. High-resolution transmission electron microscopy along with synchrotron radiation-based x-ray reflectivity and grazing incidence x-ray diffraction measurements were performed to characterize the irradiation-induced changes brought into the sequentially deposited Au and Ge island thin films. The results are attributed to the recoil implantation and the transient melting of the nanoislands followed by the formation of crystalline alloy phase.

Aluminium carbide nucleation and growing kinetics is correlated to the mechanical properties (hardness and elastic modulus), and to the friction coefficients as a function of carbon ion implantation parameters on aluminium. The microstructure of the modified surface was studied by: a) Elastic Recoil Detection Analysis (ERDA), b) Grazing Incidence X-ray Diffraction analysis (GIXRD) and c) Raman spectroscopy. Hardness and elastic modulus profiles were measured by instrumented nanoindentation technique. Pin-on-disc technique in reciprocal scratch mode was employed to obtain the friction coefficient profile. For low carbon fluences (≤2×1017 C+ cm−2) small size (≈4 nm) embedded Al4C3 precipitates were produced. Higher carbon fluences create an amorphous-like structure. Implantations performed at high substrate temperatures can produce big size precipitate (≈40 nm). Surface hardness increases as a function of carbon fluence resulting in values of about 6 GPa (20 times Al bulk value). The hardening mechanisms are associated with dislocations to precipitates bowing and/or cutting processes. Implantation parameters ruled the mechanical properties. Tribological responses are more difficult to correlate to the ion implantations conditions. However, wear is reduced when highly disordered C–C cluster are present.

Plasma immersion ion implantation (PIII) has been employed for nitrocarburizing 304 stainless steel. The sample was treated at relatively low gas pressure of nitrogen and acetylene in the range of 10−3 mbar. The microstructure variation, the austenite lattices spacing and the phase transformations were studied in-situ during heating up to 800 °C and after cooling, using synchrotron X-ray diffraction. Glow discharge optical spectroscopy (GDOS), optical microscopy and hardness profile measurements have been used before and after thermal treatment to analyse the nitrocarburized layer.

TiN and Ti1−xAlxN coatings were deposited on Al substrates using the plasma immersion ion implantation and deposition technique, employing a filtered Ti and Ti0.5Al0.5 cathodic arc in a nitrogen atmosphere. Negative pulsed bias voltages between 0 to −4.0 kV were applied with varying duty cycles, at a constant time-averaged bias. Stress measurements using X-ray diffraction reveal an increase and then a decrease in the intrinsic compressive stress at increasing on-time bias, more pronounced for Ti1−xAlxN coatings. A bias dependent preferred orientation is observed for both the coatings, with [200] being the preferred orientation at higher bias. The hardness always reduces for TiN coatings with increase in bias, whereas for Ti1−xAlxN it shows a reverse trend. The results are qualitatively explained by the role played by Al in Ti1−xAlxN. The results indicate that the peak bias plays a more dominant role than time averaged bias.

The experiments to synthesize thin MgB2 inter-metallic compound with the use of ion implantation and plasma pulse treatment are presented. Mg was implanted with 3×1018cm−2 of 80keV and 5×1018cm−2 of 100keV B+ ions and next treated with hydrogen and argon plasma pulses of duration of about 1μs and fluence between 2 and 4J/cm2. Superconducting properties were examined by magnetically modulated microwave absorption (MMMA), magnetic moment and electrical conductivity measurements. The structural properties of the implanted and pulse-treated samples were examined by the X-ray diffraction (XRD) and Rutherford backscattering (RBS) methods. The main result consists in observation of MMMA hysteresis loop demonstrating the existence of superconducting regions with Tc as high as 32K. However, the zero-resistance effect has not been obtained due to incomplete global connectivity between the superconducting regions.

A special designed high-temperature vacuum chamber for in situ X-ray diffraction (XRD) measurements was used to study structural phase formation and transformation kinetics in molybdenum during oxygen ion implantation and post-annealing treatment. Oxygen ions with an energy of 1.5MeV were implanted in polycrystalline molybdenum up to a fluence of 3×1018/cm2 at different temperatures (160–700°C). Subsequently, implanted samples were annealed up to 700°C for in situ study during synthesis of buried oxide layers. Complementary, transmission electron microscopy (TEM) and sputter Auger electron spectroscopy (AES) were employed to obtain depth-dependent information concerning both the crystal structure and its elemental composition. The formation of different molybdenum oxides during oxygen implantation and post-implantation annealing process was observed by in situ X-ray analysis. The XRD spectra of samples implanted at 160°C show that MoO3 and/or Mo4O11 precipitates have been formed, whereas implantation in the temperature range 300–700°C preferably leads to the MoO2 phase formation.

Series of carbon steels with various contents of carbon were irradiated with high intensity (5–6Jcm−2), short (μs range) nitrogen and argon plasma pulses. In all samples the near surface layer of the thickness in μm range was melted. The paper reports the results of investigation of changes induced by such treatment. The identified phases, profiles of retained nitrogen concentration, microhardness and wear resistance of the modified layer are presented and discussed.

This work presents selected results from carbon ion implantation into pure Al matrix. The carbon ions were implanted with an ion energy of 25 keV and fluences of 1×1021 and 2×1021 C+/m2 at room temperature (RT) and elevated temperature of 400 °C. Elastic recoil detection analysis (ERDA), grazing incidence X-ray diffraction analysis (GIXRD), Raman spectroscopy and high resolution electron microscopy (HRTEM) show the formation of embedded Al4C3 precipitates with carbon concentrations below its stoichiometric level. At RT ion implantation, the Al4C3 precipitates have an average grain size in the order of 2–4 nm. For carbon ion implantation at 400 °C, the precipitates grow up to approximately 20 nm in diameter and are randomly distributed in the implanted region. The carbon excess, not bound in the Al4C3 precipitates, forms highly disordered C–C clusters of approximately 0.2–0.4 nm in size. Implantation at a temperature of 400 °C reduces drastically the carbon clusters content due to the growth of the Al4C3 precipitates.

The depth dependence of elemental composition, phase distribution, and cross-sectional morphology of rf plasma nitrocarburized 304 austenitic stainless steel were investigated using glow discharge optical spectroscopy (GDOS), grazing incidence X-ray diffraction (GIXRD), and optical microscopy, respectively. A step-wise mechanical polishing method was used to remove successive sublayers of the treated surface. It was found that the properties of the nitrocarburized layer depend critically on the plasma gas composition, which controls the supersaturation of nitrogen and carbon through the compound layer depth. Iron nitride phases and/or nitrogen-expanded austenite (γN) were detected in the nitrocarburized layer prepared at high plasma nitrogen (N2) content. In the compound layer processed at high plasma carbon (C2H2) content, besides the carbon-expanded austenite phase (γC), carbide phases were found predominantly in the top-layer, in which the carbon concentration has a maximum value of ∼2 wt.%. The lattice expansion of the expanded austenite phases changes with sampling depth, depending on local variations in nitrogen and carbon content. The applied rf plasma processing power influences significantly nitrogen and carbon distribution in the treated sublayers.

Determination of structures using X-ray powder diffraction is complicated if the reflection intensities are mainly influenced by the scattering from heavy atoms and the atomic coordinates of light atoms remain uncertain. A method like EXAFS, which is sensitive to short range order, gives reliable atomic distances in the surroundings of heavy atoms with a precision of +/- 0.02 angstrom. The probability for obtaining the complete structure from X-ray powder diffraction increases if one includes parameters derived from EXAFS measurements as restraints during the procedure of structure solving. We demonstrate the potential of combining EXAFS and X-ray powder diffraction by solving the structure UO2[H2AsO4](2) center dot H2O. The procedure starts with the determination of space group and cell parameters from XRD powder data. In a second step the absolute values of the structure factor vertical bar F vertical bar are separated by iterating a decomposition formula. The heavy atom positions are determined by direct methods. In the third step atomic distances of coordination polyhedra are estimated using EXAFS. Subsequently, the complete coordination geometries around the heavy atoms including reliable distances are used as restraints in the structure solving and refinement procedure.

The hard Ti-based coating TiAlN has been produced by plasma immersion ion implantation-assisted deposition (PIIIAD) on austenitic stainless steel. In PIIIAD, the substrate is exposed to cathodic arc plasma comprising of metallic ions corresponding to the cathode composition, and the substrate is biased pulsed negative. The pulsed bias of the substrate renders alternate phases of deposition (during the bias off time) and implantation and deposition (during bias on time), thereby controlling deposition temperature, reduction of compressive stresses, increase of crystallinity and enhancing adhesion of coating to substrate. The deposition has been carried out in a neutral as well as reactive nitrogen environment, which leads to nitrogen-containing coatings. In addition to TiAlN, also, Ti, TiN and TiAl were produced to investigate the effect of the different elements. All the coatings are tested for their suitability as biocompatible coatings, and hence, the adherence of osteoblast progenitor cells to these coatings was investigated in correlation with deposition parameters and surface morphology. The results identify the coatings that are wear resistant and suitable for orthopaedic implants.

Ni-Ti surface alloy was prepared by ion-implanting Ni into Ti. The surface film was amorphous having a Ni surface content of 10–40 at.%. The material was compared with a Ni-Ti bulk alloy (44.08:55.9) regarding their redox and electrocatalytic behavior in NaOH by cyclic voltammetry. The surface was characterized by x-ray photoelectron spectroscopy, x-ray and electron diffraction, transmission electron microscopy, and atomic force microscopy. The ion-implanted material revealed an enhanced activity toward the redox conversion of Ni(OH)2 ↔ NiOOH and the anodic oxidation of glucose. The effect is discussed considering the enhanced generation of active Ni surface sites from amorphous Ni and the stabilization of higher valence Ni by Ti.

Indium tin oxide films produced by reactive middle frequency magnetron sputtering were annealed in a vacuum. The electrical and optical properties of the film have been studied in situ along with direct characterization of the crystalline structure. Even in the amorphous state, the film resistivity significantly decreases with increasing temperature due to a free-electron density enhancement, likely by the generation of oxygen vacancies. A rapid crystallization within the temperature range of 250–280°C leads to a further decrease of the resistivity due to Sn donor activation. The resistivity and the optical properties depend nonlinearly on the crystalline fraction.

Plasma immersion ion implantation-assisted deposition has been employed to develop Ti based coatings in the presence or absence of a reactive nitrogen environment. When TiN coatings have been developed on Al alloys, it has been observed that a large compressive stress develops in the coating, which can be reduced when the substrate bias is increased. The formation of stress is attributed to atomic peening effect that densifies a coating, whereas thermal spikes generated at high substrate bias reduce the stress. For TiAl coatings delivered from an alloy plasma source, the Al content decreases with increasing negative substrate bias. This is in agreement with the results of TRIDYN ballistic computer simulations, which confirm that the film composition is significantly influenced by preferential sputtering. The results indicate that time-averaged substrate bias is an ill-defined parameter to describe coating properties deposited by the above technique.

Titanium oxides are considered as blood compatible surfaces, however, it may be possible to improve the compatibility to the inner lining cells of blood vessels by addition of Ag which modifies the electronic properties of this oxide. Therefore, Ti–Ag–O films with the thickness of 200–350 nm have been deposited on Si substrates using an ion beam assisted deposition (IBAD) system which has two evaporators to allow a simultaneous deposition of Ti and Ag. The evaporation rates of Ti and Ag, as well as the flow rate of O2 have varied. For physicochemical analysis of the films, glancing incidence X-ray diffraction (GIXRD) analysis, X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were performed. The formed phases in Ti–Ag–O films consist of TiO2, AgO, Ag2O, Ag, TiAg, AgTi3, and low valent titanium oxides. The bovine aortic endothelial cell line GM07373 was grown on these surfaces in a medium with 10% fetal bovine serum. The toxicity of the layers was rated by the release of lactate dehydrogenase (LDH) from the cells and are found to be below the detection limit; the cell adhesion was investigated by fluorescent staining of the adhesion molecule vinculin and the cytoskeleton protein filamentary actin; the cell nuclei were counterstained with DAPI, showing good cell adherence, good compatibility to endothelial cells, and no indication of apoptotic cell death.

Implantation of nitrogen ions into stainless steel in combination with oxidation often results in a decrease or even complete removal of the chromium in the nitrogen containing outermost surface layer. While iron nitrides can be formed easily by this method, due to the absence of chromium, the formation of chromium nitrides is impossible and the beneficial influence of chromium in the steel for corrosion resistance cannot be used. To overcome this problem we use the following hybrid technique. A thin chromium layer is deposited on steel and subsequently implanted with nitrogen ions. Chromium can be implanted by recoil into the steel surface and thus the formation of iron/chromium nitrides should be possible. Both beam line ion implantation and plasma immersion ion implantation are used. Due to the variation of the process parameters, different implantation profiles and different compounds are produced. The produced layers are characterized by Auger electron spectroscopy, conversion electron Mössbauer spectroscopy and X-ray diffraction. The obtained results show that due to the variation of the implantation parameters, the formation of iron/chromium nitrides can be achieved and that plasma immersion ion implantation is the most suitable technique for the enrichment of chromium in the outermost surface layer of the steel when compared to the beam line implantation.