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Transition metal nitrides, as is the case of NbN, exhibit an attractive mixture of physical, chemical and mechanical properties and can be used to overcome a severe constraint of pure niobium, that is the high oxidation rate for temperature above 400 °C. In this work nitrogen ions were implanted into niobium by means of plasma based ion implantation (PBII) and high temperature PBII (HTPBII) in order to produce NbN on the surface of the material. In the case of HTPBII the treatment was performed in the temperature of 1000 °C and 1250 °C. In the process, negative pulses of 10 kV/20 μs/500 Hz were applied to Nb samples for 1 h. The depth of the modified layer reached up to 4.5 μm due to the diffusion of nitrogen atoms implanted into the material. X-ray diffraction spectra showed the presence of ɛ-NbN, β-Nb2N and γ-Nb4N3 phases. Wear rate was reduced from 1.5 × 10−2 mm3/Nm up to 2.6 × 10−6 mm3/Nm for treated samples at high temperature in comparison with pristine samples, while friction coefficient was reduced from 0.8 to 0.25. Hardness was significantly increased. Surface topography was measured by optical profilometry. Surface roughness increases with the sample temperature but it remains lower than the one obtained by conventional PBII, very probably due to the heating method, which was performed by electron bombardment.

When performing nitriding of stainless steels, there is a decrease or even complete depletion of chromium in the nitrogen rich region just beneath the surface, inhibiting the formation of passivated Cr oxide layer, beneficial to withstand corrosive attacks and Cr/Fe nitrides, responsible for hardness enhancement. To overcome this problem, a hybrid technique was used, consisting of depositing a thin chromium film on steel surface and then bombarding it with nitrogen ions. By a complex recoil process, chromium atoms are implanted into the steel matrix. Plasma immersion ion implantation (PIII) was used in this bombardment. The new Cr-rich layer allows the formation of Cr oxides and nitrides. Treated surfaces were characterized by Auger electron spectroscopy (AES) and conversion electron Mossbauer spectroscopy (CEMS), showing formation of a new Cr-rich layer. (c) 2005 Elsevier B.V. All rights reserved.

Ion nitriding is an important surface modification technique used routinely in the advanced technology industries aiming at producing high added value components with increased hardness and wear resistance. To further improve the performance of critical-part components, new methods for surface strengthening are being developed with success, like plasma immersion ion implantation (PIII) and hybrid surface treatments combining PIII and ion nitriding. In particular, a combination of high-pressure (40 Pa), high-temperature (up to 450 degreesC) glow discharge nitriding with low-pressure (8 x 10(-2) Pa) ion nitriding was implemented. Analysis of the SS304 samples treated by this hybrid method was carried out using the technique of grazing incidence X-ray diffraction (GIXRD) and the results were supported by both normal XRD and AES (Auger electron spectroscopy) measurements. Depending on the particular conditions of the treatment and the depth probed, mixed phases Of gamma(N), and gamma were measured. The improvement in hardness of the obtained surfaces (up to a factor of 2.7) was also in accordance with the results of other analysis.

Surface modification of ultra-high molecular weight polyethylene (UHMWPE) has been explored by using the non-line-of-sight plasma immersion ion implantation (PIII) technique. The polymer specimens, immersed in nitrogen plasma, were pulsed through a metallic grid at repetition rate of 100 Hz with negative high-voltage pulse of 15 kV magnitude and 10 μs duration. The UHMWPE's structural changes induced by the PIII were analyzed by laser Raman spectroscopy (LRS) at 514.5 nm, X-ray photoelectron spectroscopy (XPS) and optical microscopy. From the Raman spectra it is observed that the chain structure of UHMWPE has been damaged due to ion bombardment and a layer of hydrogenated amorphous carbon is formed. The ratio of sp3/sp2 bonded carbon in the modified layer was obtained by suitable fitting of the XPS C 1s energy peak, using a four-curve fitting procedure, which recognizes a portion of C–O and CO surface bonding. The XPS results for N 1s peak show that the implanted nitrogen ions form chemical bonds with the polymer instead of forming precipitates by self-clustering.

Hybrid surface modification involving plasma immersion ion implantation (PIII) and ion nitriding has been attempted. DC cathode nitrogen glow discharges with 600–1000 V, 50–300 mA were typically obtained using the sample support as the cathode and the vacuum chamber as the anode. In this mode, sample temperatures of 500–600 °C can be reached easily while PIII at 10 kV, 50 μs and 400 Hz alone can provide about 300 °C heating. Combining these two highly conformal treatments and achieving high temperature, high efficiency three dimensional ion implantation is our objective. X-ray diffractions (XRD and high resolution XRD in the glancing mode) showed effects of ion nitriding in the AISI 304 stainless steel samples surface which indicate very thick nitrided layer, especially when operating the glow discharge in the low pressure but with high temperature nitriding mode. Auger electron spectroscopy and microhardness measurements confirmed nitriding in the sample surface. The hybrid treatment (PIII/ion nitriding) is expected to improve further these surfaces.

A simple dc glow discharge with controlled plasma floating potential was applied as a novel source for plasma immersion ion implantation with excellent results. The glow discharge source is normally used for the conditioning of fusion device chambers, taking advantage of the available high accelerating potential which is necessary for the ion bombardment of the walls. Combining an electron-emitting hot filament with this source, it was possible to get a stable discharge at pressures as low as 8?10-4 mbar and, operating it with potentials lower then 70?V, it was possible to reduce the Si sample etching down to zero from 2500???seen at potentials of native 350?V, when exposure times of 750?min were used in the sample's surface subjected to plasma ion implantation of nitrogen. As a result, retained ion doses of 1.5?1017?cm-2 were obtained in etching-free Si surfaces.

A combined surface modification treatment consisting of ion nitriding at high pressure and high temperature, followed by a cycle at low pressure, both cycles using a gas mixture of (N-2/H-2):(50/50) in pressure, was applied to stainless-steel AISI 304. In the first cycle, in a glow discharge at 4x10(-1) mbar and temperatures of 400- 450 degreesC, high-pressure nitriding was applied to the samples. In the second cycle, in a glow discharge at 8x10(-4) mbar, low-pressure nitriding was applied to the samples. Applying this sequential hybrid treatment alternately, good nitriding was obtained. X-ray diffraction (XRD) measurements showed the effects of this hybrid ion nitriding in the AISI 304 surface, indicating thick nitrided layers, confirmed by Auger electron spectroscopy (AES). Conversion electron Mossbauer spectroscopy, combined with AES and XRD, showed phases and compounds induced by such treatments. Vickers hardness measurements showed great enhancement in the surface hardness. Applying other combinations of gas mixtures and cycles, produced diverse results in the surface, like the induction of alpha- and epsilon-phases.