F. Borgioli

XRD and XPS study on reactive plasma sprayed titanium–titanium nitride coatings

Reactive plasma spraying of titanium in a nitrogen-containing plasma gas allows the formation of hard titanium composite coatings reinforced by in situ formed titanium nitrides (TiN and Ti2N). In the present study, the formation of titanium nitrides during the reactive spraying of titanium was studied by means of two different analysis techniques: X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The diffusion and solidification sequence predicted by the Ti-N phase diagram was consistent with the experimental results. The nitrogen retained in the coating was found mainly as titanium nitrides and not as interstitial nitrogen in the titanium lattice. It is hypothesised that the formation and direct solidification of TiN occurs during the flight of the sprayed particles. The presence of solid TiN constrains the thermal contraction of titanium splats upon solidification. The observed cell distortion of the residual α-Ti is thus attributed to tensile stresses arising from the solidification process.

Glow-discharge nitriding of sintered stainless steels

Abstract The glow-discharge nitriding process is particularly suitable to harden the surface of sintered stainless steels components, owing to the high porosity levels of these materials. On wrought austenitic stainless steels this treatment produces a metastable phase, known as supersaturated austenite or S phase, which has shown high hardness values and good corrosion resistance. In the present paper the influence of glow-discharge nitriding process on the microstructural and mechanical properties of AISI 316L austenitic sintered stainless steel has been evaluated and it is compared with the results obtained with ion-nitrided martensitic (AISI 410) and ferritic (AISI 430L) sintered stainless steels. The ion-nitriding treatment, performed at 773 K for 4 and 8 h, produces modified surface layers. The microhardness profiles show high hardness values in the modified layers and a steep decrease to matrix values, thinner hardened layers and lower hardness values are observed on AISI 316L samples, in comparison with AISI 410 and AISI 430L samples. The S phase is detected on the modified layers of the ion-nitrided AISI 316L samples. The crystallographic characterisation has shown that a face centred tetragonal lattice as base for this phase fits well the diffraction spectra, in respect of the ‘traditional’ face centred cubic lattice usually adopted, since the lattice shows a strong distortion, in spite of this, the d -spacing values calculated with a f.c.t. base show a good agreement with literature data, when the used f.c.c. indexing is modified for the f.c.t. lattice.

Glow-discharge nitriding and post-oxidising treatments of AISI H11 steel

Abstract Post-oxidising treatments can be performed to improve the corrosion resistance of nitrided steel components. The glow-discharge process appears particularly attractive, since it allows to carry out both nitriding and post-oxidising treatments in a single technological operation, simply varying the treatment atmosphere and the working conditions. In the present paper the effects of using air as the treatment atmosphere of glow-discharge post-oxidising treatment have been evaluated. Nitriding treatments were performed at 773 K for 5 h, and post-oxidising treatments were carried out at 623 and 773 K for 1 h. The nitriding and nitriding+post-oxidising treatments produce modified surface layers consisting of an outer compound layer and an inner diffusion layer. When the post-oxidising treatments are performed, the compound layer consists of an oxide layer on the top of the nitride layer. With a 623 K post-oxidising treatment the oxide layer consists mainly of magnetite, Fe 3 O 4 , while when post-oxidising is carried out at 773 K it consists essentially of hematite, Fe 2 O 3 . In the inner nitride layer iron (γ′-Fe 4 N, e-Fe 2–3 N) and chromium (CrN) nitrides are present. In all the treated samples high hardness values are obtained in the modified layers. The hardness profiles of the post-oxidised samples are only slightly affected by the 773 K post-oxidising treatment. The corrosion resistance of the treated samples was tested and the results show that the nitriding+623 K post-oxidising treatment is able to significantly improve the corrosion resistance of the untreated and treated AISI H11 samples.

Corrosion resistance properties of plasma nitrided Ti–6Al–4V alloy in hydrochloric acid solutions

Abstract The corrosion properties of TiN layers obtained by glow discharge on Ti–6Al–4V samples were investigated by polarisation curves, cyclic voltammetry and loss weight tests, in different HCl solutions. The results were compared with those obtained on the untreated alloy tested in the same conditions. The corrosion resistance of nitrided samples depends on the quality of the film and increases as the thickness increases. At potential lower than 1000 mV (SSE) nitrided samples show passive behaviour even in concentrated HCl solution (4M). If the potential is higher than a threshold, which depends on the acid concentration, it is observed a high anodic current related to the TiN oxidation. This enhanced oxide growth promotes cracking of the oxide layer and the exposure of fresh TiN surface.

Air treatment of pure titanium by furnace and glow-discharge processes

Abstract The high oxygen affinity of titanium can be used to improve the surface hardness and wear resistance of titanium and titanium alloy components by means of thermal treatments. In the present paper a comparison of the effects of glow-discharge and furnace processes, carried out using air as treatment atmosphere, on the microstructure and mechanical properties of commercially pure titanium samples is reported. Both treatment types, performed at 973 and 1173 K for 0.5, 2 and 4 h, produce modified surface layers: the outer layer (compound layer) consists essentially of TiO 2 and small amounts of TiN x O y , while the inner layer (diffusion layer) consists of α-Ti crystals rich in interstitial atoms. The plasma treatment is shown to be more efficient in hardening titanium surface layers than the furnace process: by using the same treatment temperature and time, plasma treated samples have a thicker hardened layer, with higher hardness values than the furnace treated ones. A crystallographic characterisation of the α-Ti solid solution has also been performed and the a , c lattice parameters have been evaluated. Plasma treated samples show larger lattice parameters and c / a values than the furnace treated samples, suggesting a higher concentration of interstitial atoms due to the plasma treatment.

Wear resistance of Ti–6Al–4V alloy treated by means of glow-discharge and furnace treatments

Abstract The contemporary glow-discharge oxidising and nitriding treatment has shown to produce modified surface layers with enhanced hardness properties, in comparison with the conventional ion-nitriding process. The aim of the present study was to evaluate the tribological properties of ion-oxinitrided samples and to compare their wear behaviour with the one of furnace oxinitrided and ion-nitrided samples. At low coupling loads (50 N) the wear volumes of the treated samples result small and comparable for all the tested velocities. On the other hand, when high coupling loads are used (100 N), the wear of the ion-nitrided samples is higher than that of the oxinitrided ones, this effect becoming more remarkable as sliding velocity increases; moreover, the ion-oxinitriding treatment allows to achieve lower wear volumes than the ones obtained by means of the furnace oxinitriding process.

Influence of the treatment atmosphere on the characteristics of glow-discharge treated sintered stainless steels

Abstract The surface hardening of sintered stainless steel components is a major goal, in order to extend the applications of these materials. The aim of the present study was to evaluate the influence of the treatment atmosphere on the microstructure and mechanical properties of AISI 316L austenitic and AISI 410 martensitic sintered stainless steels by performing glow-discharge nitriding and nitrocarburizing treatments. The treatments, performed at 773 K for 8 h, produced modified surface layers. The use of a nitrocarburizing atmosphere is able to promote the formation of e carbonitride [Fe 2−3 (N, C)], especially on AISI 410 martensitic samples. The microhardness profiles of the treated samples show high hardness values in the modified layers and a steep decrease to matrix values. The AISI 316L samples have thinner hardened layers and lower hardness values, in comparison with AISI 410 ones. Thinner hardened layers with a steeper decrease to matrix values are obtained using a nitrocarburizing atmosphere, if compared with those of nitrided samples. On the modified layers of both the nitrided and nitrocarburized AISI 316L samples the metastable S phase is detected. The X-ray diffraction analysis has shown that its lattice parameter values, evaluated by fitting it with a face centred tetragonal lattice, are influenced by the treatment atmosphere and that the amount of this phase increases when a nitrocarburizing atmosphere is used.

Improvement of corrosion resistance of austenitic stainless steels by means of glow-discharge nitriding

Abstract Austenitic stainless steels are employed in many industrial fields due to their very good resistance to general corrosion in several environments. However, their use is limited due to the fact that they suffer localised corrosion in specific environments, particularly in chloride-ion rich solutions. Low temperature nitriding treatments can improve both corrosion resistance in chloride-ion containing media and surface hardness, due to the formation of a metastable phase known as expanded austenite or S phase; this phase can be outlined as a supersaturated interstitial solid solution of nitrogen in the expanded and distorted γ-Fe f.c.c. lattice. We review the main experimental results obtained in our research on low temperature glow-discharge nitriding of austenitic stainless steels. By means of proper treatment parameters, low temperature glow-discharge nitriding is able to markedly improve the corrosion resistance of austenitic stainless steels, such as AISI 316L and AISI 202 in chloride-ion rich solutions in comparison with the untreated alloys.

Coronal magnetic fields from microwave polarization observations

The solar active region (AR) 7530 was observed at 6 cm on July 3 and 4, 1993 with the Westerbork Synthesis Radio Telescope, using a multi-channel receiver with very narrow bandwidth. We compare the radio data with Yohkoh SXT observations and with the magnetic field extrapolated from the Marshall vector magnetograms in the force-free and current-free approximations. The comparison with soft X-rays shows that, although a general agreement exists between the shape of the radio intensity map and the X-ray loops, the brightness temperature, Tb, obtained using the parameters derived from the SXT is much lower than that observed. The comparison with the extrapolated photospheric fields shows instead that they account very well for the observed Tb above the main sunspots, if gyroresonance emission is assumed. In the observation of July 4 an inversion and strong suppression of the circular polarization was clearly present above different portions of the AR, which indicates that particular relationships exist between the electron density and the magnetic field in the region where the corresponding lines of sight cross the field quasi-perpendicularly. The extrapolated magnetic field at a much higher level (∼ 1010 cm), satisfies the constraints required by the wave propagation theory all over the AR. However, a rather low electron density is derived.

Biocompatibility studies of low temperature nitrided and collagen-I coated AISI 316L austenitic stainless steel

The biocompatibility of austenitic stainless steels can be improved by means of surface engineering techniques. In the present research it was investigated if low temperature nitrided AISI 316L austenitic stainless steel may be a suitable substrate for bioactive protein coating consisting of collagen-I. The biocompatibility of surface modified alloy was studied using as experimental model endothelial cells (human umbilical vein endothelial cells) in culture. Low temperature nitriding produces modified surface layers consisting mainly of S phase, the supersaturated interstitial solid solution of nitrogen in the austenite lattice, which allows to enhance surface microhardness and corrosion resistance in PBS solution. The nitriding treatment seems to promote the coating with collagen-I, without chemical coupling agents, in respect of the untreated alloy. For biocompatibility studies, proliferation, lactate dehydrogenase levels and secretion of two metalloproteinases (MMP-2 and MMP-9) were determined. Experimental results suggest that the collagen protection may be favourable for endothelial cell proliferation and for the control of MMP-2 release.