A Comparati ve Study of Mechanical and Tribological Properties of AISI-304 and AISI-316 Submitted to Glow Discharge Nitriding

Mechanical and tribological properties of AISI 304 and AISI 316 stainless steels submitted to glow discharge ion nitriding are reported. The atmosphere was 20:80 - N2:H2 with substrate temperatures ranging from 300 to 500 °C. Treatment at 300 °C produced expanded austenite (γN) in both steels. Increasing the temperature, the phases γ′-Fe4N and ε- Fe2+xN were present and the latter is the major phase for AISI 304. At 500 °C, the CrN phase was also identified in both steels. Hardnesses of about 13-14 GPa at near surface regions were obtained in both steels. Moreover, AISI 316 nitrided at 500 °C has the deepest hard layer. Tribological tests showed that wear can be reduced by up to a factor of six after the nitriding processes, even for a working temperature of 300 °C. The profiles during and after nanoscratch tests did not reveal significant differences after nitriding processes in both steels.

Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma

SILVA, J. S. P. Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma. 2008. 119 f. Tese (Doutorado) - Faculdade de Medicina, Universidade de São Paulo. São Paulo, 2008.

Plasma kinetic theory

Kinetic theory studies the macroscopic properties of large numbers of particles, starting from their (classical) equations of motion while the thermodynamics describes the equilibrium behavior of macroscopic objects in terms of concepts such as work, heat, and entropy. The phenomenological laws of thermodynamics tell us how these quantities are constrained as a system approaches its equilibrium. At the microscopic level, we know that these systems are composed of particles (atoms, particles), whose interactions and dynamics are reasonably well understood in terms of more fundamental theories. If these microscopic descriptions are complete, we should be able to account for the macroscopic behavior, i.e. derive the laws governing the macroscopic state functions in equilibrium. Kinetic theory attempts to achieve this objective. In particular, we shall try to answer the following questions [1]: How can we define equilibrium for a system of moving particles? Do all systems naturally evolve towards an equilibrium state? What is the time evolution of a system that is not quite in equilibrium?

Plasma diagnostics and ITO film deposition by RF-assisted closed-field dual magnetron system

Deposition of indium tin oxide (ITO) among various transparent conductive materials on flexible organic substrates has been intensively investigated among academics and industrials for a whole new array of imaginative optoelectronic products. One critical challenge coming with the organic materials is their poor thermal endurances, considering that the process currently used to produce industry-standard ITO usually involves relatively high substrate temperature in excess of 200°C and post-annealing. A lower processing temperature is thus demanded, among other desires of high deposition rate, large substrate area, good uniformity, and high quality of the deposited materials. For this purpose, we developed an RF-assisted closed-field dual magnetron sputtering system. The “prototype” system consists of a 3-inch unbalanced dual magnetron operated at a closed-field configuration. An RF coil was fabricated and placed between the two magnetron cathodes to initiate a secondary plasma. The concept is to increase the ionization faction with the RF enhancement and utilize the ion energy instead of thermal energy to facilitate the ITO film growth. The closed-field unbalanced magnetrons create a plasma in the intervening region rather than confine it near the target, thus achieving a large-area processing capability. An RF-compensated Langmuir probe was used to characterize and compare the plasmas in mirrored balanced and closed-field unbalanced magnetron configurations. The spatial distributions of the electron density ne and electron temperature Te were measured. The density profiles reflect the shapes of the plasma. Rather than intensively concentrated to the targets/cathodes in the balanced magnetrons, the plasma is more dispersive in the closed-field mode with a twice higher electron density in the substrate region. The RF assistance significantly enhances ne by one or two orders of magnitude higher. The effect of various other parameters, such as pressure, on the plasma was also studied. The ionization fractions of the sputtered atoms were measured using a gridded energy analyzer (GEA) combined with a quartz crystal microbalance (QCM). The presence of the RF plasma effectively increases the ITO ionization fraction to around 80% in both the balanced and closed-field unbalanced configurations. The ionization fraction also varies with pressure, maximizing at 5-10 mTorr. The study of the ionization not only facilitates understanding the plasma behaviors in the RF-assisted magnetron sputtering, but also provides a criterion for optimizing the film deposition process. ITO films were deposited on both glass and plastic (PET) substrates in the 3-inch RF-assisted closed-field magnetrons. The electrical resistivity and optical transmission transparency of the ITO films were measured. Appropriate RF assistance was shown to dramatically reduce the electrical resistivity. An ITO film with a resistivity of 1.2×10-3 Ω-cm and a visible light transmittance of 91% was obtained with a 225 W RF enhancement, while the substrate temperature was monitored as below 110°C. X-ray photoelectron spectroscopy (XPS) was employed to confirm the ITO film stoichiometry. The surface morphology of the ITO films and its effect on the film properties were studied using atomic force microscopy (AFM). The prototype of RF-assisted closed-field magnetron was further extended to a larger rectangular shaped dual magnetron in a flat panel display manufacturing system. Similar improvement of the ITO film conductivities by the auxiliary RF was observed on the large-area PET substrates. Meanwhile, significant deposition rates of 25-42 nm/min were achieved.

A Comparati ve Study of Mechanical and Tribological Properties of AISI-304 and AISI-316 Submitted to Glow Discharge Nitriding

Mechanical and tribological properties of AISI 304 and AISI 316 stainless steels submitted to glow discharge ion nitriding are reported. The atmosphere was 20:80 - N2:H2 with substrate temperatures ranging from 300 to 500 °C. Treatment at 300 °C produced expanded austenite (γN) in both steels. Increasing the temperature, the phases γ′-Fe4N and ε- Fe2+xN were present and the latter is the major phase for AISI 304. At 500 °C, the CrN phase was also identified in both steels. Hardnesses of about 13-14 GPa at near surface regions were obtained in both steels. Moreover, AISI 316 nitrided at 500 °C has the deepest hard layer. Tribological tests showed that wear can be reduced by up to a factor of six after the nitriding processes, even for a working temperature of 300 °C. The profiles during and after nanoscratch tests did not reveal significant differences after nitriding processes in both steels.

Physico-chemical properties of sol-gel synthesized titanosilicates for the uptake of radionuclides from aqueous solutions

Harnessing the power of nuclear reactions has brought huge benefits in terms of nuclear energy, medicine and defence as well as risks including the management of nuclear wastes. One of the main issues for radioactive waste management is liquid radioactive waste (LRW). Different methods have been applied to remediate LRW, thereunder ion exchange and adsorption. Comparative studies have demonstrated that Na2Ti2O3SiO4·2H2O titanosilicate sorption materials are the most promising in terms of Cs+ and Sr2+ retention from LRW. Therefore these TiSi materials became the object of this study. The recently developed in Ukraine sol-gel method of synthesizing these materials was chosen among the other reported approaches since it allows obtaining the TiSi materials in the form of particles with size ≥ 4mm. utilizing inexpensive and bulk stable inorganic precursors and yielded the materials with desirable properties by alteration of the comparatively mild synthesis conditions. The main aim of this study was to investigate the physico-chemical properties of sol-gel synthesized titanosilicates for radionuclide uptake from aqueous solutions. The effect of synthesis conditions on the structural and sorption parameters of TiSi xerogels was planned to determine in order to obtain a highly efficient sorption material. The ability of the obtained TiSis to retain Cs+, Sr2+ and other potentially toxic metal cations from the synthetic and real aqueous solutions was intended to assess. To our expectations, abovementioned studies will illustrate the efficiency and profitability of the chosen synthesis approach, synthesis conditions and the obtained materials. X-ray diffraction, low temperature adsorption/desorption surface area analysis, X-ray photoelectron spectroscopy, infrared spectroscopy and scanning electron microscopy with energy dispersive X-ray spectroscopy was used for xerogels characterization. The sorption capability of the synthesized TiSi gels was studied as a function of pH, adsorbent mass, initial concentration of target ion, contact time, temperature, composition and concentration of the background solution. It was found that the applied sol-gel approach yielded materials with a poorly crystalline sodium titanosilicate structure under relatively mild synthesis conditions. The temperature of HTT has the strongest influence on the structure of the materials and consequently was concluded to be the control factor for the preparation of gels with the desired properties. The obtained materials proved to be effective and selective for both Sr2+ and Cs+ decontamination from synthetic and real aqueous solutions like drinking, ground, sea and mine waters, blood plasma and liquid radioactive wastes.

Tratamento termoquímico do titânio auxiliado por plasma de ar - N2 - O2

Discs were grade II cp Ti oxynitride by plasma of Ar - N2 - O2 using different proportions of individual gases. These ratios were established from analysis of optical emission spectroscopy (OES) of plasma species. The proportions that resulted in species whose spectra showed an abrupt change of light intensity were chosen for this study. Nanohardness tests revealed that there was a correlation between the intensity of N2 + species with the hardness, because the treatments where they had a higher intensity, obtained a higher value nanohardness, although the crystalline phases have remained unchanged. With respect to topography, it was observed that in general, the surface roughness is related to the intensities of plasma species, because they may have different values depending on the behavior of the species. Images obtained by optical microscopy revealed a surface with grains of different colors to optical reflectance showed a peak of reflection in the red area. Measures the contact angle and surface tension showed hydrophilic properties and hydrophilic with little variation of polar and dispersive components of surface tension

Desenvolvimento de um sistema de nitretação por plasma em fonte pulsada e sua influencia sobre a nitretação do titânio

The pulsed plasma nitriding is a solution currently used in the metallurgical industry to resolve problems earlier in the processing of parts by using plasma DC voltage. These problems consisted mainly of edge effect and opening arches caused due to non-uniformity of electric fields on uneven surfaces. By varying the pulse width can reduce these effects. However, variations in pulse width can drastically affect the population of the plasma species and hence the final microstructure of the nitrided layer. In literature, little is known about the effect of process parameters on the properties of the plasma species and, consequently, the surface properties. We have developed a system of nitriding with pulsed source with fixed period of 800  pulse width is variable. Examined the variation of these parameters on the properties of nitrided surface when keeping constant temperature, gas composition, flow, pressure and power. It was found that the values of width and pulse repetition time of considerable influence in the intensities of the species present in plasma. Moreover, we observed the existence of the edge effect for some values of pulse widths, as well as changes in surface roughness and hardness

Influência das espécies ativas na absorção de intersticiais durante a carbonitretação a plasma do TI

Physical-chemical properties of Ti are sensible to the presence of interstitial elements. In the case of thermochemical treatments plasma assisted, the influence of different active species is not still understood. In order to contribute for such knowledge, this work purposes a study of the role played by the active species atmosphere into the Ar N2 CH4 carbonitriding plasma. It was carried out a plasma diagnostic by OES (Optical Emission Spectroscopy) in the z Ar y N2 x CH4 plasma mixture, in which z, y and x indexes represent gas flow variable from 0 to 4 sccm (cm3/min). The diagnostic presents abrupt variations of emission intensities associated to the species in determined conditions. Therefore, they were selected in order to carry out the chemical treatment and then to investigate their influences. Commercial pure Ti disks were submitted to plasma carbonitriding process using pre-established conditions from the OES measurements while some parameters such as pressure and temperature were maintained constant. The concentration profiles of interstitial elements (C and N atoms) were determined by Resonant Nuclear Reaction Analysis (NRA) resulting in a depth profile plots. The reactions used were 15N(ρ,αγ)12C and 12C(α,α)12C. GIXRD (Grazing Incidence X-Ray Diffraction) analysis was used in order to identify the presence of phases on the surface. Micro-Raman spectroscopy was used in order to qualitatively study the carbon into the TiCxN1 structure. It has been verified which the density species effectively influences more the diffusion of particles into the Ti lattice and characteristics of the layer formed than the gas concentration. High intensity of N2 + (391,4 nm) and CH (387,1 nm) species promotes more diffusion of C and N. It was observed that Hα (656,3 nm) species acts like a catalyzer allowing a deeper diffusion of nitrogen and carbon into the titanium lattice.

Influência dos parâmetros de processo na deposição de nitreto de titânio por plasma em gaiola catódica

Titanium nitride films were grown on glass using the Cathodic Cage Plasma Deposition technique in order to verify the influence of process parameters in optical and structural properties of the films. The plasma atmosphere used was a mixture of Ar, N2 and H2, setting the Ar and N2 gas flows at 4 and 3 sccm, respectively and H2 gas flow varied from 0, 1 to 2 sccm. The deposition process was monitored by Optical Emission Spectroscopy (OES) to investigate the influence of the active species in plasma. It was observed that increasing the H2 gas flow into the plasma the luminescent intensities associated to the species changed. In this case, the luminescence of N2 (391,4nm) species was not proportional to the increasing of the H2 gas into the reactor. Other parameters investigated were diameter and number of holes in the cage. The analysis by Grazing Incidence X-Ray Diffraction (GIXRD) confirmed that the obtained films are composed by TiN and they may have variations in the nitrogen amount into the crystal and in the crystallite size. The optical microscopy images provided information about the homogeneity of the films. The atomic force microscopy (AFM) results revealed some microstructural characteristics and surface roughness. The thickness was measured by ellipsometry. The optical properties such as transmittance and reflectance (they were measured by spectrophotometry) are very sensitive to changes in the crystal lattice of the material, chemical composition and film thicknesses. Therefore, such properties are appropriate tools for verification of this process control. In general, films obtained at 0 sccm of H2 gas flow present a higher transmittance. It can be attributed to the smaller crystalline size due to a higher amount of nitrogen in the TiN lattice. The films obtained at 1 and 2 sccm of H2 gas flow have a golden appearance and XRD pattern showed peaks characteristics of TiN with higher intensity and smaller FWHM (Full Width at Half Maximum) parameter. It suggests that the hydrogen presence in the plasma makes the films more stoichiometric and becomes it more crystalline. It was observed that with higher number of holes in the lid of the cage, close to the region between the lid and the sample and the smaller diameter of the hole, the deposited film is thicker, which is justified by the most probability of plasma species reach effectively the sample and it promotes the growth of the film

Propriedades tribomecânicas de superfícies de titânio carbonitretadas por plasma

Interstitial compounds of titanium have been mainly studied due to the large range of properties acquired when C, N, O and H atoms are added. In this work, surfaces of TiCxNy were produced by thermochemical treatments assisted by plasma with different proportions of Ar + N2 + CH4 gas mixture. The Ar gas flow was fixed in 4 sccm, varying only N2 and CH4 gas flows. During the thermochemical treatment, the plasma was monitored by Optical Emission Spectroscopy (OES) for the investigation of the influence of active species. After treatments, C and N concentration profile, crystalline and amorphous phases were analyzed by Nuclear Reaction (NRA). Besides tribomechanical properties of the Ti surface were studied through the nanohardness measurements and friction coefficient determination. The worn areas were evaluated by profilometry and Scanning Electronic Microscope (SEM) in order to verify the wear mechanism present in each material. It has been seen which the properties like nanohardness and friction coefficient have strong relation with luminous intensity of species of the plasma, suggesting a using of this characteristic as a parameter of process

Influência das espécies do plasma de N2 + O2 nas propriedades físicoquímicas das superfícies do pet

This work reports the influence of the poly (ethylene terephthalate) textile and films surface modification by plasmas of O2 and mixtures (N2 + O2), on their physical and chemical properties. The plasma surface polymeric modification has been used for many researchs, because it does not affect the environment with toxic agents, the alterations remains only at nanometric layers and this technique shows expressive results. Then, due to its good acceptance, the treatment was carried out in a vacuum chamber. Some parameters remained constant during all treatment, such as: Voltage 470 V; Pressure 1,250 Mbar; Current: 0, 10 A and gas flow: 10 cm3/min, using oxygen plasma alternating the treatment time 10 to 60 min with an increase of 10 min to each subsequent treatment. Also, the samples were treated with a gas mixture (nitrogen + oxygen) which was varied only the gas composition from 0 to 100% leaving the treatment time remaining constant to all treatment (10 min). The plasma treatment was characterized in-situ with Optics Emission Spectroscopy (OES), and the samples was characterized by contact angle, surface tension, Through Capillary tests, Raman spectroscopy, Infrared attenuated total reflection (IR-ATR) and atomic force microscopy, scanning electronic Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that oxygen treated fabrics presented high wettability, due to the hydrophilic groups incorporation onto the surface formed through spputering of carbon atoms. For the nitrogen atmosphere, there is the a film deposition of amine groups. Treatment with small oxygen concentration in the mixture with nitrogen has a higher spputered species of the samples

Estudo da viabilidade técnica para obtenção de superfície duplex em aço inoxidável martensítico AISI 410 através do processo de deposição a plasma por gaiola catódica

The technique of plasma nitriding by the cathode cage mainly stands out for its ability to produce uniform layers, even on parts with complex geometries. In this study, it was investigated the efficiency of this technique for obtaining duplex surface, when used, simultaneously, to nitriding treatment and thin film deposition at temperatures below 500°C. For this, were used samples of AISI 41 0 Martensitic Stainless Steel and performed plasma treatment, combining nitriding and deposition of thin films of Ti and/or TiN in a plasma atmosphere containing N2-H2. It was used a cathodic cage of titanium pure grade II, cylindrical with 70 mm diameter and 34 mm height. Samples were treated at temperature 420ºC for 2 and 12 hours in different working pressures. Optical Microscopy (OM), Scanning Electron Microscopy (SEM) with micro-analysis by Energy Dispersive Spectroscopy (EDS), X-Ray Diffraction (XRD), Atomic Force Microscopy (AFM) and analysis of Vickers Microhardness were used to investigate coating properties such as homogeneity and surface topography, chemical composition, layer thickness, crystalline phase, roughness and surface microhardness. The results showed there is a direct proportionality between the presence of H2 in plasma atmosphere and the quantity of titanium in surface chemical composition. It was also observed that the plasma treatment at lowpressure is more effective in formation of TiN thin film

Diagnóstico das espécies ativas do plasma usado em tratamentos termoquímicos do titânio

Plasma diagnostics by Optical Emission Spectroscopy were performed for electrical discharge in three gas mixture respecting the combinations z N2 y Ar x H2, z N2 y Ar x O2 e z N2 y Ar x CH4, in which the indexes z and y systematically vary from 1 to 4 and x varies from 0 to 4, every one has dimension SCCM, resulting in 80 combinations. From the all obtained spectrums, the species CH (387,1 nm), N2+ (391,4 nm), Hβ (486,1 nm), Hα (656,3 nm), Ar (750,4 nm), O (777,4 nm) e O (842,6 nm) were analyzed because of their abundance and importance on the kinetic of reaction from the plasma to surface, besides their high dependences on the gases flows. Particularly interesting z, y and x combinations were chosen in order to study the influence of active species on the surface modification during the thermochemical treatment. From the mixtures N2 Ar O2 e N2 Ar CH4 were chosen three peculiar proportions which presented luminous intensity profile with unexpected maximum or minimum values, denominated as plasma anomaly. Those plasma concentrations were utilized as atmosphere of titanium treatment maintaining constant the control parameters pressure and temperature. It has been verified a relation among luminous intensity associated to N2+ and roughness, nanohardness and O atoms diffusion into the crystalline lattice of treated titanium and it has been seen which those properties becomes more intense precisely in the higher points found in the optical profile associated to the N2+ specie. Those parameters were verified for the mixture which involved O2 gas. For the mixture which involves CH4 gas, the relation was determinate by roughness, number of nitrogen and carbon atoms diffused into the titanium structure which presented direct proportionality with the luminous intensity referent to the N2+ and CH. It has been yet studied the formation of TiCN phases on the surface which presented to be essentially directly proportional to the increasing of the CH specie and inversely proportional to the increasing of the specie N2+

Photoconductivity and electrical properties of diamond films grown by MPCVD

The electrical and photoconductive features of as-grown microwave-plasma-assisted chemical-vapour deposition (MPCVD) diamond films are studied in correlation with magnetic results obtained from electron paramagnetic resonance (EPR). Also, the morphology is analysed by atomic force microscopy (AFM) showing [111] crystals with a good uniformity of the deposit. The photoresponse as well the current-voltage features observed show an efficient photogeneration of carriers while the optoelectronic characteristics of the metal-diamond junction have an ideality factor of 1.6 together with a rectification ratio of about 10(4) at +/-2.5 V. The nature of the mechanisms responsible for the conduction is discussed. (C) 1998 Elsevier Science S.A.