Ion nitriding of a superaustenitic stainless steel: Wear and corrosion characterization

The superiority of superaustenitic stainless steel (SASS) lies in its good weldability and great resistance to stress corrosion and pitting, because of its higher chromium, molybdenum, and nitrogen contents, when compared to general stainless steels. However, some of its applications are limited by very poor wear behavior. Plasma-nitriding is a very effective treatment for producing wear resistant and hard surface layers on stainless steels without compromising the corrosion resistance. In this work, UNS S31254 SASS samples were plasma-nitrided at three different temperatures (400, 450, and 500 degrees C), under a pressure of 500 Pa, for 5 h, in order to verify the influence of the temperature on the morphology, wear, and corrosion behavior of the modified surface layers. The plasma-nitrided samples were analyzed by means of optical microscopy, micro-hardness. X-ray diffraction, wear, and corrosion tests. Wear tests were conducted in a fixed ball micro-wear machine and corrosion behavior was carried out in natural sea water by means of potentiodynamic polarization curves. For the sample which was plasma-nitrided at 400 degrees C, only the expanded austenite phase was observed, and for the treatments performed at 450 and 500 degrees C, chromium nitrides (CrN and Cr(2)N) were formed in addition to the expanded austenite. Wear volume and Knoop surface hardness increased as the plasma-nitriding temperature increased. Higher wear rates were observed at high temperatures, probably due to the increment on layer fragility. The sample modified at 400 degrees C exhibited the best corrosion behavior among all the plasma-nitriding conditions. (C) 2010 Elsevier B.V. All rights reserved.

Finite element and dimensional analysis algorithm for the prediction of mechanical properties of bulk materials and thin films

In this work, the applicability of a new algorithm for the estimation of mechanical properties from instrumented indentation data was studied for thin films. The applicability was analyzed with the aid of both three-dimensional finite element simulations and experimental indentation tests. The numerical approach allowed studying the effect of the substrate on the estimation of mechanical properties of the film, which was conducted based on the ratio h(max)/l between maximum indentation depth and film thickness. For the experimental analysis, indentation tests were conducted on AISI H13 tool steel specimens, plasma nitrated and coated with TiN thin films. Results have indicated that, for the conditions analyzed in this work, the elastic deformation of the substrate limited the extraction of mechanical properties of the film/substrate system. This limitation occurred even at low h(max)/l ratios and especially for the estimation of the values of yield strength and strain hardening exponent. At indentation depths lower than 4% of the film thickness, the proposed algorithm estimated the mechanical properties of the film with accuracy. Particularly for hardness, precise values were estimated at h(max)/l lower than 0.1, i.e. 10% of film thickness. (C) 2010 Published by Elsevier B.V.

Residual stresses in titanium nitride thin films obtained with step variation of substrate bias voltage during deposition

In this work, a series of depositions of titanium nitride (TiN) films on M2 and D2 steel substrates were conducted in a Triode Magnetron Sputtering chamber. The temperature; gas flow and pressure were kept constant during each run. The substrate bias was either decreased or increased in a sequence of steps. Residual stress measurements were later conducted through the grazing X-ray diffraction method. Different incident angles were used in order to change the penetration depth and to obtain values of residual stress at different film depths. A model described by Dolle was adapted as an attempt to calculate the values of residual stress at each incident angle as a function of the value from each individual layer. Stress results indicated that the decrease in bias voltage during the deposition has produced compressive residual stress gradients through the film thickness. On the other hand, much less pronounced gradients were found in one of the films deposited with increasing bias voltage. (C) 2010 Elsevier B.V. All rights reserved.

Structure and properties of low temperature plasma carburized austenitic stainless steels

Austenitic stainless steels cannot be conventionally surface treated at temperatures close to 550 degrees C due to intense precipitation of nitrides or carbides. Plasma carburizing allows introducing carbon in the steel at temperatures below 500 degrees C without carbide precipitation. Plasma carburizing of AISI 316L was carried out at 480 degrees C and 400 degrees C, during 20 h, using CH(4) as carbon carrier gas. The results show that carbon expanded austenite (gamma(c)), 20 mu m in depth, was formed on the surface after the 480 degrees C treatment. Carbon expanded austenite (gamma(c)), 8 mu m in depth, was formed on the surface after the 400 degrees C treatment. DRX results showed that the austenitic FCC lattice parameter increases from 0.358 nm to 0.363 nm for the 400 degrees C treatment and to 0.369 nm for the 480 degrees C treatment, giving an estimation of circa 10 at.% carbon content for the latter. Lattice distortion, resulting from the expansion and the associated compressive residual stresses increases the surface hardness to 1040 HV(0.025). Micro-scale tensile tests were conducted on specimens prepared with the conditions selected above, which has indicated that the damage imposed to the expanded austenite layer was more easily related to each separated grain than to the overall macro-scale stresses imposed by the tensile test. (C) 2009 Elsevier B.V. All rights reserved.

Improvement of the cavitation erosion resistance of UNS S31803 stainless steel by duplex treatment

A duplex surface treatment consisting of High Temperature Gas Nitriding (HTGN) followed by Low Temperature Plasma Nitriding (LTPN) was carried out in an UNS S31803 duplex stainless steel. The HTGN treatment was intended to produce a relatively thick and hard fully austenitic layer giving mechanical support to the thinner and much harder expanded austenite layer. HTGN was performed at 1200 degrees C for 3 h, in a 0.1 MPa N(2) atmosphere while LTPN, was carried out in a 75% N(2) + 25% H(2) atmosphere, at 400 degrees C for 12 h, under a 250 Pa pressure, and 450 V. An expanded austenite gamma(N) layer, 2.3 mu m thick, 1500 HVO.025 hard, was formed on top of a 100 mu m thick, 330 HV 0.1 hard, fully austenitic layer, containing 0.9 wt% N. For comparison purposes LTPN was carried out with UNS S30403 stainless steel specimens obtaining a 4.0 mu m thick, 1500 HV 0.025 hard, expanded austenite layer formed on top of a fully austenitic matrix having 190 HV 0.1. The nitrided specimens were tested in a 20 kHz vibratory cavitation-erosion testing equipment. Comparison between the duplex treated UNS S31803 steel and the low temperature plasma nitrided UNS S30403 steel, resulted in incubation times almost 9 times greater. The maximum cavitation wear rate of the LTPN UNS S30403 was 5.5 g/m(2)h, 180 times greater than the one measured for the duplex treated UNS S31803 steel. The greater cavitation wear resistance of the duplex treated UNS S31803 steel, compared to the LTPN treated UNS S30403 steel was explained by the greater mechanical support the fully austenitic, 330 HV 0.1 hard, 100 mu m layer gives to the expanded austenite layer formed on top of the specimen after LTPN. A strong crystallographic textured surface, inherited from the fully austenitic layer formed during HTGN, with the expanded austenite layer showing {101} crystallographic planes//surface contributed also to improve the cavitation resistance of the duplex treated steel. (C) 2010 Elsevier B.V. All rights reserved.

Corrosion behavior of carbon steel protected with single and bi-layer of silane films filled with silica nanoparticles

The electrochemical behaviour of carbon steel coated with bis-[trimethoxysilylpropyl]amine (BTSPA) filled with silica nanoparticles in naturally aerated 0.1 mol L-1 NaCl solutions was evaluated. The coating was prepared by adding different concentrations of silica nanoparticles (100, 200, 300, 400 and 500 ppm) to the hydrolysis solution and then a second layer without silica nanoparticles was applied. The electrochemical behavior of the coated steel was evaluated by means of open-circuit potential (E-OC), electrochemical impedance spectroscopy (EIS) and polarization curves. Surface characterization was made by atomic force microscopy (AFM), and its hydrophobicity assessed by contact angle measurements. EIS diagrams have shown an improvement of the barrier properties of the silane layer with the silica addition, which was further improved on the bi-layer system. However, a dependence on the filler concentration was verified, and the best electrochemical response was obtained for samples modified with 300 ppm of silica nanoparticles. AFM images have shown a homogeneous distribution of the silica nanoparticles on the sample surface; however particles agglomeration was detected, which degraded the corrosion protection performance. The results were explained on the basis of the improvement of the barrier properties of the coating due to the filler addition and on the onset of defective regions on the more heavily filled coatings allowing easier electrolyte penetration. (C) 2007 Elsevier B.V. All rights reserved.

Study of an alternative phosphate sealer for replacement of hexavalent chromium

This study evaluates the possibility of replacing the hexavalent chromium passivation treatment used as a sealer after phosphating of carbon steel (SAE 1010) by a treatment with niobium ammonium oxalate (Ox). Samples of carbon steel (SAE 1010) after being phosphated in a zinc phosphate bath (PZn + Ni) were immersed in solution of niobium ammonium oxalate (250 mg L(-1) of Nb) either at pH 3.0 or pH 8.0. A passivation treatment with a solution with CrO(3) (200 mg L(-1) of Cr(6+)) was also used for reference. The corrosion resistance of the phosphated samples after passivation treatments was analyzed in a NaCl 0.5 mol L(-1) solution using electrochemical impedance spectroscopy (EIS) and anodic polarization curves. Salt spray tests were also performed to evaluate their corrosion resistance. The results showed that the highest corrosion resistance was obtained by passivation in a solution with (250 mg L(-1) of Nb) at pH 8.0. (C) 2010 Elsevier B.V. All rights reserved.

Effects of mechanical properties, residual stress and indenter tip geometry on instrumented indentation data in thin films

In this work, an axisymmetric two-dimensional finite element model was developed to simulate instrumented indentation testing of thin ceramic films deposited onto hard steel substrates. The level of film residual stress (sigma(r)), the film elastic modulus (E) and the film work hardening exponent (n) were varied to analyze their effects on indentation data. These numerical results were used to analyze experimental data that were obtained with titanium nitride coated specimens, in which the substrate bias applied during deposition was modified to obtain films with different levels of sigma(r). Good qualitative correlation was obtained when numerical and experimental results were compared, as long as all film properties are considered in the analyses, and not only sigma(r). The numerical analyses were also used to further understand the effect of sigma(r) on the mechanical properties calculated based on instrumented indentation data. In this case, the hardness values obtained based on real or calculated contact areas are similar only when sink-in occurs, i.e. with high n or high ratio VIE, where Y is the yield strength of the film. In an additional analysis, four ratios (R/h(max)) between indenter tip radius and maximum penetration depth were simulated to analyze the combined effects of R and sigma(r) on the indentation load-displacement curves. In this case, or did not significantly affect the load curve exponent, which was affected only by the indenter tip radius. On the other hand, the proportional curvature coefficient was significantly affected by sigma(r) and n. (C) 2010 Elsevier B.V. All rights reserved.

Numerical study of tensile tests conducted on systems with elastic-plastic films deposited onto elastic-plastic substrates

In this work, a series of two-dimensional plane-strain finite element analyses was conducted to further understand the stress distribution during tensile tests on coated systems. Besides the film and the substrate, the finite element model also considered a number of cracks perpendicular to the film/substrate interface. Different from analyses commonly found in the literature, the mechanical behavior of both film and substrate was considered elastic-perfectly plastic in part of the analyses. Together with the film yield stress and the number of film cracks, other variables that were considered were crack tip geometry, the distance between two consecutive cracks and the presence of an interlayer. The analysis was based on the normal stresses parallel to the loading axis (sigma(xx)), which are responsible for cohesive failures that are observed in the film during this type of test. Results indicated that some configurations studied in this work have significantly reduced the value of sigma(xx) at the film/substrate interface and close to the pre-defined crack tips. Furthermore, in all the cases studied the values of sigma(xx) were systematically larger at the film/substrate interface than at the film surface. (C) 2010 Elsevier B.V. All rights reserved.

Use of diamond-like carbon with tungsten (W-DLC) films as biocompatible material

Diamond-like carbon (DLC), also known as amorphous hydrogenated carbon (a-C:H), are a class of materials with excellent mechanical, tribological and biological properties. When the DLC films are enhanced with other elements, all of these properties can be changed within a certain range. In this work, reactive magnetron sputtering was used to deposit W-DLC (hydrogenated tungsten carbide) films on Ti6A14V (implant material). Many films were made using pure tungsten (99.99%) target and different plasmas processes, with different ratio among argon and methane. It was possible to change the films composition (from pure amorphous carbon to carbon enhanced with tungsten) according to ratio of argon and methane plasma. Between all films processed, the carbon films enhanced with tungsten showed good results in the ""in vitro"" cytotoxicity testing. Raman spectroscopy was used to analyze the chemical bonds kinds and the chemical bonds quantities. The Rutherford Back Scattering (RBS) was used to analyze the films compositions. The chemical inertness was analyzed by scanning voltametry. W-DLC thin films obtained in these processes have low roughness, high chemical resistance, good adhesion and show a high biocompatibility, when compared with common DLC thin films. Hence we have concluded that the tungsten concentrations in the DLC films make an important role to improve the properties of the DLC layers. (C) 2007 Elsevier B.V. All rights reserved.

Anti-Corrosion performance of a new silane coating for corrosion protection of AZ31 Magnesium alloy in Hank’s solution

Mg alloys can be used as bioresorsable metallic implants. However, the high corrosion rate of magnesium alloys has limited their biomedical applications. Although Mg ions are essential to the human body, an excess may cause undesirable health effects. Therefore, surface treatments are required to enhance the corrosion resistance of magnesium parts, decreasing its rate to biocompatible levels and allowing its safe application as bioresorbable metallic implants. The application of biocompatible silane coatings is envisaged as a suitable strategy for retarding the corrosion process of magnesium alloys. In the current work, a new glycidoxypropyltrimethoxysilane (GPTMS) based coating was tested on AZ31 magnesium substrates subjected to different surface conditioning procedures before coating deposition. The surface conditioning included a short etching with hydrofluoric acid (HF) or a dc polarisation in alkaline electrolyte. The silane coated samples were immersed in Hank's solution and the protective performance of the coating was studied through electrochemical impedance spectroscopy (EIS). The EIS data was treated by new equivalent circuit models and the results revealed that the surface conditioning process plays a key role in the effectiveness of the silane coating. The HF treated samples led to the highest impedance values and delayed the coating degradation, compared to the mechanically polished samples or to those submitted to dc polarisation.

Friction surfacing of aluminium alloys

Dissertação para a obtenção do grau de Mestre em Engenharia Mecânica

Evolution of the functional properties of titanium–silver thin films for biomedical applications: Influence of in-vacuum annealing

In this work, the thermal stability of TiAgx thin films, deposited by magnetron sputtering, was evaluated, envisaging their application in biomedical devices, namely as electrodes for biosignal acquisition. Based on the composition and microstructural characterization, a set of four representative TiAgx thin films was selected in order to infer whether they are thermally stable in terms of functional properties. In order to achieve this purpose, the structural and morphological evolution of the films with annealing temperature was correlated with their electrical, mechanical and thermal properties. Two distinct zones were identified and two samples from each zone were extensively analysed. In the first zone (zone I), Ti was the main component (Ti-rich zone) while in the second, zone II, the Ag content was more significant. The selected samples were annealed in vacuum at four different temperatures up to 500 oC. For the samples produced within zone I, small microstructural changes were observed due to the recrystallization of the Ti structure and grain size increment. Also, no significant changes were observed with annealing temperature regarding the f l ’ functional properties, being thermally stable up to 500 oC. For higher Ag contents (zone II) the energy supplied by thermal treatments was sufficient to activate the crystallization of Ti-Ag intermetallic phases. A strong increase of the grain size of these phases was also reported. The structural and morphological organization proved to be determinant for the physical responses of the TiAgx system. The hardness and Y g’s modulus were significantly improved with the formation of the intermetallic phases. The silver addition and annealing treatments also played an important role in the electrical conductivity of the films, which was once again improved by the formation of Ti-Ag phases. The thermal diffusivity of the films was practically unchanged with the heat-treatment. This set of results shows that this intermetallic-like thin film system has good thermal stability up to high temperatures (as high as 500 oC), which in case of the highest Ag content zone is particularly evident for electrical and mechanical properties, showing an important improvement. Hardness increases about three times, while resistivity values become half of those from the lowest Ag contents zone. These set of characteristics are consistent with the targeted applications, namely in terms of biomedical sensing devices.

Dustiness and deagglomeration testing: interlaboratory comparison of systems for nanoparticle powders

Different types of aerosolization and deagglomeration testing systems exist for studying the properties of nanomaterial powders and their aerosols. However, results are dependent on the specific methods used. In order to have well-characterized aerosols, we require a better understanding of how system parameters and testing conditions influence the properties of the aerosols generated. In the present study, four experimental setups delivering different aerosolization energies were used to test the resultant aerosols of two distinct nanomaterials (hydrophobic and hydrophilic TiO2). The reproducibility of results within each system was good. However, the number concentrations and size distributions of the aerosols created varied across the four systems; for number concentrations, e.g., from 10(3) to 10(6) #/cm(3). Moreover, distinct differences were also observed between the two materials with different surface coatings. The article discusses how system characteristics and other pertinent conditions modify the test results. We propose using air velocity as a suitable proxy for estimating energy input levels in aerosolization systems. The information derived from this work will be especially useful for establishing standard operating procedures for testing nanopowders, as well as for estimating their release rates under different energy input conditions, which is relevant for occupational exposure.

Studies on Laser Induced and RF Sputtered Plasma using Optical Emission Spectroscopy and Langmuir Probe

The main objective of the present study is to understand different mechanisms involved in the production and evolution of plasma by the pulsed laser ablation and radio frequency magnetron sputtering. These two methods are of particular interest, as these are well accomplished methods used for surface coatings, nanostructure fabrications and other thin film devices fabrications. Material science researchers all over the world are involved in the development of devices based on transparent conducting oxide (TCO) thin films. Our laboratory has been involved in the development of TCO devices like thin film diodes using zinc oxide (ZnO) and zinc magnesium oxide (ZnMgO), thin film transistors (TFT's) using zinc indium oxide and zinc indium tin oxide, and some electroluminescent (EL) devices by pulsed laser ablation and RF magnetron sputtering.In contrast to the extensive literature relating to pure ZnO and other thin films produced by various deposition techniques, there appears to have been relatively little effort directed towards the characterization of plasmas from which such films are produced. The knowledge of plasma dynamics corresponding to the variations in the input parameters of ablation and sputtering, with the kind of laser/magnetron used for the generation of plasma, is limited. To improve the quality of the deposited films for desired application, a sound understanding of the plume dynamics, physical and chemical properties of the species in the plume is required. Generally, there is a correlation between the plume dynamics and the structural properties of the films deposited. Thus the study of the characteristics of the plume contributes to a better understanding and control of the deposition process itself. The hydrodynamic expansion of the plume, the composition, and SIze distribution of clusters depend not only on initial conditions of plasma production but also on the ambient gas composition and pressure. The growth and deposition of the films are detennined by the thermodynamic parameters of the target material and initial conditions such as electron temperature and density of the plasma.For optimizing the deposition parameters of various films (stoichiometric or otherwise), in-situ or ex-situ monitoring of plasma plume dynamics become necessary for the purpose of repeatability and reliability. With this in mind, the plume dynamics and compositions of laser ablated and RF magnetron sputtered zinc oxide plasmas have been investigated. The plasmas studied were produced at conditions employed typically for the deposition of ZnO films by both methods. Apart from this two component ZnO plasma, a multi-component material (lead zirconium titanate) was ablated and plasma was characterized.