Comparison of ferritic and austenitic plasma nitriding and nitrocarburizing behavior of AISI 4140 low alloy steel

This paper compares the ferritic and austenitic plasma nitriding and nitrocarburizing behavior of AISI 4140 low alloy steel carried out to improve the surface corrosion resistance. The gas composition for plasma nitriding was 85% N₂–15% H₂ and that for plasma nitrocarburizing was 85% N₂–12% H₂–3% CO₂. Both treatments were performed for 5 h, for different process temperatures of 570 and 620 °C for ferritic and austenitic plasma treatment, respectively. Optical microscopy, X-ray diffraction and potentiodynamic polarization technique in 3.5% NaCl solution, were used to study the treated surfaces. The results of X-ray analysis revealed that with increasing the treatment temperature from 570 to 620 °C for both treatments, the amount of ε phase decreased and γ′ phase increased. Nitrocarburizing treatment resulted in formation of a more amount of ε phase with respect to nitriding treatment. However, the highest amount of ε phase was observed in the ferritic nitrocarburized sample at 570 °C. The sample nitrided at 620 °C exhibited the thickest layer. The potentiodynamic polarization results revealed that after plasma nitriding and nitrocarburizing at 570 °C, corrosion potential increased with respect to the untreated sample due to the noble nitride and carbonitride phases formed on the surface. After increasing the treatment temperature from 570 to 620 °C, corrosion potential decreased due to the less ε phase development in the compound layer and more porous compound layer formed at 620 °C with respect to the treated samples at 570 °C.     

Nitriding of AISI M2 tool steel in an inductive r.f. plasma

The nitriding of AISI M2 tool steel in an inductive r.f. plasma was investigated. The plasma was sustained with a 27.12 MHz generator in gas mixtures of N₂ and H₂ at a pressure of 10 mbar. The ion nitriding was performed at a net r.f. power of 400 W at substrate temperatures of 450–500 °C. X-ray diffraction studies of the treated samples revealed that the most efficient formation of nitride phases was observed in samples nitrided in a pure N₂ plasma. As a result of the ion nitriding the surface hardness was substantially increased from a Vickers hardness VHN of 290 kgf mm^-2 for untreated samples to a maximum VHN of 1200 kgf mm^-2 for samples treated in a plasma sustained in a gas mixture with N₂:H₂ = 1:1.     

In‐situ‐Sauerstoffmesszellen für den Einsatz im Vakuum. In‐situ oxygen sensors for the use in vacuum

The use of galvanic cells with oxide‐ion‐conducting solid electrolytes as sensors in vacuum allows to measure directly the oxygen partial pressure deciding for redox processes at the surface of workpieces during heat treatments. The oxygen exists either as a free molecular gaseous component or in the thermodynamic equilibrium with other gases. The bases of the known gas potentiometry are valid also in vacuum. Reducing gases are indicated in redoxquotients as Q_H = p(H₂O)/p(H₂). For the technique of measurements with solid electrolytes in vacuum special requirements arise. Probes with air reference electrode are already offered commercially. A solid reference electrode formed with Cu and Cu₂O was tested now in the range of pressure from 1 to 10^‐7 bar. It is usable at sensor temperatures between 400 and 650 centigrades. Important disturbances by oxygen permeability of the solid electrolyte were not observed in this temperature range. Changes of the composition of rest gases in vacuum, often arising as a result of wall reactions are indicated by alterations of p(O₂) or Q_H respectively. The accuracy of measurements is improved by consideration of temperature differences between the electrodes.     

Influence of nitriding on corrosion resistance of martensitic X17CrNi16‐2 stainless steel

Nitriding increases surface hardness and improves wear resistance of stainless steels. However, nitriding can sometimes reduce their corrosion resistance. In this paper, the influence of nitriding on the corrosion resistance of martensitic stainless steel was investigated. Plasma nitriding at 440 °C and 525 °C and salt bath nitrocarburizing were carried out on X17CrNi16‐2 stainless steel. Microhardness profiles of the obtained nitrided layers were examined. Phase composition analysis and quantitative depth profile analysis of the nitrided layers were preformed by X‐ray diffraction (XRD) and glow‐discharge optical emission spectrometry (GD‐OES), respectively. Corrosion behaviour was evaluated by immersion test in 1% HCl, salt spray test in 5% NaCl and electrochemical corrosion tests in 3.5% NaCl aqueous solution. Results show that salt bath nitrocarburizing, as well as plasma nitriding at low temperature, increased microhardness without significantly reducing corrosion resistance. Plasma nitriding at a higher temperature increased the corrosion tendency of the X17CrNi16‐2 steel.     

Gas- und Plasmanitrieren der (α + β)- Titanlegierung TiAl6V4. Vergleichende Untersuchungen zu Schichtaufbau und Schichteigenschaften

The usually low wear resistance of titanium materials can be increased by the thermochemical surface treatment nitriding. In result of comparative investigations of gas and plasma nitriding it will be shown that it is possible to obtain a specific variation of the properties in the highly stressed case by means of these both technologies on example of the (α + β) alloy Ti-6Al-4V. Gas and plasma nitriding was carried out in the temperature range from 650 to 800°C over 4 to 48 h in different gas atmospheres, i. e. 100% NH₃ (gas), 100% N₂ (gas and plasma), 20% H₂ + 80% N₂ and 20% Ar + 20% H₂ (plasma). The temperature range was fixed in the middle of (α + β) region, because the core properties are influenced negative in the field of β-transustemperature. The relations between the applied nitriding technologies, the layer structure (chemical, phases, geometrical) and selected layer properties (microroughness, microhardness, fracture and wear behaviour) are described.     

Verschleißschutz und Korrosionsbeständigkeit von austenitischem Stahl durch Plasmadiffusions behandlung

In this paper, we report on a series of experiments designed to study the influence of plasma nitriding on the mechanical properties and the corrosion resistance of austenitic stainless steel. Plasma nitriding experiments were conducted on AISI 304L steel in a temperature range of 375‐475°C using pulsed‐DC plasma with different N ₂‐H ₂ gas mixtures and treatment times. First of all, the formation and the microstructure of the modified layer will be highlighted followed by the results of hardness measurement, adhesion testing, wear resistance and fatigue life tests. In addition the corrosion resistance of the modified layer is described. The microhardness after plasma nitriding is increased by a factor of five compared to the untreated material. The adhesion is examined by Rockwell indentation and scratch test. No delamination of the treated layer could be observed. The wear rate after plasma nitriding is significantly reduced compared to the untreated material. Plasma nitriding produces compressive stress within the modified layer. This treatment improves the fatigue life which can be raised by a factor of ten at a low stress level. The results show that plasma nitriding of austenitic stainless steel is a suitable process for improving the mechanical and the technological properties without significantly effecting the excellent corrosion resistance of this material.     

Comparison of compound layer nucleation mechanisms in plasma nitriding and nitrocarburizing: the effect of CHn species

This article presents a new study of the mechanisms of plasma nitriding and nitrocarburizing processes, with particular emphasis on plasma diagnostics and light element detection at the treated sample surface. The results indicate that in the nitriding process neutrals, such as Fe, N and ions (such as N⁺), are abundantly present near the cathode region, suggesting that the formation of iron nitrides occurs through the combination of these species. Light element detection by elastic recoil analysis (ERA) shows that hydrogen is not present on the nitrided surface, but it is abundant on the nitrocarburized surface. The latter result is discussed in view of existing nitriding models. The role of CH_n radicals in plasma nitrocarburizing is also discussed.     

Novel plasma nitriding-oxidizing duplex treatment of AISI 316 austenitic stainless steel

In this work, plasma nitriding and plasma nitriding-oxidizing treatment have been performed on AISI 316 austenitic stainless steel. In order to evaluate its response to this treatment, their microstructures and wear resistance have been compared with conventional plasma nitrided. The treatment of plasma nitriding was performed at temperature of 450 °C for 5 h with gas mixture of N₂/H₂:1/3 whereas plasma nitriding-oxidizing was performed with the same parameters of plasma nitriding and temperature of 450 °C with gas mixture of O₂/H₂:1/5 for 15, 30 and 60 min. The structural, mechanical and tribological properties were analyzed using XRD, SEM, microhardness testing and pin-on-disk tribotesting. The results showed that oxidation treatment reduces wear resistance of plasma nitrided sample under high loads. Furthermore the tribological evaluation indicates that by increasing the oxidation time further reduction of wear resistance can be occurred. In addition, it was found that oxidation treatment after plasma nitriding provides an important improvement in the friction coefficient against a AISI 52100 steel pin and reduces surface roughness.     

Determination of oxygen activities in highly diluted gas mixtures using a solid-state electrolyte cell

The applicability ofan oxygen sensor using stabilized zirconia as the solid-state electrolyte and catalytic Pt electrodes to measure oxygen activities in highly diluted gas mixtures was investigated. Various helium atmospheres containing low concentrations (in the µbar range) ofgaseous H₂,H₂O, CO, CO₂ and CH₄ impurities were used. For all gas mixtures considered an oxygen activity could be measured corresponding to the partial equilibrium ofH₂ and H₂O. The gas components CO and CO₂ did not affect the EMF ofthe cell, due to the low rates of their reactions at the Pt electrode relative to the H₂/H₂O equilibrium. Only CH₄ was seen to influence the measured oxygen partial pressure, P(O₂). It was found that the oxidation of CH₄ at Pt obeys a first-order rate law. Due to the extremely low kinetics of this reaction, only a slight reduction of p(O₂) from the H₂/H₂O equilibrium value of the bulk gas occurred.     

Influence of the microstructure on the corrosion resistance of plasma‐nitrided austenitic stainless steel 304L and 316L

Austenitic stainless steels are widely used in medical and food industries because of their excellent corrosion resistance. However, they suffer from weak wear resistance due to their low hardness. To improve this, plasma nitriding processes have been successfully applied to austenitic stainless steels, thereby forming a thin and very hard diffusion layer, the so‐called S‐phase. In the present study, the austenitic stainless steels AISI 304L and AISI 316L with different microstructures and surface modifications were used to examine the influence of the steel microstructure on the plasma nitriding behavior and corrosion properties. In a first step, solution annealed steel plates were cold‐rolled with 38% deformation degree. Then, the samples were prepared with three kinds of mechanical surface treatments. The specimens were plasma nitrided for 360 min in a H₂–N₂ atmosphere at 420 °C. X‐ray diffraction measurements confirmed the presence of the S‐phase at the sample surface, austenite and body centered cubic (bcc)‐iron. The specimens were comprehensively characterized by means of optical microscopy, scanning electron microscopy, glow discharge optical emission spectroscopy, X‐ray diffraction, surface roughness and nano‐indentation measurements to provide the formulation of dependencies between microstructure and nitriding behavior. The corrosion behavior was examined by potentio‐dynamic polarization measurements in 0.05 M and 0.5 M sulfuric acid and by salt spray testing.     

Characteristics of supersonic nitrogen/hydrogen-mixture and ammonia plasma jets and nitrided material properties

Spectroscopic and electrostatic probe measurements were made to examine plasma characteristics under nitriding for a 10-kW-class direct-current arc plasma jet generator with a supersonic expansion nozzle in a low pressure environment. Heat fluxes into the plate from the plasma were also evaluated. Ammonia and mixtures of nitrogen and hydrogen were used as a working gas. The H-atom electronic excitation temperature and the N₂ molecule-rotational excitation temperature intensively decreased downstream in the nozzle although the NH molecule-rotational excitation temperature did not show an axial decrease. As approaching the titanium plate, the thermodynamical non-equilibrium plasma came to be a temperature-equilibrium one. Both the electron number density near the plate and the heat flux increased with H₂ mole fraction for mixtures gases. In cases with mixtures of N₂ and H₂, a radical of NH with a radially wide distribution was considered to contribute to the better nitriding as a chemically active and non-heating process.     

Effect of plasma on nitriding of Fe-18Cr-9Ni alloy

The plasma nitriding behaviour of Fe-18Cr-9Ni alloy was compared with gas nitriding. The alloy was nitrided under the following conditions: specimen temperature: 823 K, nitriding time: mainly 108 ks, total pressure: 0.4–0.7 kPa, mixture ratio of N₂ and H₂∶ 0.25, discharge voltage: 350–450 V, current: 0.8–1.1 A. Formation of a surface layer of iron nitrides was not observed. Formation of a homogeneous internal nitriding layer, consisting of small precipitates of CrN and the γ-phase matrix, was, however, noted. The lattice constant at the specimen surface was smaller than that at greater depth. This may have been because the sputtering effect decreased the dissolved nitrogen content at the specimen surface. The sputtering of iron nitrides at the specimen surface by the plasma was experimentally confirmed through γ′-Fe₄N formation on Si beside an alloy specimen. The characteristics of the plasma nitriding mentioned above are discussed in relation to the sputtering.     

Use of metastable, dissociated and charged gas species in synthesis: a low pressure analogue of the high pressure technique

Oxidation of silver using microwave-induced oxygen plasma and oxygen-ozone gas mixture was studied as a function of temperature and partial pressure. The oxide Ag₂O was formed at temperatures well above its normal decomposition temperature in oxygen plasma at a pressure of 5 Pa. The higher oxide AgO_1–x was formed in O₂₊O₃ gas mixtures at lower temperatures. The oxygen chemical potentials for the oxidation of Ag to Ag₂O, Ag₂O to AgO_1–x and AgO to Ag₂O₃ were evaluated from thermodynamic data and compared with the experimental results to obtain information on the chemical potential of oxygen in microwave plasma and gases containing ozone. The oxygen potential of the gas phase in microwave plasma operating at a pressure of 5 Pa was found to be in excess of 36 kJ/mol at 750 K. This is equivalent to a pressure of diatomic oxygen gas greater than 3 × 10⁷ Pa. In the O₂₊O₃ mixture at ambient pressure containing 5 mole percent O₃, the oxygen potential is 112 kJ/mol at 465 K. The equivalent pressure of diatomic oxygen is 4 × 10¹⁷ Pa. Thus, metastable species such as O₃ or charged species such as O^– present in plasma can be used as a powerful reagent for the syntheses of metastable oxides. Similar techniques can be used for other metastable inorganic solids such as nitrides for functional applications.     

A new method for deposition of nano sized titanium nitride on steels

Active screen plasma nitriding is a new and common method for deposition of Iron nitride. Since techniques such as Chemical Vapor Deposition (CVD), Physical Vapor Deposition (PVD) and Plasma Assisted Chemical Vapor Deposition (PACVD) are usually applied in order to deposit the titanium nitride and each of these methods has its own problems, in this research active screen plasma nitriding method was introduced as a novel approach for deposition of nano sized titanium nitride. H11 tool steel samples were coated by plasma nitriding method at 550 °C for 5, 7.5 and 10 h, using three gas mixtures consisted of H₂/N₂ = 3, 1 and 1/3. Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) were employed to investigate the coating properties such as grain size, layer thickness and chemical composition. Results showed that the proportion of H₂ in the gas mixture was a crucial point in order to obtain a perfect coating. By increasing the coating time, the grain size and the layer thickness increased. XPS results showed that the coating was mainly consisted of TiN + TiN_0.1 together with a small amount of TiO₄.     

Plasma nitriding of AISI 52100 ball bearing steel and effect of heat treatment on nitrided layer

In this paper an effort has been made to plasma nitride the ball bearing steel AISI 52100. The difficulty with this specific steel is that its tempering temperature (~170–200°C) is much lower than the standard processing temperature (~460–580°C) needed for the plasma nitriding treatment. To understand the mechanism, effect of heat treatment on the nitrided layer steel is investigated. Experiments are performed on three different types of ball bearing races i.e. annealed, quenched and quench-tempered samples. Different gas compositions and process temperatures are maintained while nitriding these samples. In the quenched and quench-tempered samples, the surface hardness has decreased after plasma nitriding process. Plasma nitriding of annealed sample with argon and nitrogen gas mixture gives higher hardness in comparison to the hydrogen–nitrogen gas mixture. It is reported that the later heat treatment of the plasma nitrided annealed sample has shown improvement in the hardness of this steel. X-ray diffraction analysis shows that the dominant phases in the plasma nitrided annealed sample are ε (Fe_2 − 3N) and γ (Fe₄N), whereas in the plasma nitrided annealed sample with later heat treatment only α-Fe peak occurs.     

A Study on Formation and Growth Mechanism of Nitride Layers During Plasma Nitriding Process of Plastic Injection Mold Steel

Ion nitriding modifies composition of surface layer in steel used in plastic mold application and this consequently improves their lifecycle. In this study, pulsed plasma nitriding technique was used to produce a protecting hard layer on AISI P20 steel at three process temperatures of 450°C, 500°C, and 550°C for durations of 2.5, 5, 7.5, and 10 h at a constant gas mixture of 75% N₂–25% H₂. Surface morphology was studied by optical and scanning electron microscope and the phases formed on the surface layer were determined by X-ray diffraction (XRD). Elemental depth profile was measured by techniques including energy dispersive spectroscopy, wavelength dispersive spectrometer, and glow discharge spectroscopy and for identifying hardness profile, microhardness variations from surface to core of samples were recorded. Results showed that, thickness of compound layer of plastic mold steel AISI P20 was negligible. Moreover in ion nitriding of AISI P20, nitride were formed and grown in some preferred directions and upward diffusion of carbon and downward diffusion of nitrogen occurred during ion nitriding of AISI P20. XRD results showed that, ?-nitride is the dominant phase after plasma nitriding in all strategies. Furthermore, ion nitriding improved hardness of AISI P20 up to three times and as time and temperature increased, hardness and hardness depth of diffusion zone increased considerably.     

Effect of test atmosphere composition on high-temperature oxidation behaviour of CoNiCrAlY coatings produced from conventional and ODS powders

Abstract

The oxidation behaviour of free-standing CoNiCrAlY coatings produced by low-pressure plasma spraying using conventional powder and oxide dispersion strengthened (ODS) powder containing 2 wt. % Al-oxide dispersion was investigated. Thermogravimetric experiments at 1100 °C in Ar-20%O₂ and Ar-4%H₂-2%H₂O showed lower oxidation rates of the ODS than the conventional coating. In the latter material the scale growth was enhanced by extensive Y-incorporation of Y/Al-mixed oxide precipitates in the scale and apparently by Y-segregation to oxide grain boundaries. In the ODS coating the alumina dispersion bonded Y in the form of Y-aluminate thereby effectively suppressing scale ‘overdoping’. SEM/EBSD studies of all alumina scales revealed a columnar grain structure with the lateral grain size increasing approximately linearly with depth from the oxide/gas interface. For both coatings the alumina scale growth was slower in Ar–H₂–H₂O than in Ar–O₂. The result is believed to be related to a lower oxygen potential gradient and to slower grain boundary diffusion in the scale forming in H₂/H₂O containing gas.     

Influence of nitriding gases on the growth of boron nitride nanotubes

Boron nitride (BN) nanotubes of different sizes and tubular structures exhibit very different mechanical and chemical properties, as well as different applications. BN nanotubes of different sizes and nanostructures have been produced in different nitriding gases in a milling and annealing process, in which elemental boron powder was first milled in NH₃ for 150 h and subsequently annealed at 1,200 °C for 6 h. The influence of nitriding gases was investigated by using N₂, NH₃, N₂–H₂ mixture gases. A relatively slow nitriding reaction in NH₃ gas leaded to a 2D growth of BN (002) basal planes and the formation of thin BN nanotubes without the help of metal catalysts. Fast nitriding reactions occurred in N₂ or N₂–H₂ mixture gases, catalyzed by metal particles, resulted in 3D crystal growth and the formation of many large cylindrical and bamboo tubes.     

Inorganic–Organic Hybrid Nanoprobe for NIR‐Excited Imaging of Hydrogen Sulfide in Cell Cultures and Inflammation in a Mouse Model

Hydrogen sulfide (H₂S) is an important gaseous signaling agent mediated by many physiological processes and diseases. In order to explore its role in biological signaling, much effort has been focused on developing organic fluorescent probes to image H₂S. However, these downconversion H₂S probes are impractical for bio‐imaging beyond a certain depth because of the short tissue penetration of UV/visible light (as an excitation source). In most circumstance, these probes are also not suitable for long‐term assay due to photo‐bleaching. Herein, a new design to detect H₂S based on the coumarin‐hemicyanine (CHC1)‐modified upconversion nanophosphors is reported. This inorganic–organic integrated nanoprobe is demonstrated to display a fast response time with a large ratiometric upconversion luminescence (UCL) enhancement, and extraordinary photo‐stability. CHC1‐UCNPs not only can be used for ratiometric UCL monitoring of pseudo‐enzymatic H₂S production in living cells, but can also be used to identify the risk of endotoxic shock through ratiometric UCL imaging of tissue and measurement of endogenous H₂S levels in plasma. The first ratiometric UCL H₂S nanoprobe reported here may be further developed as the next‐generation diagnostic tool for the detection of inflammatory‐related diseases.     

Einfluss unterschiedlicher Oberflächenzustände vor dem Plasmanitrieren auf Eigenschaften und Zerspanungsverhalten des Schnellarbeitsstahls S 6‐5‐2

Surface states and wear behavior of drills of ground, sandblasted and plasmanitrided samples and drills made of AISI M2 high speed steel In the present work the effect of different surface conditions on plasma nitriding response of AISI M2 high speed steel was investigated. The plasma nitriding of ground and sandblasted samples and drills was performed at temperatures of 400°C and 500°C for two gas mixtures: 5 vol.% N₂ and 76 vol.% N₂ in hydrogen. Surface layers were characterized before and after plasma nitriding concerning the microstructure, roughness, microhardness, chemical composition, phase composition and residual stress states. Machining tests were carried out with drills during which drilling forces and flank wear have been measured. A significant effect of the surface state prior to nitriding on residual stress states and the properties of the nitrided layer and untreated core has been observed. Thinner nitrided layers on ground and sandblasted samples were attributed to high compressive residual stress states and a stress affected diffusion of nitrogen and carbon. In the machining tests, sandblasted drills exhibited the best performance. Lower nitrogen concentrations in the gas atmosphere without the formation of a compound layer gave the lowest drill flank wear for sandblasted surfaces while higher nitrogen concentrations led to a reduction of drilling forces and torque.