Behavior of N atoms after thermal nitridation of Si1 − xGex surface

Behavior of N atoms after thermal nitridation of Si_1 − xGe_x (100) surface in NH₃ atmosphere at 400 °C was investigated. X-ray photoelectron spectroscopy (XPS) results show that N atomic amount after nitridation tends to increase with increasing Ge fraction, and amount of N atoms bonded with Ge atoms decreases by heat treatment in H₂ at 400 °C. For nitrided Si_0.3Ge_0.7(100), the bonding between N and Si atoms forms Si₃N₄ structure whose amount is larger than that for nitrided Si(100). Angle-resolved XPS measurements show that there are N atoms not only at the outermost surface but also beneath surface especially in a deeper region around a few atomic layers for the nitrided Si(100), Si_0.3Ge_0.7(100) and Ge(100). From these results, it is suggested that penetration of N atoms through around a few atomic layers for Si, Si_0.3Ge_0.7 and Ge occurs during nitridation, and the N atoms for the nitrided Si_0.3Ge_0.7(100) dominantly form a Si₃N₄ structure which stably remains even during heat treatment in H₂ at 400 °C.     

Influence of layer microstructure on the corrosion behavior of plasma nitrided cold work tool steel

The influence of layer microstructure on the corrosion behavior of plasma nitrided cold work tool steel, of commercial name “DC53”, in 3.5% NaCl solution is reported. The specimens were nitrided at 520 °C for different treatment times using a constant [N₂ + H₂] gaseous mixture by a DC-pulsed plasma system. The microstructure of the nitrided layers was investigated by optical microscopy and X-ray diffraction. The corrosion behavior was evaluated by potentiodynamic polarization experiments. The plasma nitriding process considerably improves the corrosion resistance of material in NaCl environment as compared to the unnitrided DC53 steel. The modified surface layer consisting mainly of ε-nitride (Fe_2–3N) and a small amount of γ′-nitride (Fe₄N) confers this outstanding behavior. The corrosion resistance dependence on specific nitriding processes is reported and the role of the ε-nitride is discussed. In particular, the correlation of pitting current density, density of pits, and volume fraction of ε-nitride with nitriding time is analyzed. The results denote that the most important parameter for controlling the corrosion resistance of the material is the volume fraction of ε-nitride and the nitrided layer thickness. It is expected that a nitrided layer would be thicker and rich in ε-nitride phase to achieve a high corrosion resistance.     

Effect of chromium content on remarkably rapid nitriding in austenitic Fe-Ni-Cr alloys

Remarkably rapid nitriding which is independent of diffusion theory based on the thermal activation process, was observed during nitriding of austenitic Fe-Ni-Cr steels containing 16 and 19 mass% chromium. Increase of the chromium content in the alloys yielded increasing thickness of the nitrided layer, i.e. the internal nitriding theory did not hold in the nitriding. No rapid nitriding was observed in steels containing less than 13 mass% chromium. Hence the limiting concentration of chromium for the rapid nitriding will lie between 13 and 16 mass% chromium. A solution to the problem of abnormalities arising during nitriding of practical austenitic stainless steels which have been investigated since 1972, has been presented experimentally by nitriding various chromium-containing steels. Based on the experimental results, the origin of the rapid nitriding is discussed in connection with the free-energy function of Cr₂N and CrN to temperature. In particular, a plateau of nitrogen concentration measured in the nitrided layers leads to the conclusion that a forced nitrogen diffusion in the layer resulted in the rapid nitriding.     

Diffusion kinetics of explosively treated and plasma nitrided Ti-6Al-4V alloy

Ti-6Al-4V alloys, which were exposed to an explosive shock process, were nitrided in nitrogen plasma in the temperature range of 700-900°C for 3-12 h. During the plasma nitriding, the surface layer consisted of TiN (δ), Ti₂N (ε) and nitrogen solid solution layers (α-Ti). The growth rate of nitride and solid solution layers were found to be controlled by the diffusion of nitrogen. An effective nitriding was achieved due to high dislocation density and vacancy concentration. Based on the present layer growth data, an analytical model for multiphase diffusion was used to estimate the effective nitrogen atom diffusion coefficient in the nitride layers. The interface velocity equations were derived from Fick's law and a numerical method has been used to compute the diffusion coefficients of nitrogen in a binary multiphase Ti-TiN system. Depending on temperature and layer thickness, the activation energies of nitrogen in TiN and Ti₂N phases were found to be 18,950 (±2116) and 27,925 (±1105) cal/mole, respectively.     

Carbothermal reduction and nitridation of aluminium hydroxide

Carbothermal reduction and nitridation of aluminium hydroxide was investigated by weight-loss measurement and X-ray diffraction. Experimental results indicated that aluminium hydroxide was first dehydrated to aluminium oxide and then reduced and nitrided to aluminium nitride. Aluminium oxynitride and Al₂O were found to be intermediate products. The reaction rate was found to be increased by increasing the nitrogen flow rate, the molar ratio of C/Al(OH)₃, or reaction temperature. The rate was also found to be increased by decreasing the sample size, the grain sizes of carbon or aluminium hydroxide or initial bulk density. Empirical rate expressions of the conversion of Al(OH)₃ and carbon, as well as the yield of AIN, were also determined.     

Phase evolution in mechanical alloying and spark plasma sintering of AlxCoCrCuFeNi HEAs

ABSTRACT

Al_xCoCrCuFeNi high-entropy alloys were synthesised through mechanical alloying and spark plasma sintering. Different alloys were produced by varying the aluminium content (x?=?0.5, 1.5, 2.5 and 4). The influences of the milling duration on the evolution of microstructure, constituent phases and morphology were studied. Increasing milling time resulted in grain refinement and higher solid solution homogenisation characterised by a high internal strain. As a consequence of aluminium addition, the microstructure of materials evolved from face centered cubic (FCC) and body centered cubic (BCC) phases to FCC, BCC and ordered BCC phases. Both mechanical alloying and SPS conditions as well as aluminium content led to grain refinement and variations of mechanical properties. In particular, hardness increased with increasing aluminium content. The aluminium percentage and the evolution of consequent phases are responsible for the microstructural stability at high temperatures. In addition, with Al content increase, the further synergy of strength and ductility along with a more pronounced strain hardening was obtained.     

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.     

Duplex treatment of 304 AISI stainless steel using rf plasma nitriding and carbonitriding

Surface of 304 AISI austenitic stainless steel has been modified using duplex treatment technique of nitriding and carbonitriding. A thick modified nitrided layer, of approximately 20 µm, has been achieved when rf inductively coupled plasma was adjusted at 450 W for processing time of only 10 min. After performing the nitrided layer, the nitrided samples were carbonitrided using the same technique at different acetylene partial pressure ratios ranges from 10% to 70%, the balance was pure nitrogen. Different amount of nitrogen and carbon species are diffused underneath the surface through the nitrided layer during carbonitriding process and are found to be gas composition dependent. The treated samples were characterized by glow discharge optical spectroscopy, X-ray diffractometry, scanning electron microscopy and Vickers microhardness tester. The microstructure of the duplex treated layer indicates the formation of γ?-Fe₄N, Fe₃C, CrN and nitrogen-expanded austenite (γ_N). The thickness of the duplex treated layer increases with increasing the acetylene partial pressure ratio. The surface microhardness of duplex treated samples has been found to be gas composition dependent and increased by 1.29 fold in comparison to the nitrided sample.     

Structure and morphology of TiB2 duplex coatings deposited over X40 CrMoV 5-1-1 steel by DC magnetron sputtering

The deposition of titanium diboride (TiB₂) films over tool steel substrates (AISI H13 premium/EN X40 CrMoV 5-1-1) is being investigated due to its excellent corrosion resistance and chemical stability against liquid aluminium. The use of nitrided steels as substrates for TiB₂ deposition may contribute to increase its adhesion and the overall steel resistance in applications such as forging, extrusion and die casting of aluminium. Duplex coatings were obtained by the PVD deposition of TiB₂ films over heat treated and nitrided steel using non-reactive DC magnetron sputtering from a TiB₂ target, varying the substrate bias voltage. Well structured and crystalline TiB₂ films were obtained for the selected deposition conditions, the best crystalline coatings being obtained for the positively biased substrates. Selected films produced over die-casting pins at a bias voltage of +50 V were tested for resistance to liquid aluminium soldering by immersion tests, and compared with the nitrided steel. The duplex TiB₂ coating has a much larger chemical resistance to attack by molten aluminium alloy than the just nitrided steel. Where there is soldering, steel is rapidly attacked and a complex Al-Fe-Si intermetallic forms.     

Compositional range,thermal stability,hardness and electrical resistivity of amorphous alloys in Al-Si (or Ge)-transition metal systems

An amorphous single phase was found to be formed in wide compositional ranges in rapidly solidified Al-Si-transition metal (M) and Al-Ge-M alloys. The compositional ranges are in the range from 12 to 53 at. % Si or Ge and 8 to 23% M and Al-Si-Co and Al-Ge-Fe alloys have the widest glass-formation ranges. Because the interaction between aluminium and silicon or germanium atoms is thought to be repulsive from the immiscible equilibrium phase diagrams, the glass formation is probably due to an attractive interaction of M-Si (or Ge) and Al-M pairs. Hardness, H _v, and crystallization temperature, T _x, increase with increasing M content and the highest values reach 1120 DPN and 715 K, while the change with silicon or germanium content is much smaller for H _v and is hardly seen for T _x. Additionally, the H _v and T _x have maximum values for Al-Si (or Ge)-M (M=Cr, Mn or Fe), decrease with the decrease and increase in the group number of M element and are the lowest for Al-Si (or Ge)-Ni alloys. The compositional dependence is interpreted under the assumption that T _x and H _v of the aluminium-based amorphous alloys are mainly dominated by the attractive interaction of M-(Si or Ge) and Al-M pairs. Room-temperature resistivity, _RT, increases in the range of 220 to 1940 cm with increasing silicon or germanium and M contents. The change in _RT with the group number of M elements shows a maximum phenomenon for manganese. It has thus been clarified that the characteristics of the Al-Si-M and Al-Ge-M amorphous alloys have the different compositional dependence as compared with those for conventional metalmetalloid amorphous alloys, probably because of the unusual interaction among the constituent elements.     

Anodic film formation on high strength aluminium alloy FVS0812

Barrier-type film growth on the high strength aluminium alloy FVS0812 has been studied by a combination of transmission electron microscopy and Rutherford backscattering spectroscopy. The film is composed mainly of amorphous anodic alumina, but is contaminated with iron species incorporated into the film from the alloy. The film may also be contaminated with silicon and vanadium species at levels below the detection limit of the present experiments. The contaminant species are primarily incorporated locally into the film during oxidation of Al₁₃(Fe, V)₃Si dispersoids and the resulting film material is of reduced resistivity compared with anodic alumina of high purity. As a consequence of the presence of regions of film material of differing resistivities, the film is of irregular thickness. The average thickness corresponds to a nm/V ratio of about 1.3. Iron species incorporated into the film migrate outwards at roughly 2.1 times the rate of Al³⁺ ions. The iron species are not ejected in significant amounts to the electrolyte on reaching the film/electrolyte interface and hence, a thin layer of film material highly enriched in iron species develops at the film surface. The layer may also be enriched in vanadium species, if these are incorporated into the film and migrate more rapidly than Al³⁺ ions. Enrichment of iron, and possibly other alloying element atoms, is found in a thin layer of alloy immediately beneath the anodic film, paralleling enrichments of alloying element atoms found following anodic oxidation of other aluminium alloys. The enrichments at both the alloy/film and film/electrolyte interfaces do not appear to be continuous across the macroscopic surface of the specimens, probably due to the non-uniformity of film growth on the two-phase substrate. The maximum voltage for the selected conditions of anodizing was limited to 68 V as a result of oxygen generation at flaws which are present extensively in the anodic film. This revised version was published online in November 2006 with corrections to the Cover Date.     

Mechanical properties and thermal stability of nitrogen incorporated diamond-like carbon films

The nitrogen incorporated diamond-like carbon films were deposited on Si (100) substrates by arc ion plating (AIP) under different N₂ content in the gas mixture of Ar and N₂. The influence of N₂ content on the film microstructure and mechanical properties was studied by atomic force microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and nanoindentation. It was found that the hardness (H), elastic modulus (E), elastic recovery (R) and plastic resistance parameter (H/E) decrease with increasing the nitrogen content. The decrease of mechanical properties of DLC films resulted from nitrogen incorporation was associated with total sp³ carbon bond content and N-sp³C bond content. The structural modification as well as mechanical properties of the annealed nitrogen incorporated diamond-like carbon films was investigated as a function of annealing temperature. Raman spectra indicate that the I_D/I_G ratio starts to increase and G peak position shifts upward at the annealing temperature over 500 °C. The hardness and elastic modulus of thermally annealed nitrogen incorporated DLC films decreased slightly at lower annealing temperature and then significantly decreased at higher annealing temperature. The strong covalent bonding between C and N atoms is expected to be effective on their thermal stability enhancement.     

Nitriding behaviour of maraging steel: experiments and modelling

The microstructure and the kinetics of growth of the nitrided zone of a Mo-containing maraging steel were investigated by performing gaseous nitriding at temperatures between 713 K (440 °C) and 793 K (520 °C) and at nitriding potentials up to 0.5 atm^?1/2 for both solution-annealed and precipitation-hardened specimens. The microstructure of the nitrided zone was investigated by means of X-ray diffraction (phase constitution; crystal imperfection). Fine, initially largely coherent Mo₂N-type precipitates developed in the nitrided zone. The elemental concentration-depth profiles were determined employing glow discharge optical emission spectroscopy (GDOES). The nitrogen content within the nitrided zone exceeds the nitrogen content expected on the basis of the molybdenum content and the equilibrium solubility of nitrogen in a (stress-free) ferritic matrix: excess nitrogen occurs. A numerical model was applied to predict the nitrogen concentration-depth profile within the nitrided layer. The model describes the dependence on time and temperature of the nitrogen concentration-depth profiles with, as fit parameters, the surface nitrogen concentration, the diffusion coefficient of nitrogen in the matrix, a composition parameter of the formed nitride and the solubility product of the nitride-forming element and dissolved nitrogen in the matrix. Initial values for the surface nitrogen concentration and the composition parameter were determined experimentally with an absorption isotherm and fitted to the measured nitrogen concentration-depth profiles. The results obtained revealed the striking effects of the amount of excess nitrogen and the extent of precipitation hardening on the developing nitrogen concentration-depth profile.     

Kinetics and wear behaviour of M50NiL steel plasma nitrided at low temperature

The quenched M50NiL steel was plasma nitrided at 460°C for different time to investigate the effects of the duration time on the microstructure, microhardness and wear resistance of the nitrided layers. The results show that the plasma nitrided layer depth increases with increasing nitriding time. The plasma nitrided layer includes only the diffusion layer without compound layer. The main phases in the nitrided surface layer are nitrogen expended α′-Fe and γ′-Fe₄N. The microstructure of the nitrided layer is refined. The wear resistance of the nitrided samples can be improved significantly by plasma nitriding. The sample nitrided for 4?h possesses the highest wear resistance, due to its relatively smooth surface and ultra-fine grains in the nitrided layer.     

Surface engineering and chemical characterization in ion-nitrided titanium and titanium alloys

The chemical and physical characteristics of ion-nitrided surface layers, obtained on - titanium alloys, are examined and correlated both with the working conditions adopted in the ion-nitriding process and with the alloy chemical composition. Besides the influence of the working parameters on the morphology and on the microstructures of the ion-nitrided surface layers, mainly the alloy element distributions both in surface coatings and in the substrate are analysed for five - titanium alloys of industrial use, and for titanium c,p. as reference, ionnitrided at various treatment temperatures. The nitriding process forms, on titanium alloy parts, high-hardness surface layers consisting of TiN ( phase) and Ti₂N ( phase) nitrides and an interstitial solid solution of nitrogen in the close-packed hexagonal lattice of titanium ( phase). The presence and the extent of these phases as well as the ion-nitrided layer morphology are essentially determined by the alloy chemical composition and the working parameters. In particular a low-temperature treatment produces an extended nitrogen diffusion in the matrix beneath a thin continuous nitrided layer, while a high-temperature treatment produces prevalently a continuous nitrided surface layer. The alloy element distribution appears differentiated in the various phases and may be correlated with the different affinity of these elements with nitrogen.     

Effects of various nitriding parameters on active screen plasma nitriding behavior of a low-alloy steel

Active screen plasma nitriding (ASPN) is a novel surface modification technique that has many capabilities over the conventional DC plasma nitriding (CPN). In this study, 30CrNiMo8 low-alloy steel was active screen plasma-nitrided under various nitriding parameters such as active screen set-up parameters (different screen hole sizes, mesh sheet and plate top lids) and treatment temperature (520, 550 and 580 °C), in the gas mixture of 75% N₂+25% H₂ and chamber pressure of 500 Pa for 5 h. The properties of the nitrided specimens have been assessed by evaluating composition of phases, surface hardness, compound layer thickness and case depth using X-ray diffraction (XRD), microhardness measurements and scanning electron microscopy (SEM). It was found that the screen hole size and top lid type (mesh or plate) play an important role in transition of active species (nitrogen ions and neutrals) toward the sample surface, which in turn can affect the nitrided layer hardness and thickness. Treatment at higher temperature with bigger screen hole size resulted in a thicker compound layer and higher layer hardness. The compound layers developed on the samples treated under different conditions were dual phase consisting of γ′-Fe₄N and ε-Fe_2-3N phases.     

XPS and corrosion studies on zinc phosphate coated 7075-T6 aluminium alloy

X-ray photoelectron spectroscopy (XPS), combined with scanning electron microscopy (SEM), weight loss tests and atomic absorption spectroscopy (AAS), has been applied to investigate the corrosion protection properties of zinc phosphate when coated on 7075-T6 aluminium alloy. XPS is consistent with the coating process leading to both physically adsorbed and chemically absorbed zinc. The former is washed away by ultrasonic washing, but the chemically absorbed component, identified as ZnO _x , is incorporated into the aluminium oxide layer. This layer helps suppress the dissolution of aluminium during the corrosion process.     

Chromizing of plasma nitrided AISI 1045 steel

In this study AISI 1045 steel specimens were plasma nitrided at 803 K for 5 h, in a gas mixture of 75% N₂ + 25% H₂. The specimens were then chromized in powder mixtures consisting of ferrochromium, ammonium chloride and alumina at 1273 K for 5 h. Scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis and Vickers micro-hardness test were used as characterizing techniques. The thickness of white nitrided layer was around 5 μm, which was mainly composed of iron nitrides and its hardness was around 740 HV. Chromizing of nitride layer resulted in formation of Cr₂N chromium nitride and Fe₃N iron nitrides. A significant increase was observed in hardness after chromizing of the nitrided layer. Despite its higher hardness, the post chromised specimen showed higher wear rate than single plasma nitrided specimen.     

Investigation of the distribution and the state of rare earth elements in pure aluminium by the method of internal friction

This paper is the first part of an investigation of the distribution and the state of rare earth (RE) elements in aluminium by the method of internal friction. The grain boundary internal friction was measured for 4N pure aluminium samples with various RE contents (0 to 3%, nine in number) with a high vacuum Ke torsion pendulum. It has been found that the peak height and the background decrease with increasing RE content up to 0.5%, and that when RE content > 0.5% the peak height changes little but the background rapidly increases with RE content. A series of grain boundary internal friction parameters were obtained with the help of conventional and new methods. The various behaviours of RE in aluminium were discussed from the effect of RE content on the relaxation strength and the activation energyH. The relation between the parameter _H, which is a measurement of the distribution width ofH, and RE content was inferred.     

Relationships of diboride phases in Al–Ti(Zr)–B alloys

Abstract

The relationships of diboride phases in Al–Ti(Zr)–B alloys with a variable Ti/B ratio close to the stoichiometry of TiB₂ were studied. The formation of diboride solid solutions was confirmed. A grain refinement mechanism is proposed as that diboride particles in the Al–Ti–B master alloys reacting with aluminium upon adding into an aluminium melt and release titanium into the melt through forming a (Ti,Al)B₂ solid solution and maintain a thin dynamic Ti rich layer on the surfaces of the (Ti,Al)B₂ particles, which nucleates α-Al grains in solidification. The poisoning effect of zirconium on grain refinement of aluminium by Al–Ti–B master alloys is also discussed.