Defect-dependent nitride surface layer development upon nitriding of Fe–1 at.% Mo alloy

Upon nitriding of binary Fe–1 at.% Mo alloy in a NH₃/H₂ gas mixture under conditions (thermodynamically) allowing γ′-Fe₄N_{1– x} compound layer growth (nitriding potential: 0.7?atm^?1/2 at 753?K (480?°C) – 823?K (550?°C)), a strong dependency of the morphology of the formed compound layer on the defect density of the specimen was observed. Nitriding of cold-rolled Fe–1 at.% Mo specimens leads to the formation of a closed compound layer of approximately constant thickness, comparable to nitriding of pure iron. Within the compound layer, that is, in the near-surface region, Mo nitrides are present. The growth of the compound layer could be described by a modified parabolic growth law leading to an activation energy comparable to literature data for the activation energy of growth of a γ′-Fe₄N_{1? x} layer on pure iron. Upon low temperature nitriding (i.e. ?793?K (520?°C)) of recrystallized Fe–1 at.% Mo specimens, an irregular, ‘needle-like’ morphology of γ′-Fe₄N_{1? x} nucleated at the surface occurs. This γ′ iron nitride has an orientation relationship (OR) with the matrix close to the Nishiyama–Wassermann OR. The different morphologies of the formed compound layer can be interpreted as consequences of the ease or difficulty of precipitation of Mo as nitride as function of the defect density.     

Unusual nucleation and growth of γ′ iron nitride upon nitriding Fe–4.75 at.% Al alloy

The influence of substitutionally dissolved Al in ferritic Fe–4.75 at.% Al alloy on the nucleation and growth of γ′ iron nitride (Fe₄N_{1? x} ) was investigated upon nitriding in NH₃/H₂ gas mixtures. The nitrided specimens were characterised employing optical microscopy, scanning electron microscopy, transmission electron microscopy, electron probe microanalysis and X-ray diffraction. As compared to the nitriding of pure ferrite (α-Fe), where a layer of γ′ develops at the surface, upon nitriding ferritic Fe–4.75 at.% Al an unusual morphology of γ′ plates develops at the surface, which plates deeply penetrate the substrate. In the diffusion zone, nano-sized precipitates of γ′ and of metastable, cubic (NaCl-type) AlN occur, having, with the ferrite matrix, a Nishiyama–Wassermann orientation relationship and a Bain orientation relationship, respectively. The γ′ plates contain a high density of stacking faults and fine ε iron nitride (Fe₂N_{1? z} ) precipitates, although the formation of ε iron nitride is not expected for the employed nitriding parameters. On the basis of dedicated nitriding experiments it is shown that the unusual microstructural development is a consequence of the negligible solubility of Al in γ′ and the obstructed precipitation of the thermodynamically stable, hexagonal (wurtzite-type) AlN in ferrite.     

The nitrogen-absorption isotherm for Fe–21.5 at. % Cr alloy: dependence of excess nitrogen uptake on precipitation morphology

Nitriding of Fe–21.5 at. % Cr alloy leads to a “discontinuously coarsened”, chromium-nitride/ferrite lamellar precipitation morphology in the nitrided zone. The nitrogen-absorption isotherm for this alloy with this precipitation morphology was determined at 560°C. To assure a constant precipitation morphology the Fe–21.5 at. % Cr specimen was first homogeneously pre-nitrided (at 580°C in an ammonia/hydrogen gas mixture of nitriding potential 0.103 atm^?1/2) and then de-nitrided (at 470°C in hydrogen gas atmosphere). The amount of nitrogen remaining in the de-nitrided specimen indicated that the composition of the nitride precipitates is CrN and not (Fe, Cr)N. The measured nitrogen-absorption isotherm revealed the presence of excess nitrogen in the nitrided specimen, which is a surprise in view of the coarse, lamellar precipitation morphology. The occurrence of this excess nitrogen could be ascribed to an unexpected, minor fraction of the total chromium content in the alloy present as coherent, tiny nitride platelets within the ferrite lamellae of the “discontinuously coarsened” lamellar precipitation morphology, as evidenced by transmission electron microscopy. A possible kinetic background for this unusual phenomenon was discussed.     

Normal and excess nitrogen uptake by iron-based Fe–Cr–Al alloys: the role of the Cr/Al atomic ratio

Upon nitriding ferritic iron-based Fe–Cr–Al alloys, containing a total of 1.50 at. % (Cr?+?Al) alloying elements with varying Cr/Al atomic ratio (0.21–2.00), excess nitrogen uptake occurred, i.e. more nitrogen was incorporated in the specimens than compatible with only inner nitride formation and equilibrium nitrogen solubility of the unstrained ferrite matrix. The amount of excess nitrogen increased with decreasing Cr/Al atomic ratio. The microstructure of the nitrided zone was investigated by X-ray diffraction, electron probe microanalysis, transmission electron microscopy and electron energy loss spectroscopy. Metastable, fine platelet-type, mixed Cr_{1? x} Al _x N nitride precipitates developed in the nitrided zone for all of the investigated specimens. The degree of coherency of the nitride precipitates with the surrounding ferrite matrix is discussed in view of the anisotropy of the misfit. Analysis of nitrogen-absorption isotherms, recorded after subsequent pre- and de-nitriding treatments, allowed quantitative differentiation of different types of nitrogen taken up. The amounts of the different types of excess nitrogen as function of the Cr/Al atomic ratio are discussed in terms of the nitride/matrix misfit and the different chemical affinities of Cr and Al for N. The strikingly different nitriding behaviors of Fe–Cr–Al and Fe–Cr–Ti alloys could be explained on this basis.     

Mechanomaking of nanostructure in nitrided Fe–Cr alloys by cyclic “dissolution–precipitation” deformation-induced transformations

Structural-phase transformations in surface layers of iron and Fe? Cr? (Ni) alloys subjected to ion-plasma nitriding and subsequent cold plastic compression shear deformation in Bridgman anvils have been investigated by the methods of Mössbauer spectroscopy, transmission electron microscopy and X-ray analysis. It has been shown that the deformation-induced cyclic phase “dissolution–precipitation” transformations of nitrides in alloys lead to the formation of nitrogen oversaturated solid solutions, precipitation of secondary nitrides and nanostructurization of the metal matrix.     

57Fe Mössbauer study of Fe nitrides

Summary Magnetic properties of Fe nitrides have been re-examined by⁵⁷Fe M?ssbauer spectroscopy. Hyperfine magnetic fields for α″-Fe₁₆N₂ are 30, 31 and 39T at 298K, but the averaged hyperfine field is 33T and nearly equal to the value of pure α-Fe. σ-Fe₂ N is an antiferromagnet below 9K having a small magnetic moment less than 0.1 μ_B, although γ′-Fe₄N and ε-Fe_3–2N are ferromagnets. ZnS-type FeN is non-magnetic at 4.2K. M?ssbauer spectra obtained from NaCl-type FeN are complex and some Fe atoms in this nitride show a surprisingly large hyperfine magnetic field of 49T. Paper presented at the ICAME-95, Rimini, 10–16 September 1995.     

Constituted oxides/nitrides on nitriding 304, 430 and 17-4 PH stainless steel in salt baths over the temperature range 723 to 923 K

The progressively developed oxides and nitrides that form on nitriding 304, 430 and 17-4 PH stainless steel are analysed by X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) in this study. The experimental results show that the Cr contents and matrix structures (ferrite, austenite and martensite) play an important role in forming FeCr₂O₄, Cr₂O₃ and Fe₂O₃ oxides as well as nitrides. After a short immersion time, oxides of Cr₂O₃ and FeCr₂O₄ form in nitride films on 304 stainless steel samples. Fe₂O₃ oxide will subsequently form following an increasing immersion time. For the 430 stainless steel, Cr₂O₃ predominately forms after a short dipping time which hinders the growth of the nitride layer. As a result, this sample had the thinnest nitride film of the three for a given immersion time. After the formation of oxides, both CrN and Cr₂N were detected near the surface of the nitride films of three samples while Cr₂N phases formed in the deeper zone. The greatest amount of Fe₂O₃ oxide among the three samples was obtained on the nitriding 17-4 PH stainless steel which also had a high intensity count of N 1s.     

A study of Fe--N alloy systems

Magnetic properties of Fe nitrides have been reexamined by ⁵⁷Fe Mössbauer spectroscopy. Hyperfine magnetic fields for α″-Fe₁₆N₂, γ′-Fe₄N, ε-Fe₃N, ζ-Fe₂N, NaCl-type FeN and ZnS-type FeN have been determined at various temperatures. Although α′-, γ″-, and ε-nitride are all ferromagnets, ζ-Fe₂N is found to be an antiferromagnet below 9 K and ZnS-type FeN is non-magnetic at 4.2 K. Contrary to the ZnS-type FeN, the NaCl-type FeN is an antiferromagnet and shows a component with a surprisingly large hyperfine magnetic field of 49 T.     

Nickel-induced magnetic behaviour of nano-structured α-Fe2O3, synthesised by facile wet chemical route

We report the synthesis of pristine and nickel containing iron oxide (α-Fe₂O₃) nanocrystallites by facile environmentally benign wet chemical process. The magnetic behaviour of the samples has been found to change progressively with nickel content. The Mössbauer spectra revealed the precipitation of secondary phase of nickel ferrite (NiFe₂O₄) at ～2?wt% nickel contents. The transmission electron micrographs together with asymmetric magnetic hysteresis loop have confirmed the formation of core–shell structure. The Morin temperature of nanostructured α-Fe₂O₃ as estimated by superconducting quantum interference device has been found to be 257, 245, 247 and 242?K at nickel content of 0, 1, 2 and 4?wt%, respectively. The similar trends of increase/decrease in Morin temperature have been noticed by Mössbauer analysis. Furthermore, below Morin temperature, the temperature range of coexisted antiferromagnetic and ferromagnetic states has been found to increase with increase in nickel content.     

Microstructure and mechanical properties of a large-dimensional bulk nanocrystalline-based Fe–Al–Cr alloy prepared by an aluminothermic reaction casting and followed annealing at 1000 °C

A large-dimensional bulk nanocrystalline phase-based Fe–Al–Cr alloy with 10?wt.% Cr, which was about 200?mm in diameter and 10?mm in thickness, was prepared by an aluminothermic reaction casting and followed annealing at 1000?°C. Microstructures of the alloy were investigated by optical microscope, electron probe microscope, scanning electron microscope attached with electron backscattered diffraction, X-ray diffraction and transmission electron microscope. The magnetization curves of the alloy were tested by Lake Shore 7410 vibrating sample magnetometer. Compressive properties of the alloy were tested. The results show the alloy was consisted of a Fe–Al–Cr nanocrystalline matrix, Cr₇C₃ phase and contaminants in micrometre. Average grain size of the nanocrystalline matrix was 19?nm. Volume fraction of the Cr₇C₃ phase in the alloy was about 4.5%. After annealing, the saturated intensity of magnetization and the specific magnetic susceptibility of the alloy increased slightly from 99 emu/g and 0.083 emu/g?Oe to 104 emu/g and 0.113 emu/g?Oe, respectively. Compressive strength of the alloy was 1200?MPa and much higher than that of the small-scale nanocrystalline alloy and alloy with grains in micrometre.     

Mixing characterization of mechanically milled Fe75Si15M10 powders using Mössbauer spectroscopy

Iron nitrides are attractive as they show excellent magnetic properties which can be utilized as recording and permanent magnetic materials for potential applications. Due to the high saturation magnetization and chemical stability, γ ^′-Fe₄N compound is widely investigated as a promising high density magnetic recording material. γ ^′-Fe₄N particles were synthesized by conventional gaseous nitriding in a heated atmosphere containing ammonia as a source of nitrogen. X-ray diffraction, ⁵⁷Fe Mössbauer spectroscopy, vibrating sample magnetometer, scanning electron microscopy and transmission electron microscopy are used for the characterization of the as prepared sample.     

Coherency strain and precipitation kinetics: crystalline and amorphous nitride formation in ternary Fe–Ti/Cr/V–Si alloys

Specimens of iron-based binary Fe–Si alloy and ternary Fe–Me–Si alloys (with Me = Ti, Cr and V) were nitrided at 580 °C in a NH₃/H₂-gas mixture applying a nitriding potential of 0.1 atm^?1/2 until nitrogen saturation in the specimens was attained. In contrast with recent observations in other Fe–Me ₁–Me ₂ alloys, no “mixed” (Me ₁, Me ₂) nitrides developed in Fe–Me–Si alloys upon nitriding: first, all Me precipitates as MeN; and thereafter, all Si precipitates as Si₃N₄. The MeN precipitates as crystalline, finely dispersed, nanosized platelets, obeying a Baker–Nutting orientation relationship (OR) with respect to the ferrite matrix. The Si₃N₄ precipitates as cubically, amorphous particles; the incoherent (part of the) MeN/α-Fe interface acts as heterogeneous nucleation site for Si₃N₄. The Si₃N₄-precipitation rate was found to be strongly dependent on the degree of coherency of the first precipitating MeN. The different, even opposite, kinetic effects observed for the various Fe–Me–Si alloys could be ascribed to the different time dependences of the coherent?→?incoherent transitions of the MeN particles in the different Fe–Me–Si alloys.     

Dependence of the nitriding rate of ferritic and austenitic substrates on the crystallographic orientation of surface grains; gaseous nitriding of Fe-Cr and Ni-Ti alloys

Gaseous nitriding of ferritic Fe–Cr and austenitic Ni–Ti solid solutions reveals that the extent of the uptake of dissolved nitrogen depends on the crystallographic orientation of the surface grains of the substrate. In both ferritic and austenitic substrates, the surface nitrogen concentration and the nitriding depth decrease upon increasing the smallest angle between the surface normal and the normal of a {1?0?0} plane of the surface grain considered. This phenomenon could be ascribed to the residual compressive macrostress developed during nitriding which varies as a function of crystallographic orientation of the (surface) grains due to the elastically anisotropic nature of ferrite and austenite solid solutions investigated in this study.     

Mo nitrides and carbonitrides via metallic phase transition of MoO3 films using ammonium salt precursors in chemical vapor deposition

Transition-metal-based nitrides and carbides have been widely studied for various applications because of their excellent mechanical, electrical, and catalytic properties. Although outstanding performances of Mo nitride and carbonitride synthesized by chemical reaction methods have been reported recently for catalytic applications, a metallic phase transition method for pre-deposited MoO₃ precursor films, which is suitable for application to Si or metallic substrates, has rarely been reported. Herein, we investigate Mo nitride and carbonitride thin films synthesized via nitriding and carbonitriding of MoO₃ films using two types of ammonium salt precursors, urea and ammonium carbonate (AC), in the chemical vapor deposition (CVD) process. The phase-changed crystalline films of Mo carbonitride via the urea reaction and Mo nitride via the AC reaction were determined to be MoC_0.5N_0.5 and MoN by X-ray diffractometry, respectively. Nevertheless, amorphous states of carbons and their related compounds, unreacted residual MoO₃, and incompletely reacted MoO₂ remained in the films, as determined by other thin film analyses. When the residual MoO₂ was minimal, the films exhibited the lowest electrical resistivity, i.e., ∼10⁻⁴ Ω·cm for Mo carbonitride and ∼10⁻³ Ω·cm for Mo nitride, implying an optimum metallic phase transition. Our results pave the way for the nitriding and carbonitriding of transition metal oxides using ammonium salt precursors for a one-step reaction in the CVD process.     

The isothermal section of the Tb–Co–Cr ternary system at 873 K

The isothermal section of the phase diagram of the Tb–Co–Cr ternary system at 873?K was investigated by means of X-ray diffraction, metallography, and scanning electron microscopy equipped with energy dispersive X-ray spectroscopy. Ternary phases and their lattice parameters as a function of composition of solid solution were systematically studied. The existence of one ternary phase reported previously was confirmed. The ternary compound Tb(Co,?Cr)₁₂ crystallizes with ThMn₁₂-type structure, space group I4/mmm. The linear homogeneity range along the line of 7.69 at.% Tb in TbCo_{12? x} Cr _x was found to be about x?=?3.6–5.7, i.e., 27.7–43.8 at.% Cr. The lattice parameters are a?=?0.8326–0.8352?nm and c?=?0.4709–0.4740?nm. The maximum solid solubilities of Cr in Tb₂Co₁₇, TbCo₃, and TbCo₂ are about 20.0, 8.2, and 7.9 at.%, respectively.     

Microstructure and mechanical properties of nano-Y2O3 dispersed ferritic steel synthesized by mechanical alloying and consolidated by pulse plasma sintering

Ferritic steel with compositions 83.0Fe–13.5Cr–2.0Al–0.5Ti (alloy A), 79.0Fe–17.5Cr–2.0Al–0.5Ti (alloy B), 75.0Fe–21.5Cr–2.0Al–0.5Ti (alloy C) and 71.0Fe–25.5Cr–2.0Al–0.5Ti (alloy D) (all in wt%) each with a 1.0?wt% nano-Y₂O₃ dispersion were synthesized by mechanical alloying and consolidated by pulse plasma sintering at 600, 800 and 1000°C using a 75-MPa uniaxial pressure applied for 5?min and a 70-kA pulse current at 3?Hz pulse frequency. X-ray diffraction, scanning and transmission electron microscopy and energy disperse spectroscopy techniques have been used to characterize the microstructural and phase evolution of all the alloys at different stages of mechano-chemical synthesis and consolidation. Mechanical properties in terms of hardness, compressive strength, yield strength and Young's modulus were determined using a micro/nano-indenter and universal testing machine. All ferritic alloys recorded very high levels of compressive strength (850–2850?MPa), yield strength (500–1556?MPa), Young's modulus (175–250?GPa) and nanoindentation hardness (9.5–15.5?GPa), with up to 1–1.5 times greater strength than other oxide dispersion-strengthened ferritic steels (<1200?MPa). These extraordinary levels of mechanical properties can be attributed to the typical microstructure of uniform dispersion of 10–20-nm Y₂Ti₂O₇ or Y₂O₃ particles in a high-alloy ferritic matrix.     

Texture development during cold rolling of Fe–Cr–Ni alloy-experiments and simulations

Abstract

In the present work, evolution of microstructure and crystallographic texture during cold rolling of two phase Fe–Cr–Ni alloy was investigated. Fe–Cr–Ni alloy (in initially solution annealed condition) was uni-directionally cold rolled in a laboratory rolling mill to different thickness reductions. Scanning electron microscopy was used to observe the changes in microstructure, while X-ray diffraction was used to investigate changes in crystallographic texture of austenite and ferrite (through changes in orientation distribution function). Crystallographic texture was also simulated using different crystal plasticity models (Full constraint Taylor, relaxed constraint Taylor (lath and pancake) and co-deformation Visco Plastic Self Consistent (VPSC)). With the increase in plastic deformation, there were morphological as well as crystallographic changes in the microstructure. Strong α-fibre (RD//〈1?1?0〉) texture was developed in ferrite, while brass ({1?1?0}〈1?1?2〉) and Goss ({1?1?0}〈0?0?1〉) was dominant in austenite after 80% cold rolling. The formation of brass type texture after deformation has been attributed to the formation of shear bands and presence of strong crystallographic texture in the initial solution annealed material. Both Taylor as well as VPSC models could not capture the changes in texture with deformation accurately. For ferrite: γ-fibre (ND//〈1?1?1〉) and for austenite: Cu ({1?1?2}〈1?1?1〉) component was always present in the simulated textures. Possible reason for this could be the pining effect of interface boundaries and non-incorporation of non-crystallographic shear banding in the Taylor and VPSC models.     

Incubation time for iron-nitride layer formation upon gaseous nitriding of iron-based alloys

A model was developed to predict quantitatively the influence of alloying element (Me) dissolved in the ferrite (α) matrix on the incubation time for iron-nitride layer formation upon gaseous nitriding of iron-based alloys. The model incorporates the coupled, concurrent processes of inward diffusion of nitrogen and the depth dependency of the time dependency of the precipitation of alloying-element nitride particles in the α matrix. Experimental results were obtained by gaseous nitriding of an Fe-2.23 at.% V alloy. The incubation time for iron-nitride formation on Fe–Me alloy is generally much larger than that for iron-nitride formation on pure iron due to a pronouncedly lesser rate of increase of dissolved N content at the surface of Fe–Me alloy. The extent of segregation of N at the MeN/α-Fe interfaces has distinct influence on the incubation time.     

Heavy-ion irradiations of Fe and Fe–Cr model alloys Part 1: Damage evolution in thin-foils at lower doses

The evolution of radiation damage in Fe and Fe–Cr alloys under heavy-ion irradiation was investigated using transmission electron microscopy. Thin foils were irradiated with 100 or 150 keV Fe⁺ and Xe⁺ ions at room temperature (RT) and 300°C. Dynamic observations followed the evolution of damage and the early stages in damage development are reported. Small (2–5 nm) dislocation loops first appeared at doses between 10¹⁶ and 10¹⁷ ions m^?2 in all materials. Loop number densities depended strongly on the foil orientation in pure Fe but not in Fe–Cr alloys. Number densities did not depend strongly on Cr content. For a given material, defect yields were higher for Xe⁺ ions than for Fe⁺ ions, and were higher at RT than at 300°C. Loops with both ?100? and ½?111? Burgers vectors were identified. The proportion of ?100? loops was larger, especially in pure Fe. Dynamic observations showed that: the contrast of some new loops developed over intervals as long as 0.2 s; hopping of ½?111? loops was induced by the ion and electron beams and was pronounced in ultra-pure iron; and many loops were lost during and after ion irradiation by glide to the foil surface. The number of loops retained was strongly dependent on the foil orientation in Fe, but less so in Fe–Cr alloys. This is due to lower loop mobility in Fe–Cr alloys, probably due to pinning by Cr atoms. Reduced loop loss probably explains the higher loop number densities in Fe–Cr alloys compared with pure Fe.