Ostwald step rule in films of metastable nanocrystalline alloys Fe-C prepared by pulsed plasma vaporization

Ferromagnetic nanocrystalline Fe(C) films were prepared by pulsed plasma vaporization. A comprehensive investigation of the structure and magnetic properties made it possible to identify the type of short-range order here and to establish the sequence of structural states occurring in these films in the process of thermal relaxation: fcc-Fe(C)→hcp-Fe(C)→bcc-Fe+C. On the basis of an analysis of the metastable phase diagrams using Ostwald’s rule, it is shown that the observed scenario of the structural transformations in these metastable nanocrystalline alloys Fe(C) is a natural phenomenon. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 11, 727–732 (10 December 1999)     

Magnetic properties of rapidly quenched amorphous Fe-Sm alloys

The structural analysis and investigation of magnetic properties were carried out on rapidly quenched Fe_100−xSm_x (10.5 x 80) alloys. Amorphous alloys are fabricated in a wide composition range from x = 17 to 72.5. After heating the amorphous alloys up to 900 K, they transform into metastable phase I (T_c = 465 K)+ -Fe (x < 20), metastable phase II (T_c = 555 K)+-Fe (20 x 33.3) and Fe₂Sm+Sm (x40). The composition dependence of Curie temperature and magnetization is found to be similar to that of amorphous Fe-(Nd, Pr) alloys. A maximum coercive force of about 1.1 kOe at 300 K and 12 kOe at 77 K is obtained in the x = 40 alloy. The rapid decrease in coercive force with raising temperature can be explained by the wall pinning model proposed by Gaunt. The pronounced composition dependence of these magnetic properties for the amorphous Fe-Sm alloys can be considered to be caused by the change in the short-range atomic order with Sm concentration on the basis of the results of X-ray structural analysis.     

Structural relaxation in the CoP-CoNiP system upon low-temperature annealing

The atomic structure of alloys in the CoP-CoNiP system in the initial state and its behavior upon low-temperature annealing is investigated. It is shown that structural relaxation starts at temperatures of 150–200°C and results in local atomic ordering at the network boundaries. Crystals 2–5 nm in size start to undergo nucleation at the boundaries of structural heterogeneities when heated further to 250–300°C. The nanocrystal structure corresponds to the metastable phase delta-Co (ICSD 42684) and the unknown phase Co_{1 ? x} P _x . The estimated diffusion coefficient for CoP alloy is 10^?14 m² s^?1, according to the experimental data.     

Stability of (Fe-Tm-B) amorphous alloys: relaxation and crystallization phenomena

Fe-Tm-B base (TM=transition metal) amorphous alloys (metallic glasses) are thermodynamically metastable. This limits their use as otherwise favourable materials, e.g. magnetically soft, corrosion resistant and mechanically firm. By analogy of the mechanical strain-stress dependence, at a certain degree of thermal activation the amorphous structure reaches its limiting state where it changes its character and physical properties. Relaxation and early crystallization processes in amorphous alloys, starting already around 100°C, are reviewed involving subsequently stress relief, free volume shrinking, topological and chemical ordering, pre-crystallization phenomena up to partial (primary) crystallization. Two diametrically different examples are demonstrated from among the soft magnetic materials: relaxation and early crystallization processes in the Fe-Co-B metallic glasses and controlled crystallization of amorphous ribbons yielding rather modern nanocrystalline Finemet alloys where late relaxation and pre-crystallization phenomena overlap when forming extremely dispersive and fine-grained nanocrystals-in-amorphous-sauce structure. Mössbauer spectroscopy seems to be unique for magnetic and phase analysis of such complicated systems.     

Grain boundary segregation and relaxation in nano-grained polycrystalline alloys

The present study carries out systematic thermodynamics analysis of Grain Boundary(GB)segregation and relaxation in NanoGrained(NG)polycrystalline alloys.GB segregation and relaxation is an internal process towards thermodynamic equilibrium,which occurs naturally in NG alloys without any applied loads,causes deformation and generates internal stresses.The analysis comprehensively investigates the multiple coupling effects among chemical concentrations and mechanical stresses in GBs and grains.A hybrid approach of eigenstress and eigenstrain is developed herein to solve the multiple coupling problem.The analysis results indicate that the GB stress and grain stress induced by GB segregation and relaxation can be extremely high in NG alloys,reaching the GPa level,which play an important role in the thermal stability of NG alloys,especially via the coupling terms between stress and concentration.The present theoretic analysis proposes a novel criterion of thermal stability for NG alloys,which is determined by the difference in molar free energy between a NG alloy and its reference single crystal with the same nominal chemical composition.If the difference at a temperature is negative or zero,the NG alloy is thermal stable at that temperature,otherwise unstable.     

Metastable surface alloys produced by ion implantation,laser and electron beam treatment

Ion Implantation, Laser and Electron-beam Treatment (LET) of metals have been employed extensively to produce metastable surface alloys. Recent published work on implanted alloys is reviewed first. The dilute implanted alloys (solute concentration <10 at. %) are shown to lead to crystalline metastable solid solutions. At higher solute concentrations, an amorphous phase has been observed for several binary systems and recently for a ternary system. The physical mechanisms at play, are discussed in detail. A review of the surface alloys produced by LET of metals is then presented—with an emphasis on the mechanisms involved. In particular, general criteria governing formation of metastable solid solutions under LET are proposed and shown to have excellent agreement with available data on metals and Si.     

Shear transformations and the relaxation of the magnetic permeability aftereffect in amorphous ferrogmagnets

The relaxation of the permeability aftereffect of amorphous ferromagnets is studied as a function of aging time at different temperatures, and interpreted in terms of a superposition of processes with a distribution of activation energies, whose boundaries are experimentally determined. The results are accounted for in terms of the progressive freezing of shear stress transformations, which are the source of the magnetic aftereffect in amorphous alloys. It is suggested that a correlation must exist between shear transformations and the processes of free volume annihilation responsible for the structural relaxation in the glassy state.     

Metastable (III–V)1−xIV2x alloys

Zincblende-to-diamond-lattice structural phase transitions should occur in metastable (III–V)_1?xIV_2x alloys at a transition composition x_c that is controllable by growth conditions. The effect of this transition should be visible both in the electronic as well as the vibrational properties of these alloys. For example, in the prototypical (III–V)_1?xIV_2x alloy, (GaAs)_1?xGe_2x, the observed anomalous V-shaped bowing of the direct gap is explained in terms of the phase transition, which occurs at the minimum of the “V.” Predictions are made for the band gaps of new metastable alloys, such as (GaSb)_1?xSn_2x. Consequences of this transition for (III–V)-IV superlattices are also discussed.     

颗粒介质弹性的弛豫

颗粒介质是复杂的多体相互作用体系, 其弹性源自内部的力链结构, 弹性能量处在亚稳态, 具有复杂的弛豫行为. 在常规作用下, 颗粒介质往往呈现明显的弹性弛豫. 应力松弛是应变恒定时应力的衰减现象, 弹性弛豫是应力松弛的主要原因. 在前期工作基础上, 从弹性势能面和双颗粒温度热力学角度分析了弹性弛豫的机理, 量化了弹性应力演化不可逆过程; 基于双颗粒温度热力学计算得到了弹性能、颗粒温度和应力的演化, 其中应力松弛的计算结果与实验结果基本一致, 讨论了颗粒温度初值和输运系数的影响. 指出, 开展力链结构及其动力学研究是揭示宏观弹性弛豫机理的关键.     

Low-temperature relaxation of metastable states and quantum tunneling in antiferromagnets with Ising rare-earth ions: Dysprosium orthoaluminate

The paper reports the first observation of a magnetic relaxation of metastable states in an antiferromagnet (dysprosium orthoaluminate DyAlO₃) at low temperatures in zero magnetic field made by magnetostriction measurements. The metastable states were excited with the heat shock at the transition through the λ point of liquid helium in the course of thermal cycling. A possible mesoscopic mechanism of thermally activated and quantum magnetic relaxation is discussed.     

Study of laser-deposited metallic thin films by a combination of high-resolution ex situ and time-resolved in situ experiments

Laser-deposited metallic alloys and multilayers were studied in detail by a combination of high-resolution ex situ and time-resolved in situ experiments. The purpose of these experiments is to better understand the special properties of laser-deposited metallic films in comparison with conventionally prepared thin films. During deposition, thickness, resistance, and electron diffraction (THEED) experiments show that the film surface is resputtered, local mixing at the interfaces of multilayers on a nanometre scale occurs, and metastable phases up to large film thicknesses are formed. After deposition, a compressive stress of 1-2 GPa was measured using four-circle diffractometry, and growth defects were observed on an atomic scale by electron microscopy (HRTEM) and field ion microscopy (FIM). The obtained structural details of the metallic films can be explained by an implantation model for the laser deposition process.     

Magnetic relaxations in amorphous soft magnetic alloys

The paper reviews selected results of the extended experimental investigations of magnetic properties, time–temperature stability and workability of the soft magnetic amorphous alloys controlled by structural magnetic relaxation. Complex approach to the magnetic relaxations in multicomponent amorphous alloys is presented. The transition from magnetic after-effect to a new MAE spectrometry is illustrated on ternary amorphous CoSiB alloy.     

Metastable states,relaxation mechanisms,and fracture of liquids under severe loading conditions

The relaxation properties and fracture of glycerol, silicone oil, transformer oil, and water have been studied experimentally under shock wave loading. The power-law strain rate dependences of the stress amplitude and spall strength were found for the compression and rarefaction fronts, respectively. It was shown that temperature has a strong influence on the spall strength of glycerol near the phase transformation temperature. The power laws reflect a self-similar nature of the momentum transfer and fracture mechanisms of liquids that are conventionally observed in solids and governed by the mechanisms of defect-induced structural relaxation. The mechanisms of viscoelasticity are related to the metastable states that may give rise to a collective behavior of displacement field fluctuations (microshearing) in liquids and thus provide a viscoplastic response of liquids under high strain rate loading.     

Formation of the metastable phase upon crystallization of light amorphous Mg-Ni-Y alloys

The decomposition of the amorphous phase upon heating of the Mg₈₇Ni₁₃ and Mg₈₃Ni₁₃Y₄ amorphous alloys prepared by rapid quenching of the melt is investigated. The nanocrystalline structure is formed at the first crystallization stage and contains crystals of magnesium and the metastable phase. The structure of the metastable phase (the lattice parameters and space group) is determined. The possible chemical compositions of the metastable phase are considered. No differences are revealed in the structures of the metastable phases in the yttrium-containing and yttrium-free alloys. Heating of the alloys results in decomposition of the metastable phase. After completion of the transformations, the alloy structure consists of Mg and Mg₂Ni in accordance with the equilibrium phase diagram.     

Mössbauer study of the polymorphism in iron and iron-nickel alloys under deformation and high pressure

Structural and phase transitions in iron and binary iron-nickel alloys containing 6–32 at % nickel have been investigated by Mössbauer spectroscopy in situ under quasi-hydrostatic compression and compression shear. It is shown that the deformation decreases the onset pressure of the α-phase transition to the high-pressure ∈ and γ phases. Shear changes the transformation mechanism due to the formation of a large number of structural defects; it is an independent parameter of the phase transition kinetics. Compression shear leads to an irregular change in the hyperfine parameters of the initial and newly formed phases, which is due to the stress relaxation as in the trip effect.     

Structure property correlations in superconducting Ti-Nb alloys

Titanium-rich transition metal alloys are metastable in their quenched boc β phase. The instability is relieved by low temperature structural transformations. We have investigated this in a series of Ti-Nb alloys, through the measurements of electrical resistivity (ρ), superconducting transition temperature and upper critical field. Supporting structural evidence has been obtained from transmission electron microscopy (tem) and x-ray studies. It is shown that both ρ and dρ/dT can be used as useful indices of this instability. The enhanced value of resistivity on account of the instability results in the enhancement of upper critical field as shown from dH _c2/dT measurements.     

The structure and magnetic properties of amorphous magnetic thin films

A review of the structural and magnetic properties of amorphous ferromagnetic and ferrimagnetic thin films is presented. An attempt is made to report structural information on atomic and microstructural scales, and to stress its relevance to the magnetic properties of these materials. The more obvious microstructural features of deposited films are not present in the other important type of amorphous magnetic material prepared by rapid quenching from the melt, and present opportunities for differences in structure dependent magnetic properties. In the main, three classes of amorphous magnetic films are considered. Ferromagnetic transition metal (TM) films which are metastable only at temperatures well below room temperature are discussed. Their importance lies in the fact that they clearly represent the most fundamental amorphous phase. Ferromagnetic transition metal-metalloid (TM-Me) alloys have potential applications as magnetically soft materials. These alloys are, perhaps, the most studied amorphous magnetic materials both in deposited thin film and rapidly quenched ribbon forms. Finally, amorphous rare earth-transition metal (RE-TM) films are reviewed. They exhibit a wide variety of magnetic properties encompassing both extremely low and very high coercivities and also perpendicular magnetic anisotropy. The possible application of these materials in various types of device has encouraged much detailed research into their magnetic properties. This has highlighted the importance of preparation conditions and microstructure in defining their properties.     

Kinetic crystallisation instability in liquids with short-ranged attractions

ABSTRACT

Liquids in systems with spherically symmetric interactions are not thermodynamically stable when the range of the attraction is reduced sufficiently. However, these metastable liquids have lifetimes long enough that they are readily observable prior to crystallisation. Here we investigate the fate of liquids when the interaction range is reduced dramatically. Under these conditions, we propose that the liquid becomes kinetically unstable, i.e. its properties are non-stationary on the timescale of structural relaxation. Using molecular dynamics simulations, we find that in the square well model with range 6% of the diameter, the liquid crystallises within the timescale of structural relaxation for state points except those so close to criticality that the lengthscale of density fluctuations couples to the length of the simulation box size for typical system sizes. Even very close to criticality, the liquid exhibits significant structural change on the timescale of relaxation.     

Anomalies in the physical properties of metastable Fe-Ni alloys heated to the temperature interval of the α → γ transformation

Experimental data for the formation sequence of reverted austenite morphologies in the temperature interval of the reverse α → γ transformation in Fe-Ni metastable alloys are analyzed. Emphasis is on the mechanism behind the formation of extended crystals of a new phase, which arise in the middle of the reverse α → γ transformation temperature interval. A correlation between the formation of large extended lamellas and anomalous behavior of the physical properties of metastable Fe-Ni alloys is found.