Austenite phase formation in rapidly solidified Fe–Cr–Mn–C steels

Steels having compositions (wt%) 0.05–0.5C, 12.5–20Cr, 8–25Mn and 0–0.51N have been chill-block melt-spun to ribbons in order to investigate systematically, by X-ray diffractometry and electron microscopy, the effects of rapid solidification and of solute concentrations on the formation of the austenite phase. The austenite is most easily formed at (wt%) 16Cr–8Mn for 0.3C ribbons while ′-martensite or -martensite was observed at lower concentrations of Cr or Mn and -ferrite appeared for Cr >18 wt%. The volume fraction of austenite in the steel ribbons studied was found, by multiple regression analysis, to obey the equation

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. Thus, the effect of Mn on γ formation followed a non-linear function, containing an interaction term including the Cr and Mn contents, and first- and second-order terms involving the Mn concentration. This indicates the ranges over which Mn is a γ-former or an -former. Iso-austenitic lines, constructed on the basis of this new equation, are nearly orthogonal to those in the Schaeffler diagram for Cr–Mn steels so that use of the latter for prediction of the austenite content in the present case would be inappropriate.     

Quantitative representation of the anisotropy and tension/compression asymmetry of the critical resolved shear stress of an L12-ordered intermetallic

The anomalous anisotropy and tension (t)/compression (c)-asymmetry of the critical resolved shear stress τ_o of the L1₂-long-range ordered intermetallic γ′_NIM are analysed in the light of a published (Miner RV, Gabb TP, Gayda J, Hember, KJ. Met Trans A 1986; 17A: 507) analytical expression

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. Particles of γ′_NIM strengthen the commercial nickel-base superalloy NIMONIC 105. characterises the orientation of the specimen, and T_o≈300 K and T_peak≈ 1000 K mark the temperature (T) range in which τ_o is anomalous. Except for γ′_NIM-single crystals with the [011]-orientation, the formula describes the anisotropy and (t/c)-asymmetry of the critical resolved shear stress satisfactorily.     

Hydrogen redistribution in the solid solutions ZrV2Dx, 2.2≤x≤2.7.: II. Structure of the intermediate phase: ‘Lattice liquid crystal’. A neutron-diffraction study

We have studied the crystal structure of the uncommon phase with k=0 in ZrV₂D_x, 2.2<x<2.5, which is an intermediate between the hydrogen-disordered phase and two hydrogen superstructures, ZrV₂D_<2 with k=(1/2 1/2 1/2) and ZrV₂D_>2.7 with k=(001). This phase is a primary superstructure combining the features of the disordered phase and, depending on the hydrogen concentration, one or another superstructure with k≠0. Its lattice (translational symmetry) is the same as in the disordered phase, which is k=0. Simultaneously, the lattice sites (the hydrogen arrangement in them) are prototypes of the sites of the subsequent superstructure with k≠0. Specifically, each site of the primary superstructure with k=0 is a mix of the sites with different spatial orientation of the superstructure with k≠0. In this sense the primary superstructure can be considered as a ‘lattice liquid crystal’ whereas usual superstructure with k≠0 is a ‘lattice crystal’. In addition, we have determined the crystal structure of the ‘ordered’ phase with k=(001) in ZrV₂D_2.73. It is a transitional state between the primary superstructure and the regular superstructure with the same k.     

Effective operators and spectroscopic properties

In 1968, Wybourne¹ [J. Chem. Phys. 48 (1968) 2596] asked two major questions while pointing out that a few years earlier, “Judd and Ofelt considered only second-order contributions to the oscillator strength:

1. Are the higher-order contributions significant?

2. What new angular-dependent terms enter when the higher-order contributions are considered?”

In the present paper, the answers to these questions are discussed in the form of a report woven onto the background of Wybourne’s publication. The very last sentence of his paper might be taken as an obligation and also as a source of inspiration for all of us who have been trying to describe the properties of rare earth ions over the years. Indeed, he remarks: “At this state (1968) there would seem to be little point in extending calculations to higher orders until actual numerical estimates of the relative importance of the second- and third-order contributions are established.” In this context, the present analysis is performed up to the third-order terms, and the new effective operators are discussed. In addition, to fulfill the demand for “actual numerical estimates”, the results of ab initio calculations are presented to illustrate the hierarchy of important physical mechanisms that contribute to the f↔f transition amplitude.     

Dependence of dielectric properties of manganese-doped strontium titanate ceramics on sintering atmosphere

It is shown in this paper that the microscopic mechanism of the dielectric relaxation in Mn-doped strontium titanate (SrTiO₃–ST) ceramics is associated with the off-center displacement of ions. This was accomplished by studying the dielectric properties and electron spin resonance spectroscopy in combination with X-ray powder diffractometry and scanning electron microscopy techniques in Sr_1−xMn_xTiO₃ ceramic samples sintered in different atmospheres (air, oxygen and nitrogen) at 1500 °C. First, it is shown that manganese is incorporated into the perovskite lattice of ST, preferably as Mn²⁺ at Sr sites. However, a small amount of Mn⁴⁺ at Ti sites is also observed when fired in air or oxygen flow. The concentration of is the highest for sintering in oxygen, but firing in a reducing atmosphere (nitrogen) results solely in the incorporation of Mn²⁺ at Sr sites. Correspondingly, the dielectric relaxation observed in Sr_1−xMn_xTiO₃ markedly increases in intensity and slightly shifts towards a higher temperature for ceramics sintered in nitrogen compared with those fired in air or oxygen. All these facts are consistent with a suggestion that the off-center displacement of Mn²⁺ ions at the Sr sites of the highly polarizable ST lattice is the source of the observed relaxation behavior.     

Magnetic structures of R2RhSi3 (R=Ho, Er) compounds

Powder X-ray and neutron diffraction and magnetic measurements have been performed on R₂RhSi₃ (R=Ho and Er) compounds at low temperatures. The compounds crystallize in a derivative of the hexagonal AlB₂-type structure. The crystal structure parameters have been refined on the basis of the X-ray and neutron diffraction patterns collected in the paramagnetic region. These compounds are antiferromagnets with Néel temperatures of 5.2 K for Ho₂RhSi₃ and 5 K for Er₂RhSi₃. Both compounds exhibit collinear magnetic structures, described by the propagation vector k=(1/2,0,0) for Ho₂RhSi₃ and k=(0,0,0) for Er₂RhSi₃. This magnetic order is stable in the temperature range between 1.5 K and the Néel temperature.     

X-ray investigations of ternary R3Pd4Ge4 samples

Ternary R₃Pd₄Ge₄ samples (R=Nd, Eu, Er) were investigated by means of X-ray single crystal (four circle diffractometer Philips PW1100, MoK radiation) and powder diffraction (MX Labo diffractometer, CuK radiation). The Er₃Pd_3.68(1)Ge₄ compound belongs to the Gd₃Cu₄Ge₄ structure type, space group Immm, a=4.220(2) Å, b=6.843(2) Å, c=14.078(3) Å, R₁=0.0484 for 598 reflections with F_o>4σ(F_o) from X-ray single crystal diffraction data. No ternary R₃Pd₄Ge₄ compound when R is Nd or Eu was observed. The Nd and Eu containing samples appeared to be multiphase. Ternary phases observed in the Nd₃Pd₄Ge₄ and Eu₃Pd₄Ge₄ alloys and their crystallographic characteristics are the following: NdPd₂Ge₂, CeGa₂Al₂ structure type, space group I4/mmm, a=4.3010(2) Å, c=10.0633(2) Å (X-ray powder diffraction data); NdPd_0.6Ge_1.4, AlB₂ structure type, space group P6/mmm, a=4.2305(2) Å, c=4.1723(2) Å (X-ray powder diffraction data); Nd(Pd_0.464(1)Ge_0.536(1))₂, KHg₂ structure type, space group Imma, a=4.469(2) Å, b=7.214(2) Å, c=7.651(3) Å, R₁=0.0402 for 189 reflections with F_o>4σ(F_o) (X-ray single crystal diffraction data); Eu(Pd,Ge)₂, AlB₂ structure type, space group P6/mmm, a=4.311(2) Å, c=4.235(2) Å; EuPdGe, EuNiGe structure type, space group P2₁/c, and ternary compound with unknown structure (X-ray powder diffraction data).     

Structural and magnetic characterization of martensitic Ni–Mn–Ga thin films deposited on Mo foil

Three martensitic Ni_51.4Mn_28.3Ga_20.3 thin films sputter-deposited on a Mo foil were investigated with regard to their crystal and magnetic domain structures, as well as their magnetic and magnetostrain properties. The film thicknesses, d, were 0.1, 0.4 and 1.0μm. X-ray and electron diffraction patterns revealed a tetragonal modulated martensitic phase (10 M) in the films. The surface topography and micromagnetic structure were studied by scanning probe microscopy. A maze magnetic domain structure featuring a large out-of-plane magnetization component was found in all films. The domain width, δ, depends on the film thickness as . The thickness dependencies of the saturation magnetization, saturation magnetic field and magnetic anisotropy were clarified. Beam cantilever tests on the Ni–Mn–Ga/Mo composite as a function of magnetic field showed reversible strains, which are larger than ordinary magnetostriction.     

Investigation of hydrogen discharging and recharging processes of Ti-doped NaAlH4 by X-ray diffraction analysis (XRD) and solid-state NMR spectroscopy

The processes occurring in the course of two sequential hydrogen discharging and recharging cycles of Ti-doped sodium alanate were investigated in parallel using XRD analysis and solid-state NMR spectroscopy. Both methods demonstrate that in hydrogen storage cycles (Eq. (1)) the majority phases involved are NaAlH₄, Na₃AlH₆, Al and NaH. Only traces of other, as yet unidentified phases are observed, one of which has been tentatively assigned to an Al–Ti alloy on the basis of XRD analysis. The unsatisfactory hydrogen storage capacities heretofore observed in cycle tests are shown to be due entirely to the reaction of Na₃AlH₆ with Al and hydrogen to NaAlH₄ (Eq. (1), 2nd hydrogenation step) being incomplete. Using XRD and NMR methods it has been shown that a higher level of rehydrogenation can be achieved by adding an excess of Al powder.     

Crystallization processes and phase evolution in amorphous Fe–Pt–Nb–B alloys

Fe–Pt system is nowadays widely studied due to its potential applications as magnetic recording media. The hard magnetic FePt L1₀ phase has extremely promising potential as permanent magnet with high magnetocrystalline anisotropy. Of recent interest is also the developing of the hard magnetic phase from an amorphous precursor by appropriate crystallization processes. The melt-spun amorphous Fe₆₈Pt₁₃Nb₂B₁₇ alloy has been submitted to dynamical annealing and its phase transformation during the process has been monitored by differential scanning calorimetry and in situ energy-dispersive X-ray diffraction of the synchrotron radiation. In the first stage of crystallization, -Fe and cubic FePt phases are formed from the amorphous precursor. At around 600 °C superlattice Bragg reflections corresponding to tetragonal FePt are indexed in the XRD spectra and -Fe phase diminishes drastically. Finally, between 900 °C and 975 °C the tetragonal superlattice peaks disappear and cubic FePt phase is formed again. This reversible order–disorder transformation is accompanied by a strong uniaxial lattice expansion of the cubic FePt unit cell. The system show promising features for the co-existence of hard and soft exchange coupled magnetic phases crystallized from FePt-based amorphous precursors.     

Structure at abrupt copper–alumina interfaces: An ab initio study

The atomistic structure and the energetics of Cu(1 1 1)/-Al₂O₃(0 0 0 1) interfaces for two experimentally observed interface orientation relationships were investigated from first-principles by means of the mixed-basis pseudopotential method. In the first orientation relationship, the direction of Cu is parallel to the direction of -Al₂O₃, and in the second the Cu is rotated with respect to the -Al₂O₃ by 90° around the interface normal [0 0 0 1]. Numerous candidate systems were considered for each case, covering all high-symmetry interface configurations, and with either Al or O termination of the -Al₂O₃(0 0 0 1) surfaces. For each of the most stable interfaces, full relaxations of the positions of all atoms were performed. It is found that despite the different atomistic structures of the two interface types, their interface stabilities, in terms of the work of separation, and their local atomistic structures are similar.     

Structure of Y3TaNi6+xAl26: a filled-up substitution variant of the BaHg11 type

The crystal structure of Y₃TaNi_6+xAl₂₆ (refined composition Y₄TaNi_6+[7]Al_20+[6]) was determined by single-crystal X-ray diffraction (λ(Mo K) −0.71073 A. μ −17.827 mm¹, F(000) = 700, T = 293 K, wR = 0.015 for [8] unique reflections). This new quaternary aluminide crystallizes with a cubic structure. Pearson code cP49-12.85, (221) Pm-3m-ji'gdba, a = 8.3600(1) Å. V = 584.28(2) Å, Z = 1, M₁ = 1510.25, D_x = 4.292 mg mm¹. The structure of Y_xTaNi_6+xAl₂₆ is filled-up substitution variant of the BaHg₁₁ structure type with one additional atom site, partly occupied (around 15%) by Ni atoms, located at the centre of a cube formed by Al atoms. Distinct atom coordinates were refined for Ni and Al atoms on a site for which mixed occupation (approximately 50% Ni/50% Al) was found. The Ta atoms centre regular Al atom cuboctahedra, and the Y atoms 20-vertex polyhedra, formed by Al and Ni atoms, similar to those observed in CeMn₄Al₈ and YbFe₂Al₁₀.     

Crystal structures of the Ag4HgGe2S7 and Ag4CdGe2S7 compounds

The crystal structures of the Ag₄HgGe₂S₇ and Ag₄CdGe₂S₇ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the monoclinic Cc space group with the lattice parameters a=1.74546(8), b=0.68093(2), c=1.05342(3) nm, β=93.398(3)° for Ag₄HgGe₂S₇ and a=1.74364(8), b=0.68334(3), c=1.05350(4) nm, β=93.589(3)° for Ag₄CdGe₂S₇. Atomic parameters were refined in the isotropic approximation (R_I=0.0761 and R_I=0.0727, respectively).     

Effects of Ribbon Thickness on Structure and Soft Magnetic Properties of a High-Cu-Content FeBCuNb Nanocrystalline Alloy

The effects of ribbon thickness (t) on the structure and magnetic properties of a Fe_82.3B₁₃Cu_1.7Nb₃ alloy in melt-spun and annealed states have been investigated. Increasing the t from 15 to 23 μm changes the structure of the melt-spun ribbons from a single amorphous phase to a composite with dense α-Fe nanograins embedded in the amorphous matrix. The grain size (D_α-Fe) of the α-Fe near the free surface of the ribbon is about 6.7 nm, and it gradually decreases along the cross section toward the wheel-contacted surface. Further increasing the t to 32 μm coarsens the D_α-Fe near the free surface to 15.2 nm and aggravates the D_α-Fe ramp along the cross section. After annealing, the ribbon with t = 15 μm has relatively large α-Fe grains with D_α-Fe > 30 nm, while the thicker ribbons possessing the pre-existing nanograins form a finer nanostructure with D_α-Fe < 16 nm. The structural uniformity of the ribbon with t = 23 μm is better than that of the ribbon with t = 32 μm. The annealed ribbons with t = 23 and 32 μm possess superior soft magnetic properties to the ribbon with t = 15 μm. The ribbon with t = 23 μm exhibits a high saturation magnetic flux density of 1.68 T, low coercivity of 9.6 A/m, and high effective permeability at 1 kHz of 15,000. The ribbon with t = 32 μm has a slightly larger coercivity due to the lower structural uniformity. The formation mechanism of the fine nanostructure for the ribbons with suitable t has been discussed in terms of the competitive growth effect among the pre-existing α-Fe nanograins.     

The molybdenum diphosphate Mo1.3O(P2O7), containing Mo2 and Mo3 clusters

A novel molybdenum diphosphate, Mo_1.3O(P₂O₇), was obtained by electrochemical lithium deintercalation. The diphosphate crystallises in space group I2/a with the lattice parameters a=22.88(1), b=22.94(2), c=4.832(1) Å, γ=90.36°, Z=8. Its original framework is built up from MoO₆ octahedra, P₂O₇ groups and also from MoO₄, Mo₂O₄ and Mo₃O₈ units containing Mo₂ and Mo₃ clusters. These polyhedra delimit large octagonal and z-shaped tunnels running along c, in which the inserted cations may be located.     

Single crystal preparation and crystal structure of the Cu2Zn/Cd,Hg/SnSe4 compounds

Single crystals of Cu₂Zn/Cd/SnSe₄ were grown using a solution-fusion method. The crystal structure of the Cu₂Zn/Cd,Hg/SnSe₄ compounds were investigated using X-ray powder diffraction. These compounds crystallize in the stannite structure (space group I 2m) with the lattice parameters: a=0.56882(9), c=1.13378(9) nm, c/a=1.993 (Cu₂ZnSnSe₄), a=0.58337(2), c=1.14039(4) nm, c/a=1.955 (Cu₂CdSnSe₄) and a=0.58288(1), c=1.14179(2) nm, c/a=1.959 (Cu₂HgSnSe₄). Atomic parameters were refined in the isotropic approximation (R_I=0.0517, R_I=0.0511 and R_I=0.0695 for Cu₂ZnSnSe₄, Cu₂CdSnSe₄ and Cu₂HgSnSe₄, respectively).     

Investigation of the titanium–indium system

The phase diagram of the Ti–In system was determined using DTA, XRD and EDX analyses. The existence of the phases Ti₂In₅ [Mn₂Hg₅ type structure, space group P4/mbm, a=0.99995(3), c=0.29960(2) nm] and Ti₃In [Ni₃Sn type structure, space group P6₃/mmc, a=0.5978(1), c=0.4812(1) nm] was confirmed. The phase previously labeled Ti₃In₂ was found to exist in a narrow homogeneity region near Ti₅₆In₄₄. Rietveld refinement of the XRD powder pattern yielded solutions compatible with a Cu₃Au-type or a BiIn-type crystal structure, but not with a CuAu-type crystal structure. Furthermore, at 38.5 at.% In, a new phase was observed having a γ-brass related crystal structure [Ti₈In₅, space group , a=0.99578(6) nm]. The intermetallic phases were formed by a cascade of peritectic reactions ending in a eutectic at >99 at.% indium between Ti₂In₅ and (In) at 0.4 K below the melting temperature of pure indium.     

New Zr6CoAs2-type compounds: Y6CoBi2, Ho6CoBi2 and Tm6CoBi2

Results of a powder X-ray diffraction investigation of new ternary compounds are reported. The compounds Y₆CoBi₂ [a=0.8312(1) nm, c=0.4144(1) nm], Ho₆CoBi₂ [a=0.8246(2) nm, c=0.4095(1) nm], and Tm₆CoBi₂ [a=0.8155(2) nm, c=0.4066(1) nm] crystallize in the hexagonal Zr₆CoAs₂-type structure (space group P6b2m No. 189). The Zr₆CoAs₂-type structure is a superstructure of the Fe₂P-type structure.     

Magnetic structure of the HoPdSn compound

A polycrystalline sample of the HoPdSn compound was prepared and studied by powder neutron diffraction. This compound crystallizes in the orthorhombic TiNiSi-type structure (space group Pnma). The Ho atoms occupy the 4c position. Below T_N=3.7 K, the Ho moments equal to 6.0(1) μ_B form a magnetic structure described by the propagation vector k=(1/3,1/2,1/3) and are parallel to the a-axis.     

Structure and unusual magnetic properties in the itinerant electron system Hf0.8Ta0.2(Fe1−xCox)2

The crystal structure and magnetization of Hf_0.8Ta_0.2(Fe_1−xCo_x)₂ are investigated by X-ray powder diffraction and magnetization measurements. The compounds exhibit the Laves C14 structure for x=0.0–0.2 and the C15 structure for x≥0.3. The structural transition from C14 to C15 leads to an anomaly of the unit cell volume between x=0.2 and 0.3. When x=0.0, the compound undergoes a magnetic phase transition from ferromagnetic to paramagnetic state via the antiferromagnetic state, in which a field-induced metamagnetic transition is observed. When x=0.1 and 0.2, the compounds exhibit unusually small saturation moments, which are considered as antiferromagnetism (with weak ferromagnetic impurities) and weak ferromagnetism or ferrimagnetism, respectively. The formation of the AFM state is associated with a small bond length of Fe atom in the 6h site. When x≥0.3, the compounds exhibit a ferromagnetic to paramagnetic transition, which can be explained by itinerant electron metamagnetism.