Stacking fault energy of cryogenic austenitic steels

Stacking fault energy and stacking fault nucleation energy are defined in terms of the physical nature of stacking faults and stacking fault energy, and the measuring basis for stacking fault energy. Large quantities of experimental results are processed with the aid of a computer and an expression for calculating stacking fault energy has been obtained as γ³⁰⁰_SF(mJ·m^-2)=γ⁰_SF+1.59Ni-1.34Mn+0.06Mn²-1.75Cr+0.01Cr²+15.21Mo-5.59Si-60.69(C+1.2N)^1/2 + 26.27(C+1.2N)(Cr+Mn+Mo)^1/2+0.61[Ni·(Cr+Mn)]^1/2.     

EPR study of Fe3+ and Mn2+ in CeO2 and ThO2

Attempts were made to grow CeO₂ and ThO₂ single crystals doped with transition metal ions. Only Fe³⁺ and Mn²⁺ could be detected by the EPR technique. The EPR spectrum of Fe³⁺ in CeO₂ exhibits the well-known fine structure in cubic fields. The parameters areg=2.0044(1) anda=15.6(1)·10^?4 cm^?1. The hyperfine constantA for⁵⁷Fe in hexahedral coordination was found to be 8.9(1)·10^?4 cm^?1. The EPR spectrum of Mn²⁺ in CeO₂ reveals two cubic Mn²⁺ centers. The parameters for center 1 areg=1.9999(1) andA=86.9(1)·10^?4 cm^?1 and for center 2g=1.9984(1) andA=87.0(1)·10^?4 cm^?1. Heating the Mn doped CeO₂ samples in hydrogen, the Mn²⁺ centers transform from cubic into trigonal centers with approximate values ofg=1.9988(2),A=84.5(6)·10^?4 cm^?1 andD=203(1)·10^?4 cm^?1. The two observed Mn²⁺ centers in ThO₂ exhibita priori axial symmetry with approximate values ofg=2.0006(2),A=88.9(4)·10^?4 cm^?1 andD=33(3)·10^?4 cm^?1.     

Optically detected E.P.R. of Mn2+ in faulted cubic ZnS

We have performed optically detected E.P.R. of Mn²⁺ in faulted cubic ZnS. This experiment permits the identification of the two axial E.P.R. spectra observed in these crystals. This identification allows an estimate of the D parameter of Mn²⁺ in wurtzite.     

Optical absorption and electron spin resonance of Co2+ in cubic,hexagonal and 4H polytype zinc sulfide

Electron spin resonance and optical absorption measurements are reported for Co²⁺ in structurally pure single crystals of cubic, hexagonal, and 4H polytype ZnS. Co²⁺ spectra corresponding to the four different cation sites expected for these structures were observed, i.e. a cubic center from zinc blende, an axial center from wurtzite, and two different axial centers from the 4H polytype host. The energy of the optical ⁴A₂-⁴T₂ transition and the spin Hamiltonian parameters show characteristic differences for these four centers, which are discussed.     

The magnetostriction contribution of manganese ions in spinel ferrites

The assumption that the magnetostriction contribution from manganese ions in spinel ferrites arises from Mn³⁺ ions has been tested by an ab initio calculation of the theoretical values of the coefficients λ₁₀₀ and λ₁₁₁. The Mn³⁺ contribution on octahedral sites is found to be negligible while the possible contribution from Mn³⁺ ions on tetrahedral sites cannot be fitted to the experimental results. It is possible that the contribution from a small concentration of Mn⁴⁺ ions on tetrahedral sites could give a magnetostriction contribution which fitted both λ₁₀₀ and λ₁₁₁.     

The transition from dynamics to statics in the electron-spin-resonance spectra of impurity Mn2+ ions in strontium titanate

The electron-spin-resonance (ESR) spectra of SrTiO₃:Mn single crystals have been investigated. Results unambiguously indicate that the impurity center formed by an Mn²⁺ ion has a dynamic nature. In the high temperature range (T > 100 K), ESR spectra of Mn²⁺ ions reveal cubic symmetry; the spectrum is found to broaden significantly with a decrease in temperature. Upon cooling to T < 10 K, low-symmetry centers of Mn²⁺ ions with a strong orientational dependence emerge in the spectra. Temperature evolution of the ESR spectrum can be described within the model of a dynamic off-center Mn²⁺ ion substituting for the Sr²⁺ ion, with a transition to the static regime at low temperatures with an average localization energy of ～2.4 ± 0.4 meV for Mn²⁺ centers due to random deformations.     

Electron spin resonance of diluted solid solutions of MnO2 in Y2O3

Electron spin resonance spectra of Mn²⁺ in diluted solid solutions of MnO₂ in Y₂O₃ have been studied at room temperature for Mn concentrations between 0.20 and 2.00 mol%. Isolated Mn²⁺ ions in sites with two different symmetries were observed, as well as Mn²⁺ ions coupled by the exchange interaction. The relative concentration of isolated to coupled Mn²⁺ ions decreases with increasing manganese concentration. The results are consistent with the assumption that the manganese ions occupy preferentially the C₂ symmetry sites. A theoretical calculation based on this model yields an effective range of the exchange interaction between Mn²⁺ ions of 0.53 nm, of the same order as that of Mn²⁺ ions in CaO.     

Luminescence of Mn ions in ordered and disordered LiAl5O8

The phosphorescence and excitation spectra of Mn ions in the ordered and disordered phases of LiAl₅O₈ have been measured. In both phases Mn²⁺ ions substitute for Al³⁺ ions in two different tetrahedral sites of the LiAl₅O₈ lattice. In both sites in the ordered phase, sharp zero-phonon transitions have been observed in the low temperature phosphorescence and excitation spectra - these transitions were considerably broadened in the disordered phase due to crystal field inhomogeneity in that phase. The deviation from neutrality caused by the Mn²⁺ ions in the ordered phase is largely compensated by Mn⁴⁺ ions occupying octahedral Al³⁺ sites. On disordering, a large proportion of Mn⁴⁺ is reduced to Mn²⁺, while the remainder takes up a site with a higher proportion of Li⁺ ions as next nearest neighbours. This leads to an increase in the ionicity of the Mn⁴⁺ site in the disordered phase and hence to a larger value of the Racah parameter B.     

Thermal dependence of impurity induced fluorescence in the system RbMgxMn1-xF3

The absorption spectrum of RbMnF₃ and the excitation spectra of the system RbMg_xMn_1-xF₃ at 10 K as well as the fluorescence spectra and lifetimes of Mn²⁺ in the systems RbMg_xMn_1-xF₃ and KMg_xMn_1-xF₃ in the region 10–300 K were measured. The lifetime and fluorescence temperature dependence suggest that the origin of the fluorescence occurs at Mn²⁺ sites slightly perturbed by impurity ions and that a non-radiative energy transfer mechanism is responsible for the observed thermal quenching. By using different Mn²⁺ concentrations in the above systems the dependence of the energy transfer on the Mn²⁺ concentration is shown. Finally, a preliminary observation on laser stimulated Mn²⁺ luminescence in the system RbMg_xMn_1-xF₃ is reported.     

ESR study of Fe3+ and Mn2+ ions on trigonal sites in ilmenite structure MgTiO3

Electron spin resonance has been observed for Fe³⁺ and Mn²⁺ ions occupying sites with trigonal symmetry in undoped and doped Verneuil-grown crystals of the ilmenite type compound MgTiO₃. At 300 K, the fine structure parameters in the spin Hamiltonian are (in 10^?4cm^?1) D = +844 (± 1), (a? F) = +118 (± 1), a = 69 (± 7) for Fe³⁺ and D = +164 (± 1), (a ? F) = +10.2 (± l), a = 7.0 (± 1) for Mn²⁺. These values are compared with literature data for Fe³⁺ and Mn²⁺ in other oxides, especially Al₂o₃, with particular reference to the recent “superposition” theory of the effect of a trigonal distortion. From the orientation of the axes of cubic pseudosymmetry of the spin Hamiltonian, and with the assumption that a has the same sign for both ions, it is proposed that Fe³⁺ and Mn²⁺ occupy the same octahedral site, namely the Mg²⁺ site. Anomalous line splittings observed for one sample were attributed to twinning on (0001) or {1120} planes.     

Structural and magnetic properties in the self-doped perovskite manganites with nominal composition La0.7Sr0.3−xMnO3−δ

Perovskite manganites with nominal composition La_0.7Sr_0.3−xMnO_3−δ (0.00≤x≤0.20) have been prepared by the sol-gel method with the highest heat treatment temperature being 1073 K. The XRD patterns indicate that when the doping level is x≤0.10 the samples have only a single phase, with the R3?c perovskite structure, while for x>0.10, the samples have two phases with the R3?c perovskite being the dominant phase and Mn₃O₄ being the second phase. A quantitative analysis and Rietveld fitting of the X-ray powder diffraction data indicate that on the basis of the thermal equilibrium theory of crystal defects there are Mn²⁺ ions at the A sites and Mn³⁺ plus Mn⁴⁺ ions at the B sites in the ABO₃ perovskite phase. The curves of magnetization versus applied magnetic field at 10 K showed that the magnetic moments of the Mn²⁺ ions at the A sites are antiparallel to those of the Mn³⁺ and Mn⁴⁺ ions at the B sites.     

Structure, electric and dielectric studies of indium-substituted magnesium copper manganese ferrites

The structure, electric and dielectric properties of In-substituted Mg-Cu-Mn ferrites having the general formula of Mg_0.9Cu_0.1Mn_0.1In_xFe_1.9−xO₄ with 0.0≤x≤0.4 have been studied. X-ray diffraction (XRD) patterns of the samples indicated the formation of single-phase cubic spinel structure up to 0.2 and mixed phase (cubic and tetragonal phase) for samples x≥0.3. The relation of conductivity with temperature revealed a semiconductor to semimetal behavior as In⁺³ concentration increases. Variation in the universal exponent s with temperature indicates the presence of two hopping conduction mechanisms: the correlated barrier hopping (CHB) at low In⁺³ content x≤0.1 and small-polaron (SP) hopping at In⁺³ content x≥0.2. The variation in dielectric permittivity (ε′, ε″) with temperature at different frequencies shows a normal behavior for the studied compounds, while the variation in dielectric loss tangent with frequency at different temperatures shows abnormal behavior with more than relaxation peak. The conduction mechanism used in the present study has been discussed in the light of electron exchange between Fe³⁺ and Fe²⁺ ions and hole hopping between Mn²⁺ and Mn³⁺ ions at the octahedral B-sites.     

Electron paramagnetic resonance in Y1−cH1.92:Erc

We have investigated the EPR of isotopically enriched ¹⁶⁸Er³⁺ in Y_1?cH_1.92:Er_c where c = 100 and 1400 ppm, at both 1.4 and 9 GHz and between 1.5 and 50 K. Resonance lines were observed from Er³⁺ ions in both sites of cubic symmetry and sites of axial symmetry. We determine the numbers of Er³⁺ in cubic, and C_4v axial symmetry to be in the ratio 2:1. The cubic site resonance line is at g = 6.85 ± 0.07 and is attributed to a Γ₇ doublet. The linewidth has a linear thermal broadening of 3.9 ± 0.05 gauss K^-1 below circa 7 K. From the nonlinear thermal broadening above this temperature we determine the first excited state, in the cubic crystal field scheme, to be a Γ₈ at 35 ± 10 K above the Γ₇ ground state. We have investigated the origins of the (T = 0) residual linewidth for the ions in cubic symmetry, and conclude there to be a small but significant contribution due to unresolved transferred hyperfine structure from the surrounding hydrogen nuclei.     

Electrical properties of copper-manganese spinel solutions and their cation valence and cation distribution

The cation valence and distribution in copper manganese spinels containing 1.0-1.6 mol copper per formula unit (Cu_xMn_3−xO₄) was resolved from their electrical conductivity and thermoelectric properties. The limit of thermal stability of the cubic spinel phase was also determined for each stoichiometry. A corrected phase diagram for the Cu-Mn-O system in air is proposed accordingly. The electronic defect structure could be described through a chemical approach, involving the competition between the redox of Cu⁺ and Mn⁴⁺ to Cu²⁺ and Mn³⁺ and the disproportionation of the Jahn-Teller ion Mn³⁺ into Mn²⁺ and Mn⁴⁺. Thermodynamic parameters for the redox reaction were determined from experimental data as well as calculated, confirming the validity of the modeled defect equilibria.     

Excitation spectra and fluorescent lifetime measurements of Mn2+ in CaF2 and CdF2

The excitation spectrum of the Mn²⁺ emission has been measured in CaF₂ and CdF₂. The observed excitation bands have been assigned to transitions of the Mn²⁺ ions in a cubic environment. The calculated values for the crystal field (Dq) and Racah parameters (B,C) are Dq = 425 cm^-1 for CaF₂, Dq = 500 cm^-1 for CdF₂ and, B = 770 cm^-1 and C / B = 4.48 for both compounds. The lifetime of the fluorescent level ⁴T_1g(⁴G) has been measured in both compounds at different temperatures in the range from 10 to 500 K. The lifetime thermal dependence is explained taking into account different mechanisms (purely radiative, phonon assisted, and radiationless transitions) for the decay of excited Mn²⁺ ions.     

Mn-doped (Ba,Y)Fe12O19 hexaferrites: Crystal structure and oxidation states of Mn and Fe

We have fabricated Ba_0.95Y_0.05Fe_12-xMn_xO₁₉ samples with large Mn-doping amounts of x = 4 and 6, using the mechanical milling and heat treatment. X-ray diffraction analysis indicated the samples crystallized in the M-type hexaferrite structure. The Mn doping caused the modification, shift and broadening of some characteristic phonon-vibration modes, which were recorded by Raman spectroscopy. This is due to an incorporation of Mn ions into the M-type structure that disorders the periodic lattice and changes symmetry. Basing on X-ray absorption spectroscopy, we have found Fe in all samples stable with an oxidation state 3+ (Fe³⁺). Though Mn²⁺ and Mn³⁺ ions coexist, the concentration of Mn²⁺ in x = 4 is larger than that in x = 6. The analysis of Fourier-transform spectra have demonstrated the replacement of Mn^2+,3+ ions for Fe³⁺ in the M-type structure. The sites of Mn^2+,3+ ions in this structure have been discussed.     

A first-principles study on phase transition induced by charge ordering of Mn3+/Mn4+ in spinel LiMn2O4

A first-order transition at 290 K in LiMn₂O₄ with a cubic spinel-type structure is known to degrade the electrochemical performance of the positive electrode of rechargeable lithium-ion batteries. Using first-principles density functional theory (DFT), we confirm that the phase transition is induced by charge-ordering of Mn³⁺/Mn⁴⁺ accompanied by orbital-ordering due to Jahn–Teller distortion, which is in agreement with the previous experimental results of Rodríguez-Carvajal et al. [J. Rodríguez-Carvajal, G. Rousse, C. Masquelier, M. Hervieu, Phys. Rev. Lett. 81 (1998) 4660]. The optimized structure of the low-temperature (LT) phase has orthorhombic symmetry with five distinct crystallographic sites for Mn. The spin integration at each Mn site shows that Mn³⁺ resides at three Mn sites and the remaining two sites are occupied by Mn⁴⁺ ions. Total energy calculations indicate that the LT phase is about 0.23 eV/ LiMn₂O₄ more stable than cubic LiMn₂O₄ (high-temperature phase). The electrochemical Li extraction reaction from the LT phase is also investigated using DFT calculations. The results indicate that the reaction is initially divided into two voltage regions. Electrostatic interactions in the LT phase are calculated using a point charge model, accounting for the features of the electronic configurations and electrochemical reactions.     

Photoluminescence and efficient energy transfer from Ce3+ to Tb3+ or Mn2+ in Ca9ZnLi(PO4)7 host

Structural and spectroscopic characterizations of the Ce³⁺/Tb³⁺(Mn²⁺) solely and Ce³⁺–Tb³⁺(Mn²⁺) doubly doped phosphate compound Ca₉ZnLi(PO₄)₇ with β-Ca₃(PO₄)₂ structure have been performed by powder X-ray diffraction and photoluminescence spectra measurements. The weak green emission from Tb³⁺ and red emission from Mn²⁺ are significantly enhanced by introduction of sensitizer Ce³⁺ ions due to an efficient resonant-type energy transfer from Ce³⁺ to activators Tb³⁺ or Mn²⁺. The energy transfer efficiency and the mechanism have been estimated based on spectroscopic data. Meanwhile, the critical distances for energy transfer between the Ce³⁺ and Tb³⁺ or Mn²⁺ ions are also calculated by the method of spectral overlapping.     

Giant magnetoresistance in bulk samples of LaMnO3 with varying Mn4+ content

Magnetoresistance (MR) in bulk samples of LaMnO₃ has been investigated by varying the Mn⁴⁺ content from 10 to 33 per cent by chemical means, without aliovalent doping. With the increase in Mn⁴⁺ content, the structure of LaMnO₃ changes first from orthorhombic to rhombohedral and then to cubic and the material becomes increasingly ferromagnetic, exhibiting a resistivity maximum akin to an insulator-metal transition atT _Peak, just below the ferromagneticT _c. The magnitude of MR is highest in the cubic sample (with 33% Mn⁴⁺) around theT _Peak, and negligible in the non-magnetic orthorhombic sample (12% Mn⁴⁺).     

Effects of nickel doping on structural and optical properties of spinel lithium manganate thin films

Spinel LiNi_xMn_2−xO₄ (x≤0.9) thin films were synthesized by a sol-gel method employing spin-coating. The Ni-doped films were found to maintain cubic structure at low x but to exhibit a phase transition to tetragonal structure for x≥0.6. Such cubic-tetragonal phase transition can be explained in terms of Ni³⁺(d⁷) ions with low-spin (t_2g⁶,e_g¹) configuration occupying the octahedral sites of the compound, thus being subject to the Jahn-Teller effect. By X-ray photoelectron spectroscopy both Ni³⁺ and Ni²⁺ ions were detected where Ni²⁺ is more populated than Ni³⁺. Optical properties of the LiNi_xMn_2−xO₄ films were investigated by spectroscopic ellipsometry in the visible-ultraviolet range. The measured dielectric function spectra mainly consist of broad absorption structures attributed to charge-transfer transitions, O²⁻(2p)→Mn⁴⁺(3d) for 1.9 (t_2g) and 2.8-3.0 eV (e_g) structures and O²⁻(2p)→Mn³⁺(3d) for 2.3 (t_2g) and 3.4-3.6 eV (e_g) structures. Also, sharp absorption structures were observed at about 1.6, 1.7, and 1.9 eV, interpreted as being due to d-d crystal-field transitions within the octahedral Mn³⁺ ion. In terms of these transitions, the evolution of the optical absorption spectrum of LiMn₂O₄ by Ni doping could be explained and the related electronic structure parameters were obtained.