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Microstructure and mechanical properties of intragranular W-Cu/TiC-ZrC composite prepared by reactive melt infiltration at 1300 °C

Highlights: • W-Cu/TiC-ZrC composites with nano W dispersoids were prepared by reactive melt infiltration. • The nano-sized dispersoids were analyzed by TEM in detail. • The intragranular nano W dispersoids and ribbon like precipitates have toughening effects. - Abstract: Newly intragranular W-Cu/TiC-ZrC composites with nano W dispersoids in TiC matrix have been prepared by reactive melt infiltration at 1300 °C for 1 h in vacuum using molten Zr-Cu binary alloys and a (Ti{sub 0.75},W{sub 0.25})C solid solution powder as raw materials. The as-synthesized composites consist of major phases of W, Cu, TiC and ZrC. With the decrease of Zr content from 66 to 21 at.% in the Zr-Cu infiltrator, the reaction formed W phase in the composite has changed from micron-sized intergranular grains to nano-sized rounded inclusions in TiC{sub y} grains. The crystallographic orientation relationship at W and TiC interfaces are detected as:(0 1 1-bar ){sub W}//(1 1 1-bar ){sub TiC}&[0 1 1]{sub W}//[0 1 1]{sub TiC} and (4 1 1){sub W}//(4 2 4){sub TiC}&[0 1 1-bar ]{sub W}//[4 2-bar 3-bar ]{sub TiC}. Nano-sized lamellar structure with both W and Cu rich is detected to have super-lattice structure based on the TiC lattice. The elastic modulus, flexural strength, fracture toughness of the intragranular W-Cu/TiC-ZrC composite infiltrated with Zr{sub 14}Cu{sub 51} melt are 207.5 GPa, 457 MPa and 10.21 MPa∙m{sup 1/2}, respectively. The intragranular nano W dispersoids and ribbon like precipitates hinder crack propagation via crack deflection and bridging.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The interface character distribution of cold-rolled and annealed duplex stainless steel

The interface character distributions (ICDs) of cold-rolled and annealed duplex stainless steel specimens, previously solid-solution-heated (SHT) at 1573 K and 1323 K, are investigated using electron backscatter diffraction (EBSD) and five-parameter analysis (FPA). For the δ-ferrite phase, high concentrations of low angle grain boundaries (LAGBs) are developed, and the boundary planes are predominantly oriented on (111). High angle grain boundaries (HAGBs) with misorientations ranging from 50{sup o} to 60° are mostly pure tilt boundaries, and the boundary planes are primarily located on (112). For the austenite phase, very high density of coherent twin boundaries are introduced, implying that the boundary planes are exactly oriented on (111). The phase boundary character distribution (PBPD) appears to be connected with the K-S and N-W orientation relationships (ORs) terminating on (110) {sub F}‖(111) {sub A} and (110){sub F}‖(hkl){sub A}, respectively. - Highlights: •Five-parameter analysis was used to determine interface character distribution. •ICD results of statistical meaning were achieved. •Initial microstructure has a significant effect on ICD. •Low and high angle GBs in δ phase prefer in (111) and (112) planes, respectively. •K-S phase boundaries terminate on (110){sub F}‖(111){sub A} while N-W ones on (110){sub F}‖(hkl){sub A}.

36 MATERIALS SCIENCE↗

Investigation of Composition Uniformity in Thickness of GaInAsP Layers Grown on InP Substrates by Vapor-Phase Epitaxy

GaInPAs/InP heterostructures grown by metalorganic chemical vapor-phase deposition at a temperature of 600°C and pressure of 0.1 bar are investigated. The thicknesses of the grown GaInAsP layers amount to about 1 μm. For Ga{sub 1 –x}In{sub x}P{sub 1 –y}As{sub y} solid solutions with average compositions of x = 0.77–0.87 and y = 0.07–0.42, the variation in the content y of V-group atoms over the epitaxial-layer thickness by a value of Δy up to 0.1 atomic fractions in the sublattice of the V-group elements is revealed by secondary ion mass spectrometry. In most cases, a change in y occurs in the GaInAsP layer over a length to 200 nm from the InP heterointerface. In certain cases, y varies throughout the entire GaInPAs-layer thickness. For the epitaxial layers with satisfactory crystalline perfection, the value of Δy is less in the case of better lattice-matching between the GaInPAs epitaxial layer and the substrate. For GaInPAs layers strongly lattice-mismatched with the substrate and characterized by a low degree of crystalline perfection, the value of Δy is close to zero. All these facts enable us to assume that it is elastic deformations arising in the forming monolayer lattice-mismatched with the growing surface that affect the incorporation of V-group atoms into the forming crystalline lattice.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transmission electron microscopy study of the MgS–Tm{sub 2}S{sub 3} system

This work presents the structural–microstructural characterization of the NaCl-derivative MgS–Tm{sub 2}S{sub 3} system, which can be formulated by the expression Mg{sub (1−x)}Tm{sub (2/3)x}□{sub (1/3)x}S (□→cation vacancy). Transmission electron microscopy observations show the transition between NaCl-type and spinel-type structures when 0 ≤x≤ 0.75. The increase of Tm content in the solid solution provokes the increase of the spinel-type phase proportion, which intergrows with the NaCl-type crystals. When x≥0.75, some phases derived from NaCl-type structure through the chemical twinning at the unit cell level crystallographic operation are observed, such as CT-MgTm{sub 2}S{sub 4} and CT-MgTm{sub 4}S{sub 7}. The existence and nature of the extended defects observed along the c direction of these structures are characterized by means of Scanning-Transmission electron microscopy high-angle dark field imaging, which allows observing the presence of quasi ordered crystals with new possible complex stoichiometries at atomic resolution. - Graphical abstract: HAADF-STEM image of a disordered CT-MgYb{sub 2}S{sub 4} crystal. The disordered twin-slab sequences are marked by arrows. - Highlights: • Structural evolution of the Mg{sub (1−x)}Tm{sub (2/3)x}□{sub (1/3)x}S system was characterized by means of TEM. • The increase in Tm content provokes the transition from NaCl to spinel-type structure up to x=0.75. • Chemical twinned phases CT-MgTm{sub 2}S{sub 4} and CT-MgTm{sub 4}S{sub 7} are observed at high Tm contents. • Extended defects in CT-crystals are characterized with atomic resolution STEM-HAADF images.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Phase transitions, domain structure, and pseudosymmetry in La- and Ti-doped BiFeO{sub 3}

The phase transitions and domain structure of the promising PbO-free solid solution series, (0.95-x)BiFeO{sub 3}-xLaFeO{sub 3}-0.05La{sub 2/3}TiO{sub 3}, were investigated. X ray diffraction (XRD) revealed a transition from a ferroelectric R3c to a PbZrO{sub 3}-like (Pbam) antiferroelectric (AFE) structure at x = 0.15 followed by a transition to a paraelectric (PE, Pnma) phase at x > 0.30. The ferroelastic/ferroelectric twin domain width decreased to 10–20 nm with increasing x as the AFE phase boundary was approached but coherent antiphase tilted domains were an order of magnitude greater. This domain structure suggested the local symmetry (20 nm) is lower than the average structure (R3c, a{sup −}a{sup −}a{sup −}) of the tilted regions. The PE phase (x = 0.35) exhibited a dominant a{sup −}a{sup −}c{sup +} tilt system with Pnma symmetry but diffuse reflections at ∼1/4(ooe) positions suggest that short range antipolar order is residual in the PE phase. The complex domain structure and phase assemblage of this system challenge the conventional interpretation of phase transitions based on macroscopic symmetry. Instead, it supports the notion that frustration driven by chemical distributions at the nanometric level influences the local or pseudo-symmetry as well as the domain structure, with XRD giving only the average macroscopic structure.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Energy Transfer from Ce{sup 3+} to Tb{sup 3+} in Yttrium and Gadolinium Orthoborates Obtained by Hydrothermal Synthesis

We studied the structure, IR absorption spectra, the spectral characteristics of photoluminescence and morphology of cerium- and terbium-doped orthoborates of gadolinium and yttrium obtained by hydrothermal synthesis at 200°C, as well as solid solutions of orthoborates on the basis of yttrium, gadolinium, and lutetium with composition RECe{sub 0.01}Tb{sub 0.1}BO{sub 3} (RE = Lu{sub 0.5}Gd{sub 0.39}, Lu{sub 0.5}Y{sub 0.39}, and Y{sub 0.5}Gd{sub 0.39}). The X-ray diffraction spectrum of yttrium orthoborate Y{sub 1 –} {sub x} {sub –} {sub y}Ce{sub x}Tb{sub y}BO{sub 3} is described by a hexagonal lattice with space group P6{sub 3}/m, which, after annealing at 970°C, transforms into a monoclinic lattice with space group C2/c. High-temperature annealing of the studied orthoborates leads to a multiple, more than two orders of magnitude, increase in the luminescence intensity of Tb{sup 3+} ions when the samples are excited in the absorption band of cerium ions. This effect is the result of a significant increase in the concentration of Ce{sup 3+} ions in the orthoborates at high temperatures. It is shown that the luminescence of terbium ions is due to energy transfer from Ce{sup 3+} to Tb{sup 3+}, which proceeds with high efficiency (∼85%) by the mechanism of dipole-dipole interaction between cerium and terbium.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Anomalous Hall Effect in Frustrated Magnets

Comparative analysis of Hall effect in substitutional solid solutions Ho{sub 0.5}Lu{sub 0.5}B{sub 12}, Mn{sub 1 –} {sub x}Fe{sub x}Si (0 ≤ x ≤ 1) and Eu{sub 1 –} {sub x}Gd{sub x}B{sub 6} (x < 0.04) is carried out at temperatures 2–300 K in magnetic fields up to 8 T. Anomalous contribution to the Hall effect ρ{sub xy}{sup A} ~ ρ{sub xx}M has been identified for systems with various types of magnetic frustration. The linear scaling ρ{sub xy}{sup A} ~ ρ{sub xx} is detected in the resistivity range ρ{sub xx} ~ 0.01–1 mΩ cm lying outside the range of applicability of the classical model of asymmetric scattering. It is associated with the increase in the amplitude of spin fluctuations in the paramagnetic phase of the investigated compounds with noncollinear magnetic structure. The topological contribution to the Hall effect is extracted for Ho{sub 0.5}Lu{sub 0.5}B{sub 12} and Eu{sub 1 –} {sub x}Gd{sub x}B{sub 6}. Its amplitude is found to vary from 80 nΩ cm (Ho{sub 0.5}Lu{sub 0.5}B{sub 12}) to 7.5 μΩ cm (Eu{sub 0.97}Gd{sub 0.03}B{sub 6}).

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Relationship Between Electronic and Crystal Structure in Nd{sub 1+x}Ba{sub 2−x}Cu{sub 3}O{sub 6+δ}

In accordance with a relation between the lattice parameter c and the concentration of holes p, which has been found earlier for the YBa{sub 2}Cu{sub 3}O{sub 6+δ} compound, we obtain the p parameter in the same manner for the solid solution Nd{sub 1.2}Ba{sub 1.8}Cu{sub 3}O{sub 6+δ} with substitution of Nd{sup 3+} for Ba{sup 2+} in barium sites. For this, structural and superconducting properties of the Nd{sub 1.2}Ba{sub 1.8}Cu{sub 3}O{sub 6+δ} samples stored for specified times τ after quenching from annealing temperatures have been studied. The investigation shows that Nd{sub 1.2}Ba{sub 1.8}Cu{sub 3}O{sub 6+δ} stored for a long time has quite a low critical temperature T{sub c} extending only to T{sub c}{sup onset} = 55 K for the most oxidized sample with δ = 0.953. We find that the δ-dependence of the lattice parameter c significantly changes with time τ. When using the relation between c and p, the existence of electron doping of 0.045 per Cu in Nd{sub 1.2}Ba{sub 1.8}Cu{sub 3}O{sub 6+δ} can be inferred. This doping explains well-reduced T{sub c} in Nd{sub 1.2}Ba{sub 1.8}Cu{sub 3}O{sub 6+δ}. In addition, we observe a local drop of T{sub c} by up to 20 K for the samples with p˜0.095 (δ˜0.8) similar to decreasing T{sub c} known as “anomaly 1/8”.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural and Magnetic Properties of Mn{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} Ferrite Nanoparticles

In this work, solid solutions of Mn{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} (where x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) ferrite nanoparticles were synthesized using the novel combustion method. A powder X-ray diffraction study confirms the formation of spinel-structured Mn{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4}. Unusual increases in the lattice constant were observed from 8.358 to 8.435 Å for Zn substitution. Raman spectra show the change in local environment of tetrahedral and octahedral symmetry. Field emission scanning electron microscopy images show that the prepared samples are nanosized and there is not much difference observed in surface morphology. A magnetic study reveals that the prepared samples exhibit superparamagnetic properties with negligible coercivity and the saturation magnetizations initially increase from 31.12 emu g{sup −1} (x = 0) to 35.48 emu g{sup −1} (x = 0.2) and then decrease for further Zn substitution at 300 K. The zero-field-cooled and field-cooled magnetization studies confirm the superparamagnetic nature of prepared samples, and the observed blocking temperature decreases from 146.05 to 32.3 K. At 20 K, the measured hysteresis loop shows the coercivity and it gradually decreases from 810 to 152 Oe. The obtained results suggest that the prepared superparamagnetic Mn{sub 1−x}Zn{sub x}Fe{sub 2}O{sub 4} ferrite nanoparticles are a promising candidate material for biomedical applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Thermooptical and Dielectric Studies of a Calcium-Induced Ferroelectric Phase in a SrTiO{sub 3} Incipient Ferroelectric

We have examined temperature changes of the light refraction, birefringence, dielectric permittivity, and dielectric hysteresis loops in Sr{sub 1–x}Ca{sub x}TiO{sub 3} single crystals with x = 0.014 (SCT-1.4). The dielectric properties of Sr{sub 1–x}Ca{sub x}TiO{sub 3} with x = 0.007 (SCT-0.7) have been studied. We have performed ab initio calculations of equilibrium structures and total energies for three low-temperature phases of SrTiO{sub 3} and CaTiO{sub 3}, based on which we have determined an expected symmetry of the ground state of their solid solution and spontaneous polarization directions in a calcium-induced ferroelectric phase in Sr{sub 1–x}Ca{sub x}TiO{sub 3}. In SCT-1.4, we have separated a spontaneous contribution to the light refraction, which arises due to the spontaneous electrooptical effect caused by the spontaneous polarization and its fluctuations. From the spontaneous contribution to the light refraction, based on a previously developed our phenological approach, we have quantitatively determined for the first time the values and temperature dependences of root-mean-square fluctuations of the order parameter—the polarization P{sub sh} = 〈P{sub fl}{sup 2}〉{sup 1/2}(short-range, local polar order) in the ferroelectric phase. From optical and dielectric measurements in SCT-1.4, the average value of spontaneous polarization P{sub s} (the contribution from the long-range order) has been determined. We have estimated the values of P{sub sh} and P{sub s}, which characterize the short- and long-range orders in the ferroelectric phase of SCT-0.7. Separate determination of the values and temperature dependences of P{sub s} and P{sub sh} (which considerably exceeds the value of P{sub s} in the ordered phase) has allowed us to reveal on a quantitative level new particular features of the formation of the induced polar phase in Sr{sub 1–x}Ca{sub x}TiO{sub 3}.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

On the “alpha-phase” of Ca{sub 2−x}Sr{sub x}MnO{sub 4} and extending the chemistry of Sr{sub 7−y}Ca{sub y}Mn{sub 4}O{sub 15} to y>1

There has been renewed interest in the Ruddlesden-Popper phase (n=2) of composition Ca{sub n+1}Mn{sub n}O{sub 3} {sub n+1} in the light of recent research that has highlighted the nature of the improper ferroelectric ground state, which arises due to the couplings between specific combinations of MnO{sub 6} octahedral rotations and tilts. A fruitful route to control these octahedral degrees of freedom, and hence such desired physical properties, is through chemical substitution on the A–site cation i.e. Ca{sub 2−x}Sr{sub x}MnO{sub 4} for n =1, and in light of this, we have reinvestigated the chemistry of this solid solution. Here we focus on a common impurity phase observed during this synthesis which has been termed the “alpha-phase” in the literature. We show that this impurity phase is actually comprised mainly of a structure related to Sr{sub 7}Mn{sub 4}O{sub 15} but is found here with significantly higher Ca substitution than previously believed possible. Sr{sub 7}Mn{sub 4}O{sub 15} is an interesting structural type in its own right, but has been mainly overlooked to date, exhibiting interesting physics related to low dimensional magnetic ordering and dimer interactions, and we show here that the structural type is a likely candidate for exhibiting a multiferroic ground state. The prospect of being able to tune the lattice and the exchange interactions through further chemical substitution is likely to lead to a renewed interest in this material. - Graphical abstract: Extending the chemistry of Sr{sub 7−y}Ca{sub y}Mn{sub 4}O{sub 15} beyond y>1, revealing highly anisotropic cation ordering and tunable magnetic properties. - Highlights: • Chemistry of the unique structural type Sr{sub 7}Mn{sub 4}O{sub 15} is extended to high Ca concentrations. • Cation occupancy model is determined, showing highly anisotropic solubility of Ca on the 7 unique Sr crystallographic sites. • Anomalies in the magnetic susceptibility data are discussed with reference to symmetry arguments pointing towards a possible novel multiferroic mechanism in this material.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mössbauer Studies and the Microwave Properties of Al{sup 3+}- and In{sup 3+}-Substituted Barium Hexaferrites

The correlation of the chemical composition, the structure, and the microwave characteristic of solid solutions of the BaFe{sub 12–x}D{sub x}O{sub 19} (0.1 ≤ x ≤ 1.2) barium hexaferrite substituted with diamagnetic Al{sup 3+} and In{sup 3+} ions has been studied. The precise data on the crystal structure have been obtained by powder neutron diffraction using a high-resolution Fourier diffractometer (Dubna, JINR). The data on the distribution of the diamagnetic substituting ions in the hexaferrite structure have been obtained by Mössbauer spectroscopy. The microwave properties (the transmittance and the reflectance) have been studied in the frequency range 20–65 GHz and in external magnetic fields to 8 kOe. It is found that the transmission spectra are characterized by a peak that corresponds to the resonant frequency of the electromagnetic energy absorption, which is due to the ferromagnetic resonance phenomenon. The correlation of the chemical composition, the features of the ion distribution in the structure, and the electromagnetic properties has been revealed. It is shown that external magnetic fields shift the absorption peak of electromagnetic radiation to higher frequencies due to an increase in the magnetocrystal anisotropy. The results enable the conclusion that the features of the intrasublattice interactions and the electromagnetic properties should be explained using the phenomenological Goodenough–Kanamori model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Microstrain in tetragonal lead-zirconate-titanate: The effect of pressure on the ionic displacements

Piezoelectric materials respond to external stimuli by adjusting atomic positions. In solid-solutions, the changes occurring in atomic scale are very complex since the short- and long-range order are different. Standard methods used in diffraction data analysis fail to model the short-range order accurately. Pressure-induced cation displacements in ferroelectric Pb(Zr{sub 0.45}Ti{sub 0.55})O{sub 3} perovskite oxide are modeled by starting from a short-range order. We show that the model gives the average structure correctly and properly describes the local structure. The origin of the microstrain in lead zirconate titanate is the spatially varying Zr and Ti concentration and atomic distances, which is taken into account in the simulation. High-pressure neutron powder diffraction and simulation techniques are applied for the determination of atomic positions and bond-valences as a function of pressure. Under hydrostatic pressure, the material loses its piezoelectric properties far before the transition to the cubic phase takes place. The total cation valence +6 is preserved up to 3.31 GPa by compensating the increasing B-cation valence by decreasing Pb-displacement from the high-symmetry position. At 3.31 GPa, Pb-displacement is zero and the material is no more ferroelectric. This is also the pressure at which the Pb-valence is minimized. The average structure is still tetragonal. The model for microstrain predicts that the transition occurs over a finite pressure range: Pb-displacements are spatially varying and follow the distribution of Zr and Ti ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

From spin induced ferroelectricity to spin and dipolar glass in a triangular lattice: The CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) delafossite

The change from antiferromagnetism induced ferroelectricity to spin glass ferroelectric relaxor has been studied along the CuCr{sub 1−x}V{sub x}O{sub 2} (0≤x≤0.5) solid solution of polycrystalline samples. As x increases from CuCrO{sub 2} (x=0) to CuCr{sub 0.82}V{sub 0.18}O{sub 2}, it is found that the Néel temperature decreases from ∼24 K down to ∼13 K. This progressive weakening of the antiferromagnetism of CuCrO{sub 2} induces a rapid decrease of the spin induced ferroelectricity with polarization values going from ∼44 μC/m{sup 2} down to ∼1.5 μC/m{sup 2} for x=0.04 and x=0.08, respectively. Beyond x=0.18 (0.20≤x≤0.50), ac-magnetic susceptibility and magnetization measurements evidence a spin glass state while dielectric permittivity and polarization measurements point towards a relaxor behaviour. This shows that competing magnetic interactions in delafossites are an efficient way to transform a spin induced magnetoelectric into a multiglass (spin and dipolar) state. - Graphical abstract: The P(T) curves evidencing the aging effect on polarization in CuCr{sub 0.5}V{sub 0.5}O{sub 2}: E=135 kV/m is applied during cooling at different temperatures. The P values and the inflection point of the transition depend on the poling temperature suggesting a relaxor behaviour. This effect related to the spin glass state is not observed for the lowest vanadium content. - Highlights: • Samples of the CuCr{sub 1−x}V{sub x}O{sub 2} series have been studied. • The V content increase induces a change from antiferromagnetism to spin glass. • A behavior characterisitic of a spin and dipole glass is demonstrated. • The ferroelectricity is shown to go from spin induced to relaxor. • Competing magnetic interactions are efficient way to generate multiglass state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of chemical disorder on radiation-induced defect production and damage evolution in NiFeCoCr

Understanding chemical disorder in many concentrated solid solution alloys (CSAs) at the levels of electrons and atoms has attracted increasing attention as a path forward to reveal and identify underlying mechanisms for extraordinary mechanical properties and improved radiation tolerance. Single-phase NiFeCoCr CSA is a common base for many high-entropy alloys (HEAs) that have shown improved mechanical strength and radiation tolerance. In this study, defect production and damage evolution in NiFeCoCr under ion irradiation at room temperature to dose over 20 dpa are determined using ion channeling technique along both <100> and <110> directions utilizing multiple probing beam energies. The results obtained from the multi-axial and multi-energy channeling analysis are compared with those previously obtained for Ni crystals irradiated under similar conditions. The influence of chemical complexity on defect production and clustering at early-stage under room temperature irradiation up to dose of 1 dpa is discussed based on positron annihilation spectroscopy results. Defect structure evaluation in Ni and NiFeCoCr is also discussed based on transmission electron microscopy results over a prolonged irradiation at both room and elevated temperatures. Compared with chemically complex NiFeCoCr, larger dislocation loops thus less lattice strain are expected to form in pure Ni. Moreover, the role of chemical disorder in this CSA is also investigated based on ab initio calculations using large supercells. Finally, to understand the impact of chemical complexity effect on defect structure evolution, this integrated research effort attempts to link the relatively large charge redistribution due to difference in valence electron counts resulting from alloying different 3d transition metal elements, moderate lattice distortion arising from similar adaptable atomic size, and notable suppressed or delayed damage evolution in NiFeCoCr.

36 MATERIALS SCIENCE↗

Chromium substitution in mullite type bismuth aluminate: Bi{sub 2}Cr{sub x}Al{sub 4−x}O{sub 9} with 0≤x≤2.0

Nominal compositions Bi{sub 2}Cr{sub x}Al{sub 4−x}O{sub 9} with 0.0≤x≤2.0 (Δx=0.2) were prepared using appropriate amounts of nitrates dissolved in glycerine and heated at 800 °C for 24 h as we previously used for the preparation of solid solution series Bi{sub 2}M{sub x}/M′{sub 4−x}O{sub 9} (M/M′=Fe/Al, Ga/Al and Fe/Ga). The samples were characterized using XRD, FTIR and optical microscopic techniques. Analyses of XRD data show mullite type single phase can be prepared up to x=1.2. The lattice parameters (a, b and c) increases with increasing Cr content. Further increase in x (i.e., x≥1.4) show the presence of some additional phases indicating a limiting value for Cr doping is in the range of 1.2≤x<1.4. The effect of Cr incorporation could also be observed in the infrared absorption spectra via systematic hard mode shifts of certain lattice modes, e.g. the Bi–O related vibration changes from 96 cm{sup −1} to 93 cm{sup −1} with increasing x up to 1.2 and certain intensity changes together with shift in peak positions. Interestingly, the absence of any splitting and shift of the high energy IR absorption peak at 821 cm{sup −1} as assigned to the characteristic tetrahedral type dimer, Al{sub 2}O{sub 7}, indicate that the Cr thus partially substitutes only the octahedrally coordinated Al. This is confirmed by Rietveld structure refinements, too. - Graphical abstract: Structural model of Cr doped bismuth aluminate, Bi{sub 2}Cr{sub x}Al{sub 4−x}O{sub 9}. - Highlights: • Chromium doped bismuth aluminate, Bi{sub 2}Cr{sub x}Al{sub 4−x}O{sub 9} with mullite type structure are synthesized. • The samples are characterized by XRD and FTIR techniques. • Cr can replace only certain amount of octahedrally coordinated Al in Bi{sub 2}Al{sub 4}O{sub 9} under present experimental conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural phase transitions of robust insulating Bi{sub 1-x}La{sub x}Fe{sub 1-y}Ti{sub y}O{sub 3} multiferroics

In contrast to leaky BiFeO{sub 3}, of which two structural phase transitions of cycloidal modulated antiferromagnetic-paramagnetic and ferroelectric-paraelectric are observed below 850 °C, chemical co-substitution to form Bi{sub 1−x}La{sub x}Fe{sub 1−y}Ti{sub y}O{sub 3} ternary solid solution makes these multiferroic ceramics become robust insulating low dielectric loss and exhibit rich structural phase transitions. Differential thermal analysis and temperature-dependent X-ray diffraction measurements probe four first-order structural phase transitions, e.g., T{sub H} = 305 °C, T{sub N} = 365 °C, T{sub C} = 810 °C, and T{sub S} = 830 °C observed in the Bi{sub 0.98}La{sub 0.02}Fe{sub 0.99}Ti{sub 0.01}O{sub 3} system, which are reasonably attributed to Brazovskii-type cycloidal modulated antiferromagnetic-helimagnetic (at T{sub H}) and helimagnetic-paramagnetic (at T{sub N}) magnetic phase transitions, ferroelectric-paraelectric (at T{sub C}) and rhombohedral-cubic (at T{sub S}) structural phase transitions, respectively. Magnetic phase transition temperatures change a little but ferroelectric and lattice structural phase transition temperatures decrease gradually with increasing co-substitution up to composition-induced rhombohedral-(pseudo-)cubic structural phase boundary. The first-order nature of magnetic phase transition and emergence of helimagnetic phase were attributed to Ti{sup 3+} d{sup 1} magnetic disorder distribution in the Fe{sup 3+} d{sup 5}-O-Fe{sup 3+} d{sup 5} chains, while the first-order nature becomes weak with increasing co-substitution, owing to decreased ferroelectric rhombohedral lattice distortion. An intermediate rhombohedral paraelectric phase is discovered intervening between ferroelectric rhombohedral and paraelectric cubic phase, of which the temperature range defined by difference between T{sub C} and T{sub S} increases with increasing co-substitution. It was found that T{sub C} and T{sub S} are able to be predicted quantitatively by reduced mass of unit cell. These findings enrich our understanding of ferroic phase transitions and advance designing novel high temperature multiferroic compounds.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Synthesis, structural characterization and properties of SrAl{sub 4−x}Ge{sub x}, BaAl{sub 4−x}Ge{sub x}, and EuAl{sub 4−x}Ge{sub x} (x≈0.3–0.4)—Rare examples of electron-rich phases with the BaAl{sub 4} structure type

Three solid solutions with the general formula AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)) have been synthesized via the aluminum self-flux method, and their crystal structures have been established from powder and single-crystal X-ray diffraction. They are isotypic and crystallize with the well-known BaAl{sub 4} structure type, adopted by the three AEAl{sub 4} end members. In all structures, Ge substitutes Al only at the 4e Wyckoff site. Results from X-rays photoelectron spectroscopy on EuAl{sub 4−x}Ge{sub x} and EuAl{sub 4} indicate that the interactions between the Eu{sup 2+} cations and the polyanionic framework are enhanced in the Ge-doped structure, despite the slightly elevated Fermi level. Magnetic susceptibility measurements confirm the local moment magnetism, expected for the [Xe]4f{sup 7} electronic configuration of Eu{sup 2+} and suggest strong ferromagnetic interactions at cryogenic temperatures. Resistivity data from single-crystalline samples show differences between the title compounds, implying different bonding characteristics despite the close Debye temperatures. A brief discussion on the observed electron count and homogeneity ranges for AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba) is also presented. - Graphical abstract: AEAl{sub 4−x}Ge{sub x} (AE=Eu, Sr, Ba; 0.32(1)≤x≤0.41(1)), three “electron-rich” phases with BaAl{sub 4} structure type have been synthesized and characterized. Display Omitted - Highlights: • Three BaAl{sub 4}-type ternary aluminum germanides have been synthesized with Eu, Sr and Ba. • Eu, Sr and Ba cations have no apparent influence on the solubility of Ge. • The Ge atoms substitute Al on one of two framework sites, thereby strengthening the interactions between the cations and the polyanionic framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗