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At least 973 records · Page 54

[N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4}: Ferroelectric properties and characterization of phase transitions by Raman spectroscopy

The X-ray powder diffraction pattern shows that at room temperature, [N(CH{sub 3}){sub 3}H]{sub 2}ZnCl{sub 4} is crystallized in the orthorhombic system with Pnma space group. The phase transitions at T{sub 1} = 255 K, T{sub 2} = 282 K, T{sub 3} = 302 K, T{sub 4} = 320 K, and T{sub 5} = 346 K have been confirmed by the differential scanning calorimetry. The electrical technique was measured in the 10{sup −1}–10{sup 7 }Hz frequency range and 233–363 K temperature intervals. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 282 K. Besides, [N(CH{sub 3}){sub 3 }H]{sub 2}ZnCl{sub 4} shows classical ferroelectric behaviour near curie temperature. In order to characterize the phase transitions, Raman spectra have been recorded in the temperature range of 233–383 K and the frequency range related to the internal and external vibrations of the cations and anions (90–4000 cm{sup −1}). The temperature dependence of the Raman line shifts ν and the half-width Δν detects all phase transitions and confirms their nature, especially at 282 K that corresponds to the ferroelectric-paraelectric phase transition.

36 MATERIALS SCIENCE↗

Equation of state of bcc-Mo by static volume compression to 410 GPa

Unit cell volumes of Mo and Pt have been measured simultaneously to ≈400 GPa by x-ray powder diffraction using a diamond anvil cell and synchrotron radiation source. The body-centered cubic (bcc) phase of Mo was found to be stable up to 410 GPa. The equation of state (EOS) of bcc-Mo was determined on the basis of Pt pressure scale. A fit of Vinet EOS to the volume compression data gave K{sub 0} = 262.3(4.6) GPa, K{sub 0}′ = 4.55(16) with one atmosphere atomic volume V{sub 0} = 31.155(24) A{sup 3}. The EOS was in good agreement with the previous ultrasonic data within pressure difference of 2.5%–3.3% in the multimegabar range, though the EOS of Mo proposed from a shock compression experiment gave lower pressure by 7.2%–11.3% than the present EOS. The agreement would suggest that the Pt pressure scale provides an accurate pressure value in an ultra-high pressure range.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modulated ferromagnetic ordering and the magnetocaloric response of Eu{sub 4}PdMg

Neutron powder diffraction confirms that the primary ordering mode in Eu{sub 4}PdMg is ferromagnetic with a europium moment of 6.5(2) μ{sub B}. {sup 151}Eu Mössbauer spectroscopy shows that the unusual linear temperature dependence of the magnetisation reported for this system is an intrinsic property and not an artefact of the applied field. The form and temperature evolution of the {sup 151}Eu Mössbauer spectra strongly suggest that there is an incommensurate modulation to the magnetic structure that modifies the basic ferromagnetic order. This modulated structure may be the origin of the broad magnetocaloric response previously observed in Eu{sub 4}PdMg.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

The magnetic transition in ε-Fe{sub 2}O{sub 3} nanoparticles: Magnetic properties and hyperfine interactions from Mössbauer spectroscopy

The nanoparticles of ε-Fe{sub 2}O{sub 3} enriched with {sup 57}Fe isotope in amorphous silica matrix were prepared by sol-gel technique starting from a single molecular precursor for both Fe{sub 2}O{sub 3} and silica. From the X-ray powder diffraction pattern ε-Fe{sub 2}O{sub 3} was identified as the major phase and α-Fe{sub 2}O{sub 3} and β-Fe{sub 2}O{sub 3} were observed as minor iron oxide phases. Using the log-normal distribution for fitting the experimental data from the TEM micrographs, the characteristic size of particles d{sub 0} ∼ 25 nm was derived. The rather high coercivity of ∼2.1 T at room temperature was confirmed for our nanoparticle system. From the dependences of magnetization on temperature a two-step magnetic transition spread between 100 K and 153 K was indicated. From the {sup 57}Fe Mössbauer spectra measured in the temperature range of 4.2–300 K, the hyperfine parameters for one tetrahedral and three octahedral sites of ε-Fe{sub 2}O{sub 3} structure were identified. The in-field spectra in the external magnetic fields up to 6 T were taken both above and below the indicated two-step magnetic transition. Their dependence on temperature and external magnetic field suggests that the first step in the temperature range of 153 K–130 K is related to the spin reorientation of the local magnetic moments in the magnetic sublattices and the second step in temperatures 130 K–100 K may be associated with the intermediate spin–high spin state transition of Fe{sup 3+} cation in the tetrahedral sublattice expressed in the change of the hyperfine magnetic field.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Record Seebeck coefficient and extremely low thermal conductivity in nanostructured SnSe

SnSe has been prepared by arc-melting, as mechanically robust pellets, consisting of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy, and transport measurements. A microscopic analysis from NPD data demonstrates a quite perfect stoichiometry SnSe{sub 0.98(2)} and a fair amount of anharmonicity of the chemical bonds. The Seebeck coefficient reaches a record maximum value of 668 μV K{sup −1} at 380 K; simultaneously, this highly oriented sample exhibits an extremely low thermal conductivity lower than 0.1 W m{sup −1} K{sup −1} around room temperature, which are two of the main ingredients of good thermoelectric materials. These excellent features exceed the reported values for this semiconducting compound in single crystalline form in the moderate-temperatures region and highlight its possibilities as a potential thermoelectric material.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spin orientation, structure, morphology, and magnetic properties of hematite nanoparticles

Monodisperse hematite (α-Fe{sub 2}O{sub 3}) nanoparticles were synthesized by forced hydrolysis of acidic Fe{sup 3+} solution. Rietveld analysis was applied to the X-ray powder diffraction data to refine the lattice constants and atomic positions. The lattice constants for a hexagonal unit cell were determined to be a ∼ 0.50327 and c ∼ 1.37521 nm. High resolution transmission electron microscopy was employed to study the morphology of the particles. Atomic scale micrographs and diffraction patterns from several zone axes were obtained. These reveal the high degree of crystallinity of the particles. A series of observations made on the particles by tilting them through a range of ±45° revealed the particles to be micaceous with stacking of platelets with well defined crystallographic orientations. The Morin transition in these nanoparticles was found to occur at 210 K, which is lower temperature than 263 K of bulk hematite. It was ascertained from the previous Mössbauer studies that the spin orientation for nano-sized hematite particle flips from 90° to 28° with respect to the c-axis of the hexagonal structure during the Morin transition, which is in contrast to that observed in bulk hematite where spin orientation flips from 90° to 0°.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Exploring the high-pressure behavior of the three known polymorphs of BiPO{sub 4}: Discovery of a new polymorph

We have studied the structural behavior of bismuth phosphate under compression. We performed x-ray powder diffraction measurements up to 31.5 GPa and ab initio calculations. Experiments were carried out on different polymorphs: trigonal (phase I) and monoclinic (phases II and III). Phases I and III, at low pressure (P < 0.2–0.8 GPa), transform into phase II, which has a monazite-type structure. At room temperature, this polymorph is stable up to 31.5 GPa. Calculations support these findings and predict the occurrence of an additional transition from the monoclinic monazite-type to a tetragonal scheelite-type structure (phase IV). This transition was experimentally found after the simultaneous application of pressure (28 GPa) and temperature (1500 K), suggesting that at room temperature the transition might by hindered by kinetic barriers. Calculations also predict an additional phase transition at 52 GPa, which exceeds the maximum pressure achieved in the experiments. This transition is from phase IV to an orthorhombic barite-type structure (phase V). We also studied the axial and bulk compressibility of BiPO{sub 4}. Room-temperature pressure-volume equations of state are reported. BiPO{sub 4} was found to be more compressible than isomorphic rare-earth phosphates. The discovered phase IV was determined to be the less compressible polymorph of BiPO{sub 4}. On the other hand, the theoretically predicted phase V has a bulk modulus comparable with that of monazite-type BiPO{sub 4}. Finally, the isothermal compressibility tensor for the monazite-type structure is reported at 2.4 GPa showing that the direction of maximum compressibility is in the (0 1 0) plane at approximately 15° (21°) to the a axis for the case of our experimental (theoretical) study.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Titanium doped LSCM anode for hydrocarbon fuelled SOFCs

La{sub 0.75}Sr{sub 0.25}Cr{sub 0.5-x}Mn{sub 0.5}Ti{sub x}O{sub 3} (x = 0.1, 0.2) has been synthesized in solid state reaction method and tested as a potential anode material for solid oxide fuel cells. Rietveld refinement of X-ray powder diffraction data using Fullprof software shows that the materials crystallize in the rhombohedral symmetry in the R-3C space group. The cell parameters are: a = b = 5.5286 (4) Å, c = 13.408(1) Å, α = β = 90°, γ = 120°. Particle size distribution measurements show that the average particle size for x = 0.1 and 0.2 was 232.66 nm and 176.63 nm, respectively. The potential on particles were found to be −22.86 mV and −27.73 mV, for x = 0.1 and x = 0.2, respectively. Thermal expansion measurement using thermo-mechanical analyzer shows that the thermal expansion coefficient is 13.96 × 10{sup −6}/°C which is close to the thermal expansion of the state-of–the art YSZ electrolyte. Microstructure has been observed from scanning electron microscopy which shows a porous structure. Energy dispersive X-ray shows that the percentage of the different cations and anions in the structure are close to the chemical occupancies.

36 MATERIALS SCIENCE↗

Structural transitions, magnetic properties, and electronic structures of Co(Fe)-doped MnNiSi compounds

The structural transitions, magnetic properties, and electronic structures of Co(Fe)-doped MnNiSi compounds are investigated by x-ray powder diffraction, differential scanning calorimetry (DSC), magnetic measurements, and first-principles calculations. Results indicate that all samples undergo a martensitic transition from the Ni{sub 2}In-type parent phase to TiNiSi-type orthorhombic phase at high temperatures. The substitution of Co(Fe) for Mn in Mn{sub 1−x}Co{sub x}NiSi (x = 0.2, 0.3, and 0.4) and Mn{sub 1−y}Fe{sub y}NiSi (y = 0.26, 0.30, 0.36, 0.46, and 0.55) samples decreases the structural transition temperature and Curie temperature of martensite. The martensite phases show a typical ferromagnetic behavior with saturation field being basically unchanged with increasing Co(Fe) content, while the saturation magnetization shows a decreasing tendency. The theoretically calculated moments are in good agreement with the experimentally measured results. The orbital hybridizations between different 3d elements are analyzed from the distribution of density of states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oxygen stoichiometry: A key parameter to tune structural phase diagram of La{sub 0.2}Sr{sub 0.8}MnO{sub 3-δ}

Low temperature x-ray powder diffraction studies, in conjunction with transmission electron microscopy on stoichiometric (δ = 0.01) and oxygen deficient (δ =0.12) samples of La{sub 0.2}Sr{sub 0.8}MnO{sub 3-δ} manganites have been carried out. These studies revealed that oxygen stoichiometry plays a key role in controlling ground state of electron doped manganites. It is observed that the La{sub 0.2}Sr{sub 0.8}MnO{sub 2.99} undergoes a first order phase transition from cubic (Pm-3m) to JT-distorted twin tetragonal (I4/mcm) phase associated with C-type antiferromagnetic ordering at ∼260K. This JT-distortion induced cubic to tetragonal phase transition get totally suppressed in La{sub 0.2}Sr{sub 0.8}MnO{sub 2.88}. The basic perovskite lattice of the off-stoichiometric La{sub 0.2}Sr{sub 0.8}MnO{sub 2.88} remains cubic down to 80K but undergoes a well-developed charge-ordering transition with 9x9 modulations at ∼260K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A co-precipitation preparation, crystal structure and photoluminescent properties of Er5%:Gd{sub 2}O{sub 3} nanorods

An inexpensive preparation method is being reported for obtaining erbium doped gadolinium oxide (Er5%:Gd{sub 2}O{sub 3}) nanoscale rods. The elongated nanoscale systems, as-formed through a co-precipitation process, are characterized by using X-ray powder diffraction (XRD) patterns, scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) mapping, Ultra Violet-visible (UV-vis.) absorption spectroscopy and photoluminescence (PL) spectroscopy. In addition, the Williamson–Hall (W–H) plot is also performed to distinguish the effect of crystalline size-induced broadening and strain-induced broadening at full-width at half-maximum (FWHM) of the XRD profile. The XRD patterns of as-formed and calcined products show that the phase confirmation. As revealed from the SEM micrographs, the morphology of the products show that the rod-like nanoparticles. The EDX micrographs show that the presence of elements in our samples. The band gap values in calcined samples are found to be in the range of 3.569 eV. Upon 230 nm excitation on calcined samples, three broad emission peaks are observed from PL studies. The possible mechanism for the formation of Er5%:Gd{sub 2}O{sub 3} nanorods is briefly discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Study on synthesis and electrochemical properties of hematite nanotubes for energy storage in supercapacitor

Hematite nanotubes (α-Fe{sub 2}O{sub 3} NTs) are synthesized via a cost-effective and environmental-friendly hydrothermal technique. Field emission scanning electron microscopy and X-ray powder diffraction analyses reveal the formation of α-Fe{sub 2}O{sub 3} NTs with high crystallinity and purity. Optical behavior of α-Fe{sub 2}O{sub 3} NTs is studied employing UV-visible spectroscopy. Electrochemical properties of the as-prepared electrode material are investigated by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy in a three electrode cell. The synthesized α-Fe{sub 2}O{sub 3} NTs present enhanced pseudocapacitive performance with high specific capacity of 230 Fg{sup −1} at current density of 1 Ag{sup −1}. The prepared α-Fe{sub 2}O{sub 3} NTs can be utilized as a potential electrode material for electrochemical capacitor applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Effect of Zn doping on structural and dielectric properties of tetragonal Ni{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5)

A series of Ni-Zn ferrite with compositional formula Ni{sub 1-x}Zn{sub x}Fe{sub 2}O{sub 4} (0.0 ≤ x ≤ 0.5) were prepared by solid-state reaction route. The influence of the Zn content on the structural and dielectric properties of NiFe{sub 2}O{sub 4} was investigated using X-ray powder diffraction (XRD), Raman spectroscopy and dielectric measurements. XRD analysis reveals that the samples are polycrystalline single-phase cubic spinel in structure excluding the presence of any secondary phase corresponding to any structure. Slight variation in the lattice parameter of Zn doped NiFe{sub 2}O{sub 4} has been observed due to difference in ionic radii of cations. Raman analysis reveals the doublet like nature of A{sub 1g} mode for all synthesized samples. Small shift in Raman modes and increment in the line width has been observed with the doping ions. Furthermore, room temperature dielectric properties of all the prepared samples have been reported. It is observed that for each sample the dielectric constant decreases with an increase of frequency and becomes constant at higher frequencies.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural and spectroscopic investigations on deuteron glasses belonging to the potassium dihydrogen phosphate family

X-ray powder diffraction and Raman measurements were performed on the mixed crystals of deuterated potassium dihydrogen phosphate (DKDP) and deuterated ammonium dihydrogen phosphate (DADP) grown at our lab. These crystals are known to behave like deuteron glasses due to frustration between ferroelectric and antiferroelectric ordering. Both spectral as well as structural studies indicate that crystals belonging to the glassy regions of the crystal composition have stronger O-D-O hydrogen bonds as compared to those belong to the ferroelectric or antiferroelectric regions of the crystal composition.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped MgB{sub 2} superconductor nanomaterials

Undoped and carbon-doped magnesium diboride (MgB{sub 2}) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB{sub 2} samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp{sup 3}-hybridized carbon radicals were detected. A strong reduction in the critical temperature T{sub c} was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

The magnetic structures and transitions of a potential multiferroic orthoferrite ErFeO{sub 3}

Rare-earth orthoferrites are very interesting due to their appealing optical and multiferroic properties. In this study, the magnetic structures and transitions of a typical rare-earth orthoferrite, ErFeO{sub 3}, have been reinvestigated in detail. The spin-reorientation transition of the Fe{sup 3+} magnetic phase and the low-temperature magnetic ordering of Er{sup 3+} were observed by neutron powder diffraction. The corresponding magnetic structures have been solved anew by symmetry analysis and refinement of the diffraction results. The magnetic moments of Fe{sup 3+} align in an antiferromagnetic way along the c axis with a weak ferromagnetic component along the b axis below the Néel temperature and above the spin-reorientation transition. Below the spin-reorientation transition, the Fe{sup 3+} moments rotate into an antiferromagnetic ordering state along the b axis with weak ferromagnetic alignment along the c axis. The spin-reorientation takes place in the bc plane. The Er{sup 3+} moments align antiferromagnetically with a C{sub y} mode below 4.5 K. For the Fe{sup 3+} moments, an additional C{sub x} mode is induced by the ordering of the Er{sup 3+} moments. Namely, they change from G{sub y}F{sub z} mode into C{sub x}G{sub y}F{sub z} mode in the Pnma space-group setting. This study resolves the long-lasting dispute about the magnetic structure of ErFeO{sub 3} at low temperature.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Hybrid improper ferroelectricity in Ruddlesden-Popper Ca{sub 3}(Ti,Mn){sub 2}O{sub 7} ceramics

The hybrid improper ferroelectricity (HIF) has been proposed as a promising way to create multiferroic materials with strong magnetoelectric coupling by the first-principle calculation, and the experimental evidences of HIF in Ruddlesden-Poper Ca{sub 3}(Ti{sub 1−x}Mn{sub x}){sub 2}O{sub 7} (x = 0, 0.05, 0.1, and 0.15) ceramics have been shown in the present work. The room temperature ferroelectric hysteresis loops are observed in these ceramics, and a polar orthorhombic structure with two oxygen tilting modes has been confirmed by the X-ray powder diffraction. A first-order phase transition around 1100 K in Ca{sub 3}Ti{sub 2}O{sub 7} was evidenced, and the temperatures of phase transitions decrease linearly with increasing of the contents of Mn{sup 4+} ions. Based on the result of first-principle calculations, the polarization should be reversed by switching through the mediated Amam phase in Ca{sub 3}Ti{sub 2}O{sub 7} ceramics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Direct observation of the electronic structure in thermoelectric half-Heusler alloys Zr{sub 1−x}M{sub x}NiSn (M = Y and Nb)

This study investigates the electronic and local crystal structures of the hole-doped Zr{sub 1−x}Y{sub x}NiSn and electron-doped Zr{sub 1−x}Nb{sub x}NiSn alloys using synchrotron radiation photoemission spectroscopy (SR-PES) and synchrotron radiation X-ray powder diffraction (SR-XRD) measurements, thereby clarifying the mechanisms underlying the thermoelectric performance of the p- and n-type alloys. SR-XRD analysis reveals an interstitial Ni disorder in the half-Heusler structure and the substitution of the dopant Y and Nb atoms at the Zr site. SR-PES result shows that the variation in the electronic structure of the alloys due to doping can be explained on the basis of the rigid band model. The asymmetric pseudo-gap near the Fermi level, which is rather unexpected from the band structure calculation because of the presence of the interstitial Ni disorder, could possibly be the reason underlying poor thermoelectric performance of p-type half-Heusler ZrNiSn alloys when compared with the n-type counterparts.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗