AlH3 between 65 and 110 GPa: Implications of electronic band and phonon structures

A first-principles density-functional-theory method has been used to reinvestigate the mechanical and dynamical stability of the metallic phase of AlH₃ between 65 and 110 GPa. The electronic properties and phonon dynamics as a function of pressure are also explored. We find electron–phonon superconductivity in the cubic Pm-3n structure with critical temperature T_c = 37 K at 70 GPa which decreases rapidly with the increase of pressure. Further unlike a previously calculated T_c-value of 24 K at 110 GPa, we do not find any superconductivity of significance at this pressure which is consistent with experimental observation.     

Pressure-induced coordination crossover in magnetite; the breakdown of the Verwey–Mott localization hypothesis

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC), whereby charge density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse-spinel phase. The CC transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure the CC-transition temperature increases with pressure, reaching 300 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

Magnetic frustration in the antiferromagnetic Kondo lattice YbPtAl: Anomalous magnetic behavior at high pressures

We have investigated the magnetic and electronic properties of the antiferromagnetic Kondo lattice YbPtAl using the ¹⁷⁰Yb Mössbauer effect at ambient pressure (1.8<T<10 K), electrical resistance (1.8<T<300 K) and X-ray diffraction (T=300 K) techniques at high pressures up to 26 GPa. We find a complex magnetic state in YbPtAl at ambient pressure and an unusual volume-induced change of T_N. It is suggested, that the anomalous volume dependence of T_N is due to the interplay between frustrated anisotropic exchange interactions and magnetocrystalline anisotropy. The magnetic frustration originates from the topology of the crystal lattice.     

Pressure-induced magnetic transition in MnRhAs

The magnetic properties of a Fe₂P-type intermetallic compound MnRhAs have been investigated under high pressure up to 8.0 GPa by AC susceptibility measurement. Initially, both the antiferromagnetic (AF(I)) to the canted state magnetic transition temperature T_t and the canted state to another antiferromagnetic one (AF(II)) transition temperature T_C increase with compression. At 4.0 GPa, however, T_t decreases abruptly, while the increasing rate of T_C becomes larger above this pressure. A pressure-induced magnetic phase transition was seen at around this pressure when T_t and T_C are plotted in the pressure–temperature phase diagram. The transition from the antiferromagnetic to the ferromagnetic state observed below 160 K with increasing pressure is not frequently observed.     

In situ Raman spectroscopy of cubic boron nitride to 90 GPa and 800 K

The temperature and pressure dependences of the Raman spectrum of the transverse-optical mode of cubic boron nitride were calibrated for applications to a Raman spectroscopy pressure sensor in optical cells to about 800 K and 90 GPa. A significant deviation from linearity of the pressure dependence is confirmed at pressures above 20 GPa. At ambient temperature, dv/dP slopes are 3.41(7) and 2.04(7) cm⁻¹/GPa at 0 and 90 GPa, respectively. A polynomial expression is used to fit the pressure–temperature dependence of the Raman line. The pressure dependence does not significantly change with temperature, as determined from experiments conducted up to 800 K. At 0 GPa, the dv/dP slope is 3.46(7) cm⁻¹/GPa at 800 K. At pressures above 90 GPa, the Raman spectrum of the transverse-optical mode cannot be observed because of an overlap of the signals of cubic boron nitride and diamond used as the anvils in the high-pressure cell.     

(p, ρ, T) and (ps, ρs,Ts) properties,and apparent molar volumes Vϕ of LiI (aq) at T = 298.15 to 398.15 K and at pressures up to p = 60 MPa

(p, ρ, T) and (p_s, ρ_s, T_s) properties, and apparent molar volumes V_ϕ of LiI (aq) at T = 298.15 to 398.15 K, at pressures up to p = 60 MPa were reported, and apparent molar volumes at infinite dilution V_ϕ⁰ have been evaluated. An empirical correlation for density of lithium iodide (aq) with pressure, temperature and molality was derived. The experiments were carried out at molalities m = 0.11053, 0.32532, 0.70013, 1.40459, 2.95059, and 4.88147 mol kg^− 1 of lithium iodide.     

Investigation on bulk Nd–Fe–Al amorphous/nano-crystalline alloy

Cylindrical ingots of bulk amorphous Nd₇₀Fe₂₀Al₁₀ with a diameter of 8 mm were prepared by a copper mold casting method. It was proved experimentally with X-ray diffraction, scanning electron microscopy and differential scanning calorimetry that the as-prepared alloy samples consisted mainly of the amorphous phase with a minute amount of nano-crystalline phase. The onset crystallization temperature (T_x) and the melting temperature (T_m) of the samples were 743 and 823 K, respectively, from DSC results. The temperature interval between T_x and T_m, ΔT=T_m−T_x, is 80 K and the resulting ratio of T_x/T_m is 0.90. Both a high T_x/T_m ratio and a small ΔT are considered the reasons for the good glass-forming ability. The Curie temperature (T_c) of these samples was 525 K from magneto-thermal gravimetric analysis. This measured value is higher than the highest T_c among binary Nd–Fe amorphous alloys. Annealing treatments were carried out for the as-cast samples to obtain dual-phase samples with different volume fractions of nano-crystalline phase. Magnetic measurement results indicated that the hard magnetic behavior is weakest for samples with 40% of nano-crystalline phase. The curve of the measured hysteresis loop area versus the volume fraction of nano-crystalline phase concaves upward, which agrees with what we predicated in our previous simulation results.     

Dynamics of vortices in type-II superconductors with periodic square columnar pins

The dynamics of a two-dimensional vortex system with strong periodic square columnar pins is investigated. For the case vortex number matching pinning number, we find that the vortex liquid is frozen into square lattice via a continuous transition, and the freezing (melting) temperature T_m is the same as the thermal depinning temperature of vortices, which are different from the first-order phase transition at weak pinning. The zero-temperature critical depinning force F_c0 is exactly the same as the maximum pinning force, and the depinning property at T = 0 can be expressed by scaling v ～ (F ? F_c0)^β with the exponent β close to 0.5. The v–F curves at temperatures below T_m show that vortices are pinned at small driving force.     

Magnetic properties of GdCo12B6 compound under high pressures

The effects of hydrostatic pressure up to 10 kbar on Curie temperature T_C, compensation temperature T_COMP and spontaneous magnetization M_S of ferrimagnetic GdCo₁₂B₆ compound have been studied. Two antiferromagnetically coupled sublattices that are carrying magnetization of typically 0.42 μ_B/Co atom and 7 μ_B/Gd cancel out at compensation temperature at about 50 K and magnetic ordering temperature T_C=163±2 K. The volume dependence of intrinsic magnetic properties of the GdCo₁₂B₆ compound has been determined by studying it under hydrostatic pressure. The observed increase of M_S with pressure (dM_S/dp=+0.005 μ_B kbar^?1 at 5 K) is attributed predominantly to the pressure induced decrease of Co magnetic moments. The crucial role of Co in this behavior is confirmed by the change of sign of the pressure slope at temperatures above T_COMP and by the fact that the estimated decrease of m_Co is also quite comparable with pressure induced decrease of M_S in YCo₁₂B₆ (dM_S/dp=?0.007 μ_B kbar^?1). The decrease of m_Co is also responsible for the increase of T_COMP with pressure (dT_COMP/dp=+0.06 K kbar^?1). The decrease of T_C with pressure (dT_C/dp=?0.55 K kbar^?1) is comparable to the decrease observed on RCo₁₂B₆ compounds with non-magnetic R and can be attributed to the volume dependence of Co–Co exchange interactions. The remarkable role of the hybridization as a consequence of small distances between Co and B atoms could be a background of this rather unexpected volume stability of magnetic properties.     

Strain effect on surface melting of Si(1 1 1)

We study the strain effect on the surface melting of Si(1 1 1) flat surfaces using Monte Carlo simulation and the empirical Tersoff–Dodson potential. The in-plane strain effect on the atomic structures and the atomic dynamics were investigated at a fixed temperature of 0.82T_m. Surface melting of Si(1 1 1) was induced by either compressive or tensile strain. As the strength of strain increases beyond the critical strength of about 1.5 and 2.5%, respectively, for compressive and tensile strain, the waiting time for surface melting decreases. In the lateral pair correlation function of the melting layers, only the nearest-neighbor correlation remains. Si atoms in the melting layers has a constant diffusion coefficient irrespective of the sign and strength of applied strain.     

Thermoelectric power of CuCrxVySe4 p-type spinel semiconductors

Structural, electrical and magnetic measurements of polycrystalline CuCr_xV_ySe₄ spinels with x=1.79, 1.64 and 1.49 and y=0.08, 0.22 and 0.45, respectively, are presented. The compounds under study crystallize in regular system of a normal spinel type MgAl₂O₄ structure with the space group symmetry Fd3m. The chromium spins are coupled ferromagnetically and show both strong long- and short-range magnetic interactions evidenced by the large values of the Curie (T_C) and Curie–Weiss (θ_CW) temperatures, decreasing from T_C=407 K and θ_CW=415 K for y=0.08, via T_C=349 K and θ_CW=367 K for y=0.22 to T_C=283 K and θ_CW=293 K for y=0.45, respectively. In all the studied spinels a change of the electrical conductivity character from the semiconductive into the metallic one above 230 K was observed. A detailed thermoelectric power analysis showed a domination of diffusion thermopower component, maximum of phonon drag component at 230 K, a decrease of impurity component with increasing V content, as well as the weak magnon excitations at 40 K.     

First-principles investigation on high-pressure structural evolution of MnTiO3

First-principle calculations using density-functional theory with linearized augmented plane wave method and projector-augmented method have been performed for the high-pressure MnTiO₃ polymorphs and their possible dissociation products. Theoretical results demonstrate that ilmenite-type MnTiO₃ transforms into perovskite phase at 27 GPa and 0 K. The lithium niobate phase of MnTiO₃ is confirmed to be metastable according to its higher Gibbs free energy compared with that of ilmenite at ambient conditions. In ilmenite and lithium niobate phases, MnO₆ octahedra become more distorted while TiO₆ octahedra become more regular with increasing pressure. In orthorhombic perovskite phase, the structural distortion deviated from the ideal cubic perovskite is enhanced at higher pressure. Based on the non-spin-polarized calculations, perovskite phase MnTiO₃ is predicted to dissociate into Fm3?m-MnO+P2₁/c-MnTi₂O₅ at 29 GPa.     

Addendum to “Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)” by K.-S. Lee et al. [J. Phys. Chem. Solids 73 (2012) 890]

While a paper mentioned above being published on line, we have become aware of the high-pressure neutron diffraction study of squaric acid (H₂C₄O₄) by C.L. Bull et al. They developed that neutron diffraction experiments could be performed under quasi-hydrostatic conditions to pressures of up to 18 GPa and showed that the tetragonal phase of H₂C₄O₄ was still observed at 14.5 GPa (above the critical pressure of P_c=0.75 GPa at room temperature) beyond the previous pressure limits of 7 GPa. Taking the high-pressure neutron diffraction results into consideration, modified temperature-pressure phase diagram in the paper stated above is reported.     

Pressure effect on magnetic properties of NdMn2−xFexGe2 (0.1⩽x⩽1.0) series of solid solutions

Temperature and pressure dependence of magnetic properties in the NdMn_2−xFe_xGe₂ series of solid solutions (0.1⩽x⩽1.0) are reported. The (P, T) magnetic phase diagrams are determined on the basis of the AC magnetic susceptibility measured in a weak magnetic field. The measurements were carried out under hydrostatic pressure up to 1.5 GPa in the temperature range 80−430 K. The reported data show that in the studied series of solid solutions, a drastic change in magnetic properties takes place in a narrow dilution parameter range (0.4⩽x⩽0.5). While taking into account the magnetic properties, the studied range of Fe content could be divided into four regions. Only in the case of x=0.3 and 0.4, the external pressure significantly influences the magnetic properties of the samples.     

Structural,magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

At ambient pressure CaFe₂As₂ has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ～ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ～0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ～1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe₂As₂ transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.     

A preliminary study on a new LiBOB/acetamide solid phase transition electrolyte

New solid electrolytes containing acetamide and lithium bioxalato borate (LiBOB) with different molar ratios have been investigated. Their melting points (T_m) are around 42 °C. The ionic conductivities and activation energies vary drastically below and above T_m, indicating a typical feature of phase transition electrolyte. The ionic conductivity of the LiBOB/acetamide electrolyte with a molar ratio of 1:8 is 5 × 10^? 8 S cm^? 1 at 25 °C but increases to 4 × 10^? 3 S cm^? 1 at 60 °C. It was found that anode materials, such as graphite and Li₄Ti₅O₁₂, could not discharge and charge properly in this electrolyte at 60 °C due to the difficulty in forming a stable passivating layer on the anodes. However, a Li/LiFePO₄ cell with this electrolyte can be charged properly after heating to 60 °C, but cannot be charged at room temperature. Although the LiBOB/acetamide electrolytes are not suitable for Li-ion batteries due to poor electrode compatibility, the current results indicate that a solid electrolyte with a slightly higher phase transition temperature than room temperature may find potential application in stationary battery for energy storage where the electrolyte is at high conductive liquid state at elevated temperature and low conductive solid state at low temperature. The interaction between acetamide and LiBOB in the electrolyte is also studied by Raman and FTIR spectroscopy.     

High pressure studies on Fe-pnictide superconductors

A review of high pressure studies on Fe-pnictide superconductors is given. The pressure effects on the magnetic and superconducting transitions are discussed for different classes of doped and undoped FeAs-compounds: ROFeAs (R = rare-earth), AeFe₂As₂ (Ae = Ca, Sr, Ba), and AFeAs (A = Li, Na). Pressure tends to decrease the magnetic transition temperature in the undoped or only slightly doped compounds. The superconducting T_c increases with low pressure for underdoped FeAs-pnictides, remains approximately constant for optimal doping, and decreases linearly in the overdoped range. The undoped LaOFeAs and AeFe₂As₂ become superconducting under pressure although non-hydrostatic pressure condition seems to play a role in CaFe₂As₂. The superconductivity in the (undoped) AFeAs is explained as a chemical pressure effect due to the volume contraction caused by the small ionic size of the A-elements. The binary FeSe shows the largest pressure coefficient of T_c in the Se-deficient superconducting phase.     

Giant magnetic refrigerant capacity in Ho3Al2 compound

Magnetic properties and magnetocaloric effects (MCEs) of the intermetallic Ho₃Al₂ compound are investigated by magnetization and heat capacity measurements. Two successive magnetic transitions, a spin-reorientation (SR) transition at T_SR=31 K followed by a ferromagnetic (FM) to paramagnetic (PM) transition at T_C=40 K, are observed. Both magnetic transitions contribute to the MCE and result in a large magnetic entropy change (ΔS_M) in a wide temperature range. The maximum values of ?ΔS_M and adiabatic temperature change (ΔT_ad) reach 18.7 J/kg K and 4.8 K for the field changes of 0–5 T, respectively. In particular, a giant value of refrigerant capacity (RC) is estimated to be 704 J/kg for a field change of 5 T, which is much higher than those of many potential refrigerant materials with similar transition temperatures.     

Synthesis and critical current density promotion for Nb-doped 2212-BPSCCO HTc-superconducting materials

Although BPSCCO superconducting regime has very low stability under high oxygen pressures as reported in the literature, we managed to synthesize relatively pure 2212-BPSCCO and their Nb-doped samples having general formula Bi_1−xNb_xPbSr₂CaCu₂O₈, where x = 0.1, 0.2, 0.4 and 0.6 mole, respectively, at moderate oxygen pressure (∼30 bar). The superconducting measurements proved that the best recorded T_c ∼ 69 K was for the undoped 2212-BPSCCO, while the lowest T_c ∼ 58 K was recorded for the maximum doped sample x = 0.6 mole indicating that superconductive transition temperatures T_cs decrease regularly with increasing Nb-dopant concentration from x = 0.1 to 0.6, respectively. The lattice parameter c exhibited a slight length compression as Nb-dopant ratio increases from 0.1 to 0.6 mole, respectively. From SE-microscopic analysis, the average grain size was estimated and found in between 0.44 and 1.6 μm which is considered relatively high to that reported in the literature. The measured J_c’s values were found to be enhanced remarkably as Nb-dopant concentration increases.     

Cavitation milling of natural cellulose to nanofibrils

Cavitation holds the promise of a new and exciting approach to fabricate both top down and bottom up nanostructures. Cavitation bubbles are created when a liquid boils under less than atmospheric pressure. The collapse process occurs supersonically and generates a host of physical and chemical effects. We have made an attempt to fabricate natural cellulose material using hydrodynamic as well as acoustic cavitation. The cellulose material having initial size of 63 micron was used for the experiments. 1% (w/v) slurry of cellulose sample was circulated through the hydrodynamic cavitation device or devices (orifice) for 6 h. The average velocity of the fluid through the device was 10.81 m/s while average pressure applied was 7.8 kg/cm². Cavitation number was found to be 2.61. The average particle size obtained after treatment was 1.36 micron. This hydrodynamically processed sample was sonicated for 1 h 50 min. The average size of ultrasonically processed particles was found to be 301 nm. Further, the cellulose particles were characterized with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) to see the effect of cavitation on crystallinity (X_c) as well as on melting temperature (T_m). Cellulose structures consist of amorphous as well as crystalline regions. The initial raw sample was 86.56% crystalline but due to the effect of cavitation, the crystallinity reduced to 37.76%. Also the melting temperature (T_m) was found to be reduced from 101.78 °C of the original to 60.13 °C of the processed sample. SEM images for the cellulose (processed and unprocessed) shows the status and fiber–fiber alignment and its orientation with each other. Finally cavitation has proved to be very efficient tool for reduction in size from millimeter to nano scale for highly crystalline materials.