Topological Quantum Phase Transition and Superconductivity Induced by Pressure in the Bismuth Tellurohalide BiTeI

A pressure‐induced topological quantum phase transition has been theoretically predicted for the semiconductor bismuth tellurohalide BiTeI with giant Rashba spin splitting. In this work, evolution of the electrical transport properties in BiTeI and BiTeBr is investigated under high pressure. The pressure‐dependent resistivity in a wide temperature range passes through a minimum at around 3 GPa, indicating the predicted topological quantum phase transition in BiTeI. Superconductivity is observed in both BiTeI and BiTeBr, while resistivity at higher temperatures still exhibits semiconducting behavior. Theoretical calculations suggest that superconductivity may develop from the multivalley semiconductor phase. The superconducting transition temperature, T_c, increases with applied pressure and reaches a maximum value of 5.2 K at 23.5 GPa for BiTeI (4.8 K at 31.7 GPa for BiTeBr), followed by a slow decrease. The results demonstrate that BiTeX (X = I, Br) compounds with nontrivial topology of electronic states display new ground states upon compression.     

Pressure dependence of the superconducting transition temperature in alkali tungsten bronzes

The superconducting transition temperatures have been measured for the tetragonal I phase of Na_0.23WO₃, the hexagonal phase of K_0.33 WO₃, and the hexagonal phase of Rb_0.33WO₃ for pressures up to 20,000 bar. The slope of the curves is + 1.7 × 10^–5 K/bar for the sodium bronze, –5.8 × 10^–5 K /bar for the potassium bronze, and –1.5 × 10^–5 K/bar for the rubidium bronze. A sharp change in slope of the transition temperature vs. pressure curve for the potassium bronze at 4000 bar may indicate a phase change.Prepared for the U.S. Energy Research and Development Administration under Contract No. W-7405-eng-82.     

Record‐High Superconductivity in Niobium–Titanium Alloy

The extraordinary superconductivity has been observed in a pressurized commercial niobium–titanium alloy. Its zero‐resistance superconductivity persists from ambient pressure to the pressure as high as 261.7 GPa, a record‐high pressure up to which a known superconducting state can continuously survive. Remarkably, at such an ultra‐high pressure, although the ambient pressure volume is shrunk by 45% without structural phase transition, the superconducting transition temperature (T_C) increases to ≈19.1 K from ≈9.6 K, and the critical magnetic field (H_C2) at 1.8 K has been enhanced to 19 T from 15.4 T. These results set new records for both the T_C and the H_C2 among all the known alloy superconductors composed of only transition metal elements. The remarkable high‐pressure superconducting properties observed in the niobium–titanium alloy not only expand the knowledge on this important commercial superconductor but also are helpful for a better understanding on the superconducting mechanism.     

Simulation of structural phase transitions in ionic crystals under conditions of high pressures and temperatures

Structural phase transitions of the B1–B2 type in alkali halide crystals are investigated at a temperature other than 0 K. The pressure of B1–B2 phase transition is calculated as a function of temperature. The calculated pressure of B1–B2 transition in these crystals is weakly and almost linearly dependent on temperature. For a number of ionic crystals, the p ₀(T) curve has a maximum at some value of temperature.     

Solid-solid transition temperatures in SrCl2 from differential thermal analyses to 0.6 GPa

The reversible phase transition between the high-temperature, cubic C1 and the low-temperature, orthorhombic C23 polymorphs of SrCl₂ has been investigated by differential thermal analysis under hydrostatic pressure to 0.63 GPa. The C23→C1 transition temperature varies linearly with pressure at the rate of 0.42₄ μK(Pa)^?1 from the highest pressures down to ca. 0.34 GPa, and also linearly with slope 1.73 μK(Pa)^?1 at pressures ?0.26 GPa; the reverse, C1→C23 transition is not observed or deduced ?0.21 GPa. The observed curvature for the C1–C23 phase boundary over the range ?0.26–0.34 GPa, 1000–1050 K can be attributed to intersection with the “diffuse” transition in C1; the latter transition, however, could not be observed unambiguously. Linear extrapolation to 0.1 MPa places the C23→C1 transition near 553 K, which implies that C23 - not C1 - is the stable low-temperature polymorph. The recently-investigated transitions in PbF₂ closely parallel these in in SrCl₂.     

Giant Room‐Temperature Magnetodielectric Response in a MOF at 0.1 Tesla

A giant room‐temperature magnetodielectric (MD) response upon the application of a small magnetic field is of fundamental importance for the practical application of a new generation of devices. Here, the giant room‐temperature magnetodielectric response is demonstrated in the metal–organic framework (MOF) of [NH₂(CH₃)₂]_n [Fe^IIIFe^II_{(1?x )}Ni^II_x (HCOO)₆]_n (x ≈ 0.63–0.69) ( 1) with its MD coefficient remaining between ?20% and ?24% in the 300–410 K temperature range, even at 0.1 T. Because a room‐temperature magnetodielectric response has never been observed in MOFs, the present work not only provides a new type of magnetodielectric material but also takes a solid step toward the practical application of MOFs in a new generation of devices.     

Suitability of commercial strain gauge pressure transducers for low temperature application

Three types of pressure transducers have been tested: one for pressures up to 10⁶ Nm^?2 (10 bar) and two others for pressures between 0–5 × 10⁴ Nm^?2 (0–0.5 bar) and 0–2 × 10⁵ Nm^?2 (0–2 bar) against background pressures as high as 10⁶ Nm^?2 (10 bar). The transducers have been operated in the temperature range between 3.5–300 K. The operating principle is a strain gauge method using non-bonded resistive wires as sensing elements. The transducers have an overall accuracy of about 1% of full scale output. Hysteresis effects are negligible. In the temperature range between 4.2–300 K the thermal sensitivity shift per K is 0.01% and the zero shift is about 0.006% per K of full scale output.     

Thermoelectric properties of Zn4Sb3 prepared by hot pressing

Polycrystalline specimens of the thermoelectric material Zn₄Sb₃ were prepared by the hot-pressing method at various temperatures and pressures and their thermoelectric properties were evaluated in a temperature range from 298 K to 673 K. A single phase of Zn₄Sb₃ was obtained in the samples prepared at 673 K with a pressure above 150 MPa, whereas ZnSb was placed in the Zn₄Sb₃ matrix for the samples prepared at 100 MPa. The electrical transport properties of the single phase compound showed p-type conduction and metallic transport behavior based on the temperature dependence. The sample produced at 673 K under a pressure of 200 MPa exhibited the highest ZT value of 1.36 at 673 K. This study suggests that the dense and single-phase Zn₄Sb₃ compound is a route to achieve a high thermoelectric performance.     

Equilibrium Phase Diagram of Polymerized C60 and Kinetics of Decomposition of the Polymerized Phases

Abstract

Equilibrium phase diagram (T=0–1000 K; p=0–8 GPa) of pressure‐temperature polymerized C₆₀ has been constructed. It included rhombohedral; orthorhombic and tetragonal polymerized phases of C₆₀ along with fcc monomeric phases of C₆₀. The isothermal kinetics of depolymerization (T=373–513 K) of the O‐, R‐, T‐ and D‐phases was studied by means of the IR‐spectroscopy. The isothermal rate of decomposition goes up along the series: (T‐)<(O‐)<(R‐)<(D‐).     

Structural,magnetic and magnetocaloric investigation of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>1−x</Subscript>Ni<Subscript>x</Subscript>O<Subscript>3</Subscript> (x = 0, 0.025 and 0.075) manganite

In this paper, we report the structural, magnetic and magnetocaloric properties of Ni-doped La_0.67Ba_0.33Mn_1?xNi_xO₃ (x?=?0, 0.025 and 0.075) manganites. Our compounds were synthesized using the sol–gel method. The structural analysis using Rietveld refinement shows that Ni-doped LaBaMnO₃ system crystallizes in the rhombohedral symmetry with \({\text{R}}\bar {3}{\text{c}}\) space group. Magnetization measurements versus temperature in a magnetic applied field of 0.05 T reveal that all the compositions exhibit a transition from a ferromagnetic to paramagnetic phase with increasing temperature. A systematic decrease in the transition temperature is clearly observed upon Ni doping and a near room temperature T_C (302 K) is achieved with x?=?0.075 composition. The maximum magnetic entropy change \(\left( { - ~\Delta {\text{S}}_{{\text{M}}}^{{\hbox{max} }}} \right)\) in a magnetic field change of 5 T is found to be 2.12, 2.78 and 1.78 J/kg K for x?=?0, 0.025 and 0.075, respectively. At this value of magnetic field, large relative cooling power values are obtained in our samples, especially for x?=?0.075 (271 J/kg) making it a promising candidate for magnetic refrigeration near room temperature.     

Effect of orientation on the high-temperature superelasticity in Co49Ni21Ga30 single crystals

The temperature interval ΔT _SE of superelasticity in [001]-, [$ \bar 1 $ \bar 1 23]-, and [$ \bar 1 $ \bar 1 24]-oriented Co₄₀Ni₂₁Ga₃₀ (at. %) single crystals strained at compression has been studied. It is established that ΔT _SE in the [001]-oriented single crystal amounts to 441 K and the reversible B2-L1₀ martensite transformations in loaded samples take place at T ₂ = 698 K. In [$ \bar 1 $ \bar 1 23]- and [$ \bar 1 $ \bar 1 24]-oriented samples, ΔT _SE decreases to 233 K and the superelasticity is observed up to T ₂ = 523 K.     

Anwendung des instrumentierten Kerbschlagbiegeversuchs zur Ermittlung von Referenztemperaturen nach dem Master‐Curve‐Konzept

Application of the Instrumented Impact Test for the Determination of Reference Temperatures Using the Master Curve Concept The instrumented impact test is suitable for the determination of fracture mechanical parameters. In this paper the determination of the dynamic fracture toughness values in the lower ductile‐to‐brittle transition region is presented. The fracture toughness is determined at the onset of cleavage fracture and evaluated by the Master Curve (MC) concept. The MC concept allows to quantify the variation of fracture toughness with the temperature within the lower ductile‐to‐brittle transition region. Limit curves of fracture toughness for defined failure probabilities and a reference temperature can be determined using this method. This paper presents the application of the master curve concept to the reference temperature determination through the thickness of reactor pressure vessel (RPV) steel plate. The reference temperatures determined dynamic fracture toughness values (T₀^dy) are compared with quasi‐static reference temperatures (T₀^st) and Charpy‐V transition temperatures (TT). T₀^dy, T₀^st and TT increase from the surface to the middle of the RPV steel plate. Compared with T₀^st, the T₀^dy values are higher approximately 70 to 90 K.     

Original Supercritical Water Device for Continuous Production of Nanopowders

Well‐crystallized ZnO, ZrO₂, TiO₂, CeO₂, Y₂O₃ and La₂O₃ nanoparticles are synthesized under supercritical water conditions (T > 647 K and P > 22.1 MPa) using a home‐made continuous process. At room temperature, metallic salts with or without aqueous hydroxide solution (KOH or NaOH) are pressurized to 25–30 MPa. Then, the reactant(s) is/are rapidly heated to 673–773 K by mixing with the supercritical water in a patented reactor. Residence time is in the range from 2 to 8 s. XRD, TEM and surface area analyses highlight the production of pure and well‐crystallized nanoparticles with a uniform size distribution.     

Formation of ternary Mg-Cu-Dy bulk metallic glasses

The glass-forming ability (GFA) of ternary Mg-Cu-Dy alloys was systematically investigated by using differential scanning calorimetry (DSC) and X-ray diffractometry (XRD) techniques. The results showed that a series of ternary Mg-Cu-Dy bulk metallic glasses (BGMs) with a diameter of 4–8 mm were successfully fabricated in the system with conventional Cu-mold casting method. Mg₅₅Cu₃₂Dy₁₃, Mg₆₀Cu₂₇Dy₁₃, Mg₆₅Cu₂₅Dy₁₀ and Mg₇₀Cu₁₇Dy₁₃ BMGs exhibit a clear glass transition, a broad supercooled liquid region and different crystallization and melting behaviours. They have supercooled liquid region (ΔT _x) from 41 K to 65 K, reduced glass transition temperature (T _rg) from 0·5363 to 0·5974 and γ parameter from 0·4038 to 0·4136. The γ shows a relatively good agreement with the GFA of the BGMs. On the other hand, a high fracture compressive strength of 624 MPa was obtained for Mg₆₀Cu₂₇Dy₁₃ BMG.     

Stress analysis of a stepped rounded D‐ring with a ratio of H1/H2 = 3.0 under uniform squeeze rate and internal pressure by photoelastic experimental hybrid method

Stresses occurring in a stepped rounded D‐ring designed to have a ratio of H₁/H₂ = 3.0 and compressed to 20% squeeze and pressurized with internal pressures of 0 MPa, 0.98 MPa, 1.96 MPa, 3.92 MPa, 4.9 MPa and 5.89 MPa are analyzed using photoelastic experimental hybrid method. It was observed that when a pressure of 0 MPa and 20% compression are applied, the photoelastic isochromatic fringes of the stepped rounded D‐ring with a ratio of H₁/H₂ = 3.0 were almost symmetrical. However, as the applied internal pressure increased, the circular portion of the D‐ring moved over the step on the front side along the points 1_r–2_r towards the restraining wall of the front side of the groove. During the motion of the circular portion, the space between the restraining wall and the step on the front side was slowly filled; but unlike the D‐ring with a ratio of H₁/H₂ = 1.0 where complete filling occurred earlier before extrusion, complete filling of this space delayed until the portion of the D‐ring near the extrusion gap extruded. It was further noted that an internal pressure of up to 5.89 MPa was required to initiate extrusion in the D‐ring with a ratio of H₁/H₂ = 3.0.     

Abnormal Pressure‐Induced Photoluminescence Enhancement and Phase Decomposition in Pyrochlore La2Sn2O7

La₂Sn₂O₇ is a transparent conducting oxide (TCO) material and shows a strong near‐infrared fluorescent at ambient pressure and room temperature. By in situ high‐pressure research, pressure‐induced visible photoluminescence (PL) above 2 GPa near 2 eV is observed. The emergence of unusual visible PL behavior is associated with the seriously trigonal lattice distortion of the SnO₆ octehedra, under which the Sn–O1–Sn exchange angle θ is decreased below 22.1 GPa, thus enhancing the PL quantum yield leading to Sn ³P₁ → ¹S₀ photons transition. Besides, bandgap closing followed by bandgap opening and the visible PL appearing at the point of the gap reversal, which is consistent with high‐pressure phase decomposition, are discovered. The high‐pressure PL results demonstrate a well‐defined pressure window (7–17 GPa) with flat maximum PL yielding and sharp edges at both ends, which may provide a great calibration tool for pressure sensors for operation in the deep sea or at extreme conditions.     

The First 2D Homochiral Lead Iodide Perovskite Ferroelectrics: [R‐ and S‐1‐(4‐Chlorophenyl)ethylammonium]2PbI4

2D organic–inorganic lead iodide perovskites have recently received tremendous attention as promising light absorbers for solar cells, due to their excellent optoelectronic properties, structural tunability, and environmental stability. However, although great efforts have been made, no 2D lead iodide perovskites have been discovered as ferroelectrics, in which the ferroelectricity may improve the photovoltaic performance. Here, by incorporating homochiral cations, 2D lead iodide perovskite ferroelectrics [R‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ and [S‐1‐(4‐chlorophenyl)ethylammonium]₂PbI₄ are successfully obtained. The vibrational circular dichroism spectra and crystal structural analysis reveal their homochirality. They both crystalize in a polar space group P1 at room temperature, and undergo a 422F1 type ferroelectric phase transition with transition temperature as high as 483 and 473.2 K, respectively, showing a multiaxial ferroelectric nature. They also possess semiconductor characteristics with a direct bandgap of 2.34 eV. Nevertheless, their racemic analogue adopts a centrosymmetric space group P2₁/c at room temperature, exhibiting no high‐temperature phase transition. The homochirality in 2D lead iodide perovskites facilitates crystallization in polar space groups. This finding indicates an effective way to design high‐performance 2D lead iodide perovskite ferroelectrics with great application prospects.     

Thermal Conductivity of Crystalline Deuterated Methane

The preliminary results of thermal conductivity experiment carried out on solid CD₄ at equilibrium vapor pressure in the temperature range 1.2–30 K are reported. The dependence of the thermal conductivity on temperature shows a clear change at the temperatures 27.0 and 22.1 K, which correspond to the phase transitions, from phase I to II and from phase II to III, respectively. In the orientationally ordered phase III of the deuterated methane, the thermal conductivity of CD₄ depends on thermal history of the sample.     

The influence of brazing conditions on joint strength in Al2O3/Al2O3 bonding

The brazing of alumina ceramic to itself was performed using Ag₅₇Cu₃₈Ti₅ filler alloy. The bonding was carried out in a vacuum of 7 × 10^?3 Pa, and the joining conditions were at 1073, 1123, 1173, 1223, 1273 and 1323 K for 1.8ks under a pressure of 0.01 MPa, at 1123 K with a pressure of 0.01 MPa for 0, 0.3, 0.9, 1.8, 2.7 and 3.6 ks, and at 1123 K for 1.8 ks with pressures of 0, 0.01, 0.05, 0.10, 0.15, 0.20 and 0.30 MPa, to determine the effects of joining temperature, pressure and holding time on the joint strength. The joint strength was measured by shear tests. The interface microstructures and fractured surfaces after testing were observed by scanning electron microscopy (SEM). It was shown that the shear strength of Al₂O₃/Al₂O₃ joints was largely affected by the joining conditions; it first increased and then decreased with increasing joining temperature, pressure and holding time and depended mainly on the strength of interfacial reaction layer itself and the interface bonding strength between the reaction layer and the ceramic. The maximum joint strength was obtained when the reaction occurred under a suitable temperature, pressure and time, and the reaction layer thickness was about 2 μm. SEM observations revealed that there were four types of fracture and each kind corresponded to a different strength.     

Organic metal (EDO-TTF)2PF6 with multi-instability

Abstract

The multi-instability of the electronic structure of (EDO-TTF)₂PF₆, where EDO-TTF means ethylene-dioxytetrathiafulvalene, is reviewed. This complex showed the metal–insulator transition at 280 K associated with distinct molecular deformations. The mechanism is interpreted as the cooperation of Peierls transition, charge ordering, and the order–disorder transition of the countercomponent. The charge ordering pattern in the low-temperature phase is of the novel [0, 0, 1, 1] type. The sensitivity of the electronic state to external perturbations is demonstrated applying not only static but also instantaneous stimuli. In the latter case, the photo-induced phase transition is ultrafast and highly efficient. One photon causes the transition of several hundreds of donor molecules in the low-temperature phase to relax into a highly conducting metastable state within about 1.5 ps. In the early stage of the transient state, the charge ordering of the [1, 0, 1, 0] type occurs. As for the chemical modifications of this material, the partial deuteration of this complex increases the metal–insulator transition temperature. The introduction of a methyl group greatly modulates the electronic structure of the complex, i.e. (methyl-EDO-TTF)₂X (X=BF₄, ClO₄) shows a two-dimensional electronic structure. The working hypotheses for developing the systems with multi-instability are described.