TiC-MgO composite: an X-ray transparent and machinable heating element in a multi-anvil high pressure apparatus

ABSTRACT

TiC-MgO composite was developed as a heating element for X-ray study in the multi-anvil high pressure apparatus. We synthesized TiC-MgO blocks (50–70 wt.% of TiC) by compression in a cold isostatic press followed by baking in a gas flow furnace. Heaters of tubular shape were manufactured from the synthesized blocks either by lathe or numerically controlled milling machine. The so-produced heating elements have been proved to generate temperatures up to 2250?K at 10?GPa, condition where classical graphite heaters are not suitable anymore due to graphite-diamond transition. These new heaters have been successfully used for in situ X-ray radiography and diffraction measurements on liquid Fe alloys, exploiting excellent X-ray transparency.     

Boron-doped diamond as a new heating element for internal-resistive heated diamond-anvil cell

We have developed an internal-resistive heated diamond-anvil cell (IHDAC) with a new resistance heater – boron-doped diamond (BDD) – along with an optimized design of the cell assembly, including a composite gasket. Our proposed technique is capable of heating a silicate/oxide material with (1) long-term stability (>1?h at 2500?K) and (2) uniform radial temperature distribution (±35?K at 2500?K across a 40-µm area), which are clear advantages over the conventional laser-heated and internal-heated DACs. In addition, the achieved temperature in this study was greater than 3500?K, which mostly covers the possible geotherm of the entire lower mantle. In situ X-ray diffraction (XRD) measurement and ex situ chemical analyses confirmed that weak XRD intensity from the BDD heater and chemical inertness (no boron diffusion into silicate samples). This newly developed IHDAC with a BDD heater can be used to determine the phase diagrams of mantle materials with high precision and be used in lower-mantle petrology.     

Resistively heated,high pressure,membrane and screw driven diamond anvil cell

ABSTRACT

High temperature is of paramount importance in high pressure science. One of the leading tools in this respect is the resistively heated diamond anvil cell (DAC), where the heat is provided by small heaters, positioned close to the diamond/gasket/sample region (internally heated DAC, IHDAC) or by wrapping the DAC body into bigger heaters (externally heated DAC, EHDAC). Although IHDACs can reach sample temperatures higher than 1000?K, they are difficult to handle and the heater/diamond/gasket/sample region may be affected by strong thermal gradients potentially hindering accurate temperature measurements. Here we present a novel EHDAC, which overcomes these issues by uniquely joining: (i) high mechanical precision for multi-Mbar, (ii) high temperature alloys for operating to 1000?K, (iii) membrane or screw driven, easily switchable between each other, (iv) operation into a vacuum chamber, (v) uniform temperature, (vi) facile handling, and (vii) possibility to add internal heaters for achieving even higher temperatures.     

Synthesis of Co2N by a simple direct nitriding reaction between nitrogen and cobalt under 10 GPa and 1800 K using diamond anvil cell and YAG laser heating

Synthesis of cobalt nitrides has been tried in a supercritical nitrogen fluid at high pressure (about 10 GPa) and high temperature (about 1800 K) using diamond anvil cell and YAG laser heating system. We have succeeded to synthesize a single phase of the CFe₂-type Co₂N easily in a short time. This is the first synthesis by a simple reaction between the pure cobalt and pure nitrogen (supercritical fluid nitrogen). The cell parameters of the synthesized Co₂N are a=4.662(9) Å, b=4.332(5) Å and c=2.749(9) Å, respectively.     

Mössbauer study of 57Fe in CVD diamond following 57Mn implantation

⁵⁷Fe Mössbauer spectroscopy, following the implantation of radioactive parent ⁵⁷Mn^?+? ions, has been performed on two chemical vapour deposited diamond samples, one synthesized in 2003 (CVD03) and the other in 2005 (CVD05). The spectra of sample CVD05 were as observed previously in natural IIa diamonds: single lines corresponding to substitutional and interstitial Fe were superimposed on a broad quadrupole split doublet. The site fraction of Fe_i reached 30% at 900 K. The spectra of the CVD03 sample showed, in addition to the above features, a strong contribution (>30%) from a quadrupole doublet attributable to the presence of intrinsic amorphous inclusions in the crystallites. This observation has been confirmed by X-ray diffraction.     

Bromine metallization studied by X-ray absorption spectroscopy

The experimental data carried out by M?ssbauer and magnetic resonances investigations of the structural phase transitions in K₂ZnCl₄ crystals are discussed by a simple electrostatic model, calculating, the lattice contributions to the local electric potential V(r), electric field intensity E(r) and electric field gradient tensor, (r) and taking into account both the fractional electric point charges and rigid lattice approximations. The validity of the model is proved by a good fit of the computing results and experimental data of quadrupole splitting parameters at K sites obtained by ³⁹K-NMR methods in high temperature incommensurate phase ( Pnam symmetry). The experimental results obtained by M?ssbauer and EPR methods in commensurate phase (Pna2₁ symmetry) of iron and copper doped K₂ZnCl₄ crystals are explained by relaxing the rigid lattice approximation. The insertion of probe ions appear to be done on not-exactly-Zn²⁺ site. Received 3 February 1999 and Received in final form 4 May 1999     

In-beam Mössbauer study of 57Fe using a secondary 57Mn beam and ion implantation

We have succeeded in obtaining well-resolved M?ssbauer spectra of ⁵⁷Fe arising from short-lived ⁵⁷Mn ( T _1/2 = 1.45 min) in Si and KMnO₄. The M?ssbauer spectra of ⁵⁷Fe in Si are well fitted with a curve consisting of two singlet lines, one being assigned as the interstitial Fe atoms and the other as substitutional ones. The relative intensities of the two lines infer that 60% of ⁵⁷Fe ( ←⁵⁷Mn) atoms land at the interstitial sites and 40% at the substitutional sites at temperatures between 30 K and 296 K. The result for the KMnO₄ sample suggests a presence of an exotic chemical species corresponding to a higher valence state than Fe^{6 +}. Received: 1 May 2001 / Accepted: 4 December 2001     

Possible superconductivity at 140k

Abstract

We present here the results of our resistive investigations of a sample of the Y-Ba-Cu-O system which strongly suggest the possibility of superconductivity at 140K. The composition of this sample is Y_0.7Ba_0.3CuO_2,3?δ which is different from that of the single phase system YBa₂Cu₃O_6+x.     

Electrical and structural properties of VO2 in an electric field

We examined the electrical and local structural properties of a VO₂ film at different electric fields using electrical resistance and x-ray absorption fine structure (XAFS) measurements at the V K edge in the temperature range of 30–100 °C. The T_c value of the metal-to-insulator transition (MIT) during both heating and cooling decreases with electric field. When the electric field exceeds a certain value, the MIT becomes sharper due to Joule heating. The MIT, the structural phase transition (SPT), and the pre-edge peak transition of the VO₂ do not congruently occur at a uniform temperature. A metallic VO₂ is observed in only the rutile (or M2) symmetry. An electric field induces a substantial amount of conduction electrons in insulating VO₂. Simultaneously measured resistance and XAFS reveal that Joule heating caused by an external electric field significantly affects the MIT and SPT of VO₂.     

Ferroelectric phase transition in deuterated dihydrogen phosphate,studied by infrared spectroscopy

Abstract

The temperature dependence of polar phonon spectra of K(H_1?X D_X)₂ PO₄ single crystal with x = 0.9 for the electric field polarised parallel and perpendicular to the ferroelectric axis is reported between 7 and 300 K, in the para- and ferroelectric phase.     

Photoluminescence enhancement in manganese-doped magnesium stannate phosphors synthesized by millimeter-wave irradiation

We have investigated photoluminescence (PL) of Mg₂SnO₄:Mn phosphors synthesized by the irradiation with millimeter-wave of 24 GHz. The PL spectrum at room temperature is dominated by a green band peaking at 500 nm, suggesting the existence of tetrahedral Mn²⁺ sites. When the phosphors are grown by the millimeter-wave heating, the 500 nm band is so much intense compared to those by the electric furnace heating. To clarify the origin of the PL enhancement, we have carried out the measurements of scanning electron microscope (SEM) and electron spin resonance (ESR). The SEM image exhibits the growth of small round particles with an average size of 1.6 μm. Such well-grown micron-sized particles were not observed under the electric furnace heating. The ESR spectra exhibit six prominent lines, the intensity of which becomes greater for the phosphors obtained by the millimeter-wave heating. From this observation, it is supposed that the PL enhancement is mainly due to the increase in the number of tetrahedral Mn²⁺ sites. Therefore, the millimeter-wave heating has an important advantage over the electric furnace heating in the synthesis of Mg₂SnO₄:Mn phosphors.     

Electrical resistivity and critical temperature of Bi-based High-TC superconductors to 1 GPa

Abstract

We have measured the electrical resistance R of a sintered, two-phase, high-T_C superconductor with the nominal composition BiSrCaCu₂O_x, as a function of T and p. We find d(lnR)/dp ? -0.06 GPa^?1 at 295 K, while dT_C/dp is 2.5 K/GPa for the phase with T_c ? 76 and 2 K/GPa for that with T_C ? 106 K.     

Phase transitions in h-thiourea under electric‐field

Abstract

Dielectric constant, spontaneous polarization and pyroelectric response measurements were performed on thin samples (e < 100 μm) of H-thiourea as a function of temperature and applied electric field. Along with previous data obtained by optical birefringence, X-ray and neutron diffraction techniques, the results put in evidence three features in the modulated region between the ferroelectric state and the paraelectric one. The tricritical point is determined for E_tr ? 2075 V/mm and T_tr ? 192 K.     

Quadrupolar susceptibility and magnetic phase diagram of PrNi2Cd20 with non-Kramers doublet ground state

ABSTRACT

In this study, ultrasonic measurements were performed on a single crystal of cubic PrNi₂Cd₂₀, down to a temperature of 0.02?K, to investigate the crystalline electric field ground state and search for possible phase transitions at low temperatures. The elastic constant (C₁₁?C₁₂)/2, which is related to the Γ₃-symmetry quadrupolar response, exhibits the Curie-type softening at temperatures below ～30?K, which indicates that the present system has a Γ₃ non-Kramers doublet ground state. A leveling-off of the elastic response appears below ～0.1?K toward the lowest temperatures, which implies the presence of level splitting owing to a long-range order in a finite-volume fraction associated with Γ₃-symmetry multipoles. A magnetic field–temperature phase diagram of the present compound is constructed up to 28?T for H || [110]. A clear acoustic de Haas–van Alphen signal and a possible magnetic-field-induced phase transition at H ～26?T are also detected by high-magnetic-field measurements.     

Photoluminescence of a-Si:H films grown by plasma-enhanced chemical vapor deposition and doped with erbium from the metallorganic compound Er(HFA)3·DME

Using standard low-temperature (<300 °C) plasma-enhanced chemical vapor deposition (PE CVD) technology, films of a Si(Er): H were obtained that emitted light in the neighborhood of 1.54 μm at room temperature. The Er source was the specially synthesized fluorine-containing metallorganic complex Er(HFA)₃·DME where HFA=CF₃C(O)CHC(O)CF₃ and DME=CH₃OCH₂CH₂OCH₃, which possesses a low transition temperature to the gas phase (of order 100 °C) at working pressures (0.1–0.5 Torr) for the PE CVD method. Distinctive features of the photoluminescence spectrum of a-Si(Er):H were investigated in the range 0.5–1.7 μm for T=77 and 300 K. The presence of photoconductivity in the synthesized films is evidence of their satisfactory electronic quality. Fiz. Tverd. Tela (St. Petersburg) 40, 1433–1436 (August 1998)     

Considerable increase in thermal conductivity of a polycrystalline CVD diamond upon isotope enrichment

We measured the temperature dependence of thermal conductivity of a polycrystalline CVD diamond with natural isotope composition and an isotope enriched (99.96% ¹²C) sample at temperatures from 5 to 420 K. The isotope enriched diamond demonstrates a considerable growth of thermal conductivity at temperatures above 80 K compared to the diamond with natural composition of isotopes. At room temperature the thermal conductivity reaches 24.3 W·cm^?1K^?1, and the isotope effect makes up not less than 34%.     

On the microstructure of the charge density wave observed in La1− x Ca x MnO3

We have used low temperature (90?K) transmission electron microscopy to investigate the ‘charge ordering’ modulation in the mixed valent manganite, La_{1? x} Ca _x MnO₃. It has been stated that Mn³⁺ and Mn⁴⁺ ions order at low temperature to produce a structural modulation composed of supercells whose size is an integer multiple of the unmodulated unit cell. Here, we use convergent beam electron diffraction to show that the periodicity of the modulation need not be an integer multiple of the undistorted cell, even on the smallest scales. We therefore suggest that this modulation is a charge density wave with a uniform periodicity. We show that the modulation wavevector lies close to the a* axis of the crystal but need not be exactly collinear. A typical grain of size 0.5?µm in La_0.48Ca_0.52MnO₃ had a wavevector which varied on a scale of tens of nanometres with an average of ?q??=?0.450a * and a standard deviation Δq?=?0.004?a* in its magnitude and Δθ?=?0.56° in its direction at 90?K. The magnitude of the wavevector in this composition fell by 20% as the temperature was increased from 90?K to room temperature. This change occurred by nucleation and growth. Although weak, the modulation was still present at room temperature, some 30?K above the ‘charge ordering temperature’.     

Study of the glassy magnetic behaviour and charge-ordering phase transitions in La0.75Ca0.25FeO3−δ perovskite

Abstract

In this work, La_0.75Ca_0.25FeO_3?δ perovskite sample was prepared by the coprecipitation method. The nanoparticle was found to crystallize in the orthorhombic (Pbnm) phase as confirmed by X-ray diffraction (XRD) and transmission electron microscopic (TEM). The oxygen non-stoichiometry (δ) and magnetic states of iron ions (three magnetic sextets and non-magnetic doublet) were investigated by Mössbauer spectroscopy at room temperature (RT). The shape of the magnetic hysteresis loop of the sample reveals the existence of a weak ferromagnetism at RT. The magnetization vs. temperature curves, measured in the 9 to 200 K range, showed that the sample exhibits two magnetic-phase transition temperatures at 29 K (T_g) and 120 K (T_CO). The magnetization isotherms, M (H), around these magnetic-phase transition temperatures for the sample are analyzed.     

Synthesis,heating, and melting of stoichiometric glass (CaSiO3·SiO2)

Thermodynamic analysis (TERRA program) of synthesis, heating, and melting of stoichiometric glass CaSiO₃·SiO₂ has been carried out. Chemically pure substances silica and lime are subjected to exothermic reaction with further external heating and melting. Wollastonite is synthesized, the chemical reaction generates heat Q _chr = ?505.3 kJ/kg, and temperature increases T = 820 K. When T _melt = 1812–1814 K, wollastonite melts, and a mixture of liquid wollastonite and condensed silica is formed. At T _melt = 1995–1997 K, silica melts, and stoichiometric glass (CaSiO₃·SiO₂) is formed. Evolutions of temperature and melting of wollastonite and silica have been studied by detailed step-by-step thermodynamic calculation (ΔT = 0.1 K).     

Dielectric and structural relaxation phenomena in Na0.5Bi0.5TiO3 single crystal

Abstract

Dielectric permittivity studies of Na_0.5Bi_0.5TiO₃ single crystals in a broad range of frequency up to 10 MHz and temperature 300—823 K are reported. In this temperature range dielectric dispersion below 1 MHz has been found. The obtained data were fitted to the Cole-Cole relation. The mean relaxation time τ is strongly temperature dependent (0.04 ? 2.6 × 10^?5 s). A remarkable hysteresis effect in the values of τ on cooling and heating took place. The Δε(T) dependence (the maximal value of Δε ～ 400) is similar to the global ε′(T) response at low frequency. An isothermal structural transformation in Na_0.5Bi_0.5TiO₃ was observed by X-ray measurements. The order of the time in which the transformation takes place (～300 minutes) corresponds to the time in which the strongest time evolution of electric permittivity and time changes of dielectric dispersion were detected.