High-pressure High-temperature Synthesis Research Articles

A New High-Pressure High-Temperature Phase of Silver Antimonate AgSbO3 with Strong Ag-O Hybridization.

We report on a new polymorph of silver antimonate AgSbO3 discovered with the use of high-pressure high-temperature synthesis at 16 GPa and 1380 °C. The crystal structure is determined from X-ray powder diffraction, and we find this new high-pressure phase crystallizes in monoclinic space group C2/c with the following values: a = 8.4570(3) Å, b = 9.8752(3) Å, c = 8.9291(3) Å, β = 91.1750(12)°, and V = 745.56(4) Å3. We synthesized the high-pressure (16 GPa) AgSbO3 phase from the ilmenite phase as a precursor. This high-pressure monoclinic AgSbO3 consists of a three-dimensional network of corner- and edge-sharing SbO6 octahedra with channels along the c-direction containing Ag atoms. We also synthesize AgSbO3 in the defect pyrochlore phase at 4 GPa from the same ilmenite precursor and compare the Raman spectra and the cation-anion bonding of all three AgSbO3 phases. The absence of a cubic perovskite form of AgSbO3 even at pressures of ≤16 GPa is likely due to the covalency of the Sb-O bonds and the moderate electronegativity of Ag+. Hybridization of Ag d and O p orbitals results in a variation of Ag-O distances that correlates with the band gap, which is in qualitative agreement with the density of states around the Fermi level from our density functional calculations. We compare AgSbO3 with other ABX3 compounds to elucidate the dependence of the structure on the constituent atoms.

High-pressure high-temperature synthesis and characterization of B10C

The boron-rich boron carbide materials have been traditionally synthesized by adding boron powder to B4C material and subjecting it to hot pressing sintering for materials composition containing 8.8–20 at. % carbon in boron (composition range of B10.4C to B4C). Our study explores a synthesis route for B10C starting from high-purity boron and carbon and direct conversion under high pressure and high temperature (HPHT) conditions of 2000 °C and 6–8 GPa. Synthesis was verified via x-ray diffraction analysis, showing the conversion of the high-purity boron and carbon powder mixture into a hexagonal B10C structure (R-3m space group) with lattice parameters of a = b = 5.6115 Å and c = 12.197 Å. The concentration of boron was measured through x-ray photoelectron spectroscopy, confirming the B10C ratio. The measured nanoindentation mean hardness of B10C was 40 GPa. Raman spectroscopy of the HPHT synthesized sample shows characteristic vibrational breathing modes of boron icosahedron and an additional intense band at a vibrational frequency of 380 cm−1. This Raman band, which appears notably weaker in earlier studies and B4C samples, is assigned to the linear chain of B–B–B and attributed to the maximal incorporation of boron within the hexagonal structure.

High-pressure high-temperature synthesis of NdRe2.

In this study, we report the synthesis of a new cubic neodymium-rhenium metallic alloy NdRe2 through the utilization of high pressure and laser heating in a diamond anvil cell. NdRe2 crystallizes in the space group with a lattice parameter equal to 7.486 (2) Å and Z = 8at 24 (1) GPa and 2,200 (100) K. It was studied using high-pressure single-crystal X-ray diffraction. The compound crystallizes in the cubic MgCu2 structure type. Its successful synthesis further proves that high-pressure high-temperature conditions can be used to obtain alloys holding a Laves phase structure. Ab initio calculations were done to predict the mechanical properties of the material. We also discuss the usage of extreme conditions to synthesize and study materials present in the nuclear waste.

Improvement of thermoelectric properties of xNb:(1-x)SrTiO3 composite ceramics by high-pressure high-temperature synthesis

The high stability and low cost are considered comparative advantages of the SrTiO3 chalcogenide oxide thermoelectric material. However, the pure SrTiO3 material is characterized by low electrical conductivity and high thermal conductivity, which could eventually lead to poor overall thermoelectric performance, and limit its application in the field of high temperature thermoelectricity. The development of composite-based metal materials with SrTiO3 by using suitable methods is arising as the most promising approach to improve their electrical properties. Along these lines, in this work, xNb: (1-x) SrTiO3 composite ceramics were successfully synthesized by using the high temperature and high-pressure (HPHT) method. The Nb powder was oxidized into various niobium oxides exhibiting their own thermoelectric properties under HPHT conditions to optimize the thermoelectric properties of the Nb/SrTiO3 composites. From our analysis, it was demonstrated that with the increase of the Nb powder content, the electrical properties were significantly improved. In addition, the fabricated Nb/SrTiO3 composite ceramics possessed a special “pore” microstructure, which significantly reduced the thermal conductivity of the material. In this work, the physical phase, microscopic morphology, and thermoelectric properties of the synthesized samples were also systematically tested and analyzed, and the maximum zT value of 0.28@973 K was obtained for the final sample with x = 0.4. The implementation of the HPHT method for the preparation of chalcogenide oxide composite ceramics provides valuable insights for the improvement of their thermoelectric properties.

A closed bipolar electrochemical cell for the interrogation of BDD single particles: Electrochemical advanced oxidation

A closed bipolar electrochemical cell containing two conductive boron-doped diamond (BDD) particles of size ∼ 250 – 350 μm, produced by high-pressure high-temperature (HPHT) synthesis, has been used to demonstrate the applicability of single BDD particles for electrochemical oxidative degradation of the dye, methylene blue (MB). The cell is fabricated using stereolithography 3D printing and the BDD particles are located at either end of a solution excluded central channel. Platinum wire electrodes placed in each of the two outer solution compartments are used to drive electrochemical reactions at the two BDD particles, which, under bipolar conditions do not require direct electrical connection to a potential source. Experiments using ultra high-performance liquid chromatography coupled with mass spectrometry (UHPLC-MS) show that the anodic pole BDD particle is able to electrochemically remove > 99 % of the dye (originally present at 1 × 10−4 M) to undetectable UHPLC-MS products in 600 s. Monitoring of the time dependant change in MB peak area, from the UHPLC chromatograms, enables a pseudo first order rate constant of 0.54 min−1 to be determined for MB removal. Given the large scale at which such particles can be produced (tonnes), such data bodes well for scale up opportunities using HPHT-grown BDD particles, where the particles can be assembled into high surface area electrode formats.

Synthesis of Ultra-Incompressible and Recoverable Carbon Nitrides Featuring CN4 Tetrahedra.

Carbon nitrides featuring three-dimensional frameworks of CN4 tetrahedra are one of the great aspirations of materials science, expected to have a hardness greater than or comparable to diamond. After more than three decades of efforts to synthesize them, no unambiguous evidence of their existence has been delivered. Here, the high-pressure high-temperature synthesis of three carbon-nitrogen compounds, tI14-C3 N4 , hP126-C3 N4 , and tI24-CN2 , in laser-heated diamond anvil cells, is reported. Their structures are solved and refined using synchrotron single-crystal X-ray diffraction. Physical properties investigations show that these strongly covalently bonded materials, ultra-incompressible and superhard, also possess high energy density, piezoelectric, and photoluminescence properties. The novel carbon nitrides are unique among high-pressure materials, as being produced above 100GPa they are recoverable in air at ambient conditions.

High-pressure reactions between the pnictogens: the rediscovery of BiN.

We explore chemical reactions within pnictogens with an example of bismuth and nitrogen under extreme conditions. Understanding chemical reactions between Bi and N, elements representing the first and the last stable elements of the nitrogen group, and the physical properties of their compounds under ambient and high pressure is far from being complete. Here, we report the high-pressure high-temperature synthesis of orthorhombic Pbcn BiN (S.G. #60) from Bi and N2 precursors at pressures above 40GPa. Using synchrotron single-crystal X-ray diffraction on the polycrystalline sample, we solved and refined the compound's structure and studied its behavior and compressibility on decompression to ambient pressure. We confirm the stability of Pbcn BiN to pressures as low as 12.5(4)GPa. Below that pressure value, a group-subgroup phase transformation occurs, resulting in the formation of a non-centrosymmetric BiN solid with a space group Pca21 (S.G. #29). We use ab initio calculations to characterize the polymorphs of BiN. They also provide support and explanation for our experimental observations, in particular those corresponding to peculiar Bi-N bond evolution under pressure, resulting in a change in the coordination numbers of Bi and N as a function of pressure within the explored stability field of Pbcn BiN.

High-pressure high-temperature preparation of CeGe3

Abstract The metastable compound CeGe3 was obtained by high-pressure high-temperature synthesis from pre-reacted Ce and Ge at 3 GPa of pressure and 1873 K, with subsequent annealing over several hours at 1173 K. The product crystallises in a 2 × 2 × 2 superstructure of the cubic Cu3Au-type structure with space group F m 3 ‾ m $Fm\overline{3}m$ and a = 8.6970(2) Å. CeGe3 decomposes at 520(10) K into CeGe2−x and elemental Ge.

Modular Principle for Complex Disordered Tetrahedral Frameworks in Quenched High-Pressure Phases of Phosphorus Oxide Nitrides.

The crystal structures of the new phosphorus oxide nitrides P40 O31 N46 and P74 O59 N84 , which were synthesized from amorphous phosphorus oxide nitride imide, exhibit complex frameworks built up from P(O,N)4 tetrahedra. The latter form various chain-like building units with various degrees of branching. These modular units can be combined and arranged in different ways, which leads to closely related structures and several disordered configurations in each compound. As the material was obtained by high-pressure high-temperature synthesis, the disorder is most likely a consequence of quenching a high-pressure phase with P(O,N)5 trigonal bipyramids. Under ambient conditions, P atoms are expected to relax by moving to the centers of the face-sharing tetrahedra that constitute the bipyramid. Diffraction patterns acquired with microfocused synchrotron radiation reveal that domains of both compounds are intergrown with H3 P8 O8 N9 , whose tetrahedral framework represents a cutout of the structures of both P40 O31 N46 and P74 O59 N84 . Powder diffraction patterns do not indicate any further phases.

Non-destructive analysis of a mixed H2O–CO2 fluid in experimental noble-metal capsule by means of freezing and high-energy synchrotron X-ray diffraction

High-pressure high-temperature syntheses that involve volatile-bearing aqueous fluids are typically accomplished by enclosing the samples in gas-tight welded shut noble-metal capsules, from which the bulk volatile content must be extracted to be analyzed with mass spectroscopy, hence making the analysis non-replicable. Here we describe a novel non-destructive method that ensures the identification and the quantitative estimate of the volatiles directly in the sealed capsule, focusing on fluid H2O–CO2 mixtures equilibrated with graphite at conditions of geological interest (1 GPa, 800 °C). We used a high-energy (77 keV) synchrotron X-ray radiation combined with a cryostat to produce X-ray diffraction patterns and X-ray diffraction microtomographic cross-sections of the volatile-bearing samples down to –180 °C, thus encompassing the conditions at which crystalline phases-solid CO2 and clathrate (CO2 hydrate)-form. The uncertainty of the method is < 15 mol%, which reflects the difference between the volatile proportion estimated by both Rietveld refinement of the diffraction data and by image analysis of the microtomograms, and the reference value measured by quadrupole mass spectrometry. Therefore, our method can be reliably applied to the analysis of frozen H2O–CO2 mixtures and, moreover, has the potential to be extended to experimental fluids of geological interest containing other volatiles, such as CH4, SO2 and H2S.

Comparative analysis of labor input required to produce one carat at different methods of synthesis and mining of diamonds

Diamond is a form of carbon that has been attracting attention for hundreds of years, owing to its physical and chemical properties of hardness, thermal conductivity, chemical inertness, and transparency. Labor and the long-term impact of a diverse workforce, is one of the most important factors in diamond mining and production and must be considered when assessing economic benefits. In the present study, we examined the labor input required to obtain one carat of diamond, via three methods: open-cast mining, high-pressure high-temperature synthesis and 2.45-GHz microwave plasma chemical vapor deposition. We discovered that to produce a carat of (near-) colorless diamond, the labor inputs are approximately 1.83 h and 3.43 h of work using the HPHT and 2.45-GHz MP CVD methods, respectively. We noted a lower labor input of work per carat for the mining of diamonds of assorted sizes and colors from the two main DeBeers diamond fields in Botswana (Orapa and Jwaneng). This paper is based on our observations and public reports, and we think that our findings will be helpful in understanding the labor input per carat for the analyzed methods, understanding the main technological challenges facing the diamond industry that could potentially affect future labor productivity.

Structural Transitions in Boron Carboxynitride (BNCO) during High-Pressure High-Temperature (HPHT) Synthesis and Sintering

Structural Transitions in Boron Carboxynitride (BNCO) during High-Pressure High-Temperature (HPHT) Synthesis and Sintering

Gadolinium trisilicide − a paramagnetic representative of the YbSi3 type series

Abstract Binary gadolinium trisilicide GdSi3 was prepared by high-pressure high-temperature synthesis at typically 9.5(5) GPa and 870 K before quenching to ambient conditions. At ambient pressure, GdSi3 exhibits an exothermic decomposition at 647(10) K into the thermodynamically stable phases GdSi2–x and Si, indicating its metastable character. Powder X-ray diffraction data is consistent with the YbSi3-type crystal structure comprising slabs of condensed Si2 dumbbells, which enclose layered arrangements of gadolinium cations. Quantum chemical analysis of the chemical bonding shows, that the framework is formed by silicon dumbbells with homopolar bonds. The magnetic moment of 8.13(8) µ B is consistent with Gd4f 7 (Gd3+ state) and antiferromagnetic ordering is observed below 64(1) K.

Silicon-Vacancy Nanodiamonds as High Performance Near-Infrared Emitters for Live-Cell Dual-Color Imaging and Thermometry.

Nanodiamonds (NDs) with color centers are excellent emitters for various bioimaging and quantum biosensing applications. In our work, we explore new applications of NDs with silicon-vacancy centers (SiV) obtained by high-pressure high-temperature (HPHT) synthesis based on metal-catalyst-free growth. They are coated with a polypeptide biopolymer, which is essential for efficient cellular uptake. The unique optical properties of NDs with SiV are their high photostability and narrow emission in the near-infrared region. Our results demonstrate for the first time that NDs with SiV allow live-cell dual-color imaging and intracellular tracking. Also, intracellular thermometry and challenges associated with SiV atomic defects in NDs are investigated and discussed for the first time. NDs with SiV nanoemitters provide new avenues for live-cell bioimaging, diagnostic (SiV as a nanosized thermometer), and theranostic (nanodiamonds as drug carrier) applications.

Anomalous Formation of Irradiation-Induced Nitrogen-Vacancy Centers in 5 nm-Sized Detonation Nanodiamonds

Nanodiamonds containing negatively charged nitrogen-vacancy (NV$^-$) centers are versatile room-temperature quantum sensors in a growing field of research. Yet, knowledge regarding the NV-formation mechanism in very small particles is still limited. This study focuses on the formation of the smallest NV$^-$-containing diamonds, 5 nm detonation nanodiamonds (DNDs). As a reliable method to quantify NV$^-$ centers in nanodiamonds, half-field signals in electron paramagnetic resonance (EPR) spectroscopy are recorded. By comparing the NV$^-$ concentration with a series of nanodiamonds from high-pressure high-temperature (HPHT) synthesis (10 - 100 nm), it is shown that the formation process in 5 nm DNDs is unique in several aspects. NV$^-$ centers in DNDs are already formed at the stage of electron irradiation, without the need for high-temperature annealing. The effect is explained in terms of "self-annealing", where size and type dependent effects enable vacancy migration close to room temperature. Although our experiments show that NV$^-$ concentration generally increases with particle size, remarkably, the NV$^-$ concentration in 5 nm DNDs surpasses that of 20 nm-sized nanodiamonds. Using Monte Carlo simulations, we show that the ten times higher substitutional nitrogen concentration in DNDs compensates the vacancy loss induced by the large relative particle surface. Upon electron irradiation at a fluence of $1.5 \times 10 ^{19}$ e$^-$/cm$^2$, DNDs show a 12.5-fold increment in the NV$^-$ concentration with no sign of saturation. These findings can be of interest for the creation of defects in other very small semiconductor nanoparticles beyond NV-nanodiamonds as quantum sensors.

Size-Dependent Thermal Stability and Optical Properties of Ultra-Small Nanodiamonds Synthesized under High Pressure.

Diamond properties down to the quantum-size region are still poorly understood. High-pressure high-temperature (HPHT) synthesis from chloroadamantane molecules allows precise control of nanodiamond size. Thermal stability and optical properties of nanodiamonds with sizes spanning range from <1 to 8 nm are investigated. It is shown that the existing hypothesis about enhanced thermal stability of nanodiamonds smaller than 2 nm is incorrect. The most striking feature in IR absorption of these samples is the appearance of an enhanced transmission band near the diamond Raman mode (1332 cm). Following the previously proposed explanation, we attribute this phenomenon to the Fano effect caused by resonance of the diamond Raman mode with continuum of conductive surface states. We assume that these surface states may be formed by reconstruction of broken bonds on the nanodiamond surfaces. This effect is also responsible for the observed asymmetry of Raman scattering peak. The mechanism of nanodiamond formation in HPHT synthesis is proposed, explaining peculiarities of their structure and properties.

Tribological properties of carbon-containing composite materials prepared by high-pressure high-temperature synthesis

The composite materials (CM) based on Co, Ti-Cu, and Pt and reinforced with diamond-like carbon particles and diamonds with different component ratios have been obtained by high-pressure high-temperature synthesis (5–9 GPa, 800–1800 °C). The methods of optical microscopy, dynamic indentation, and tribological tests were used to establish the correlation between the structure and properties of the reinforcing phase and CM and to define the limits of the applicability of the CM as tribotechnical materials. Low friction coefficients (0.08–0.06) were demonstrated by the CM reinforced with a superhard (35–40 GPa) diamond-like phase obtained from ball-milled fullerites with a cobalt binder as well as by the CM with diamonds regardless of the binder type and particle size. The wear resistance of the cobalt-based CM increases with increasing hardness of the reinforcing diamond-like particles. The condition for obtaining super wear-resistant CM from metal-fullerene mixtures is the synthesis at a temperature of about 800 °C, which ensures the collapse of fullerene molecules, but limits the graphitization of the diamond-like structure.

First detection of low field microwave absorption in the disordered multiferroic double perovskite BiFe0.5Mn0.5O3

BiFe0.5Mn0.5O3 (BFMO) is an intriguing magnetic double perovskite, only obtainable through high pressure-high temperature synthesis. It shows bulk multiferroic properties, namely the coexistence between a spin canted antiferromagnetic structure superimposed to an externally induced electric polarization at least from 77 K. In particular, the system is characterized by a significant weak ferromagnetic hysteresis loop and by a very rare phenomenon: the spontaneous magnetization reversal (MRV) versus temperature in the low field regime. To clarify the BFMO exotic magnetic phase in the low field regime, the Electron Spin Resonance (ESR) and the low field microwave absorption (LFMA) techniques were used, providing the first observation of LFMA in the bulk BFMO as an additional functionality of this material. A striking feature is that the hysteresis in LFMA signals vanishes above 45 K, while the bulk M-H loop hysteresis, measured in the same field range of LFMA, persists till room temperature. The temperature at which LFMA hysteresis vanishes qualitatively matches the position of the magnetic susceptibility’s second derivative peak, corresponding to the temperature at which the local second order mechanism responsible for MRV is maximum. The line shape of LFMA completely changes above 45 K and the ESR linewidth starts decreasing above this temperature, indicating the role of defect/disorder induced inhomogeneity. The temperature evolution of LFMA hysteresis and line shapes as a measure of the competition between Fe- and Mn-rich clusters suggests a sort of local frustration at the microscopic scale, responsible for the peculiar magnetization reversal of this system.

High-pressure high-temperature synthesis and thermal equation of state of high-entropy transition metal boride

A high-entropy transition metal boride (Hf0.2 Ti0.2 Zr0.2 Ta0.2 Mo0.2)B2 sample was synthesized under high-pressure and high-temperature starting from ball-milled oxide precursors (HfO2, TiO2, ZrO2, Ta2O5, and MoO3) mixed with graphite and boron-carbide. Experiments were conducted in a large-volume Paris–Edinburgh press combined with in situ energy dispersive x-ray diffraction. The hexagonal AlB2 phase with an ambient pressure volume V0 = 27.93 ± 0.03 Å3 was synthesized at a pressure of 0.9 GPa and temperatures above 1373 K. High-pressure high-temperature studies on the synthesized high-entropy transition metal boride sample were performed up to 7.6 GPa and 1873 K. The thermal equation of state fitted to the experimental data resulted in an ambient pressure bulk-modulus K0 = 344 ± 39 GPa, dK/dT = −0.108 ± 0.027 GPa/K, and a temperature dependent volumetric thermal expansion coefficient α = α0 + α1T + α2 T−2. The thermal stability combined with a high bulk-modulus establishes this high-entropy transition metal boride as an ultrahard high-temperature ceramic material.

Synthesis of diamonds in the C – Mn - Ni - (H) system and the diamond-shaped mechanism

Studying the dependence of the degree (α) and rate (ϑ) of the phase transformation of graphite into diamond on the synthesis time at different temperatures of the developed synthetic diamonds using the technology of high-pressure high-temperature synthesis in a metal melt (HPHT), we determined the critical mass of diamonds, which indicates the entry of the system into the stability region of graphite, where the graphitization of diamonds occurs. The role of implanted metals and hydrogen in the formation of synthetic diamonds and on its properties was also investigated.