High-pressure Samples Research Articles

Multiscale Modeling of the Strength and Ductility Paradox for High-Pressure Torsion Samples With Gradient Microstructure

Abstract Severely plastically deformed microstructures of pure copper were produced by subjecting cylindrical copper samples to high-pressure torsion. The effects of this procedure on introducing gradient microstructure and subsequent mechanical behavior were investigated by utilizing electron backscatter diffraction and performing Vickers hardness/tensile testing. A crystal plasticity-continuum dislocation dynamics modeling effort was performed to predict the mechanical performance of these samples. The model includes mechanisms based on the gradient of dislocation density and grain size, back stress fields of grain boundaries, dislocation density transmission across grain boundaries, and stress/strain gradient effects.

Synthesis and characterization of G/TiO1.80 bulk composite thermoelectric material under high temperature and high pressure

The primary purpose of this work is to introduce the second phase of graphene (G) into non-stoichiometric TiO1.80 successfully and optimize the thermoelectric properties of this composite material through high pressure and high temperature (HPHT) technology. The purpose of doping Ti powder under high pressure is to create a closed reducing atmosphere to change the ratio of titanium to oxygen in the titanium oxide base. The addition of graphene can considerably improve the electrical properties of the material and reduce its resistivity. An X-ray diffractometer, X-ray photoelectron spectrometer, scanning electron microscope, and transmission electron microscope were used to analyze and characterize the phase structure, chemical bond, micro morphology and crystal morphology of the samples. An abundance of grain boundaries and lattice dislocation defects can inhibit the lattice thermal conductivity. We also tested and analyzed the thermoelectric performance of the high-temperature and high-pressure synthetic samples through a variable temperature system. The variation of the absorption intensity of the ultraviolet UV spectrum with wavelength shows that high pressure can reduce the band gap, which is beneficial to the carrier transition and improves the conductivity of semiconductors. HPHT optimizes both the electrical and the thermal parameters of the sample. At a final sintering pressure of 5.0 GPa, the dimensionless figure of merit (zT) of the bulk composite material G/TiO1.80 was found to be 0.23 at 700 °C.

Preparing Lamellae from Vitreous Biological Samples using a Dual-Beam Scanning Electron Microscope for Cryo-Electron Tomography.

Presented here is a protocol for preparing cryo-lamellae from plunge-frozen grids of Plasmodium falciparum-infectedhuman erythrocytes, which could easily be adapted for other biological samples. The basic principles for preparing samples, milling, and viewing lamellae are common to all instruments and the protocol can be followed as a general guide to on-grid cryo-lamella preparation for cryo-electron microscopy (cryoEM) and cryo-electron tomography (cryoET). Electron microscopy grids supporting the cells are plunge-frozen into liquid nitrogen-cooled liquid ethane using a manual or automated plunge freezer, then screened on a light microscope equipped with a cryo-stage. Frozen grids are transferred into a cryo-scanning electron microscope equipped with a focused ion beam (cryoFIB-SEM). Grids are routinely sputter coated prior to milling, which aids dispersal of charge build-up during milling. Alternatively, an e-beam rotary coater can be used to apply a layer of carbon-platinum to the grids, the exact thickness of which can be more precisely controlled. Once inside the cryoFIB-SEM an additional coating of an organoplatinum compound is applied to the surface of the grid via a gas injection system (GIS). This layer protects the front edge of the lamella as it is milled, the integrity of which is critical for achieving uniformly thin lamellae. Regions of interest are identified via SEM and milling is carried out in a step-wise fashion, reducing the current of the ion beam as the lamella reaches electron transparency, in order to avoid excessive heat generation. A grid with multiple lamellae is then transferred to a transmission electron microscope (TEM) under cryogenic conditions for tilt-series acquisition. A robust and contamination-free workflow for lamella preparation is an essential step for downstream techniques, including cellular cryoEM, cryoET, and sub-tomogram averaging. Development of these techniques, especially for lift-out and milling of high-pressure frozen samples, is of high-priority in the field.

Effect of high pressure and high temperature on the Na2O · 2CaO · 3SiO2 glass-ceramic’s structural properties

In this study, the Soda-lime-silicate system, with the Na2O·2CaO·3SiO2 (N1C2S3) composition, was used to study the effect of high pressure on structural properties of this glass-ceramic. Samples were produced and submitted to a single stage crystallization heat treatment at 720 °C for 30 min simultaneously in atmospheric pressure, 2.5 GPa, 4.0 GPa or 7.7 GPa. All characterizations were performed ex-situ. The major crystalline phase obtained is the Combeite, regardless of the pressure used, with indications of a β−CaSiO3 or Cristobalite-II phase transition happening due to the high pressure. Raman and Infrared spectroscopy showed that the phase transition could be a CaO precipitation on the material, due to the breaking of Si–O bonds and presence of Ca–O vibrational modes present on the high pressure samples. All results point to the Combeite crystalline phase being highly stable under pressures up to 7.7 GPa.

Annealing of Al-Zn-Mg-Cu Alloy at High Pressures: Evolution of Microstructure and the Corrosion Behavior.

Extruded Al-Zn-Mg-Cu alloy samples with grains aligned parallel to the extrusion direction were subjected to high-pressure annealing. The effects of annealing pressure on the microstructure, hardness, and corrosion properties (evaluated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS)) were investigated. Phase analysis showed the presence of MgZn2 and α-Al phases, the MgZn2 phase dissolved into the matrix, and its amount decreased with the increasing annealing pressure. The recrystallization was inhibited, and the grains were refined, leading to an increase in the Vickers hardness with increasing the annealing pressure. The corrosion resistance was improved after high-pressure treatment, and a stable passivation layer was observed. Meanwhile, the number of corrosion pits and the width of corrosion cracks decreased in the high-pressure annealed samples.

High-pressure small-angle X-ray scattering cell for biological solutions and soft materials.

Pressure is a fundamental thermodynamic parameter controlling the behavior of biological macromolecules. Pressure affects protein denaturation, kinetic parameters of enzymes, ligand binding, membrane permeability, ion trans-duction, expression of genetic information, viral infectivity, protein association and aggregation, and chemical processes. In many cases pressure alters the molecular shape. Small-angle X-ray scattering (SAXS) is a primary method to determine the shape and size of macromolecules. However, relatively few SAXS cells described in the literature are suitable for use at high pressures and with biological materials. Described here is a novel high-pressure SAXS sample cell that is suitable for general facility use by prioritization of ease of sample loading, temperature control, mechanical stability and X-ray background minimization. Cell operation at 14 keV is described, providing a q range of 0.01 < q < 0.7 Å-1, pressures of 0-400 MPa and an achievable temperature range of 0-80°C. The high-pressure SAXS cell has recently been commissioned on the ID7A beamline at the Cornell High Energy Synchrotron Source and is available to users on a peer-reviewed proposal basis.

Combining High-Pressure Perturbation with NMR Spectroscopy for a Structural and Dynamical Characterization of Protein Folding Pathways.

High-hydrostatic pressure is an alternative perturbation method that can be used to destabilize globular proteins. Generally perfectly reversible, pressure exerts local effects on regions or domains of a protein containing internal voids, contrary to heat or chemical denaturant that destabilize protein structures uniformly. When combined with NMR spectroscopy, high pressure (HP) allows one to monitor at a residue-level resolution the structural transitions occurring upon unfolding and to determine the kinetic properties of the process. The use of HP-NMR has long been hampered by technical difficulties. Owing to the recent development of commercially available high-pressure sample cells, HP-NMR experiments can now be routinely performed. This review summarizes recent advances of HP-NMR techniques for the characterization at a quasi-atomic resolution of the protein folding energy landscape.

Influence of heat treatment on microstructure and nanohardness of TiAl alloy solidified under high pressure

The Ti-48at.%Al alloy solidified under different pressures was prepared using a tungsten-carbide six-anvil apparatus and then heat treated at different temperatures. The effect of heat treatment on microstructure and mechanical properties of high pressure solidified Ti-48Al alloy was investigated. The results showed that the phase constitution of the Ti-48Al alloy solidified under high pressure did not change after heat treatment. After 1,100 °C/12 h AC (air cooling), the value of c/a showed a slight increase. The Widmanstatten structure was formed in the samples solidified under 2 GPa and 4 GPa. More defects were found in the high-pressure samples. The volume fraction of α2 particles increased with an increase in pressure. After 1,150 °C/4 h AC, the discontinuous coarsening phenomenon could only be found in the 4 GPa solidified samples. The formation of α2 phase can lead to the increase of nanohardness. Compared with the samples before heat treatment, the nanohardness increased about 1.0–1.2 GPa.

Содержание двойных связей в полиэтилене

The content of double bonds in high-pressure polyethylene of various brands obtained from Russian and foreign manufacturers was studied. The essence of the method was to build a calibration curve on an infrared Fourier spectrometer for standard substances with a previously known arrangement of the double bond, saturation of double bonds in the initial polyethylene using gaseous bromine, and subsequent assessment of the locations and number of double bonds in the studied brands of high pressure polyethylene. The calibration substances were trans-4-decene with a purity of 96%, 1-decene with a purity of 95%, and 2-methyl-1-heptene with a purity of 98%. To record infrared spectra, calibration substances were dissolved in carbon disulfide with a purity of 99.5%. The spectra of the calibration substances were recorded in the transmission mode. The recording of the spectra of the high-pressure polyethylene samples was carried out in the reflection mode. To calculate the molar adsorption coefficient of individual calibration substances, the areas of the peak absorption of individual substances were allocated. The Peak Separation NETZSCH software was used for this purpose. For all analyzed samples, both brominated and not brominated, the ratio of the areas of absorption peaks was calculated. For each sample of high-pressure polyethylene, the content of trans-vinylidene, vinyl, and vinylidene groups C=C per 1000 carbon atoms was determined. The total number of double bonds was calculated as the sum of all analyzed bonds contained in the polyethylene sample. The accuracy of the analysis method performed by a single laboratory on a single sample is ±10% of double bonds per 1000 carbon atoms. The technique allows one to evaluate such a characteristic of low density polyethylene as the content of double bonds. This characteristic is essential for the efficient development of crosslinkable polyethylene compounds.

Ambient and High Pressure CuNiSb2: Metal-Ordered and Metal-Disordered NiAs-Type Derivative Pnictides.

The mineral Zlatogorite, CuNiSb2, was synthesized in the laboratory for the first time by annealing elements at ambient pressure (CuNiSb2-AP). Rietveld refinement of synchrotron powder X-ray diffraction data indicates that CuNiSb2-AP crystallizes in the NiAs-derived structure (P3m1, #164) with Cu and Ni ordering. The structure consists of alternate NiSb6 and CuSb6 octahedral layers via face-sharing. The formation of such structure instead of metal disordered NiAs-type structure (P63/mmc, #194) is validated by the lower energy of the ordered phase by first-principle calculations. Interatomic crystal orbital Hamilton population, electron localization function, and charge density analysis reveal strong Ni-Sb, Cu-Sb, and Cu-Ni bonding and long weak Sb-Sb interactions in CuNiSb2-AP. The magnetic measurement indicates that CuNiSb2-AP is Pauli paramagnetic. First-principle calculations and experimental electrical resistivity measurements reveal that CuNiSb2-AP is a metal. The low Seebeck coefficient and large thermal conductivity suggest that CuNiSb2 is not a potential thermoelectric material. Single crystals were grown by chemical vapor transport. The high pressure sample (CuNiSb2-8 GPa) was prepared by pressing CuNiSb2-AP at 700 °C and 8 GPa. However, the structures of single crystal and CuNiSb2-8 GPa are best fit with a disordered metal structure in the P3m1 space group, corroborated by transmission electron microscopy.

Effects of the synergy of pressure regulation and europium substitution on the microstructure and thermoelectric properties of Type-I clathrates EuxBa8−xCu6Si16Ge24

The effects of the synergy of pressure regulation and Eu substitution on the microstructure and thermoelectric (TE) properties are investigated for type-I clathrates Eu[Formula: see text]Ba[Formula: see text]Cu6Si[Formula: see text]Ge[Formula: see text] ([Formula: see text], 0.5, 1, 1.5). The rare-earth-substituted and high-pressure modulated samples show complicated morphologies composed of abundant grains and rich in lattice defects. The Seebeck coefficient and the electrical conductivity of the rare-earth-substituted samples synthesized by HPHT method are consistent with [Formula: see text]-type conduction and metal-like behavior. The carrier concentration increases and the Hall carrier mobility decreases with increasing Eu substitution at room temperature. Although the increase of Eu filling rate decreased the Seebeck coefficient of the samples, it increased the power factor (PF) of the samples significantly. The thermal conductivity also reduced on account of Eu filling. As a result, a minimum [Formula: see text] value (0.67 Wm[Formula: see text]K[Formula: see text]) and a relatively higher zT value (0.68) are achieved. Compared to the Eu-free sample, the achieved zT value of the Eu-substituted sample is a [Formula: see text][Formula: see text]62% enhancement. So, high-pressure technique is an effective route to synthesize clathrate materials and optimize TE properties simultaneously.

Phenol-Furfural Resin/Montmorillonite Based High-Pressure Green Composite from Renewable Feedstock (Saccharum munja) with Improved Thermo-Mechanical Properties.

This research endeavour aimed to explore the potential of a native, nonedible and low market value plant feedstock, i.e., Saccharum munja for green synthesis of woodware materials and improve its features by incorporating an economical blending material. A significant amount of furfural, i.e., 58%, was extracted from Saccharum munja through the modified acid digestion method. Extracted furfural was reacted with phenol to prepare phenol-furfural resin, an alternative to phenol-formaldehyde resin but with no harmful effects for humans. The synthesized resin was also blended with montmorillonite clay after modification via Dimethyl Sulfoxide (DMSO) treatment for improved thermo-mechanical properties. These resins and composites were characterized by XRD, SEM, and FTIR spectroscopy. Resultant resins and composites were further employed as a binding agent to make high-pressure composite from leftover plant residue by hot-press method. The resultant product was subjected to TGA analysis and furnished high value of degradation temperature (Tdeg), i.e., 607 °C. Prepared high-pressure composite samples were mechanically tested through compression tests by Tinius Olsen Testing Machine and hardness tests by Rockwell Hardness Tester. Its tensile strength value was 58.3 MPa while hardness value was found to be 64 RHB which was greater than mild copper with hardness value 48.9 RHB. Thus, green high-pressure composite material was successfully developed by employing Saccharum munja and montmorillonite clay while no toxic resin was used, nor was any residue left over.

Sintering Process of Cu–28Zn Brass Alloy: Statistical Investigation

In this study, the effect of process parameters on the super-solidus liquid-phase sintering of Cu–28Zn brass alloy was evaluated by using response surface methodology. Compaction pressure of green samples, sintering temperature, and sintering time were considered as the input variables, while sintering density, densification parameter, porosity percentage, volumetric shrinkage percentage, and impact energy were considered as process responses. Microstructural, fractography, and hardness tests were investigated. Results indicated that the sintering densities of low-pressure compacted samples and high-pressure compacted samples were 7.44 and 7.17 $${\raise0.7ex\hbox{${\text{g}}$} \!\mathord{\left/ {\vphantom {{\text{g}} {{\text{cm}}^{3} }}}\right.\kern-0pt} \!\lower0.7ex\hbox{${{\text{cm}}^{3} }$}}$$, and the porosity percentages of those samples were 10.25% and 13.03%, respectively. Observations revealed that increase in sintering temperature and sintering time led to the generation of the super-solidus liquid phase with filled pores. Microstructural observations and fractography revealed the effect of liquid-phase distribution to the physical and mechanical properties. Finally, it was found that the sintering temperature had the most significant effect on the sintering density, densification parameter, porosity percentage, volumetric shrinkage percentage, and impact energy. The compaction pressure and sintering time had lower effect on all responses.

Quantitative High-Resolution Imaging of Live Microbial Cells at High Hydrostatic Pressure

The majority of the Earth’s microbial biomass exists in the deep biosphere, in the deep ocean, and within the Earth’s crust. Although other physical parameters in these environments, such as temperature or pH, can differ substantially, they are all under high pressures. Beyond emerging genomic information, little is known about the molecular mechanisms underlying the ability of these organisms to survive and grow at pressures that can reach over 1000-fold the pressure on the Earth’s surface. The mechanisms of pressure adaptation are also important in food safety, with the increasing use of high-pressure food processing. Advanced imaging represents an important tool for exploring microbial adaptation and response to environmental changes. Here, we describe implementation of a high-pressure sample chamber with a two-photon scanning microscope system, allowing for the first time, to our knowledge, quantitative high-resolution two-photon imaging at 100 MPa of living microbes from all three kingdoms of life. We adapted this setup for fluorescence lifetime imaging microscopy with phasor analysis (FLIM/Phasor) and investigated metabolic responses to pressure of live cells from mesophilic yeast and bacterial strains, as well as the piezophilic archaeon Archaeoglobus fulgidus. We also monitored by fluorescence intensity fluctuation-based methods (scanning number and brightness and raster scanning imaging correlation spectroscopy) the effect of pressure on the chromosome-associated protein HU and on the ParB partition protein in Escherichia coli, revealing partially reversible dissociation of ParB foci and concomitant nucleoid condensation. These results provide a proof of principle that quantitative, high-resolution imaging of live microbial cells can be carried out at pressures equivalent to those in the deepest ocean trenches.

A fully validated high-throughput liquid chromatography tandem mass spectrometry method for automatic extraction and quantitative determination of endogenous nutritional biomarkers in dried blood spot samples

Dried blood spot (DBS) sampling demonstrates multiple advantages over traditional venous blood collection in terms of quantifying biomarkers for clinical applications. The process is more convenient, less invasive and requires smaller sample size. More importantly, it lowers risk of infection and allows easier sample transportation and storage. In this study, an automated high-throughput DBS-LC-MS/MS method was developed for quantifying endogenous biomarkers in DBS (or 20 μL whole blood) and later applied in riboflavin (i.e. vitamin B2) quantification. The method consists of four steps, including internal standard spraying, high pressure sample extraction, LC-MS/MS sample analysis and automatic extraction module cleaning. The last two steps overlap, thus reducing sample preparation time and shorten the sample analysis cycle to five minutes per sample. The method was validated to be selective and sensitive (LLOQ=2 ng/mL) over a range of 2–120 ng/mL. Matrix effect was compensated by the application of internal standard, while within-run precision, between-run precision, accuracy, stability and ruggedness of the developed method were all assessed to be satisfactory. Quantitative analysis of riboflavin in 133 whole blood samples using the developed method demonstrated strong correlation compared with those quantified using traditional manual sample preparation followed by LC-MS/MS analysis (R = 0.9774). In conclusion, an automated high-throughput DBS-LC-MS/MS method was developed and validated to be sensitive, accurate and robust, suggesting great potential in the quantification of endogenous biomarkers in blood or other biofluids.

Tuneable Magneto-Resistance by Severe Plastic Deformation

Bulk metallic samples were synthesized from different binary powder mixtures consisting of elemental Cu, Co, and Fe using severe plastic deformation. Small particles of the ferromagnetic phase originate in the conductive Cu phase, either by incomplete dissolution or by segregation phenomena during the deformation process. These small particles are known to give rise to granular giant magneto-resistance. Taking advantage of the simple production process, it is possible to perform a systematic study on the influence of processing parameters and material compositions on the magneto-resistance. Furthermore, it is feasible to tune the magneto-resistive behavior as a function of the specimens’ chemical composition. It was found that specimens of low ferromagnetic content show an almost isotropic drop in resistance in a magnetic field. With increasing ferromagnetic content, percolating ferromagnetic phases cause an anisotropy of the magneto-resistance. By changing the parameters of the high pressure torsion process, i.e., sample size, deformation temperature, and strain rate, it is possible to tailor the magnitude of giant magneto-resistance. A decrease in room temperature resistivity of ~3.5% was found for a bulk specimen containing an approximately equiatomic fraction of Co and Cu.

Facile Synthesis of LiH-Stabilized Face-Centered-Cubic YH3 High-Pressure Phase by Ball Milling Process.

A face-centered-cubic (FCC) YH3 phase is known to be stable only under high pressure (HP) of more than gigapascal order, and it reverts to the hexagonal YH3 ambient-pressure phase when the pressure is released. We previously found that the FCC YH3 can be stabilized even at ambient pressure by substituting Y for 10 mol % Li (LiH-stabilized YH3, LSY). The LSY was synthesized by heat treatment under gigapascal HP, but this process is unfavorable for mass production; that is, only a few tens of milligrams of a sample can be obtained in a single batch. In this study, we overcame this problem by applying a ball milling (BM) process for synthesizing the LSY phase, and the yield by the BM process reached on the order of grams. We confirmed that the structure of the BM sample was the same as that of the HP sample by X-ray diffractometry, Raman spectroscopy, and neutron total scattering pair distribution function analyses. The crystallinity of the BM sample, however, was lower than that of the HP sample. The difference in the crystallinity affects the thermal stability of the LSY. The BM sample with a lower crystallinity released hydrogen at a lower temperature. The BM sample was found to reversibly desorb/absorb hydrogen maintaining its initial FCC structure when the rehydrogenation temperature was at 423 K. However, when the rehydrogenation temperature of BM sample was more than 573 K, the FCC structure changed to the hexagonal ambient pressure phase due to thermal instability of FCC phase for the BM sample.

Hydrogen embrittlement of structural steels: Effect of the displacement rate on the fracture toughness of high-pressure hydrogen pre-charged samples

The aim of this paper is to study the effect of the displacement rate on the fracture toughness under internal hydrogen of two different structural steels grades used in energy applications. To this end, steel specimens were pre-charged with gaseous hydrogen at 19.5 MPa and 450 °C for 21 h and then fracture toughness tests were carried out in air at room temperature. Permeation experiments were also conducted to obtain the hydrogen diffusion coefficients of the steels. It was observed that the lower the displacement rate and the higher the steel yield strength, the stronger the reduction in fracture toughness due to the presence of internal hydrogen. A change in the fracture micromechanism was also detected. All these findings were justified in terms of hydrogen diffusion and accumulation in the crack front region in the different steel specimens.

Investigation of the temperature in dense carbon near the solid-liquid phase transition between 100 GPa and 200 GPa with spectrally resolved X-ray scattering

We present experiments investigating dense carbon at pressures between 100 GPa and 200 GPa and temperatures between 5,000 K and 15,000 K. High-pressure samples with different temperatures were created by laser-driven shock compression of graphite and varying the initial density from 1.53 g/cm3 to 2.21 g/cm3 and the drive laser intensity from 7.1 TW/cm2 to 14.2 TW/cm2. In order to deduce temperatures, spectrally resolved X-ray scattering was applied to determine ion-ion structure factors at a scattering vector of k = 4.12·1010m−1, which shows high sensitivity to temperature for the investigated sample conditions. After comparison to corresponding DFT-MD simulations, we were able to assign each structure factor a temperature. This information is indicative of the expected temperature range for the melting line of carbon at high pressures and can be compared to theoretical predictions.

Increased nitrogen-vacancy centre creation yield in diamond through electron beam irradiation at high temperature

The nitrogen-vacancy (NV) centre is a fluorescent defect in diamond that is of critical importance for applications from ensemble sensing to biolabelling. Hence, understanding and optimising the creation of NV centres in diamond is vital for technological progress in these areas. We demonstrate that simultaneous electron irradiation and annealing of a high-pressure high-temperature diamond sample increases the NV centre creation efficiency from substitutional nitrogen defects by up to 117% with respect to a sample where the processes are carried out consecutively, but using the same process parameters. This increase in fluorescence is supported by visible and infrared absorption spectroscopy experiments. Our results pave the way for a more efficient creation of NV centres in diamond as well as higher overall NV densities in the future.