Recension of boron nitride phase diagram based on high-pressure and high-temperature experiments

Cubic boron nitride and hexagonal boron nitride are the two predominant crystalline structures of boron nitride.They can interconvert under varying pressure and temperature conditions.However,this transformation requires overcoming significant potential barriers in dynamics,which poses great difficulty in determining the c-BN/h-BN phase boundary.This study used high-pressure in situ differential thermal measurements to ascertain the temperature of h-BN/c-BN conversion within the commonly used pressure range(3-6 GPa)for the industrial synthesis of c-BN to constrain the P-T phase boundary of h-BN/c-BN in the pressure-temperature range as much as possible.Based on the analysis of the experimental data,it is determined that the relationship between pressure and temperature conforms to the following equation:P=a+1/bT.Here,P denotes the pressure(GPa)and T is the temperature(K).The coefficients are a=-3.8±0.8 GPa and b=229.8±17.1 GPa/K.These findings call into question existing high-pressure and high-temperature phase diagrams of boron nitride,which seem to overstate the phase boundary temperature between c-BN and h-BN.The BN phase diagram obtained from this study can provide critical temperature and pressure condition guidance for the industrial synthesis of c-BN,thus optimizing synthesis efficiency and product performance.

Various admixtures to mitigate the long-term strength retrogression of Portland cement cured under high pressure and high temperature conditions

In order to investigate the problem of long-term strength retrogression in oil well cement systems exposed to high pressure and high temperature(HPHT)curing conditions,various influencing factors,including cement sources,particle sizes of silica flour,and additions of silica fume,alumina,colloidal iron oxide and nano-graphene,were investigated.To simulate the environment of cementing geothermal wells and deep wells,cement slurries were directly cured at 50 MPa and 200?C.Mineral compositions(as determined by X-ray diffraction Rietveld refinement),water permeability,compressive strength and Young’s modulus were used to evaluate the qualities of the set cement.Short-term curing(2e30 d)test results indicated that the adoption of 6 m m ultrafine crystalline silica played the most important role in stabilizing the mechanical properties of oil well cement systems,while the addition of silica fume had a detrimental effect on strength stability.Long-term curing(2e180 d)test results indicated that nano-graphene could stabilize the Young’s modulus of oil well cement systems.However,none of the ad-mixtures studied here can completely prevent the strength retrogression phenomenon due to their inability to stop the conversion of amorphous to crystalline phases.

A Comprehensive Method for the Optimization of Cement Slurry and to Avoid Air Channeling in High Temperature and High-Pressure Conditions

Air channeling in the annulus between the casing and the cement sheath and/or between the cement sheath and formation is the main factor affecting the safe operation of natural gas wells at high temperatures and pressures.Prevention of this problem requires,in general,excellent anti-channeling performances of the cement sheath.Three methods to predict such anti-channeling performances are proposed here,which use the weightless pressure of cement slurry,the permeability of cement stone and the volume expansion rate of cement sheath as input parameters.Guided by this approach,the anti-channeling performances of the cement slurry are evaluated by means of indoor experiments,and the cement slurry is optimized accordingly.The results show that the dangerous transition time of the cement slurry with optimized dosage of admixture is only 76 min,the permeability of cement stone is 0.005 md,the volume shrinkage at final setting is only 0.72%,and the anti-channeling performances are therefore maximized.The effective utilization of the optimized cement slurry in some representative wells(LD10–1-A1 and LD10–1-A2 in LD10–1 gas field)is also discussed.

Mechanical Analysis of a Multi-Test String in High-Temperature and High-Pressure Deep Wells

The mechanical behavior of the test string in deep wells is generally relatively complex as a result of the high temperature and high pressure,severe dogleg and buckling effects,which in some circumstances can even lead to string failure.Traditional computational methods for the analysis of these behaviors are often inaccurate.For this reason,here a more accurate mechanical model of the test string is introduced by considering variables such as temperature,pressure,wellbore trajectory,and buckling,as well as combining them with the deformation and string constraint conditions brought in by changes in temperature and pressure during the tripping,setting,and test operations.The model is validated by applying it to a specific high-pressure gas well(located in Northeast Sichuan).

High-pressure and high-temperature sintering of pure cubic silicon carbide:A study on stress-strain and densification

Silicon carbide(SiC)is a high-performance structural ceramic material with excellent comprehensive properties,and is unmatched by metals and other structural materials.In this paper,raw SiC powder with an average grain size of 5μm was sintered by an isothermal-compression process at 5.0 GPa and 1500?C;the maximum hardness of the sintered samples was31.3 GPa.Subsequently,scanning electron microscopy was used to observe the microscopic morphology of the recovered SiC samples treated in a temperature and extended pressure range of 0-1500?C and 0-16.0 GPa,respectively.Defects and plastic deformation in the SiC grains were further analyzed by transmission electron microscopy.Further,high-pressure in situ synchrotron radiation x-ray diffraction was used to study the intergranular stress distribution and yield strength under non-hydrostatic compression.This study provides a new viewpoint for the sintering of pure phase micron-sized SiC particles.

Fretting Wear Characteristics of Nuclear Fuel Cladding in High-Temperature Pressurized Water

In pressurized water reactor(PWR),fretting wear is one of the main causes of fuel assembly failure.Moreover,the operation condition of cladding is complex and harsh.A unique fretting damage test equipment was developed and tested to simulate the fretting damage evolution process of cladding in the PWR environment.It can simulate the fretting wear experiment of PWR under different temperatures(maximum temperature is 350℃),displacement amplitude,vibration frequency,and normal force.The fretting wear behavior of Zr-4 alloy under different temperature environments was tested.In addition,the evolution of wear scar morphology,profile,and wear volume was studied using an optical microscope(OM),scanning electron microscopy(SEM),and a 3D white light interferometer.Results show that higher water temperature evidently decreased the cladding wear volume,the wear mechanism of Zr-4 cladding changed from abrasive wear to adhesive wear and the formation of an oxide layer on the wear scar reduced the wear volume and maximum wear depth.

Porosity, permeability and rock mechanics of Lower Silurian Longmaxi Formation deep shale under temperature-pressure coupling in the Sichuan Basin, SW China

To investigate the porosity, permeability and rock mechanics of deep shale under temperature-pressure coupling, we selected the core samples of deep shale from the Lower Silurian Longmaxi Formation in the Weirong and Yongchuan areas of the Sichuan Basin for porosity and permeability experiments and a triaxial compression and sound wave integration experiment at the maximum temperature and pressure of 120 ℃ and 70 MPa. The results show that the microscopic porosity and permeability change and the macroscopic rock deformation are mutually constrained, both showing the trend of steep and then gentle variation. At the maximum temperature and pressure, the porosity reduces by 34%–71%, and the permeability decreases by 85%–97%. With the rising temperature and pressure, deep shale undergoes plastic deformation in which organic pores and clay mineral pores are compressed and microfractures are closed, and elastic deformation in which brittle mineral pores and rock skeleton particles are compacted. Compared with previous experiments under high confining pressure and normal temperature,the experiment under high temperature and high pressure coupling reveals the effect of high temperature on stress sensitivity of porosity and permeability. High temperature can increase the plasticity of the rock, intensify the compression of pores due to high confining pressure, and induce thermal stress between the rock skeleton particles, allowing the reopening of shale bedding or the creation of new fractures along weak planes such as bedding, which inhibits the decrease of permeability with the increase of temperature and confining pressure. Compared with the triaxial mechanical experiment at normal temperature, the triaxial compression experiment at high temperature and high pressure demonstrates that the compressive strength and peak strain of deep shale increase significantly due to the coupling of temperature and pressure. The compressive strength is up to 435 MPa and the peak strain exceeds 2%, indicating that high temperature is not conducive to fracture initiation and expansion by increasing rock plasticity. Lithofacies and mineral composition have great impacts on the porosity, permeability and rock mechanics of deep shale. Shales with different lithologies are different in the difficulty and extent of brittle failure. The stress-strain characteristics of rocks under actual geological conditions are key support to the optimization of reservoir stimulation program.

High temperature and high pressure rheological properties of high-density water-based drilling fluids for deep wells

To maintain tight control over rheological properties of high-density water-based drilling fluids, it is essential to understand the factors influencing the theology of water-based drilling fluids. This paper examines temperature effects on the rheological properties of two types of high-density water-based drilling fluids （fresh water-based and brine-based） under high temperature and high pressure （HTHP） with a Fann 50SL rheometer. On the basis of the water-based drilling fluid systems formulated in laboratory, this paper mainly describes the influences of different types and concentration of clay, the content of a colloid stabilizer named GHJ-1 and fluid density on the rheological parameters such as viscosity and shear stress. In addition, the effects of aging temperature and aging time of the drilling fluid on these parameters were also examined. Clay content and proportions for different densities of brine-based fluids were recommended to effectively regulate the rheological properties. Four theological models, the Bingham, power law, Casson and H-B models, were employed to fit the rheological parameters. It turns out that the H-B model was the best one to describe the rheological properties of the high-density drilling fluid under HTHP conditions and power law model produced the worst fit. In addition, a new mathematical model that describes the apparent viscosity as a function of temperature and pressure was established and has been applied on site.

Experimental Study on the Electrical Conductivity of Orthopyroxene at High Temperature and High Pressure under Different Oxygen Fugacities

At presure 1.0-4.0 GPa and temperature 1073-1423 K and under oxygen partial pressure conditions, a YJ-3000t multi-anvil solid high-pressure apparatus and Sarltron-1260 Impedance/Gain-Phase analyzer were employed to conduct an in-situ measurement of the electrical conductivity of orthopyroxene. The buffering reagents consist of Ni＋NiO, Fe＋Fe3O4, Fe＋FeO and Mo＋MoO2 in order to control the environmental oxygen fugacity. Experimental results made clear that： （1） within the measuring frequency range from 10-1 to 106 Hz, the complex impedance （R） is of intensive dependence on the frequency; （2） The electrical conductivity （a） tends to increase along to the rise of temperature （T）, and Log a vs. 1/ T fit the Arrenhius linear relations; （3） Under the control of oxygen buffer Fe＋Fe3O4, with the rise of pressure, the activation enthalpy tends to increase whereas the electrical conductivity tends to decrease. The activation energy and activation volume of the main current carders of orthopyroxene have been obtained, which are （1.715±0.035） eV and （0.03±0.01） cm^3/mol, respectively; （4） Under given pressure and temperature, the electrical conductivity tends to increase with increasing oxygen fugacity, while under given pressure the activation enthalpy tends to decrease with increasing oxygen fugacity; and （5） The sample＇s small polarons mechanism has provided a reasonable explanations to the conduction behavior at high temperature and high pressure.

Polycrystalline cubic boron nitride prepared with cubic-hexagonal boron nitride under high pressure and high temperature

Polycrystalline cubic boron nitride(Pc BN)compacts,using the mixture of submicron cubic boron nitride(c BN)powder and hexagonal BN(h BN)powder as starting materials,were sintered at pressures of 6.5–10.0 GPa and temperature of1750℃without additives.In this paper,the sintering behavior and mechanical properties of samples were investigated.The XRD patterns of samples reveal that single cubic phase was observed when the sintering pressure exceeded 7.5 GPa and h BN contents ranged from 20 vol.%to 24 vol.%,which is ascribed to like-internal pressure generated at grain-to-grain contact under high pressure.Transmission electron microscopy(TEM)analysis shows that after high pressure and high temperature(HPHT)treatments,the submicron c BN grains abounded with high-density nanotwins and stacking faults,and this contributed to the outstanding mechanical properties of Pc BN.The pure bulk Pc BN that was obtained at 7.7 GPa/1750℃possessed the outstanding properties,including a high Vickers hardness(~61.5 GPa),thermal stability(~1290℃in air),and high density(~3.46 g/cm^(3)).

Growth and annealing study of hydrogen-doped single diamond crystals under high pressure and high temperature

A series of diamond crystals doped with hydrogen is successfully synthesized using LiH as the hydrogen source in a catalyst-carbon system at a pressure of 6.0 GPa and temperature ranging from 1255 C to 1350 C.It is shown that the high temperature plays a key role in the incorporation of hydrogen atoms during diamond crystallization.Fourier transform infrared micro-spectroscopy reveals that most of the hydrogen atoms in the synthesized diamond are incorporated into the crystal structure as sp 3-CH 2-symmetric（2850 cm-1） and sp 3 CH 2-antisymmetric vibrations（2920 cm-1）.The intensities of these peaks increase gradually with an increase in the content of the hydrogen source in the catalyst.The incorporation of hydrogen impurity leads to a significant shift towards higher frequencies of the Raman peak from 1332.06 cm-1 to 1333.05 cm-1 and gives rise to some compressive stress in the diamond crystal lattice.Furthermore,hydrogen to carbon bonds are evident in the annealed diamond,indicating that the bonds that remain throughout the annealing process and the vibration frequencies centred at 2850 and 2920 cm-1 have no observable shift.Therefore,we suggest that the sp 3 C-H bond is rather stable in diamond crystals.

Prospect of HDR geothermal energy exploitation in Yangbajing,Tibet,China,and experimental investigation of granite under high temperature and high pressure

Hot dry rock （HDR） geothermal energy, almost inexhaustible green energy, was first put forward in the 1970s. The development and testing of HDR geothermal energy are well reported in USA, Japan, UK, France and other countries or regions. In this paper, the geological characters of Yangbajing basin were first analyzed, including the continental dynamic environments to form HDR geothermal fields in Tibet, the tectonic characteristics of south slope of Nyainqentanglha and Dangxiong-Yangbajing basin, and the in-situ stresses based on the investigations conducted, and then the site-specific mining scheme of HDR geothermal resources was proposed. For the potential development of HDR geothermal energy, a series of experiments were conducted on large-scale granite samples, 200 mm in diameter and 400 mm in length, at high temperature and high triaxial pressure for cutting fragmentation and borehole stability. For the borehole stability test, a hole of 40 mm in diameter and 400 mm in length was aforehand drilled in the prepared intact granite sample. The results indicate that the cutting velocity obviously increases with temperature when bit pressure is over a certain value, while the unit rock-breaking energy consumption decreases and the rock-breaking efficiency increases with temperature at the triaxial pressure of 100 MPa. The critical temperature and pressure that can result in intensive damage to granite are 400-500℃ and 100-125 MPa, respectively.

Effects of FeNi-phosphorus-carbon system on crystal growth of diamond under high pressure and high temperature conditions

This paper reports the crystal growth of diamond from the Fe Ni–Carbon system with additive phosphorus at high pressures and high temperatures of 5.4–5.8 GPa and 1280–1360°C. Attributed to the presence of additive phosphorus,the pressure and temperature condition, morphology, and color of diamond crystals change obviously. The pressure and temperature condition of diamond growth increases evidently with the increase of additive phosphorus content and results in the moving up of the V-shape region. The surfaces of the diamonds also become coarse as the additive phosphorus added in the growth system. Raman spectra indicate that diamonds grown from the Fe Ni-phosphorus-carbon system have more crystal defects and impurities. This work provides a new way to enrich the doping of diamond and improve the experimental exploration for future material applications.

Effects of a carbon convection field on large diamond growth under high-pressure high-temperature conditions

Large diamond crystals were successfully synthesized by a FeNi C system using the temperature gradient method under high-pressure high-temperature conditions. The assembly of the growth cell was improved and the growth process of diamond was investigated. Effects of the symmetry of the carbon convection field around the growing diamond crystal were investigated systematically by adjusting the position of the seed crystal in the melted catalyst/solvent. The results indicate that the morphologies and metal inclusion distributions of the synthetic diamond crystals vary obviously in both symmetric and non-symmetric carbon convection fields with temperature. Moreover, the finite element method was applied to analyze the carbon convection mode of the melted catalyst/solvent around the diamond crystal. This work is helpful for understanding the growth mechanism of diamond.

Experimental Study on Water-rock Reactions with CO2 Fluid in a Deep Sandstone Formation under High Temperature and Pressure

Qiongdongnan Basin has a tectonic geological background of high temperature and high pressure in a deep reservoir setting,with mantle-derived CO2.A water-rock reaction device was used under high temperature and high pressure conditions,in conjunction with scanning electron microscope(SEM)observations,to carry out an experimental study of the diagenetic reaction between sandstone at depth and CO2-rich fluid,which is of great significance for revealing the dissolution of deep clastic rock reservoirs and the developmental mechanism of secondary pores,promoting deep oil and gas exploration.In this study,the experimental scheme of the water-rock reaction system was designed according to the parameters of the diagenetic background of the deep sandstone reservoir in the Qiongdongnan Basin.Three groups of single mineral samples were prepared in this experiment,including K-feldspar samples,albite samples and calcite samples.Using CO2 as a reaction solution,a series of diagenetic reaction simulation experiments were carried out in a semi-closed high temperature and high pressure simulation system.A field emission scanning electron microscope(SEM)was used to observe the microscopic appearance of the mineral samples after the water-rock reaction,the characteristics of dissolution under high temperature and high pressure,as well as the development of secondary pores.The experimental results showed that the CO2-rich fluid has an obvious dissolution effect on K-feldspar,albite and calcite under high temperature and high pressure.For the three minerals,the main temperature and pressure window for dissolution ranged from 150℃to 300℃and 45 MPa to 60 MPa.Scanning electron microscope observations revealed that the dissolution effect of K-feldspar is most obvious under conditions of 150℃and 45 MPa,in contrast to conditions of200℃and 50 MPa for albite and calcite.Through the comparative analysis of experimental conditions and procedures,a coupling effect occurred between the temperature and pressure change and the dissolution strength and calcite.Under high temperature and high pressure,pressure changed the solubility of CO2,furthermore,the dissolution effect and strength of the sandstone components were also affected.The experiment revealed that high temperature and high pressure conditions with CO2-rich fluid has a significant dissolution effect on aluminosilicate minerals and is conducive to the formation of secondary pores and effective reservoirs.Going forward with the above understanding has important implications for the promotion of deep oil and gas exploration.

B-C Bond in Diamond Single Crystal Synthesized with h-BN Additive at High Pressure and High Temperature

The synthesis of diamond single crystal in the Fe64Ni36-C system with h-BN additive is investigated at pressure 6.5 GPa and temperature range of 1300-1400℃. The color of the obtained diamond crystals translates from yellow to dark green with increasing the h-BN addition. Fourier-transform infrared （FTIR） results indicate that sp2 hybridization B-N-B and B-N structures generate when the additive content reaches a certain value in the system. The two peaks are located at 745 and 1425cm-1, respectively. Fhrthermore, the FTIR characteristic peak resulting from nitrogen pairs is noticed and it tends to vanish when the h-BN addition reaches 1.1 wt%. Furthermore, Raman peak of the synthesized diamond shifts down to a lower wavenumber with increasing the h-BN ~ddition content in the synthesis system.

Synthesis of large diamond crystals containing high-nitrogen concentration at high pressure and high temperature using Ni-based solvent by temperature gradient method

This paper reprots that with Ni-based catalyst/solvent and with a dopant of NAN3, large green single crystal diamonds with perfect shape are successfully synthesized by temperature gradient method under high pressure and high temperature in a China-type cubic anvil high-pressure apparatus （SPD-6 × 1200）, and the highest nitrogen concentration reaches approximately 121-1257 ppm calculated by infrared absorption spectra. The synthesis conditions are about 5.5 CPa and 1240-1300 ℃. The growth behaviour of diamond with high-nitrogen concentration is investigated in detail. The results show that, with increasing the content of NaN3 added in synthesis system, the width of synthesis temperature region for growth high-quality diamonds becomes narrower, and the morphology of diamond crystal is changed from cube-octahedral to octahedral at same temperature and pressure, the crystal growth rate is slowed down, nevertheless, the nitrogen concentration doped in synthetic diamond increases.

Synthesis and characterizations of boron and nitrogen co-doped high pressure and high temperature large single-crystal diamonds with increased mobility

We synthesized and investigated the boron-doped and boron/nitrogen co-doped large single-crystal diamonds grown under high pressure and high temperature(HPHT) conditions(5.9 GPa and 1290℃). The optical and electrical properties and surface characterization of the synthetic diamonds were observed and studied. Incorporation of nitrogen significantly changed the growth trace on surface of boron-containing diamonds. X-ray photoelectron spectroscopy(XPS) measurements showed good evident that nitrogen atoms successfully incorporate into the boron-rich diamond lattice and bond with carbon atoms. Raman spectra showed differences on the as-grown surfaces and interior between boron-doped and boron/nitrogen co-doped diamonds. Fourier transform infrared spectroscopy(FTIR) measurements indicated that the nitrogen incorporation significantly decreases the boron acceptor concentration in diamonds. Hall measurements at room temperature showed that the carriers concentration of the co-doped diamonds decreases, and the mobility increases obviously. The highest hole mobility of sample BNDD-1 reached 980 cm^(2)·V^(-1)·s^(-1), possible reasons were discussed in the paper.

Two-step high-pressure high-temperature synthesis of nanodiamonds from naphthalene

Nanodiamonds have outstanding mechanical properties,chemical inertness,and biocompatibility,which give them potential in various applications.Current methods for preparing nanodiamonds often lead to products with impurities and uneven morphologies.We report a two-step high-pressure high-temperature(HPHT) method to synthesize nanodiamonds using naphthalene as the precursor without metal catalysts.The grain size of the diamonds decreases with increasing carbonization time(at constant pressure and temperature of 11.5 GPa and 700℃,respectively).This is discussed in terms of the different crystallinities of the carbon intermediates.The probability of secondary anvil cracking during the HPHT process is also reduced.These results indicate that the two-step method is efficient for synthesizing nanodiamonds,and that it is applicable to other organic precursors.

Modeling viscosity of methane,nitrogen,and hydrocarbon gas mixtures at ultra-high pressures and temperatures using group method of data handling and gene expression programming techniques

Accurate gas viscosity determination is an important issue in the oil and gas industries.Experimental approaches for gas viscosity measurement are timeconsuming,expensive and hardly possible at high pressures and high temperatures(HPHT).In this study,a number of correlations were developed to estimate gas viscosity by the use of group method of data handling(GMDH)type neural network and gene expression programming(GEP)techniques using a large data set containing more than 3000 experimental data points for methane,nitrogen,and hydrocarbon gas mixtures.It is worth mentioning that unlike many of viscosity correlations,the proposed ones in this study could compute gas viscosity at pressures ranging between 34 and 172 MPa and temperatures between 310 and 1300 K.Also,a comparison was performed between the results of these established models and the results of ten wellknown models reported in the literature.Average absolute relative errors of GMDH models were obtained 4.23%,0.64%,and 0.61%for hydrocarbon gas mixtures,methane,and nitrogen,respectively.In addition,graphical analyses indicate that the GMDH can predict gas viscosity with higher accuracy than GEP at HPHT conditions.Also,using leverage technique,valid,suspected and outlier data points were determined.Finally,trends of gas viscosity models at different conditions were evaluated.