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.

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.

Pressure Prediction for High-Temperature and High-Pressure Formation and Its Application to Drilling in the Northern South China Sea

There are plentiful potential hydrocarbon resources in the Yinggehai and Qiongdongnan basins in the northern South China Sea. However, the special petrol-geological condition with high formation temperature and pressure greatly blocked hydrocarbon exploration. The conventional means of drills, including methods in the prediction and monitoring of underground strata pressure, can no longer meet the requirements in this area. The China National Offshore Oil Corporation has allocated one well with a designed depth of 3200 m and pressure coefficient of 2.3 in the Yinggehai Basin (called test well in the paper) in order to find gas reservoirs in middle-deep section in the Miocene Huangliu and Meishan formations at the depth below 3000 m. Therefore, combined with the '863' national high-tech project, the authors analyzed the distribution of overpressure in the Yinggehai and Qiongdongnan basins, and set up a series of key technologies and methods to predict and monitor formation pressure, and then apply the results to pressure prediction of the test well. Because of the exact pressure prediction before and during drilling, associated procedure design of casing and their allocation in test well has been ensured to be more rational. This well is successfully drilled to the depth of 3485 m (nearly 300 m deeper than the designed depth) under the formation pressure about 2.3 SG (EMW), which indicate that a new step in the technology of drilling in higher temperature and pressure has been reached in the China National Offshore Oil Corporation.

Rheological properties of oil-based drilling fluids at high temperature and high pressure

The rheological properties of two kinds of oil-based drilling fluids with typically composition were studied at pressures up to 138 MPa and temperatures up to 204 ℃ using the RheoChan 7400 Rheometer.The experimental results show that the apparent viscosity,plastic viscosity and yield point decrease with the increase of temperature,and increase with the increase of pressure.The effect of pressure on the apparent viscosity,plastic viscosity and yield point is considerable at ambient temperature.However,this effect gradually reduces with the increase of temperature.The major factor influencing the rheological properties of oil-based drilling fluids is temperature instead of pressure in the deep sections of oil wells.On the basis of numerous experiments,the model for predict the apparent viscosity,plastic viscosity and yield point of oil-based drilling fluids at high temperature and pressure was established using the method of regressive analysis.It is confirmed that the calculated data are in good agreement with the measured data,and the correlation coefficients are more than 0.98.The model is convenient for use and suitable for the application in drilling operations.

Gas-Liquid Mass Transfer in a Slurry Bubble Column Reactor under High Temperature and High Pressure

The gas-liquid mass transfer of H2 and CO in a high temperature and high-pressure three-phase slurry bubble column reactor is studied. The gas-liquid volumetric mass transfer coefficients kLa are obtained by measuring the dissolution rate of H2 and CO. The influences of the main operation conditions, such as temperature, pressure, superficial gas velocity and solid concentration, are studied systematically. Two empirical correlations are proposed to predict kLa values for H2 and CO in liquid paraffin/solid particles slurry bubble column reactors.

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.

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)).

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.

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.

The effect of high-pressure and high-temperature drying treatments on the deresination ratio of Pinus massoniana

This study investigated the possibility of using high-temperature and high-pressure schedules to treat Pinus massoniana wood in order to reduce its oil content. We discuss the effect of drying temperature, absolute pressure and the holding time on the deresination ratio in R massoniana wood and establish a model for the deresination ratio as a function of drying temperature, absolute pressure and holding time. The results show that the deresination ratio in- creased from 7.14% to 87.04% when the temperature increased from 150 to 200℃, the absolute pressure from 0.1 to 0.6 MPa and the holding time from 1 to 3 h. The optimal model for the deresination ratio （Y） with drying temperature （t）, absolute pressure （p） and holding time （r） is： Y = 0.284t ＋ 113.424p ＋ 3.518r - 42.486, with a coefficient of determina- tion （R2） of 0.930. Compared with drying temperature and holding time, absolute pressure plays the more significant role in the deresination process. This study could provide a theoretical basis to the practical production of R massoniana wood.

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.

P-Wave Velocity in Rocks of Dabieshan, China at High Pressure and High Temperature: Constraints for Composition of Lower Crust and Crust-Mantle Recycling

P-wave velocities in the rocks of Dabieshan, central China were measured at pressures up to 5.0 GPa and temperatures up to 1 300℃. The ultrahigh pressure eclogites have the highest density and P-wave velocity (Vp) and lower anisotropy. Pressure derivatives of the eclogites range from 0. 22 to 0. 33 km. s-1 GPa-1. Average temperature derivative of the eclogites is - 3. 41×10-4 km. s-1. °C -1. The density and VP of the eclogites imply that there will be two united possibilities related to crust-mantle recycling after the eclogite formed in the deep lithosphere. One is that some eclogites in the deep lithosphere were detached and sunk into deeper mantle due to their denser density. Another is that some eclogites returned to the crust and exposed to the surface.Small amounts (<12%) of eclogites may be still exist in the deep crust beneath Dabieshan based on our calculation.

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.

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.

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.

Stability of Titanium-aluminium Nitride (Ti_2AlN) at High Pressure and High Temperatures

The stability of Ti2AlN at high pressure of 5 GPa and different temperatures of 700-1 600 ℃ was investigated using X-ray diffraction （XRD）,scanning electron microscopy （SEM） equipped with an energy dispersive spectrometer （EDS）.Ti2AlN was found to be stable at temperatures as high as 1 400 ℃under 5 GPa for 20 min,and was proved that it held better structure stability than Ti2AlC under 5 GPa through comparative experiments of Ti2AlN and Ti2AlC （representative compounds of M2AX phases （211 phase））.The reaction process at high pressure had some difference from that at ambient pressure/vacuum,and Ti2AlN directly decomposed to TiN and TiAl at 5 GPa and 1 500 ℃ for 20 min.Moreover,the mechanism of phase segregation was discussed.In addition,the behavior of Ti2AlN contacting with Zr at high pressure and high temperature （HPHT） was also studied.

Effects of Combined Instantaneous High-Pressure and Medium Temperature on Peroxidase Activity in Wax Gourd Juices

Based on the instantaneous pressurization and depressurization produced by high pressure single pole cylinder pump and valve, the effects of the continuous processing on the peroxidase (POD) activity in wax gourd juices were investigated. Results showed that the processing factors such as pressure, temperature, pH and processing time are important to the POD activity. POD in crude juices could be inactivated apparently above 50 MPa(pH 4.6, 35℃, 4 min), and activated at 20 MPa ( P < 0.01). Its remarkable inactivation could also be observed at 45 and 55℃ (20 MPa, pH 4.6, 4 min), and the evident activation appears at the material temperature 35℃ ( P < 0.01). The pH 3.0 could destroy POD almost completely (20 MPa, 35℃, 4 min), while pH 6.0 could not influence apparently the POD activity in crude juices( P > 0.05). In addition, the rules of POD activity along with the treatment time are variational under different processing pressures. The higher the treating pressure is, the shorter the processing time is needed to inactivate POD.

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.

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.