The regulation of ferrocene-based catalysts on heat transfer in highpressure combustion of ammonium perchlorate/hydroxyl-terminated polybutadiene/aluminum composite propellants

The regulation of the burning rate pressure exponent for the ammonium perchlorate/hydroxylterminated polybutadiene/aluminum(AP/HTPB/Al)composite propellants under high pressures is a crucial step for its application in high-pressure solid rocket motors.In this work,the combustion characteristics of AP/HTPB/Al composite propellants containing ferrocene-based catalysts were investigated,including the burning rate,thermal behavior,the local heat transfer,and temperature profile in the range of 7-28 MPa.The results showed that the exponent breaks were still observed in the propellants after the addition of positive catalysts(Ce-Fc-MOF),the burning rate inhibitor((Ferrocenylmethyl)trimethylammonium bromide,Fc Br)and the mixture of Fc Br/catocene(GFP).However,the characteristic pressure has increased,and the exponent decreased from 1.14 to 0.66,0.55,and 0.48 when the addition of Ce-FcMOF,Fc Br and Fc Br/GFP in the propellants.In addition,the temperature in the first decomposition stage was increased by 7.50℃ and 11.40℃ for the AP/Fc Br mixture and the AP/Fc Br/GFP mixture,respectively,compared to the pure AP.On the other hand,the temperature in the second decomposition stage decreased by 48.30℃ and 81.70℃ for AP/Fc Br and AP/Fc Br/GFP mixtures,respectively.It was also found that Fc Br might generate ammonia to cover the AP surface.In this case,a reaction between the methyl in Fc Br and perchloric acid caused more ammonia to appear at the AP surface,resulting in the suppression of ammonia desorption.In addition,the coarse AP particles on the quenched surface were of a concave shape relative to the binder matrix under low and high pressures when the catalysts were added.In the process,the decline at the AP/HTPB interface was only exhibited in the propellant with the addition of Ce-Fc-MOF.The ratio of the gas-phase temperature gradient of the propellants containing catalysts was reduced significantly below and above the characteristic pressure,rather than 3.6 times of the difference in the blank propellant.Overall,the obtained results demonstrated that the pressure exponent could be effectively regulated and controlled by adjusting the propellant local heat and mass transfer under high and low pressures.

Pre-Drilling Prediction Techniques on the High-Temperature High-Pressure Hydrocarbon Reservoirs Offshore Hainan Island,China

Decreasing the risks and geohazards associated with drilling engineering in high-temperature high-pressure(HTHP) geologic settings begins with the implementation of pre-drilling prediction techniques(PPTs). To improve the accuracy of geopressure prediction in HTHP hydrocarbon reservoirs offshore Hainan Island, we made a comprehensive summary of current PPTs to identify existing problems and challenges by analyzing the global distribution of HTHP hydrocarbon reservoirs, the research status of PPTs, and the geologic setting and its HTHP formation mechanism. Our research results indicate that the HTHP formation mechanism in the study area is caused by multiple factors, including rapid loading, diapir intrusions, hydrocarbon generation, and the thermal expansion of pore fluids. Due to this multi-factor interaction, a cloud of HTHP hydrocarbon reservoirs has developed in the Ying-Qiong Basin, but only traditional PPTs have been implemented, based on the assumption of conditions that do not conform to the actual geologic environment, e.g., Bellotti's law and Eaton's law. In this paper, we focus on these issues, identify some challenges and solutions, and call for further PPT research to address the drawbacks of previous works and meet the challenges associated with the deepwater technology gap. In this way, we hope to contribute to the improved accuracy of geopressure prediction prior to drilling and provide support for future HTHP drilling offshore Hainan Island.

A Study of High-Temperature and High-Pressure Experiment of Correlativity between Deformational System of Au-Bearing Rocks and Element Adjustment

Modelling of migration and accumulation of elements Au and Ag in rocks under temperatures of 350–450°C and a confining pressure of 300 MPa and axial pressure of 100–150 MPa is conducted. It is found that the contents of gold and silver get higher in metallic sulphides such as pyrite, chalcopyrite and sphalerite as well as in quartz and muscovite, and get lower in chlorite, biotite, seriate, albite and calcite, showing that tectono-dynamics is one of the important factors for petrogenesis and metallogenesis.

Reaction mechanism of metal and pyrite under high-pressure and high-temperature conditions and improvement of the properties

Pyrite tailings are the main cause of acid mine wastewater.We propose an idea to more effectively use pyrite,and it is modified by exploiting the reducibility of metal represented by Al under high-pressure and high-temperature(HPHT)conditions.Upon increasing the Al addition,the conductivity of pyrite is effectively improved,which is nearly 734 times higher than that of unmodified pyrite at room temperature.First-principles calculations are used to determine the influence of a high pressure on the pyrite lattice.The high pressure increases the thermal stability of pyrite,reduces pyrite to highconductivity Fe7S8(pyrrhotite)by Al.Through hardness and density tests the influence of Al addition on the hardness and toughness of samples is explored.Finally we discuss the possibility of using other metal-reducing agents to improve the properties of pyrite.

Combustion Characteristics of Solid Sustained-Release Energetic Materials

A solid sustained-release energetic material sample,an eruption device and a complete test system were prepared further to analyse the combustion characteristics of solid sustainedrelease energetic materials.The high-temperature heat flux generated by the combustion of the samples from the eruption device was used to penetrate the Q235 target plate.In addition,the meaning and calculation formula of energy density characterising the all-around performance of heat flux were proposed.The numerical simulation of the combustion effect of samples was carried out.According to the data comparison,the numerical simulation results agreed with the experimental results,and the maximum deviation between the two was less than 8.9%.In addition,the structure of the combustion wave and high-temperature jet was proposed and analysed.Based on theoretical analysis,experimental research and numerical simulation,the theoretical burning rate formula of the sample was established.The maximum error between the theoretically calculated mass burning rate and the experimental results was less than 9.8%.Therefore,using the gas-phase steady-state combustion model to study the combustion characteristics of solid sustained-release energetic materials was reasonable.The theoretical burning rate formula also had high accuracy.Therefore,the model could provide scientific and academic guidance for the theoretical research,system design and practical application of solid sustained-release energetic materials in related fields.

Dissolution-precipitation mechanism of self-propagating high-temperature synthesis of TiC-Cu cermets

The mechanism of self-propagating high-temperature synthesis （SHS） of TiC-Cu cermets was studied using a combustion front quenching method. Microstructural evolution in the quenched sample was observed using scanning electron microscope （SEM） with energy dispersive X-ray （EDX） spectrometry, and the combustion temperature was measured. The results showed that the combustion reaction started with local formation of Ti-Cu melt and could be described with the dissolution-precipitation mechanism, namely, Ti, Cu, and C particles dissolved into the Ti-Cu solution and TiC particles precipitated in the saturated Ti-Cu-C liquid solution. The local formation of Ti-Cu melt resulted from the solid diffusion between Ti and Cu particles.

Analysis of Aluminum Dust Cloud Combustion Using Flame Emission Spectroscopy

In this study,aluminum flame analysis was researched in order to develop a measurement method for high-energy-density metal aluminum dust cloud combustion,and the flame temperature and UV-VIS-IR emission spectra were precisely measured using a spectrometer.Because the micron-sized aluminum flame temperature was higher than 2 400 K,Flame temperature was measured by a non-contact optical technique,namely,a modified two-color method using 520 and 640nm light,as well as by apolychromatic fitting method.These methods were applied experimentally after accurate calibration.The flame temperature was identified to be higher than 2 400 Kusing both methods.By analyzing the emission spectra,we could identify AlO radicals,which occur dominantly in aluminum combustion.This study paves the way for realization of a measurement technique for aluminum dust cloud combustion flames,and it will be applied in the aluminum combustors that are in development for military purposes.

High-pressure Raman study of MgV_2O_6synthesized at highpressure and high temperature

A new structural phase of MgV2O6 was obtained by a high-pressure, high-temperature （HPHT） synthesis method. The new phase was investigated by the Rietveld analysis of X-ray powder diffraction data, showing space group Pbcn （No. 60） symmetry and a = 13.6113（6）A （1A =0.1 nm）, b = 5.5809（1）A, c = 4.8566（3）A, V = 368.93（2）A3 （Z = 4）. High pressure behavior was studied by Raman spectroscopy at room temperature. Under 22.5 GPa, there was no sign of a structural phase transition in the spectra, demonstrating stability of the HPHT phase up to the highest pressure.

Combustion Synthesis of h-BN-SiC Ceramic Composites

The feasibility was demonstrated to fabricate h-BN-SiC ceramics through combustion synthesis of the mixture of boron carbide and silicon powders under 100 MPa nitrogen pressure. The mass fraction of BN and SiC in the combustion products were found to be 72 % and 28 % respectively. The thermodynamics of the synthesis reaction and the adiabatic combustion temperature were calculated on the theoretical ground. The bending strengths of the ceramics were measured to be 65.2 MPa at room temperature and 55 MPa at 1350℃ The phase composition and microstructure of the combustion products were identified by X-ray diffraction （XRD） and scanning electron microscopy （SEM）.

Preparation of β-SiC by combustion synthesis in a large-scale reactor

The feasibility of 5 kg β-SiC synthesized in one batch was demonstrated through igniting the mixture of Si, C-black and polytetrafluoroethylene （PTFE） under different nitrogen pressures. The effect of experimental parameters, including the contents of PTFE, nitrogen pressure, preheating, and raw materials distribution forms were investigated. The results show that the products are β-SiC with equiaxed grains. The average grain size is less than 200 nm. The powders loaded loosely promote reaction heat dispersing, resulting in small grains. High purity β-SiC powders are obtained when the PTFE content is as low as 5wt%, which simplifies the process and decreases the cost effectively. The ceramic sintered from the obtained β-SiC powders presents the hardness of 22.20 GPa, the bending strength as high as 715.15 MPa and the fracture toughness of 8.179 MPa·m^1/2, which are higher than those of ceramics fabricated with α-SiC produced by combustion synthesis.

Structural Stability of Natural Magnesiochromite at High-Temperature-Pressure Conditions

The podiform chromitites in the Luobusha ophiolite have been thought to experience a very deep formation,but the maximum depth is still an open issue.Here,we have investigated the structural stability of natural magnesiochromite using the synchrotron-based powder X-ray diffraction and diamond anvil cells up to 48.6 GPa and 2450 K.The results have shown that spinel-type magnesiochromite first decomposes into corundum-type‘Cr_(2)O_(3)’+B1-type‘MgO’at 11–14 GPa and 1250–1450 K,then modified ludwigite(mLd)-type‘Mg_(2)Cr_(2)O_(5)’+corundum-type‘Cr_(2)O_(3)’at 14.3–20.5 GPa and 1300–2000 K,and finally CaTi_(2)O_(4)-type phase at 24.5 GPa.During the quenching procession from high-temperature-pressure conditions,the mLd-type phase appeared again and was kept at ambient conditions.We also obtained the isothermal equation states of spinel-type and CaTi_(2)O_(4)-type phases,revealing the composition effect on their elasticities.Based on the updated results,we propose chromitites could not experience pressure exceeding∼14.3 GPa(approximate maximum depth∼400 km)in the subduction-recycling genesis model.

Characteristics of High-Pressure Spray of a Gasoline Direct Injection Injector Under Non-Flash Boiling and Flash Boiling Conditions

The increasingly stringent emission regulations and fuel consumption requirements have elevated the demands of internal combustion engines with higher fuel efficiency and lower emissions.It has been widely demonstrated that fash boiling spray can generate shorter and wider spray with improved atomization and evaporation to promote a better air-fuel mixing process.In this study,macroscopic(far-field)spray morphologies and primary breakup(near-field)characteristics of a two-hole gasoline direct injection injector are investigated under non-flash boiling and flash boiling conditions.High speed macroscopic and microscopic imaging was used to capture the overall spray structure and near-field characteristics,respectively.N-Hexane is used as the test fuel with the injection pressure ranging from 10 MPa up to 40 MPa.For sub-cooled liquid fuel sprays,increasing fuel pressure contributes to enhanced fuel atomization and evaporation.Evident collapses occurred under fare flash boiling conditions,and higher injection pressure weakened this phenomenon since the spray cone angle decreased due to a higher injection velocity.

Experimental study on reactions between alkaline basaltic melt and orthopyroxenes: constraints on the evolution of lithospheric mantle in the North China Craton

The experimental results of the reactions between an alkaline basaltic melt and mantle orthopyroxenes under high-temperature and high-pressure conditions of 1300–1400℃ and 2.0–3.0 GPa using a six-anvil apparatus are reported in this paper.The reactions are proposed to simulate the interactions between melts from the asthenospheric mantle and the lithospheric mantle.The starting melt in the experiments was made from the alkaline basalt occurring in Fuxin,Liaoning Province,and the orthopyroxenes were separated from the mantle xenoliths in Damaping,Hebei Province.The results show that clinopyroxenes were formed in all the reactions between the alkaline basaltic melt and orthopyroxenes under the studied P–T conditions.The formation of clinopyroxene in the reaction zone is mainly controlled by dissolution–crystallization,and the chemical compositions of the reacted melt are primarily infl uenced by the diff usion eff ect.Temperature is the most important parameter controlling the reactions between the melt and orthopyroxenes,which has a direct impact on the melting of orthopyroxenes and the diff usion of chemical components in the melt.Temperature also directly controls the chemical compositions of the newly formed clinopyroxenes in the reaction zone and the reacted melt.The formation of clinopyroxenes from the reactions between the alkaline basaltic melt and orthopyroxenes can result in an increase of CaO and Al_(2)O_(3) contents in the rocks containing this mineral.Therefore,the reactions between the alkaline basaltic melt from the asthenospheric mantle and orthopyroxenes from the lithospheric mantle can lead to the evolution of lithospheric mantle in the North China Craton from refractory to fertile with relatively high CaO and Al 2 O 3 contents.In addition,the reacted melts in some runs were transformed from the starting alkaline basaltic into tholeiitic after reactions,indicating that tholeiitic magma could be generated from alkaline basaltic one via reactions between the latter and orthopyroxene.

Gold solubility in silicate melts and fluids:Advances from high-pressure and high-temperature experiments

The solubility of Au in silicate melts and fluids governs the enrichment and migration of Au during the formation of magmatic-hydrothermal Au deposits.Large Au deposits require vast amounts of Au to migrate from the upper mantle-lower crust to the shallow crust,and high Au solubility in magma and hydrothermal fluid facilitates the formation of Au-rich magma and fluid in the crust and mantle source and efficient transport.This paper reviews recent high-pressure and high-temperature experimental studies on Au species in magmas and hydrothermal fluids,the partitioning behavior of Au between silicate melts and fluids,and the effects of temperature,pressure,oxygen fugacity,sulfur fugacity,silicate melt composition,and volatiles(H2O,CO2,chlorine,and sulfur)on the solubility of Au in magma.We show that the solubility of Au in magma is largely controlled by the volatiles in the magma:the higher the content of reduced sulfur(S2-and HS-)in the magma,the higher the solubility of Au.Under high-temperature,high-pressure,H2O-rich,and intermediate oxygen fugacity conditions,magma can dissolve more reduced sulfur species,thus enhancing the ability of the magma to transport Au.If the ore-forming elements of the Au deposits in the North China Craton originate from mantle-derived magmas and fluids,we can conclude,in terms of massive Au migration,that these deep Au-rich magmas might have been generated under H2 O-rich and moderately oxidized conditions(S2-coexists with S6+).The big mantle wedge beneath East Asia was metasomatized by melts and fluids from the dehydration of the Early Cretaceous paleo-Pacific stagnant slab,which not only caused thinning of the North China Craton,but also created physicochemical conditions favorable for massive Au migration.

Trace element composition in tuite decomposed from natural apatite in high-pressure and high-temperature experiments

Tuite has been suggested as a potential reservoir for trace elements in the deep mantle,but no evidence confirms this supposition.By using a natural apatite as starting material,the trace-element-bearing tuite large crystals were obtained under highpressure and high-temperature conditions(15 GPa and 1800 K).X-ray diffraction pattern and Micro-Raman spectrum of the run product confirm that tuite was synthesized.The concentrations of trace elements in tuite crystals were analyzed by laser ablation-inductively coupled plasma-mass spectrometry(LA-ICP-MS).The rare earth element patterns of tuite show enrichment of light rare earth elements relative to heavy rare earth elements.Tuite shows high concentrations of Th and Sr,and negative anomalies of Rb,Nb,and Hf.The results show that tuite can accommodate a large amount of trace elements.Tuite might be an important host to accommodate trace elements if there is much apatite subducted into the deep mantle.

Recent advance in hollow-core fiber high-temperature and high-pressure sensing technology [Invited]

The pure-silica hollow-core fiber(HCF) has excellent thermostabilities that can benefit a lot of high-temperature sensing applications.The air-core microstructure of the HCF provides an inherent gas container, which can be a good candidate for gas or gas pressure sensing.This paper reviews our continuous efforts to design, fabricate, and characterize the hightemperature and high-pressure sensors with HCFs, aiming at improving the sensing performances such as dynamic range,sensitivity, and linearity.With the breakthrough advances in novel anti-resonant HCFs, sensing of high temperature and high pressure with HCFs will continuously progress and find increasing applications.

High-temperature High-pressure Hydrothermal Synthesis of Dy3＋-doped YNbO4 Single Crystal and Its Luminescence Properties

Single crystal Dy3＋ doped YNbO4phosphors were prepared via a high-temperature high-pressure hydrothermal procedure. Under excitation at 270 nm, the Dy3＋-doped YNbO4 phosphor shows bright white emission, which is composed of two strong bands at 492 and 576 nm corresponding to the characteristic 4F9/2→6H15/2 and aF9/2→6H13/2 transitions of Dy3＋, respectively. The dominant band was observed at 352 nm, which corresponds to the 6H15/2→6p7/2 transition of Dy3＋. Nearly white light was achieved at 2ex 270, 310 and 388 nm and the CIE（International Commission on Illumination） values were （0.3135, 0.3421）, （0.3088, 0.3380） and （0.3146, 0.3296）, respectively.

Mechanism Construction and Simulation for High-temperature Combustion of n-Propylcyclohexane

A detailed mechanism covering 545 species and 3105 reactions for high-temperature combustion of n-propylcyclohexane（n-PCH）, generated via a mechanism generation program（ReaxGen） developed by our research group, was validated in this study. A semi-detailed mechanism involved with 195 species and 573 reactions and a skeletal mechanism concerned with 108 species and 393 reactions were obtained by means of rate-of-production analysis and path flux analysis（PFA）, respectively. In order to validate the reliability of these mechanisms, ignition delay time, laminar flame speed and concentration profiles of important species were simulated with the help of CHEMKIN software. Numerically predicted results of our mechanisms are in very good agreement with available experimental data. Finally, major reaction pathways of n-PCH combustion and important reactions during the combustion process were investigated by reaction pathway analysis and sensitivity analysis, respectively. The results indicate that these mechanisms are reliable for describing the auto-ignition characteristics of n-PCH. These mechanisms would also be helpful to computational fluid dynamics（CFD） for engine design. Moreover, this systematic approach used in our study, which combines mechanism construction, simplification, validation and analysis for n-PCH, may also be employed to construct mechanisms for the high-temperature combustion of other cycloalkanes with one ring.

Quantitative temperature imaging at elevated pressures and in a confined space with CH4/air laminar flames by filtered Rayleigh scattering

Laminar methane/air premixed flames at different pressures in a newly developed high-pressure laminar burner are studied through Cantera simulation and filtered Rayleigh scattering(FRS).Different gas component fractions are obtained through the detailed numerical simulations.And this approach can be used to correct the FRS images of large variations in a Rayleigh cross section in different flame regimes.The temperature distribution above the flat burner is then presented without stray light interference from soot and wall reflection.Results also show that the extent of agreement with the single point measurement by the thermocouple is<6%.Finally,this study concludes that the relative uncertainty of the presented filtered Rayleigh scattering diagnostics is estimated to be below 10%in single-shot imaging.

Development of a simplified n-heptane/methane model for high-pressure direct-injection natural gas marine engines

High-pressure direct-injection (HPDI) of natu- ral gas is one of the most promising solutions for future ship engines, in which the combustion process is mainly controlled by the chemical kinetics. However, the employment of detailed chemical models for the multi-dimensional combustion simulation is significantly expensive due to the large scale of the marine engine. In the present paper, a reduced n-heptane/methane model consisting of 35-step reactions was constructed using multiple reduction approaches. Then this model was further reduced to include only 27 reactions by utilizing the HyChem (Hybrid Chemistry) method. An overall good agreement with the experimentally measured ignition delay data of both n-heptane and methane for these two reduced models was achieved and reasonable predictions for the measured laminar flame speeds were obtained for the 35-step model. But the 27-step model cannot predict the laminar flame speed very well. In addition, these two reduced models were both able to reproduce the experimentally measured in-cylinder pressure and heat release rate profiles for a HPDI natural gas marine engine, the highest error of predicted combustion phase being 6.5%. However, the engine-out CO emission was over-predicted and the highest error of predicted NOx emission was less than 12.9%. The predicted distributions of temperature and equivalence ratio by the 35-step and 27-step models are similar to those of the 334-step model. However, the predicted distributions of OH and CH2O are significantly different from those of the 334-step model. In short, the reduced chemical kinetic models developed provide a high-efficient and dependable method to simulate the characteristics of combustion and emissions in HPDI natural gas marine engines.