Enhancing layered perovskite ferrites with ultra-high-density nanoparticles via cobalt doping for ceramic fuel cell anode

Nanoparticles anchored on the perovskite surface have gained considerable attention for their wide-ranging applications in heterogeneous catalysis and energy conversion due to their robust and integrated structural configuration.Herein,we employ controlled Co doping to effectively enhance the nanoparticle exsolution process in layered perovskite ferrites materials.CoFe alloy nanoparticles with ultra-high-density are exsolved on the(PrBa)_(0.95)(Fe_(0.8)Co_(0.1)Nb_(0.1))2O_(5+δ)(PBFCN_(0.1))surface under reducing atmosphere,providing significant amounts of reaction sites and good durability for hydrocarbon catalysis.Under a reducing atmosphere,cobalt facilitates the reduction of iron cations within PBFCN_(0.1),leading to the formation of CoFe alloy nanoparticles.This formation is accompanied by a cation exchange process,wherein,with the increase in temperature,partial cobalt ions are substituted by iron.Meanwhile,Co doping significantly enhance the electrical conductivity due to the stronger covalency of the Cosingle bondO bond compared with Fesingle bondO bond.A single cell with the configuration of PBFCN_(0.1)-Sm_(0.2)Ce_(0.8)O_(1.9)(SDC)|SDC|Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3−δ)(BSCF)-SDC achieves an extremely low polarization resistance of 0.0163Ωcm^(2)and a high peak power density of 740 mW cm^(−2)at 800℃.The cell also shows stable operation for 120 h in H_(2)with a constant current density of 285 mA cm^(−2).Furthermore,employing wet C_(2)H_(6)as fuel,the cell demonstrates remarkable performance,achieving peak power densities of 455 mW cm^(−2)at 800℃and 320 mW cm^(−2)at 750℃,marking improvements of 36%and 70%over the cell with(PrBa)_(0.95)(Fe_(0.9)Nb_(0.1))_(2)O_(5+δ)(PBFN)-SDC at these respective temperatures.This discovery emphasizes how temperature influences alloy nanoparticles exsolution within doped layered perovskite ferrites materials,paving the way for the development of high-performance ceramic fuel cell anodes.

A novel box-counting method for quantitative fractal analysis of threedimensional pore characteristics in sandstone

Fractal theory offers a powerful tool for the precise description and quantification of the complex pore structures in reservoir rocks,crucial for understanding the storage and migration characteristics of media within these rocks.Faced with the challenge of calculating the three-dimensional fractal dimensions of rock porosity,this study proposes an innovative computational process that directly calculates the three-dimensional fractal dimensions from a geometric perspective.By employing a composite denoising approach that integrates Fourier transform(FT)and wavelet transform(WT),coupled with multimodal pore extraction techniques such as threshold segmentation,top-hat transformation,and membrane enhancement,we successfully crafted accurate digital rock models.The improved box-counting method was then applied to analyze the voxel data of these digital rocks,accurately calculating the fractal dimensions of the rock pore distribution.Further numerical simulations of permeability experiments were conducted to explore the physical correlations between the rock pore fractal dimensions,porosity,and absolute permeability.The results reveal that rocks with higher fractal dimensions exhibit more complex pore connectivity pathways and a wider,more uneven pore distribution,suggesting that the ideal rock samples should possess lower fractal dimensions and higher effective porosity rates to achieve optimal fluid transmission properties.The methodology and conclusions of this study provide new tools and insights for the quantitative analysis of complex pores in rocks and contribute to the exploration of the fractal transport properties of media within rocks.

3D digital-image correlation insight into generalized relaxation behavior of sandstone under stress and pore pressure coupling

The occurrence of geological hazards and the instability of geotechnical engineering structures are closely related to the time-dependent behavior of rock.However,the idealization boundary condition for constant stress in creep or constant strain in relaxation is not usually attained in natural geological systems.Therefore,generalized relaxation tests that explore the simultaneous changes of stress and strain with time under different stress levels with constant pore-water pressure are conducted in this study.The results show that in area Ⅰ,area Ⅱ,and area Ⅲ,the stress and strain both change synchronously with time and show similar evolutionary laws as the strain-time curve for creep or the stress-time curve for relaxation.When the applied stress level surpasses the δ_(ci) or δ_(cd) threshold,the variations in stress and strain and their respective rates of change exhibit a significant increase.The radial deformation and its rate of change exhibit greater sensitivity in response to stress levels.The apparent strain deforms homogeneously at the primary stage,and subsequently,gradually localizes due to the microcrack development at the secondary stage.Ultimately,interconnection of the microcracks causes the formation of a shear-localization zone at the tertiary stage.The strain-time responses inside and outside the localization zone are characterized by local strain accumulation and inelastic unloading during the secondary and tertiary stages,respectively.The width of the shear-localization zone is found to range from 4.43 mm to 7.08 mm and increased with a longer time-to-failure.Scanning electron microscopy(SEM)reveals a dominant coalescence of intergranular cracks on the fracture surface,and the degree of physiochemical deterioration caused by water-rock interaction is more severe under a longer lifetime.The brittle sandstone’s time-dependent deformation is essentially controlled by microcrack development during generalized relaxation,and its expectancy-life is determined by its initial microstructural state and the rheological path.

Dynamic mechanical characteristics of deep Jinping marble in complex stress environments

To reveal the dynamic mechanical characteristics of deep rocks,a series of impact tests under triaxial static stress states corresponding to depths of 300-2400 m were conducted.The results showed that both the strain rates and the stress environments in depth significantly affect the mechanical characteristics of rocks.The sensitivity of strain rate to the dynamic strength and deformation modulus shows a negative correlation with depth,indicating that producing penetrative cracks in deep environments is more difficult when damage occurs.The dynamic strength shows a tendency to decrease and then increase slightly,but decreases sharply finally.Transmissivity demonstrates a similar trend as that of strength,whereas reflectivity indicates the opposite trend.Furthermore,two critical depths with high dynamically induced hazard possibilities based on the China Jinping Underground Laboratory(CJPL)were proposed for deep engineering.The first critical depth is 600-900 m,beyond which the sensitivity of rock dynamic characteristics to the strain rate and restraint of circumferential stress decrease,causing instability of surrounding rocks under axial stress condition.The second one lies at 1500-1800 m,where the wave impedance and dynamic strength of deep surrounding rocks drop sharply,and the dissipation energy presents a negative value.It suggests that the dynamic instability of deep surrounding rocks can be divided into dynamic load dominant and dynamic load induced types,depending on the second critical depth.

Preliminary research and scheme design of deep underground in situ geo-information detection experiment for Geology in Time

The deep earth,deep sea,and deep space are the main parts of the national“three deep”strategy,which is in the forefront of the strategic deployment clearly defined in China’s 14th Five-Year Plan(2021-2025)and the Long-Range Objectives Through the Year 2035.It is important to reveal the evolutionary process and mechanism of deep tectonics to understand the earth’s past,present and future.The academic con-notation of Geology in Time has been given for the first time,which refers to the multi-field evolution response process of geological bodies at different time and spatial scales caused by geological processes inside and outside the Earth.Based on the deep in situ detection space and the unique geological envi-ronment of China Jinping Underground Laboratory,the scientific issue of the correlation mechanism and law between deep internal time-varying and shallow geological response is given attention.Innovative research and frontier exploration on deep underground in situ geo-information detection experiments for Geology in Time are designed to be carried out,which will have the potential to explore the driving force of Geology in Time,reveal essential laws of deep earth science,and explore innovative technologies in deep underground engineering.

Deep sea mineral resources and underground space as well as infrastructure for sustainable and liveable cities

This issue covers the papers on two special themes:(1)Mineral resources from deep sea—Science and Engineering and(2)Planning and development of underground space and infrastructure for sustainable and liveable cities.

Geothermal energy for sustainable and green energy supply in the future

Deep Underground Science and Engineering(DUSE)publishes this special issue on geothermal energy.The guest editors of this special issue are Prof.Ranjith Pathegama Gamage(Monash University,Australia),Prof.Zhongwei Huang(China University of Petroleum,Beijing,China),and Prof.Bing Bai(Institute of Rock and Soil Mechanics,Chinese Academy of Sciences,Wuhan,China).Geothermal energy is one sustainable and renewable energy and currently a hot research topic in research and development.Geothermal energy supply is one of the long-term efforts for carbon footprint reductions to tackle climate change issues.The development of geothermal energy includes exploration and extraction processes.This special issue is to highlight the challenges on the exploration and extraction of geothermal energy such as initial high cost and difficulties in heat extraction from deep underground.This special issue focuses on new geothermal extraction system,new theory,new technology,new application of latest techniques such as artificial intelligence,and potential environmental effects.

Size effect of fracture characteristics for anisotropic quasi-brittle geomaterials

Understanding the size effect exhibited by the fracture mechanism of anisotropic geomaterials is important for engineering practice. In this study, the anisotropic features of the nominal strength, apparent fracture toughness, effective fracture energy and fracture process zone(FPZ) size of geomaterials were first analyzed by systematic size effect fracture experiments. The results showed that the nominal strength and the apparent fracture toughness decreased with increasing bedding plane inclination angle.The larger the specimen size was, the smaller the nominal strength and the larger the apparent fracture toughness was. When the bedding inclination angle increased from 0° to 90°, the effective fracture energy and the effective FPZ size both first decreased and then increased within two complex variation stages that were bounded by the 45° bedding angle. Regardless of the inherent anisotropy of geomaterials,the nominal strength and apparent fracture toughness can be predicted by the energy-based size effect law, which demonstrates that geomaterials have obvious quasi-brittle characteristics. Theoretical analysis indicated that the true fracture toughness and energy dissipation can be calculated by linear elastic fracture mechanics only when the brittleness number is higher than 10;otherwise, size effect tests should be adopted to determine the fracture parameters.

Design and development of the deep-rock in-situ condition-preserved coring calibration platform

To systematically validate and calibrate the theory and technology of the deep in-situ conditionpreserved coring, the in-situ conditions at different depths should be simulated, and the full-size coring tests should be carried out in this simulated environment. Therefore, a deep-rock in-situ conditionpreserved coring calibration platform was designed and developed. The self-tightening sealing structure and the quick-disassembly structure were designed on the basis of an innovative segmented nonuniformdiameter structure, which was a breakthrough from the traditional high-pressure vessel frame and was verified by finite element simulation and actual testing under extreme working conditions, respectively.To simulate the actual deep in-situ environment with a temperature of 150℃ and pressure of 140 MPa for a large Φ450 mm×H1400 mm core, temperature and pressure control systems were designed by coupling, and a pre-embedded high-pressure-resistant temperature sensor was designed. Finally, highprecision assembly automation, complex movement coordination of the coring device with the platform,and rotary dynamic sealing were achieved by utilizing the combination of adaptive cabin body servo control and an adaptive mechanical structure in a limited space, laying a solid foundation for the calibration of in-situ condition-preserved coring.

Numerical analysis on mechanical difference of sandstone under in-situ stress,pore pressure preserved environment at depth

Deep in-situ rock mechanics considers the influence of the in-situ environment on mechanical properties,differentiating it from traditional rock mechanics.To investigate the effect of in-situ stress,pore pressure preserved environment on the mechanical difference of sandstone,four tests are numerically modeled by COMSOL:conventional triaxial test,conventional pore pressure test,in-situ stress restoration and reconstruction test,and in-situ pore pressure-preserved test(not yet realized in the laboratory).The in-situ stress restoration parameter is introduced to characterize the recovery effect of in-situ stress on elastic modulus and heterogeneous distribution of sandstone at different depths.A random function and nonuniform pore pressure coefficient are employed to describe the non-uniform distribution of pore pressure in the in-situ environment.Numerical results are compared with existing experimental data to validate the models and calibrate the numerical parameters.By extracting mechanical parameters from numerical cores,the stress-strain curves of the four tests under different depths,in-situ stress and pore pressure are compared.The influence of non-uniform pore pressure coefficient and depth on the peak strength of sandstone is analyzed.The results show a strong linear relationship between the in-situ stress restoration parameter and depth,effectively characterizing the enhanced effect of stress restoration and reconstruction methods on the elastic modulus of conventional cores at different depths.The in-situ pore pressurepreserved test exhibits lower peak stress and peak strain compared to the other three tests,and sandstone subjected to non-uniform pore pressure is more prone to plastic damage and failure.Moreover,the influence of non-uniform pore pressure on peak strength gradually diminished with increasing depth.

A novel fractal-statistical scaling model of rocks considering strain rate

The scaling-dependent behaviors of rocks are significant to the stability and safe operation of the structures built in or on rock masses for practical engineering.Currently,many size effect models are employed to connect laboratory measurements at small scales and engineering applications at large scales.However,limited works consider the strain rate effect.In this study,an fractal-statistical scaling model incorporating strain rate is proposed based on a weakest-link approach,fractal theory and dynamic fracture mechanics.The proposed scaling model consists of 8 model parameters with physical meaning,i.e.rate-dependent parameter,intrinsic material parameter,dynamic strain rate,quasi-static strain rate,quasi-static fracture toughness,micro-crack size,micro-crack intensity and fractal dimension,enabling the proposed scaling model to model the scaling behaviors under different external conditions.Theoretical predictions are consistent with experimental data on red sandstone,proving the reliability and effectiveness of the proposed scaling model.Thus,the scaling behaviors of rocks under dynamic loading conditions can be captured by the proposed fractal-statistical scaling model.The sensitivity analysis indicates that the nominal strength difference becomes more obvious with a higher strain rate,larger fractal dimension,smaller micro-crack size or lower micro-crack intensity.Therefore,the proposed scaling model has the potential to capture the scaling behaviors considering the thermal effect,weathering effect,anisotropic characteristic etc.,as the proposed scaling model incorporated model parameters with physical meaning.The findings of this study are of fundamental importance to understand the scaling behaviors of rock under dynamic loading condition,and thus would facilitate the appropriate design of rock engineering.

Research progress and application of deep in-situ condition preserved coring and testing

With the depletion of shallow resources,the exploration of deep earth resources has become a global strategy.The study of the different patterns in the physical mechanical properties of rocks at different occurrence depths is the basis for exploring deep into the earth,with the core and premise being the acquisition and testing of deep in-situ core specimens.Based on the original idea of deep in-situ condition preserved coring(ICP-Coring)and testing,combined with theoretical modeling,numerical analysis,test platform development,indoor testing and engineering application,the principles and technologies of deep ICP-Coring are developed.This principle and technology consists of five parts:in-situ pressurepreserved coring(IPP-Coring),in-situ substance-preserved coring(ISP-Coring),in-situ temperaturepreserved coring(ITP-Coring),in-situ light-preserved coring(ILP-Coring),and in-situ moisturepreserved coring(IMP-Coring).The theory and technology of temperature and pressure reconstruction at different occurrence depths and in different environments are proposed,and prototype trial production was completed by following the principle of displacement and tests based on the in-situ reconstructed environment.The notable advances are as follows:(1)Deep in-situ coring system:A pressure-preserved controller with an ultimate bearing capacity greater than 140 MPa,highperformance(temperature-resistant,pressure-resistant,and low thermally conductive)temperaturepreserved materials,an active temperature control system,and high-barrier quality-preserved membrane materials were developed;a deep ICP-Coring capacity calibration platform was independently developed,a deep in-situ coring technology system was developed,and the acquisition of deep in-situ cores was realized.(2)In-situ storage displacement system:Following the dual-circuit hydraulic design idea,a single-drive source push-pull composite grabbing mechanism was designed;the design of the overall structure for the deep in-situ displacement storage system and ultrahigh pressure cabin structure was completed,which could realize docking the coring device and core displacement in the in-situ reconstructed environment.(3)Test analysis system:A noncontact acoustic-electric-magnetic test system was developed under the in-situ reconstructed environment,and the errors between the test results and traditional contact test results were mostly less than 10%;a detachable deep in-situ core true triaxial test system was developed,which could perform loading tests for deep in-situ cores.The relevant technological achievements were successfully applied to the exploration and development of deep resources,such as deep mines,deep-sea natural gas hydrates,and deep oil and gas.The research results provide technical and equipment support for the construction of a theoretical system for deep in-situ rock mechanics,the development of deep earth resources and energy,and the scientific exploration of different layers and occurrence depths(deep and ultradeep)of the Earth.

Study of a low-disturbance pressure-preserving corer and its coring performance in deep coal mining conditions

With the increasing depth of coal mining,the requirements for coring devices that maintain pressure are increasing.To adapt to the special environment in deep coal seams and improve the accuracy of testing gas content,a low-disturbance pressure-preserving corer was developed.The measurement of gas content using this corer was analyzed.The coring test platform was used to complete a coring function test.A pressurized core with a diameter of 50 mm was obtained.The pressure was 0.15 MPa,which was equal to the pressure of the liquid column of the cored layer,indicating that the corer can be successfully used in a mud environment.Next,a pressure test of the corer was conducted.The results showed that under conditions of low pressure(8 MPa)and high pressure(25 MPa),the internal pressure of the corer remained stable for more than 1 h,indicating that the corer has good ability to maintain pressure.Therefore,the corer can be applied at deep coal mine sites.The results of this research can be used to promote the safe exploitation of deep coal mines and the exploitation of methane resources in coalbeds.

Development of a pressure coring system for the investigation of deep underground exploration

To provide a more accurate evaluation of the scale of deep underground resources,a new pressure coring system was carefully developed and its strength and safety of the engineering were verified by theoretical analyses and numerical simulation.The designed pressure coring system can obtain cores with length of 3 m and diameter of 50 mm at 70 MPa.The results of the ball-drop operation experiment demonstrate that differential motion assembly can effectively cut a safety pin by applying a tensile force of 4852 N,and it can lift the core tube through the center pole to complete a series of mechanical actions to seal the pressure.Additionally,by maintaining pressures at 70 MPa for 30 min,the pressure sealing capacity of the system was proven.Furthermore,a core sample with a diameter of 50 mm was obtained through a core drilling experiment and the coring performance of the pressure coring system was verified.This study can not only enrich the existing onshore coring technology but also provide a theoretical guide and design criteria for the development of similar pressure coring systems to meet the demand for deeper underground exploration.

Direct measurement and theoretical prediction model of interparticle adhesion force between irregular planetary regolith particles

Interparticle adhesion force has a controlling effect on the physical and mechanical properties of planetary regolith and rocks.The current research on the adhesion force of planetary regolith and rock particles has been primarily based on the assumption of smooth spherical particles to calculate the intergranular adhesion force;this approach lacks consideration for the adhesion force between irregular shaped particles.In our study,an innovative approach was established to directly measure the adhesion force between the arbitrary irregular shaped particles;the probe was modified using simulated lunar soil particles that were a typical representation of planetary regolith.The experimental results showed that for irregular shaped mineral particles,the particle size and mineral composition had no significant influence on the interparticle adhesion force;however,the complex morphology of the contact surface predominantly controlled the adhesion force.As the contact surface roughness increased,the adhesion force gradually decreased,and the rate of decrease gradually slowed;these results were consistent with the change trend predicted via the theoretical models of quantum electrodynamics.Moreover,a theoretical model to predict the adhesion force between the irregular shaped particles was constructed based on Rabinovich’s theory,and the prediction results were correlated with the experimental measurements.

A graphene-enhanced high-barrier and fast-curing film for deep in situ condition preserved coring in coal seams

Scientific research on deep in situ resources is highly important to the theory and technology system construction for deep in-situ resource exploitation.To obtain high-condition preserved core samples,it is vital to maintain the original material,humidity and luminous flux information inside the core.Therefore,this study proposes a research and development strategy for a high-toughness and highbarrier sealing film based on the molecular structure design and filler synergistic enhancement via a deep solid-state sealing film using in situ substance preservation(ISP),in situ moisture preservation(IMP)and in situ light preservation(ILP)coring principles.A graphene/epoxy composite sealing film with a high barrier,high strength and high toughness was developed.The oxygen permeability of the film was 0.23 cm^(3)/(m^(2)·d),the water vapor permeability was 1.26 g/(m^(2)·d),and the light transmittance was 0.The tensile strength reached 15.4 MPa,and the toughness was 5242.9 kJ/m^(3).The results from the film substance and moisture preservation performance verification experiments showed that the sealing film had an excellent sealing effect on small molecules,such as water,alkanes and even ions,which further verified that the sealing film greatly contributed to the maintenance and preservation of deep in-situ resource reserves and abundance.

New understandings on initiation and evolution of disasters in deep underground

The editors wish to highlight the articles appearing in this issue.The first article,entitled“New physics of supersonic ruptures”by Boris G.Tarasov,concerns the development of a new theory on the potential occurrence of ruptures after deep underground earthquakes.Two other articles belong to our first special theme of“Disaster evolution in deep underground.”The final two articles introduce a nonlocal damage fracture phasefield model for rock‐like materials and the gas–liquid displacement in microcleats for mass transfer through gas‐or water‐driven displacement.These five papers indeed explore various aspects of deep underground science and engineering and constitute an integral component of deep underground fundamentals.

A research on excavation compensation theory for large deformation disaster control and a review on the multiphysical-multiscale responses of salt rock for underground gas storage

We highlight two articles in this issue:A research article titled“Excavation compensation theory and supplementary technology system for large deformation disasters”by Manchao He et al.and a review article titled“Mineralogy,microstructures and geomechanics of rock salt for underground gas storage”by Veerle Vandeginste et al.

Editorial highlights

With the increasing scarcity of shallow resources,the mining depth of coal mines has gradually increased,and the safety problem has become increasingly prominent.The grouting technology for deep roadways in fractured rocks is one of key technologies for safe mining of deep resources.This paper by the team of Hongpu Kang,academician of the Chinese Academy of Engineering,systematically summarizes and analyzes the research findings in the theory,design,materials,processes,and equipment for the grouting reinforcement of fractured rocks surrounding the deep roadways.Several field cases in the Kouzidong coal mine are demonstrated on the application of pregrouting in front of heading faces,grouting in excavation,and postgrouting so as to evaluate the effects of these grouting reinforcements.

Mechanical behavior of coal under different mining rates:A case study from laboratory experiments to field testing

During the development of hot dry rock,the research on thermal fatigue damage caused by thermal shock of cold and heat cycles is the basis that ensures the long-term utilization of geothermal resources,but there are not enough relevant studies at present.Based on this,the thermal damage tests of granite at different temperatures(250,350,450°C)and quenching cycles(1,5,10,15 cycles)were carried out.Preliminary reveals the damage mechanism and heat transfer law of the quenching cycle effect on hot dry rock.The results show that with the increase of temperature and cycles,the uneven thermal expansion of minerals and the thermal shock caused by quenching promote the crack development of granite,resulting in the decrease of P-wave velocity,thermal conductivity and uniaxial compressive strength of granite.Meanwhile,the COMSOL was used to simulate the heat transfer of hot dry rock under different heat treatment conditions.It concluded that the increase in the number of quenching cycles reduced the heat transfer capacity of the granite,especially more than 10 quenching cycles,which also reflects that the thermal fatigue damage leads to a longer time for the temperature recovery of the hot dry rock mass.In addition,the three-dimensional nonlinear fitting relationship among thermal conductivity,temperature and cycle number was established for the first time,which can better reveal the change rule of thermal conductivity after quenching thermal fatigue effect of hot dry rock.The research results provide theoretical support for hot dry rock reservoir reconstruction and production efficiency evaluation.