Antagonism effect of residual S triggers the dual-path mechanism for water oxidation

Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understanding the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu_(1-x)Co_(x)S as a platform,we explore the regulating effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and operando~(18)O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu_(1-x)Co_(x)S can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu_(0.4)Co_(0.6)S-derived Cu_(0.4)Co_(0.6)OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.

Microdynamic mechanical properties and fracture evolution mechanism of monzogabbro with a true triaxial multilevel disturbance method

The far-field microdynamic disturbance caused by the excavation of deep mineral resources and underground engineering can induce surrounding rock damage in high-stress conditions and even lead to disasters.However,the mechanical properties and damage/fracture evolution mechanisms of deep rock induced by microdynamic disturbance under three-dimensional stress states are unclear.Therefore,a true triaxial multilevel disturbance test method is proposed,which can completely simulate natural geostress,excavation stress redistribution(such as stress unloading,concentration and rotation),and subsequently the microdynamic disturbance triggering damaged rock failure.Based on a dynamic true triaxial test platform,true triaxial microdynamic disturbance tests under different frequency and amplitudes were carried out on monzogabbro.The results show that increasing amplitude or decreasing frequency diminishes the failure strength of monzogabbro.Deformation modulus gradually decreases during disturbance failure.As frequency and amplitude increase,the degradation rate of deformation modulus decreases slightly,disturbance dissipated energy increases significantly,and disturbance deformation anisotropy strengthens obviously.A damage model has been proposed to quantitatively characterize the disturbance-induced damage evolution at different frequency and amplitude under true triaxial stress.Before disturbance failure,the micro-tensile crack mechanism is dominant,and the micro-shear crack mechanism increases significantly at failure.With the increase of amplitude and frequency,the micro-shear crack mechanism increases.When approaching disturbance failure,the acoustic emission fractal dimension changes from a stable value to local large oscillation,and finally increases sharply to a high value at failure.Finally,the disturbance-induced failure mechanism of surrounding rock in deep engineering is clearly elucidated.

Spatio-temporal Evolution of the Rural Regional System and Its Evolution Mechanism in Huang-Huai-Hai Area of China

The problem of rural development arises from the evolution of rural regional system.It is urgent to deepen the research on the evolution process and mechanism of rural regional system.However,there are relatively few studies on rural development from the perspective of the evolution process,driving mechanism and evolution mechanism of rural regional system.Therefore,this study took Huang-Huai-Hai Area for example,started with the systematicness of the rural regional system,the spatio-temporal pattern and driving mechanism of rural regional system evolution,and further summarized and refined the evolution mechanism of the rural regional system.The methods of spatial pattern analysis,gray correlation degree and geographical detection were adopted.The results showed that the problems in rural areas were often dominated by one factor and produced by the joint action of many factors.Factors such as county urbanization,county economy,county public service,agricultural mechanization,surrounding cities and convenient transportation will affect the evolution of rural regional systems.Based on the evolution of the elements in the rural regional system,the evolution types of rural regional system can be divided into decline type,equilibrium type and growth type.This study can provide a reference for understanding the process of rural rise and fall and can also guide rural revitalization and rural sustainable development.

Understanding the boundary and mechanism of gas-induced explosion for lithium-ion cells:Experimental and theoretical analysis

Thermal runaway(TR)of lithium-ion(Li-ion)batteries(LIBs)involves multiple forms of hazards,such as gas venting/jetting,fire,or even explosion.Explosion,as the most extreme case,is caused by the generated flammable gases,and a deflagration to detonation transition(DDT)may occur in this process.Here,overheat-to-TR tests and the corresponding outgas-induced explosion tests were conducted on 42 Ah Li-ion cells with Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O2cathode.The sum of CO_(2),H_(2),C_(2)H_(4),CO,and CH4accounted for more than 90%of the gases.Lower/upper explosion limits(LEL/UEL),laminar flame speed,and ideal stable detonation pressure were calculated to interpret the explosion characteristics and boundary.It turned out that shockwave was easily to be compressed and accelerated under higher state of charge(SOC)conditions.Thus,Li-ion cells explosion may evolve into unstable detonation in encapsulated battery pack and its evolution mechanism was explained,which provides a new idea for explosion-proof design of LIBs system.Additionally,a comprehensive assessment method was developed to intuitively characterize TR hazards.Severity of explosion presented an upward trend with the increase of SOC while the sensitivity was not the same.This study provides a further anatomy of TR,which is instructive to the safety of power battery systems.

Permeability evolution mechanism and the optimum permeability determination of uranium leaching from low-permeability sandstone treated with low-frequency vibration

Low-frequency vibrations can effectively improve natural sandstone permeability,and higher vibration frequency is associated with larger permeability.However,the optimum permeability and permeability evolution mechanism for uranium leaching and the relationship between permeability and the change of chemical reactive rate affecting uranium leaching have not been determined.To solve the above problems,in this study,identical homogeneous sandstone samples were selected to simulate lowpermeability sandstone;a permeability evolution model considering the combined action of vibration stress,pore water pressure,water flow impact force,and chemical erosion was established;and vibration leaching experiments were performed to test the model accuracy.Both the permeability and chemical reactions were found to simultaneously restrict U6þleaching,and the vibration treatment increased the permeability,causing the U6þleaching reaction to no longer be diffusion-constrained but to be primarily controlled by the reaction rate.Changes of the model calculation parameters were further analyzed to determine the permeability evolution mechanism under the influence of vibration and chemical erosion,to prove the correctness of the mechanism according to the experimental results,and to develop a new method for determining the optimum permeability in uranium leaching.The uranium leaching was found to primarily follow a process consisting of(1)a permeability control stage,(2)achieving the optimum permeability,(3)a chemical reactive rate control stage,and(4)a channel flow stage.The resolution of these problems is of great significance for facilitating the application and promotion of lowfrequency vibration in the CO_(2)+O_(2) leaching process.

Light Inducing the Geometric Conversion of NiO_(6) to Trigger a Faster Oxygen Evolution Reaction Pathway:The Coupled Oxygen Evolution Mechanism

Developing highly active and robust oxygen evolution reaction(OER)electrocatalysts is still a critical challenge for water electrolyzers and metal-air batteries.Realizing the dynamic evolution of the intermediate and charge transfer during OER and developing a clear OER mechanism is crucial to design high-performance OER catalysts.Recently in Nature,Xue and colleagues revealed a new OER mechanism,coupled oxygen evolution mechanism(COM),which involves a switchable metal and oxygen redox under light irradiation in nickel oxyhydroxide-based materials.This newly developed mechanism requires a reversible geometric conversion between octahedron(NiO_(6))and square planar(NiO_(4))to achieve electronic states with both“metal redox”and“oxygen redox”during OER.The asymmetric structure endows NR-NiOOH with a nonoverlapping region between the dz^(2) orbitals and a_(1g)^(*)bands,which facilitate the geometric conversion and enact the COM pathway.As a result,NR-NiOOH exhibited better OER activity and stability than the traditional NiOOH.

Recent Advances in the Comprehension and Regulation of Lattice Oxygen Oxidation Mechanism in Oxygen Evolution Reaction

Water electrolysis,a process for producing green hydrogen from renewable energy,plays a crucial role in the transition toward a sustainable energy landscape and the realization of the hydrogen economy.Oxygen evolution reaction(OER)is a critical step in water electrolysis and is often limited by its slow kinetics.Two main mechanisms,namely the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM),are commonly considered in the context of OER.However,designing efficient catalysts based on either the AEM or the LOM remains a topic of debate,and there is no consensus on whether activity and stability are directly related to a certain mechanism.Considering the above,we discuss the characteristics,advantages,and disadvantages of AEM and LOM.Additionally,we provide insights on leveraging the LOM to develop highly active and stable OER catalysts in future.For instance,it is essential to accurately differentiate between reversible and irreversible lattice oxygen redox reactions to elucidate the LOM.Furthermore,we discuss strategies for effectively activating lattice oxygen to achieve controllable steady-state exchange between lattice oxygen and an electrolyte(OH^(-)or H_(2)O).Additionally,we discuss the use of in situ characterization techniques and theoretical calculations as promising avenues for further elucidating the LOM.

Test selection and optimization for PHM based on failure evolution mechanism model

The test selection and optimization （TSO） can improve the abilities of fault diagnosis, prognosis and health-state evalua- tion for prognostics and health management （PHM） systems. Traditionally, TSO mainly focuses on fault detection and isolation, but they cannot provide an effective guide for the design for testability （DFT） to improve the PHM performance level. To solve the problem, a model of TSO for PHM systems is proposed. Firstly, through integrating the characteristics of fault severity and propa- gation time, and analyzing the test timing and sensitivity, a testability model based on failure evolution mechanism model （FEMM） for PHM systems is built up. This model describes the fault evolution- test dependency using the fault-symptom parameter matrix and symptom parameter-test matrix. Secondly, a novel method of in- herent testability analysis for PHM systems is developed based on the above information. Having completed the analysis, a TSO model, whose objective is to maximize fault trackability and mini- mize the test cost, is proposed through inherent testability analysis results, and an adaptive simulated annealing genetic algorithm （ASAGA） is introduced to solve the TSO problem. Finally, a case of a centrifugal pump system is used to verify the feasibility and effectiveness of the proposed models and methods. The results show that the proposed technology is important for PHM systems to select and optimize the test set in order to improve their performance level.

Formation mechanism of calcium hexaluminate

To investigate the formation mechanism of calcium hexaluminate（CaAl_（12）O_（19）, CA_6）, the analytically pure alumina and calcia used as raw materials were mixed in CaO/Al_2O_3 ratio of 12.57：137.43 by mass. The raw materials were ball-milled and shaped into green specimens, and fired at 1300-1600°C. Then, the phase composition and microstructure evolution of the fired specimen were studied, and a first principle calculation was performed. The results show that in the reaction system of CaO and Al_2O_3, a small amount of CA_6 forms at 1300°C, and greater amounts are formed at 1400°C and higher temperatures. The reaction is as follows： CaO ·2Al_2O_3（CA_2） ＋ 4Al_2O_3 → CA_6. The diffusions of Ca^（2＋） in CA_2 towards Al_2O_3 and Al^（3＋） in Al_2O_3 towards CA_2 change the structures in different degrees of difficulty. Compared with the difficulty of structural change and the corresponding lattice energy change, it is deduced that the main formation mechanism is the diffusion of Ca^（2＋） in CA_2 towards Al_2O_3.

Origin, Evolution and Mechanism of the Jehol Fauna

This paper deals with the geographic distribution and geological setting of the Jehol (northeastHebei-southwest Liaoning-southeast Inner Mongolia) fauna, and discusses the origination and the evolution ofits major biological groups. It is demonstrated that the Yan-Liao (northern Hebei-western Liaoning) area is theprovenance for the fauna. Why the fauna originated and developed in the area was intimately related to suchfactors as the palaeoclimate, palaeogeography, crustal movement, volcanism and frequent reversals of magnet-ic polarity at that time, in addition to the internal factors of the organisms themselves.

The Evolution of the Extinction and Growth Mechanism of the Silver Nanoplates

The time-dependence evolution of the extinction spectra of the silver nanoplates is studied to analyze the underlying physical mechanism of the growth process. As the synthesis cycles increase, the wavelength of the absorption peak is first blue-shifted and then is followed by the red shift, attributing to the mode alteration of the longitudinal surface plasmon resonance of the silver nanoplates. The capping agents are also optimized for the convenient and speedy growth of the large integrated Ag nanostructure. These observations expand the comprehensive understanding of plasmon resonance of the Ag nanoplates, and give a better manipulation of their applications in the plasmonie nanodevices.

Stall Evolution Mechanism of a Centrifugal Compressor with a Wide-Long Vaneless Diffuser

The rotating stall mechanism is of high importance for the stability of centrifugal compressors and thermal power cycles.The majority of research concerning this topic has concentrated on the initial stall phase.However,the evolution of stall cells in wide-long diffusers has not been comprehensively studied.In this paper,the causes of rotating stall in the wide-long diffuser and the three-dimensional evolution mechanism of stall cells during the stall process were thoroughly analyzed.During the stall induction phase,an annulus vortex structure was found in the reverse-flow zone near the hub side of the diffuser outlet,which was the initial form of stall cells.The whole evolution process of stall cells was divided into three phases as the flow rate decreased.During the initial stall phase,the dynamic equilibrium was built under effects of the impeller wake and the adverse pressure gradient.As a result,the number of stall cells was kept at seven and the size of stall cells remained constant.During the transition phase,the flow in the diffuser became unstable.Stall cells extended to the impeller outlet,and the effect of the wake flow was strengthened significantly.Stall cells started integrating and separating regularly.As a result,the number and propagation speed of stall cells varied periodically at a constant mass flow rate.During the deep stall phase,the size of stall cells remained unchanged,and the number of stall cells kept at one.This study has important practical guidance and engineering value for the high-efficiency design and safe operation of centrifugal compressors.

Floor stress evolution laws and its effect on stability of floor roadway

According to the distribution of abutment stress in a stope,this research established the mechanical model of mining abutment pressure transmission in floor base on the theory of semi-infnite plate body in elasticity.This study takes the 762 working face of Haizi Coal Mine as a case in point,and analyzed the dynamic evolution law of seam floor stress during the mining process.With an organic combination of the mining floor stress and surrounding rock stress,the study obtained the change laws of the maximum principle stress and the minimum one for the floor roadway surrounding rock when mining the upper working face.Considering the non-constant pressure force state and the cracks revolution mechanisms of floor roadway surrounding rock,the research built the mechanical model of roadway stress.Simulation results verify the reliability of the above conclusions.Moreover,this model could provide the theoretical basis and technical support for controlling floor roadway surrounding rock.

New Knowledge-based Genetic Algorithm for Excavator Boom Structural Optimization

Due to the insufficiency of utilizing knowledge to guide the complex optimal searching, existing genetic algorithms fail to effectively solve excavator boom structural optimization problem. To improve the optimization efficiency and quality, a new knowledge-based real-coded genetic algorithm is proposed. A dual evolution mechanism combining knowledge evolution with genetic algorithm is established to extract, handle and utilize the shallow and deep implicit constraint knowledge to guide the optimal searching of genetic algorithm circularly. Based on this dual evolution mechanism, knowledge evolution and population evolution can be connected by knowledge influence operators to improve the conflgurability of knowledge and genetic operators. Then, the new knowledge-based selection operator, crossover operator and mutation operator are proposed to integrate the optimal process knowledge and domain culture to guide the excavator boom structural optimization. Eight kinds of testing algorithms, which include different genetic operators, arc taken as examples to solve the structural optimization of a medium-sized excavator boom. By comparing the results of optimization, it is shown that the algorithm including all the new knowledge-based genetic operators can more remarkably improve the evolutionary rate and searching ability than other testing algorithms, which demonstrates the effectiveness of knowledge for guiding optimal searching. The proposed knowledge-based genetic algorithm by combining multi-level knowledge evolution with numerical optimization provides a new effective method for solving the complex engineering optimization problem.

Evolution of Microstructure and Mechanical Property during Long-Term Aging in Udimet 720Li

Thermal stabilities of microstructure and mechanical property have been investigated on super- alloy U72OLi, which is of great interest of application for jet engine and land-based turbine disc. The results showed that, the primary and secondary γ’?particles maintain good thermal stability at 650 and 7000C with aging time up to 3000 h, while the tertiary γ’?is apparently dependent on aging temperature and time. The tertiary γ’?particles undergo a procedure of coarsening, dissolution and eventually complete disappearance with the increasing of aging time and temper- ature. They exhibit unusual high sensibility upon aging temperature, which is attributed to the lattice misfit between the γ’?precipitates and the matrix in the alloy. The grain boundary phase M23C6 remains stable without forming of sigma phase even with aging time up to 3000 h at 700℃. Microhardness decreases apparently with increasing aging time and aging temperature. Theoretical analysis based on dislocation mechanism indicates that the change of microhardness should be attributed to the evolution of the tertiary γ’?during aging.

Effects of Heating and Hot Extrusion Process on Microstructure and Properties of Inconel 625 Alloy

The effects of the heating process and hot extrusion on the microstructure and properties of inconel 625 alloy were studied. The experimental results showed that the properties of Inconel 625 alloy could be improved through the heating process and hot extrusion concomitant with a reduced corrosion rate. The M23C6 carbide, generated in the heating process, was retained and distributed at the grain boundary during the process of hot extrusion, which had an important influence on both elongation and corrosion resistance. The improvement of the comprehensive properties of the material, as measured by a tensile test at room temperature, was correlated with the dissolution of segregation Nb. A typical ductile fracture changed to a cleavage fracture where secondary cracks could be clearly seen. With the increase of the extrusion ratio, the real extrusion temperature was higher, which led to more dissolution of the M23C6 carbide, decreased the number of secondary cracks, enhanced the effect of solid solution strengthening, and reduced the intergranular corrosion rate. Under the condition of a high extrusion ratio and a high extrusion speed, the less extrusion time made it possible to obtain organization with a smaller average grain size. Moreover, in this case, the M23C6 carbide and segregated Nb did not have enough time to diffuse. Thus all samples exhibited medium strengths and corrosion rates after extrusion.

An experimental study on fracture mechanical behavior of rock-like materials containing two unparallel fissures under uniaxial compression

Strength and deformability characteristics of rock with pre-existing fissures are governed by cracking behavior. To further research the effects of pre-existing fissures on the mechanical properties and crack coalescence process, a series of uniaxial compression tests were carried out for rock-like material with two unparallel fissures.In the present study, cement, quartz sand, and water were used to fabricate a kind of brittle rock-like material cylindrical model specimen. The mechanical properties of rock-like material specimen used in this research were all in good agreement with the brittle rock materials. Two unparallel fissures（a horizontal fissure and an inclined fissure） were created by inserting steel during molding the model specimen.Then all the pre-fissured rock-like specimens were tested under uniaxial compression by a rock mechanics servocontrolled testing system. The peak strength and Young＇s modulus of pre-fissured specimen all first decreased and then increased when the fissure angle increased from 0？to 75？.In order to investigate the crack initiation, propagation and coalescence process, photographic monitoring was adopted to capture images during the entire deformation process.Moreover, acoustic emission（AE） monitoring technique was also used to obtain the AE evolution characteristic of prefissured specimen. The relationship between axial stress, AE events, and the crack coalescence process was set up： when a new crack was initiated or a crack coalescence occurred, thecorresponding axial stress dropped in the axial stress–time curve and a big AE event could be observed simultaneously.Finally, the mechanism of crack propagation under microscopic observation was discussed. These experimental results are expected to increase the understanding of the strength failure behavior and the cracking mechanism of rock containing unparallel fissures.

SEMI-SOLID MICROSTRUCTURE AND ITS EVOLUTION OF WROUGHT ALUMINUM ALLOY BY DIRECTLYHEATING-ISOTHERMAL TREATMENT

Microstructure evolution of wrought aluminum alloy extruded rods and the mechanism of liquid phase formation during reheating were investigated. And the relation between the volume fraction of liquid phase and the recrystallization microstructure was proposed. The results show that increase in reheating temperature and time can augment the volume fraction of liquid phase and accelerate the grain spheroidization, as a result of which the requirement of semi-solid forming can be satisfied. Due to the higher aberration energy of grain boundary, the melting point is lowered as a result of the easy diffusion of atoms. At higher reheating temperature the grain boundary melts, the growth of the recrystallized grain is inhibited and the grain is refined. The composition of the low melt-point phase along the recrystallized grains was determined using EDS. It can be seen from the experimental results that when the extrusion rod of the wrought aluminum alloy is reheated at 610℃ for 20min, perfect fine equiaxial grains can be obtained, the average grain size is about 66.34μm and the volume fraction of solid phase is about 68%.

Mechanically Driven Alloying and Structural Evolution of Nanocrystalline Fe_(60)Cu_(40) Powder

Highly supersaturated nanocrystalline fcc Fe60Cu40 alloy has been prepared by mechanical alloying of elemental powders. The phase transformation is monitored by X-ray diffraction (XRD),Mossbauer spectroscopy and extended X-ray absorption fine structure (EXAFS). The powder obtained after milling is of single fcc structure with grain size of nanometer order. The Mossbauer spectra of the milled powder can be fitted by two subspectra whose hyperfine magnetic fields are 16 MA/m and 20 MA/m while that of pure Fe disappeared. EXAFS results show that the radial structure function (RSF) of Fe K-edge changed drastically and finally became similar to that of reference Cu K-edge, while that of Cu K-edge nearly keeps unchanged in the process of milling. These imply that bcc Fe really transforms to fcc structure and alloying between Fe and Cu occurs truly on an atomic scale. EXAFS results indicate that iron atoms tend to segregate at the boundaries and Cu atoms are rich in the fcc lattice. Annealing experiments show that the Fe atoms at the interfaces are easy to cluster to α-Fe at a lower temperature, whereas the iron atoms in the lattice will form γ-Fe first at temperature above 350℃, and then transform to bcc Fe

Microstructure and mechanical properties of reaction-bonded B_(4)C–SiC composites

Reaction-bonded B_(4)C–SiC composites are highly promising materials for numerous advanced technological applications.However,their microstructure evolution mechanism remains unclear.Herein,B_(4)C–SiC composites were fabricated through the Si-melt infiltration process.The influences of the sintering time and the B_(4)C content on the mechanical properties,microstructure,and phase evolution were investigated.X-ray diffraction results showed the presence of SiC,boron silicon,boron silicon carbide,and boron carbide.Scanning electron microscopy results showed that with the increase in the boron carbide content,the Si content decreased and the unreacted B_(4)C amount increased when the sintering temperature reached 1650°C and the sintering time reached 1 h.The unreacted B_(4)C diminished with increasing sintering time and temperature when B_(4)C content was lower than 35wt%.Further microstructure analysis showed a transition area between B_(4)C and Si,with the C content marginally higher than in the Si area.This indicates that after the silicon infiltration,the diffusion mechanism was the primary sintering mechanism of the composites.As the diffusion process progressed,the hardness increased.The maximum values of the Vickers hardness,flexural strength,and fracture toughness of the reaction-bonded B_(4)C–SiC ceramic composite with 12wt%B_(4)C content sintered at 1600°C for 0.5 h were about HV 2400,330 MPa,and 5.2 MPa·m^(0.5),respectively.