In combination with theoretical calculations,experiments were conducted to investigate the evolution behavior of nonmetallic inclusions(NMIs)during the manufacture of large-scale heat-resistant steel ingots using 9CrM...In combination with theoretical calculations,experiments were conducted to investigate the evolution behavior of nonmetallic inclusions(NMIs)during the manufacture of large-scale heat-resistant steel ingots using 9CrMoCoB heat-resistant steel and CaF_(2)–CaO–Al_(2)O_(3)–SiO_(2)–B_(2)O_(3)electroslag remelting(ESR)-type slag in an 80-t industrial ESR furnace.The main types of NMI in the consumable electrode comprised pure alumina,a multiphase oxide consisting of an Al_(2)O_(3)core and liquid CaO–Al_(2)O_(3)–SiO_(2)–MnO shell,and M_(23)C_(6)carbides with an MnS core.The Al_(2)O_(3)and MnS inclusions had higher precipitation temperatures than the M_(23)C_(6)-type carbide under equilibrium and nonequilibrium solidification processes.Therefore,inclusions can act as nucleation sites for carbide layer precipitation.The ESR process completely removed the liquid CaO–Al_(2)O_(3)–SiO_(2)–MnO oxide and MnS inclusion with a carbide shell,and only the Al_(2)O_(3)inclusions and Al_(2)O_(3)core with a carbide shell occupied the remelted ingot.The M_(23)C_(6)-type carbides in steel were determined as Cr_(23)C_(6)based on the analysis of transmission electron microscopy results.The substitution of Cr with W,Fe,or/and Mo in the Cr_(23)C_(6)lattice caused slight changes in the lattice parameter of the Cr_(23)C_(6)carbide.Therefore,Cr_(21.34)Fe_(1.66)C_(6),(Cr_(19)W_(4)C_(6),Cr_(18.4)Mo_(4.6)C_(6),and Cr_(16)Fe_(5)Mo_(2)C_(6)can match the fraction pattern of Cr_(23)C_(6)carbide.The Al_(2)O_(3)inclusions in the remelted ingot formed due to the reduction of CaO,SiO_(2),and MnO components in the liquid inclusion.The increased Al content in liquid steel or the higher supersaturation degree of Al_(2)O_(3)precipitation in the remelted ingot than that in the electrode can be attributed to the evaporation of CaF_(2)and the increase in CaO content in the ESR-type slag.展开更多
The microstructural evolution and phase transformations during partial remelting of in-situ Mg2Sip/AM60B composite modified by SiC and Sr were investigated. The results indicate that SiC and Sr are effective for refi...The microstructural evolution and phase transformations during partial remelting of in-situ Mg2Sip/AM60B composite modified by SiC and Sr were investigated. The results indicate that SiC and Sr are effective for refining primary α-Mg grains and Mg2Si particles. After being partially remelted, a semisolid microstructure with small and spheroidal primary α-Mg particles can be obtained. The microstructural evolution during partial remelting can be divided into four stages: the initial rapid coarsening, structural separation, spheroidization and final coarsening, which are essentially caused by the phase transformations of β→α, α+β→L and α→L, α→L, and α→L and L→α, respectively. The Mg2Si particles have not obvious effect on the general microstructural evolution steps, but can slower the evolution progress and change the coarsening mechanism. During partial remelting, Mg2Si particles first become blunt and then become spheroidal because of melting of their edges and corners, and finally are coarsened owing to Ostwald ripening.展开更多
The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistenc...The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistence theory.The study focused on the effects of slag composition and deoxidizer type on the oxygen content of low alloy steel during the electroslag remelting(ESR)process.The measured and predicted values of the oxygen content in remelted ingots,and the contents of FeO and MnO in slags were compared and analyzed.Results show that the measured content of total oxygen has a certain correlation with the trend of dissolved oxygen predicted by the model when using Ca-Si alloys as deoxidizer,but it is not correlated with the trend of dissolved oxygen predicted by the model when using Al as deoxidizer.The deoxidation mechanisms of Ca-Si and Al are different.Ca-Si alloy directly reacts with FeO and MnO in slag to reduce the oxygen potential of slag,hence it can inhibit the transfer of oxygen from the slag to molten steel.While,when Al deoxidizer is used,the oxygen content in steel is mainly reduced through floating up the alumina inclusions.Compared to Al,utilizing Ca-Si alloy as a deoxidizer is more effective in reducing the oxygen content and the amount of inclusions in ESR ingot.展开更多
It has always been challenging work to reconcile the contradiction between the strength and plasticity of titanium materials.Laser powder bed fusion(LPBF) is a convenient method to fabricate innovative composites incl...It has always been challenging work to reconcile the contradiction between the strength and plasticity of titanium materials.Laser powder bed fusion(LPBF) is a convenient method to fabricate innovative composites including those inspired by gradient layered materials.In this work,we used LPBF to selectively prepare Ti N/Ti gradient layered structure(GLSTi)composites by using different N_(2)–Ar ratios during the LPBF process.We systematically investigated the mechanisms of in-situ synthesis Ti N,high strength and ductility of GLSTi composites using microscopic analysis,TEM characterization,and tensile testing with digital image correlation.Besides,a digital correspondence was established between the N_(2) concentration and the volume fraction of LPBF in-situ synthesized Ti N.Our results show that the GLSTi composites exhibit superior mechanical properties compared to pure titanium fabricated by LPBF under pure Ar.Specifically,the tensile strength of GLSTi was more than 1.5times higher than that of LPBF-formed pure titanium,reaching up to 1100 MPa,while maintaining a high elongation at fracture of 17%.GLSTi breaks the bottleneck of high strength but low ductility exhibited by conventional nanoceramic particle-strengthened titanium matrix composites,and the hetero-deformation induced strengthening effect formed by the Ti N/Ti layered structure explained its strength-plasticity balanced principle.The microhardness exhibits a jagged variation of the relatively low hardness of 245 HV0.2 for the pure titanium layer and a high hardness of 408 HV0.2 for the N_(2) in-situ synthesis layer.Our study provides a new concept for the structure-performance digital customization of 3D-printed Ti-based composites.展开更多
The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined ...The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.展开更多
This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualis...This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.展开更多
The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poo...The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.展开更多
Conservation programs require rigorous evaluation to ensure the preservation of genetic diversity and viability of conservation populations. In this study, we conducted a comparative analysis of two indigenous Chinese...Conservation programs require rigorous evaluation to ensure the preservation of genetic diversity and viability of conservation populations. In this study, we conducted a comparative analysis of two indigenous Chinese chicken breeds, Gushi and Xichuan black-bone, using whole-genome SNPs to understand their genetic diversity, track changes over time and population structure. The breeds were divided into five conservation populations(GS1, 2010, ex-situ;GS2, 2019, ex-situ;GS3, 2019, in-situ;XB1, 2010, in-situ;and XB2, 2019, in-situ) based on conservation methods and generations. The genetic diversity indices of three conservation populations of Gushi chicken showed consistent trends, with the GS3 population under in-situ strategy having the highest diversity and GS2 under ex-situ strategy having the lowest. The degree of inbreeding of GS2 was higher than that of GS1 and GS3. Conserved populations of Xichuan black-bone chicken showed no obvious changes in genetic diversity between XB1 and XB2. In terms of population structure, the GS3 population were stratified relative to GS1 and GS2. According to the conservation priority, GS3 had the highest contribution to the total gene and allelic diversity in GS breed, whereas the contribution of XB1 and XB2 were similar. We also observed that the genetic diversity of GS2 was lower than GS3, which were from the same generation but under different conservation programs(in-situ and ex-situ). While XB1 and XB2 had similar levels of genetic diversity. Overall, our findings suggested that the conservation programs performed in ex-situ could slow down the occurrence of inbreeding events, but could not entirely prevent the loss of genetic diversity when the conserved population size was small, while in-situ conservation populations with large population size could maintain a relative high level of genetic diversity.展开更多
Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in li...Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in liquid environment.Herein,Mg-9Al-1Fe and Mg-9Al-1Fe-1Gd alloys were designed to highlight the impact of intermetallic on the corrosion behaviour.In-situ AFM with a special electrolyte circulation system and quasi-in-situ SEM observation were used to monitor the corrosion process of the designed alloys.SEM-EDS and TEM-SAED were applied to identify the intermetallic in the designed alloys,and their volta potentials were measured by SKPFM.According to the real-time and real-space in-situ AFM monitor,the corrosion process consisted of dissolution of anodicα-Mg phase,accumulation of corrosion products around cathodic phase and shedding of some fine cathodic phase.Then,the localized corrosion process of Mg alloy was revealed combined with the results of the monitor of corrosion process and Volta potential difference.展开更多
It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization an...It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization and grain growth is critical to the success of the technique.In the present work,by using in-situ high temperature EBSD,the mechanisms that control recrystallization and grain growth of an extruded pure Mg were studied.The experimental results revealed that the grains of priority for dynamic recrystallization exhibit fading competitiveness under static recrystallization.It is also found that grain boundary movement or grain growth is likely to show an inverse energy gradient effect,i.e.,low energy grains tend to swallow or grow into high energy grains,and grain boundaries of close to 30°exhibit superior growth advantage to others.Another finding is that{10-12}tensile twin boundaries are sites of hardly observed for recrystallization,and are finally swallowed by adjacent recrystallized grains.The above findings may give comprehensive insights of static recrystallization and grain growth of Mg,and may guide the design of advanced materials processing in microstructural engineering.展开更多
We developed a new preparation to protect probiotic cells from adverse environmental conditions and improve their livability,which is called Lactobacillus casei-Sodium alginate-Chitosan (LSC).The LSC was prepared by m...We developed a new preparation to protect probiotic cells from adverse environmental conditions and improve their livability,which is called Lactobacillus casei-Sodium alginate-Chitosan (LSC).The LSC was prepared by mixing probiotics with sodium alginate-chitosan sol.The preparation contained complex calcium ions,which were released in the acidic environment of gastric juice,thus crosslinking to form in-situ gel.Different proportions of sodium alginate-chitosan were prepared to add to simulate gastrointestinal fluid to get the best ratio.The optimal ratio of LSC preparation was compared with traditional gel microspheres to observe the survival effect of probiotics in gastrointestinal fluid environment.Compared with sodium alginate sol,the porosity of sodium alginate-chitosan sol is lower,which is beneficial to the protection of probiotics.When the ratio of chitosan to sodium alginate is 1.5:1.5 (w/v),the protective effect is the best.The protective ability of LSC is 64 times that of traditional microspheres,and it has the potential of synergistic anti-tumor.A probiotic preparation with simple preparation process and better protection effect compared with traditional microspheres was prepared,which has joint anti-tumor potential.展开更多
A method for in-situ stress measurement via fiber optics was proposed. The method utilizes the relationship between rock mass elastic parameters and in-situ stress. The approach offers the advantage of long-term stres...A method for in-situ stress measurement via fiber optics was proposed. The method utilizes the relationship between rock mass elastic parameters and in-situ stress. The approach offers the advantage of long-term stress measurements with high spatial resolution and frequency, significantly enhancing the ability to measure in-situ stress. The sensing casing, spirally wrapped with fiber optic, is cemented into the formation to establish a formation sensing nerve. Injecting fluid into the casing generates strain disturbance, establishing the relationship between rock mass properties and treatment pressure.Moreover, an optimization algorithm is established to invert the elastic parameters of formation via fiber optic strains. In the first part of this paper series, we established the theoretical basis for the inverse differential strain analysis method for in-situ stress measurement, which was subsequently verified using an analytical model. This paper is the fundamental basis for the inverse differential strain analysis method.展开更多
Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Pal...Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.展开更多
Titanium matrix composites reinforced with ceramic particles are considered a promising engineering material due to their combination of high specific strength,low density,and high modulus.In this study,the TA15-based...Titanium matrix composites reinforced with ceramic particles are considered a promising engineering material due to their combination of high specific strength,low density,and high modulus.In this study,the TA15-based composites reinforced with a volume fraction of 10% to 25%(TiB+TiC)were prepared using powder metallurgy and casting technique.Microstructural characterization and phase constitution were examined using optical microscopy(OM),scanning electron microscopy(SEM),and X-ray diffraction(XRD).In addition,the microhardness,room temperature(RT)and high temperature(HT)tensile properties of the composites were evaluated.Results revealed that the reinforcements are distributed uniformly even in the composites with a high volume of TiB and TiC.However,as the volume fraction exceeds 15%,TiB and TiC particles become coarsening and exhibit rod-like and dendritic-like morphology.Microhardness increases gradually from 321.2 HV for the base alloy to a maximum of 473.3 HV as the reinforcement increases to 25vol.%.Tensile test results indicate that a reinforcement volume fraction above 20% is beneficial for enhancing tensile strength and yield strength at high temperatures,but it has an adverse effect on room temperature elongation.Conversely,if the reinforcement volume fraction is below 20%,it can improve high-temperature elongation when the temperature exceeds 600℃.展开更多
For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical...For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.展开更多
Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key hal...Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.展开更多
In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fractur...In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fracture network,is developed using a self-developed thermal-flow-chemical(TFC)simulator.Analysis of the model elucidates the in-situ conversion process in three stages and defines the transformation of fluids into three distinct outcomes according to their end stages.The findings indicate that kerogen decomposition increases fluid pressure,activating fractures and subsequently enhancing permeability.A comprehensive analysis of activated fracture permeability and heating power reveals four distinct production modes,highlighting that increasing heating power correlates with higher cumulative fluid production.Activated fractures,with heightened permeability,facilitate the mobility of heavy oil toward production wells but hinder its cracking,thereby limiting light hydrocarbon production.Additionally,energy efficiency research demonstrates the feasibility of the in-situ conversion in terms of energy utilization,especially when considering the surplus energy from high-fluctuation energy sources such as wind and solar power to provide heating.展开更多
Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electr...Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.展开更多
The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of interme...The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.展开更多
The deformation behavior of the as-extruded Mg-Y-Ni alloys with different volume fraction of long period stacking ordered(LPSO)phase during tension and compression was investigated by in-situ synchrotron diffraction.T...The deformation behavior of the as-extruded Mg-Y-Ni alloys with different volume fraction of long period stacking ordered(LPSO)phase during tension and compression was investigated by in-situ synchrotron diffraction.The micro-yielding,macro-yielding,tension-compression asymmetry and strain hardening behavior of the alloys were explored by combining with deformation mechanisms.The micro-yielding is dominated by basal slip of dynamic recrystallized(DRXed)grains in tension,while it is dominated by extension twinning of non-dynamic recrystallized(non-DRXed)grains in compression.At macro-yielding,the non-DRXed grains are still elastic deformed in tension and the basal slip of DRXed grains in compression are activated.Meanwhile,the LPSO phase still retains elastic deformation,but can bear more load,so the higher the volume fraction of hard LPSO phase,the higher the tensile/compressive macro-yield strength of the alloys.Benefiting from the low volume fraction of the non-DRXed grains and the delay effect of LPSO andγphases on extension twinning,the as-extruded alloys exhibit excellent tension-compression symmetry.When the volume fraction of LPSO phase reaches∼50%,tension-compression asymmetry is reversed,which is due to the fact that the LPSO phase is stronger in compression than in tension.The tensile strain hardening behavior is dominated by dislocation slip,while the dominate mechanism for compressive strain hardening changes from twinning in theα-Mg grains to kinking of the LPSO phase with increasing volume fraction of LPSO phase.The activation of kinking leads to the constant compressive strain hardening rate of∼2500 MPa,which is significantly higher than the tensile strain hardening rate.展开更多
基金the Korea Evaluation Institute of Industrial Technology(KEIT,No.20009956)the Korea Institute for Advancement of Technology(KIAT,No.P0023676,HRD Program for Industrial Innovation)+1 种基金funded by the Ministry of Trade,Industry and Energy(MOTIE),Koreathe Swedish Foundation for International Cooperation in Research and Higher Education(STINT)for supporting the collaboration between KTH(Sweden)and Hanyang University(Korea)。
文摘In combination with theoretical calculations,experiments were conducted to investigate the evolution behavior of nonmetallic inclusions(NMIs)during the manufacture of large-scale heat-resistant steel ingots using 9CrMoCoB heat-resistant steel and CaF_(2)–CaO–Al_(2)O_(3)–SiO_(2)–B_(2)O_(3)electroslag remelting(ESR)-type slag in an 80-t industrial ESR furnace.The main types of NMI in the consumable electrode comprised pure alumina,a multiphase oxide consisting of an Al_(2)O_(3)core and liquid CaO–Al_(2)O_(3)–SiO_(2)–MnO shell,and M_(23)C_(6)carbides with an MnS core.The Al_(2)O_(3)and MnS inclusions had higher precipitation temperatures than the M_(23)C_(6)-type carbide under equilibrium and nonequilibrium solidification processes.Therefore,inclusions can act as nucleation sites for carbide layer precipitation.The ESR process completely removed the liquid CaO–Al_(2)O_(3)–SiO_(2)–MnO oxide and MnS inclusion with a carbide shell,and only the Al_(2)O_(3)inclusions and Al_(2)O_(3)core with a carbide shell occupied the remelted ingot.The M_(23)C_(6)-type carbides in steel were determined as Cr_(23)C_(6)based on the analysis of transmission electron microscopy results.The substitution of Cr with W,Fe,or/and Mo in the Cr_(23)C_(6)lattice caused slight changes in the lattice parameter of the Cr_(23)C_(6)carbide.Therefore,Cr_(21.34)Fe_(1.66)C_(6),(Cr_(19)W_(4)C_(6),Cr_(18.4)Mo_(4.6)C_(6),and Cr_(16)Fe_(5)Mo_(2)C_(6)can match the fraction pattern of Cr_(23)C_(6)carbide.The Al_(2)O_(3)inclusions in the remelted ingot formed due to the reduction of CaO,SiO_(2),and MnO components in the liquid inclusion.The increased Al content in liquid steel or the higher supersaturation degree of Al_(2)O_(3)precipitation in the remelted ingot than that in the electrode can be attributed to the evaporation of CaF_(2)and the increase in CaO content in the ESR-type slag.
基金Project(G2010CB635106)supported by the National Basic Research Program of ChinaProject(NCET-10-0023)supported by the Program for New Century Excellent Talents in University of ChinaProject supported by the Program for Hongliu Outstanding Talents of Lanzhou University of Technology,China
文摘The microstructural evolution and phase transformations during partial remelting of in-situ Mg2Sip/AM60B composite modified by SiC and Sr were investigated. The results indicate that SiC and Sr are effective for refining primary α-Mg grains and Mg2Si particles. After being partially remelted, a semisolid microstructure with small and spheroidal primary α-Mg particles can be obtained. The microstructural evolution during partial remelting can be divided into four stages: the initial rapid coarsening, structural separation, spheroidization and final coarsening, which are essentially caused by the phase transformations of β→α, α+β→L and α→L, α→L, and α→L and L→α, respectively. The Mg2Si particles have not obvious effect on the general microstructural evolution steps, but can slower the evolution progress and change the coarsening mechanism. During partial remelting, Mg2Si particles first become blunt and then become spheroidal because of melting of their edges and corners, and finally are coarsened owing to Ostwald ripening.
文摘The thermodynamic equilibrium of deoxidation reactions between molten slag and steel was calculated using a slag-steel coupling thermodynamic model and the mass conservation model based on the ion-molecular coexistence theory.The study focused on the effects of slag composition and deoxidizer type on the oxygen content of low alloy steel during the electroslag remelting(ESR)process.The measured and predicted values of the oxygen content in remelted ingots,and the contents of FeO and MnO in slags were compared and analyzed.Results show that the measured content of total oxygen has a certain correlation with the trend of dissolved oxygen predicted by the model when using Ca-Si alloys as deoxidizer,but it is not correlated with the trend of dissolved oxygen predicted by the model when using Al as deoxidizer.The deoxidation mechanisms of Ca-Si and Al are different.Ca-Si alloy directly reacts with FeO and MnO in slag to reduce the oxygen potential of slag,hence it can inhibit the transfer of oxygen from the slag to molten steel.While,when Al deoxidizer is used,the oxygen content in steel is mainly reduced through floating up the alumina inclusions.Compared to Al,utilizing Ca-Si alloy as a deoxidizer is more effective in reducing the oxygen content and the amount of inclusions in ESR ingot.
基金supported by the Guangdong Basic and Applied Basic Research Foundation (2020B1515120013,2022B1515120066)National Natural Science Foundation of China (Nos.U2001218, 51875215)+1 种基金Key-Area Research and Development Program of Guangdong Province (2020B090923001)Special Support Foundation of Guangdong Province (No.2019TQ05Z110)。
文摘It has always been challenging work to reconcile the contradiction between the strength and plasticity of titanium materials.Laser powder bed fusion(LPBF) is a convenient method to fabricate innovative composites including those inspired by gradient layered materials.In this work,we used LPBF to selectively prepare Ti N/Ti gradient layered structure(GLSTi)composites by using different N_(2)–Ar ratios during the LPBF process.We systematically investigated the mechanisms of in-situ synthesis Ti N,high strength and ductility of GLSTi composites using microscopic analysis,TEM characterization,and tensile testing with digital image correlation.Besides,a digital correspondence was established between the N_(2) concentration and the volume fraction of LPBF in-situ synthesized Ti N.Our results show that the GLSTi composites exhibit superior mechanical properties compared to pure titanium fabricated by LPBF under pure Ar.Specifically,the tensile strength of GLSTi was more than 1.5times higher than that of LPBF-formed pure titanium,reaching up to 1100 MPa,while maintaining a high elongation at fracture of 17%.GLSTi breaks the bottleneck of high strength but low ductility exhibited by conventional nanoceramic particle-strengthened titanium matrix composites,and the hetero-deformation induced strengthening effect formed by the Ti N/Ti layered structure explained its strength-plasticity balanced principle.The microhardness exhibits a jagged variation of the relatively low hardness of 245 HV0.2 for the pure titanium layer and a high hardness of 408 HV0.2 for the N_(2) in-situ synthesis layer.Our study provides a new concept for the structure-performance digital customization of 3D-printed Ti-based composites.
基金financially supported by the National Natural Science Foundation of China (51971080)the Shenzhen Bureau of Science,Technology and Innovation Commission (GXWD20201230155427003-20200730151200003 and JSGG20200914113601003)。
文摘The function of solid electrolytes and the composition of solid electrolyte interphase(SEI)are highly significant for inhibiting the growth of Li dendrites.Herein,we report an in-situ interfacial passivation combined with self-adaptability strategy to reinforce Li_(0.33)La_(0.557)TiO_(3)(LLTO)-based solid-state batteries.Specifically,a functional SEI enriched with LiF/Li_(3)PO_(4) is formed by in-situ electrochemical conversion,which is greatly beneficial to improving interface compatibility and enhancing ion transport.While the polarized dielectric BaTiO_(3)-polyamic acid(BTO-PAA,BP)film greatly improves the Li-ion transport kinetics and homogenizes the Li deposition.As expected,the resulting electrolyte offers considerable ionic conductivity at room temperature(4.3 x 10~(-4)S cm^(-1))and appreciable electrochemical decomposition voltage(5.23 V)after electrochemical passivation.For Li-LiFePO_(4) batteries,it shows a high specific capacity of 153 mA h g^(-1)at 0.2C after 100 cycles and a long-term durability of 115 mA h g^(-1)at 1.0 C after 800 cycles.Additionally,a stable Li plating/stripping can be achieved for more than 900 h at 0.5 mA cm^(-2).The stabilization mechanisms are elucidated by ex-situ XRD,ex-situ XPS,and ex-situ FTIR techniques,and the corresponding results reveal that the interfacial passivation combined with polarization effect is an effective strategy for improving the electrochemical performance.The present study provides a deeper insight into the dynamic adjustment of electrode-electrolyte interfacial for solid-state lithium batteries.
基金supported by a grant from the Research Grants Council of the Hong Kong Special Administrative Region(152131/18E).
文摘This study offers significant insights into the multi-physics phenomena of the SLM process and the subsequent porosity characteristics of ZK60 Magnesium(Mg)alloys.High-speed in-situ monitoring was employed to visualise process signals in real-time,elucidating the dynamics of melt pools and vapour plumes under varying laser power conditions specifically between 40 W and 60 W.Detailed morphological analysis was performed using Scanning-Electron Microscopy(SEM),demonstrating a critical correlation between laser power and pore formation.Lower laser power led to increased pore coverage,whereas a denser structure was observed at higher laser power.This laser power influence on porosity was further confirmed via Optical Microscopy(OM)conducted on both top and cross-sectional surfaces of the samples.An increase in laser power resulted in a decrease in pore coverage and pore size,potentially leading to a denser printed part of Mg alloy.X-ray Computed Tomography(XCT)augmented these findings by providing a 3D volumetric representation of the sample internal structure,revealing an inverse relationship between laser power and overall pore volume.Lower laser power appeared to favour the formation of interconnected pores,while a reduction in interconnected pores and an increase in isolated pores were observed at higher power.The interplay between melt pool size,vapour plume effects,and laser power was found to significantly influence the resulting porosity,indicating a need for effective management of these factors to optimise the SLM process of Mg alloys.
基金the financial support from the National Natural Science Foundation of China(Nos.52034011 and 52204328)the Science and Technology Innovation Program of Hunan Province(2023RC305)the Changsha Municipal Natural Science Foundation(kq2202085)。
文摘The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.
基金supported by the Key Research Project of the Shennong Laboratory,Henan Province,China(SN012022-05)the National Natural Science Foundation of China(32272866)+1 种基金the Young Elite Scientists Sponsorship Program by CAST(2021QNRC001)the Starting Foundation for Outstanding Young Scientists of Henan Agricultural University,China(30500664&30501280)。
文摘Conservation programs require rigorous evaluation to ensure the preservation of genetic diversity and viability of conservation populations. In this study, we conducted a comparative analysis of two indigenous Chinese chicken breeds, Gushi and Xichuan black-bone, using whole-genome SNPs to understand their genetic diversity, track changes over time and population structure. The breeds were divided into five conservation populations(GS1, 2010, ex-situ;GS2, 2019, ex-situ;GS3, 2019, in-situ;XB1, 2010, in-situ;and XB2, 2019, in-situ) based on conservation methods and generations. The genetic diversity indices of three conservation populations of Gushi chicken showed consistent trends, with the GS3 population under in-situ strategy having the highest diversity and GS2 under ex-situ strategy having the lowest. The degree of inbreeding of GS2 was higher than that of GS1 and GS3. Conserved populations of Xichuan black-bone chicken showed no obvious changes in genetic diversity between XB1 and XB2. In terms of population structure, the GS3 population were stratified relative to GS1 and GS2. According to the conservation priority, GS3 had the highest contribution to the total gene and allelic diversity in GS breed, whereas the contribution of XB1 and XB2 were similar. We also observed that the genetic diversity of GS2 was lower than GS3, which were from the same generation but under different conservation programs(in-situ and ex-situ). While XB1 and XB2 had similar levels of genetic diversity. Overall, our findings suggested that the conservation programs performed in ex-situ could slow down the occurrence of inbreeding events, but could not entirely prevent the loss of genetic diversity when the conserved population size was small, while in-situ conservation populations with large population size could maintain a relative high level of genetic diversity.
基金support by the National Natural Science Foundation of China(51961026)the Interdisciplinary Innovation Fund of Nanchang University(Project No.2019-9166-27060003).
文摘Revealing the localized corrosion process of Mg alloy is considered as one of the most significant ways for improving its corrosion resistance.The reliable monitor should be high distinguishability and real-time in liquid environment.Herein,Mg-9Al-1Fe and Mg-9Al-1Fe-1Gd alloys were designed to highlight the impact of intermetallic on the corrosion behaviour.In-situ AFM with a special electrolyte circulation system and quasi-in-situ SEM observation were used to monitor the corrosion process of the designed alloys.SEM-EDS and TEM-SAED were applied to identify the intermetallic in the designed alloys,and their volta potentials were measured by SKPFM.According to the real-time and real-space in-situ AFM monitor,the corrosion process consisted of dissolution of anodicα-Mg phase,accumulation of corrosion products around cathodic phase and shedding of some fine cathodic phase.Then,the localized corrosion process of Mg alloy was revealed combined with the results of the monitor of corrosion process and Volta potential difference.
文摘It has been a common method to improve the mechanical properties of metals by manipulating their microstructures via static recrystallization,i.e.,through heat treatment.Therefore,the knowledge of recrystallization and grain growth is critical to the success of the technique.In the present work,by using in-situ high temperature EBSD,the mechanisms that control recrystallization and grain growth of an extruded pure Mg were studied.The experimental results revealed that the grains of priority for dynamic recrystallization exhibit fading competitiveness under static recrystallization.It is also found that grain boundary movement or grain growth is likely to show an inverse energy gradient effect,i.e.,low energy grains tend to swallow or grow into high energy grains,and grain boundaries of close to 30°exhibit superior growth advantage to others.Another finding is that{10-12}tensile twin boundaries are sites of hardly observed for recrystallization,and are finally swallowed by adjacent recrystallized grains.The above findings may give comprehensive insights of static recrystallization and grain growth of Mg,and may guide the design of advanced materials processing in microstructural engineering.
基金Funded by the National Natural Science Foundation of China(No.52003211)。
文摘We developed a new preparation to protect probiotic cells from adverse environmental conditions and improve their livability,which is called Lactobacillus casei-Sodium alginate-Chitosan (LSC).The LSC was prepared by mixing probiotics with sodium alginate-chitosan sol.The preparation contained complex calcium ions,which were released in the acidic environment of gastric juice,thus crosslinking to form in-situ gel.Different proportions of sodium alginate-chitosan were prepared to add to simulate gastrointestinal fluid to get the best ratio.The optimal ratio of LSC preparation was compared with traditional gel microspheres to observe the survival effect of probiotics in gastrointestinal fluid environment.Compared with sodium alginate sol,the porosity of sodium alginate-chitosan sol is lower,which is beneficial to the protection of probiotics.When the ratio of chitosan to sodium alginate is 1.5:1.5 (w/v),the protective effect is the best.The protective ability of LSC is 64 times that of traditional microspheres,and it has the potential of synergistic anti-tumor.A probiotic preparation with simple preparation process and better protection effect compared with traditional microspheres was prepared,which has joint anti-tumor potential.
基金the Project Support of NSFC(No.U19B6003-05 and No.52074314)。
文摘A method for in-situ stress measurement via fiber optics was proposed. The method utilizes the relationship between rock mass elastic parameters and in-situ stress. The approach offers the advantage of long-term stress measurements with high spatial resolution and frequency, significantly enhancing the ability to measure in-situ stress. The sensing casing, spirally wrapped with fiber optic, is cemented into the formation to establish a formation sensing nerve. Injecting fluid into the casing generates strain disturbance, establishing the relationship between rock mass properties and treatment pressure.Moreover, an optimization algorithm is established to invert the elastic parameters of formation via fiber optic strains. In the first part of this paper series, we established the theoretical basis for the inverse differential strain analysis method for in-situ stress measurement, which was subsequently verified using an analytical model. This paper is the fundamental basis for the inverse differential strain analysis method.
基金financially supported by the Shenzhen Science and Technology Program (JCYJ20200109105805902,JCYJ20220818095805012)the National Natural Science Foundation of China (22208221,22178221,42377487)+2 种基金the Scientific and Technological Plan of Guangdong Province (2019B090905005,2019B090911004)the Natural Science Foundation of Guangdong Province (2021A1515110751)the Guangdong Basic and Applied Basic Research Foundation (2022A1515110477,2021B1515120004)。
文摘Sluggish storage kinetics is considered as the main bottleneck of cathode materials for fast-charging aqueous zinc-ion batteries(AZIBs).In this report,we propose a novel in-situ self-etching strategy to unlock the Palm tree-like vanadium oxide/carbon nanofiber membrane(P-VO/C)as a robust freestanding electrode.Comprehensive investigations including the finite element simulation,in-situ X-ray diffraction,and in-situ electrochemical impedance spectroscopy disclosed it an electrochemically induced phase transformation mechanism from VO to layered Zn_(x)V_(2)O_5·nH_(2)O,as well as superior storage kinetics with ultrahigh pseudocapacitive contribution.As demonstrated,such electrode can remain a specific capacity of 285 mA h g^(-1)after 100 cycles at 1 A g^(-1),144.4 mA h g^(-1)after 1500 cycles at 30 A g^(-1),and even 97 mA h g^(-1)after 3000 cycles at 60 A g^(-1),respectively.Unexpectedly,an impressive power density of 78.9 kW kg^(-1)at the super-high current density of 100 A g^(-1)also can be achieved.Such design concept of in-situ self-etching free-standing electrode can provide a brand-new insight into extending the pseudocapacitive storage limit,so as to promote the development of high-power energy storage devices including but not limited to AZIBs.
基金financially supported by the National Key Research&Development Program of China(Nos.2020YFB2008300,2020YFB2008303)。
文摘Titanium matrix composites reinforced with ceramic particles are considered a promising engineering material due to their combination of high specific strength,low density,and high modulus.In this study,the TA15-based composites reinforced with a volume fraction of 10% to 25%(TiB+TiC)were prepared using powder metallurgy and casting technique.Microstructural characterization and phase constitution were examined using optical microscopy(OM),scanning electron microscopy(SEM),and X-ray diffraction(XRD).In addition,the microhardness,room temperature(RT)and high temperature(HT)tensile properties of the composites were evaluated.Results revealed that the reinforcements are distributed uniformly even in the composites with a high volume of TiB and TiC.However,as the volume fraction exceeds 15%,TiB and TiC particles become coarsening and exhibit rod-like and dendritic-like morphology.Microhardness increases gradually from 321.2 HV for the base alloy to a maximum of 473.3 HV as the reinforcement increases to 25vol.%.Tensile test results indicate that a reinforcement volume fraction above 20% is beneficial for enhancing tensile strength and yield strength at high temperatures,but it has an adverse effect on room temperature elongation.Conversely,if the reinforcement volume fraction is below 20%,it can improve high-temperature elongation when the temperature exceeds 600℃.
基金financially supported by the National Key R&D Program of China(No.2022YFC2906100).
文摘For the rational manipulation of the production quality of high-temperature metallurgical engineering,there are many challenges in understanding the processes involved because of the black box chemical/electrochemical reactors.To overcome this issue,various in-situ characterization methods have been recently developed to analyze the interactions between the composition,microstructure,and solid-liquid interface of high-temperature electrochemical electrodes and molten salts.In this review,recent progress of in-situ hightemperature characterization techniques is discussed to summarize the advances in understanding the processes in metallurgical engineering.In-situ high-temperature technologies and analytical methods mainly include synchrotron X-ray diffraction(s-XRD),laser scanning confocal microscopy,and X-ray computed microtomography(X-rayμ-CT),which are important platforms for analyzing the structure and morphology of the electrodes to reveal the complexity and variability of their interfaces.In addition,laser-induced breakdown spectroscopy,high-temperature Raman spectroscopy,and ultraviolet-visible absorption spectroscopy provide microscale characterizations of the composition and structure of molten salts.More importantly,the combination of X-rayμ-CT and s-XRD techniques enables the investigation of the chemical reaction mechanisms at the two-phase interface.Therefore,these in-situ methods are essential for analyzing the chemical/electrochemical kinetics of high-temperature reaction processes and establishing the theoretical principles for the efficient and stable operation of chemical/electrochemical metallurgical processes.
基金support from National Natural Science Foundation of China(Grant Nos.22125903,22209174)the National Key R&D Program of China(Grants 2022YFA1504100)+2 种基金Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL202016,DNL202019)DICP(DICP I2020032).
文摘Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.
基金supported by the National Natural Science Foundation of China (Grant No.42090023)the Alliance of International Science Organization (ANSO)Scholarship for Young Talents+3 种基金the Key Deployment Program of Chinese Academy of Sciences (YJKYYQ20190043,ZDBS-LY-DQC003,KFZD-SW-422,ZDRW-ZS-2021-3-1)the Scientific Research and Technology Development Project of China National Petroleum Corpo ration (2022DJ5503)the CAS Key Technology Talent ProgramSupercomputing Laboratory,IGGCAS。
文摘In-situ conversion presents a promising technique for exploiting continental oil shale formations,characterized by highly fractured organic-rich rock.A 3D in-situ conversion model,which incorporates a discrete fracture network,is developed using a self-developed thermal-flow-chemical(TFC)simulator.Analysis of the model elucidates the in-situ conversion process in three stages and defines the transformation of fluids into three distinct outcomes according to their end stages.The findings indicate that kerogen decomposition increases fluid pressure,activating fractures and subsequently enhancing permeability.A comprehensive analysis of activated fracture permeability and heating power reveals four distinct production modes,highlighting that increasing heating power correlates with higher cumulative fluid production.Activated fractures,with heightened permeability,facilitate the mobility of heavy oil toward production wells but hinder its cracking,thereby limiting light hydrocarbon production.Additionally,energy efficiency research demonstrates the feasibility of the in-situ conversion in terms of energy utilization,especially when considering the surplus energy from high-fluctuation energy sources such as wind and solar power to provide heating.
基金supported by the Science and Technology Foundation of Guizhou Province,China(No.[2020]1Y163)the National Natural Science Foundation of China(No.41827802).
文摘Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.
基金Funded by the National Natural Science Foundation of China(No.52103285)the 111 National Project(No.B20002)。
文摘The nucleation and growth mechanism of nanoparticles is an important theory,which can guide the preparation of nanomaterials.However,it is still lacking in direct observation on the details of the evolution of intermediate state structure during nucleation and growth.In this work,the evolution process of bismuth nanoparticles induced by electron beam was revealed by in-situ transmission electron microscopy(TEM)at atomic scale.The experimental results demonstrate that the size,stable surface and crystallographic defect have important influences on the growth of Bi nanoparticles.Two non-classical growth paths including single crystal growth and polycrystalline combined growth,as well as,corresponding layer-by-layer growth mechanism along{012}stable crystal plane of Bi nanoparticles with dodecahedron structure were revealed by in-situ TEM directly.These results provide important guidance and a new approach for in-depth understanding of the nucleation and growth kinetics of nanoparticles.
基金supported by National Natural Science Foundation of China(no.U21A2047,no.51971076 and no.52001069).
文摘The deformation behavior of the as-extruded Mg-Y-Ni alloys with different volume fraction of long period stacking ordered(LPSO)phase during tension and compression was investigated by in-situ synchrotron diffraction.The micro-yielding,macro-yielding,tension-compression asymmetry and strain hardening behavior of the alloys were explored by combining with deformation mechanisms.The micro-yielding is dominated by basal slip of dynamic recrystallized(DRXed)grains in tension,while it is dominated by extension twinning of non-dynamic recrystallized(non-DRXed)grains in compression.At macro-yielding,the non-DRXed grains are still elastic deformed in tension and the basal slip of DRXed grains in compression are activated.Meanwhile,the LPSO phase still retains elastic deformation,but can bear more load,so the higher the volume fraction of hard LPSO phase,the higher the tensile/compressive macro-yield strength of the alloys.Benefiting from the low volume fraction of the non-DRXed grains and the delay effect of LPSO andγphases on extension twinning,the as-extruded alloys exhibit excellent tension-compression symmetry.When the volume fraction of LPSO phase reaches∼50%,tension-compression asymmetry is reversed,which is due to the fact that the LPSO phase is stronger in compression than in tension.The tensile strain hardening behavior is dominated by dislocation slip,while the dominate mechanism for compressive strain hardening changes from twinning in theα-Mg grains to kinking of the LPSO phase with increasing volume fraction of LPSO phase.The activation of kinking leads to the constant compressive strain hardening rate of∼2500 MPa,which is significantly higher than the tensile strain hardening rate.