This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive e...This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive elements (Y and Hf) and refractory elements (Ta and Re)on the growth mechanisms of thermally grown oxide(TGO).The findings indicate that,in contrast to air conditions,elevated levels of water vapor significantly diminish the oxidation resistance of the bond coatings,leading to considerable porosity defects in both the central and lower regions of the TGO.Furthermore,this environment hinders the development of the"peg"structure at the TGO/metal interface,thereby accelerating the premature delamination of the coating.Additionally,the presence of doped elements such as Hf,Ta,and Y leads to their segregation at the Al_(2)O_(3)grain boundaries within the TGO,creating grain boundary structures characterized by a high density of defects.This defective architecture promotes the inward diffusion of water molecules at elevatedtemperatures,causing hydrogen atoms generated from oxidation and reduction reactions at the TGO/metal interface to become entrapped within the Al_(2)O_(3)lattice at the base of the TGO,rather than escaping efficiently.Ultimately,this phenomenon contributes to the formation of internal porosity defects during the oxidation of TGO in a steam environment.展开更多
Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coating...Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coatings were evaluated at 1323 K in stair air.The results revealed that the nanocrystalline NiCrAlY coating exhibited better isothermal and cyclic oxidation resistance compared to the conventional NiCrAlY at 1323 K.The mass gain and parabolic rate constant Kp of the nanocrystalline NiCrAlY coating were 45.2%and 44.7%lower than those of the conventional NiCrAlY coating,respectively.During cyclic oxidation,the tendency for spallation of the oxide scale was evidently decreased by nanocrystallization due to the formation of a continuous,compact,adherent,and slow-growing exclusiveα-Al_(2)O_(3)scale.The mechanism responsible for the improvement of the nanocrystalline NiCrAlY coating was discussed.展开更多
Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynam...Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.展开更多
The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solution...The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solutions to this problem.Here,we synthesized a ZnV_(2)O_(6)/Bi_(2)WO_(6)nanocomposite and catalyzed the cycloaddition of CO_(2)to epoxides for the green synthesis of cyclic carbonates under visible light irradiation.The present nanocomposite photocatalyst exhibited up to 96%yield of cyclic carbonates.The photocatalyst was found to be efficient for photocatalytic cycloaddition reactions,and the recovered photocatalyst showed stability in up to five consecutive photocatalytic experiments.The current methodology of cyclic carbonate production is a significant step toward the mitigation of atmospheric CO_(2)and can work well with the development of nanocomposite photocatalysts.展开更多
To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretre...To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.展开更多
The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical pr...The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.展开更多
Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materi...Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.展开更多
In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers ...In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers featuring monocyclic,dicyclic,or tricyclic pendant motifs was designed and prepared based on malic acid derivatives.Polyesters with precise chemical structures and uniform chain lengths were prepared modularly through iterative growth.Meticulous control over the chemical details allows for a close investigation of the topological effects on the polymer properties.Compared to their linear side chain counterparts,the presence of cyclic pendant groups has a significant impact on chain conformation,leading to a reduction in hydrodynamic volume and an enhancement in the glass transition temperature.These results underscore the potential of tailoring polymer properties through rational engineering of side chain topology.展开更多
Drilling and blasting tunneling is a cyclic process in which tunnel rock undergoes repeated blast loading,affecting its dynamic characteristics,energy evolution,and damage progression.To explore the dynamic mechanical...Drilling and blasting tunneling is a cyclic process in which tunnel rock undergoes repeated blast loading,affecting its dynamic characteristics,energy evolution,and damage progression.To explore the dynamic mechanical properties and damage mechanisms of carbonaceous slate under cyclic impact loads of varying intensities,cyclic dynamic tests are conducted using a triaxial split Hopkinson pressure bar.This study analyzes the stress-strain relationship,energy damage evolution,and macro-to-micro failure characteristics.The results show that peak stress and strain are significantly influenced by impact intensity and the number of impacts.The initial dynamic stress is positively correlated with the impact intensity,but with more impact,the dynamic stress decreases while the peak strain increases.Energy evolution follows a pattern of"slow growthfluctuating growthrapid growth,"with the crack initiation stress and its proportion decreasing.CT and SEM analyses reveal that as the impact intensity increases,failure becomes more chaotic,the fracture volume increases,and the fracture mode shifts from interlayer and intergranular to through-layer and trans-granular fractures.These findings provide an experimental basis for soft rock tunnel stability analysis.展开更多
The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batte...The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).展开更多
Large-scale geological energy storage plays a crucial role in balancing the intermittency of renewable energy.As an energy storage medium,soaked sandstone has a wide range of applications in geological energy storage....Large-scale geological energy storage plays a crucial role in balancing the intermittency of renewable energy.As an energy storage medium,soaked sandstone has a wide range of applications in geological energy storage.Understanding the damage characteristics in soaked sandstones is essential for ensuring the stability and longevity of these energy storage systems.This study involved multi-stage cyclic loading tests conducted on soaked sandstone to explore the damage evolution throughout the loading process.The findingsreveal several important insights:(1)The plastic hysteresis loops observed during multi-stage cyclic loading evolved from dense to sparse.An increase in stress level led to greater damage in the rock,as evidenced by an increase in accumulated peak/plastic strains.(2)Energy density and stress level are related by quadratic polynomial relationships.The elastic and dissipated energy densities are related by a linear law.The average energy storage coefficientdecreased by up to 24.1%with increasing stress amplitude,reflectingchanges in energy dynamics within the samples.(3)AE counts,amplitude,and frequency provided critical insights into rock damage and fracture patterns.The greater the loading rate and stress amplitude,the lower the proportion of high-amplitude,high-peak frequency,and shear-type fractures.Increasing stress amplitude caused a maximum 16.63%reduction in the AE bvalue,indicating shifts in fracture behavior under varying stress conditions.(4)The increase in loading rate and stress amplitude promotes the transformation of micropores and mesopores to macropores/microcracks.(5)Damage variables,definedin terms of cumulative dissipation energy,aligned closely with the fatigue damage model under multi-stage cyclic loading.Accelerated damage primarily occurred during the finalstages of fatigue loading,highlighting critical periods in the degradation of soaked sandstones.This study can offer guidance for designing operational parameters for energy storage geological bodies dominated by soaked sandstones.展开更多
Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,...Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.展开更多
Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achievin...An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achieving a critical load of 87.8 N.Silicon doping induced nanocrystallization and amorphization,increasing the hardness to 26 GPa.At high temperatures,a nanoscale Cr-rich(Cr,Al)_(2)O_(3) layer was formed,effectively inhibiting oxygen diffusion.The coating underwent unique phase transformations,during which Cr_(2)N and amorphous Si3N4 were converted into dispersed SiCr_(3) nanoparticles,which stabilized Cr atoms and suppressed their outward diffusion.Ab initio molecular dynamics simulations revealed that Cr atoms exhibited higher chemical activity and oxygen-capture capability than Al atoms and Si atoms served as diffusion barriers by pinning onto the oxidized surface,considerably improving the oxidation resistance of the coating.展开更多
Triterpenoids are valuable medicinal scaffolds,characterized by excellent pharmacological properties and the presence of hydroxyl and carboxyl groups that allow for further structural modifications.Expanding the scope...Triterpenoids are valuable medicinal scaffolds,characterized by excellent pharmacological properties and the presence of hydroxyl and carboxyl groups that allow for further structural modifications.Expanding the scope of oxidative modifications on these molecules is crucial for increasing their synthetic structural diversity and unlocking new potential pharmacological activities.However,the progress has been limited by the scarcity of suitable tailoring enzymes.Here,we reported a break-through in achieving targeted and remote dual-site oxidation of licorice triterpenoids using a single P450 mutant.This approach successfully enabled the selective synthesis of the rare triterpenoid,liquiritic acid and 24-OH-liquiritic acid.Our findings demonstrate that microenvironmental accessibility engineering of triterpenoid substrates within the P450 enzyme is essential for continuous and regioselective oxidation.This study not only sheds light on the mechanistic aspects of P450 catalysis but also expands the enzymatic toolkit for selective oxidative modifications in triterpenoid biosynthesis.展开更多
Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the effica...Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.展开更多
The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application ...The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.展开更多
Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert...Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.展开更多
This study presents and verifies a hybrid methodology for reliable determination of parameters in structural rheological models(Zener,Burgers,and Maxwell)describing the viscoelastic behavior of polyurethane specimens ...This study presents and verifies a hybrid methodology for reliable determination of parameters in structural rheological models(Zener,Burgers,and Maxwell)describing the viscoelastic behavior of polyurethane specimens manufactured using extrusion-based 3D printing.Through comprehensive testing,including cyclic compression at strain rates ranging from 0.12 to 120 mm/min(0%-15%strain)and creep/relaxation experiments(10%-30%strain),the lumped parameters were independently determined using both analytical and numerical solutions of the models’differential equations,followed by cross-verification in additional experiments.Numerical solutions for creep and relaxation problems were obtained using finite element analysis,with the three-parameter Mooney-Rivlin model and Prony series employed to simulate elastic and viscous stress components,respectively.Energy dissipation per cycle was quantified during cyclic compression tests.The results demonstrate that all three models adequately describe material behavior within the 0%-15%strain range across various strain rates.Comparative analysis revealed the Burgers model’s superior performance in characterizing creep and stress relaxation at low strain levels.While Zener and Burgers model parameters from uniaxial compression showed limited applicability for energy dissipation calculations,the generalized Maxwell model effectively captured viscoelastic properties across different strain rates.Notably,parameters derived from creep tests provided a more universal assessment of dissipative properties due to optimization based on characteristic curve regions.Both parameter sets described polyurethane’s elastic-hysteretic behavior with approximately 20%error,proving significantly more accurate than the linear strain-time dependence hypothesis.Finite element analysis(FEA)complemented numerical modeling by demonstrating that while the generalized Maxwell model effectively describes initial rapid stress-strain changes,FEA provides superior characterization of steady-state processes.This computational approach yields more physically representative results compared to simplified analytical solutions,despite certain limitations in transient analysis.展开更多
During deep coal mining,an instability failure of coal usually occurs under the combined effect of initial damage and triaxial cyclic loading and unloading(TCLU).Therefore,this study investigated the impact of initial...During deep coal mining,an instability failure of coal usually occurs under the combined effect of initial damage and triaxial cyclic loading and unloading(TCLU).Therefore,this study investigated the impact of initial damage on mechanical behavior and acoustic emission(AE)characteristics of coal under TCLU.Initial damage variables(IDVs)of coal specimens were quantified using preloading,followed by TCLU experiments to assess the deformation,energy distribution,and fracture development.The results revealed that the increase in IDVs significantly reduced the structural integrity of coal specimens,increased the cumulative irreversible strain,and enhanced the dissipated energy owing to microfracture expansion.Moreover,AE monitoring showed earlier activation of fractures and a higher occurrence of large-scale rupture events of coal specimens with high IDVs,which correlated with decreasing AE b values(reflecting the different scales of fracture within specimens)and increasing S values(reflecting the AE activity within specimens).Additionally,computed tomography analysis revealed intensified fracture networks and increasing three-dimensional fractal dimensions of coal specimens with higher IDVs.Finally,the coupling effect of TCLU and initial damage on the weakening mechanism of coal was investigated.Initial damage significantly reduced the structural integrity of coal by increasing the number of weak planes within coal specimens,contributing to the earlier activation and rapid expansion of fractures at low stress levels under TCLU and eventually accelerating the weakening process of coal.This study provides a scientific basis and theoretical support for the prevention and control of dynamic disasters in deep coal mining.展开更多
基金financially supported by the National Key R&D Program of China(No.2023YFB3711200)the National Natural Science Foundation of China(No.U21A2044)the Science Center for Gas Turbine Project(No.P2022-B-IV-008-001)
文摘This research presents a thorough assessment of the cyclic oxidation characteristics of Y-and Hf-doped NiCoCrAlTaRe superalloy bond coatings in a pure steam atmosphere,emphasizing the distinct influences of reactive elements (Y and Hf) and refractory elements (Ta and Re)on the growth mechanisms of thermally grown oxide(TGO).The findings indicate that,in contrast to air conditions,elevated levels of water vapor significantly diminish the oxidation resistance of the bond coatings,leading to considerable porosity defects in both the central and lower regions of the TGO.Furthermore,this environment hinders the development of the"peg"structure at the TGO/metal interface,thereby accelerating the premature delamination of the coating.Additionally,the presence of doped elements such as Hf,Ta,and Y leads to their segregation at the Al_(2)O_(3)grain boundaries within the TGO,creating grain boundary structures characterized by a high density of defects.This defective architecture promotes the inward diffusion of water molecules at elevatedtemperatures,causing hydrogen atoms generated from oxidation and reduction reactions at the TGO/metal interface to become entrapped within the Al_(2)O_(3)lattice at the base of the TGO,rather than escaping efficiently.Ultimately,this phenomenon contributes to the formation of internal porosity defects during the oxidation of TGO in a steam environment.
基金financially supported by the National Natural Science Foundation of China(No.52101075)China Postdoctoral Science Foundation(Nos.2021M700557,2022M723272)+1 种基金Postdoctoral Scienceof Chongqing Natural Science Foundation(Nos.cstc2021jcyj-bshX0053,cstc2021jcyj-bshX0039)Scientific Research Foundation of Chongqing University of Technology(No.2020ZDZ004)。
文摘Two kinds of NiCrAlY coatings(Ni-25Cr-10Al-0.5Y)were prepared on K417 superalloy using ion plating(AIP)and magnetron sputtering(MS),respectively.The isothermal and cyclic oxidation behaviors of the two NiCrAlY coatings were evaluated at 1323 K in stair air.The results revealed that the nanocrystalline NiCrAlY coating exhibited better isothermal and cyclic oxidation resistance compared to the conventional NiCrAlY at 1323 K.The mass gain and parabolic rate constant Kp of the nanocrystalline NiCrAlY coating were 45.2%and 44.7%lower than those of the conventional NiCrAlY coating,respectively.During cyclic oxidation,the tendency for spallation of the oxide scale was evidently decreased by nanocrystallization due to the formation of a continuous,compact,adherent,and slow-growing exclusiveα-Al_(2)O_(3)scale.The mechanism responsible for the improvement of the nanocrystalline NiCrAlY coating was discussed.
基金Supported by the National Natural Science Foundation of China(Nos.52293472,22473096 and 22471164)。
文摘Among various architectures of polymers,end-group-free rings have attracted growing interests due to their distinct physicochemical performances over the linear counterparts which are exemplified by reduced hydrodynamic size and slower degradation.It is key to develop facile methods to large-scale synthesis of polymer rings with tunable compositions and microstructures.Recent progresses in large-scale synthesis of polymer rings against single-chain dynamic nanoparticles,and the example applications in synchronous enhancing toughness and strength of polymer nanocomposites are summarized.Once there is the breakthrough in rational design and effective large-scale synthesis of polymer rings and their functional derivatives,a family of cyclic functional hybrids would be available,thus providing a new paradigm in developing polymer science and engineering.
基金sponsored in part by the National Natural Science Foundation of China(No.21477167)the Science and Technology Research Plan Program of Henan Province(Nos.222102320328,232102210075,232102320137)the Key Science Research Program Foundation of High Education Schools of Henan Province(No.23B610010).
文摘The present levels of CO_(2)emission in the atmosphere require the development of technologies to achieve carbon neutrality using inexpensive processes.Conversion of CO_(2)into cyclic carbonates is one of the solutions to this problem.Here,we synthesized a ZnV_(2)O_(6)/Bi_(2)WO_(6)nanocomposite and catalyzed the cycloaddition of CO_(2)to epoxides for the green synthesis of cyclic carbonates under visible light irradiation.The present nanocomposite photocatalyst exhibited up to 96%yield of cyclic carbonates.The photocatalyst was found to be efficient for photocatalytic cycloaddition reactions,and the recovered photocatalyst showed stability in up to five consecutive photocatalytic experiments.The current methodology of cyclic carbonate production is a significant step toward the mitigation of atmospheric CO_(2)and can work well with the development of nanocomposite photocatalysts.
基金National Natural Science Foundation of China(52071274)Key Research and Development Projects of Shaanxi Province(2023-YBGY-442)Science and Technology Nova Project-Innovative Talent Promotion Program of Shaanxi Province(2020KJXX-062)。
文摘To mitigate the impact of interdiffusion reactions between the silicide slurry and Ta12W alloy substrate during vacuum sintering process on the oxidation resistance of the silicide coating,a micro-arc oxidation pretreatment was employed to construct a Ta_(2)O_(5)ceramic layer on the Ta12W alloy surface.Subsequently,a slurry spraying-vacuum sintering method was used to prepare a Si-Cr-Ti-Zr coating on the pretreated substrate.Comparative studies were conducted on the microstructure,phase composition,and isothermal oxidation resistance(at 1600℃)of the as-prepared coatings with and without the micro-arc oxidation ceramic layer.The results show that the Ta_(2)O_(5)layer prepared at 400 V is more continuous and has smaller pores than that prepared at 350 V.After microarc oxidation pretreatment,the Si-Cr-Ti-Zr coating on Ta12W alloy consists of three distinct layers:an upper layer dominated by Ti_(5)Si_(3),Ta_(5)Si_(3),and ZrSi;a middle layer dominated by TaSi_(2);a coating/substrate interfacial reaction layer dominated by Ta_(5)Si_(3).Both the Si-Cr-Ti-Zr coatings with and without the Ta_(2)O_(5)ceramic layer do not fail after isothermal oxidation at 1600℃for 5 h.Notably,the addition of the Ta2O5 ceramic layer reduces the high-temperature oxidation rate of the coating.
基金supported by the Key R&D Program of Shandong Province,China(No.2025CXGC 010412)the National Key Research and Development Program of China(No.2022YFB3709300)the National Natural Science Foundation of China(No.U21A2048).
文摘The limited high-temperature oxidation resistance of Mg alloys is a key factor restricting their development and application.The addition of some rare earth elements(REs),owing to their unique physical and chemical properties,can significantly enhance the oxidation resistance of Mg alloys.Based on our previous study,we conclude that REs such as Gd,Y,and Ce enhance the oxidation resistance of Mg-RE alloys.This article comprehensively reviews recent research progress on high-temperature oxidation behavior and the potential mechanism in Mg-RE alloys.Based on the thermodynamic and kinetic analyses,the evolution of the complex oxide system formed during the high-temperature oxidation of Mg-RE alloys is first summarized.The diffusion behavior and concentration control mechanisms of REs during the oxidation process and how these mechanisms affect the sustained growth of the oxide film and antioxidant properties were elucidated.Moreover,the different structures of the oxide films were classified,and their properties were discussed.Finally,this paper introduces the applications of commonly used REs in Mg alloys and frontier research on their oxidation mechanisms.Based on the above review,we propose that future research perspectives can be explored in terms of expanding the experimental temperature range for oxidation tests,optimizing the chemical composition by adding trace REs to study their synergistic mechanism,revealing the underlying oxidation mechanism through advanced in situ microscopic characterization methods,and investigating the mechanical properties of oxide films using diverse approaches.
文摘Platinum group metals have high melting points,strong corrosion resistance,stable chemical properties,and low oxygen permeability in high-temperature oxygen-containing environments.As thermal protective coating materials,they have gained essential applications in the aerospace field and have excellent prospects for application in frontier military fields,such as protecting hot-end components of hypersonic aircraft.This research reviewed the latest research progress of platinum group metal coatings with hightemperature oxidation resistance,including coating preparation techniques,oxidation failure,and alloying modification.The leading preparation techniques of current platinum group metal coatings were discussed,as well as the advantages and disadvantages of various existing preparation techniques.Besides,the intrinsic properties,failure forms,and failure mechanisms of coatings of single platinum group metal in high-temperature oxygen-containing environments were analyzed.On this basis,the necessity,main methods,and main achievements of alloying modification of platinum group metals were summarized.Finally,the future development of platinum group coatings with high-temperature oxidation resistance was discussed and prospected.
基金financially supported by the National Natural Science Foundation of China(No.22273026)Scientific Research Innovation Capability Support Project for Young Faculty(No.ZYGXQNJSKYCXNLZCXM-I15)+3 种基金Basic and Applied Basic Research Foundation of Guangdong Province(2024A1515012401)GJYC program of Guangzhou(No.2024D03J0002)the China Postdoctoral Science Foundation(No.2024M750938)Postdoctoral Fellowship Program of CPSF(No.GZC20240492)for their financial support。
文摘In contrast to cyclic polymers with ring-like backbones,side-chain cyclization is another intriguing structural feature that has not been extensively studied.In this study,a library of orthogonally protected monomers featuring monocyclic,dicyclic,or tricyclic pendant motifs was designed and prepared based on malic acid derivatives.Polyesters with precise chemical structures and uniform chain lengths were prepared modularly through iterative growth.Meticulous control over the chemical details allows for a close investigation of the topological effects on the polymer properties.Compared to their linear side chain counterparts,the presence of cyclic pendant groups has a significant impact on chain conformation,leading to a reduction in hydrodynamic volume and an enhancement in the glass transition temperature.These results underscore the potential of tailoring polymer properties through rational engineering of side chain topology.
基金support from the Joint Funds of the National Natural Science Foundation of China(Grant No.U23A2060)the National Natural Science Foundation of China(Grant Nos.42177143 and 52474150).
文摘Drilling and blasting tunneling is a cyclic process in which tunnel rock undergoes repeated blast loading,affecting its dynamic characteristics,energy evolution,and damage progression.To explore the dynamic mechanical properties and damage mechanisms of carbonaceous slate under cyclic impact loads of varying intensities,cyclic dynamic tests are conducted using a triaxial split Hopkinson pressure bar.This study analyzes the stress-strain relationship,energy damage evolution,and macro-to-micro failure characteristics.The results show that peak stress and strain are significantly influenced by impact intensity and the number of impacts.The initial dynamic stress is positively correlated with the impact intensity,but with more impact,the dynamic stress decreases while the peak strain increases.Energy evolution follows a pattern of"slow growthfluctuating growthrapid growth,"with the crack initiation stress and its proportion decreasing.CT and SEM analyses reveal that as the impact intensity increases,failure becomes more chaotic,the fracture volume increases,and the fracture mode shifts from interlayer and intergranular to through-layer and trans-granular fractures.These findings provide an experimental basis for soft rock tunnel stability analysis.
基金supported by the Low-Cost Long-Life Batteries program,China(No.WL-24-08-01)the National Natural Science Foundation of China(No.22279007)。
文摘The outstanding performance of O3-type NaNi_(1/3)Fe_(1/3)Mn_(1/3)O_(2)(NFM111)at both high and low temperatures coupled with its impressive specific capacity makes it an excellent cathode material for sodium-ion batteries.However,its poor cycling,owing to highpressure phase transitions,is one of its disadvantages.In this study,Cu/Ti was introduced into NFM111 cathode material using a solidphase method.Through both theoretically and experimentally,this study found that Cu doping provides a higher redox potential in NFM111,improving its reversible capacity and charge compensation process.The introduction of Ti would enhance the cycling stability of the material,smooth its charge and discharge curves,and suppress its high-voltage phase transitions.Accordingly,the NaNi_(0.27)Fe_(0.28)Mn_(0.33)Cu_(0.05)Ti_(0.06)O_(2)sample used in the study exhibited a remarkable rate performance of 142.97 mAh·g^(-1)at 0.1 C(2.0-4.2 V)and an excellent capacity retention of 72.81%after 300 cycles at 1C(1C=150 mA·g^(-1)).
基金sponsored by National Natural Science Foundation of China(Grant Nos.U22B6003 and 52304070)Key Laboratory of Geomechanics and Geotechnical Engineering Safety,Chinese Academy of Sciences(Grant No.SKLGME-JBGS2404).
文摘Large-scale geological energy storage plays a crucial role in balancing the intermittency of renewable energy.As an energy storage medium,soaked sandstone has a wide range of applications in geological energy storage.Understanding the damage characteristics in soaked sandstones is essential for ensuring the stability and longevity of these energy storage systems.This study involved multi-stage cyclic loading tests conducted on soaked sandstone to explore the damage evolution throughout the loading process.The findingsreveal several important insights:(1)The plastic hysteresis loops observed during multi-stage cyclic loading evolved from dense to sparse.An increase in stress level led to greater damage in the rock,as evidenced by an increase in accumulated peak/plastic strains.(2)Energy density and stress level are related by quadratic polynomial relationships.The elastic and dissipated energy densities are related by a linear law.The average energy storage coefficientdecreased by up to 24.1%with increasing stress amplitude,reflectingchanges in energy dynamics within the samples.(3)AE counts,amplitude,and frequency provided critical insights into rock damage and fracture patterns.The greater the loading rate and stress amplitude,the lower the proportion of high-amplitude,high-peak frequency,and shear-type fractures.Increasing stress amplitude caused a maximum 16.63%reduction in the AE bvalue,indicating shifts in fracture behavior under varying stress conditions.(4)The increase in loading rate and stress amplitude promotes the transformation of micropores and mesopores to macropores/microcracks.(5)Damage variables,definedin terms of cumulative dissipation energy,aligned closely with the fatigue damage model under multi-stage cyclic loading.Accelerated damage primarily occurred during the finalstages of fatigue loading,highlighting critical periods in the degradation of soaked sandstones.This study can offer guidance for designing operational parameters for energy storage geological bodies dominated by soaked sandstones.
基金supported by the National Key Research and Development Program of China(2024YFA1612900)the National Natural Science Foundation of China(Grant No.52103365 and No.12375270)the Guangdong Innovative and Entrepreneurial Research Team Program,China(Grant No.2021ZT09L227).
文摘Fine-grained nuclear graphite is a key material in high-temperature gas-cooled reactors(HTGRs).During air ingress accidents,core graphite components undergo severe oxidation,threatening structural integrity.Therefore,understanding the oxidation behavior of nuclear graphite is essential for reactor safety.The influence of oxidation involves multiple factors,including temperature,sample size,oxidant,impurities,filler type and size,etc.The size of the filler particles plays a crucial role in this study.Five ultrafine-and superfine-grained nuclear graphite samples(5.9-34.4μm)are manufactured using identical raw materials and manufacturing processes.Isothermal oxidation tests conducted at 650℃-750℃ are used to study the oxidation behavior.Additionally,comprehensive characterization is performed to analyze the crystal structure,surface morphology,and nanoscale to microscale pore structure of the samples.Results indicate that oxidation behavior cannot be predicted solely based on filler grain size.Reactive site concentration,characterized by active surface area,dominates the chemical reaction kinetics,whereas pore tortuosity,quantified by the structural parameterΨ,plays a key role in regulating oxidant diffusion.These findings clarify the dual role of microstructure in oxidation mechanisms and establish a theoretical and experimental basis for the design of high-performance nuclear graphite capable of long-term service in high-temperature gas-cooled reactors.
基金financially supported by the National Natural Science Foundation of China (22472199)Chinese Universities Scientific Fund (15055009)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金financially supported by the National Science and Technology Major Project(No.2024ZD1404705)。
文摘An advanced AlCrSiN/AlCrN/CrN/Cr multilayer coating was developed via hybrid multiarc ion plating and high-power impulse magnetron sputtering.The multilayer design enhanced the substrate-coating compatibility,achieving a critical load of 87.8 N.Silicon doping induced nanocrystallization and amorphization,increasing the hardness to 26 GPa.At high temperatures,a nanoscale Cr-rich(Cr,Al)_(2)O_(3) layer was formed,effectively inhibiting oxygen diffusion.The coating underwent unique phase transformations,during which Cr_(2)N and amorphous Si3N4 were converted into dispersed SiCr_(3) nanoparticles,which stabilized Cr atoms and suppressed their outward diffusion.Ab initio molecular dynamics simulations revealed that Cr atoms exhibited higher chemical activity and oxygen-capture capability than Al atoms and Si atoms served as diffusion barriers by pinning onto the oxidized surface,considerably improving the oxidation resistance of the coating.
基金supported by grants from the National Natural Science Foundation of China(Nos.22108154,22138006,32171430).
文摘Triterpenoids are valuable medicinal scaffolds,characterized by excellent pharmacological properties and the presence of hydroxyl and carboxyl groups that allow for further structural modifications.Expanding the scope of oxidative modifications on these molecules is crucial for increasing their synthetic structural diversity and unlocking new potential pharmacological activities.However,the progress has been limited by the scarcity of suitable tailoring enzymes.Here,we reported a break-through in achieving targeted and remote dual-site oxidation of licorice triterpenoids using a single P450 mutant.This approach successfully enabled the selective synthesis of the rare triterpenoid,liquiritic acid and 24-OH-liquiritic acid.Our findings demonstrate that microenvironmental accessibility engineering of triterpenoid substrates within the P450 enzyme is essential for continuous and regioselective oxidation.This study not only sheds light on the mechanistic aspects of P450 catalysis but also expands the enzymatic toolkit for selective oxidative modifications in triterpenoid biosynthesis.
基金supported by the National Key R&D Program of China(2021YFA1502802)the National Natural Science Foundation of China(U21B2092,22202213,22402210,22502215,22502214,22572200,and 22579171)+4 种基金the International Partnership Program of Chinese Academy of Sciences(172GJHZ2022028MI)the Shenyang Bureau of Science and Technology(24-213-3-25)the Natural Science Foundation of Liaoning Province(2025BS0153)Zhongke Technology Achievement Transfer and Transformation Center of Henan Province 2025119The XAS experiments were conducted in Beijing Synchrotron Radiation Facility(BSRF)and Shanghai Synchrotron Radiation Facility(SSRF).
文摘Single-atom catalysts(SACs)have demonstrated excellent performance in heterogeneous catalytic reactions owing to their maximized atomic efficiency,distinctive geometric,and electronic configurations.However,the efficacy of SACs remains limited for certain reactions requiring simultaneous activation of multiple reactants over metallic active sites.Herein,we report an atomically dispersed Pt1Ru1 dual-atom pair site anchored on nanodiamond@graphene(ND@G)for CO oxidation.The Pt1Ru1 dual-atom catalyst shows an exceptional turnover frequency(TOF)of 17.6.10^(-2)s^(-1)at significantly lower temperature(30℃),achieving a tenfold increase in TOF compared to singleatom Pt1/ND@G catalyst(1.5.10^(-2)s^(-1))and surpassing to previously reported Pt-based catalysts under similar conditions.Moreover,the catalyst demonstrates excellent stability,maintaining its activity for 40 h at 80℃without significant deactivation.The superior catalytic performance of Pt-Ru dual-atom catalysts is attributed to the synergistic effect between Pt and Ru atoms with enhanced metallicity for improving simultaneous adsorption and activation of CO and O_(2),and the tuning of conventional competitive reactant adsorption into a non-competitive pathway over dual-atom pair sites.The present work manifests the advantages of dual-atom pair sites in heterogeneous catalysis and paves the way for precise design of catalysts at the atomic scale.
基金supported by the National Natural Science Foundation of China(22075040,U21A20330,22131004)the National Key R&D Program of China(2022YFB3805900)+2 种基金the Jilin Provincial Scientific and Technological Development Program(20240602105RC)the Innovation Platform for Academicians of Hainan Provincethe Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(YSPTZX202321)。
文摘The development of efficient photocatalysts for crucial organic transformation,such as aerobic oxidation,remains challenging.Although powdered porous materials offer abundant accessible active sites,their application in liquid-phase catalysis is often limited by insufficient light absorption and inevitable charge recombination,which are inherent drawbacks of conventional heterogeneous catalysts.Here,through rational design and nanoscale-engineering of porous aromatic frameworks(PAFs)comprising porphyrin and porous organic cage,a quasi-homogeneous porous photocatalyst with high catalytic activity and controllable dimension was developed.The interface-directed growth in oil-in-water emulsion shaped the morphology of photoactive PAFs from powders to nanoflakes,which facilitated the light absorbance and catalyst-substrate interaction.Compared with PAF powders,PAF nanoflakes exhibited superior photocatalytic activity for aerobic oxidation.For mustard gas simulant(2-chloroethyl ethyl sulfide,CEES),PAF nanoflakes exhibited ultrafast detoxification rates in room air with a half-life(t_(1/2))as fast as 26s,which even exceeded other catalysts in pure oxygen.It also completely catalyzed the aerobic oxidation of thioether within 15 min,which is almost the fastest rate among any reported organic photocatalysts.Furthermore,the efficient catalytic performance under mild conditions caused by improved light enrichment,surface charge transfer and carrier lifetime was elucidated.
基金support from the Australian Research Council(ARC)Linkage Project(No.LP230100166).
文摘Selective depression of pyrite remains a major bottleneck in copper flotation,particularly when high-pyrite ores are processed and saline water is used.In such environments,conventional approaches using lime and inert grinding media often fail to discriminate ef-fectively between pyrite and valuable copper minerals due to strong copper activation on pyrite surfaces.This study introduced a novel approach using inorganic radicals generated from peroxymonosulfate(PMS)to selectively oxidize and depress pyrite.Flotation tests with synthetic high-pyrite ore blends showed that PMS significantly reduced pyrite recovery while maintaining or improving chalcopyrite flot-ation.Ethylenediaminetetraacetic acid(EDTA)extraction confirmed selective oxidation of pyrite,and electron paramagnetic resonance(EPR)spectroscopy identified hydroxyl(·OH)and sulfate(SO_(4)^(·-))radicals as the dominant reactive species.Iron ions from grinding me-dia and mineral surfaces were identified as key activators of PMS.A major insight was pyrite’s dual role,acting both as a radical scav-enger and an activator,which made it highly reactive and susceptible to radical-induced oxidation.This process converted surface copper-sulfur species into copper hydroxides,effectively suppressing pyrite flotation.While previous studies have applied EPR to detect radicals in simplified activator/precursor systems,this study provides the first direct mechanistic evidence of radical-driven selectivity in flotation by detecting inorganic radicals in a complex flotation slurry,thereby demonstrating their persistence under industrially relevant conditions and establishing a foundation for more effective and targeted flotation strategies.
文摘This study presents and verifies a hybrid methodology for reliable determination of parameters in structural rheological models(Zener,Burgers,and Maxwell)describing the viscoelastic behavior of polyurethane specimens manufactured using extrusion-based 3D printing.Through comprehensive testing,including cyclic compression at strain rates ranging from 0.12 to 120 mm/min(0%-15%strain)and creep/relaxation experiments(10%-30%strain),the lumped parameters were independently determined using both analytical and numerical solutions of the models’differential equations,followed by cross-verification in additional experiments.Numerical solutions for creep and relaxation problems were obtained using finite element analysis,with the three-parameter Mooney-Rivlin model and Prony series employed to simulate elastic and viscous stress components,respectively.Energy dissipation per cycle was quantified during cyclic compression tests.The results demonstrate that all three models adequately describe material behavior within the 0%-15%strain range across various strain rates.Comparative analysis revealed the Burgers model’s superior performance in characterizing creep and stress relaxation at low strain levels.While Zener and Burgers model parameters from uniaxial compression showed limited applicability for energy dissipation calculations,the generalized Maxwell model effectively captured viscoelastic properties across different strain rates.Notably,parameters derived from creep tests provided a more universal assessment of dissipative properties due to optimization based on characteristic curve regions.Both parameter sets described polyurethane’s elastic-hysteretic behavior with approximately 20%error,proving significantly more accurate than the linear strain-time dependence hypothesis.Finite element analysis(FEA)complemented numerical modeling by demonstrating that while the generalized Maxwell model effectively describes initial rapid stress-strain changes,FEA provides superior characterization of steady-state processes.This computational approach yields more physically representative results compared to simplified analytical solutions,despite certain limitations in transient analysis.
基金supported by the National Key R&D Program of China(Grant No.2022YFC3004704)the National Natural Science Foundation of China(Grant No.52174166)Graduate Research and Innovation Foundation of Chongqing,China(Grant No.CYB23031),which were gratefully acknowledged.
文摘During deep coal mining,an instability failure of coal usually occurs under the combined effect of initial damage and triaxial cyclic loading and unloading(TCLU).Therefore,this study investigated the impact of initial damage on mechanical behavior and acoustic emission(AE)characteristics of coal under TCLU.Initial damage variables(IDVs)of coal specimens were quantified using preloading,followed by TCLU experiments to assess the deformation,energy distribution,and fracture development.The results revealed that the increase in IDVs significantly reduced the structural integrity of coal specimens,increased the cumulative irreversible strain,and enhanced the dissipated energy owing to microfracture expansion.Moreover,AE monitoring showed earlier activation of fractures and a higher occurrence of large-scale rupture events of coal specimens with high IDVs,which correlated with decreasing AE b values(reflecting the different scales of fracture within specimens)and increasing S values(reflecting the AE activity within specimens).Additionally,computed tomography analysis revealed intensified fracture networks and increasing three-dimensional fractal dimensions of coal specimens with higher IDVs.Finally,the coupling effect of TCLU and initial damage on the weakening mechanism of coal was investigated.Initial damage significantly reduced the structural integrity of coal by increasing the number of weak planes within coal specimens,contributing to the earlier activation and rapid expansion of fractures at low stress levels under TCLU and eventually accelerating the weakening process of coal.This study provides a scientific basis and theoretical support for the prevention and control of dynamic disasters in deep coal mining.
