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
Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effec...Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effective alternative to commercially available COCs because of using low-cost DCPD as cyclic olefin monomer,these inherent unsaturated double bonds on E/DCPD copolymers cause low heat resistance,oxidation,and crosslinking during processing and storage.And E/DCPD copolymers usually showed lower glass-transition temperature(T_(g))compared with commercially available COCs.In this study,we studied the E-DCPD copolymerization catalyzed by a scandium complex and the sequential hydrogenation catalyzed by a nickel compound to prepare saturated copolymers H-(E/DCPD).The polymerization activities are high up to 5.86×10^(6)g/(molSc·h),and the resultant H-(E/DCPD)copolymers showed narrow polymer dispersity index(PDI=1.5–2.0).By changing the polymerization conditions,a series of H-(E/DCPD)copolymers with tunable DCPD incorporation(28.4 mol%–44.9 mol%)and a wide range of T_(g)(123–171°C)were obtained.H-(E/DCPD)copolymers exhibited excellent optical properties(transparency>90%,refractive index of 1.543),similar to those of commercial COCs,making them an alternative for high-performance optical applications.This method solves the problems of traditional E/DCPD copolymers and provides a practical way to produce stable and low-cost COCs,and is comparable with commercially available COC resins.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
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
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
The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps...The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.展开更多
Intermittent joints are common in rock masses and are subjected to cyclic shear loads from seismic events,environmental factors,and human activities.In this study,we conducted cyclic shear tests to investigate the eff...Intermittent joints are common in rock masses and are subjected to cyclic shear loads from seismic events,environmental factors,and human activities.In this study,we conducted cyclic shear tests to investigate the effect of joint geometry(persistence,overlap,and spacing)on the cyclic shear behavior of intermittent joints under constant normal stiffness conditions.Our results revealed step‐path failure surfaces comprising tensile and shear failure surfaces.Shear failure surface controlled the degradation of shear properties,with shear strength decreasing progressively with cycles,ranging from 74.07%to 97.94%.Intermittent joints exhibited significant compressibility,with dilation predominant in early cycles and compression in later ones.Shear strength and dilation were more sensitive to joint persistence and spacing than overlap.Friction coefficients showed nonmonotonic variations with cycle number.High persistence,moderate overlap,and small spacing were identified as the most destabilizing combination.These findings offer valuable insights for stability assessment and deformation characterization in deep rock engineering.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
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
Herein,one-pot chemocatalytic conversion of xylose to value-added C_(5)/C_(4) cyclic ethers over a novel ZrO_(2)-doped Ni-Pd catalyst supported on H-βzeolite was demonstrated.Optimized catalyst,namely,Ni_(2) Pd_(0.5)...Herein,one-pot chemocatalytic conversion of xylose to value-added C_(5)/C_(4) cyclic ethers over a novel ZrO_(2)-doped Ni-Pd catalyst supported on H-βzeolite was demonstrated.Optimized catalyst,namely,Ni_(2) Pd_(0.5)Zr_(1)/H-β(25),achieved a high xylose transformation(>99%)with high selectivities toward 2-methyltetrahydrofuran(48.6%)and tetrahydropyran(20.2%)under mild reaction conditions(200℃,1.0 MPa H_(2),and 2 h).Systematic investigation of the physicochemical properties of the catalyst revealed that ZrO_(2) doping induced O vacancies,enhanced H_(2) activation,and improved metal dispersion,thereby promoting hydrogenation and hydrodeoxygenation.In situ diffuse reflectance infrared Fourier transform spectroscopy using furfural and furfuryl alcohol probes confirmed preferential adsorption geometries and electronic interactions at metal-ZrO_(2) interfaces.Time-resolved and feedstock variation studies further elucidated the reaction mechanism and highlighted the roles of key intermediates.The proposed catalyst exhibited excellent recyclability with only a minor decline in performance after multiple xylose conversion cycles.This study provides mechanistic insights and design principles for the development of efficient multifunctional catalysts for biomass valorization.展开更多
Cyclic volatile methyl siloxanes(cVMSs)are widely used in industrial and consumer products because of their thermal stability,low reactivity,and reduced surface tension[1].Their extensive use has resulted in environme...Cyclic volatile methyl siloxanes(cVMSs)are widely used in industrial and consumer products because of their thermal stability,low reactivity,and reduced surface tension[1].Their extensive use has resulted in environmental pollution globally.Recognized as very persistent and very bioaccumulative(vPvB),compounds such as octamethylcyclotetrasiloxane(D4),decamethylcyclopentasiloxane(D5),and dodecamethylcyclohexasiloxane(D6)are regulated in the European Union[2]and are monitored worldwide.展开更多
The microbial-induced calcite precipitation(MICP)technique has been developed as a sustainable methodology for the improvement of the engineering characteristics of sandy soils.However,the efficiency of MICP-treated s...The microbial-induced calcite precipitation(MICP)technique has been developed as a sustainable methodology for the improvement of the engineering characteristics of sandy soils.However,the efficiency of MICP-treated sand has not been well established in the literature considering cyclic loading under undrained conditions.Furthermore,the efficacy of different bacterial strains in enhancing the cyclic properties of MICP-treated sand has not been sufficiently documented.Moreover,the effect of wetting-drying(WD)cycles on the cyclic characteristics of MICP-treated sand is not readily available,which may contribute to the limited adoption of MICP treatment in field applications.In this study,strain-controlled consolidated undrained(CU)cyclic triaxial testing was conducted to evaluate the effects of MICP treatment on standard Ennore sand from India with two bacterial strains:Sporosarcina pasteurii and Bacillus subtilis.The treatment durations of 7 d and 14 d were considered,with an interval of 12 h between treatments.The cyclic characteristics,such as the shear modulus and damping ratio,of the MICP-treated sand with the different bacterial strains have been estimated and compared.Furthermore,the effect of WD cycles on the cyclic characteristics of MICP-treated sand has been evaluated considering 5–15 cycles and aging of samples up to three months.The findings of this study may be helpful in assessing the cyclic characteristics of MICP-treated sand,considering the influence of different bacterial strains,treatment duration,and WD cycles.展开更多
Red clay,widely used as a subgrade material in southern China,requires a reliable evaluation of its dynamic behavior to ensure infrastructure safety.Long-term cyclic triaxial tests were conducted on red clay from typi...Red clay,widely used as a subgrade material in southern China,requires a reliable evaluation of its dynamic behavior to ensure infrastructure safety.Long-term cyclic triaxial tests were conducted on red clay from typical,complex subway subgrades to investigate its dynamic properties and shakedown behavior under intermittent cyclic loading.Results show that intermittent cyclic loading,especially with multiple amplitudes,causes greater axial plastic strain and lower post-cyclic strength than continuous loading.These effects diminish with increasing confining pressure.Notably,axial strain partially recovers during loading intervals,with recovery ratios depending on the number and sequence of pauses.Based on the rules of cumulative plastic strain rates and cumulative plastic strain increments,shakedown behavior for red clay under intermittent cyclic loading is divided into three categories:plastic shakedown,critical shakedown,and plastic creep.A quantitative shakedown limit criterion is proposed using the Boltzmann function.Shakedown behavior significantly influences the post-cyclic strengths,and the influence diminishes as confining pressure increases.Samples exhibiting plastic creep and plastic shakedown behavior have the lowest and highest strengths,and those with critical shakedown behaviors have medium strengths.Cyclic loading with relatively low-stress amplitude causes a hardening effect,while cyclic loading intermittence or cyclic loading with relatively high-stress amplitude causes a degradation effect,and both effects are mitigated by higher confining pressures.展开更多
The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycl...The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.展开更多
An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and exte...An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and extension tests were conducted to study the parameters of the model. Results showed that the relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain were nearly unique, when the initial octahedral shear stress ratios of specimens were equal to 0.3, 0.5 and 0.7. The relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain determined from the cyclic triaxial compression tests were basically the same as those determined from the cyclic triaxial extension tests. Furthermore, the relationships were not related to the initial stress condition, the test stress state and the octahedral cyclic shear stress ratio. The relationships determined from the cyclic triaxial tests under no deviatoric stress were basically the same as those determined from the cyclic triaxial tests under deviatoric stress. The change of the octahedral cyclic accumulative strain with the number of cycles was unique under different tests stress states. An equivalent visco-elastic constitutive model of saturated soft clay under UU condition was initially established.展开更多
A cyclic quenching treatment(CQT)succeeded in turning a 2.3 GPa maraging steel with a Charpy impact energy of 9 J into a new grade with the same strength but a Charpy impact energy of 20 J upon 4 cyclic treatments.The...A cyclic quenching treatment(CQT)succeeded in turning a 2.3 GPa maraging steel with a Charpy impact energy of 9 J into a new grade with the same strength but a Charpy impact energy of 20 J upon 4 cyclic treatments.The improvement of mechanical properties is attributed to the refinement and increased chemical heterogeneity of the martensitic substructure,rather than the refinement of prior austenite grain(PAG),as well as the Transformation-Induced Plasticity(TRIP)effect facilitated by small austenite grains.The role of local segregation of Ni during CQT in the formation of Ni-rich austenite grains,Ni-rich martensite laths and Ni-poor martensite laths,was investigated and verified by DICTRA simulations.This study highlights the important influence of Ni partitioning behavior during CQT,providing insights into microstructural evolution and mechanical properties.展开更多
This work aims to reveal the mechanical responses and energy evolution characteristics of skarn rock under constant amplitude-varied frequency loading paths.Testing results show that the fatigue lifetime,stress−strain...This work aims to reveal the mechanical responses and energy evolution characteristics of skarn rock under constant amplitude-varied frequency loading paths.Testing results show that the fatigue lifetime,stress−strain responses,deformation,energy dissipation and fracture morphology are all impacted by the loading rate.A pronounced influence of the loading rate on rock deformation is found,with slower loading rate eliciting enhanced strain development,alongside augmented energy absorption and dissipation.In addition,it is revealed that the loading rate and cyclic loading amplitude jointly influence the phase shift distribution,with accelerated rates leading to a narrower phase shift duration.It is suggested that lower loading rate leads to more significant energy dissipation.Finally,the tensile or shear failure modes were intrinsically linked to loading strategy,with cyclic loading predominantly instigating shear damage,as manifest in the increased presence of pulverized grain particles.This work would give new insights into the fortification of mining structures and the optimization of mining methodologies.展开更多
Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment ...Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.展开更多
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supported by the National Natural Science Foundation of China(Nos.52273017 and 52273016)Strategic Priority Program of the Chinese Academy of Sciences(No.ZDRW-CN-2023-1)Natural Science Foundation of Jilin Province(No.SKL202302033).
文摘Cyclic olefin copolymers(COCs)are highly valuable optical resins,but their productions on industry are fully limited by the monomer norbornene.Although ethylene/dicyclopentadiene(E/DCPD)copolymers provide a cost-effective alternative to commercially available COCs because of using low-cost DCPD as cyclic olefin monomer,these inherent unsaturated double bonds on E/DCPD copolymers cause low heat resistance,oxidation,and crosslinking during processing and storage.And E/DCPD copolymers usually showed lower glass-transition temperature(T_(g))compared with commercially available COCs.In this study,we studied the E-DCPD copolymerization catalyzed by a scandium complex and the sequential hydrogenation catalyzed by a nickel compound to prepare saturated copolymers H-(E/DCPD).The polymerization activities are high up to 5.86×10^(6)g/(molSc·h),and the resultant H-(E/DCPD)copolymers showed narrow polymer dispersity index(PDI=1.5–2.0).By changing the polymerization conditions,a series of H-(E/DCPD)copolymers with tunable DCPD incorporation(28.4 mol%–44.9 mol%)and a wide range of T_(g)(123–171°C)were obtained.H-(E/DCPD)copolymers exhibited excellent optical properties(transparency>90%,refractive index of 1.543),similar to those of commercial COCs,making them an alternative for high-performance optical applications.This method solves the problems of traditional E/DCPD copolymers and provides a practical way to produce stable and low-cost COCs,and is comparable with commercially available COC resins.
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financial support from the National Key R&D Program of China(2022YFA1504500 and 2023YFA1506300)the National Natural Science Foundation of China(22588201,22225204,and 22472169)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0600100)Liaoning Binhai Laboratory(LBLG-2024-03)。
文摘The traditional ammonia synthesis via the Haber–Bosch process requires large consumption of highpurity H_(2) and causes significant carbon emissions owing to the energy-intensive and complex hydrogen production steps conducted under harsh reaction conditions.Herein,we report a cyclic catalytic process for the production of NH_(3) by directly utilizing earth-abundant CH_(4) as a hydrogen source for N_(2) hydrogenation while simultaneously co-producing H_(2) over an alumina-supported iron catalyst(Fe/Al_(2)O_(3)).It achieves exceptional productivities of 2300μmol g^(-1)h^(-1)for NH_(3) and 400 mmol g^(-1)h^(-1)for H_(2) at700℃.By eliminating the coke that results from CH_(4) pyrolysis through a reaction with the greenhouse gas CO_(2) to produce valuable CO,we establish an atom-economic cyclic catalytic process while producing a CO stream intrinsically separated in the regeneration step.Mechanistic investigations indicate that the iron species in Fe/Al_(2) O_(3) serve as tri-functional active sites for CH_(4) pyrolysis,N_(2) hydrogenation,and coke elimination to produce CO,thus enabling an efficient and environmentally friendly cyclic catalytic process.
基金National Natural Science Foundation of China,Grant/Award Number:42172292Shandong Energy Group,Grant/Award Number:SNKJ2022A01-R26Taishan Scholars Project Special Funding。
文摘Intermittent joints are common in rock masses and are subjected to cyclic shear loads from seismic events,environmental factors,and human activities.In this study,we conducted cyclic shear tests to investigate the effect of joint geometry(persistence,overlap,and spacing)on the cyclic shear behavior of intermittent joints under constant normal stiffness conditions.Our results revealed step‐path failure surfaces comprising tensile and shear failure surfaces.Shear failure surface controlled the degradation of shear properties,with shear strength decreasing progressively with cycles,ranging from 74.07%to 97.94%.Intermittent joints exhibited significant compressibility,with dilation predominant in early cycles and compression in later ones.Shear strength and dilation were more sensitive to joint persistence and spacing than overlap.Friction coefficients showed nonmonotonic variations with cycle number.High persistence,moderate overlap,and small spacing were identified as the most destabilizing combination.These findings offer valuable insights for stability assessment and deformation characterization in deep rock engineering.
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)).
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.
基金supported by the Bio&Medical Technology Development Program(no.RS-2022-NR067354)established by the National Research Foundation(NRF)funded by the Korean Ministry of Science and ICT(MSIT)+2 种基金an NRF grant funded by the Korean MSIT(no.RS-2023-00261322)Additional support from the Korea Institute of Energy Technology Evaluation and Planning(KETEP)the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(RS-2024-00469587)was also appreciated。
文摘Herein,one-pot chemocatalytic conversion of xylose to value-added C_(5)/C_(4) cyclic ethers over a novel ZrO_(2)-doped Ni-Pd catalyst supported on H-βzeolite was demonstrated.Optimized catalyst,namely,Ni_(2) Pd_(0.5)Zr_(1)/H-β(25),achieved a high xylose transformation(>99%)with high selectivities toward 2-methyltetrahydrofuran(48.6%)and tetrahydropyran(20.2%)under mild reaction conditions(200℃,1.0 MPa H_(2),and 2 h).Systematic investigation of the physicochemical properties of the catalyst revealed that ZrO_(2) doping induced O vacancies,enhanced H_(2) activation,and improved metal dispersion,thereby promoting hydrogenation and hydrodeoxygenation.In situ diffuse reflectance infrared Fourier transform spectroscopy using furfural and furfuryl alcohol probes confirmed preferential adsorption geometries and electronic interactions at metal-ZrO_(2) interfaces.Time-resolved and feedstock variation studies further elucidated the reaction mechanism and highlighted the roles of key intermediates.The proposed catalyst exhibited excellent recyclability with only a minor decline in performance after multiple xylose conversion cycles.This study provides mechanistic insights and design principles for the development of efficient multifunctional catalysts for biomass valorization.
基金supported by the Shanghai 3-year Public Health Action Plan(grant number:GWVI-11.1-39).
文摘Cyclic volatile methyl siloxanes(cVMSs)are widely used in industrial and consumer products because of their thermal stability,low reactivity,and reduced surface tension[1].Their extensive use has resulted in environmental pollution globally.Recognized as very persistent and very bioaccumulative(vPvB),compounds such as octamethylcyclotetrasiloxane(D4),decamethylcyclopentasiloxane(D5),and dodecamethylcyclohexasiloxane(D6)are regulated in the European Union[2]and are monitored worldwide.
基金the financial support provided by the Ministry of Education(MoE),Government of IndiaThe second author acknowledges Coal India Limited for providing financial assistance for the research(Project No.CIL/R&D/01/73/2021).
文摘The microbial-induced calcite precipitation(MICP)technique has been developed as a sustainable methodology for the improvement of the engineering characteristics of sandy soils.However,the efficiency of MICP-treated sand has not been well established in the literature considering cyclic loading under undrained conditions.Furthermore,the efficacy of different bacterial strains in enhancing the cyclic properties of MICP-treated sand has not been sufficiently documented.Moreover,the effect of wetting-drying(WD)cycles on the cyclic characteristics of MICP-treated sand is not readily available,which may contribute to the limited adoption of MICP treatment in field applications.In this study,strain-controlled consolidated undrained(CU)cyclic triaxial testing was conducted to evaluate the effects of MICP treatment on standard Ennore sand from India with two bacterial strains:Sporosarcina pasteurii and Bacillus subtilis.The treatment durations of 7 d and 14 d were considered,with an interval of 12 h between treatments.The cyclic characteristics,such as the shear modulus and damping ratio,of the MICP-treated sand with the different bacterial strains have been estimated and compared.Furthermore,the effect of WD cycles on the cyclic characteristics of MICP-treated sand has been evaluated considering 5–15 cycles and aging of samples up to three months.The findings of this study may be helpful in assessing the cyclic characteristics of MICP-treated sand,considering the influence of different bacterial strains,treatment duration,and WD cycles.
基金the support of the National Natural Science Foundation of China(Grant No.52108319)the Natural Science Foundation of Jiangxi Province(20224BAB214069)。
文摘Red clay,widely used as a subgrade material in southern China,requires a reliable evaluation of its dynamic behavior to ensure infrastructure safety.Long-term cyclic triaxial tests were conducted on red clay from typical,complex subway subgrades to investigate its dynamic properties and shakedown behavior under intermittent cyclic loading.Results show that intermittent cyclic loading,especially with multiple amplitudes,causes greater axial plastic strain and lower post-cyclic strength than continuous loading.These effects diminish with increasing confining pressure.Notably,axial strain partially recovers during loading intervals,with recovery ratios depending on the number and sequence of pauses.Based on the rules of cumulative plastic strain rates and cumulative plastic strain increments,shakedown behavior for red clay under intermittent cyclic loading is divided into three categories:plastic shakedown,critical shakedown,and plastic creep.A quantitative shakedown limit criterion is proposed using the Boltzmann function.Shakedown behavior significantly influences the post-cyclic strengths,and the influence diminishes as confining pressure increases.Samples exhibiting plastic creep and plastic shakedown behavior have the lowest and highest strengths,and those with critical shakedown behaviors have medium strengths.Cyclic loading with relatively low-stress amplitude causes a hardening effect,while cyclic loading intermittence or cyclic loading with relatively high-stress amplitude causes a degradation effect,and both effects are mitigated by higher confining pressures.
文摘The ring has been a romantic fascination throughout the ages,embodying not only beauty and order but also harboring numerous undisclosed properties awaiting discovery.In the realm of supramolecular chemistry,macrocycles,with a cyclic structure and a central cavity like a doughnut,captivate the attention of scientists[1].In 1967,Pedersen's groundbreaking revelation that alkali metal ions could"fall into"the cavities of a cyclic ether named crown ether,even in organic solvents,unveiled a novel universe of macrocycle chemistry.Since then,numerous macrocyclic structures in nature have been discovered,isolated,and scrutinized.Drawing inspiration from nature,chemists endeavor to explore the vast potential of macrocyclic compounds by designing and synthesizing artificial macrocycles with diverse structural features and recognition properties.
基金Supported by National Natural Science Foundation of China ( No. 51179120)
文摘An equivalent visco-elastic model of saturated soft clay was studied under unconsolidated undrained (UU) condition, which can be used to evaluate the stability of ocean foundation. Cyclic triaxial compression and extension tests were conducted to study the parameters of the model. Results showed that the relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain were nearly unique, when the initial octahedral shear stress ratios of specimens were equal to 0.3, 0.5 and 0.7. The relationships of the damping ratio and the octahedral shear modulus with the octahedral cyclic shear strain determined from the cyclic triaxial compression tests were basically the same as those determined from the cyclic triaxial extension tests. Furthermore, the relationships were not related to the initial stress condition, the test stress state and the octahedral cyclic shear stress ratio. The relationships determined from the cyclic triaxial tests under no deviatoric stress were basically the same as those determined from the cyclic triaxial tests under deviatoric stress. The change of the octahedral cyclic accumulative strain with the number of cycles was unique under different tests stress states. An equivalent visco-elastic constitutive model of saturated soft clay under UU condition was initially established.
基金sponsored by the National Natural Science Foun-dation of China(Grant Nos.52271122,52203384).
文摘A cyclic quenching treatment(CQT)succeeded in turning a 2.3 GPa maraging steel with a Charpy impact energy of 9 J into a new grade with the same strength but a Charpy impact energy of 20 J upon 4 cyclic treatments.The improvement of mechanical properties is attributed to the refinement and increased chemical heterogeneity of the martensitic substructure,rather than the refinement of prior austenite grain(PAG),as well as the Transformation-Induced Plasticity(TRIP)effect facilitated by small austenite grains.The role of local segregation of Ni during CQT in the formation of Ni-rich austenite grains,Ni-rich martensite laths and Ni-poor martensite laths,was investigated and verified by DICTRA simulations.This study highlights the important influence of Ni partitioning behavior during CQT,providing insights into microstructural evolution and mechanical properties.
基金Project(52174069) supported by the National Natural Science Foundation of ChinaProject(8202033) supported by the Beijing Natural Science Foundation,ChinaProject(KCF2203) supported by the Henan Key Laboratory for Green and Efficient Mining&Comprehensive Utilization of Mineral Resources (Henan Polytechnic University),China。
文摘This work aims to reveal the mechanical responses and energy evolution characteristics of skarn rock under constant amplitude-varied frequency loading paths.Testing results show that the fatigue lifetime,stress−strain responses,deformation,energy dissipation and fracture morphology are all impacted by the loading rate.A pronounced influence of the loading rate on rock deformation is found,with slower loading rate eliciting enhanced strain development,alongside augmented energy absorption and dissipation.In addition,it is revealed that the loading rate and cyclic loading amplitude jointly influence the phase shift distribution,with accelerated rates leading to a narrower phase shift duration.It is suggested that lower loading rate leads to more significant energy dissipation.Finally,the tensile or shear failure modes were intrinsically linked to loading strategy,with cyclic loading predominantly instigating shear damage,as manifest in the increased presence of pulverized grain particles.This work would give new insights into the fortification of mining structures and the optimization of mining methodologies.
基金supported by the National Natural Science Foundation of China(U22A20120,52071135,51871090,U1804135,and 52301269)the Natural Science Foundation of Hebei Province for Innovation Groups Program(C2022203003)Fundamental Research Funds for the Universities of Henan Province(NSFRF220201).
文摘Designing catalysts with high catalytic activity and stability is the key to achieve the commercial application of MgH_(2).Herein,the sulfur doped Ti_(3)C_(2)(S-Ti_(3)C_(2))was successfully prepared by heat treatment of Ti_(3)C_(2)MXene under Ar/H_(2)S atmosphere to facilitate the hydrogen release and uptake from MgH_(2).The S-Ti_(3)C_(2)exhibited pleasant catalytic effect on the hydriding/dehydriding kinetics and cyclic stability of MgH_(2).The addition of 5 wt%S-Ti_(3)C_(2)into MgH_(2)resulted in a reduction of 114℃in the starting dehydriding temperature compared to pure MgH_(2).MgH_(2)+5 wt%S-Ti_(3)C_(2)sample could quickly release 6.6 wt%hydrogen in 17 min at 220℃,and 6.8 wt%H_(2)was absorbed in 25 min at 200℃.Cyclic testing revealed that MgH_(2)+5 wt%S-Ti_(3)C_(2)system achieved a reversible hydrogen capacity of 6.5 wt%.Characterization analysis demonstrated that Ti-species(Ti0,Ti^(2+),Ti-S,and Ti^(3+))as active species significantly lowered the dehydrogenation temperature and promoted the re-/dehydrogenation kinetics of MgH_(2),and sulfur doping can effectively improve the stability of Ti0 and Ti^(3+),contributing to the improvement of cyclic stability of MgH_(2).This study provides strategy for the construction of catalysts for hydrogen storage materials.
