Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that ra...Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.展开更多
We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic m...We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.展开更多
Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced...Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.展开更多
Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although th...Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.展开更多
Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesi...Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesized by solid-state reaction at 700℃for 2 h via a kinetically favorable mechanism and characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),AC impedance spectroscopy,etc.It has been revealed that the as-synthesized melilite La_(2)Ga_(3)O_(7.5)shows an orthorhombic symmetry with crystal cell parameters a=11.4690(1)A,b=11.2825(4)A,and c=10.3735(4)A,while has more Raman active modes than LaSrGa_(3)O_(7)with a tetragonal structure,which was also synthesized under the same conditions for comparison,but tends to slowly decompose into perovskite LaGaO_(3)and Ga2O_(3)when annealed at 700℃for over 20 h driven by its meta-stability.Moreover,the metastable La2Ga3O7.5 shows a higher XPS binding energy for the excess oxide ions in the crystal structure than those at normal lattice sites.Its intrinsic grain oxide ion conductivity can reach as high as 0.04 and 0.51 mS·cm^(-1)at 550 and 700℃,respectively,characterized by a simple Arrhenius relationship ln(σT)-1/T with invariable activation energy,E_(a)=1.22 eV,over the temperature range from 300 to 700℃,along with an apparent grain boundary conductivity that is about double that from the grains thanks to the clean grain boundaries.This paper provides a new strategic approach to the synthesis of complex oxides that may be of high performance but are difficultly achieved by the conventional ceramic method at high temperatures.展开更多
We investigate the quantum dynamics of the 1D spinless Fermi-Hubbard model with a linear-tilted potential.Surprisingly in a strong resonance regime,we show that the model can be described by the kinetically constraine...We investigate the quantum dynamics of the 1D spinless Fermi-Hubbard model with a linear-tilted potential.Surprisingly in a strong resonance regime,we show that the model can be described by the kinetically constrained effective Hamiltonian,and it can be spontaneously divided into two commuting parts dubbed Hamiltonian dimerization,which are composed of two distinct sets of constrained nearest-neighbor hopping terms:one set acting exclusively on odd bonds and the other on even bonds.Specifically it is shown that each part can be independently mapped onto the well-known PXP model;therefore the dimerized Hamiltonian is equivalent to a two-fold PXP model.As a consequence,we numerically demonstrate this system can host the so-called quantum many-body scars,which present dynamical revivals and ergodicity-breaking behaviors.However,in sharp contrast with traditional quantum many-body scars,here the scarring states in our model driven by different parts of the Hamiltonian will revive in different periods,and those of double parts can display a biperiodic revival pattern,both originating from the Hamiltonian dimerization.Besides,the condition of off-resonance is also discussed,and we show the crossover from quantum many-body scar to ergodicity breaking is diagnosed via level statistics.Our model provides a platform for understanding the interplay of Hilbert space fragmentation and the constrained quantum systems.展开更多
The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the micro...The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.展开更多
This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with t...This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.展开更多
The present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has...The present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has been employed as a coating agent.The SEM micrographs revealed distinct features of both pure AN and NC,contrasting with the irregular granular surface topography of the coated AN particles,demonstrating the adherence of NC on the AN surface.Structural analysis via infrared spectroscopy(IR)demonstrated a successful association of AN and NC,with slight shifts observed in IR bands indicating interfacial interactions.Powder X-ray Diffraction(PXRD)analysis further elucidated the structural changes induced by the coating process,revealing that the NC coating altered the crystallization pattern of its pure form.Thermal analysis demonstrates distinct profiles for pure and coated AN,for which the coated sample exhibits a temperature increase and an enthalpy decrease of the room temperature allotropic transition by 6℃,and 36%,respectively.Furthermore,the presence of NC coating alters the intermolecular forces within the composite system,leading to a reduction in melting enthalpy of coated AN by~39%compared to pure AN.The thermal decomposition analysis shows a two-step thermolysis process for coated AN,with a significant increase in the released heat by about 78%accompanied by an increase in the activation barrier of NC and AN thermolysis,demonstrating a stabilized reactivity of the AN-NC particles.These findings highlight the synergistic effect of NC coating on AN particles,which contributed to a structural and reactive stabilization of both AN and NC,proving the potential application of NC-coated AN as a strategically advantageous oxidizer in composite solid propellant formulations.展开更多
Natural gas hydrates widely accumulate in submarine sediments composed of clay minerals.However,due to the complex physiochemistry and micron-sized particles of clay minerals,their effects on methane hydrate(MH)format...Natural gas hydrates widely accumulate in submarine sediments composed of clay minerals.However,due to the complex physiochemistry and micron-sized particles of clay minerals,their effects on methane hydrate(MH)formation and dissociation are still in controversy.In this study,montmorillonite and illite were separately mixed with quartz sand to investigate their effects on MH formation and dissociation.The microstructure of synthesized samples was observed by cryo-SEM innovatively to understand the effects of montmorillonite and illite on MH phase transition in micron scale.Results show that montmorillonite and illite both show the inhibition on MH formation kinetics and water-to-hydrate conversion,and illite shows a stronger inhibition.The 10 wt%montmorillonite addition significantly retards MH formation rate,and the 20 wt%montmorillonite has a less inhibition on the rate.The increase of illite mass ratio(0-20 wt%)retards the rate of MH formation.As the content of clay minerals increase,the water-to-hydrate conversion decreases.Cryo-SEM images presented that montmorillonite aggregates separate as individual clusters while illite particles pack as face-to-face configuration under the interaction with water.The surface-overlapped illite aggregates would make sediments pack tightly,hinder the contact between gas and water,and result in the more significant inhibition on MH formation kinetics.Under the depressurization method,the addition of clay minerals facilitates MH dissociation rate.Physicochemical properties of clay minerals and MH distribution in the pore space lead to the faster dissociation rate in clay-containing sediments.The results of this study would provide beneficial guides on geological investigations and optimizing strategies of natural gas production in marine hydrate-bearing sediments.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
Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated therma...Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.展开更多
To address the challenges posed by high reaction temperatures and the slow kinetics of Mg-based alloys with high hydrogen storage density,Mg−RE−TM(RE=rare earth,TM=metallic element)alloys have been extensively researc...To address the challenges posed by high reaction temperatures and the slow kinetics of Mg-based alloys with high hydrogen storage density,Mg−RE−TM(RE=rare earth,TM=metallic element)alloys have been extensively researched and hold great promise.In this study,a series of Mg−RE−TM based Mg_(90)Y_(2)Ce_(2)Ni_(3)Al_(3-x)Sc_(x)(x=0,0.3,0.6,0.9,1.2)alloys were prepared.The addition of Sc element has been found to enhance the activation and kinetic properties of the alloy.Compared with the significant differences in the first four dehydrogenation curves of the Sc0 sample,the first activated dehydrogenation curve of the Sc1.2 alloy overlaps with the fully activated dehydrogenation curve.The dehydrogenation activation energy decreased from 96.56 kJ/mol in the Sc0 alloy to 63.69 kJ/mol in the Sc0.9 alloy.Through analysis of the microstructure,phase composition,and hydrogen absorption and desorption kinetics of the alloy,the mechanisms for improving the hydrogen storage properties of the alloy were elucidated.The nucleation-growth-impingement Avrami model was employed to accurately simulate the hydrogen storage kinetics.The results showed that stage II was prolonged and accelerated at high temperature,and the growth rate and hydrogen storage of stage I were increased at low temperature in hydrogen absorption.Microstructure analysis revealed the presence of Mg,CeMg_(12),Mg_(47)Y,and YNi_(2)Al_(3) phases in the Sc0 sample.Upon the addition of Sc element,a new phase,ScNiAl,was formed,and the coarse grain size of the main phase was significantly refined.This refinement provides faster diffusion channels for hydrogen atoms,accelerating the phase transition between Mg alloys and hydrides.The microstructure changes explain the improved activation properties,effective hydrogen absorption and desorption capacity,and kinetic properties of the Mg-based samples.展开更多
Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the inte...Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.展开更多
The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(...The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was the diffusion in the molten slag.The dissolution rate of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was affected by the composition and size of inclusion.The functional relationship between the dimensionless inclusion capacity(Zh)and the dimensionless dissolution rate(Ry)of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was calculated as Ry=2.10×10^(-6)Zh^(0.160),while it was Ry=2.10×10^(-6)Zh^(0.0087)for Al_(2)O_(3)-CaO complex inclusions.On this basis,the complete dissolution time and rate of the complex inclusions were calculated by using the function relation between the Zh and Ry numbers.展开更多
The reaction rate constant is a crucial kinetic parameter that governs the charge and discharge performance of batteries,particularly in high-rate and thick-electrode applications.However,conventional estimation or fi...The reaction rate constant is a crucial kinetic parameter that governs the charge and discharge performance of batteries,particularly in high-rate and thick-electrode applications.However,conventional estimation or fitting methods often overestimate the charge transfer overpotential,leading to substantial errors in reaction rate constant measurements.These inaccuracies hinder the accurate prediction of voltage profiles and overall cell performance.In this study,we propose the characteristic time-decomposed overpotential(CTDO)method,which employs a single-layer particle electrode(SLPE)structure to eliminate interference overpotentials.By leveraging the distribution of relaxation times(DRT),our method effectively isolates the characteristic time of the charge transfer process,enabling a more precise determination of the reaction rate constant.Simulation results indicate that our approach reduces measurement errors to below 2%,closely aligning with theoretical values.Furthermore,experimental validation demonstrates an 80% reduction in error compared to the conventional galvanostatic intermittent titration technique(GITT)method.Overall,this study provides a novel voltage-based approach for determining the reaction rate constant,enhancing the applicability of theoretical analysis in electrode structural design and facilitating rapid battery optimization.展开更多
The cavity characteristics in liquid-filled containers caused by high-velocity impacts represent an important area of research in hydrodynamic ram phenomena.The dynamic expansion of the cavity induces liquid pressure ...The cavity characteristics in liquid-filled containers caused by high-velocity impacts represent an important area of research in hydrodynamic ram phenomena.The dynamic expansion of the cavity induces liquid pressure variations,potentially causing catastrophic damage to the container.Current studies mainly focus on non-deforming projectiles,such as fragments,with limited exploration of shaped charge jets.In this paper,a uniquely experimental system was designed to record cavity profiles in behind-armor liquid-filled containers subjected to shaped charge jet impacts.The impact process was then numerically reproduced using the explicit simulation program ANSYS LS-DYNA with the Structured Arbitrary Lagrangian-Eulerian(S-ALE)solver.The formation mechanism,along with the dimensional and shape evolution of the cavity was investigated.Additionally,the influence of the impact kinetic energy of the jet on the cavity characteristics was analyzed.The findings reveal that the cavity profile exhibits a conical shape,primarily driven by direct jet impact and inertial effects.The expansion rates of both cavity length and maximum radius increase with jet impact kinetic energy.When the impact kinetic energy is reduced to 28.2 kJ or below,the length-to-diameter ratio of the cavity ultimately stabilizes at approximately 7.展开更多
Burial dissolution is a critical diagenetic process influencing ultra-deep carbonate reservoir development and preservation.Artificial carbonate samples with different internal structures were prepared,and high-temper...Burial dissolution is a critical diagenetic process influencing ultra-deep carbonate reservoir development and preservation.Artificial carbonate samples with different internal structures were prepared,and high-temperature and highpressure dissolution kinetic simulations were conducted.The results demonstrate that the intensity of burial dissolution is controlled by temperature and pressure,while tectonic-fluid activity influences the development pattern of burial dissolution,ultimately determining the direction of its differential modification.Extensive burial dissolution is likely to occur primarily at relatively shallow depths,significantly influencing reservoir formation,preservation,modification,and adjustment.The development of faults facilitates the maintenance of the intensity of burial dissolution.The maximum intensity of burial dissolution occurs at the tips and overlap zones of faults and intersections of multiple faults.The larger the scale of the faults,the more conducive it is to the development of burial dissolution.Burial dissolution fosters the formation of fault networks characterized by enhanced reservoir capacity and permeability.Burial dissolution controlled by episodic tectonic-fluid activity is a plausible explanation for forming the Tarim Basin's ultra-deep fault-controlled“stringbead-like”reservoirs.展开更多
This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that ...This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength steels.展开更多
With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic ...With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.展开更多
文摘Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.
文摘We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.
基金supported by Ministry of Science and Technology of China(No.2012YQ090194 and No.2013AA102204)the National Natural Science Foundation of China(No.21676191,No.21476165,and No.21621004)
文摘Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.
基金This work was supported in part by a grant from Russian Scientific Foundation(Project No.17-75-30064).
文摘Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.
基金supported by the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions,China.
文摘Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesized by solid-state reaction at 700℃for 2 h via a kinetically favorable mechanism and characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),AC impedance spectroscopy,etc.It has been revealed that the as-synthesized melilite La_(2)Ga_(3)O_(7.5)shows an orthorhombic symmetry with crystal cell parameters a=11.4690(1)A,b=11.2825(4)A,and c=10.3735(4)A,while has more Raman active modes than LaSrGa_(3)O_(7)with a tetragonal structure,which was also synthesized under the same conditions for comparison,but tends to slowly decompose into perovskite LaGaO_(3)and Ga2O_(3)when annealed at 700℃for over 20 h driven by its meta-stability.Moreover,the metastable La2Ga3O7.5 shows a higher XPS binding energy for the excess oxide ions in the crystal structure than those at normal lattice sites.Its intrinsic grain oxide ion conductivity can reach as high as 0.04 and 0.51 mS·cm^(-1)at 550 and 700℃,respectively,characterized by a simple Arrhenius relationship ln(σT)-1/T with invariable activation energy,E_(a)=1.22 eV,over the temperature range from 300 to 700℃,along with an apparent grain boundary conductivity that is about double that from the grains thanks to the clean grain boundaries.This paper provides a new strategic approach to the synthesis of complex oxides that may be of high performance but are difficultly achieved by the conventional ceramic method at high temperatures.
基金supported by the National Key R&D Program of China(Grant No.2023YFA1406002)the Innovation Program for Quantum Science and Technology(Grant No.2021ZD0301200)。
文摘We investigate the quantum dynamics of the 1D spinless Fermi-Hubbard model with a linear-tilted potential.Surprisingly in a strong resonance regime,we show that the model can be described by the kinetically constrained effective Hamiltonian,and it can be spontaneously divided into two commuting parts dubbed Hamiltonian dimerization,which are composed of two distinct sets of constrained nearest-neighbor hopping terms:one set acting exclusively on odd bonds and the other on even bonds.Specifically it is shown that each part can be independently mapped onto the well-known PXP model;therefore the dimerized Hamiltonian is equivalent to a two-fold PXP model.As a consequence,we numerically demonstrate this system can host the so-called quantum many-body scars,which present dynamical revivals and ergodicity-breaking behaviors.However,in sharp contrast with traditional quantum many-body scars,here the scarring states in our model driven by different parts of the Hamiltonian will revive in different periods,and those of double parts can display a biperiodic revival pattern,both originating from the Hamiltonian dimerization.Besides,the condition of off-resonance is also discussed,and we show the crossover from quantum many-body scar to ergodicity breaking is diagnosed via level statistics.Our model provides a platform for understanding the interplay of Hilbert space fragmentation and the constrained quantum systems.
基金financially supported by the National Science Foundation of China(Nos.51974212 and 52274316)the China Baowu Low Carbon Metallurgy Innovation Foundation(No.BWLCF202116)+1 种基金the Science and Technology Major Project of Wuhan(No.2023020302020572)the Foundation of Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education(No.FMRUlab23-04)。
文摘The utilization of iron coke provides a green pathway for low-carbon ironmaking.To uncover the influence mechanism of iron ore on the behavior and kinetics of iron coke gasification,the effect of iron ore on the microstructure of iron coke was investigated.Furthermore,a comparative study of the gasification reactions between iron coke and coke was conducted through non-isothermal thermogravimetric method.The findings indicate that compared to coke,iron coke exhibits an augmentation in micropores and specific surface area,and the micropores further extend and interconnect.This provides more adsorption sites for CO_(2) molecules during the gasification process,resulting in a reduction in the initial gasification temperature of iron coke.Accelerating the heating rate in non-isothermal gasification can enhance the reactivity of iron coke.The metallic iron reduced from iron ore is embedded in the carbon matrix,reducing the orderliness of the carbon structure,which is primarily responsible for the heightened reactivity of the carbon atoms.The kinetic study indicates that the random pore model can effectively represent the gasification process of iron coke due to its rich pore structure.Moreover,as the proportion of iron ore increases,the activation energy for the carbon gasification gradually decreases,from 246.2 kJ/mol for coke to 192.5 kJ/mol for iron coke 15wt%.
基金financially supported by the National Natural Science Foundation of China(Nos.21171018 and 51271021)the State Key Laboratory for Advanced Metals and Materials。
文摘This study investigated the microstructure and hydrogen absorption properties of a rare-earth high-entropy alloy(HEA),YGdTbDyHo.Results indicated that the YGdTbDyHo alloy had a microstructure of equiaxed grains,with the alloy elements distributed homogeneously.Upon hydrogen absorption,the phase structure of the HEA changed from a solid solution with an hexagonal-close-packed(HCP)structure to a high-entropy hydride with an faced-centered-cubic(FCC)structure without any secondary phase precipitated.The alloy demonstrated a maximum hydrogen storage capacity of 2.33 H/M(hydrogen atom/metal atom)at 723 K,with an enthalpy change(ΔH)of-141.09 kJ·mol^(-1)and an entropy change(ΔS)of-119.14 J·mol^(-1)·K^(-1).The kinetic mechanism of hydrogen absorption was hydride nucleation and growth,with an apparent activation energy(E_(a))of 20.90 kJ·mol^(-1).Without any activation,the YGdTbDyHo alloy could absorb hydrogen quickly(180 s at 923 K)with nearly no incubation period observed.The reason for the obtained value of 2.33 H/M was that the hydrogen atoms occupied both tetrahedral and octahedral interstices.These results demonstrate the potential application of HEAs as a high-capacity hydrogen storage material with a large H/M ratio,which can be used in the deuterium storage field.
文摘The present work aims to stabilize the room temperature allotropic transition of ammonium nitrate(AN)particles utilizing a microencapsulation technique,which involves solvent/non-solvent in which nitrocellulose(NC)has been employed as a coating agent.The SEM micrographs revealed distinct features of both pure AN and NC,contrasting with the irregular granular surface topography of the coated AN particles,demonstrating the adherence of NC on the AN surface.Structural analysis via infrared spectroscopy(IR)demonstrated a successful association of AN and NC,with slight shifts observed in IR bands indicating interfacial interactions.Powder X-ray Diffraction(PXRD)analysis further elucidated the structural changes induced by the coating process,revealing that the NC coating altered the crystallization pattern of its pure form.Thermal analysis demonstrates distinct profiles for pure and coated AN,for which the coated sample exhibits a temperature increase and an enthalpy decrease of the room temperature allotropic transition by 6℃,and 36%,respectively.Furthermore,the presence of NC coating alters the intermolecular forces within the composite system,leading to a reduction in melting enthalpy of coated AN by~39%compared to pure AN.The thermal decomposition analysis shows a two-step thermolysis process for coated AN,with a significant increase in the released heat by about 78%accompanied by an increase in the activation barrier of NC and AN thermolysis,demonstrating a stabilized reactivity of the AN-NC particles.These findings highlight the synergistic effect of NC coating on AN particles,which contributed to a structural and reactive stabilization of both AN and NC,proving the potential application of NC-coated AN as a strategically advantageous oxidizer in composite solid propellant formulations.
基金supported by the Key Research Program of the Institute of Geology&Geophysics,CAS(Grant No.IGGCAS-201903).
文摘Natural gas hydrates widely accumulate in submarine sediments composed of clay minerals.However,due to the complex physiochemistry and micron-sized particles of clay minerals,their effects on methane hydrate(MH)formation and dissociation are still in controversy.In this study,montmorillonite and illite were separately mixed with quartz sand to investigate their effects on MH formation and dissociation.The microstructure of synthesized samples was observed by cryo-SEM innovatively to understand the effects of montmorillonite and illite on MH phase transition in micron scale.Results show that montmorillonite and illite both show the inhibition on MH formation kinetics and water-to-hydrate conversion,and illite shows a stronger inhibition.The 10 wt%montmorillonite addition significantly retards MH formation rate,and the 20 wt%montmorillonite has a less inhibition on the rate.The increase of illite mass ratio(0-20 wt%)retards the rate of MH formation.As the content of clay minerals increase,the water-to-hydrate conversion decreases.Cryo-SEM images presented that montmorillonite aggregates separate as individual clusters while illite particles pack as face-to-face configuration under the interaction with water.The surface-overlapped illite aggregates would make sediments pack tightly,hinder the contact between gas and water,and result in the more significant inhibition on MH formation kinetics.Under the depressurization method,the addition of clay minerals facilitates MH dissociation rate.Physicochemical properties of clay minerals and MH distribution in the pore space lead to the faster dissociation rate in clay-containing sediments.The results of this study would provide beneficial guides on geological investigations and optimizing strategies of natural gas production in marine hydrate-bearing sediments.
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.
基金financially supported by the National Key Research and Development Program of China (No. 2021YFB4000604)the National Natural Science Foundation of China (No. 52271220)+2 种基金the 111 Project (No. B12015)the Fundamental Research Funds for the Central UniversitiesHaihe Laboratory of Sustainable Chemical Transformations, Guangxi Collaborative Innovation Centre of Structure and Property for New Energy and Materials, Science Research and Technology Development Project of Guilin (No. 20210102-4)
文摘Novel hydrogen storage materials have propelled progress in hydrogen storage technologies.Magnesium hydride(MgH_(2))is a highly promising candidate.Nevertheless,several drawbacks,including the need for elevated thermal conditions,sluggish dehydrogena-tion kinetics,and high thermodynamic stability,limit its practical application.One effective method of addressing these challenges is cata-lyst doping,which effectively boosts the hydrogen storage capability of Mg-based materials.Herein,we review recent advancements in catalyst-doped MgH_(2) composites,with particular focus on multicomponent and high-entropy catalysts.Structure-property relationships and catalytic mechanisms in these doping strategies are also summarized.Finally,based on existing challenges,we discuss future research directions for the development of Mg-based hydrogen storage systems.
基金National Natural Science Foundation of China(51871125)the Major Programs of Central Iron and Steel Research Institute(No.23020230ZD)for financial support of the work.
文摘To address the challenges posed by high reaction temperatures and the slow kinetics of Mg-based alloys with high hydrogen storage density,Mg−RE−TM(RE=rare earth,TM=metallic element)alloys have been extensively researched and hold great promise.In this study,a series of Mg−RE−TM based Mg_(90)Y_(2)Ce_(2)Ni_(3)Al_(3-x)Sc_(x)(x=0,0.3,0.6,0.9,1.2)alloys were prepared.The addition of Sc element has been found to enhance the activation and kinetic properties of the alloy.Compared with the significant differences in the first four dehydrogenation curves of the Sc0 sample,the first activated dehydrogenation curve of the Sc1.2 alloy overlaps with the fully activated dehydrogenation curve.The dehydrogenation activation energy decreased from 96.56 kJ/mol in the Sc0 alloy to 63.69 kJ/mol in the Sc0.9 alloy.Through analysis of the microstructure,phase composition,and hydrogen absorption and desorption kinetics of the alloy,the mechanisms for improving the hydrogen storage properties of the alloy were elucidated.The nucleation-growth-impingement Avrami model was employed to accurately simulate the hydrogen storage kinetics.The results showed that stage II was prolonged and accelerated at high temperature,and the growth rate and hydrogen storage of stage I were increased at low temperature in hydrogen absorption.Microstructure analysis revealed the presence of Mg,CeMg_(12),Mg_(47)Y,and YNi_(2)Al_(3) phases in the Sc0 sample.Upon the addition of Sc element,a new phase,ScNiAl,was formed,and the coarse grain size of the main phase was significantly refined.This refinement provides faster diffusion channels for hydrogen atoms,accelerating the phase transition between Mg alloys and hydrides.The microstructure changes explain the improved activation properties,effective hydrogen absorption and desorption capacity,and kinetic properties of the Mg-based samples.
基金supported by the Russian Science Foundation(23-29-00830).
文摘Morphology and growth rate of carbon dioxide hydrate on the interface between liquid carbon dioxide and humic acid solutions were studied in this work.It was found that after the growth of the hydrate film at the interface,further growth of hydrate due to the suction of water in the capillary system formed between the wall of the cuvette and the end boundary of the hydrate layer occurs.Most probably,substantial effects on the formation of this capillary system may be caused by variations in reactor wall properties,for example,hydrophobic-hydrophilic balance,roughness,etc.We found,that the rate of CO_(2) hydrate film growth on the surface of the humic acid aqueous solution is 4-fold to lower in comparison with the growth rate on the surface of pure water.We suppose that this is caused by the adsorption of humic acid associates on the surface of hydrate particles and,as a consequence,by the deceleration of the diffusion of dissolved carbon dioxide to the growing hydrate particle.
基金support from the National Key R&D Program(No.2023YFB3709900)the National Natural Science Foundation of China(Grant No.U22A20171)+1 种基金the High Steel Center at the North China University of Technologythe University of Science and Technology Beijing,China.
文摘The dissolution behavior of complex inclusions in refining slag was studied using confocal laser scanning microscope.Based on the dissolution curve of complex inclusions,the main rate-limiting link of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was the diffusion in the molten slag.The dissolution rate of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was affected by the composition and size of inclusion.The functional relationship between the dimensionless inclusion capacity(Zh)and the dimensionless dissolution rate(Ry)of CaO-SiO_(2)-Al_(2)O_(3)complex inclusions was calculated as Ry=2.10×10^(-6)Zh^(0.160),while it was Ry=2.10×10^(-6)Zh^(0.0087)for Al_(2)O_(3)-CaO complex inclusions.On this basis,the complete dissolution time and rate of the complex inclusions were calculated by using the function relation between the Zh and Ry numbers.
基金supported by the National Key R&D Program of China 2022YFB2404300the National Natural Science Foundation of China U22B2069the China Postdoctoral Science Foundation 2024M761006。
文摘The reaction rate constant is a crucial kinetic parameter that governs the charge and discharge performance of batteries,particularly in high-rate and thick-electrode applications.However,conventional estimation or fitting methods often overestimate the charge transfer overpotential,leading to substantial errors in reaction rate constant measurements.These inaccuracies hinder the accurate prediction of voltage profiles and overall cell performance.In this study,we propose the characteristic time-decomposed overpotential(CTDO)method,which employs a single-layer particle electrode(SLPE)structure to eliminate interference overpotentials.By leveraging the distribution of relaxation times(DRT),our method effectively isolates the characteristic time of the charge transfer process,enabling a more precise determination of the reaction rate constant.Simulation results indicate that our approach reduces measurement errors to below 2%,closely aligning with theoretical values.Furthermore,experimental validation demonstrates an 80% reduction in error compared to the conventional galvanostatic intermittent titration technique(GITT)method.Overall,this study provides a novel voltage-based approach for determining the reaction rate constant,enhancing the applicability of theoretical analysis in electrode structural design and facilitating rapid battery optimization.
基金financial support from the National Natural Science Foundation of China(Grant No.11572159).
文摘The cavity characteristics in liquid-filled containers caused by high-velocity impacts represent an important area of research in hydrodynamic ram phenomena.The dynamic expansion of the cavity induces liquid pressure variations,potentially causing catastrophic damage to the container.Current studies mainly focus on non-deforming projectiles,such as fragments,with limited exploration of shaped charge jets.In this paper,a uniquely experimental system was designed to record cavity profiles in behind-armor liquid-filled containers subjected to shaped charge jet impacts.The impact process was then numerically reproduced using the explicit simulation program ANSYS LS-DYNA with the Structured Arbitrary Lagrangian-Eulerian(S-ALE)solver.The formation mechanism,along with the dimensional and shape evolution of the cavity was investigated.Additionally,the influence of the impact kinetic energy of the jet on the cavity characteristics was analyzed.The findings reveal that the cavity profile exhibits a conical shape,primarily driven by direct jet impact and inertial effects.The expansion rates of both cavity length and maximum radius increase with jet impact kinetic energy.When the impact kinetic energy is reduced to 28.2 kJ or below,the length-to-diameter ratio of the cavity ultimately stabilizes at approximately 7.
基金supported by the National Natural Science Foundation of China(Grant No.U21B2062)supported by the Key Laboratory for Carbonate Reservoirs of China National Petroleum Corporation。
文摘Burial dissolution is a critical diagenetic process influencing ultra-deep carbonate reservoir development and preservation.Artificial carbonate samples with different internal structures were prepared,and high-temperature and highpressure dissolution kinetic simulations were conducted.The results demonstrate that the intensity of burial dissolution is controlled by temperature and pressure,while tectonic-fluid activity influences the development pattern of burial dissolution,ultimately determining the direction of its differential modification.Extensive burial dissolution is likely to occur primarily at relatively shallow depths,significantly influencing reservoir formation,preservation,modification,and adjustment.The development of faults facilitates the maintenance of the intensity of burial dissolution.The maximum intensity of burial dissolution occurs at the tips and overlap zones of faults and intersections of multiple faults.The larger the scale of the faults,the more conducive it is to the development of burial dissolution.Burial dissolution fosters the formation of fault networks characterized by enhanced reservoir capacity and permeability.Burial dissolution controlled by episodic tectonic-fluid activity is a plausible explanation for forming the Tarim Basin's ultra-deep fault-controlled“stringbead-like”reservoirs.
基金supported by the National Natural Science Foundation of China(No.52271089)the financial support from the C hina Postdoctoral Science Foundation(No.2023M732192)。
文摘This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength steels.
基金financially supported by the National Natural Science Foundation of China(No.52204310)the Guizhou Provincial Key Laboratory of Coal Clean Utilization(No.[2020]2001)+5 种基金the China Postdoctoral Science Foundation(Nos.2020TQ0059 and 2020M570967)the Natural Science Foundation of Liaoning Province(No.2021–MS–083)the Fundamental Research Funds for the Central Universities,China(No.N2125010)the Open Project Program of Key Laboratory of Metallurgical Emission Reduction&Resources Recycling(Anhui University of Technology),Ministry of Education(No.JKF22–02)the Foundation of Liupanshui Normal University(No.LPSSYZDZK202205)the Key Laboratory for Anisotropy and Texture of Materials,Ministry of Education,China。
文摘With the continuous increase in the disposal volume of spent lithium-ion batteries(LIBs),properly recycling spent LIBs has become essential for the advancement of the circular economy.This study presents a systematic analysis of the chlorination roasting kinetics and proposes a new two-step chlorination roasting process that integrates thermodynamics for the recycling of LIB cathode materials.The activation energy for the chloride reaction was 88.41 kJ/mol according to thermogravimetric analysis–derivative thermogravimetry data obtained by using model-free,model-fitting,and Z(α)function(αis conversion rate).Results indicated that the reaction was dominated by the first-order(F1)model when the conversion rate was less than or equal to 0.5 and shifted to the second-order(F2)model when the conversion rate exceeded 0.5.Optimal conditions were determined by thoroughly investigating the effects of roasting temperature,roasting time,and the mass ratio of NH_(4)Cl to LiCoO_(2).Under the optimal conditions,namely 400℃,20 min,and NH_(4)Cl/LiCoO_(2)mass ratio of 3:1,the leaching efficiency of Li and Co reached 99.43% and 99.05%,respectively.Analysis of the roasted products revealed that valuable metals in LiCoO_(2)transformed into CoCl_(2) and LiCl.Furthermore,the reaction mechanism was elucidated,providing insights for the establishment of a novel low-temperature chlorination roasting technology based on a crystal structure perspective.This technology can guide the development of LIB recycling processes with low energy consumption,low secondary pollution,high recovery efficiency,and high added value.
