Magnesium and magnesium alloys,serving as crucial lightweight structural materials and hydrogen storage elements,find extensive applications in space technology,aviation,automotive,and magnesium-based hydrogen industr...Magnesium and magnesium alloys,serving as crucial lightweight structural materials and hydrogen storage elements,find extensive applications in space technology,aviation,automotive,and magnesium-based hydrogen industries.The global production of primary magnesium has reached approximately 1.2 million tons per year,with anticipated diversification in future applications and significant market demand.Nevertheless,approximately 80%of the world’s primary magnesium is still manufactured through the Pidgeon process,grappling with formidable issues including high energy consumption,massive carbon emission,significant resource depletion,and environmental pollution.The implementation of the relative vacuum method shows potential in breaking through technological challenges in the Pidgeon process,facilitating clean,low-carbon continuous magnesium smelting.This paper begins by introducing the principles of the relative vacuum method.Subsequently,it elucidates various innovative process routes,including relative vacuum ferrosilicon reduction,aluminum thermal reduction co-production of spinel,and aluminum thermal reduction co-production of calcium aluminate.Finally,and thermodynamic foundations of the relative vacuum,a quantitative analysis of the material,energy flows,carbon emission,and production cost for several new processes is conducted,comparing and analyzing them against the Pidgeon process.The study findings reveal that,with identical raw materials,the relative vacuum silicon thermal reduction process significantly decreases raw material consumption,energy consumption,and carbon dioxide emissions by 15.86%,30.89%,and 26.27%,respectively,compared to the Pidgeon process.The relative vacuum process,using magnesite as the raw material and aluminum as the reducing agent,has the lowest magnesium-to-feed ratio,at only 3.385.Additionally,its energy consumption and carbon dioxide emissions are the lowest,at 1.817 tce/t Mg and 7.782 t CO_(2)/t Mg,respectively.The energy consumption and carbon emissions of the relative vacuum magnesium smelting process co-producing calcium aluminate(12CaO·7Al_(2)O_(3),3CaO·Al_(2)O_(3),and CaO·Al_(2)O_(3))are highly correlated with the consumption of dolomite in the raw materials.When the reduction temperature is around 1473.15 K,the critical volume fraction of magnesium vapor for different processes varies within the range of 5%–40%.Production cost analysis shows that the relative vacuum primary magnesium smelting process has significant economic benefits.This paper offers essential data support and theoretical guidance for achieving energy efficiency,carbon reduction in magnesium smelting,and the industrial adoption of innovative processes.展开更多
A series of Al-xSi-yGe filler metals(x=4–12 and y=10–40,wt%)were prepared,and the effect of Si and Ge on microstructure and melting characteristics of filler metals was studied.The thermodynamic model of Al-Si-Ge te...A series of Al-xSi-yGe filler metals(x=4–12 and y=10–40,wt%)were prepared,and the effect of Si and Ge on microstructure and melting characteristics of filler metals was studied.The thermodynamic model of Al-Si-Ge ternary alloy was established to analyze the phase formation mechanism of filler metals based on Miedema model,Tanaka model,and Toop equation.This research provided a basis for the composition optimization of filler metals and the analysis of metallurgical reaction process between filler metals and base materials.Results show that Al-Si-Ge alloy is composed of Al-Ge eutectic phase,Al-Si eutectic phase,and primary Si.Ge addition promotes the precipitation of primary Si.Ge is the main melting point depressant element of filler metals.With the increase in Ge content from 10wt%to 40wt%,the solid phase line of filler metals remains unchanged,whereas the liquidus temperature decreases from 567.65°C to 499.96°C.With the increase in Ge content of filler metal,Ge content in eutectic Si phase is increased,the endothermic peak of Al-Si eutectic reaction according to thermogravimetry curve becomes smoother,and Al-Si eutectic temperature is decreased.Ge addition can reduce the free energy of Al-Si alloy system.The lowest point of free energy is located on Al-Ge side.The eutectic Ge phase with the composition similar to pure Ge composition is the most likely to appear in the microstructure of filler metals,whereas the eutectic Si phase with the composition similar to pure Si composition is the least likely to appear.The thermodynamic calculation results are consistent with the experiment results.展开更多
The low-temperature embrittlement limits the service temperature of ferritic and duplex stainless steels.The effects of alloying elements added to Fe-Cr binary system on the low-temperature embrittlement have been rev...The low-temperature embrittlement limits the service temperature of ferritic and duplex stainless steels.The effects of alloying elements added to Fe-Cr binary system on the low-temperature embrittlement have been reviewed critically.Prior literature on the underlying phase transformation,i.e.,phase separation(PS)and changes of mechanical properties,is surveyed.The available literature indicates that the rate of PS is accelerated by Ni or Co in Fe-Cr binary system.The increased kinetics of PS also lead to an enhanced hardening rate during aging for Ni and Co alloyed Fe-Cr alloys.In low Cr(<17 wt.%)ferritic alloys,the additions of Al or Co can reduce embrittlement because these elements contribute to lowering the driving force for PS.The influence of other alloying elements such as Mo,Cu,Mn,Nb,and Ti is inconclusive but also discussed here.Thermodynamic and kinetic calculations were performed to evaluate current CALPHAD databases and to further investigate the thermodynamic and kinetic reasons for the effect of the additional alloying elements added to Fe-Cr alloy on PS.Some indications were provided for improving physically-based predictions of low-temperature embrittlement as well as opportunities to mitigate the phenomenon by alloying.展开更多
Gas-phase synthesis of glycolide(GL)from methyl glycolate(MG)is of great significance for producing biodegradable polyglycolic acid.Here,we report a detailed thermodynamics study for the gas-phase synthesis of GL from...Gas-phase synthesis of glycolide(GL)from methyl glycolate(MG)is of great significance for producing biodegradable polyglycolic acid.Here,we report a detailed thermodynamics study for the gas-phase synthesis of GL from MG,which involves complex reaction pathways,by utilizing the Gibbs free energy minimization method.The results indicate that the decompositions of MG and GL and the polymerization of MG are thermodynamically favorable as compared with the target pathway,i.e.,the cyclization of MG.Effects of the reaction conditions including temperature,pressure and feed composition on the formation of GL and linear polymers have also been addressed,which demonstrate that the higher temperature and lower pressure can effectively inhibit the formation of linear methyl ester dimer and improve the selectivity to GL.In addition,the higher N_(2)/MG ratio is beneficial for the formation of GL in the process promoted by catalysts.These thermodynamics results indicate that the process promoted by catalysts would benefit from the kinetics control by high-performance catalysts and the operation at high temperature,low pressure and high N_(2)/MG ratio to enhance the yield of targeted GL.The insights demonstrated here from thermodynamics are valuable for guiding the design of catalysts and/or optimization of reaction conditions for the gas-phase synthesis of GL from MG.展开更多
Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.I...Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.In this study,a nonisothermal crystallization thermodynamics behavior of C-F-xA and C-F-xM systems was examined using differential scanning calorimetry,and a phase identification and microstructure analysis for C-F-xA and C-F-xM systems were carried out by X-ray diffraction and scanning electron microscopy.Results showed that in C-F-2A and C-F-2M systems,the increased cooling rates promoted the precipitation of CaFe_(2)O_(4)(CF)but inhibited the formation of Ca_(2)Fe_(2)O_(5)(C2F).In addition,C-F-2A system exhibited a lower theoretical initial crystallization temperature(1566 K)compared to the C-F system(1578 K).This temperature further decreases to 1554 K and 1528 K in the C-F-4A and C-F-8A systems,respectively.However,in C-F-xM system,the increased MgO content raised the crystallization temperature.This is because that the enhanced precipitation of MF(a spinel phase mainly comprised Fe_(3)O_(4)and MgFe_(2)O_(4))and C2F phases suppressed the CF precipitation reaction.In kinetic calculations,the Ozawa method revealed the apparent activation energies of the C-F-2A and C-F-2M systems.Malek's method revealed that the crystallization process in C-F-2A system initially followed a logarithmic law(lnαor lnα2),later transitioning to a reaction order law((1-α)-1or(1-α)^(-1/2),n=2/3)or the lnα2function of the exponential law.In C-F-2M system,it consistently followed the sequencef(α)=(1-α)^(2)(αis the crystallization conversion rate;n is the Avrami constant;?(α)is the differential equations for the model function of C_(2)F and CF crystallization processes).展开更多
Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulf...Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulfur(S_(8))[1].However,the electrochemical conversion reaction of S_(8) is an exceedingly complex process that involves the generation of multiple intermediates(e.g.,lithium polysulfides(LiPSs))and multiphase transitions[1,2].Currently,the mechanistic investigations of the electrochemical conversion reaction of S_(8) upon discharging a LSB cell heavily rely on electrochemical titration and spectroscopic techniques[3].Nevertheless,the considerable complexity and intrinsic instability of the LSB system present substantial obstacles to obtaining accurate information for all sulfur-containing species,which significantly obstructs in-depth elucidation of the fundamental discharge mechanism of LSB[3,4].展开更多
Low-heat Portland(LHP)cement is a new type of Portland cement that has been widely used in recent years due to its low heat of hydration,which makes it exceptional in temperature control for mass concrete construction...Low-heat Portland(LHP)cement is a new type of Portland cement that has been widely used in recent years due to its low heat of hydration,which makes it exceptional in temperature control for mass concrete construction.However,limited studies have investigated the impact of temperature and magnesium oxide(MgO)content on LHP cement-based materials.This study utilizes thermodynamic simulations to study the hydration process,pore structure,and autogenous shrinkage of LHP cement pastes with different water-to-cement ratios(0.3,0.4,and 0.5),curing temperatures(5,15,20,and 30℃),and MgO contents(mass fractions of 2%,4%,and 5%).Higher curing temperature is found to promote the hydration reactions in cement paste.Moreover,the incorporation of 4%MgO moderately decreases both porosity and dimensional shrinkage in pastes.The microstructural evolution of different LHP pastes is examined through a comparative analysis,lending insights into LHP cement-based material applications.展开更多
Dynamic transformation(DT)of austenite(γ)to ferrite(α)in the hot deformation of various carbon steels was widely investigated.However,the nature of DT remains unclear due to the lack of quantitative analysis of stre...Dynamic transformation(DT)of austenite(γ)to ferrite(α)in the hot deformation of various carbon steels was widely investigated.However,the nature of DT remains unclear due to the lack of quantitative analysis of stress partitioning between two phases and the uncertainty of local distribution of substitu-tional elements at the interface in multi-component carbon steels used in the previous studies.Therefore,in the present study,a binary Fe-Ni alloy withα+γduplex microstructure in equilibrium was prepared and isothermally compressed inα+γtwo-phase region to achieve a quantitative analysis of microstruc-ture evolution,stress partitioning,and thermodynamics during DT.γtoαDT during isothermal compres-sion andαtoγreverse transformation on isothermal annealing under unloaded condition after deforma-tion were accompanied by Ni partitioning.The lattice strains during thermomechanical processing were obtained via in-situ neutron diffraction measurement,based on which the stress partitioning behavior betweenγandαwas discussed by using the generalized Hooke’s law.A thermodynamic framework for the isothermal deformation in solids was established based on the basic laws of thermodynamics,and it was shown that the total Helmholtz free energy change in the deformable material during the isothermal process should be smaller than the work done to the deformable material.Under the present thermody-namic framework,the microstructure evolution in the isothermal compression of Fe-14Ni alloy was well explained by considering the changes in chemical free energy,plastic and elastic energies,and the work done to the material.In addition,the stabilization of the softαphase in Fe-14Ni alloy by deformation was rationalized since theγtoαtransformation decreased the total Helmholtz free energy by decreasing the elastic and dislocation energies.展开更多
Rare earth elements and transition metals have been found to improve the hydrogen storage characteristics of magnesium-based alloys.This study investigated the Mg-Ho-Fe(MHF) ternary alloy prepared using the vacuum ind...Rare earth elements and transition metals have been found to improve the hydrogen storage characteristics of magnesium-based alloys.This study investigated the Mg-Ho-Fe(MHF) ternary alloy prepared using the vacuum induction melting technique.X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),pressure-composition-temperature(PCT),and differential scanning calorimetry(DSC) were used to analyze the alloy's phase transitions,microstructure,thermodynamics,and kinetic properties.The results reveal that the Mg_(98)Ho_(1.5)Fe_(0.5) alloy forms a solid solution with Ho and Fe in the magnesium matrix.Upon hydrogen absorption,the activated alloy transforms into a mixture of Mg/MgH_(2) phases and nanoscale HoH_(2) phases.Notably,only the MgH_(2) phase decomposes during hydrogen desorption,while the HoH_(2) phase remains unchanged,exhibiting a positive catalytic effect.The alloy demonstrates excellent hydrogen absorption kinetics,achieving a capacity of 5.56 wt% H_(2) within 10 min at 360℃,owing to the combined catalytic effects of Ho and Fe.The activation energy for hydrogen desorption is found to be 135.87 kJ/mol,which is lower than that of the activation energies of pure MgH_(2) and MgFe alloys,indicating an enhancement in desorption kinetics.Moreover,the enthalpy and entropy changes for hydrogen absorption and desorption are determined to be-70.51 kJ/mol H_(2),-125.62 J/(K·mol) H_(2),72.83 kJ/mol H_(2),and 128.95 J/(K·mol) H_(2),respectively.Furthermore,it is worth noting that the thermodynamic properties of the alloy are improved due to the catalytic effect of Ho and Fe.展开更多
The spatiotemporally-nonlocal phenomena in heat conduction become significant but challenging for metamaterials with artificial microstructures.However,the microstructure-dependent heat conduction phenomena are captur...The spatiotemporally-nonlocal phenomena in heat conduction become significant but challenging for metamaterials with artificial microstructures.However,the microstructure-dependent heat conduction phenomena are captured under the hypothesis of spatiotemporally local equilibrium.To capture the microstructure-dependent heat conduction phenomena,a generalized nonlocal irreversible thermodynamics is proposed by removing both the temporally-local and spatially-local equilibrium hypotheses from the classical irreversible thermodynamics.The generalized nonlocal irreversible thermodynamics has intrinsic length and time parameters and thus can provide a thermodynamics basis for the spatiotemporally-nonlocal law of heat conduction.To remove the temporallylocal equilibrium hypothesis,the generalized entropy is assumed to depend not only on the internal energy but also on its first-order and high-order time derivatives.To remove the spatially local equilibrium hypothesis,the thermodynamics flux field in the dissipation function is assumed to relate not only to the thermodynamics force at the reference point but also to the thermodynamics force of the neighboring points.With the developed theoretical framework,the thermodynamics-consistent spatiotemporally-nonlocal models can then be developed for heat transfer problems.Two examples are provided to illustrate the applications of steady-state and transient heat conduction problems.展开更多
Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocompo...Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.展开更多
It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the hea...It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the heat capacity statement. It is pointed out that such three statements correspond to three thermodynamic parameters, which are, respectively, the entropy,temperature, and heat capacity, and can be obtained by extrapolating the experimental results of different parameters at ultralow temperatures to absolute zero. It is expounded that because there is no need for additional assumptions in the derivation of the Nernst equation, the Nernst theorem should be renamed as the Nernst statement. Moreover, it is proved that both the Nernst statement and the heat capacity statement are mutually deducible and equivalent, while the unattainability of absolute zero temperature is only a corollary of the Nernst statement or the heat capacity statement so that it is unsuitably referred to as one statement of the third law of thermodynamics. The conclusion is that the Nernst statement and the heat capacity statement are two equivalent statements of the third law of thermodynamics.展开更多
We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and ...We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and the remnant state,respectively,and discuss their consistency.Then,we investigate the quantum tunneling from the event horizon of massless scalar particle by using the null geodesic method,and charged massive boson W^(±)and fermions by using the Hamilton-Jacob method.It is shown that the same Hawking temperature can be obtained from these tunneling processes of different particles and methods.Next,by using the generalized uncertainty principle(GUP),we study the quantum corrections to the tunneling and the temperature.Then the logarithmic correction to the black hole entropy is obtained.展开更多
In heart failure with preserved ejection fraction,significant left ventricular diastolic abnormalities are present,despite a normal systolic ejection fraction.This article will consider whether this is consistent with...In heart failure with preserved ejection fraction,significant left ventricular diastolic abnormalities are present,despite a normal systolic ejection fraction.This article will consider whether this is consistent with the law of conservation of energy,also know as the first law of thermodynamics.展开更多
According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also ...According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also the identifier of thermodynamic equilibrium, makes each and every point along the reversible path a state of equilibrium, and the reversible path, as expressed by a noted thermodynamic author, “a dense succession of equilibrium states”. The difficulties with these notions are plural. The fact, for example, that systems need to be forced out of equilibrium via the expenditure of work, would make any spontaneous reversible process a consumer of work, this in opposition to common thermodynamic wisdom that makes spontaneous reversible processes the most efficient transformers of work-producing-potential into actual work. The solution to this and other related impasses is provided by Dialectical Thermodynamics via its previously proved notion assigning a negative entropy change to the energy upgrading process represented by the transformation of heat into work. The said solution is here exemplified with the ideal-gas phase isomerization of butane into isobutane.展开更多
This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared...This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).展开更多
The reaction kinetics of alloys based on magnesium are known to be greatly improved by the partial substitution of Mg with rare earths and transition metals,particularly Ni.The enhanced superficial hydrogen dissociati...The reaction kinetics of alloys based on magnesium are known to be greatly improved by the partial substitution of Mg with rare earths and transition metals,particularly Ni.The enhanced superficial hydrogen dissociation rate,the weakened Mg-H bond and the lower activation energy following element replacement are thought to be related to the better performance.The experimental alloys Ce5Mg_(95-x)Ni_(x)(x=5,10,15)were smelted by the vacuum induction melting.The phase transformation and structural evolution of experimental alloys before and after reaction with hydrogen were char-acterized by X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The cast specimens contain CeMg_(12),Mg and Mg_(2)Ni phases,and the increase in Ni content results in an obvious growth of Mg_(2)Ni phase.The isothermal and non-isothermal hydrogenation and dehydrogenation kinetics of the experimental specimens were investi-gated using the Sievert apparatus,differential scanning calorimetry and thermal gravimetric analyzer.The activation energy may be calculated using the Arrhenius and Kissinger equations.The experimental alloys have been shown to have good activation properties,with a reversible hydriding and dehydriding capacities of around 5.0 wt.%in the first cycle.The initial dehydrogenation temperature of MgH_(2) decreases from 557.5 to 537.7 K with changing Ni content from 5 to 15 at.%.The dehydrogenation activation energy also reduces from 77.09 to 62.96 kJ/mol,which explains the improved hydrogen storage performance caused by Ni substitution.It can be shown that the impact of Ni on the decomposition enthalpy of MgH_(2) is quite modest,with the absolute enthalpy(ΔHr)only decreasing from 78.48 to 76.15 kJ/mol.展开更多
Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the infe...Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.展开更多
The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the a...The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.展开更多
A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of ...A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of main components of crude lead,separation coefficients and vapor-liquid equilibrium composition of Pb-i（i stands for an impurity） system at different temperatures.The behaviors of impurities in the vacuum distillation refining process were investigated.The results show that the vacuum distillation should be taken to obtain lead from crude lead,in which Zn,As and partial Sb are volatilized at lower temperature of 923-1023 K.Lead is distilled from the residue containing Cu,Sn,Ag and Bi at higher temperature of 1323-1423 K,but the impurity Bi is also volatilized along with lead and cannot be separated from lead.展开更多
基金supported by the China Postdoctoral Science Foundation(No.2023T160088)the Youth Fund of the National Natural Science Foundation of China(No.52304324).
文摘Magnesium and magnesium alloys,serving as crucial lightweight structural materials and hydrogen storage elements,find extensive applications in space technology,aviation,automotive,and magnesium-based hydrogen industries.The global production of primary magnesium has reached approximately 1.2 million tons per year,with anticipated diversification in future applications and significant market demand.Nevertheless,approximately 80%of the world’s primary magnesium is still manufactured through the Pidgeon process,grappling with formidable issues including high energy consumption,massive carbon emission,significant resource depletion,and environmental pollution.The implementation of the relative vacuum method shows potential in breaking through technological challenges in the Pidgeon process,facilitating clean,low-carbon continuous magnesium smelting.This paper begins by introducing the principles of the relative vacuum method.Subsequently,it elucidates various innovative process routes,including relative vacuum ferrosilicon reduction,aluminum thermal reduction co-production of spinel,and aluminum thermal reduction co-production of calcium aluminate.Finally,and thermodynamic foundations of the relative vacuum,a quantitative analysis of the material,energy flows,carbon emission,and production cost for several new processes is conducted,comparing and analyzing them against the Pidgeon process.The study findings reveal that,with identical raw materials,the relative vacuum silicon thermal reduction process significantly decreases raw material consumption,energy consumption,and carbon dioxide emissions by 15.86%,30.89%,and 26.27%,respectively,compared to the Pidgeon process.The relative vacuum process,using magnesite as the raw material and aluminum as the reducing agent,has the lowest magnesium-to-feed ratio,at only 3.385.Additionally,its energy consumption and carbon dioxide emissions are the lowest,at 1.817 tce/t Mg and 7.782 t CO_(2)/t Mg,respectively.The energy consumption and carbon emissions of the relative vacuum magnesium smelting process co-producing calcium aluminate(12CaO·7Al_(2)O_(3),3CaO·Al_(2)O_(3),and CaO·Al_(2)O_(3))are highly correlated with the consumption of dolomite in the raw materials.When the reduction temperature is around 1473.15 K,the critical volume fraction of magnesium vapor for different processes varies within the range of 5%–40%.Production cost analysis shows that the relative vacuum primary magnesium smelting process has significant economic benefits.This paper offers essential data support and theoretical guidance for achieving energy efficiency,carbon reduction in magnesium smelting,and the industrial adoption of innovative processes.
基金National Natural Science Foundation of China(U22A20191)。
文摘A series of Al-xSi-yGe filler metals(x=4–12 and y=10–40,wt%)were prepared,and the effect of Si and Ge on microstructure and melting characteristics of filler metals was studied.The thermodynamic model of Al-Si-Ge ternary alloy was established to analyze the phase formation mechanism of filler metals based on Miedema model,Tanaka model,and Toop equation.This research provided a basis for the composition optimization of filler metals and the analysis of metallurgical reaction process between filler metals and base materials.Results show that Al-Si-Ge alloy is composed of Al-Ge eutectic phase,Al-Si eutectic phase,and primary Si.Ge addition promotes the precipitation of primary Si.Ge is the main melting point depressant element of filler metals.With the increase in Ge content from 10wt%to 40wt%,the solid phase line of filler metals remains unchanged,whereas the liquidus temperature decreases from 567.65°C to 499.96°C.With the increase in Ge content of filler metal,Ge content in eutectic Si phase is increased,the endothermic peak of Al-Si eutectic reaction according to thermogravimetry curve becomes smoother,and Al-Si eutectic temperature is decreased.Ge addition can reduce the free energy of Al-Si alloy system.The lowest point of free energy is located on Al-Ge side.The eutectic Ge phase with the composition similar to pure Ge composition is the most likely to appear in the microstructure of filler metals,whereas the eutectic Si phase with the composition similar to pure Si composition is the least likely to appear.The thermodynamic calculation results are consistent with the experiment results.
基金support from the China Scholarship Council(CSC No.201700260207)Swedish Iron and Steel Research Office(Jernkontoret)The EIT RawMaterials Upscaling project EndureIT(No.18317)is acknowledged by PH and WM for financial support.
文摘The low-temperature embrittlement limits the service temperature of ferritic and duplex stainless steels.The effects of alloying elements added to Fe-Cr binary system on the low-temperature embrittlement have been reviewed critically.Prior literature on the underlying phase transformation,i.e.,phase separation(PS)and changes of mechanical properties,is surveyed.The available literature indicates that the rate of PS is accelerated by Ni or Co in Fe-Cr binary system.The increased kinetics of PS also lead to an enhanced hardening rate during aging for Ni and Co alloyed Fe-Cr alloys.In low Cr(<17 wt.%)ferritic alloys,the additions of Al or Co can reduce embrittlement because these elements contribute to lowering the driving force for PS.The influence of other alloying elements such as Mo,Cu,Mn,Nb,and Ti is inconclusive but also discussed here.Thermodynamic and kinetic calculations were performed to evaluate current CALPHAD databases and to further investigate the thermodynamic and kinetic reasons for the effect of the additional alloying elements added to Fe-Cr alloy on PS.Some indications were provided for improving physically-based predictions of low-temperature embrittlement as well as opportunities to mitigate the phenomenon by alloying.
基金supported by the National Natural Science Foundation of China(22478106,22178102,and 22332003)Shanghai Rising-Star Program(23QA1401900)+1 种基金Young Elite Scientists Sponsorship Programby CAST(2023QNRC001)the Open Project of Yunnan Precious Metals Laboratory Co.,Ltd(YPML-2023050272).
文摘Gas-phase synthesis of glycolide(GL)from methyl glycolate(MG)is of great significance for producing biodegradable polyglycolic acid.Here,we report a detailed thermodynamics study for the gas-phase synthesis of GL from MG,which involves complex reaction pathways,by utilizing the Gibbs free energy minimization method.The results indicate that the decompositions of MG and GL and the polymerization of MG are thermodynamically favorable as compared with the target pathway,i.e.,the cyclization of MG.Effects of the reaction conditions including temperature,pressure and feed composition on the formation of GL and linear polymers have also been addressed,which demonstrate that the higher temperature and lower pressure can effectively inhibit the formation of linear methyl ester dimer and improve the selectivity to GL.In addition,the higher N_(2)/MG ratio is beneficial for the formation of GL in the process promoted by catalysts.These thermodynamics results indicate that the process promoted by catalysts would benefit from the kinetics control by high-performance catalysts and the operation at high temperature,low pressure and high N_(2)/MG ratio to enhance the yield of targeted GL.The insights demonstrated here from thermodynamics are valuable for guiding the design of catalysts and/or optimization of reaction conditions for the gas-phase synthesis of GL from MG.
基金financially supported by the National Natural Science Foundation of China(Nos.52204331 and 52374315)the Major Industrial Innovation Plan of Anhui Provincial Development and the Reform Commission,China(No.AHZDCYCX-LSDT2023-01)。
文摘Al_(2)O_(3)and MgO serve as the primary gangue components in sintered ores,and they are critical for the formation of CaO-Fe_(2)O_(3)-xAl_(2)O_(3)(wt%,C-F-xA)and CaO-Fe_(2)O_(3)-xM gO(wt%,C-F-xM)systems,respectively.In this study,a nonisothermal crystallization thermodynamics behavior of C-F-xA and C-F-xM systems was examined using differential scanning calorimetry,and a phase identification and microstructure analysis for C-F-xA and C-F-xM systems were carried out by X-ray diffraction and scanning electron microscopy.Results showed that in C-F-2A and C-F-2M systems,the increased cooling rates promoted the precipitation of CaFe_(2)O_(4)(CF)but inhibited the formation of Ca_(2)Fe_(2)O_(5)(C2F).In addition,C-F-2A system exhibited a lower theoretical initial crystallization temperature(1566 K)compared to the C-F system(1578 K).This temperature further decreases to 1554 K and 1528 K in the C-F-4A and C-F-8A systems,respectively.However,in C-F-xM system,the increased MgO content raised the crystallization temperature.This is because that the enhanced precipitation of MF(a spinel phase mainly comprised Fe_(3)O_(4)and MgFe_(2)O_(4))and C2F phases suppressed the CF precipitation reaction.In kinetic calculations,the Ozawa method revealed the apparent activation energies of the C-F-2A and C-F-2M systems.Malek's method revealed that the crystallization process in C-F-2A system initially followed a logarithmic law(lnαor lnα2),later transitioning to a reaction order law((1-α)-1or(1-α)^(-1/2),n=2/3)or the lnα2function of the exponential law.In C-F-2M system,it consistently followed the sequencef(α)=(1-α)^(2)(αis the crystallization conversion rate;n is the Avrami constant;?(α)is the differential equations for the model function of C_(2)F and CF crystallization processes).
文摘Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulfur(S_(8))[1].However,the electrochemical conversion reaction of S_(8) is an exceedingly complex process that involves the generation of multiple intermediates(e.g.,lithium polysulfides(LiPSs))and multiphase transitions[1,2].Currently,the mechanistic investigations of the electrochemical conversion reaction of S_(8) upon discharging a LSB cell heavily rely on electrochemical titration and spectroscopic techniques[3].Nevertheless,the considerable complexity and intrinsic instability of the LSB system present substantial obstacles to obtaining accurate information for all sulfur-containing species,which significantly obstructs in-depth elucidation of the fundamental discharge mechanism of LSB[3,4].
基金supported by the National Natural Science Foundation of China(Nos.51602229 and U2040222)the Opening Project of Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education(Tongji University)+1 种基金the Joint Fund Project of Hubei Provincial Natural Science Foundation(No.2023AFD196)the Opening Funding of Henan Key Laboratory of Green Building Materials Manufacturing and Intelligent Equipment(No.2024LGSYS02),China.
文摘Low-heat Portland(LHP)cement is a new type of Portland cement that has been widely used in recent years due to its low heat of hydration,which makes it exceptional in temperature control for mass concrete construction.However,limited studies have investigated the impact of temperature and magnesium oxide(MgO)content on LHP cement-based materials.This study utilizes thermodynamic simulations to study the hydration process,pore structure,and autogenous shrinkage of LHP cement pastes with different water-to-cement ratios(0.3,0.4,and 0.5),curing temperatures(5,15,20,and 30℃),and MgO contents(mass fractions of 2%,4%,and 5%).Higher curing temperature is found to promote the hydration reactions in cement paste.Moreover,the incorporation of 4%MgO moderately decreases both porosity and dimensional shrinkage in pastes.The microstructural evolution of different LHP pastes is examined through a comparative analysis,lending insights into LHP cement-based material applications.
基金by JST FOREST Program(Grant No.JPMJFR203W,Japan)MEXT through Grant-in-Aid for Scientific Research(B)(No.19H02473,2019-2021)+2 种基金Grant-in-Aid for Scientific Research on Innovative Areas(Research in a proposed research area)(No.18H05456,2018-2022)the partial support through the research grant funded by the Amada Foundation(2022-2023)the financial support from the Amada Foundation(AF-2022017-B2).L.L.gratefully acknowledges the financial support provided by China Scholarship Council(No.201806295030)and thanks Dr.Elango Chandiran。
文摘Dynamic transformation(DT)of austenite(γ)to ferrite(α)in the hot deformation of various carbon steels was widely investigated.However,the nature of DT remains unclear due to the lack of quantitative analysis of stress partitioning between two phases and the uncertainty of local distribution of substitu-tional elements at the interface in multi-component carbon steels used in the previous studies.Therefore,in the present study,a binary Fe-Ni alloy withα+γduplex microstructure in equilibrium was prepared and isothermally compressed inα+γtwo-phase region to achieve a quantitative analysis of microstruc-ture evolution,stress partitioning,and thermodynamics during DT.γtoαDT during isothermal compres-sion andαtoγreverse transformation on isothermal annealing under unloaded condition after deforma-tion were accompanied by Ni partitioning.The lattice strains during thermomechanical processing were obtained via in-situ neutron diffraction measurement,based on which the stress partitioning behavior betweenγandαwas discussed by using the generalized Hooke’s law.A thermodynamic framework for the isothermal deformation in solids was established based on the basic laws of thermodynamics,and it was shown that the total Helmholtz free energy change in the deformable material during the isothermal process should be smaller than the work done to the deformable material.Under the present thermody-namic framework,the microstructure evolution in the isothermal compression of Fe-14Ni alloy was well explained by considering the changes in chemical free energy,plastic and elastic energies,and the work done to the material.In addition,the stabilization of the softαphase in Fe-14Ni alloy by deformation was rationalized since theγtoαtransformation decreased the total Helmholtz free energy by decreasing the elastic and dislocation energies.
基金Project supported by the Fundamental Research Program of Shanxi Province (202203021211193,202203021211190)the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi(2022L291,2022L274)+1 种基金the National Natural Science Foundation of China (51761032,51871125,52071227)the Key Scientific Research Project in Shanxi Province(202102050201003)。
文摘Rare earth elements and transition metals have been found to improve the hydrogen storage characteristics of magnesium-based alloys.This study investigated the Mg-Ho-Fe(MHF) ternary alloy prepared using the vacuum induction melting technique.X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),pressure-composition-temperature(PCT),and differential scanning calorimetry(DSC) were used to analyze the alloy's phase transitions,microstructure,thermodynamics,and kinetic properties.The results reveal that the Mg_(98)Ho_(1.5)Fe_(0.5) alloy forms a solid solution with Ho and Fe in the magnesium matrix.Upon hydrogen absorption,the activated alloy transforms into a mixture of Mg/MgH_(2) phases and nanoscale HoH_(2) phases.Notably,only the MgH_(2) phase decomposes during hydrogen desorption,while the HoH_(2) phase remains unchanged,exhibiting a positive catalytic effect.The alloy demonstrates excellent hydrogen absorption kinetics,achieving a capacity of 5.56 wt% H_(2) within 10 min at 360℃,owing to the combined catalytic effects of Ho and Fe.The activation energy for hydrogen desorption is found to be 135.87 kJ/mol,which is lower than that of the activation energies of pure MgH_(2) and MgFe alloys,indicating an enhancement in desorption kinetics.Moreover,the enthalpy and entropy changes for hydrogen absorption and desorption are determined to be-70.51 kJ/mol H_(2),-125.62 J/(K·mol) H_(2),72.83 kJ/mol H_(2),and 128.95 J/(K·mol) H_(2),respectively.Furthermore,it is worth noting that the thermodynamic properties of the alloy are improved due to the catalytic effect of Ho and Fe.
基金Project supported by the National Key Research and Development Program of China(No.2021YFB1714600)the National Natural Science Foundation of China(No.52175095)the Young Top-Notch Talent Cultivation Program of Hubei Province of China。
文摘The spatiotemporally-nonlocal phenomena in heat conduction become significant but challenging for metamaterials with artificial microstructures.However,the microstructure-dependent heat conduction phenomena are captured under the hypothesis of spatiotemporally local equilibrium.To capture the microstructure-dependent heat conduction phenomena,a generalized nonlocal irreversible thermodynamics is proposed by removing both the temporally-local and spatially-local equilibrium hypotheses from the classical irreversible thermodynamics.The generalized nonlocal irreversible thermodynamics has intrinsic length and time parameters and thus can provide a thermodynamics basis for the spatiotemporally-nonlocal law of heat conduction.To remove the temporallylocal equilibrium hypothesis,the generalized entropy is assumed to depend not only on the internal energy but also on its first-order and high-order time derivatives.To remove the spatially local equilibrium hypothesis,the thermodynamics flux field in the dissipation function is assumed to relate not only to the thermodynamics force at the reference point but also to the thermodynamics force of the neighboring points.With the developed theoretical framework,the thermodynamics-consistent spatiotemporally-nonlocal models can then be developed for heat transfer problems.Two examples are provided to illustrate the applications of steady-state and transient heat conduction problems.
基金the National Natural Science Foundation of China(Nos.51871125,51761032,52001005 and 51731002)Major Science and Technology Innovation Projects in Shandong Province(No.2019JZZY010320)for financial support of the work.
文摘Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.
基金Project supported by the National Natural Science Foundation of China (Grant No. 12075197)the Fundamental Research Fund for the Central Universities of China (Grant No. 20720210020)。
文摘It is found from textbooks and literature that there are three different statements for the third law of thermodynamics,i.e., the Nernst theorem, the unattainability statement of absolute zero temperature, and the heat capacity statement. It is pointed out that such three statements correspond to three thermodynamic parameters, which are, respectively, the entropy,temperature, and heat capacity, and can be obtained by extrapolating the experimental results of different parameters at ultralow temperatures to absolute zero. It is expounded that because there is no need for additional assumptions in the derivation of the Nernst equation, the Nernst theorem should be renamed as the Nernst statement. Moreover, it is proved that both the Nernst statement and the heat capacity statement are mutually deducible and equivalent, while the unattainability of absolute zero temperature is only a corollary of the Nernst statement or the heat capacity statement so that it is unsuitably referred to as one statement of the third law of thermodynamics. The conclusion is that the Nernst statement and the heat capacity statement are two equivalent statements of the third law of thermodynamics.
基金Project supported by the Natural Science Foundation of Zhejiang Province,China (Grant No.LY14A030001)。
文摘We calculate the thermodynamic quantities in the quantum corrected Reissner-Nordstr?m-AdS(RN-AdS)black hole,and examine their quantum corrections.By analyzing the mass and heat capacity,we give the critical state and the remnant state,respectively,and discuss their consistency.Then,we investigate the quantum tunneling from the event horizon of massless scalar particle by using the null geodesic method,and charged massive boson W^(±)and fermions by using the Hamilton-Jacob method.It is shown that the same Hawking temperature can be obtained from these tunneling processes of different particles and methods.Next,by using the generalized uncertainty principle(GUP),we study the quantum corrections to the tunneling and the temperature.Then the logarithmic correction to the black hole entropy is obtained.
文摘In heart failure with preserved ejection fraction,significant left ventricular diastolic abnormalities are present,despite a normal systolic ejection fraction.This article will consider whether this is consistent with the law of conservation of energy,also know as the first law of thermodynamics.
文摘According to the second law of thermodynamics, as currently understood, any given transit of a system along the reversible path proceeds with a total entropy change equal to zero. The fact that this condition is also the identifier of thermodynamic equilibrium, makes each and every point along the reversible path a state of equilibrium, and the reversible path, as expressed by a noted thermodynamic author, “a dense succession of equilibrium states”. The difficulties with these notions are plural. The fact, for example, that systems need to be forced out of equilibrium via the expenditure of work, would make any spontaneous reversible process a consumer of work, this in opposition to common thermodynamic wisdom that makes spontaneous reversible processes the most efficient transformers of work-producing-potential into actual work. The solution to this and other related impasses is provided by Dialectical Thermodynamics via its previously proved notion assigning a negative entropy change to the energy upgrading process represented by the transformation of heat into work. The said solution is here exemplified with the ideal-gas phase isomerization of butane into isobutane.
文摘This work investigated the removal, kinetics and thermodynamics of iron(II) ions (Fe(II)) by adsorption in static and dynamic conditions in aqueous media on activated carbons (AC-i30min, AC-i1h, and AC-i24h), prepared from palm nut shells collected in the city of Franceville to Gabon, using potassium hydroxide (KOH) as the activating agent. Results on the elimination of Fe(II) in static and dynamic adsorption on prepared activated carbons (ACs) showed that the AC-i24h adsorbent has the best Fe(II) adsorption capacities at saturation (Qsat). The Qsat obtained on AC-i24h in static and dynamic conditions (17.87 and 10.38 mg/g, respectively) were higher than those of AC-i30min (13.89 and 5.54 mg/g respectively) and AC-i1h (14.92 and 8.64 mg/g respectively). Moreover, the static adsorption was more effective in the removal of Fe(II) ions in aqueous media in our experimental conditions. The percentage removal (%E) of Fe(II) obtained on prepared activated carbons in static conditions was better than those obtained in dynamic conditions, especially on AC-i24h, where the %E was 89.27% in static and 61.56% in dynamic. In kinetics, results showed that the pseudo-second-order kinetic model best described the adsorption mechanisms of Fe(II) on prepared activated carbons in static adsorption, with mainly of chemisorption on the solid surfaces. However, in dynamic conditions, the pseudo-first-order kinetic model was more suitable. In addition to the weak interactions between Fe(II) and the activated carbon surfaces, strong interactions (chemisorption) were also observed. Also, thermodynamic data obtained on AC-i24h in static adsorption indicated that the adsorption of Fe(II) was spontaneous and increased with temperature (ΔG˚ H˚ = 503.54 KJ/mol).
基金supported by the National Natural Science Foundation of China(Nos.51871125,51761032,51901105 and 52001005)Major Science and Technology Innovation Projects in Shandong Province(2019JZZY010320)+1 种基金Natural Science Foundation of Inner Mongolia,China(2019BS05005)Inner Mongolia University of Science and Technology Innovation Fund(2019QDL-B11).
文摘The reaction kinetics of alloys based on magnesium are known to be greatly improved by the partial substitution of Mg with rare earths and transition metals,particularly Ni.The enhanced superficial hydrogen dissociation rate,the weakened Mg-H bond and the lower activation energy following element replacement are thought to be related to the better performance.The experimental alloys Ce5Mg_(95-x)Ni_(x)(x=5,10,15)were smelted by the vacuum induction melting.The phase transformation and structural evolution of experimental alloys before and after reaction with hydrogen were char-acterized by X-ray diffraction,scanning electron microscopy and transmission electron microscopy.The cast specimens contain CeMg_(12),Mg and Mg_(2)Ni phases,and the increase in Ni content results in an obvious growth of Mg_(2)Ni phase.The isothermal and non-isothermal hydrogenation and dehydrogenation kinetics of the experimental specimens were investi-gated using the Sievert apparatus,differential scanning calorimetry and thermal gravimetric analyzer.The activation energy may be calculated using the Arrhenius and Kissinger equations.The experimental alloys have been shown to have good activation properties,with a reversible hydriding and dehydriding capacities of around 5.0 wt.%in the first cycle.The initial dehydrogenation temperature of MgH_(2) decreases from 557.5 to 537.7 K with changing Ni content from 5 to 15 at.%.The dehydrogenation activation energy also reduces from 77.09 to 62.96 kJ/mol,which explains the improved hydrogen storage performance caused by Ni substitution.It can be shown that the impact of Ni on the decomposition enthalpy of MgH_(2) is quite modest,with the absolute enthalpy(ΔHr)only decreasing from 78.48 to 76.15 kJ/mol.
基金supported by the National Natural Science Foundation of China (52374299,52304320 and 52204306)the Outstanding Youth Foundation of Hunan Province (2023JJ10044)+1 种基金the Key Project of Hunan Provincial Department of Education (22A0211)the Natural Science Foundation of Hunan Province (2023JJ40014)。
文摘Introducing high-valence Ta element is an essential strategy for addressing the structu ral deterioration of the Ni-rich LiNi_(1-x-y)Co_(x)Mn_(y)O_(2)(NCM)cathode,but the enlarged Li/Ni cation mixing leads to the inferior rate capability originating from the hindered Li~+migration.Note that the non-magnetic Ti~(4+)ion can suppress Li/Ni disorder by removing the magnetic frustration in the transition metal layer.However,it is still challenging to directionally design expected Ta/Ti dual-modification,resulting from the complexity of the elemental distribution and the uncertainty of in-situ formed coating compounds by introducing foreign elements.Herein,a LiTaO_3 grain boundary(GB)coating and bulk Ti-doping have been successfully achieved in LiNi_(0.834)Co_(0.11)Mn_(0.056)O_(2) cathode by thermodynamic guidance,in which the structural formation energy and interfacial binding energy are employed to predict the elemental diffusion discrepancy and thermodynamically stable coating compounds.Thanks to the coupling effect of strengthened structural/interfacial stability and improved Li~+diffusion kinetics by simultaneous bulk/GB engineering,the Ta/Ti-NCM cathode exhibits outstanding capacity retention,reaching 91.1%after 400 cycles at 1 C.This elaborate work contributes valuable insights into rational dual-modification engineering from a thermodynamic perspective for maximizing the electrochemical performances of NCM cathodes.
基金Project(2007AA06Z129) supported by the High-tech Research and Development Program of China
文摘The adsorption behavior of D301 for molybdenum blue was investigated.The thermodynamics parameters in adsorption process were calculated and the adsorption kinetics was studied.The experimental results show that the adsorption characteristic of D301 for molybdenum blue fits well with the Freundlich adsorption isotherm equation.In the adsorption process of D301 for molybdenum blue,both the enthalpy change ΔH and entropy change ΔS are positive,while the free energy change ΔG is negative when temperatures are in the range of 303-333 K.It is indicated that the adsorption is a spontaneous and endothermic process,and the elevated temperatures benefit to the adsorption.Kinetic studies show that the kinetic data are well described by double driving-force model,and the adsorption rate of molybdenum blue on D301 is controlled by the intraparticle diffusion during the adsorption process.The total kinetic equation is determined.
基金Project (2012CB722803) supported by the National Basic Research Program of ChinaProject (U1202271) supported by the National Natural Science Foundation of China
文摘A novel technique was developed to remove impurities from crude lead by vacuum distillation.The thermodynamics on vacuum distillation refining process of crude lead was studied by means of saturated vapor pressure of main components of crude lead,separation coefficients and vapor-liquid equilibrium composition of Pb-i（i stands for an impurity） system at different temperatures.The behaviors of impurities in the vacuum distillation refining process were investigated.The results show that the vacuum distillation should be taken to obtain lead from crude lead,in which Zn,As and partial Sb are volatilized at lower temperature of 923-1023 K.Lead is distilled from the residue containing Cu,Sn,Ag and Bi at higher temperature of 1323-1423 K,but the impurity Bi is also volatilized along with lead and cannot be separated from lead.
