It has recently been shown that incident particles, neutrons, can initiate the freezing in a supercooled water volume. This new finding may have ramifications for the interpretation of both experimental data on the nu...It has recently been shown that incident particles, neutrons, can initiate the freezing in a supercooled water volume. This new finding may have ramifications for the interpretation of both experimental data on the nucleation of laboratory samples of supercooled water and perhaps more importantly on the interpretation of ice nucleation involved in cloud physics. For example, if some fraction of the cloud nucleation previously attributed to dust, soot, or aerosols has been caused by cosmogenic neutrons, fresh consideration is required in the context of climate models. Moreover, as cosmogenic neutrons, most being muon-induced, have much greater flux at high latitudes, estimates of ice nucleates in these regions may be larger than required to accurately model cloud and condensation properties. This discrepancy has been pointed out in IPCC reports. Our paper discusses the connection between the new concept of neutrons nucleating supercooled water and the need for a new source of nucleation in high latitude clouds, ideally causing others to review current data, or to analyse future data with this idea in mind. .展开更多
Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable...Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable development in the steel industry.We had pre-viously found the possibility of recovering Fe and P resources,i.e.,magnetite(Fe_(3)O_(4)) and calcium phosphate(Ca_(10)P_(6)O_(25)),contained in steel-making slags by adjusting oxygen partial pressure and adding modifier B_(2)O_(3).As a fundamental study for efficiently recovering Fe and P from steelmaking slag,in this study,the crystallization behavior of the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt has been observed in situ,using a confocal scanning laser microscope(CLSM).The kinetics of nucleation and growth of Fe-and P-rich phases have been calculated using a classical crys-tallization kinetic theory.During cooling,a Fe_(3)O_(4) phase with faceted morphology was observed as the 1st precipitated phase in the isothermal interval of 1300-1150℃,while Ca_(10)P_(6)O_(25),with rod-shaped morphology,was found to be the 2nd phase to precipitate in the interval of 1150-1000℃.The crystallization abilities of Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases in the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt were quantified with the in-dex of(T_(U)−T_(I))/T_(I)(where T_(I) represents the peak temperature of the nucleation rate and TU stands for that of growth rate),and the crystalliza-tion ability of Fe_(3)O_(4) was found to be larger than that of Ca_(10)P_(6)O_(25) phase.The range of crystallization temperature for Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases was optimized subsequently.The Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases are the potential sources for ferrous feedstock and phosphate fertilizer,respectively.展开更多
Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their ...Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.展开更多
The freezing of water is one of the most common processes in nature and affects many aspects of human activity. Ice nucleation is a crucial part of the freezing process and usually occurs on material surfaces. There i...The freezing of water is one of the most common processes in nature and affects many aspects of human activity. Ice nucleation is a crucial part of the freezing process and usually occurs on material surfaces. There is still a lack of clear physical pictures about the central question how various features of material surfaces affect their capability in facilitating ice nucleation. Via molecular dynamics simulations, here we show that the detailed features of surfaces, such as atomic arrangements, lattice parameters, hydrophobicity, and function forms of surfaces’ interaction to water molecules, generally affect the ice nucleation through the average adsorption energy per unit-area surfaces to individual water molecules, when the lattice of surfaces mismatches that of ice. However, for the surfaces whose lattice matches ice, even the detailed function form of the surfaces’ interaction to water molecules can largely regulate the icing ability of these surfaces. This study provides new insights into understanding the diverse relationship between various microscopic features of different material surfaces and their nucleation efficacy.展开更多
Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has...Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has not yet attracted enough attention from researchers to our knowledge. Here, we propose that thermodynamic nucleation overpotential of Zn deposition can be boosted through complexing agent and select sodium L-tartrate(Na-L) as example. Theoretical and experimental characterization reveals L-tartrate anion can partially replace H_(2)O in the solvation sheath of Zn^(2+), increasing de-solvation energy. Concurrently, the Na^(+) could absorb on the surface of Zn anode preferentially to inhibit the deposition of Zn^(2+) aggregation. In consequence, the overpotential of Zn deposition could increase from 32.2 to 45.1 mV with the help of Na-L. The Zn-Zn cell could achieve a Zn utilization rate of 80% at areal capacity of 20 mAh cm^(-2). Zn-LiMn_(2)O_(4) full cell with Na-L additive delivers improved stability than that with blank electrolyte. This study also provides insight into the regulation of nucleation overpotential to achieve homogeneous Zn deposition.展开更多
Due to the significant differences in the formation temperature and crystal structure between the primaryα-Mg and eutecticβ-Mg_(17)Al_(12),it is a great challenge to achieve simultaneous refinement of the primary an...Due to the significant differences in the formation temperature and crystal structure between the primaryα-Mg and eutecticβ-Mg_(17)Al_(12),it is a great challenge to achieve simultaneous refinement of the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation.Surprisingly,we found that theα-Mg andβ-Mg_(17)Al_(12) in the AZ80 alloy can be simultaneously refined after 0.2 wt.%Sm addition,with the grain size decreasing from∼217±15μm to∼170±10μm and theβ-Mg_(17)Al_(12) morphology changing from a typical continuous network to a nod-like or spherical structure.The simultaneous refinement mechanism is investigated through solidification simulation,transmission electron microscopy(TEM),and differential thermal analysis(DTA).In the AZ80-0.2Sm alloy,many Al8Mn4Sm particles can be observed near the center of theα-Mg grains or inside theβ-Mg_(17)Al_(12).Crystallographic calculations further reveal that the Al8Mn4Sm has good crystallographic matching with both theα-Mg andβ-Mg_(17)Al_(12),so it possesses the potency to serve as heterogeneous nucleation sites for both phases.The promoted heterogeneous nucleation on the Al8Mn4Sm decreases the undercooling required by the nucleation of the primary and eutectic phases,which enhances the heterogeneous nucleation rate,thus causing the simultaneous refinement of theα-Mg andβ-Mg_(17)Al_(12).The orientation relationships between the Al8Mn4Sm and Mg/Mg_(17)Al_(12) are identified,which are[1210]_(Mg)//[010]_(Al8Mn4Sm),(1010)_(Mg)//(301)_(Al8Mn4Sm) and[112]_(Mg_(17)Al_(12))//[010]_(Al8Mn4Sm),(110)_(Mg_(17)Al_(12))//(301)_(Al8Mn4Sm),respectively.Furthermore,the refinement of theβ-Mg_(17)Al_(12) accelerates its dissolution during the solution treatment,which is beneficial for cost saving in industrial applications.Other Al8Mn4RE compounds such as Al8Mn4Y might have the same positive effect on the simultaneous refinement due to the similar physicochemical properties of rare earth elements.This work not only proves the possibility of simultaneously refining the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation,but also provides new insights into the development of refiners for cast Mg alloys.展开更多
According to classical nucleation theory, gas nuclei can generate and grow into a cavitation bubble when the liquid pressure exceeds a threshold. However, classical nucleation theory does not include boundary effects....According to classical nucleation theory, gas nuclei can generate and grow into a cavitation bubble when the liquid pressure exceeds a threshold. However, classical nucleation theory does not include boundary effects. An enclosed spherical liquid cavity surrounded by elastic medium is introduced to model the nucleation process in tissue. Based on the equilibrium pressure relationship of a quasi-static process, the expressions of the threshold and the modified nucleation rate are derived by considering the tissue elasticity. It is shown that the constraint plays an important role in the nucleation process. There is a positive correlation between nucleation threshold pressure and constraint, which can be enhanced by an increasing tissue elasticity and reducing the size of the cavity. Meanwhile, temperature is found to be a key parameter of nucleation process, and cavitation is more likely to occur in confined liquids at temperature T > 100℃. In contrast, less influences are induced by these factors, such as bulk modulus, liquid cavity size, and acoustic frequency. Although these theoretical predictions of the thresholds have been demonstrated by many previous researches, much lower thresholds can be obtained in liquids containing dissolved gases, e.g., the nucleation threshold is about-21 MPa in a liquid of 0.8-nm gas nuclei at room temperature. Moreover, when there is a gas nucleus of 20 nm, the theoretical threshold pressure might be less than1 MPa.展开更多
The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(...The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(100 ﹣ x)SiO<sub>2</sub> (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li<sub>2</sub>O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates I<sub>st</sub> of lithium disilicate crystals in the 23.4Li<sub>2</sub>O·76.6SiO<sub>2</sub>, 26Li<sub>2</sub>O·74SiO<sub>2</sub> and 29.1Li<sub>2</sub>O·70.9SiO<sub>2</sub> glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates I<sub>st</sub> for the glass of the stoichiometric lithium disilicate composition 33.51Li<sub>2</sub>O·66.5SiO<sub>2</sub>. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li<sub>2</sub>O-SiO<sub>2</sub> system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.展开更多
Understanding the behaviours of ice nucleation in non-isothermal conditions is of great importance for the preparation and retention of supercooled water. Here ice nucleation in supercooled water under temperature gra...Understanding the behaviours of ice nucleation in non-isothermal conditions is of great importance for the preparation and retention of supercooled water. Here ice nucleation in supercooled water under temperature gradients is analyzed thermodynamically based on classical nucleation theory(CNT). Given that the free energy barrier for nucleation is dependent on temperature, different from a uniform temperature usually used in CNT, an assumption of linear temperature distribution in the ice nucleus was made and taken into consideration in analysis. The critical radius of the ice nucleus for nucleation and the corresponding nucleation model in the presence of a temperature gradient were obtained. It is observed that the critical radius is determined not only by the degree of supercooling, the only dependence in CNT, but also by the temperature gradient and even the Young's contact angle. Effects of temperature gradient on the change in free energy, critical radius,nucleation barrier and nucleation rate with different contact angles and degrees of supercooling are illustrated successively.The results show that a temperature gradient will increase the nucleation barrier and decrease the nucleation rate, particularly in the cases of large contact angle and low degree of supercooling. In addition, there is a critical temperature gradient for a given degree of supercooling and contact angle, at the higher of which the nucleation can be suppressed completely.展开更多
How natural gas hydrates nucleate and grow is a crucial scientific question.The research on it will help solve practical problems encountered in hydrate accumulation,development,and utilization of hydrate related tech...How natural gas hydrates nucleate and grow is a crucial scientific question.The research on it will help solve practical problems encountered in hydrate accumulation,development,and utilization of hydrate related technology.Due to its limitations on both spatial and temporal dimensions,experiment cannot fully explain this issue on a micro-scale.With the development of computer technology,molecular simulation has been widely used in the study of hydrate formation because it can observe the nucleation and growth process of hydrates at the molecular level.This review will assess the recent progresses in molecular dynamics simulation of hydrate nucleation and growth,as well as the enlightening significance of these developments in hydrate applications.At the same time,combined with the problems encountered in recent hydrate trial mining and applications,some potential directions for molecular simulation in the research of hydrate nucleation and growth are proposed,and the future of molecular simulation research on hydrate nucleation and growth is prospected.展开更多
Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compare...Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compared with the thermodynamics of hydrate formation,understanding the nucleation mechanism is challenging and has drawn substantial attention in recent decades.In this paper,we attempt to give a comprehensive review of the recent progress of studies of clathrate hydrate nucleation.First,the existing hypotheses on the hydrate nucleation mechanism are introduced and discussed.Then,we summarize recent experimental studies on induction time,a key parameter evaluating the velocity of the nucleation process.Subsequently,the memory effect is particularly discussed,followed by the suggestion of several promising research perspectives.展开更多
The effects of strain rates on the hot working characteristics and nucleation mechanisms of dynamic recrystallization (DRX) were studied by optical microscopy and electron backscatter diffraction (EBSD) technique. Hot...The effects of strain rates on the hot working characteristics and nucleation mechanisms of dynamic recrystallization (DRX) were studied by optical microscopy and electron backscatter diffraction (EBSD) technique. Hot compression tests were conducted using a Gleeble-1500 simulator at a true strain of 0.7 in the temperature range of 1000 to 1150 °C and strain rate range of 0.01 to 10.00 s-1. It is found that the size and volume fraction of the DRX grains in hot-deformed Inconel 625 superalloy firstly decrease and then increase with increasing strain rate. Meanwhile, the nucleation mechanism of DRX is closely related to the deformation strain rate due to the deformation thermal effect. The discontinuous DRX (DDRX) with bulging of original grain boundaries is the primary nucleation mechanism of DRX, while the continuous DRX (CDRX) with progressive subgrain rotation acts as a secondary nucleation mechanism. The twinning formation can activate the nucleation of DRX. The effects of bulging of original grain boundaries and twinning formation are firstly gradually weakened and then strengthened with the increasing strain rate due to the deformation thermal effect. On the contrary, the effect of subgrain rotation is firstly gradually strengthened and then weakened with the increasing strain rate.展开更多
In the present work we studied the induction periods of hydrate formation of natural gas in pure water, aqueous solutions of surfactants, and in the presence of surfactant together with aluminum oxide nanopowder, the ...In the present work we studied the induction periods of hydrate formation of natural gas in pure water, aqueous solutions of surfactants, and in the presence of surfactant together with aluminum oxide nanopowder, the activity of which as hydrate formation inducer was studied previously. Sodium dodecyl sulfate(SDS) or neonol AF-9-12 were used as the surfactants. It was demonstrated that the addition of either surfactants or aluminum oxide powder under our experimental conditions causes a decrease in the induction period of hydrate formation from ~105 min for pure water to 30–35 min for water with additives. In the case of the simultaneous presence of surfactants and aluminum oxide powder in the system, induction period decreased to ~20 min. So, the synergistic effect of the combination of surfactant and oxide powder on gas hydrate nucleation was demonstrated. Possible reasons of this effect have been discussed.展开更多
A crystal plasticity model is developed to predict the fatigue crack nucleation of polycrystalline materials,in which the accumulated dislocation dipoles are considered to be the origin of damage.To describe the overa...A crystal plasticity model is developed to predict the fatigue crack nucleation of polycrystalline materials,in which the accumulated dislocation dipoles are considered to be the origin of damage.To describe the overall softening behavior under cyclic loading,a slip system-level dislocation density-related damage model is proposed and implemented in the finite element analysis with Voronoi tessellation.The numerical model is applied to calibrate the stress-strain relationship at different cycles before fatigue crack nucleation.The parameters determined from the numerical analysis are substituted into a modified phase transformation model to predict the critical fatigue crack nucleation cycle.Comparing with the experimental results of Sn-3.0Ag-0.5Cu(SAC305)alloy and P91 steel,the proposed method can describe the constitutive behavior and predict the fatigue crack nucleation accurately.展开更多
he evolution and nucleation of microcracks in typical tectonics are investigated in the experiment of fracture of marble specimen. The change of state during nucleation of microcracks is observed. The controlling effe...he evolution and nucleation of microcracks in typical tectonics are investigated in the experiment of fracture of marble specimen. The change of state during nucleation of microcracks is observed. The controlling effect of tectonics on evolution of microcracks is analyzed by using thc damage mechanics theory. These characteristics can be analogized to kilometer meters as the first effect of earthquake precursors. These studies may be helpful to interpret-the foreshock or general foreshock in the moderate or short stage before strong earthquakes. The other physical precursors are second or third effect. The local density of microcracks increasing abruptly may be helpful to interpret the phenomenon that part precursor records appear catastrophic jump. The part out of nucleation where some microcracks heal and the density change reversibly may be helpful to interpret the phenomenon that some precursors records appear reverse change. The area difference of microcracks accumulation and evolution in different part of typital tectonics is studied. This difference may be helpful to interpret the characteristics (including the area) of earthquake preparation of diffcrent tectonics, and further to interpret the difference of the precursors beween plate edge and intraplate. These differences may be introduced by the scholars with different points of view as to discuss about the existence of precursors before earthquakes. However, when the precursor records are studied, one must notice the geology background in different areas.展开更多
The grain density,Nv,in the solid state after solidification of AZ91/SiC composite is a function of maximum undercooling,ΔT,of a liquid alloy.This type of function depends on the characteristics of heterogeneous nucl...The grain density,Nv,in the solid state after solidification of AZ91/SiC composite is a function of maximum undercooling,ΔT,of a liquid alloy.This type of function depends on the characteristics of heterogeneous nucleation sites and number of SiC present in the alloy.The aim of this paper was selection of parameters for the model describing the relationship between the grain density of primary phase and undercooling.This model in connection with model of crystallisation,which is based on chemical elements diffusion and grain interface kinetics,can be used to predict casting quality and its microstructure.Nucleation models have parameters,which exact values are usually not known and sometimes even their physical meaning is under discussion.Those parameters can be obtained after mathematical analysis of the experimental data.The composites with 0,1,2,3 and 4wt.% of SiC particles were prepared.The AZ91 alloy was a matrix of the composite reinforcement SiC particles.This composite was cast to prepare four different thickness plates.They were taken from the region near to the thermocouple,to analyze the undercooling for different composites and thickness plates and its influence on the grain size.The microstructure and thermal analysis gave set of values that connect mass fraction of SiC particles,and undercooling with grain size.These values were used to approximate nucleation model adjustment parameters.Obtained model can be very useful in modelling composites microstructure.展开更多
High resolution electron microscopy studies of rure earth-rich phase particles in a melt-quenched Ti-5Al-4Sn-2Zr-1MO-0.25Si-1Nd alloy indicate that the α-Ti matrix crystallizes prior to the rare earth-rich phase part...High resolution electron microscopy studies of rure earth-rich phase particles in a melt-quenched Ti-5Al-4Sn-2Zr-1MO-0.25Si-1Nd alloy indicate that the α-Ti matrix crystallizes prior to the rare earth-rich phase particles. According to a new nucleation model, the heteropeneous nucleation of the rare earth-rich phase particles at the matrix interface is easier than the homogeneous nucleation off the interface matrix, which is consistent with the results of the HREM obseroations.展开更多
Undercoolings up to 397 K(0.283 T_E)have been obtained for Ni-32.5% Sn eutectic alloymelted by superheating-cooling cycles and denucleating with inorganic glasses.The predomi-nant dissipation of heat for highly underc...Undercoolings up to 397 K(0.283 T_E)have been obtained for Ni-32.5% Sn eutectic alloymelted by superheating-cooling cycles and denucleating with inorganic glasses.The predomi-nant dissipation of heat for highly undercooled alloy melt is through radiation.An approxi-mate method is consequently derived to calculate its mean specific heat from measured coolingcurves.With the aid of high speed cinematography,it is revealed that the surface or interfaceheterogeneous nucleation takes place in preference to homogeneous nucleation even though theundercooling has exceeded 0.2 T_E.展开更多
It is deduced from thermodynamic relations and confirmed by experiment results that the nucle-ation rate and nucleation temperature of nucleating agents in the glass are dependent upon their melting entropy △Sm melti...It is deduced from thermodynamic relations and confirmed by experiment results that the nucle-ation rate and nucleation temperature of nucleating agents in the glass are dependent upon their melting entropy △Sm melting temperature Tm and crystal - type transition in terms of some mathematical expressions.展开更多
Nucleation sites of α-Al grains after addition of an Al-Ti-B master alloy into pure aluminium have been investigated using EPMA. The results show that either TiAl3 or boride particales can nucleate α-Al grains. But ...Nucleation sites of α-Al grains after addition of an Al-Ti-B master alloy into pure aluminium have been investigated using EPMA. The results show that either TiAl3 or boride particales can nucleate α-Al grains. But the number of TiAl3 nucleants is reduced with the holding time prolonged and the boride-nuclei are increasing gradually. Based on these results, a new refining method, adding molten Al-Ti-B into commercially pure aluminium, which has a quicker and better refining efficiency is presented.展开更多
文摘It has recently been shown that incident particles, neutrons, can initiate the freezing in a supercooled water volume. This new finding may have ramifications for the interpretation of both experimental data on the nucleation of laboratory samples of supercooled water and perhaps more importantly on the interpretation of ice nucleation involved in cloud physics. For example, if some fraction of the cloud nucleation previously attributed to dust, soot, or aerosols has been caused by cosmogenic neutrons, fresh consideration is required in the context of climate models. Moreover, as cosmogenic neutrons, most being muon-induced, have much greater flux at high latitudes, estimates of ice nucleates in these regions may be larger than required to accurately model cloud and condensation properties. This discrepancy has been pointed out in IPCC reports. Our paper discusses the connection between the new concept of neutrons nucleating supercooled water and the need for a new source of nucleation in high latitude clouds, ideally causing others to review current data, or to analyse future data with this idea in mind. .
基金supported by Jiangsu University(No.19JDG011)the Project of the National Natural Science Foundation of China(Nos.51874272,52111540265)the Open Foundation of State Key Laboratory of Mineral Processing(No.BGRIMM-KJSKL-2022-23).
文摘Recovering the iron(Fe)and phosphorus(P)contained in steelmaking slags not only reduces the environmental burden caused by the accumulated slag,but also is the way to develop a circular economy and achieve sustainable development in the steel industry.We had pre-viously found the possibility of recovering Fe and P resources,i.e.,magnetite(Fe_(3)O_(4)) and calcium phosphate(Ca_(10)P_(6)O_(25)),contained in steel-making slags by adjusting oxygen partial pressure and adding modifier B_(2)O_(3).As a fundamental study for efficiently recovering Fe and P from steelmaking slag,in this study,the crystallization behavior of the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt has been observed in situ,using a confocal scanning laser microscope(CLSM).The kinetics of nucleation and growth of Fe-and P-rich phases have been calculated using a classical crys-tallization kinetic theory.During cooling,a Fe_(3)O_(4) phase with faceted morphology was observed as the 1st precipitated phase in the isothermal interval of 1300-1150℃,while Ca_(10)P_(6)O_(25),with rod-shaped morphology,was found to be the 2nd phase to precipitate in the interval of 1150-1000℃.The crystallization abilities of Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases in the CaO-SiO_(2)-FeO-P_(2)O_(5)-B_(2)O_(3) melt were quantified with the in-dex of(T_(U)−T_(I))/T_(I)(where T_(I) represents the peak temperature of the nucleation rate and TU stands for that of growth rate),and the crystalliza-tion ability of Fe_(3)O_(4) was found to be larger than that of Ca_(10)P_(6)O_(25) phase.The range of crystallization temperature for Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases was optimized subsequently.The Fe_(3)O_(4) and Ca_(10)P_(6)O_(25) phases are the potential sources for ferrous feedstock and phosphate fertilizer,respectively.
基金financially supported by the National Natural Science Foundation of China(21674068,52173133,52161145402)the Sichuan Science and Technology Department(2021YFH0180)。
文摘Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.
基金supported by the National Natural Science Foundation of China (Grant No. 12174388)。
文摘The freezing of water is one of the most common processes in nature and affects many aspects of human activity. Ice nucleation is a crucial part of the freezing process and usually occurs on material surfaces. There is still a lack of clear physical pictures about the central question how various features of material surfaces affect their capability in facilitating ice nucleation. Via molecular dynamics simulations, here we show that the detailed features of surfaces, such as atomic arrangements, lattice parameters, hydrophobicity, and function forms of surfaces’ interaction to water molecules, generally affect the ice nucleation through the average adsorption energy per unit-area surfaces to individual water molecules, when the lattice of surfaces mismatches that of ice. However, for the surfaces whose lattice matches ice, even the detailed function form of the surfaces’ interaction to water molecules can largely regulate the icing ability of these surfaces. This study provides new insights into understanding the diverse relationship between various microscopic features of different material surfaces and their nucleation efficacy.
基金supported by the National Key R&D Program of China (2022YFB3305400)Beijing Natural Science Foundation (Z220021)+3 种基金Science and Technology Innovation Program Talent Cultivation Project of Beijing Institute of Technology (2021CX01012)the National Natural Science Foundation of China (51972030, 22202011)Beijing Outstanding Young Scientists Program (BJJWZYJH01201910007023)Natural Science Foundation of Shandong Province (ZR2022QB056)。
文摘Dendrite formation severely compromises further development of zinc ion batteries. Increasing the nucleation overpotential plays a crucial role in achieving uniform deposition of metal ions. However, this strategy has not yet attracted enough attention from researchers to our knowledge. Here, we propose that thermodynamic nucleation overpotential of Zn deposition can be boosted through complexing agent and select sodium L-tartrate(Na-L) as example. Theoretical and experimental characterization reveals L-tartrate anion can partially replace H_(2)O in the solvation sheath of Zn^(2+), increasing de-solvation energy. Concurrently, the Na^(+) could absorb on the surface of Zn anode preferentially to inhibit the deposition of Zn^(2+) aggregation. In consequence, the overpotential of Zn deposition could increase from 32.2 to 45.1 mV with the help of Na-L. The Zn-Zn cell could achieve a Zn utilization rate of 80% at areal capacity of 20 mAh cm^(-2). Zn-LiMn_(2)O_(4) full cell with Na-L additive delivers improved stability than that with blank electrolyte. This study also provides insight into the regulation of nucleation overpotential to achieve homogeneous Zn deposition.
基金Financial supports from The National Natural Science Foundation of China(Nos.52104376,U19A2084,52074132,and 52004100)China Postdoctoral Science Foundation(2021T140250 and 2021M701376)+1 种基金Partial financial support came from The Science and Technology Development Program of Jilin Province(Nos.20200401025GX and 20200201002JC)Program for JLU Science and Technology Innovative Research Team(JLUSTIRT,2017TD-09)。
文摘Due to the significant differences in the formation temperature and crystal structure between the primaryα-Mg and eutecticβ-Mg_(17)Al_(12),it is a great challenge to achieve simultaneous refinement of the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation.Surprisingly,we found that theα-Mg andβ-Mg_(17)Al_(12) in the AZ80 alloy can be simultaneously refined after 0.2 wt.%Sm addition,with the grain size decreasing from∼217±15μm to∼170±10μm and theβ-Mg_(17)Al_(12) morphology changing from a typical continuous network to a nod-like or spherical structure.The simultaneous refinement mechanism is investigated through solidification simulation,transmission electron microscopy(TEM),and differential thermal analysis(DTA).In the AZ80-0.2Sm alloy,many Al8Mn4Sm particles can be observed near the center of theα-Mg grains or inside theβ-Mg_(17)Al_(12).Crystallographic calculations further reveal that the Al8Mn4Sm has good crystallographic matching with both theα-Mg andβ-Mg_(17)Al_(12),so it possesses the potency to serve as heterogeneous nucleation sites for both phases.The promoted heterogeneous nucleation on the Al8Mn4Sm decreases the undercooling required by the nucleation of the primary and eutectic phases,which enhances the heterogeneous nucleation rate,thus causing the simultaneous refinement of theα-Mg andβ-Mg_(17)Al_(12).The orientation relationships between the Al8Mn4Sm and Mg/Mg_(17)Al_(12) are identified,which are[1210]_(Mg)//[010]_(Al8Mn4Sm),(1010)_(Mg)//(301)_(Al8Mn4Sm) and[112]_(Mg_(17)Al_(12))//[010]_(Al8Mn4Sm),(110)_(Mg_(17)Al_(12))//(301)_(Al8Mn4Sm),respectively.Furthermore,the refinement of theβ-Mg_(17)Al_(12) accelerates its dissolution during the solution treatment,which is beneficial for cost saving in industrial applications.Other Al8Mn4RE compounds such as Al8Mn4Y might have the same positive effect on the simultaneous refinement due to the similar physicochemical properties of rare earth elements.This work not only proves the possibility of simultaneously refining the primary and eutectic phases in Mg-Al based alloys via heterogeneous nucleation,but also provides new insights into the development of refiners for cast Mg alloys.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 11974232 and 11727813)。
文摘According to classical nucleation theory, gas nuclei can generate and grow into a cavitation bubble when the liquid pressure exceeds a threshold. However, classical nucleation theory does not include boundary effects. An enclosed spherical liquid cavity surrounded by elastic medium is introduced to model the nucleation process in tissue. Based on the equilibrium pressure relationship of a quasi-static process, the expressions of the threshold and the modified nucleation rate are derived by considering the tissue elasticity. It is shown that the constraint plays an important role in the nucleation process. There is a positive correlation between nucleation threshold pressure and constraint, which can be enhanced by an increasing tissue elasticity and reducing the size of the cavity. Meanwhile, temperature is found to be a key parameter of nucleation process, and cavitation is more likely to occur in confined liquids at temperature T > 100℃. In contrast, less influences are induced by these factors, such as bulk modulus, liquid cavity size, and acoustic frequency. Although these theoretical predictions of the thresholds have been demonstrated by many previous researches, much lower thresholds can be obtained in liquids containing dissolved gases, e.g., the nucleation threshold is about-21 MPa in a liquid of 0.8-nm gas nuclei at room temperature. Moreover, when there is a gas nucleus of 20 nm, the theoretical threshold pressure might be less than1 MPa.
文摘The crystal growth and nucleation in glasses in the lithium silicate system have been investigated. Phase separation in ultimately homogenized glasses of the lithium silicate system xLi<sub>2</sub>O·(100 ﹣ x)SiO<sub>2</sub> (where x = 23.4, 26.0, 29.1, and 33.5 mol% Li<sub>2</sub>O) has been studied. The glasses of these compositions have been homogenized using the previously established special temperature-time conditions, which make it possible to provide a maximum dehydration and removal of bubbles from the glass melt. The parameters of nucleation and growth of phase separated in homogeneities and homogeneous crystal nucleation have been determined. The absolute values of the stationary nucleation rates I<sub>st</sub> of lithium disilicate crystals in the 23.4Li<sub>2</sub>O·76.6SiO<sub>2</sub>, 26Li<sub>2</sub>O·74SiO<sub>2</sub> and 29.1Li<sub>2</sub>O·70.9SiO<sub>2</sub> glasses with the compositions lying in the metastable phase separation region have been compared with the corresponding rates I<sub>st</sub> for the glass of the stoichiometric lithium disilicate composition 33.51Li<sub>2</sub>O·66.5SiO<sub>2</sub>. It has been found that the crystal growth rate has a tendency toward a monotonic increase with an increase in the temperature, whereas the dependences of the crystal growth rate on the time of low temperature heat treatment exhibit an oscillatory behavior with a monotonic decrease in the absolute value of oscillations. The character of crystallization in glasses with the compositions lying in the phase separation region of the Li<sub>2</sub>O-SiO<sub>2</sub> system is compared with that in the glass of the stoichiometric lithium disilicate composition. The conclusion has been made that the phase separation weakly affects the nucleation parameters of the lithium disilicate and has a strong effect on the crystal growth.
文摘Understanding the behaviours of ice nucleation in non-isothermal conditions is of great importance for the preparation and retention of supercooled water. Here ice nucleation in supercooled water under temperature gradients is analyzed thermodynamically based on classical nucleation theory(CNT). Given that the free energy barrier for nucleation is dependent on temperature, different from a uniform temperature usually used in CNT, an assumption of linear temperature distribution in the ice nucleus was made and taken into consideration in analysis. The critical radius of the ice nucleus for nucleation and the corresponding nucleation model in the presence of a temperature gradient were obtained. It is observed that the critical radius is determined not only by the degree of supercooling, the only dependence in CNT, but also by the temperature gradient and even the Young's contact angle. Effects of temperature gradient on the change in free energy, critical radius,nucleation barrier and nucleation rate with different contact angles and degrees of supercooling are illustrated successively.The results show that a temperature gradient will increase the nucleation barrier and decrease the nucleation rate, particularly in the cases of large contact angle and low degree of supercooling. In addition, there is a critical temperature gradient for a given degree of supercooling and contact angle, at the higher of which the nucleation can be suppressed completely.
基金jointly supported by Pilot National Laboratory for Marine Science and Technology (Qingdao)the IGGCAS (IGGCAS-201903 and SZJJ201901)the Chinese Academy of Sciences (ZDBSLY-DQC003)。
文摘How natural gas hydrates nucleate and grow is a crucial scientific question.The research on it will help solve practical problems encountered in hydrate accumulation,development,and utilization of hydrate related technology.Due to its limitations on both spatial and temporal dimensions,experiment cannot fully explain this issue on a micro-scale.With the development of computer technology,molecular simulation has been widely used in the study of hydrate formation because it can observe the nucleation and growth process of hydrates at the molecular level.This review will assess the recent progresses in molecular dynamics simulation of hydrate nucleation and growth,as well as the enlightening significance of these developments in hydrate applications.At the same time,combined with the problems encountered in recent hydrate trial mining and applications,some potential directions for molecular simulation in the research of hydrate nucleation and growth are proposed,and the future of molecular simulation research on hydrate nucleation and growth is prospected.
基金Supported by the National Key Research and Development Program of China(2016YFC0304003,2017YFC0307302)the National Natural Science Foundation of China(21636009,51576209,21522609)the Innovative Talents Support Program for Postgraduates(BX201700288)
文摘Insights into the mechanism of hydrate nucleation are of great significance for the development of hydrate-based technologies,hydrate relevant flow assurance,and the exploration of in situ natural gas hydrates.Compared with the thermodynamics of hydrate formation,understanding the nucleation mechanism is challenging and has drawn substantial attention in recent decades.In this paper,we attempt to give a comprehensive review of the recent progress of studies of clathrate hydrate nucleation.First,the existing hypotheses on the hydrate nucleation mechanism are introduced and discussed.Then,we summarize recent experimental studies on induction time,a key parameter evaluating the velocity of the nucleation process.Subsequently,the memory effect is particularly discussed,followed by the suggestion of several promising research perspectives.
基金co-funded by the National Natural Science Foundation of China and Baoshan Iron & Steel Co., Ltd. (No. 50834008)
文摘The effects of strain rates on the hot working characteristics and nucleation mechanisms of dynamic recrystallization (DRX) were studied by optical microscopy and electron backscatter diffraction (EBSD) technique. Hot compression tests were conducted using a Gleeble-1500 simulator at a true strain of 0.7 in the temperature range of 1000 to 1150 °C and strain rate range of 0.01 to 10.00 s-1. It is found that the size and volume fraction of the DRX grains in hot-deformed Inconel 625 superalloy firstly decrease and then increase with increasing strain rate. Meanwhile, the nucleation mechanism of DRX is closely related to the deformation strain rate due to the deformation thermal effect. The discontinuous DRX (DDRX) with bulging of original grain boundaries is the primary nucleation mechanism of DRX, while the continuous DRX (CDRX) with progressive subgrain rotation acts as a secondary nucleation mechanism. The twinning formation can activate the nucleation of DRX. The effects of bulging of original grain boundaries and twinning formation are firstly gradually weakened and then strengthened with the increasing strain rate due to the deformation thermal effect. On the contrary, the effect of subgrain rotation is firstly gradually strengthened and then weakened with the increasing strain rate.
文摘In the present work we studied the induction periods of hydrate formation of natural gas in pure water, aqueous solutions of surfactants, and in the presence of surfactant together with aluminum oxide nanopowder, the activity of which as hydrate formation inducer was studied previously. Sodium dodecyl sulfate(SDS) or neonol AF-9-12 were used as the surfactants. It was demonstrated that the addition of either surfactants or aluminum oxide powder under our experimental conditions causes a decrease in the induction period of hydrate formation from ~105 min for pure water to 30–35 min for water with additives. In the case of the simultaneous presence of surfactants and aluminum oxide powder in the system, induction period decreased to ~20 min. So, the synergistic effect of the combination of surfactant and oxide powder on gas hydrate nucleation was demonstrated. Possible reasons of this effect have been discussed.
基金The work was supported by the National Natural Science Foundations of China(Grants 11572249,11772257 and 11602196)Y.Yao acknowledges the Alexander von Humboldt Foundation for supporting his stay at the Max-Planck-Institut fiir Eisenforschung.
文摘A crystal plasticity model is developed to predict the fatigue crack nucleation of polycrystalline materials,in which the accumulated dislocation dipoles are considered to be the origin of damage.To describe the overall softening behavior under cyclic loading,a slip system-level dislocation density-related damage model is proposed and implemented in the finite element analysis with Voronoi tessellation.The numerical model is applied to calibrate the stress-strain relationship at different cycles before fatigue crack nucleation.The parameters determined from the numerical analysis are substituted into a modified phase transformation model to predict the critical fatigue crack nucleation cycle.Comparing with the experimental results of Sn-3.0Ag-0.5Cu(SAC305)alloy and P91 steel,the proposed method can describe the constitutive behavior and predict the fatigue crack nucleation accurately.
文摘he evolution and nucleation of microcracks in typical tectonics are investigated in the experiment of fracture of marble specimen. The change of state during nucleation of microcracks is observed. The controlling effect of tectonics on evolution of microcracks is analyzed by using thc damage mechanics theory. These characteristics can be analogized to kilometer meters as the first effect of earthquake precursors. These studies may be helpful to interpret-the foreshock or general foreshock in the moderate or short stage before strong earthquakes. The other physical precursors are second or third effect. The local density of microcracks increasing abruptly may be helpful to interpret the phenomenon that part precursor records appear catastrophic jump. The part out of nucleation where some microcracks heal and the density change reversibly may be helpful to interpret the phenomenon that some precursors records appear reverse change. The area difference of microcracks accumulation and evolution in different part of typital tectonics is studied. This difference may be helpful to interpret the characteristics (including the area) of earthquake preparation of diffcrent tectonics, and further to interpret the difference of the precursors beween plate edge and intraplate. These differences may be introduced by the scholars with different points of view as to discuss about the existence of precursors before earthquakes. However, when the precursor records are studied, one must notice the geology background in different areas.
基金supported financially by the European Community under Marie Curie Transfer of Knowledge grant No. MTKD-CT-2006-042468 (AGH No.27.27.170.304)Polish Ministry of Science and Higher Education for financial support under grant No. N507-44-66-34 (AGH No.18.18.170.325)
文摘The grain density,Nv,in the solid state after solidification of AZ91/SiC composite is a function of maximum undercooling,ΔT,of a liquid alloy.This type of function depends on the characteristics of heterogeneous nucleation sites and number of SiC present in the alloy.The aim of this paper was selection of parameters for the model describing the relationship between the grain density of primary phase and undercooling.This model in connection with model of crystallisation,which is based on chemical elements diffusion and grain interface kinetics,can be used to predict casting quality and its microstructure.Nucleation models have parameters,which exact values are usually not known and sometimes even their physical meaning is under discussion.Those parameters can be obtained after mathematical analysis of the experimental data.The composites with 0,1,2,3 and 4wt.% of SiC particles were prepared.The AZ91 alloy was a matrix of the composite reinforcement SiC particles.This composite was cast to prepare four different thickness plates.They were taken from the region near to the thermocouple,to analyze the undercooling for different composites and thickness plates and its influence on the grain size.The microstructure and thermal analysis gave set of values that connect mass fraction of SiC particles,and undercooling with grain size.These values were used to approximate nucleation model adjustment parameters.Obtained model can be very useful in modelling composites microstructure.
文摘High resolution electron microscopy studies of rure earth-rich phase particles in a melt-quenched Ti-5Al-4Sn-2Zr-1MO-0.25Si-1Nd alloy indicate that the α-Ti matrix crystallizes prior to the rare earth-rich phase particles. According to a new nucleation model, the heteropeneous nucleation of the rare earth-rich phase particles at the matrix interface is easier than the homogeneous nucleation off the interface matrix, which is consistent with the results of the HREM obseroations.
文摘Undercoolings up to 397 K(0.283 T_E)have been obtained for Ni-32.5% Sn eutectic alloymelted by superheating-cooling cycles and denucleating with inorganic glasses.The predomi-nant dissipation of heat for highly undercooled alloy melt is through radiation.An approxi-mate method is consequently derived to calculate its mean specific heat from measured coolingcurves.With the aid of high speed cinematography,it is revealed that the surface or interfaceheterogeneous nucleation takes place in preference to homogeneous nucleation even though theundercooling has exceeded 0.2 T_E.
文摘It is deduced from thermodynamic relations and confirmed by experiment results that the nucle-ation rate and nucleation temperature of nucleating agents in the glass are dependent upon their melting entropy △Sm melting temperature Tm and crystal - type transition in terms of some mathematical expressions.
文摘Nucleation sites of α-Al grains after addition of an Al-Ti-B master alloy into pure aluminium have been investigated using EPMA. The results show that either TiAl3 or boride particales can nucleate α-Al grains. But the number of TiAl3 nucleants is reduced with the holding time prolonged and the boride-nuclei are increasing gradually. Based on these results, a new refining method, adding molten Al-Ti-B into commercially pure aluminium, which has a quicker and better refining efficiency is presented.
