Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks obs...Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks observed in voltammograms have demonstrated the capability of ethylene glycol solutions to electrodeposit Sn.The temperature-dependence of diffusion coefficient values derived from potentiodynamic and potentiostatic studies helped to determine and validate estimations of the activation energy for Sn(II)bulk diffusion.Chronoamperometric results have identified that,the suitable model to describe the early stage of Sn electrodeposition could be composed of Sn three-dimensional nucleation and diffusion-controlled growth and water reduction contributions,which was duly validated by theoretical and experimental approaches.From the model,typical kinetic parameters such as the nucleation frequency of Sn(A),number density of Sn nuclei(N_(0)),and diffusion coefficient of Sn(II)ions(D),were determined.The presence of Sn nuclei with excellent quality and their structures were verified using SEM,EDX,and XRD techniques.展开更多
Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trol...Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.展开更多
The nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy was investigated using optical microscopy and scanning electron microscopy equipped with electron backscattering diffraction(EBSD).By revealing ...The nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy was investigated using optical microscopy and scanning electron microscopy equipped with electron backscattering diffraction(EBSD).By revealing the eutectic cells and analyzing the crystallographic orientation,it was found that both the eutectic Si and Al phases in an eutectic cell were not single crystal,representing an eutectic cell consisting of small 'grains'.It is also suggested that the eutectic nucleation mode can not be determined based on the crystallographic orientation between eutectic Al phases and the neighboring primary dendrite Al phases.However,the evolution of primary dendrite Al phases affects remarkably the following nucleation and growth of eutectic cell.The coarse flake-fine fibrous transition of eutectic Si morphology involved in impurity elements modification may be independent of eutectic nucleation.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
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
The nucleation and growth of grains in a series of Al-based alloys produced by electrolysis are observed under SEM. The atomic Ti/AI ratios of the nuclei and the distribution of Ti at certain points are analyzed by po...The nucleation and growth of grains in a series of Al-based alloys produced by electrolysis are observed under SEM. The atomic Ti/AI ratios of the nuclei and the distribution of Ti at certain points are analyzed by point EDS. The particles in different atomic Ti/AI ratios might act as the nuclei of α-Al. At the early stage of growth, the spherical Ti-enriched regions might form around these particles within very limited temperature ranges in which the reactions such as the peritectic reactions etc occur. At the latter stage of growth, the dendrites freely develop in the radial orientations, and the concentration of Ti decreases linearly along the dendrite arm and becomes negligible in the region near the periphery of the dendrite. It is believed that the nucleation is closely related with the number and dispersion of primary spherical areas in the melts, and the segregation of Ti leads to the free growth of dendrite, which is necessary for the formation of equiaxial grains.展开更多
The nucleation and growth mechanism of electrodeposited Ni−W alloy were investigated.Cyclic voltammetry(CV)and chronoamperometry(CA)were used to examine the electrochemical behavior and nucleation mechanism of the ele...The nucleation and growth mechanism of electrodeposited Ni−W alloy were investigated.Cyclic voltammetry(CV)and chronoamperometry(CA)were used to examine the electrochemical behavior and nucleation mechanism of the electrodeposited Ni−W alloy.The nucleation type and kinetic parameters of the electrodeposited Ni−W alloy were obtained from the CA analysis results.SEM,AFM,and TEM were also used to investigate the nucleation and growth process of the electrodeposition of Ni−W alloy.The results demonstrate that the nucleation and initial stages of the growth phase of the Ni−W alloy undergo the formation,movement,and aggregation of atoms,single crystals,and nanoclusters.When the size of single crystal increases up to approximately 10 nm and the average size of the crystal granules is approximately 68 nm,they no longer grow.Increasing the applied potential increases the number of nuclei but does not affect the size of the final crystal granules.Therefore,the electrodeposited Ni−W alloy shows a nanocrystalline structure.展开更多
The processes of nucleation and growth of lead from the dilute electrolytes on copper substrates were investigated bychronoamperometry and by scanning electron microscopic (SEM) analysis of the deposits obtained in th...The processes of nucleation and growth of lead from the dilute electrolytes on copper substrates were investigated bychronoamperometry and by scanning electron microscopic (SEM) analysis of the deposits obtained in the potentiostatic regime ofelectrolysis. In the dependence of electrodeposition conditions, the nucleation of Pb followed either progressive or instantaneoustype. The type of nucleation changed from progressive to instantaneous one with increasing the concentration of Pb(II) ions and theoverpotential of electrodeposition. Regardless of the type nucleation, a novel type of Pb particles like cobweb was formed by thepotentiostatic electrodeposition in the moment of nucleation and at the early stages of growth. On the basis of the shape ofcobweb-like particles and the electrodeposition conditions leading to their formation, these particles were situated in the group ofspongy-like ones. Also, comparative morphological analysis of Pb deposits obtained in the conditions of progressive andinstantaneous nucleation confirmed the existence of two limiting types of nucleation.展开更多
The population balance modeling is regarded as a universally accepted mathematical framework for dynamic simulation of various particulate processes, such as crystallization, granulation and polymerization. This artic...The population balance modeling is regarded as a universally accepted mathematical framework for dynamic simulation of various particulate processes, such as crystallization, granulation and polymerization. This article is concerned with the application of the method of characteristics (MOC) for solving population balance models describing batch crystallization process. The growth and nucleation are considered as dominant phenomena, while the breakage and aggregation are neglected. The numerical solutions of such PBEs require high order accuracy due to the occurrence of steep moving fronts and narrow peaks in the solutions. The MOC has been found to be a very effective technique for resolving sharp discontinuities. Different case studies are carried out to analyze the accuracy of proposed algorithm. For validation, the results of MOC are compared with the available analytical solutions and the results of finite volume schemes. The results of MOC were found to be in good agreement with analytical solutions and superior than those obtained by finite volume schemes.展开更多
Lithium metal is the ultimate anode choice for high energy rechargeable lithium batteries owing to its ultra-high theoretical capacity,however,Li dendrites and low Coulombic efficiency(CE)caused by disordered Li plati...Lithium metal is the ultimate anode choice for high energy rechargeable lithium batteries owing to its ultra-high theoretical capacity,however,Li dendrites and low Coulombic efficiency(CE)caused by disordered Li plating restrict its practical application.Herein,we develop an ultrathin Sn-decorated Cu substrate(Sn@Cu)fabricated by an electroless plating method to induce ordered Li nucleation and growth behavior.The lithiophilic Sn interfacial layer is found to play a critical role to lower the Li nucleation over-potential and promote fast Li-migration kinetics,and the underlying mechanism is revealed using the first principle calculations.Accordingly,a dense dendrite-free and Li deposition with large granular morphology is obtained,which significantly improved the CE and cycling performance of Li‖Sn@Cu half cells symmetric cells.Symmetric cells using the Li-Sn@Cu electrode display a much-prolonged life span(>1200 h)with low overpotential(~18 mV)at a high current density of 1 mA cm^(-2).Moreover,full cells paired with commercial LiFePO_(4) cathode(1.8 mAh cm^(-2))deliver enhanced cycling stability(0.5 C,300 cycles)and excellent rate performance.This work provides a simple and effective way to bring about high efficiency and long lifespan substrates for practical applications.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
In this work,highly monodispersed Pt-Ni alloy nanoparticles were directly deposited on carbon substrate through a facile electrodeposition strategy in the solvent system of N,N-dimethylformamide(DMF).A series of carbo...In this work,highly monodispersed Pt-Ni alloy nanoparticles were directly deposited on carbon substrate through a facile electrodeposition strategy in the solvent system of N,N-dimethylformamide(DMF).A series of carbon supported Pt-Ni alloy electrocatalysts were synthesized under different applied electrode potentials.Among all as-obtained samples,the Pt-Ni/C electrocatalyst deposited at-1.73 V exhibits the optimal specific activity up to 1.850 mA cm^(-2)at 0.9 V vs.RHE,which is 6.85 times higher than that of the commercial Pt/C.Comprehensive physiochemical characterizations and computational evaluations via density functional theory were conducted to unveil the nucleation and growth mechanism of PtNi alloy formation.Compared to the aqueous solution,DMF solvent molecule must not be neglected in avoiding particle agglomeration and synthesis of monodispersed nanoparticles.During the alloy co-deposition process,Ni sites produced through the reduction of Ni(Ⅱ)precursor not only facilitates Pt-Ni alloy crystal nucleation but also in favor of further Pt reduction on the Ni-inserted Pt surface.As for the deposition potential,it adjusts the final particle size.This work provides a hopeful extended Pt-based catalyst layer production strategy for proton exchange membrane fuel cells and a new idea for the nucleation and growth mechanism exploration for electrodeposited Pt alloy.展开更多
The TEM observation on the single-side thinned specimens was made of the nucleation and growth of boride during boronization for steel 20 and the influence of prior room temperature deformation.The results of X-ray di...The TEM observation on the single-side thinned specimens was made of the nucleation and growth of boride during boronization for steel 20 and the influence of prior room temperature deformation.The results of X-ray diffraction and electron probe microstructure analysis show that only Fe_2B formed in the surface layer of specimens at the beginning of boronization;the atomic concentration of B in the surface layer increased with the increase of deformation monotonously;and the segregation of B atoms in the dislocation cells hindered the recovery and recrystallization of the deformed structure of the matrix and accelerated the nucleation and growth of boride in the surface layer.展开更多
Martensites distributed along the austenite grain boundaries and twin boundaries have been examined in Fe-C,Fe-Ni-C and Fe-Cr-Mn-Mo-C alloys.The martensites may nucleate preferentially and grow easily along these boun...Martensites distributed along the austenite grain boundaries and twin boundaries have been examined in Fe-C,Fe-Ni-C and Fe-Cr-Mn-Mo-C alloys.The martensites may nucleate preferentially and grow easily along these boundaries.In the mixed martensites,the preferentially formed one is plate or butterfly martensite展开更多
A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model...A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model is compared with the experimental value obtained from SAXS data.The model provides a non-ideal improvement in the supersaturation calculation and considers the impact of both mass transfer and surface reaction on the particle growth rate.The nucleation and growth rates are coupled depending on the change in monomer concentration over time,based on which the particle size and distribution are calculated.The growth curve of the silica particles from 3 nm to 20 nm and the change in particle number from 0 to over 10^(20) are calculated,which are consistent with the experimental values,establishing the reliability of the model.The calculations of the growth rate reveal that mass transfer controls the growth of silica particles before 10 min and the surface reaction is the rate-determining step after 10 min.The changes in the model parameters obtained by fitting with the SAXS data under different reaction conditions indicate the sensitivity of the corresponding process to different conditions.Moreover,the relationship between the particle growth rate and monomer concentration change is analyzed using the proposed model.展开更多
The mechanism of chemical-vapor-deposited (CVD) diamond film growth has attracted increasing attention recent years, mainly due to the fact that further technological advancement (such as obtaining high-quality films,...The mechanism of chemical-vapor-deposited (CVD) diamond film growth has attracted increasing attention recent years, mainly due to the fact that further technological advancement (such as obtaining high-quality films, controlling film growth, and heteroepitaxial growth, etc.) requires a more detailed understanding of the fundamental phenomena responsible for diamond growth.展开更多
A self-made directional solidification device was used to fabricate d 80 mm high purity aluminum ingots. SEM and AFM were used to detect the shape of grain boundaries. The orientation of the grain was studied by X-ray...A self-made directional solidification device was used to fabricate d 80 mm high purity aluminum ingots. SEM and AFM were used to detect the shape of grain boundaries. The orientation of the grain was studied by X-ray diffractometry. The results show that the nucleation points locate at the intersections of three adjacent grains. The lattice orientation of grains does not alter in the horizontal direction, but gradually approaches the optimum growth direction in the vertical direction during the growth process. All the grains suffer the competition and only the one whose orientation is closest to the preferred direction can occupy the final growth space.展开更多
The electrocrystalliztion nucleation and growth process of Ni-Fe alloy was studied using cyclic voltammetry and chronoamperometry. The results show that, in the case of high deposition overpotential, the nucleation/gr...The electrocrystalliztion nucleation and growth process of Ni-Fe alloy was studied using cyclic voltammetry and chronoamperometry. The results show that, in the case of high deposition overpotential, the nucleation/growth process of Ni-Fe binary alloy is 3-D instantaneous, and the growth rate of the previously formed nuclei increases with overpotential. However, at low overpotential, no distinguished nucleation current can be observed.Meanwhile, the discrepancy between the experimental non-dimensional variables(I/Im)2 and those calculated from the theoretical model was elucidated in the light of the molecular orbital theorem.展开更多
Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as p...Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.展开更多
Based on the assumptions of parabolic variation of nucleation rate versus time and transformation kinetics depending mainly on nucleation rate, a different model for bainitic transformation kinetics in hypoeutectoid s...Based on the assumptions of parabolic variation of nucleation rate versus time and transformation kinetics depending mainly on nucleation rate, a different model for bainitic transformation kinetics in hypoeutectoid steels was established. And this model was proved to be effective in the description of bainitic transformation by comparison with the result of conventional Avrami equation.展开更多
文摘Thermodynamic and kinetic aspects of Sn nucleation and growth processes onto a glassy carbon electrode from SnCl2·2H2O dissolved in ethylene glycol solutions were studied.Typical reduction and oxidation peaks observed in voltammograms have demonstrated the capability of ethylene glycol solutions to electrodeposit Sn.The temperature-dependence of diffusion coefficient values derived from potentiodynamic and potentiostatic studies helped to determine and validate estimations of the activation energy for Sn(II)bulk diffusion.Chronoamperometric results have identified that,the suitable model to describe the early stage of Sn electrodeposition could be composed of Sn three-dimensional nucleation and diffusion-controlled growth and water reduction contributions,which was duly validated by theoretical and experimental approaches.From the model,typical kinetic parameters such as the nucleation frequency of Sn(A),number density of Sn nuclei(N_(0)),and diffusion coefficient of Sn(II)ions(D),were determined.The presence of Sn nuclei with excellent quality and their structures were verified using SEM,EDX,and XRD techniques.
基金support from the National Natural Science Foundation of China(Grant Nos.52372083,52173255),the Collaborative Innovation Center for Advanced Micro/nanomaterials and Equipment(Co-constructed by Jiangsu Province and Ministry of Education)support from the Natural Science Foundation of Jiangsu Province,China(Grant No.BK20230538).
文摘Nucleation of lithium sulfide(Li_(2)S)induced by electrocatalysts plays a crucial role in mitigating the shut-tle effect.However,short-chain polysulfides on electrocatalysts surfaces tend to re-dissolve into elec-trolytes,delaying Li_(2)S supersaturation and its nucleation.In this study,we draw inspiration from the ribosome-driven protein synthesis process in cells to prepare ultrasmall nitrogen-doped MoS_(2) nanocrys-tals anchored on porous nitrogen-doped carbon networks(N-MoS_(2)-NC)electrocatalysts.Excitedly,the ex-situ SEM demonstrates that ribosome-inspired N-MoS_(2)-NC electrocatalysts induce early nucleation and rapid growth of three-dimensional Li_(2)s during discharge.Theoretical calculations reveal that the Li-s bond length in N-MoS_(2)-Li_(2)S(100)is shorter,and the corresponding interfacial formation energy is lower than in MoS_(2)-Li_(2)S(100).This accelerated conversion of lithium polysulfides to Li_(2)S can enhance the utilization of active substances and inhibit the shuttle effect.This study highlights the potential of ribosome-inspired N-MoS_(2)-NC in improving the electrochemical stability of Li-S batteries,providing valuable insights for future electrocatalyst design.
基金Project(XKY2009035) supported by the Key Laboratory for Ecological-Environment Materials of Jiangsu Province,ChinaProject(11KJD430006) supported by the Natural Science Fund for Colleges and Universities in Jiangsu Province,ChinaProject(AE201034) supported by the Research Finds of Key Laboratory for Advanced Technology in Environmental Protection of Jiangsu Province,China
文摘The nucleation and growth of eutectic cell in hypoeutectic Al-Si alloy was investigated using optical microscopy and scanning electron microscopy equipped with electron backscattering diffraction(EBSD).By revealing the eutectic cells and analyzing the crystallographic orientation,it was found that both the eutectic Si and Al phases in an eutectic cell were not single crystal,representing an eutectic cell consisting of small 'grains'.It is also suggested that the eutectic nucleation mode can not be determined based on the crystallographic orientation between eutectic Al phases and the neighboring primary dendrite Al phases.However,the evolution of primary dendrite Al phases affects remarkably the following nucleation and growth of eutectic cell.The coarse flake-fine fibrous transition of eutectic Si morphology involved in impurity elements modification may be independent of eutectic nucleation.
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.
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The nucleation and growth of grains in a series of Al-based alloys produced by electrolysis are observed under SEM. The atomic Ti/AI ratios of the nuclei and the distribution of Ti at certain points are analyzed by point EDS. The particles in different atomic Ti/AI ratios might act as the nuclei of α-Al. At the early stage of growth, the spherical Ti-enriched regions might form around these particles within very limited temperature ranges in which the reactions such as the peritectic reactions etc occur. At the latter stage of growth, the dendrites freely develop in the radial orientations, and the concentration of Ti decreases linearly along the dendrite arm and becomes negligible in the region near the periphery of the dendrite. It is believed that the nucleation is closely related with the number and dispersion of primary spherical areas in the melts, and the segregation of Ti leads to the free growth of dendrite, which is necessary for the formation of equiaxial grains.
基金financial support from the Science and Technology Project of Hunan Province,China(No.2018TP1012)。
文摘The nucleation and growth mechanism of electrodeposited Ni−W alloy were investigated.Cyclic voltammetry(CV)and chronoamperometry(CA)were used to examine the electrochemical behavior and nucleation mechanism of the electrodeposited Ni−W alloy.The nucleation type and kinetic parameters of the electrodeposited Ni−W alloy were obtained from the CA analysis results.SEM,AFM,and TEM were also used to investigate the nucleation and growth process of the electrodeposition of Ni−W alloy.The results demonstrate that the nucleation and initial stages of the growth phase of the Ni−W alloy undergo the formation,movement,and aggregation of atoms,single crystals,and nanoclusters.When the size of single crystal increases up to approximately 10 nm and the average size of the crystal granules is approximately 68 nm,they no longer grow.Increasing the applied potential increases the number of nuclei but does not affect the size of the final crystal granules.Therefore,the electrodeposited Ni−W alloy shows a nanocrystalline structure.
基金supported by the Ministry of Education,Science and Technological Development of the Republic of Serbia under the research project:“Electrochemical synthesis and characterization of nanostructured functional materials for application in new technologies”(Project No.172046)
文摘The processes of nucleation and growth of lead from the dilute electrolytes on copper substrates were investigated bychronoamperometry and by scanning electron microscopic (SEM) analysis of the deposits obtained in the potentiostatic regime ofelectrolysis. In the dependence of electrodeposition conditions, the nucleation of Pb followed either progressive or instantaneoustype. The type of nucleation changed from progressive to instantaneous one with increasing the concentration of Pb(II) ions and theoverpotential of electrodeposition. Regardless of the type nucleation, a novel type of Pb particles like cobweb was formed by thepotentiostatic electrodeposition in the moment of nucleation and at the early stages of growth. On the basis of the shape ofcobweb-like particles and the electrodeposition conditions leading to their formation, these particles were situated in the group ofspongy-like ones. Also, comparative morphological analysis of Pb deposits obtained in the conditions of progressive andinstantaneous nucleation confirmed the existence of two limiting types of nucleation.
文摘The population balance modeling is regarded as a universally accepted mathematical framework for dynamic simulation of various particulate processes, such as crystallization, granulation and polymerization. This article is concerned with the application of the method of characteristics (MOC) for solving population balance models describing batch crystallization process. The growth and nucleation are considered as dominant phenomena, while the breakage and aggregation are neglected. The numerical solutions of such PBEs require high order accuracy due to the occurrence of steep moving fronts and narrow peaks in the solutions. The MOC has been found to be a very effective technique for resolving sharp discontinuities. Different case studies are carried out to analyze the accuracy of proposed algorithm. For validation, the results of MOC are compared with the available analytical solutions and the results of finite volume schemes. The results of MOC were found to be in good agreement with analytical solutions and superior than those obtained by finite volume schemes.
基金financially supported by the National Natural Science Foundation of China(22075216,21773177)the Fundamental Research Funds for Central University(2042021kf0194)。
文摘Lithium metal is the ultimate anode choice for high energy rechargeable lithium batteries owing to its ultra-high theoretical capacity,however,Li dendrites and low Coulombic efficiency(CE)caused by disordered Li plating restrict its practical application.Herein,we develop an ultrathin Sn-decorated Cu substrate(Sn@Cu)fabricated by an electroless plating method to induce ordered Li nucleation and growth behavior.The lithiophilic Sn interfacial layer is found to play a critical role to lower the Li nucleation over-potential and promote fast Li-migration kinetics,and the underlying mechanism is revealed using the first principle calculations.Accordingly,a dense dendrite-free and Li deposition with large granular morphology is obtained,which significantly improved the CE and cycling performance of Li‖Sn@Cu half cells symmetric cells.Symmetric cells using the Li-Sn@Cu electrode display a much-prolonged life span(>1200 h)with low overpotential(~18 mV)at a high current density of 1 mA cm^(-2).Moreover,full cells paired with commercial LiFePO_(4) cathode(1.8 mAh cm^(-2))deliver enhanced cycling stability(0.5 C,300 cycles)and excellent rate performance.This work provides a simple and effective way to bring about high efficiency and long lifespan substrates for practical applications.
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.
文摘In this work,highly monodispersed Pt-Ni alloy nanoparticles were directly deposited on carbon substrate through a facile electrodeposition strategy in the solvent system of N,N-dimethylformamide(DMF).A series of carbon supported Pt-Ni alloy electrocatalysts were synthesized under different applied electrode potentials.Among all as-obtained samples,the Pt-Ni/C electrocatalyst deposited at-1.73 V exhibits the optimal specific activity up to 1.850 mA cm^(-2)at 0.9 V vs.RHE,which is 6.85 times higher than that of the commercial Pt/C.Comprehensive physiochemical characterizations and computational evaluations via density functional theory were conducted to unveil the nucleation and growth mechanism of PtNi alloy formation.Compared to the aqueous solution,DMF solvent molecule must not be neglected in avoiding particle agglomeration and synthesis of monodispersed nanoparticles.During the alloy co-deposition process,Ni sites produced through the reduction of Ni(Ⅱ)precursor not only facilitates Pt-Ni alloy crystal nucleation but also in favor of further Pt reduction on the Ni-inserted Pt surface.As for the deposition potential,it adjusts the final particle size.This work provides a hopeful extended Pt-based catalyst layer production strategy for proton exchange membrane fuel cells and a new idea for the nucleation and growth mechanism exploration for electrodeposited Pt alloy.
文摘The TEM observation on the single-side thinned specimens was made of the nucleation and growth of boride during boronization for steel 20 and the influence of prior room temperature deformation.The results of X-ray diffraction and electron probe microstructure analysis show that only Fe_2B formed in the surface layer of specimens at the beginning of boronization;the atomic concentration of B in the surface layer increased with the increase of deformation monotonously;and the segregation of B atoms in the dislocation cells hindered the recovery and recrystallization of the deformed structure of the matrix and accelerated the nucleation and growth of boride in the surface layer.
文摘Martensites distributed along the austenite grain boundaries and twin boundaries have been examined in Fe-C,Fe-Ni-C and Fe-Cr-Mn-Mo-C alloys.The martensites may nucleate preferentially and grow easily along these boundaries.In the mixed martensites,the preferentially formed one is plate or butterfly martensite
基金financially supported by the National Natural Science Foundation of China(21878169,21991102)the National Key Research and Development Program of China(2019YFA0905100)the Tsinghua University Initiative Scientific Research Program(2018Z05JZY010)。
文摘A mathematical model is developed for the calculation of the nucleation and growth process of silica nanostructured particles prepared by using the drop-by-drop method,and the calculation results of the proposed model is compared with the experimental value obtained from SAXS data.The model provides a non-ideal improvement in the supersaturation calculation and considers the impact of both mass transfer and surface reaction on the particle growth rate.The nucleation and growth rates are coupled depending on the change in monomer concentration over time,based on which the particle size and distribution are calculated.The growth curve of the silica particles from 3 nm to 20 nm and the change in particle number from 0 to over 10^(20) are calculated,which are consistent with the experimental values,establishing the reliability of the model.The calculations of the growth rate reveal that mass transfer controls the growth of silica particles before 10 min and the surface reaction is the rate-determining step after 10 min.The changes in the model parameters obtained by fitting with the SAXS data under different reaction conditions indicate the sensitivity of the corresponding process to different conditions.Moreover,the relationship between the particle growth rate and monomer concentration change is analyzed using the proposed model.
文摘The mechanism of chemical-vapor-deposited (CVD) diamond film growth has attracted increasing attention recent years, mainly due to the fact that further technological advancement (such as obtaining high-quality films, controlling film growth, and heteroepitaxial growth, etc.) requires a more detailed understanding of the fundamental phenomena responsible for diamond growth.
基金Project(2002AA6070) supported by the Hi-tech Research and Development Program of China
文摘A self-made directional solidification device was used to fabricate d 80 mm high purity aluminum ingots. SEM and AFM were used to detect the shape of grain boundaries. The orientation of the grain was studied by X-ray diffractometry. The results show that the nucleation points locate at the intersections of three adjacent grains. The lattice orientation of grains does not alter in the horizontal direction, but gradually approaches the optimum growth direction in the vertical direction during the growth process. All the grains suffer the competition and only the one whose orientation is closest to the preferred direction can occupy the final growth space.
基金Projects(20203015 ,50499335) supported by the National Natural Science Foundation of China Project supported by theState Key Laboratory for Corrosion and Protection , China
文摘The electrocrystalliztion nucleation and growth process of Ni-Fe alloy was studied using cyclic voltammetry and chronoamperometry. The results show that, in the case of high deposition overpotential, the nucleation/growth process of Ni-Fe binary alloy is 3-D instantaneous, and the growth rate of the previously formed nuclei increases with overpotential. However, at low overpotential, no distinguished nucleation current can be observed.Meanwhile, the discrepancy between the experimental non-dimensional variables(I/Im)2 and those calculated from the theoretical model was elucidated in the light of the molecular orbital theorem.
基金supported by the National Key Research and Development Program of China(No.2017YFB0702100)the National Natural Science Foundation of China(11404017)+2 种基金the Technology Foundation for Selected Overseas Chinese Scholar,Ministry of Human Resources and Social Security of Chinasupport by the European Regional Development Fund in the IT4Innovations national supercomputing center-Path to Exascale project,No.CZ.02.1.01/0.0/0.0/16_013/0001791 within the Operational Programme Research,Development and Educationby the Ministry of Education by the Ministry of Education,Youth,and Sport of the Czech Republic and grant No.17-27790S of the Czech Science Foundations
文摘Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.
文摘Based on the assumptions of parabolic variation of nucleation rate versus time and transformation kinetics depending mainly on nucleation rate, a different model for bainitic transformation kinetics in hypoeutectoid steels was established. And this model was proved to be effective in the description of bainitic transformation by comparison with the result of conventional Avrami equation.