Production and decay of subcritical nuclei in a solid solution

The decay of “subcritical” nuclei in a solid solution has been revealed in the investigation of the CuCl phase nucleation kinetics in glass. As soon as “supercritical” nuclei with an average radius R = 1.1 nm are created at 500°C, a sharp temperature increase up to 650°C transforms most nuclei created in the first annealing stage into “subcritical” ones, and this results in the decay of 80% of the nuclei in 5 min, while the remaining 20% of the nuclei grow in size to 2.4 nm. Their growth provides a sixfold increase in the CuCl phase growth rate against that in conventional annealing at 650°C. The kinetic dependences of the nucleation parameters—the amount of the phase and the average radius and concentration of the particles—were determined by the intrinsic absorption spectra of the CuCl nanocrystals. The critical radius of the CuCl nanomelt at 650°C has been estimated as 1.3 nm and the evaporation heat of the CuCl phase molecules in glass, as 13 kJ/mol. It is shown that multistage annealing makes it possible not only to control the parameters of the particles of the new phase, but also to determine the critical parameters of the initial nucleation stage.     

Formation and growth of CuCl phase nuclei in glass

In glass, the CuCl phase starts to form a certain time after the onset of supersaturation. As the temperature is increased, the transient period (stage of formation of critical nuclei) shortens and the growth kinetics of the CuCl phase switches from the first to second stage. The observed pattern of the CuCl phase growth kinetics is fully consistent with the Zel’dovich-Frenkel classical theory of new-phase formation. The delay time is determined by the radius of the critical nucleus (CuCl nanomelt) and the diffusion coefficient of the limiting component, the Cu⁺ ions. The radius of the critical nucleus is about 1 nm and does not vary within a broad temperature range. The activation energy for the CuCl phase growth process does not change in the transition from the formation of critical nuclei to the first and, subsequently, second stage.     

Suppression of ice nucleation in supercooled water under temperature gradients

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.     

Initial nucleation stages and properties of CuCl nanoparticles in glasses

The time variation and temperature dependence of a CuCl phase nucleation in a glass was studied by exciton spectroscopy. The phase formation kinetics at three temperatures was measured. A time delay in attaining a stationary rate of the new phase growth was observed at all temperatures, in agreement with the Zeldovich theory. The kinetic parameters of the CuCl phase formation were determined in the initial stage, when the critical nuclei possessing a zero surface energy (and an effective radius below 1.3 nm) appear in the glass matrix. The first-order phase transition in the new phase is 200 K below the melting temperature of CuCl single crystals. The temperature dependence of the CuCl phase nucleation rate reveals the second and third stages of the new phase formation. The activation energies for diffusion of the CuCl phase components in the glass matrix are determined.     

非晶一次晶化过程微观组织演化和生长动力学的相场法研究

在晶化物理模型中添加扩散系数对晶化过程的影响, 采用相场方法研究初始形核率和初始形核半径对一次晶化过程中微观组织和生长动力学的影响。结果表明: 随着初始形核率的增加, 相同时间内非晶一次晶化的晶粒数量逐渐增加, 晶粒尺寸逐渐减小。晶化分数随着演化时间和初始形核率的增加逐渐增大, 初始形核率越大, 相同演化时间内的晶化分数越高。不同初始形核半径情况下, 非晶一次晶化过程中的晶粒数量和尺寸随着演化时间的增加基本保持不变。晶化分数随着演化时间的增加而增大。不同初始形核率和初始形核半径情况下所对应的生长指数均小于1, 表明初始形核率和初始形核半径对晶化方式无影响, 均为一次晶化。改变初始形核率和初始形核半径可调控一次晶化微观组织结构, 而晶粒尺寸及晶化分数直接关系到合金性能。     

Effect of preliminary low-temperature annealing on the kinetics of nucleation

The changes observed in the kinetics of CuCl nucleation in glass due to preliminary low-temperature annealing have been investigated using optical spectroscopy. The influence of the number of nuclei formed at a temperature of 500°C on the growth rate of the CuCl phase at 650°C has been examined. The amount of the CuCl phase in the sample is determined from the optical absorption coefficient in the range of band-to-band transitions in the CuCl nanocrystals. The average radius of CuCl particles is calculated from the position of the maximum of the exciton band. It has been demonstrated that the preliminary formation of CuCl nuclei at 500°C for 3 h makes it possible to increase the growth rate of the CuCl phase by a factor of 6. In the sample with preliminarily formed nuclei, there occur two opposite processes: thermal decomposition of part of the small nuclei, which have become subcritical at 650°C; and the growth of larger nuclei, which have become supercritical at 650°C due to the diffusive inflow of the components of the new phase. When the equilibrium concentration is reached, the new phase contains particles with a smaller radius but at a higher concentration as compared to those in the case of the conventional nucleation at 650°C.     

A study of cavitation nucleation in pure water using molecular dynamics simulation

To discover the microscopic mechanism responsible for cavitation nucleation in pure water, nucleation processes in pure water are simulated using the molecular dynamics method. Cavitation nucleation is generated by uniformly stretching the system under isothermal conditions, and the formation and development of cavitation nuclei are simulated and discussed at the molecular level. The processes of energy, pressure, and density are analyzed, and the tensile strength of the pure water and the critical volume of the bubble nuclei are investigated. The results show that critical states exist in the process of cavitation nucleation. In the critical state, the energy, density, and pressure of the system change abruptly, and a stable cavitation nucleus is produced if the energy barrier is broken and the critical volume is exceeded. System pressure and water density are the key factors in the generation of cavitation nuclei. When the critical state is surpassed, the liquid is completely ruptured, and the volume of the cavitation nucleus rapidly increases to larger than 100 nm³; at this point, the surface tension of the bubble dominates the cavitation nucleus, instead of intermolecular forces. The negative critical pressure for bubble nucleation is -198.6 MPa, the corresponding critical volume is 13.84 nm³, and the nucleation rate is 2.42×10³² m^-3·^-1 in pure water at 300 K. Temperature has a significant effect on nucleation: as the temperature rises, nucleation thresholds decrease, and cavitation nucleation occurs earlier.     

Shear‐Enhanced Nucleation of Isotactic Polypropylene in Limited Space

The nucleation rate was measured by directly counting the number of nuclei, which were developed while an isotactic polypropylene melt was flowing under shear in a thin film. The nucleation rate was enhanced with an increased rate of shear, e.g., by a factor of 10 larger at the rate of shear of 14 s^?1 compared with the quiescent state, at 134°C. The ratio of the shear‐enhanced nucleation rate to the nucleation rate in the quiescent state was larger at a higher temperature of crystallization, i.e., about 10 times at 134°C to 590 times at 140°C. The increase of the nucleation rate under shear flow was explained by a reduction of the lateral and end (fold) surface free energies; the product σ _s ² σ _e decreased to 3.2×10^?7 for the sheared melt, from 6.0×10^?7 (J m^?2)³ for the isotropic state. The free energy reduction was caused by transition of the nucleus formation mode from three‐dimensional folded chain nuclei to two‐dimensional bundle nuclei, in which chains lie down on the glass substrate, aligning parallel to the flow direction.     

Fe-Cr合金辐照空洞微结构演化的相场法模拟

Fe-Cr合金作为包壳材料在高温高辐照强度等极端环境下服役,产生空位和间隙原子等辐照缺陷,辐照缺陷簇聚诱发空洞、位错环等缺陷团簇,引起辐照肿胀、晶格畸变,导致辐照硬化或软化致使材料失效.理解辐照缺陷簇聚和长大过程的组织演化,能更有效调控组织获得稳定服役性能.本文采用相场法研究Fe-Cr合金中空洞的演化,模型考虑了温度效应对点缺陷的影响以及空位和间隙的产生和复合.选择400—800 K温度区间、0—16 dpa辐照剂量范围的Fe-Cr体系为对象,研究在不同服役温度和辐照剂量下的空位扩散、复合和簇聚形成空洞的过程.在400—800 K温度区间,随着温度的升高,Fe-Cr合金空洞团簇形核率呈现出先升高后下降的趋势.考虑空位与间隙的重新组合受温度的影响可以很好地解释空洞率随温度变化时出现先升高后降低的现象.由于温度的变化将影响Fe-Cr合金中原子离位阀能,从而影响产生空位和间隙原子.同一温度下,空洞半径和空洞的体积分数随辐照剂量的增大而增大.辐照剂量的增大,级联碰撞反应加强,空位与间隙原子大量产生,高温下空位迅速的扩散聚集在Fe-Cr合金中将形成更多数量以及更大尺寸的空洞.     

Molecular dynamics simulations of aggregation of copper nanoparticles with different heating rates

Molecular dynamics simulations were employed to investigate the heating rates’ effect on aggregation of two copper nanoparticles. The aggregation can be distinguished into three distinct regimes by the contacting and melting of nanoparticles. The nanoparticles contacting at a lower temperature during the sintering with lower heating rate, meanwhile, some temporary stacking fault exists at the contacting neck. The aggregation properties of the system, i.e. neck diameter, shrinkage ratio, potential energy, mean square displacement (MSD) and relative gyration radius, experience drastic changes due to the free surface annihilation. After the nanoparticles coalesced for a stable period, the shrinkage ratio, MSD, relative gyration radius and neck diameter of the system are dramatically changed during the melting process. It is shown that the shrinkage ratio and MSD have relative larger increasing ratio for a lower heating rate. While the evolution of the relative gyration radius and neck diameter is only sensitive to the temperature.     

冷却速率对温敏聚N-异丙基丙烯酰胺胶体结晶过程的影响

冷却速率对结晶过程具有重要的影响. 本文采用温敏poly-N-isopropylacrylamide (PNIPAM) 胶体晶体体系实时观察了冷却速率对结晶晶粒尺寸的影响. 通过高倍透射明场观察和Bragg衍射观察研究连续冷却下的晶粒形核和生长实时演化过程, 发现随着冷却速率的增加, PNIPAM胶体晶体晶粒尺寸不断减少. 晶粒尺寸与冷却速率符合幂指数关系, 与金属体系具有相似的演化规律.     

大块非晶临界冷却速率的非等温转变计算模型

在非等温转变理论以及非稳态形核理论基础上提出了计算大块非晶合金连续冷却转变曲线和 临界冷却速率的新模型,以用于评估合金的非晶形成能力. 依据此模型对Zr基和Pd基8种合金 进行了计算，计算结果与实验值符合较好. 计算结果表明，影响临界冷却速率的主要因素为 黏度、临界形核功和临界结晶分数. 随着黏度增大，临界冷却速率降低；随临界形核功增大 ，临界冷却速率急剧降低；随临界结晶分数增大，临界冷却速率起初降低较快，达到一定程 度后下降速率趋于缓慢. 关键词： 临界冷却速率 非晶形成能力 大块非晶 连续冷却转变曲线     

Nonisothermal nucleation in the CuCl solid solution in glass: Dissolution of subcritical CuCl nuclei with a positive jump of the nucleation temperature

The processes of nucleation in a CuCl solid solution in glass with a positive temperature jump from T ₁ = 500°C to T ₂ = 550, 600, and 650°C have been investigated using optical spectroscopy and exciton-thermal analysis. The dissolution of a part of the particles of the CuCl nanomelt formed previously at T ₁ has been observed at T ₂. Variations in the shape of the radius distribution curve of the CuCl particles due to the dissolution of initial nuclei have been determined from the melting kinetics of CuCl particles during linear heating of the sample. The nonisothermal nucleation of CuCl in glass under conditions of the temperature jump has been simulated numerically. The results of calculations of the variations in the radius distribution of CuCl particles are in agreement with the experiment. The calculated data on the variation in time of the critical radius r _c and the concentration of CuCl monomers in glass after the temperature jump have been obtained.     

Liquid nucleation at superheated grain boundaries

Grain boundaries with relatively low energies can be superheated above the melting temperature and eventually melt by heterogeneous nucleation of liquid droplets. We propose a thermodynamic model of this process based on the sharp-interface approximation with a disjoining potential. The distinct feature of the model is its ability to predict the shape and size of the critical nucleus by using a variational approach. The model reduces to the classical nucleation theory in the limit of large nuclei but is more general and remains valid for small nuclei. Contrary to the classical nucleation theory, the model predicts the existence of a critical temperature of superheating and offers a simple formula for its calculation. The model is tested against molecular dynamic simulations in which liquid nuclei at a superheated boundary were obtained by an adiabatic trapping procedure. The simulation results demonstrate a reassuring consistency with the model.     

Radial oscillation and translational motion of a gas bubble in a micro-cavity

According to classical nucleation theory, a gas nucleus can grow into a cavitation bubble when the ambient pressure is negative. Here, the growth process of a gas nucleus in a micro-cavity was simplified to two “events”, and the full confinement effect of the surrounding medium of the cavity was considered by including the bulk modulus in the equation of state. The Rayleigh–Plesset-like equation of the cavitation bubble in the cavity was derived to model the radial oscillation and translational motion of the cavitation bubble in the local acoustic field. The numerical results show that the nucleation time of the cavitation bubble is sensitive to the initial position of the gas nucleus. The cavity size affects the duration of the radial oscillation of the cavitation bubble, where the duration is shorter for smaller cavities. The equilibrium radius of a cavitation bubble grown from a gas nucleus increases with increasing size of the cavity. There are two possible types of translational motion: reciprocal motion around the center of the cavity and motion toward the cavity wall. The growth process of gas nuclei into cavitation bubbles is also dependent on the compressibility of the surrounding medium and the magnitude of the negative pressure. Therefore, gas nuclei in a liquid cavity can be excited by acoustic waves to form cavitation bubbles, and the translational motion of the cavitation bubbles can be easily observed owing to the confining influence of the medium outside the cavity.     

Dependence of peak height of glow curves on heating rate in thermoluminescence

The area under the glow curve (no thermal quenching and same dose) is conserved only in TL-time plots and is not conserved (scales by a factor by which heating rate is increased) in TL-temperature plots. This increase in area under TL-temperature glow curves with increase in heating rate at a constant dose should not be interpreted as increase in sensitivity of the dosimeter and is the consequence of transformation of time to temperature scale (temperature scale obtained from time scale by multiplying with β, T=T₀+βt). This is further supported by the fact that the light output or integrated counts seen by the PMT do not change (ignoring statistical fluctuations) with increase in heating rate at a constant dose. Further for a given heating rate, the glow peak height is similar in time and temperature plots and the glow peak height increases with increase in heating rate. However to conserve area in TL-temperature plots, the TL intensity should be divided by the respective heating rate, which will lead to the decrease of glow peak height in I/β-temperature plots and is the artifact of the normalization process. However for normalized glow curves (I/β-temperature), the glow peak height decreases with increase in heating rate, which is actually true for I/β or TL/β versus temperature plots. Hence it is recommended that in such cases where normalized glow curves (I/β versus temperature) are presented, the obtained peak height must be multiplied by β. By doing so, glow peak height increases with increase in heating rate. In addition to the above, studies are also carried out by considering thermal quenching effect and it is found that a logical way to measure thermal quenching quantitatively is to record the decrease of integrated counts (PMT current) with increase in heating rate at a constant dose, i.e. the integrated peak area (PMT current or TL-time or TL/β-temperature) must be plotted against the heating rate and the same should be used for interpretation of thermal quenching effect. Only this proves the fact whether the decrease of TL intensity (TL/β-temperature) is due to thermal quenching or not.     

Theoretical model of ice nucleation induced by inertial acoustic cavitation. Part 2: Number of ice nuclei generated by a single bubble

In the preceding paper (part 1), the pressure and temperature fields close to a bubble undergoing inertial acoustic cavitation were presented. It was shown that extremely high liquid water pressures but quite moderate temperatures were attained near the bubble wall just after the collapse providing the necessary conditions for ice nucleation. In this paper (part 2), the nucleation rate and the nuclei number generated by a single collapsing bubble were determined. The calculations were performed for different driving acoustic pressures, liquid ambient temperatures and bubble initial radius. An optimal acoustic pressure range and a nucleation temperature threshold as function of bubble radius were determined. The capability of moderate power ultrasound to trigger ice nucleation at low undercooling level and for a wide distribution of bubble sizes has thus been assessed on the theoretical ground.     

纳米尺度下气泡核化生长的分子动力学研究

采用分子动力学方法模拟纳米尺度下液体在固体壁面上发生核化沸腾的过程,主要研究壁面浸润性对气泡初始核化过程和气泡生长速率的影响以及固-液界面效应在液体核化沸腾的能量传递过程中所起到的作用.研究结果发现：壁面浸润性越强,气泡在固壁处越容易核化.该结果与经典核化理论中“疏水壁面易于产生气泡”的现象产生了明显的区别.其根本原因是在纳米尺度下,固-液界面热阻效应不能被忽略.一方面,在相同的壁温下,通过增强固-液相互作用,可以显著降低界面热阻,使得热量传递效率提高,导致靠近壁面处的流体温度升高,气泡核化等待时间缩短,有利于液体沸腾核化.另一方面,气泡的生长速率随着壁面浸润性的增强而明显升高.当气泡体积生长到一定程度时,会在壁面处形成气膜,从而导致壁面传热性能恶化.因此,通过壁面的热流密度呈现出先增大后减小的规律.     

Agglomeration of As antisites in As-rich low-temperature GaAs: nucleation without a critical nucleus size

To investigate the early stages of nucleation and growth of As precipitates in GaAs grown at low substrate temperature, we make use of a self-consistent-charge density-functional based tight-binding method. Since a pair of As antisites already shows a significant binding energy which increases when more As antisites are attached, there is no critical nucleus size. Provided that all excess As has precipitated, the clusters may grow in size since the binding energies increase with increasing agglomeration size. These findings close the gap between experimental investigation of point defects and the detection of nanometer-size precipitates in transmission electron microscopy.     

液滴外延下生长参数对InAs纳米结构形貌的影响

利用液滴外延法在GaAs(001)衬底表面制备InAs量子点,通过控制变量分别研究沉积速率、沉积量对In液滴在GaAs表面生长过程中的影响.使用原子力显微镜(Atomic Force Microscope, AFM)表征InAs纳米结构形貌,得出结论：(1)沉积速率主要通过影响In液滴成核率来控制液滴的密度,即随着沉积速率的增大,In原子在衬底表面的成核率增加,InAs量子点密度增加,实验符合生长动力学经典成核理论.(2)沉积量的改变主要影响液滴的熟化过程,即随着沉积量的增大,可参与生长的活跃的In原子增加,促进了液滴熟化,使得扩散坍塌的原子数量增加,导致在InAs纳米结构中出现多量子点现象.