过热液氦均匀核化速率的确定

预测不同压力下过热液氦的均匀核化速率是十分重要的,它与液氦的极限过热度密切相关。文中通过回顾动力学理论、分子聚集理论、涨落理论等研究液体均匀核化的方法,对过热液氦的均匀核化速率进行了计算,并且对各种方法进行了比较与分析。结果表明,用能量涨落理论来计算过热液氦的均匀核化速率是一种比较合理的方法。     

Thermodynamic and kinetic considerations of nucleation and stabilization of acoustic cavitation bubbles in water

Qualitative explanation for a homogeneous nucleation of acoustic cavitation bubbles in the incompressible liquid water with simple phenomenological approach has been provided via the concept of the desorbtion of the dissolved gas and the vaporization of local liquid molecules. The liquid medium has been viewed as an ensemble of lattice structures. Validity of the lattice structure approach against the Brownian motion of molecules in the liquid state has been discussed. Criterion based on probability for nucleus formation has been defined for the vaporization of local liquid molecules. Energy need for the enthalpy of vaporization has been considered as an energy criterion for the formation of a vaporous nucleus. Sound energy, thermal energy of the liquid bulk (Joule-Thomson effect) and free energy of activation, which is associated with water molecules in the liquid state (Brownian motion) as per the modified Eyring's kinetic theory of liquid are considered as possible sources for the enthalpy of vaporization of water molecules forming a single unit lattice. The classical nucleation theory has then been considered for expressing further growth of the vaporous nucleus against the surface energy barrier. Effect of liquid property (temperature), and effect of an acoustic parameter (frequency) on an acoustic cavitation threshold pressure have been discussed. Kinetics of nucleation has been considered.     

Local structure of liquid carbon controls diamond nucleation

Diamonds melt at temperatures above 4000 K. There are no measurements of the steady-state rate of the reverse process, i.e., diamond nucleation from the melt, because experiments are difficult at these extreme temperatures and pressures. Using numerical simulations, we estimate the diamond nucleation rate and find that it increases by many orders of magnitude when the pressure is increased at constant supersaturation. The reason is that by increasing the pressure the local coordination of the liquid changes from threefold to fourfold, and we show that the free-energy cost to create a diamond-liquid interface is lower in the fourfold than in the threefold liquid. We speculate that this mechanism for nucleation control is relevant for crystallization in many network-forming liquids. We conclude that homogeneous diamond nucleation is likely in carbon-rich stars and unlikely in gaseous planets.     

On the homogeneous nucleation and propagation of dislocations under shock compression

The dynamic response of crystalline materials subjected to extreme shock compression is not well understood. The interaction between the propagating shock wave and the material’s defect occurs at the sub-nanosecond timescale which makes in situ experimental measurements very challenging. Therefore, computer simulation coupled with theoretical modelling and available experimental data is useful to determine the underlying physics behind shock-induced plasticity. In this work, multiscale dislocation dynamics plasticity (MDDP) calculations are carried out to simulate the mechanical response of copper reported at ultra-high strain rates shock loading. We compare the value of threshold stress for homogeneous nucleation obtained from elastodynamic solution and standard nucleation theory with MDDP predictions for copper single crystals oriented in the [0 0 1]. MDDP homogeneous nucleation simulations are then carried out to investigate several aspects of shock-induced deformation such as; stress profile characteristics, plastic relaxation, dislocation microstructure evolution and temperature rise behind the wave front. The computation results show that the stresses exhibit an elastic overshoot followed by rapid relaxation such that the 1D state of strain is transformed into a 3D state of strain due to plastic flow. We demonstrate that MDDP computations of the dislocation density, peak pressure, dynamics yielding and flow stress are in good agreement with recent experimental findings and compare well with the predictions of several dislocation-based continuum models. MDDP-based models for dislocation density evolution, saturation dislocation density, temperature rise due to plastic work and strain rate hardening are proposed. Additionally, we demonstrated using MDDP computations along with recent experimental reports the breakdown of the fourth power law of Swegle and Grady in the homogeneous nucleation regime.     

可膨胀过热水系统多气核演化过程与临界过热度分析

使用分子动力学方法,研究过热水系统均质沸腾核化过程.采用Langevin 动力学方法控制体积可变系统的温度与压力,更好地模拟了沸腾实际物理过程.得到了液相系统体积连续膨胀、分子间距逐渐增大,最终稳定在汽相的现象学规律.当过热温度较高时,亚稳态液相系统可能在局部形成不同大小的近球形区域：气核,这些气核是不稳定的,处于不断演化之中.通过分析分子所受引力与斥力的共同作用,得到了气核形成与消亡以及多个气核融合的机理.比较了模拟结果与经典沸腾理论的差异,提出了气核生长是比气泡生长更为微观过程的认识.通过研究不同过热 关键词： 过热水系统 分子动力学 气核 临界过热度     

Two-phase flow model for energetic proton beam induced pressure waves in mercury target systems in the planned European Spallation Source

Two-phase flow calculations are presented to investigate the thermo-hydraulical effects of the interaction between 2 ms long 1.3 GeV proton pulses with a closed mercury loop which can be considered as a model system of the target of the planned European Spallation Source (ESS) facility. The two-fluid model consists of six first-order partial differential equations that present one dimensional mass, momentum and energy balances for mercury vapor and liquid phases are capable to describe quick transients like cavitation effects or shock waves. The absorption of the proton beam is represented as instantaneous heat source in the energy balance equations. Densities and internal energies of the mercury liquid-vapor system is calculated from the van der Waals equation, but general method how to obtain such properties using arbitrary equation of state is also presented. A second order accurate high-resolution shock-capturing numerical scheme is applied with different kind of limiters in the numerical calculations. Our analysis show that even 75 degree temperature heat shocks cannot cause considerable cavitation effects in mercury.     

The kinetics of homogeneous nucleation of silver nanoparticles stabilized by polymers

The formation of Ag nanoparticles synthesized by homogeneous nucleation, stabilized by polymers (PVA and PVP) was monitored by UV–Vis spectrophotometry and transmission electron microscopy. Our aim was to differentiate between the two main phases of particle formation, i.e. nucleation and growth and to characterize their rates with the help of appropriate kinetic equations. Time resolved spectrophotometric measurements revealed that particle formation is an autocatalytic process: a slow, continuous nucleation phase (3–5 min) is followed by a rapid, autocatalytic growth phase where the maximal particle size is 5–7 nm. By freezing the reaction mixture, the process of particle growth can be followed from 5 to 40 min on TEM pictures. The first order rate constants were calculated and they are strongly depend on the polymer concentration. If the growing particles are attached by PEI to the surface of a solid support, the formation of silver nanoparticles can also be followed by atomic force microscopy (AFM) and we can control the particle growth on mica surface. The cross section analysis of the pictures show, that the particle growing process can be also monitored at solid–liquid interface.     

Use of chlorinated carbon and silicon precursors for epitaxial growth of 4H‐SiC at very high growth rates

A possibility to apply the advantages of chlorinated carbon precursors, which had been previously used in low‐temperature epitaxial growth of 4H‐SiC, to achieve very high growth rates at higher growth temperatures was investigated. Silicon tetrachloride was used as the silicon precursor to suppress gas‐phase homogeneous nucleation. The temperature increase from 1300 °C (which is the temperature of the previously reported low‐temperature halo‐carbon epitaxial growth) to 1600 °C enabled an increase of the precursor flow rates and consequently of the growth rate from 5 to more than 100 μm/h without morphology degradation. High quality of the epilayers was confirmed by low‐temperature photoluminescence spectroscopy and time‐resolved luminescence. No evidences of homogeneous nucleation were detected, however, liquid Si droplet formation on the epilayer surface seems to remain a bottleneck at very high growth rate. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Formation of argon cluster with proton seeding

ABSTRACT

We employ force-field molecular dynamics simulations to investigate the kinetics of nucleation to new liquid or solid phases in a dense gas of particles, seeded with ions. We use precise atomic pair interactions, with physically correct long-range behaviour, between argon atoms and protons. Time dependence of molecular cluster formation is analysed at different proton concentration, temperature and argon gas density. The modified phase transitions with proton seeding of the argon gas are identified and analysed. The seeding of the gas enhances the formation of nano-size atomic clusters and their aggregation. The strong attraction between protons and bath gas atoms stabilises large nano-clusters and the critical temperature for evaporation. An analytical model is proposed to describe the stability of argon-proton droplets and is compared with the molecular dynamics simulations.     

Estimation of the Possibility of Using the Classical Theory of Nucleation in the Calculation of the Limiting Superheat for a Metastable Liquid in the Region of Onset of Nucleate Boiling

Experimental data obtained at VTI for the onset of nucleate boiling of water in a uniformly heated pipe with a diameter of 5.77 and 6.34 mm at a mass flow rate Wj = 1400–5000 kg/(m2 s) and at a pressure of P = 9.81, 14.7, 19.62 MPa are presented in comparison with a theoretical calculation on the homogeneous nucleation mechanism in a metastable liquid for the liquid superheating limits obtained using the classical Gibbs formula [1]. It is assumed that the thermodynamic instability of the process in the area under the spinodal affects the breakage of metastable liquid films with the formation of holes through the entire thickness thereof, which ultimately leads to the formation of unwettable dry spots (spinodal dewetting) and causes a spontaneous transition to the film boiling mode.     

Decline of nucleation in the heating process with a high heating rate

The effect of the heating rate on the nucleation of metallic glass in a rapid heating process starting from the glass transition temperature is investigated. The critical nucleus radius increases with the increase of the temperature of the undercooling liquid. If the increment rate of the critical nucleus radius, owing to the heating process, is higher than the growth rate of the nuclei, the nuclei generated at the low temperature will become the embryos at the high temperature. This means that the high heating rate can make no nucleation happen in the heating process. In consideration of the interfacial energy, the growth rate of the nuclei increases with the increase of their size and the growth rate of the critical nucleus is zero. Thus, the lower heating rate can also make the nuclei decline partially. Finally, this theory is used to analyze the nucleation process during laser remelting metallic glass.     

Phase transitions in femtosecond laser ablation

In this study we simulate an interaction of femtosecond laser pulses (100 fs, 800 nm, 0.1-10 J/cm²) with metal targets of Al, Au, Cu, and Ni. For analysis of laser-induced phase transitions, melting and shock waves propagation as well as material decomposition we use an Eulerian hydrocode in conjunction with a thermodynamically complete two-temperature equation of state with stable and metastable phases. Isochoric heating, material evaporation from the free surface of the target and fast propagation of the melting and shock waves are observed. On rarefaction the liquid phase becomes metastable and its lifetime is estimated using the theory of homogeneous nucleation. Mechanical spallation of the target material at high strain rates is also possible as a result of void growth and confluence. In our simulation several ablation mechanisms are taken into account but the main issue of the material is found to originate from the metastable liquid state. It can be decomposed either into a liquid-gas mixture in the vicinity of the critical point, or into droplets at high strain rates and negative pressure. The simulation results are in agreement with available experimental findings.     

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.     

Deformation-induced martensite and nanotwins by cryogenic laser shock peening of AISI 304 stainless steel and the effects on mechanical properties

Laser shock peening (LSP) of stainless steel 304 was carried out at room and cryogenic temperature (liquid nitrogen temperature). It was found that the deformation-induced martensite was generated by LSP only when the laser-generated plasma pressure is sufficiently high. Compared to room temperature laser shock peening (RT-LSP), cryogenic laser shock peening (CLSP) generates a higher volume fraction of martensite at the same laser intensity. This is due to the increase in the density of potential embryos (deformation bands) for martensite nucleation by deformation at cryogenic temperature. In addition, CLSP generates a high density of deformation twins and stacking faults. After CLSP, an innovative microstructure, characterised by networks of deformation twins, stacking faults and composite structure (martensite and austenite phases), contributes to material strength and microstructure stability improvement. The combined effect of higher surface hardness and a more stabilised microstructure results in greater fatigue performance improvement of the CLSP samples compared to that of the RT-LSP samples.     

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.     

Transport properties of supercooled confined water

This article presents an overview of recent experiments performed on transport properties of water in the deeply supercooled region, a temperature region of fundamental importance in the science of water. We report data of nuclear magnetic resonance, quasi-elastic neutron scattering, Fourier-transform infrared spectroscopy, and Raman spectroscopy, studying water confined in nanometer-scale environments. When contained within small pores, water does not crystallise, and can be supercooled well below its homogeneous nucleation temperature T_h. On this basis it is possible to carry out a careful analysis of the well known thermodynamical anomalies of water. Studying the temperature and pressure dependencies of water dynamics, we show that the liquid-liquid phase transition (LLPT) hypothesis represents a reliable model for describing liquid water. In this model, water in the liquid state is a mixture of two different local structures, characterised by different densities, namely the low density liquid (LDL) and the high-density liquid (HDL). The LLPT line should terminate at a special transition point: a low-T liquid-liquid critical point. We discuss the following experimental findings on liquid water: (i) a crossover from non-Arrhenius behaviour at high T to Arrhenius behaviour at low T in transport parameters; (ii) a breakdown of the Stokes-Einstein relation; (iii) the existence of a Widom line, which is the locus of points corresponding to maximum correlation length in the p-T phase diagram and which ends in the liquid-liquid critical point; (iv) the direct observation of the LDL phase; (v) a minimum in the density at approximately 70 K below the temperature of the density maximum. In our opinion these results represent the experimental proofs of the validity of the LLPT hypothesis.     

金属熔体中气泡形核的理论分析

引入界面接触角，考虑表面张力对气泡形貌的影响，以熔体中均质形核、夹杂物的平表面上异质形核和圆锥形凹坑内异质形核三种典型模型对气泡形核机理进行理论研究.研究发现，三种形核模型下具有相等的微米量级的气泡临界形核半径，并随气压的增大而减小.结果表明，用以制备藕状规则多孔金属的Gasar工艺中能够形成的最小气孔的直径为微米量级(0.1—1.0 MPa气压).在圆锥形凹坑内异质形核时存在最佳圆锥顶角(对应最小气泡体积)，其值与气压无关，只随接触角的增大而增大.在接触角处于90°—180°范围内，最佳圆锥顶角下圆锥形 关键词： 气泡 形核 多孔金属 Gasar     

Monitoring hydrate formation and dissociation in sandstone and bulk with magnetic resonance imaging

Magnetic resonance imaging (MRI) has been shown to be a very effective tool for monitoring the formation and dissociation of hydrates because of the large intensity contrast between the images of the liquid components and the solid hydrate. Tetrahydrofuran/water hydrate was used because the two liquid components are miscible and form hydrate at ambient pressure. These properties made this feasibility study proceed much faster than using methane/water, which requires high pressure to form the hydrate. The formation and dissociation was monitored first in a THF/water-saturated Berea sandstone plug and second in the bulk. In both cases it appeared that nucleation was needed to begin the formation process, i.e., the presence of surfaces in the sandstone and shaking of the bulk solution. Dissociation appeared to be dominated by the rate of thermal energy transfer. The dissociation temperature of hydrate formed in the sandstone plug was not significantly different from the dissociation temperature in bulk.     

Nucleation kinetics,growth and hardness parameters of l-alanine alaninium picrate (LAAP) single crystals

Amino acids are considered to be the building blocks of proteins and are gaining importance due to their interesting optical behavior. l-alanine is an amino acid which dissolves in water and it can react with other acids to form new compounds. In this work, l-alanine is mixed with picric acid to prepare l-alanine alaninium picrate (LAAP) salt. Solubility and metastable zone width were measured for LAAP salt and induction period was measured at different supersaturation ratios. The critical nucleation parameters were evaluated based on the classical theory of homogeneous nucleation. Using the optimized nucleation parameters, single crystals of LAAP salt were grown by slow evaporation technique. XRD and FTIR studies were carried out to understand structural and molecular formation of the crystal. Microhardness measurements were performed on the grown LAAP crystal and various parameters such as work hardening constant, stiffness constant, yield strength, resistance pressure and corrected hardness were evaluated. Nonlinear optical behavior of the sample was analyzed.     

Theory of the nucleation of protein macromolecular ions

Protein molecules are amphoteric and exist in aqueous solution as macromolecular ions that carry a charge which depends upon temperature and pH. Despite the repulsive Coulomb forces acting between them, protein macromolecular ions can form crystals in pH buffered solutions of strong electrolytes. It is proposed that the first step in the mechanism of crystallization is the formation of crystal nuclei made from partially discharged macromolecular ions that have exchanged H⁺ with the buffer. We suggest that the strength of the bare Coulomb repulsive force is weakened by the Debye-Hückel plasma screening provided by the inert electrolyte. This screening causes the rate of nucleus formation to increase with increasing ionic strength. Extending classic nucleation theory to account for these various charge effects, the results are applied to the case of lysozyme and a calculation is made of the dependence of the steady state nucleation rate upon temperature, pH, ionic strength, and protein supersaturation. It is found that the nucleation rate increases with increasing temperature and increasing ionic strength. Under condition of fixed temperature, supersaturation, and inionic strength, the nucleation rate has local maxima at low pH, where individual lysozyme macro ions are highly charged, and at pH ? 11, where they have zero average net charge. At both pH values, the nucleus that determines the rate has minimum size. In contrast to standard nucleation theory, which ignores charge, it is found that the size of the nucleus that controls the rate is different from the size of the nucleus that has the lowest concentration. All other conditions being the same, it is predicted that lysozyme crystals should nucleate most rapidly near pH = 2 and near pH = 11.