The thermodynamics of cluster formation in nucleation theory

We have derived a precise thermodynamic definition of the standard free energy to form a cluster which is used in nucleation theory. The results [Eq. (9)] have a form differing slightly from the form usually used in nucleation theory and show that the Lothe-Pound correction factor is based on a misconception concerning the standard states involved.     

过冷水法冰浆制取的实验设计与分析

动态冰蓄冷技术是目前蓄能技术重要的研究方向之一,其中冰浆制取方式是研究的关键课题。冰浆具有良好的流动性,大的相变潜热和快速的释冷特性,是常规载冷剂的潜在替代物。该文给出了过冷水法冰浆制取的实验装置,采用纯净水和自来水为试样,在不同的条件下进行了对比实验,并分析了管内冻结情况。     

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.     

Density and bond-orientational relaxations in supercooled water

ABSTRACT

Recent computational studies have reported evidence of a metastable liquid–liquid phase transition (LLPT) in molecular models of water under deeply supercooled conditions. A competing hypothesis suggests, however, that non-equilibrium artefacts associated with coarsening of the stable crystal phase have been mistaken for an LLPT in these models. Such artefacts are posited to arise due to a separation of time scales in which density fluctuations in the supercooled liquid relax orders of magnitude faster than those associated with bond-orientational order. Here, we use molecular simulation to investigate the relaxation of density and bond-orientational fluctuations in three molecular models of water (ST2, TIP5P and TIP4P/2005) in the vicinity of their reported LLPT. For each model, we find that density is the slowly relaxing variable under such conditions. We also observe similar behaviour in the coarse-grained mW model of water. Our findings, therefore, challenge the key physical assumption underlying the competing hypothesis.     

The effect of ultrasonic waves on the nucleation of pure water and degassed water

In order to clarify the mechanism of nucleation of ice induced by ultrasound, ultrasonic waves have been applied to supercooled pure water and degassed water, respectively. For each experiment, water sample is cooled at a constant cooling rate of 0.15 °C/min and the ultrasonic waves are applied from the water temperature of 0 °C until the water in a sample vessel nucleates. This nucleation temperature is measured. The use of ultrasound increased the nucleation temperature of both degassed water and pure water. However, the undercooling temperature for pure water to nucleate is less than that of degassed water. It is concluded that cavitation and fluctuations of density, energy and temperature induced by ultrasound are factors that affect the nucleation of water. Cavitation is a major factor for sonocrystallisation of ice.     

Information-theoretic stability and evolution criteria in irreversible thermodynamics

Generalized information gains are used to derive stability conditions, for steady states, periodic orbits and invariant sets, and general evolution criteria, both global and local with respect to the time variable, in irreversible thermodynamics. Meixner's passivity condition and the Glansdorff-Prigogine stability and evolution criteria are found to be special cases thereof. The information gain quantities include Kullback's three kinds of divergences, the first two of which are dual to each other and yield criteria which are symmetric in the average densities of the system's extensive variables and the conjugate parameters, but which are nonsymmetric in the irreversible fluxes and forces, while the third one does not involve the entropy function of the system. Furthermore, Renyi's information gain of order and Csiszar'sf-divergence are treated. The latter is used to construct a most general information gain quantity as a Liapunov function and evolution criterion, which, however, for local stability and evolution conditions is still equivalent to the use of the second-order variation of the entropy.Supported by the Deutsche Forschungsgemeinschaft.     

相对论热力学中玻意耳定律与焦耳定律之间的关系

证明在相对论热力学理论系统中,焦耳定律是玻意耳定律的推论,但玻意耳定律不是焦耳定律的推论.     

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.     

非相对论热力学中玻意耳定律与焦耳定律的相互独立性

证明在非相对论热力学理论系统中,焦耳定律不是玻意耳定律的推论,玻意耳定律也不是焦耳定律的推论．用热力学证明理想气体的低温热容满足关系式∫0ε[Cv(θ）/θ]dθ= ∞,并对以往的争论给予一些评论．     

Dynamics of hydrogen bonds in water and consequences for the unusual behaviour of supercooled water

The dynamics of liquid water is evaluated by the coherent quasi-elastic scattering at two different momentum transfers, in order to discriminate hydrogen bond lifetime from molecular dynamics. The results indicate a possible issue for the puzzle of the behaviour of supercooled water.      

Fragile to strong crossover and Widom line in supercooled water: A comparative study

The aim of this paper is to discuss the relationship between the dynamics and thermodynamics of water in the supercooled region. Reviewed case studies comprehend bulk water simulated with the SPC/E, TIP4P and TIP4P/2005 potentials, water at protein interfaces, and water in solution with electrolytes. Upon supercooling, the fragile to strong crossover in the α-relaxation of water is found to occur when the Widom line emanating from the liquid-liquid critical point is crossed. This appears to be a general characteristic of supercooled water, not depending on the applied interaction potential and/or different local environments.     

力学、热力学及电磁波导中的正则变换和辛描述

从正则变换入手,讨论经典力学中正则变换的辛描述,得到了正则变换的条件,给出了热力学系统满足正则变换条件的证明,同时给出了在辛体系下电磁波导的正则变换的物理意义.通过正则变换给出在辛体系下力学、热力学、电磁学公式的相似性,在统一理论方面做出有益探讨.     

Ultrasound cavitation induced nucleation in metal solidification: An analytical model and validation by real-time experiments

Microstructural refinement of metallic alloys via ultrasonic melt processing (USMP) is an environmentally friendly and promising method. However, so far there has been no report in open literature on how to predict the solidified microstructures and grain size based on the ultrasound processing parameters.In this paper, an analytical model is developed to calculate the cavitation enhanced undercooling and the USMP refined solidification microstructure and grain size for Al-Cu alloys. Ultrafast synchrotron X-ray imaging and tomography techniques were used to collect the real-time experimental data for validating the model and the calculated results. The comparison between modeling and experiments reveal that there exists an effective ultrasound input power intensity for maximizing the grain refinement effects for the Al-Cu alloys, which is in the range of 20-45 MW/m². In addition, a monotonous increase in temperature during USMP has negative effect on producing new nuclei, deteriorating the benefit of microstructure refinement due to the application of ultrasound.     

Temperature dependent anomalous fluctuations in water: shift of ≈1 kbar between experiment and classical force field simulations

Here we report on the temperature dependence of the anomalous behaviour of water in terms of (i) its growth in tetrahedral structures, (ii) instantaneous spatial correlations from small angle x-ray scattering (SAXS) data, (iii) estimates of thermodynamic response functions of isothermal compressibility and (iv) thermal expansion coefficient. Water’s thermal expansion coefficient is estimated for the first time at supercooled conditions from liquid water’s structure factor. We used previously published data from classical force-fields of TIP4P/2005 and iAMOEBA to compare experimental data with molecular dynamics simulations and observe that these force-fields underestimate water’s anomalous behaviour but perform better upon increasing pressure. We demonstrate that the molecular dynamics simulations can describe better the temperature dependent anomalous behaviour of ambient pressure water if simulated at 1?kbar. The deviation in anomalous fluctuations in the simulations is not restricted to ≈228?K but extends all the way to ambient temperatures.     

利用扩展系综法计算水的自由能

利用扩展系综法得到了正则系综下水的TIP4P模型的自由能值为-21．485±0．035kJ/mol， 并与其他方法所得的结果作了比较.提出了选择该方法中关键参数(平衡因子)的有效方法， 并讨论了该方法的可移植性. 关键词： 自由能 TIP4P水模型 扩展系综 分子动力学模拟 水分子团     

Electronic structure and activation energy of hydrogen in NEG alloy using nonlinear response theory

Electronic structure of hydrogen in NEG alloy [Zr_0.70V_0.246Fe_0.054] is calculated by using nonlinear response theory [Kohn and Sham,Phys. Rev. A140,1133 (1965)]. The configurational energy is calculated by assuming the ideal hcp structure for NEG alloy. The calculated configurational energy predicts that hydrogen prefers octahedral (0)-site in NEG alloy.s-Type shallow bound state of energy -1.580 x 10^-5 Ryd. suggests that hydrogen does not form NEG hydride and it stays as a free ion in NEG alloy. This conclusion confirms the prediction of Tripathiet al.     

Reply to “Comment to ‘Dynamics of supercooled confined water measured by deep inelastic neutron scattering’ by Y. Finkelstein and R. Moreh”

We reply to the comment [Front. Phys. 14(5), 53605 (2019)] by Y. Finkelstein and R. Moreh on our article Front. Phys. 13(1), 138205 (2018). We agree with some of their criticisms about our calculation of the temperature effect on the kinetic energy of hydrogen atoms of supercooled confined water; we also agree with their statement that, in view of the current sensitivity of the technique, possible effects of the liquid–liquid water transition are hardly detected with deep inelastic neutron scattering (DINS). However, we disagree with their use of the translational mass ratio of a single water molecule and, in general, with their underestimation of collective effects.     

The dipole moment distribution on water is improved by using large flexibility and large bending angle

A highly flexible model of water with fixed charges is used to study properties of water. The bending angle of an isolated molecule is 125^○ that was chosen to match the experimental dipole moment. The geometry of water in the liquid phase is made closer to that of the rigid SPC/E model by decreasing the bending angle spring constant, k _Θ. The new model, called SPCE-FHΘ, is a modified version of the recently proposed SPCE-FH [J. Alejandre, G.A. Chapela, F. Bresme and J.-P. Hansen, J. Chem. Phys. 130, 174505 (2009)] to simulate ionic solutions which includes short ranged interactions on the hydrogen atoms. By increasing angle flexibility it is possible to obtain, in the liquid phase at ambient conditions, bending angles ?Θ(HOH)? ～ 109^○, dipole moment ?μ? ～ 2.5 D and dielectric constant ?ε? ～ 80. The dipole moment distribution at room temperature goes from 1.5 to 3.5 D due to large fluctuations in bending angle and has the same trend found in ab initio simulations of liquid water. The dipole moment profile at the interface of water varies from 1.9 D in the vapour phase to 2.5 D in the liquid region at 400 K. The SPCE-FHΘ gives dipole moment, dielectric constant, coexisting densities and surface tension along the liquid–vapour coexistence line closer to the experimental values than those obtained for the SPC/E force field.