Diamagnetic susceptibility of solid and liquid paraffins

Experimental values for the diamagnetic susceptibility of a series of mono-disperse n-paraffins ranging between 6 and 50 carbon atoms in the solid (melt and solution crystallized) and in the liquid state are reported. From the dependence of the molecular susceptibility, ScHM, on the molecular weight, information about the intermolecular interactions between adjacent chain molecules and on the arrangement of the methyl end-groups is obtained. The ScHM values of melt- and solution-crystallized paraffins are, within experimental error, indistinguishable from each other. For C₁₂H₂₆ and C₄₄H₉₀ the specific susceptibility ScHM /M rises at the melting point within a few °C and reaches a plateau which characterizes the liquid state II. For the paraffin C₂₄H₅₀ an intermediate plateau between the melting point and the final true liquid state is observed and is called liquid state I. After cooling below the melting point TM, the ScHM value of the equilibrium state can be obtained after a short time only from liquid state I, while from liquid state II days and weeks are needed for this. By combining this information with the observed ScHM values, it is concluded that in liquid state I a higher or smectic-like order exists similar to mesophases, well-known in liquid crystals, while in the real liquid state II this order is lost.     

Stages of melting of graphene model in two-dimensional space

Spontaneous melting of a perfect crystalline graphene model in 2D space is studied via molecular dynamics simulation. Model containing 10⁴ atoms interacted via long-range bond-order potential (LCBOP) is heated up from 50 to 8,450 K in order to see evolution of various thermodynamic quantities, structural characteristics and occurrence of various structural defects. We find that spontaneous melting of our graphene model in 2D space exhibits a first-order behaviour of the transition from solid 2D graphene sheet into a ring-like structure 2D liquid. Occurrence and clustering of Stone–Wales defects are the first step of melting process followed by breaking of C–C bonds, occurrence/growth of various types of vacancies and multi-membered rings. Unlike that found for melting of a 2D crystal with an isotropic bonding, these defects do not occur homogeneously throughout the system, they have a tendency to aggregate into a region and liquid phase initiates/grows from this region via tearing-like or crack-propagation-like mechanism. Spontaneous melting point of our graphene model occurs at T_m = 7,750 K. The validity of classical nucleation theory and Berezinsky–Kosterlitz–Thouless–Nelson–Halperin–Young (BKTNHY) one for the spontaneous melting of our graphene model in strictly 2D space is discussed.     

Freezing of a modulated liquid: The superionic-to-normal transition of strontium chloride

The anionic component in SrCl₂ near melting is treated as a modulated liquid in the periodic potential of the sublattice of cations. With decreasing temperature from the melting point, we find a diffuse disorder—order transition. The calculated behaviours of the order parameter and of thermodynamic properties approximate those observed for SrCl₂ across its superionic transition.     

Relationship between crystalline order and melting mechanisms of solids

The mechanism for homogeneous nucleation of the liquid phase in Lennard-Jones solids is studied by combining the Landau free energy approach with some of the methodology developed to characterise transition path ensembles. The second-order bond orientational order parameter, Q ₆ which indexes the overall degree of crystalline order, is shown to provide a dynamically significant collective coordinate describing the melting process. Trajectories generated from configurations sampled in the vicinity of the maximum in the Landau free energy curve, F(Q ₆), are shown to have equal likelihood of teminating in either the solid or liquid-like free energy minima. It is also demonstrated that Q ₆ is necessary but not sufficient as a dynamical coordinate to describe melting and it is necessary to explore possiblities for additional coordinates which are critical for initiating melting. Our sudy suggests that the additional coordinates for describing the melting process would be some type of localised defect, much smaller in spatial extent than the size of the critical nucleus predicted by classical nucleation theory.      

Correlation study of structural,electrical and mechanical properties of quenched tin–zinc–cadmium solder alloys

It is important, for electronic application, to decrease the melting point of SnZn₉ solder alloy because it is too high as compared with the most popular eutectic Pb–Sn solder alloy. Adding Cd causes structural changes such as phase transformations, dissolution of atoms and formation of Cd crystals in the quenched SnZn₉ alloy, and its physical properties are affected by this change. For example, the melting point is decreased towards the melting point of the Pb–Sn eutectic alloy, or even much less. The structure, electrical and mechanical properties of quenched Sn_{91? x} Zn₉Cd _x (x?=?0 or x?≥?5) alloys have been investigated. Adding Cd to a quenched SnZn₉ alloy increases its electrical resistivity and decreases its elastic modulus and internal friction. The Sn₇₁Zn₉Cd₂₀ alloy has the lowest melting point (162 °C) and electrical and internal frictions as compared with commercial Pb–Sn solder alloys.     

Solid-liquid phase transition in small water clusters: a molecular dynamics simulation study

Water clusters, (H₂O) _n , of varying sizes (n = 8, 12, 16, 20, 24, 28, 32, 36, and 40) have been studied at different temperatures from 0 to 200 K using molecular dynamics simulations. Transitions between solid and liquid phases were investigated to estimate the melting temperature of the clusters. Although the melting temperatures showed non-monotonic behaviour as a function of cluster size, their general tendency follows the classical relationship T _m ∝ n ^?1/3 to the cluster size n. Moreover, it was observed that the liquid-solid surface tension decreased with the cluster size in a similar way to the liquid-vapour surface tension in bulk water. Upon cooling, ice-like crystals were formed from the smaller clusters with n up to 20, while the larger clusters were transformed to glassy structures. The decrease in the glass transition temperature with the cluster size was observed to be much less than the corresponding melting temperature. The mutual order of the melting and glass-transition temperatures were found to be reversed compared with that observed for bulk water.     

Liquid water: A very complex fluid

Although H₂O has been the topic of considerable research since the beginning of the century, the peculiar physical properties are still not well understood. First we discuss some of the anomalies of this ‘complex fluid’. Then we describe a qualitative interpretation in terms of percolation concepts. Finally, we discuss recent experiments and simulations relating to the hyothesis that, in addition to the known critical point in water, there exists a ‘second’ critical point at low temperatures. In particular, we discuss very recent measurements of the compression-induced melting and decompression-induced melting lines of high-pressure forms of ice. We show how knowledge of these lines enables one to obtain an approximation for the Gibbs potential G(P, T) and the equation of state V(P,T) for water, both of which are consistent with the possible continuity of liquid water and the amorphous forms of solid water.     

Positronium decay and formation in paraffin wax from polarized and unpolarized positrons

Summary Ps formation and decay in heterogeneousn-alkane samples (paraffin waxes) have been studied both in the solid and in the liquid phase; then, in the solid phase, the positron's residual degree of polarization was measured at the instant of Ps formation. Differently from what is already known in homogeneousn-alkane samples, Ps shows, many degrees below the melting point, a mean lifetime longer than that typical of the liquid phase; furthermore, the mean lifetime's values pertaining to the transition between solid and liquid do not show a sharp variation across the melting temperature but gradually decrease over a range of temperatures of several degrees. Positronium decay in static magnetic fields indicates that o-Ps magnetic quenching in liquid phase is regular, and corresponds to a contact density value α=|ψ(0)|²/|ψ(0)|_vac ²=0.79±0.07; instead, in the solid phase, o-Ps magnetic quenching shows anomalous behaviour for fields weaker than 7kG. Positrons' residual polarization measurements do not reveal the presence of depolarization effects during the whole slowing-down process until Ps is formed.     

The NaNO3–KNO3 phase diagram

Many papers have been published in relation to the NaNO₃–KNO₃ phase diagram determination in the last 160 years. These papers fall in two categories: (1) the solid–liquid equilibrium is assumed to be of the eutectic type, and (2) the solid–liquid equilibrium is considered as a loop with a minimum. The discordance between the two views is related to the slow transition kinetics that complicate the assessment of thermal ‘fluctuations’, and also to the appearance of a metastable form of potassium nitrate. The main result of this paper is the experimental phase diagram constructed with new experimental data so that we can assure that the second option is correct. This phase diagram is defined by a eutectoid invariant, an asymmetric immiscibility gap and a continuous solid solution with a minimum of melting point. Additionally, the ABθ model simulates correctly the experimental piece of evidence.     

Titanium Melting Curve: Data Consistency Assessment,Problems and Achievements

Experimental data for the thermodynamic properties of titanium on the melting curve in the pressure range from atmospheric value to 90 GPa are analyzed and brought into correspondence. The problems that have been considered are (i) the lack of data for the solid β-phase density near the normal melting point and (ii) the formation probability of a triple point on the melting curve for the coexisting β-, ω-, and liquid phases of titanium. To estimate the change of the volume upon melting 3d elements from Mendeleev’s periodic system, a correlation between the change of the volume, ΔV _m , and the change of the entropy, ΔS _m , on the melting curve at atmospheric pressure is suggested and effectively used.     

Positron annihilation in solid and liquid metals

The angular correlation of the gamma rays resulting from the annihilation of positrons in 15 solid and liquid metals and semiconductors has been studied. Experiments have been done on each material at room temperature and at temperatures above and below the melting point.

The elements investigated fall into three categories according to the way the angular correlation distribution changes as the melting point is reached. To within the experimental angular resolution (0.5 milliradians) no change in the angular correlation distribution is observed for Li, Se, Na, and Tl upon heating from room temperature to beyond the melting point. The elements Sb, Bi, Ga, Hg, Sn and Te exhibit changes in their angular correlation distributions only upon being melted, whereas for the metals Al, Cd, In, Pb and Zn changes occur when the specimen is heated from room temperature to temperatures below the melting point.

Changes in the angular correlation distribution upon heating or melting are generally manifested as (a) a narrowing of the central part of the curve, (b) a rounding-off of the parts of the curve near the Fermi cut-off angle and (c) a change in the area of the broad background curve as compared with the area under the central peak.     

Calorimetric fragility of maltitol

The heat capacity of maltitol has been measured with an adiabatic calorimeter for the crystal from 100 K to 425 K (T _m = 420 K), for the glass from 249 K to T _g (around 311 K) and for the liquid from T _g to 400 K. The heat of melting is 55.068 kJ/mol. The calorimetric glass transition occurs at about T _g = 311 K with a sudden jump of the heat capacity ΔC _p (T _g ) of about 243.6 J/(K mol). The excess entropy between the undercooled liquid and the crystal was calculated from the heat capacity data and was used to estimate the Kauzmann temperature T _K which was found 50 K below T _g . ΔC _p (T _g ) and T _K for maltitol were compared to other compounds like sugars, polyol and hydrogen bonded liquids. It has been found that the glass former maltitol is a "fragile" liquid on the thermodynamic point of view.     

The melting mechanism in binary Pd0.25Ni0.75 nanoparticles: molecular dynamics simulations

The melting mechanism for Pd_0.25Ni_0.75 alloy nanoparticles (NPs) was investigated using molecular dynamics (MD) simulations with quantum Sutton-Chen many-body potentials. NPs of six different sizes ranging from 682 to 22,242 atoms were studied to observe the effect of size on the melting point. The melting temperatures of the NPs were estimated by following the changes in both the thermodynamic and structural quantities such as the total energy, heat capacity and Lindemann index. We also used a thermodynamics model to better estimate the melting point and to check the accuracy of MD simulations. We observed that the melting points of the NPs decreased as their sizes decreased. Although the MD simulations for the bulk system yielded higher melting temperatures because of the lack of a seed for the liquid phase, the melting temperatures determined for both the bulk material and the NPs are in good agreement with those predicted from the thermodynamics model. The melting mechanism proceeds in two steps: firstly, a liquid-like shell is formed in the outer regions of the NP with increasing temperature. The thickness of the liquid-like shell increases with increasing temperature until the shell reaches a critical thickness. Then, the entire Pd–Ni NP including core-related solid-like regions melts at once.     

Freezing and melting of binary mixtures confined in a nanopore

This paper reports on a Grand Canonical Monte Carlo study of the freezing and melting of Lennard–Jones Ar/Kr mixtures confined in a slit pore composed of two strongly attractive structureless walls. For all molar compositions and temperatures, the pore, which has a width of 1.44?nm, accommodates two contact layers and one inner layer. Different wall/fluid interactions are considered, corresponding to pore walls that have a larger affinity for either Ar or Kr. The solid/liquid phase diagram of the confined mixture is determined and results compared with data for the bulk mixture. The structure of the confined mixture is studied using 2D order parameters and both positional g(r) and bond orientational G₆(r) pair correlation functions. It is found that in the confined solid phase, both the contact and inner layers have a hexagonal crystal structure. It is shown that the freezing temperature of the Ar/Kr confined mixture is higher than the bulk freezing point for all molar compositions. Also, it is found that the freezing temperature becomes larger as the ratio α of the wall/fluid to the fluid/fluid interactions increases, in agreement with previous simulation studies on pure substances confined in nanopores. In the case of pore walls having a stronger affinity for Kr atoms (ε _Ar/W<ε _Kr/W), it is observed that both the contact and inner layers of the confined mixture undergo, at the same temperature, a transition from the liquid phase to the crystal phase. The freezing of Ar/Kr mixtures confined between the walls having a stronger affinity for Ar (ε _Ar/W?>?ε _Kr/W) is more complex: for Kr molar concentration lower than 0.35, we observe the presence of an intermediate state between all layers being 2D hexagonal crystals and all the layers being liquid. This intermediate state consists of a crystalline contact layer and a liquid-like inner layer. It is also shown that the qualitative variations of the increase of freezing temperature with the molar composition depend on the affinity of the pore wall for the different components. These results confirm that, in addition to the parameter α the ratio of the wall/fluid interactions for the two species, η=?_Ar/W/?_Kr/W, is a key variable in determining the freezing and melting behaviour of the confined mixture.     

Flowing liquid crystal simulating the Schwarzschild metric

We show how to simulate the equatorial section of the Schwarzschild metric through a flowing liquid crystal in its nematic phase. Inside a liquid crystal in the nematic phase, a traveling light ray feels an effective metric, whose properties are linked to perpendicular and parallel refractive indexes, n _o and n _e respectively, of the rod-like molecule of the liquid crystal. As these indexes depend on the scalar order parameter of the liquid crystal, the Beris-Edwards hydrodynamic theory is used to connect the order parameter with the velocity of a liquid crystal flow at each point. This way we calculate a radial velocity profile that simulates the equatorial section of the Schwarzschild metric, in the region outside of Schwarzschild’s radius, in the nematic phase of the liquid crystal. In our model, the higher flow velocity can be on the order of some meters per second.     

Study of oxygen vacancy ordering in mullite at high temperatures

High temperature X-ray diffraction and quenching experiments of mullite single crystals with Al₂O₃:SiO₂ ratio 2:1 have been performed to investigate the stability of the oxygen vacancy ordering close to the melting point of mullite. The experiments show that the structure of mullite exhibits an extremely stable, temperature-independent incommensurate modulation. Inspection of satellite reflections at different temperatures leads to the conclusion that the ordering scheme of oxygen vacancies after the crystallization of mullite persists to the melting point and does not show any disordering effects. The experimental results are in agreement with former theoretical calculations using a statistical mechanics approach which yield the critical temperature T_c > 3000°C.     

Evidence of maximum in the melting curve of hydrogen at megabar pressures

Hydrogen at high pressures of ∼400 GPa might be in a zero-temperature liquid ground state (N. Ashcroft, J. Phys.: Condens. Matter A 12, 129 (2000), E. G. Brovrnan et al., Sov. Phys. JETP 35, 783 (1972)). If metallic hydrogen is liquid, the melting T _melt(P) line should possess a maximum. Here we report on the experimental evaluation of the melting curve of hydrogen in the megabar pressure range. The melting curve of hydrogen has been shown to reach a maximum with T _melt = 1050 ± 60 K at P = 106 GPa and the melting temperature of hydrogen decreases at higher pressures so that T _melt = 880 ± 50 K at P = 146 GPa. The data were acquired with the aid of a laser heating technique where diamond anvils were not deteriorated by the hot hydrogen. Our experimental observations are in agreement with the theoretical prediction of unusual behavior of the melted hydrogen [S. Bonev et al., Nature 481, 669 (2004)]. The article is published in the original.     

不同势下铱团簇结构和熔化行为的分子动力学模拟

采用分子动力学方法及淬火技术,结合Gupta势和Sutton-Chen势,模拟研究了包含13,14,55,56,147及148个原子数的铱团簇的熔化行为. 结果表明,Gupta势和Sutton-Chen势对所研究的Ir团簇的基态几何结构和熔化行为给出了基本一致的描述：两种不同势给出了完全相同的基态几何结构;两种势给出的Ir团簇熔点及预熔化区间随团簇尺寸的变化关系基本一致;对于小Ir_n团簇（n=13,14）两类势均表现出比热峰值相对于均方根键长涨落饱和值滞后的现象. 但是 关键词： 铱团簇 分子动力学 Gupta势和Sutton-Chen势 熔化     

Physical study of bismuth alloys containing Pb,Sn and Cd

For the purpose of studying some physical properties in addition to the mechanism of the melting phenomena, five bismuth alloys Bi_55.5Pb_44.5, Bi₅₀Pb₂₅Sn₂₅, Bi₅₀Pb₂₅Cd₂₅, Bi₅₀Pb₂₅Sn_18.75Cd_6.25 and Bi₅₀Pb₂₅Sn_6.25Cd_18.75 of melting points in the range from 338.5 to 396.5 K were prepared and studied by different techniques. The near-surface materials have been characterized by microhardness together with the wetting characteristics on CuZn₃₀ substrates as a function of time. The mechanism of melting from the point of view of the order of reaction (n) was explored by applying two different techniques, namely, differential thermal analysis and the electrical resistivity as a function of temperature.     

Microscopic theory of a strongly correlated two-dimensional electron gas

The rearrangement of the Fermi surface in a diluted two-dimensional electron gas beyond the topological quantum critical point has been examined within an approach based on the Landau theory of Fermi liquid and a nonperturbative functional method. The possibility of a transition of the first order in the coupling constant at zero temperature between the states with a three-sheet Fermi surface and a transition of the first order in temperature between these states at a fixed coupling constant has been shown. It has also been shown that a topological crossover, which is associated with the joining of two sheets of the Fermi surface and is characterized by the maxima of the density of states N(T) and ratio C(T)/T of the specific heat to the temperature, occurs at a very low temperature T _⋄ determined by the structure of a state with the three-sheet Fermi surface. A momentum region where the distribution n(p, T) depends slightly on the temperature, which is manifested in the maximum of the specific heat C(T) near T _*, appears through a crossover at temperatures T ∼ T _* > T _⋄. It has been shown that the flattening of the single-particle spectrum of the strongly correlated two-dimensional electron gas results in the crossover from the Fermi liquid behavior to a non-Fermi liquid one with the density of states N(T) ∝ T ^−α with the exponent α }~ 2/3.