Melting of isolated tin nanoparticles

The melting of isolated neutral tin cluster distributions with mean sizes of about 500 atoms has been investigated in a molecular beam experiment by calorimetrically measuring the clusters' formation energies as a function of their internal temperature. For this purpose the possibility to adjust the temperature of the clusters' internal degrees of freedom by means of the temperature of the cluster source's nozzle was exploited. The melting point of the investigated tin clusters was found to be lowered by 125 K and the latent heat of fusion per atom is reduced by 35% compared to bulk tin. The melting behavior of the isolated tin clusters is discussed with respect to the occurrence of surface premelting.     

Low-temperature vibrational properties of tin nanoparticles in porous glass

The heat capacity has been studied in the temperature range 2.2–40 K and in magnetic fields up to 2 T in tin, which has been embedded in nanometer-size pores in glass having diameter ∼7 nm, in bulk tin and in glass with empty pores. Comparison of the properties of tin nanoparticles and bulk tin has been performed. An increase in the coefficient of electronic heat capacity has been found in nanostructured tin as compared with the bulk tin, and also a considerable deviation of the low-temperature lattice heat capacity from the Debye law in the temperature region T > 3 K has been found. The fact that the density of thermal vibrations in nanocrystalline tin for low energies is higher than in bulk tin has been established using low-temperature heat capacity data.     

Extreme superheating and supercooling of encapsulated metals in fullerenelike shells

Nanometer-sized tin and lead crystals exhibit drastically altered melting and solidification behavior when encapsulated in fullerenelike graphitic shells. The melting transitions of encapsulated Sn and Pb nanocrystals are shown in an in situ electron microscopy study to occur at unexpectedly high temperatures, significantly higher than the melting point of the corresponding bulk materials. Atomistic simulations are used to show that the driving force for superheating is a pressure buildup of up to 3 GPa, that prevails inside graphitic shells under electron irradiation.     

A facile way for preparing tin nanoparticles from bulk tin via ultrasound dispersion

In this paper, we reported a facile and rapid process to prepare tin nanoparticles from bulk tin via ultrasound dispersion. The morphology and structure of synthesized tin nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) and thermogravimetric analysis (TGA). The results show that the morphology of tin nanoparticles is spherical and the structure of tin nanoparticles has the same crystal structure as the bulk tin. In addition, the tribological property of tin nanoparticles as additives in oil is evaluated on a four-ball tester and the results show that tin nanoparticles exhibit good performance in wear.     

The origin of the redshift in Brillouin spectra of silica films containing tin nanoparticles

The abrupt change of velocity in surface acoustic waves in thin films of amorphous SiO_x containing nanometre scale -Sn crystals is shown to be directly associated with the size-dependent melting of the nanoparticles, confirming preliminary experiments. High resolution thin film powder diffraction using synchrotron radiation shows that the abrupt redshift in the Brillouin spectra satellites occurs at the same temperature as the melting of the nanoparticles, evident for the loss of the Bragg peaks. Effective medium theory is used to explain the origin of the anomaly. A central peak in the Brillouin spectrum, the intensity of which shows a maximum at the melting temperature, can be interpreted in terms of overdamped fluctuations in the dielectric function. The melting temperature as a function of particle size is in agreement with theoretical predictions. No evidence for strain could be found on the X-ray diffraction profiles; the a- and c-axis thermal expansion coefficients are the same as those in bulk tin. Received 30 March 2000 and Received in final form 24 July 2000     

Superheating and solid-liquid phase coexistence in nanoparticles with nonmelting surfaces

We present a phenomenological model of melting in nanoparticles with facets that are only partially wet by their liquid phase. We show that in this model, as the solid nanoparticle seeks to avoid coexistence with the liquid, the microcanonical melting temperature can exceed the bulk melting point and that the onset of coexistence is a first-order transition. We show that these results are consistent with molecular dynamics simulations of aluminum nanoparticles which remain solid above the bulk melting temperature.     

Correlation between the size-dependent melting and crystallization temperatures of metal nanoparticles

The correlation between the melting and crystallization temperatures of metal nanoparticles is investigated by means of the thermodynamic approach. Size-dependent variations in the melting temperature of aluminum, tin, and copper nanoparticles are calculated with allowance for the corresponding size dependences of surface tensions in solid and liquid phases and interfacial tension. Size-dependent variations in crystallization temperature are determined under the assumption that a certain effective surface layer (skin-layer) arises before melting.     

Tin oxide nanocubes, and tin-core/tin oxide-shell nanostructures, with and without a hollow interior

A number of nanoscale tin oxide structures including 2–5 nm tin oxide hollow nanoparticles, 3–5 nm tin oxide nanocubes, 80–120 nm tin-core/tin oxide-shell nanocubes, and hollow tin oxide nanocubes, have been prepared from phenanthroline (phen)-capped Sn nanoparticles. Transmission electron microscopy revealed the existence of a hollow interior in the tin-core/tin oxide-shell nanostructures. It is believed that the low melting Sn core was hollowed out by electron beam irradiation of the sample during microscopy. The 2–5 nm tin oxide hollow nanoparticles and 80–120 nm tin oxide hollow nanocubes had thin but stable shells capable of preserving the integrity of the large cavity within.     

Comparative investigation of microjetting generated from monocrystalline tin surface and polycrystalline tin surface under plane impact loading

With considering the scattering effect of grain boundary and the grain orientation, the molecular dynamics is used for the first time to comparatively investigate microjetting generated by monocrystalline tin surface and polycrystalline tin surface under plane impact loading in this work. The research results show that when the impact velocity is low, the scattering effect of grain boundary and different grain orientations in a polycrystalline tin will cause the sample to melt inhomogeneously, leading the shock wave front to attenuate, meanwhile, the inhomogeneous melting can result in jet deviating. Comparing with monocrystalline tin, the jet head velocity, jet velocity coefficient, and jet mass coefficient of polycrystalline tin at low impact velocity are all low. Moreover, as the impact velocity increases, this influence decreases and the microjetting results of polycrystalline tin and monocrystalline tin tend to be consistent with each other.     

纳米团簇熔化过程的分子动力学模拟

本文采用分子动力学结合嵌入原子多体势,模拟了不同半径的Ni纳米团簇的升温熔化过程,研究团簇尺寸对熔点和表面能的影响.模拟结果表明:团簇的熔点显著低于体材料的熔点.团簇熔化的过程首先是在团簇的表面出现预熔,然后向团簇内部扩展,直到整个团簇完全熔为液态.在模拟的纳米尺度范围内,团簇的熔点与团簇尺寸基本成线性关系.团簇的表面能随着团簇尺寸的增大而减小,而且表面能均高于体材料的表面能.     

Molecular dynamics simulations on the melting of gold nanoparticles

Molecular dynamics is employed to study the melting of bulk gold and gold nanoparticles. PCFF, Sutton-Chen and COMPASS force fields are adopted to study the melting point of bulk gold and we find out that the Sutton-Chen force field is the most accurate model in predicting the melting point of bulk gold. Consequently, the Sutton-Chen force field is applied to study the melting points of spherical gold nanoparticles with different diameters. Variations of diffusion coefficient, potential energy and translational order parameter with temperature are analyzed. The simulated melting points of gold nanoparticles are between 615～1115 K, which are much lower than that of bulk gold (1336 K). As the diameter of gold nanoparticle drops, the melting point also descends. The melting mechanism is also analyzed for gold nanoparticles.     

Surface theory of melting

We demonstrate that melting is a surface initiated process. The surface becomes unstable before the bulk and the process of melting consists in the unstable surface that proceeds into the otherwise stable bulk.     

Studies of pulsed laser melting and rapid solidification using amorphous silicon

Pulsed laser melting of ion implantation-amorphized silicon layers, and the subsequent solidification of undercooled liquid silicon, have been studied experimentally and theoretically. Measurements of the time of the onset of melting of amorphous silicon layers, during an incident laser pulse, have been combined with measurements of the duration of melting, and with modified melting model calculations to demonstrate that the thermal conductivity, K_a, of amorphous silicon is very low (K_a0.02 W/cm K). K_a is also found to be the dominant parameter determining the dynamical response of amorphous silicon to pulsed laser radiation; the latent heat of fusion and melting temperature of amorphous silicon are relatively unimportant. Transmission electron microscopy indicates that bulk (volume) nucleation occurs directly from the highly undercooled liquid silicon that can be prepared by pulsed laser melting of amorphous silicon layers at low laser energy densities. A modified thermal melting model has been constructed to simulate this effect and is presented. Nucleation of crystalline silicon apparently occurs at a nucleation temperature, T_n, that is higher than the temperature, T_a, of the liquid-to-amorphous phase transition. The model calculations demonstrate that the release of latent heat by bulk nucleation occurring during the melt-in process is essential to obtaining agreement with experimentally observed depths of melting. These calculations also show that this release of latent heat accompanying bulk nucleation can result in the existence of buried molten layers of silicon in the interior of the sample after the surface has solidified. It is pointed out that the occurrence of bulk nucleation implies that the liquid-to-amorphous phase transition (produced using picosecond or ultraviolet nanosecond laser pulses) cannot be explained by purely thermodynamic considerations.     

Thermodynamic model for the size-dependent melting of prism-shaped nanoparticles

We report on the size-dependent melting of prism-shaped nanoparticles based on thermodynamic model and applied to understand the melting of prism-shaped indium nanoparticles. It is shown here that the bulk melting temperature cannot be extrapolated from the nanoscale and the extrapolated value will always be lower than the bulk melting temperature as has been observed experimentally.     

Grain boundary wetting phase transition and analysis of the energy characteristics of grain boundaries in the Sns-(Zn/Sn)l system

Regularities of the interaction of tin grain boundaries (special Σ5 and general Σ17 〈001〉) and a Sn-Zn melt of equilibrium composition were studied. The grain boundary wetting phase transition temperature was determined; for Σ5 and Σ17, it is 216°C. More than 90% of the general grain boundaries were completely wetted by the melt over a range of temperatures, from the eutectic melting temperature to the tin melting temperature. It was shown that the anisotropy of interphase energy at the solid tin-Zn-Sn melt interface is 64 ± 10 mJ m^?2 at 216°C. The energies of the Σ5 and Σ17 grain boundaries in the range of 201–216°C were obtained on the basis of the experimental dependence of the dihedral angle on temperature.     

Disorder effect on heat capacity,self-diffusion coefficient,and choosing best potential model for melting temperature,in gold–copper bimetallic nanocluster with 55 atoms

Molecular dynamics simulation has been implemented for doping effect on melting temperature, heat capacity, self-diffusion coefficient of gold–copper bimetallic nanostructure with 55 total gold and copper atom numbers and its bulk alloy. Trend of melting temperature for gold–copper bimetallic nanocluster is not same as melting temperature copper–gold bulk alloy. Molecular dynamics simulation of our result regarding bulk melting temperature is consistence with available experimental data. Molecular dynamics simulation shows that melting temperature of gold–copper bimetallic nanocluster increases with copper atom fraction. Semi-empirical potential model and quantum Sutton–Chen potential models do not change melting temperature trend with copper doping of gold–copper bimetallic nanocluster. Self-diffusion coefficient of copper atom is greater than gold atom in gold–copper bimetallic nanocluster. Semi-empirical potential within the tight-binding second moment approximation as new application potential model for melting temperature of gold–copper bulk structure shows better result in comparison with EAM, Sutton–Chen potential, and quantum Sutton–Chen potential models.     

MEAM势与Tersoff势比较研究——碳化硅熔化与凝固行为

运用分子动力学方法对比模拟研究了碳化硅的体熔化、表面熔化和晶体生长过程.分别采用MEAM 势和Tersoff势两种势函数描述碳化硅.结果表明:体熔化时,两种势函数描述的SiC的原子平均能量、 Lindemann指数和结构有序参数与温度的变化关系相似,但MEAM势对应的体熔点(4250 K)比Tersoff势(4750 K) 的要高.表面熔化时,两种势函数描述的SiC在相同的过热度下熔化速度相近;而在相同的温度条件下,MEAM 作用的SiC表面熔化速度更快.这是由于MEAM势SiC的热力学熔点(3338 K)低于Tersoff势SiC的热力学熔点 (3430 K)的缘故.两种势函数作用的SiC在晶体生长方面差异很大.MEAM势SiC的晶体生长速度与过冷度有关, 过冷度约为400 K时晶体生长速度最快.但Tersoff势SiC晶体却在过冷度为0—1000 K的范围内均不能生长. 综合考虑,MEAM势比Tersoff势能更好地描述碳化硅的熔化和凝固行为.     

Solidification of tin on quasicrystalline surfaces

A two-phase alloy of β-Sn and Al₆₃Cu₂₅Fe₁₂ quasicrystal produced by melt-spinning was annealed and aged to form various microstructures of tin in a quasicrystalline (QC) or microcrystalline (MC) matrix. The morphology and structure of the interfaces was studied by scanning and transmission electron microscopy and was related to melting and solidification behavior of tin studied by differential scanning calorimetry. In a MC matrix the tin phase occurred as nanoparticles and solidified with an undercooling of about 35°C. In a QC matrix, tin formed intergranular layers on faceted matrix grains. Tin showed multiple solidification peaks in undercooling ranging from 8°C to 43°C, indicating several distinct nucleation sites which compete with each other and are selected kinetically. The interfacial energy (depending on the structural state of the matrix) had a more dominating effect on the solidification of tin than the size, shape and the distribution of the tin particles. It was also concluded that solidification of tin is easier on quasicrystalline surfaces than on aluminum.     

Étude expérimentale de la résistance thermique de contact entre l'étain en cours de fusion et un creuset refroidi

This paper deals with the analysis of the thermal contact conditions during the melting of tin on different cooled walls, for different heat situations and for different cooling flows. Two experimental set ups are studied. A polished nickel substrate covers the melting-pot of the first one. Semi intrinsic thermocouples are implemented to measure the temperature of the substrate. This will allow a better study of the thermal contact resistance distribution on the wall. The second melting-pot is made of copper. Its surface roughness is variable. The heat system is stronger. The results obtained with the first experimental set-up show that the thermal contact resistance is time-dependent and non-uniformly spread. However, the heat evacuation is relatively uniformly spread while the heat power increases. Tests carried out with the second experimental set-up point out huge temperature oscillations which are attributed to unstable thermal contact conditions. This thermal behaviour can be explained by the buckling of the tin crust. The apparition of buckling seems to be favoured by a higher dissipated power and by a higher thermal conductivity of the melting pot.     

Superheating and induced melting at semiconductor interfaces

We present ab initio density-functional simulations of the state of several semiconductor surfaces at temperatures near the bulk melting temperatures. We find that the solid-liquid phase-transition temperature at the surface can be altered via a microscopic (single-monolayer) coating with a different lattice-matched semiconducting material. Our results show that a single-monolayer GaAs coating on a Ge(110) surface above the Ge melting temperature can dramatically reduce the diffusion coefficient of the germanium atoms, going so far as to prevent melting of the bulk layers on the 10 ps time scale. In contrast, a single-monolayer coating of Ge on a GaAs(110) surface introduces defects into the bulk and induces melting of the top layer of GaAs atoms 300 K below the GaAs melting point. To our knowledge, these calculations represent the first ab initio investigation of the superheating and induced melting phenomena.