Gas-solid Phase Transition Research Articles

Two-dimensional bilayer ice in coexistence with three-dimensional ice without confinement

Icing plays an important role in various physical-chemical process. Although the formation of two-dimensional ice requires nanoscale confinement, two-dimensional bilayer ice in coexistence with three-dimensional ice without confinement remains poorly understood. Here, a critical value of a surface energy parameter is identified to characterize the liquid-solid interface interaction, above which two-dimensional and three-dimensional coexisting ice can surprisingly form on the surface. The two-dimensional ice growth mechanisms could be revealed by capturing the growth and merged of the metastable edge structures. The phase diagram about temperature and pressure vs energy parameters is predicted to distinguish liquid water, two-dimensional ice and three-dimensional ice. Furthermore, the deicing characteristics of coexisting ice demonstrate that the ice adhesion strength is linearly related to the ratio of ice-surface interaction energy to ice temperature. In addition, for gas-solid phase transition, the phase diagram about temperature and energy parameters is predicted to distinguish gas, liquid water, two-dimensional ice and three-dimensional ice. This work gives a perspective for studying the singular structure and dynamics of ice in nanoscale and provides a guide for future experimental realization of the coexisting ice.

Simulation of the micro-gas desublimation crystallization during pressurization of cryogenic propellant

The desublimation crystallization of trace impurity gas at the temperature of liquid hydrogen and liquid oxygen is a common problem in cryogenic engineering, which usually leads to the failure of cryogenic liquid transportation. Liquid hydrogen and liquid oxygen are important aerospace propellants. In the pressurization process of cryogenic liquid propellant, a small amount of water vapor and other gases in the pressurized gas would appear desublimation and crystallization at low temperature. Inevitably, as the tail gas of hydrogen combustion, water vapor sometimes diffused into cryogenic liquid. This kind of desublimation crystallization was accompanied by heat and mass transfer, accompanied by gas-solid phase transition, moving boundary, random and extremely complicated crystallization growth process. It was of great engineering practical significance to study the heat and mass transfer mechanism and law of this complex desublimation phase change phenomenon for the progress and development of engineering technologies such as refrigeration, cryogenics and aerospace. In this paper, based on the homogeneous desublimation theory, the pressurization system of liquid oxygen tank with oxygen containing trace water vapor was taken as the research object, and the basic data of ice crystal formation and growth during pressurization, such as crystallization quantity, crystallization speed and size distribution, were calculated theoretically. It provided a theoretical basis for the experimental study of the real dynamic characteristics and laws of desublimation crystallization in the propulsion system. The research methods and conclusions in this paper also had some guiding significance for the use of liquid hydrogen in the storage, transportation and use of the hydrogen energy.

A framework to simulate the blowout of CO2 through wells in geologic carbon storage

It is important to evaluate the risks associated with CO2 leakage in large scale carbon capture and storage (CCS) projects. Leaky wells are considered a major concern for potential CO2 leakage in geologic carbon storage. The most rapid and spectacular mode of CO2 leakage is the blowout of a CO2 storage well. The Sheep Mountain CO2 blowout in March 1982 is an example of this type of catastrophe wherein several thousand tons of CO2 were released into the atmosphere every day. The blowout was stopped only in early April. In the current work we present a numerical framework to simulate blowouts of CO2 wells accounting for the supercritical-liquid–gas–solid phase transitions of CO2 during the process. It is an in-house finite volume method based code for CO2 transport in open wells, relying on a hybrid Span–Wagner equations of state. We present extensive verification and validation of the code against numerical and experimental data in the literature. When applied to well blowouts, our numerical method is able to identify the locations along the well where CO2 transitions between its different phases. Our simulations show that while the heat transfer between CO2 and the casing has a significant impact on the transient characteristics of the blowout, it does not affect the steady-state leakage rate significantly. We also find that the CO2 leakage rate increases as the total depth of the well increases, with an average leakage rate of 2.09×104 tons per day across all the well depths simulated ranging between 1 km and 3.5 km. Our simulations show that when the temperature and pressure at the well bottom are appreciably lower than the geothermal temperature and hydrostatic pressure at the given depth, CO2 is released as dry ice at the wellhead. The dry ice modeled here has a significant time-averaged mass fraction of 30% at quasi-steady state, and causes rapid fluctuations in the CO2 leakage rate.

Numerical modeling of the formation of D-T mixture spherical layer in micro-targets of LTS

The article presents a two-dimensional economical computational model of the formation of D-T mixture cryogenic layer in a spherical shell. The model is based on the description of the motion of the gas phase in the Boussinesq approximation. The thermal problem is a Stefan problem with a gas-solid phase transition. The technique is based on the finite volume method, the use of a structured mobile grid, whose movement is associated with the separation of the phase front, implicit approximations and the method of splitting two-dimensional equations in directions into one-dimensional equations. It is numerically shown that, due to natural radioactivity, the target is symmetrized. A calculated estimation of the symmetrization time for one geometry of the target with different filling coefficients is carried out.

Dielectrophoresis and colloidal phase transitions for ultra-broadband optical limiting

We demonstrate wavelength-independent optical limiting based on colloidal phase transitions induced by the dielectrophoretic force from focused electromagnetic radiation. The focused radiation acts as an optical trap that increases the particle density. The increased density then leads to a colloidal gas-solid phase transition and an aggregate that effectively blocks the incoming radiation when it passes a threshold power. The process is reversible, with the colloidal particles returning to a homogenous distribution after the incoming radiation is removed. We demonstrate the effect using polystyrene nanoparticles mixed with pluronics and polyethylene glycol polymers in low-concentration KCl salt solutions. We observe the light-induced phase separation under confocal fluorescent microscope, and we provide a proof-of-principle demonstration of optical limiting using a 100μm thick colloid cell.

The Inverse-Square Interaction Phase Diagram: Unitarity in the Bosonic Ground State

Ground-state properties of bosons interacting via inverse square potential (three dimensional Calogero-Sutherland model) are analyzed. A number of quantities scale with the density and can be naturally expressed in units of the Fermi energy and Fermi momentum multiplied by a dimensionless constant (Bertsch parameter). Two analytical approaches are developed: the Bogoliubov theory for weak and the harmonic approximation (HA) for strong interactions. Diffusion Monte Carlo method is used to obtain the ground-state properties in a non-perturbative manner. We report the dependence of the Bertsch parameter on the interaction strength and construct a Padé approximant which fits the numerical data and reproduces correctly the asymptotic limits of weak and strong interactions. We find good agreement with beyond-mean field theory for the energy and the condensate fraction. The pair distribution function and the static structure factor are reported for a number of characteristic interactions. We demonstrate that the system experiences a gas-solid phase transition as a function of the dimensionless interaction strength. A peculiarity of the system is that by changing the density it is not possible to induce the phase transition. We show that the low-lying excitation spectrum contains plasmons in both phases, in agreement with the Bogoliubov and HA theories. Finally, we argue that this model can be interpreted as a realization of the unitary limit of a Bose system with the advantage that the system stays in the genuine ground state contrarily to the metastable state realized in experiments with short-range Bose gases.

Perfluoropentacene adsorption on Cu(110)

The adsorption of perfluoropentacene (PFP) on the Cu(110) surface has been investigated using reflectance difference spectroscopy (RDS), low-energy electron diffraction, and low-temperature scanning tunneling microscopy. The PFP molecules within the first monolayer align their long molecular axis exclusively oriented along the [001] azimuthal direction of the Cu substrate. In comparison with the adsorption behavior of pentacene on the same surface, a strong effect of the fluorination regarding the molecular orientation and the intermolecular and molecule-substrate interactions was identified. Furthermore, a two-dimensional gas-solid phase transition accompanied by a reversible azimuthal rotation of the PFP molecules was observed at the beginning of the second monolayer growth. The change of the optical anisotropy associated with this reorientation was used to explore the two-dimensional (2D) condensation as a function of coverage and temperature by RDS, and the 2D heat of condensation in the PFP bilayer on Cu(110) was determined to be 105 meV.

Gas-Solid Phase Transition in Laser Multiple Filamentation.

While propagating in transparent media, near-infrared multiterawatt (TW) laser beams break up in a multitude of filaments of typically 100-200um diameter with peak intensities as high as 10 to 100 TW/cm^{2}. We observe a phase transition at incident beam intensities of 0.4 TW/cm^{2}, where the interaction between filaments induce solidlike two-dimensional crystals with a 2.7mm lattice constant, independent of the initial beam diameter. Below 0.4 TW/cm^{2}, we evidence a mixed phase state in which some filaments are closely packed in localized clusters, nucleated on inhomogeneities (seeds) in the transverse intensity profile of the beam, and other are sparse with almost no interaction with their neighbors, similar to a gas. This analogy with a thermodynamic gas-solid phase transition is confirmed by calculating the interaction Hamiltonian between neighboring filaments, which takes into account the effect of diffraction, Kerr self-focusing, and plasma generation. The shape of the effective potential is close to a Morse potential with an equilibrium bond length close to the observed value.

Thermokinetic characterisation of tin(II) chloride

Thermokinetic behaviour of SnCl2 was investigated using differential scanning calorimetry and thermogravimetry techniques under non-isothermal conditions in air, complemented by electron microscopy and Raman spectroscopy. According to the results obtained, the oxidation of SnCl2 at the heating rates of 5 and 100 °C min−1 leads to the in situ formation of highly crystalline SnO2 nanostructures in the form of nanoparticles and nanorods, respectively. The oxidation of SnCl2 was found to be a liquid–solid (LS) phase transition at the heating rates equal or lower than 10 °C min−1 and a gas–solid phase transition at the heating rates equal or greater than 20 °C min−1. The activation energy of melting, vaporisation and LS oxidation of SnCl2 was determined to be 198, 93 and 91 kJ mol−1, respectively.

Magnesium vapor nucleation in phase transitions and condensation under vacuum conditions

Recent findings related to coagulable magnesium vapor nucleation and growth in vacuum were assessed critically, with emphasis on understanding these processes at a fundamental molecular level. The effects of magnesium vapor pressure, condensation temperature, and condensation zone temperature gradient on magnesium vapor nucleation in phase transitions and condensation from atomic collision and coacervation with collision under vacuum conditions were discussed. Magnesium powder and magnesium lump condensates were produced under different conditions and characterized by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS). The right condensation zone temperature approach to the liquid transition primarily improved the magnesium vapor concentration rate. The gas–solid phase transition was primarily inhibited by setting a small condenser temperature gradient. Under the right condensation temperature and temperature gradients, increasing magnesium vapor partial pressure improved crystallization and reduced the oxidation rate.

Microphase formation at a 2D solid-gas phase transition.

Density modulated micro-separated phases (microphases) occur at 2D liquid interfaces in the form of alternating regions of high and low density domains. Brewster angle microscopy (BAM) images demonstrate the existence of microphases in cluster, stripe, and mosaic morphologies at the buried interface between hexane and water with fluoro-alkanol surfactant dissolved in the bulk hexane. At high temperature, the surfactant assembles at the interface in a 2D gaseous state. As the system is cooled additional surfactants condense onto the interface, which undergoes a 2D gas-solid phase transition. Microphase structure is observed within a few degrees of this transition in the form of clusters and labyrinthine stripes. Microphases have been observed previously in a number of other systems; nevertheless, we demonstrate that adsorption transitions at the liquid-liquid interface provide a convenient way to observe a full sequence of temperature-dependent 2D phases, from gas to cluster to stripe to mosaic to inverted stripe phases, as well as coexistence between some of these microphases. Cracking and fracture of the clusters reveal that they are a solid microphase. Theories of microphases often predict a single length scale for cluster and stripe phases as a result of the competition between an attractive and a repulsive interaction. Our observation that two characteristic length scales are required to describe clusters whose diameter is much larger than the stripe period, combined with the solid nature of the clusters, suggests that a long-range elastic interaction is relevant. These results complement earlier X-ray measurements on the same system.

Azimuthal Reorientation of Pentacene upon 2D Condensation

We report a novel two-dimensional gas-solid phase transition of pentacene molecules on the Cu(110)-(2 × 1)O surface where the 2D condensation is accompanied by a reversible azimuthal rotation of the pentacene molecules. The change of the optical anisotropy associated with this reorientation allows us to explore the 2D condensation as a function of coverage and temperature by reflectance difference spectroscopy. As a result, the 2D heat of condensation of pentacene on Cu(110)-(2 × 1)O is determined to be 84 meV, which is more than one order of magnitude smaller than the respective value for 3D crystallization.

Mechanics of Growing Solids and Phase Transitions

Phase transitions can be usually observed in nature and technology which effectively utilize certain types of these transitions. An approach to modeling phase transition processes on the basis of the mathematical theory of growing solids is developed. Liquid-solid and gas-solid phase transitions are under consideration. Main attention is paid to the processes of solid phase growth and deformation.

Two-Dimensional Spin-Polarized Hydrogen at Zero Temperature

The ground-state properties of spin polarized hydrogen H↓ in two dimensions (2D) are obtained by means of diffusion Monte Carlo calculations. Using the most accurate to date ab initio H↓–H↓ interatomic potential we have studied hydrogen gas phase, from the very dilute regime until densities above its freezing point. For very low densities, the equation of state of the gas can be described in terms of the gas parameter na 2, where a is the s-wave scattering length in 2D. The solid phase in 2D has also been studied up to high pressures and the gas-solid phase transition determined using the double-tangent Maxwell construction.

On the theory of phase transitions in magnetic fluids

Particles of magnetic fluids (ferrofluids), as is known from experiments, can condense to bulk dense phases at low temperatures (that are close to room temperature) in response to an external magnetic field. It is also known that a uniform external magnetic field increases the threshold temperature of the observed condensation, thus stimulating the condensation process. Within the framework of early theories, this phenomenon is interpreted as a classical gas-liquid phase transition in a system of individual particles involved in a dipole-dipole interaction. However, subsequent investigations have revealed that, before the onset of a bulk phase transition, particles can combine to form a chain cluster or, possibly, a topologically more complex heterogeneous cluster. In an infinitely strong magnetic field, the formation of chains apparently suppresses the onset of a gas-liquid phase transition and the condensation of magnetic particles most likely proceeds according to the scenario of a gas-solid phase transition with a wide gap between spinodal branches. This paper reports on the results of investigations into the specific features of the condensation of particles in the absence of an external magnetic field. An analysis demonstrates that, despite the formation of chains, the condensation of particles in this case can proceed according to the scenario of a gas-liquid phase transition with a critical point in the continuous binodal. Consequently, a uniform magnetic field not only can stimulate the condensation phase transition in a system of magnetic particles but also can be responsible for a qualitative change in the scenario of the phase transition. This inference raises the problem regarding a threshold magnetic field in which there occurs a change in the scenario of the phase transition.

Quantum Monte Carlo simulation of spin-polarized H

The ground-state properties of spin polarized hydrogen $\mathrm{H}\ensuremath{\downarrow}$ are obtained by means of diffusion Monte Carlo calculations. Using the most accurate to date ab initio $\mathrm{H}\ensuremath{\downarrow}\text{\ensuremath{-}}\mathrm{H}\ensuremath{\downarrow}$ interatomic potential we have studied its gas phase, from the very dilute regime until densities above its freezing point. At very small densities, the equation of state of the gas is very well described in terms of the gas parameter $\ensuremath{\rho}{a}^{3}$, with $a$ the $s$-wave scattering length. The solid phase has also been studied up to high pressures. The gas-solid phase transition occurs at a pressure of $173\phantom{\rule{0.3em}{0ex}}\mathrm{bar}$, a much higher value than suggested by previous approximate descriptions.

Spoilt for choice: assessing phase behavior models for the evolution of homochirality

The observation of single chirality in biological systems has intrigued scientists for more than one hundred years. Here we discuss several recent experimental studies showing amplification of enantiomeric excess based on amino acid phase behavior. Comparing observations of solution-solid and gas-solid phase transitions highlights the underlying fundamental physical chemistry principles that rationalize the observed enantioenrichment in both cases.

Gas-liquid phase separation in oppositely charged colloids: Stability and interfacial tension

We study the phase behavior and the interfacial tension of the screened Coulomb (Yukawa) restricted primitive model (YRPM) of oppositely charged hard spheres with diameter sigma using Monte Carlo simulations. We determine the gas-liquid and gas-solid phase transitions using free energy calculations and grand-canonical Monte Carlo simulations for varying inverse Debye screening length kappa. We find that the gas-liquid phase separation is stable for kappasigma<or=4, and that the critical temperature decreases upon increasing the screening of the interaction (decreasing the range of the interaction). In addition, we determine the gas-liquid interfacial tension using grand-canonical Monte Carlo simulations. The interfacial tension decreases upon increasing the range of the interaction. In particular, we find that simple scaling can be used to relate the interfacial tension of the YRPM to that of the restricted primitive model, where particles interact with bare Coulomb interactions.

Theoretical investigation of the coexistence of α and β-nitric acid trihydrates (NAT) molecular conformations

In this letter we document the possibility of the existence of a second molecular configuration for nitric acid trihydrates. Density functional theory (DFT) methods have been used for studying the nitric acid trihydrates α and β-NAT conformations, their spectroscopic and thermodynamics properties and dipole moments have been calculated. This study describes the gas–solid phase transition of the NAT and provides two possible pathways for the molecular structure transformation between α and β-NAT.

Possible flakes of molecular hydrogen in the early Universe

The thermochemistry of H 2 and HD in non-collapsed, non-reionized primordial gas up to the end of the dark age is investigated with recent radiation-matter and chemical reaction rates taking into account the efficient coolant HD, and the possibility of a gas-solid phase transition of H 2 . In the standard big-bang model we find that these molecules can freeze out and lead to the growth of flakes of solid molecular hydrogen at redshifts z 6-12 in the unperturbed medium and under-dense regions. While this freezing caused by the mere adiabatic cooling of the expanding matter is less likely to occur in collapsed regions due to their higher than radiation background temperature, on the other hand the super-adiabatic expansion in voids strongly favors it. Later reionization (at z 5-6) eventually destroys all these H 2 flakes. The possible occurrence of H 2 flakes is important for the degree of coupling between matter and radiation, as well as for the existence of a gas-grain chemistry at the end of the dark age.