Search results for "Metastability"
showing 10 items of 262 documents
Nucleation in physical and nonphysical systems
2003
Abstract The aggregation of particles out of an initially homogeneous situation is well known in physics. Depending on the system under consideration and its control parameters, the cluster formation in a supersaturated (metastable or unstable) situation has been observed in nucleation physics as well as in other branches. We investigate the well-known example of condensation (formation of liquid droplets) in an undercooled vapour to conclude that the formation of bound states as a phase transition is related to transportation science. We present a comparison of nucleation in an isothermal–isochoric container with traffic congestion on a circular one-lane freeway. The analysis is based, in …
Computation of Unstable Binodals Not Requiring Concentration Derivatives of the Gibbs Energy
1998
The equilibrium of three liquid phases in a binary mixture implies the existence of tie lines and binodals that are different from the normal experimentally observable ones. First of all, there are the metastable extensions of the binodal built up by S/S tie lines. These S/S tie lines fulfill the equilibrium condition of the minimum of the Gibbs energy of the entire two-phase system. Both coexisting phases are located within the meta(stable) region. There are two additional types of tie lines: U/U (maximum of the Gibbs energy; both end points within the unstable area) and U/S tie lines (saddle point; one end point within the (meta)stable, the other within the unstable region). All types of…
Liquid-vapour phase behaviour of a symmetrical binary fluid mixture
1998
Using Monte-Carlo simulation and mean field calculations, we study the liquid-vapour phase diagram of a square well binary fluid mixture as a function of a parameter $\delta$ measuring the relative strength of interactions between particles of dissimilar and similar species. The results reveal a rich variety of liquid-vapour coexistence behaviour as $\delta$ is tuned. Specifically, we uncover critical end point behaviour, a triple point involving a vapour and two liquids of different density, and tricritical behaviour. For a certain range of $\delta$, the mean field calculations also predict a `hidden' (metastable) liquid-vapour binodal.
Demixing time and temperature influence on porosity and interconnection of PLLA scaffolds prepared via TIPS
2009
Scaffolds suitable for tissue engineering applications were prepared by Thermally Induced Phase Separation (TIPS) starting from a ternary solution PLLA/ dioxane/water. The experimental protocol consisted of three consecutive steps, a first quench from the homogeneous solution to an appropriate demixing temperature (within the binodal region), a liquid-liquid demixing stage for a given time and a final quench from the demixing temperature to a low temperature (within the spinodal region). A large variety of morphologies, in terms of average pore size and interconnection were obtained upon modifying the demixing time and temperature, owing to the interplay of nucleation and growth processes d…
Evidence for long-lived, optically generated quenchers of excitons in single-walled carbon nanotubes.
2011
The nonlinear dependence of near-infrared photoluminescence (PL) emission on excitation intensity has been measured for individual nanotubes representing six different (n,m) species. Significant deviations from linearity are observed for intensities as low as ~100 W/cm(2), and an approximate inverse correlation is found between nonlinearity and PL action cross section (brightness). A model in which all PL nonlinearity arises from exciton-exciton annihilation is insufficient to account for the experimental data using realistic parameters. It is proposed that additional nonlinear quenching arises from photoinduced quenching states or species with longer lifetimes than emissive excitons. Evide…
Nucleation mechanism for the direct graphite-to-diamond phase transition
2011
Graphite and diamond have comparable free energies, yet forming diamond from graphite is far from easy. In the absence of a catalyst, pressures that are significantly higher than the equilibrium coexistence pressures are required to induce the graphite-to-diamond transition. Furthermore, the formation of the metastable hexagonal polymorph of diamond instead of the more stable cubic diamond is favored at lower temperatures. The concerted mechanism suggested in previous theoretical studies cannot explain these phenomena. Using an ab initio quality neural-network potential we performed a large-scale study of the graphite-to-diamond transition assuming that it occurs via nucleation. The nucleat…
New Pressure-Induced Polymorphic Transitions of Anhydrous Magnesium Sulfate
2017
The effects of pressure on the crystal structure of the three known polymorphs of magnesium sulfate have been theoretically study by means of DFT calculations up to 45 GPa. We determined that at ambient conditions gamma MgSO4 is an unstable polymorph, which decompose into MgO and SO3, and that the response of the other two polymorphs to hydrostatic pressure is non isotropic. Additionally we found that at all pressures beta MgSO4 has a largest enthalpy than alpha MgSO4. This indicates that beta MgSO4 is thermodynamically unstable versus alpha MgSO4 and predicts the occurrence of a beta alpha phase transition under moderate compression. Our calculations also predict the existence under pressu…
Capillary Hysteresis in Nanopores: Theoretical and Experimental Studies of Nitrogen Adsorption on MCM-41
1995
Capillary hysteresis in cylindrical nanopores has been studied using MCM-41 as the prime example of a mesoporous material. These materials, due to their regular pore structure, can be considered to be candidates for reference adsorbents for standardizing adsorption measurements and methods for characterization of porous solids. They provide a unique opportunity for verification of theoretical models employed for predicting phase equilibrium in confined geometry. Three samples with monodisperse pore channels have been synthesized and examined using X-ray diffraction (XRD). Nitrogen adsorption isotherms were modeled using nonlocal density functional theory (NLDFT) in a wide range of pore size…
Interplay between spin crossover and proton migration along short strong hydrogen bonds
2021
The iron(ii) salt [Fe(bpp)2](isonicNO)2·HisonicNO·5H2O (1) (bpp = 2,6-bis(pyrazol-3-yl)pyridine; isonicNO = isonicotinate N-oxide anion) undergoes a partial spin crossover (SCO) with symmetry breaking at T1 = 167 K to a mixed-spin phase (50% high-spin (HS), 50% low-spin (LS)) that is metastable below T2 = 116 K. Annealing the compound at lower temperatures results in a 100% LS phase that differs from the initial HS phase in the formation of a hydrogen bond (HB) between two water molecules (O4W and O5W) of crystallisation. Neutron crystallography experiments have also evidenced a proton displacement inside a short strong hydrogen bond (SSHB) between two isonicNO anions. Both phenomena can al…
Spatial separation of atomic states in a laser cooled ion crystal
1999
A laser cooled ion crystal containing several hundred Ca+ ions has been stored in a linear Paul trap. Cooling is provided by a red detund laser at the 4S1/2−4P1/2 resonance transition. A second laser serves for repumping of those ions which decay from the excited 4P1/2 level to the metastable 3D3/2 state. The ions can be additionally excited by a third laser to a long lived metastable 3D5/2 energy level which decouples them from the cooling laser radiation. The light pressure acting upon the laser cooled ions pushes them into the direction of the laser beam. The ions in the metastable 3D5/2 state, however, do not experience any light pressure force and diffuse to the crystal side which poin…