Anisotropic surface melting in lyotropic cubic crystals

From experiments with metal crystals, in the vicinity of their crystal/liquid/vapor triple points, it is known that melting of crystals starts on their surfaces and is anisotropic. Recently, we have shown that anisotropic surface melting occurs also in lyotropic systems. In our previous paper (Eur. Phys. J. E 19, 223 (2006)), we have focused on the case of poor faceting at the Pn3m/L1 interface in C12EO2/water binary mixtures. There anisotropic melting occurs in the vicinity of a Pn3m/L3/L1 triple point. In the present paper, we focus on the opposite case of a rich devil's-staircase-type faceting at Ia3d/vapor interfaces in monoolein/water and phytantriol/water mixtures. We show that anisotropic surface melting takes place in these systems in a narrow humidity range close to the Ia3d-L2 transition. As whole (hkl) sets of facets disappear one after another when the transition is approached, surface melting occurs in a facet-by-facet type.     

Ratchet effect in faceting

The paper deals with a new phenomenon, named ratchet effect, envisioned theoretically as a likely consequence of metastability of crystal facets and expected to occur upon a temperature cycling. In experiments, Pn3m lyotropic crystals surrounded by the isotropic L1 phase in the mixture C₁₂EO₂/water are used. At equilibrium, the Pn3m/L1 interface contains small (111)-type facets in coexistence with rough surfaces. In agreement with theoretical expectations, it is shown that upon a saw-tooth-shaped temperature cycling, facets are growing until the rough surfaces are completely eliminated. A model of the ratchet effect is proposed.Received: 8 January 2004, Published online: 25 March 2004PACS: 64.70.Md Phase transitions in liquid crystals - 68.35.Md Surface thermodynamics, surface energies - 61.30.-v Liquid crystals     

Concave and convex shapes of the Pn3m/L1 interface

Shapes of the interface between the L1 and cubic Pn3m phases in the mixture C₁₂EO₂/water are studied. The concave and convex variants of the interface are realised using Pn3m crystals surrounded by the L1 phase and L1 inclusions on surfaces and in the bulk of the Pn3m phase. It is shown that both variants of the Pn3m/L1 interface contain the (111)-type facets in coexistence with everywhere else rough surfaces. The matching between facets and curved parts of the interface is angular. In the vicinity of the upper limit of the L1 + Pn3m coexistence domain, additional (200)-type facets appear on the interface. The influence of the contact angle at glass walls on shapes of crystals and of inclusions is discussed.Received: 16 June 2003, Published online: 11 November 2003PACS: 64.70.Md Phase transitions in liquid crystals - 68.35.Md Surface thermodynamics, surface energies - 61.30.-v Liquid crystals     

Structure and fluctuations of the premelted liquid film of ice at the triple point

ABSTRACT

In this paper, we study the structure of the ice/vapour interface in the neighbourhood of the triple point for the TIP4P/2005 model. We probe the fluctuations of the ice/film and film/vapour surfaces that separate the liquid film from the coexisting bulk phases at basal, primary prismatic and secondary prismatic planes. The results are interpreted using a coupled sine Gordon plus Interface Hamiltonian model. At large length scales, the two bounding surfaces are correlated and behave as a single complex ice/vapour interface. For small length, on the contrary, the ice/film and film/vapour surfaces behave very much like independent ice/water and water/vapour interfaces. The study suggests that the basal facet of the TIP4P/2005 model is smooth, the prismatic facet is close to a roughening transition, and the secondary prismatic facet is rough. For the faceted basal face, our fluctuation analysis allows us to estimate the step free energy in good agreement with experiment. Our results allow for a quantitative characterisation of the extent to which the adsorbed quasi-liquid layer behaves as water and explains experimental observations which reveal similar activation energies for crystals grown in bulk vapour or bulk water.     

Melting and nonmelting of solid surfaces and nanosystems

We present an extensive but concise review of our present understanding, largely based on theory and simulation work from our group, on the equilibrium behavior of solid surfaces and nanosystems close to the bulk melting point. In the first part we define phenomena, in particular surface melting and nonmelting, and review some related theoretical approaches, from heuristic theories to computer simulation. In the second part we describe the surface melting/nonmelting behavior of several different classes of solids, ranging from van der Waals crystals, to valence semiconductors, to ionic crystals and metals. In the third part, we address special cases such as strained solids, the defreezing of glass surfaces, and rotational surface melting. Next, we digress briefly to surface layering of a liquid metal, possibly leading to solid-like or hexatic two-dimensional phases floating on the liquid. In the final part, the relationship of surface melting to the premelting of nanoclusters and nanowires is reviewed.     

An intermediate monoclinic phase and electromechanical interactions in xPbTiO3-(1−x)Pb(Zn1/3Nb2/3)O3 crystals

The elastic matching of phases in the vicinity of the morphotropic phase boundary in xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ crystals is investigated in an external electric field with strength E ‖ [001]. The field dependences of the unit cell parameters of the monoclinic phase are determined experimentally in the range 0≤E≤2 MV/m. The results obtained are used in analyzing specific features in the electromechanical properties of xPbTiO₃-(1?x)Pb(Zn_1/3Nb_2/3)O₃ crystals (0.08?x?0.09), in which the monoclinic phase is intermediate between the rhombohedral and tetragonal phases and can coexist with these phases. A correlation between the optimum volume concentrations of domains or twins in different two-phases states is revealed and interpreted for the first time.     

Melting mechanism of monolayers adsorbed in cylindrical pores: An influence of the pore wall roughness

We have analyzed the mechanism of melting of layers adsorbed in cylindrical pores of porous materials. The goal was to understand the melting mechanism of simple fluids adsorbed in pores with heterogeneous wall surface. The studied system was a monolayer of methane molecules adsorbed in MCM-41 pore of diameter d = 4 nm. Both experimental (neutron scattering) and simulation (Monte Carlo) results proved extremely strong influence of the wall roughness on the melting mechanism. The most striking difference between melting on smooth and rough surfaces was in the temperatures of the transition. The transformation between solid-like and liquid-like monolayer phases adsorbed on a rough surface was observed in a very large temperature range and the solid like properties were observed even above the bulk methane melting temperature.     

Nematic liquid crystals at rough and fluctuating interfaces

Nematic liquid crystals at rough and fluctuating interfaces are analyzed within the Frank elastic theory and the Landau–de Gennes theory. We study specifically interfaces that locally favor planar anchoring. In the first part we reconsider the phenomenon of Berreman anchoring on fixed rough surfaces, and derive new simple expressions for the corresponding azimuthal anchoring energy. Surprisingly, we find that for strongly aligning surfaces, it depends only on the geometrical surface anisotropy and the bulk elastic constants, and not on the precise values of the chemical surface parameters. In the second part, we calculate the capillary waves at nematic-isotropic interfaces. If one neglects elastic interactions, the capillary wave spectrum is characterized by an anisotropic interfacial tension. With elastic interactions, the interfacial tension, i.e., the coefficient of the leading q² term of the capillary wave spectrum, becomes isotropic. However, the elastic interactions introduce a strongly anisotropic cubic q³ term. The amplitudes of capillary waves are largest in the direction perpendicular to the director. These results are in agreement with previous molecular dynamics simulations.     

Superheating in metal nanoparticles with non-melting surfaces

We construct microcanonical caloric curves for aluminium nanoparticles with non-melting surface facets and diameters of up to 11 nm using molecular dynamics simulations. We find that fcc aluminium particles can be superheated above the bulk melting temperature, but only for a finite range of particle sizes i.e. diameters between 5–9 nm. We also observe a critical particle size where solid-liquid phase coexistence becomes stable, and a second larger critical size where premelted (100) facets can coexist with solid (111) facets. Ultimately, it is the premelting of the (100) facets that appears to limit the superheating effect in these particles.     

Yang-Lee zeros of the Potts model

The Yang-Lee zeros of the three-component ferromagnetic Potts model in one dimension in the complex plane of an applied field are determined. The phase diagram consists of a triple point where three phases coexist. Emerging from the triple point are three lines on which two phases coexist and which terminate at critical points (Yang-Lee edge singularity). The zeros do not all lie on the imaginary axis but along the three two-phase lines. The model can be generalized to give rise to a tricritical point which is a new type of Yang-Lee edge singularity. Gibbs phase rule is generalized to apply to coexisting phases in the complex plane.Supported in part by the National Science Foundation under Grant No. DMR-81-06151.     

Steady state shapes of periodic profiles on (110), (100), and (111) surfaces of nickel

Periodic surface profiles with amplitudes of ≦0.4 μm and periodicities of 4–20 μm were prepared on Ni(110), (100), and (111) single crystal surfaces. These crystals were annealed in ultra-high vacuum (UHV) at 1073–1327 K after they had been cleaned by Ar ion bombardment and investigated by Auger electron spectroscopy. The geometry of the profiles was studied in UHV by laser diffraction and outside the vacuum by interference microscopy. The profiles have sinusoidal shapes on Ni(110) but trapezoidal shapes on both the (100) and (111) surfaces. This type of faceting can be understood on the basis of the anisotropic surface energy of Ni, with cusps at the (100) and (111) orientations. Model calculations show in the case of anisotropic surface energy that periodic profiles develop facets which correspond to the low surface energy orientations (close-packed surfaces).     

Computer simulations of the effect of atomic structure and coordination on the stabilities and melting behaviour of copper surfaces and nano-particles

We have studied the structures and stabilities of copper nano-particles and the melting properties of copper surfaces using interatomic potential-based molecular dynamics simulations, where the (1 1 1) surface has been shown to be the most stable in terms of surface energy and melting behaviour. Low energy shapes of nano-particles are influenced by the surfaces present and therefore have a higher proportion of (1 1 1) surface. The effect of surface structure on stability becomes less marked as the size of the nano-particle is increased. Melting is observed to occur below the bulk melting temperature in all the surfaces investigated, at increasingly lower temperatures from the (1 1 1), (1 0 0), (1 1 0) down to the (2 1 0) surface, confirming their order of decreasing stability. The melting processes of defective close-packed copper surfaces were also simulated. Steps, kinks, and facets were all shown to accelerate the melting of the surfaces. The melting is shown to initiate at the site of the defect and the results demonstrate that it is the low-coordinated atoms, at the step edge or kink, that are more mobile at lower temperatures. These features facilitate surface melting even further below the melting temperature than was observed for the perfect surfaces. Furthermore, facets of (1 0 0) surface were shown to be unstable even at moderate temperatures on the close-packed surface.     

Local melting/solidification during peritectic solidification in a steep temperature gradient: analysis of a directionally solidified Al–25at%Ni

Melting of primary Al₃Ni₂ phase and solidification of Al₃Ni peritectic phase during directional solidification of an Al–25at%Ni peritectic alloy have been investigated. In a steep temperature gradient of up to 50 K/mm and at a pulling rate of 20 μm/s, an incomplete coverage of peritectic Al₃Ni phase on the surface of the primary Al₃Ni₂ phase has been observed. Below the peritectic temperature in the presence of the incomplete coverage, melting of primary Al₃Ni₂ on the one side and solidification to the Al₃Ni peritectic phase on the other side proceed swiftly via diffusion through the interphase liquid layer. Theoretical calculations based on an incomplete-coverage-related melting/solidification model are in close agreement with the experimental measurements.     

Surface supercooling and stability of n-alkane films

The surface tension of n-octadecane was studied in the vicinity of the bulk melting point using both the maximum bubble pressure and Wilhelmy plate methods. The bubble surfaces were found to be supercooled below the surface freezing point. The onset of surface freezing is indicated by a sharp drop in surface tension at a constant temperature. This transition is accompanied by an increased film stability resulting in longer bubble lifetimes at the liquid surface. Variations in bubble lifetime reflect changes in the interfacial mechanical properties of the film from liquidlike to solidlike.     

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.     

MgO粒子掺杂对NdBCO超导块材熔化温度的影响

采用改进后的顶部籽晶熔渗生长(RE+011 TSIG)工艺,通过在固相先驱粉中掺杂不同含量的MgO来有效地提高NdBCO籽晶的熔化温度,从而成功地制备出直径为32 mm的大尺寸单畴SmBCO超导块材.结果表明,MgO的掺杂对NdBCO超导块材的熔化温度有着明显的提高,随着固相先驱粉中MgO掺杂量的增加,Mg²⁺离子逐渐进入到Nd123相的晶格中,当掺杂量达到16 wt%时呈现出饱和状态,且NdBCO超导块材的熔化温度提高近18℃,可有效地抑制在制备SmBCO超导块材的过程中出现的NdBCO籽晶熔化现象.     

Stability of inverse bicontinuous cubic phases in lipid-water mixtures

We investigate the stability of seven inverse bicontinuous cubic phases [ G, D, P, C(P), S, I-WP, F-RD] in lipid-water mixtures based on a curvature model of membranes. Lipid monolayers are described by parallel surfaces to triply periodic minimal surfaces. The phase behavior is determined by the distribution of the Gaussian curvature on the minimal surface and the porosity of each structure. Only G, D, and P are found to be stable, and to coexist along a triple line. The calculated phase diagram agrees very well with experimental results for 2:1 lauric acid/DLPC.     

Shift of triple point in confined systems with curved interfaces

The unified thermodynamic approach to the analysis of melting/freezing phenomena in confined systems is proposed. The approach relates the shift of the triple point in a confined system in comparison with the bulk system with the physico-chemical parameters of the bulk system and the boundary layer. The application of general equations to particular types of confinement is illustrated for small particles and substance embedded inside porous matrices. The analysis of equations derived indicates that for the systems considered the shift of triple point in the boundary layers and in the uniform core part of the system in the general case differ from each other. The shift of triple point may be either positive or negative and may be controlled for paricles by variation of the interfacial energy, and for the pores by variation of interfacial energy and/or pore walls wettability.     

Strain-mediated phase coexistence in heteroepitaxial films

We present experimental evidence of the equilibrium coexistence between crystalline phases in heteroepitaxial films of MnAs on GaAs. The phases, which can coexist in the bulk system only at one temperature point, coexist in the epitaxial film over a wide temperature interval. An apparent contradiction with the Gibbs phase rule is resolved by the presence of strain in the film.     

Entropy-driven triple point wetting in hard-rod mixtures

We theoretically study binary mixtures of thin and thick hard rods with diameter ratio more extreme than 1:4. The bulk phase diagram of these systems exhibits a triple point, where an isotropic (I) phase coexists with two nematic phases ( N1 and N2) of different composition. Using density functional theory, we predict that the I-N2 interface is completely wet by N1 upon approach of the the I-N1-N2 triple point. This entropic triple point wetting should be experimentally observable in colloidal suspensions of rodlike particles.