Spinodal Decomposition in Tellurite-Based Glasses Induced by Excimer Laser Irradiation

Tellurite-based glasses in the TeO2-K3Li2Nb5O15, TeO2-Ba5Li2Ti2Nb8O30, and V2Te2O9 were fabricated by the conventional melt-quenching technique. Amorphous and glassy characteristics of the as-quenched samples were established via the X-ray powder diffraction technique and differential thermal analysis, respectively. The as-quenched samples were irradiated by an excimer laser (248 nm). The effect of laser power, duration of irradiation, and the frequency of the laser pulses on the surface features of the above glasses were studied. The optical microscopic studies carried out on the above systems revealed the presence of quasi-periodic and periodic structures on their surfaces. The local compositional variations of these structures were confirmed by back-scattered electron imaging using scanning electron microscope accompanied by energy-dispersive X-ray analysis. These results were convincing enough to state that the glasses in the present investigations had undergone spinodal decomposition on laser irradiation. The incidence of the interconnected texture of two different phases was observed owing to the quenching effect produced by the heating and cooling cycle of the successive laser pulses. Ring- and line-shaped patterns were also observed, respectively, when the pulse frequency of the laser and the duration of irradiation were increased.

Spinodal decomposition of a Co-Ti-Nb alloy

The microstructural evolution on aging a Co-3 wt pct Ti-2 wt pct Nb alloy has been followed by transmission electron microscopy and diffraction to show that the solid solution decomposed by the spinodal mode. The strengthening observed has been correlated with the differences in lattice parameters of the coexisting phases. The several stages of coarsening have been documented to yield information about their kinetics and morphological changes.Formerly Visiting Assistant Professor, Department of Mechanical and Industrial Engineering, University of Illinois at Urbana-Champaign, 1206 West Green Street, Urbana, IL 61801, is with .

Inherent structures of phase-separating binary mixtures: Nucleation, spinodal decomposition, and pattern formation

An energy landscape view of phase separation and nonideality in binary mixtures is developed by exploring their potential energy landscape (PEL) as functions of temperature and composition. We employ molecular dynamics simulations to study a model that promotes structure breaking in the solute-solvent parent binary liquid, at low temperatures. The PEL of the system captures the potential energy distribution of the inherent structures (IS) of the system and is obtained by removing the kinetic energy (including that of intermolecular vibrations). The broader distribution of the inherent structure energy for structure breaking liquid than that of the structure making liquid demonstrates the larger role of entropy in stabilizing the parent liquid of the structure breaking type of binary mixtures. At high temperature, although the parent structure of the structure breaking binary mixture is homogenous, the corresponding inherent structure is found to be always phase separated, with a density pattern that exhibits marked correlation with the energy of its inherent structure. Over a broad range of intermediate inherent structure energy, bicontinuous phase separation prevails with interpenetrating stripes as signatures of spinodal decomposition. At low inherent structure energy, the structure is largely phase separated with one interface where as at high inherent structure energy we find nucleation type growth. Interestingly, at low temperature, the average inherent structure energy (< EIS >) exhibits a drop with temperature which signals the onset of crystallization in one of the phases while the other remains in the liquid state. The nonideal composition dependence of viscosity is anticorrelated with average inherent structure energy.

Effect of convection and viscoelasticity on spinodal decomposition in fluids

Current analytical work on the effect of convection and viscoelasticity on the early and late stages of spinodal decomposition is briefly described. In the early stages, the effect of viscoelastic stresses was analysed using a simple Maxwell model for the stress, which was incorporated in the Langevin equation for the momentum field. The viscoelastic stresses are found to enhance the rate of decomposition. In the late stages, the pattern formed depends on the relative composition of the two species. Droplet spinodal decomposition occurs when the concentration of one of the species is small. Convective transport does not have a significant effect on the growth of a single droplet, but it does result in an attractive interaction between non - Brownian droplets which could lead to coalescence. The effect of convective transport for the growth of random interfaces in a near symmetric quench was analysed using an 'area distribution function', which gives the distribution of surface area of the interface in curvature space. It was found that the curvature of the interface decreases proportional to t in the late stages of spinodal decomposition, and the surface area also decreases proportional to t.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.

Calculating the equation of state parameters and predicting the spinodal curve of isotactic polypropylene/poly(ethylene-co-octene) blend by molecular dynamics simulations combined with Sanchez-Lacombe lattice fluid theory

Molecular dynamics simulations are adopted to calculate the equation of state characteristic parameters P*, rho*, and T* of isotactic polypropylene (iPP) and poly(ethylene-co-octene) (PEOC), which can be further used in the Sanchez-Lacombe lattice fluid theory (SLLFT) to describe the respective physical properties. The calculated T* is a function of the temperature, which was also found in the literature. To solve this problem, we propose a Boltzmann fitting of the data and obtain T* at the high-temperature limit. With these characteristic parameters, the pressure-volume-temperature (PVT) data of iPP and PEOC are predicted by the SLLFT equation of state. To justify the correctness of our results, we also obtain the PVT data for iPP and PEOC by experiments. Good agreement is found between the two sets of data. By integrating the Euler-Lagrange equation and the Cahn-Hilliard relation, we predict the density profiles and the surface tensions for iPP and PEOC, respectively. Furthermore, a recursive method is proposed to obtain the characteristic interaction energy parameter between iPP and PEOC. This method, which does not require fitting to the experimental phase equilibrium data, suggests an alternative way to predict the phase diagrams that are not easily obtained in experiments.

Self-assembly of crystalline-coil diblock copolymer in solvents with varying selectivity: From spinodal-like aggregates to spheres, cylinders, and lamellae

We have investigated systematically the morphology of thin films spin-coated from solutions of a semicrystalline diblock copolymer, poly(L-lactic acid)-block-polystyrene (PLLA-b-PS), in solvents with varying selectivity. In neutral solvents (chloroform and tetrahydrofuran (THF)), a spinodal-like pattern was obtained and the pattern boundary was sharpened by diluting the solution. Meanwhile, loose spherical associates, together with larger aggregates composed of these associates by unimer bridges, formed partly due to crystallization of the PLLA blocks in relatively concentrated solutions. In slightly PS-selective solvent (e.g., benzene), both loose and compact spherical micelles were obtained, depending on the polymer concentration, coexisting with unimers. When enhancing the selectivity with mixed solvents, for example, mixing the neutral solvent and the slightly selective solvent with a highly PS-selective solvent, CS2, loose assemblies (nanorods in CS2/THF mixtures and polydisperse aggregates in CS2/benzene mixtures) and well-developed lamellar micelles were obtained.

Statistical thermodynamics of polydisperse polymer systems in the framework of lattice fluid model: Effect of molecular weight and its distribution on the spinodal in polymer solution

With the aid of thermodynamics of Gibbs, the expression of the spinodal was derived for the polydisperse polymer-solvent system in the framework of Sanchez-Lacombe Lattice Fluid Theory (SLLFT). For convenience, we considered that a model polydisperse polymer contains three sub-components. According to our calculation, the spinodal depends on both weight-average ((M) over bar (w)) and number-average ((M) over bar (n)) molecular weights of the polydisperse polymer, but the z-average molecular weight ((M) over bar (z)) dependence on the spinodal is invisible. The dependence of free volume on composition, temperature, molecular weight, and its distribution results in the effect of (M) over bar (n) on the spinodal. Moreover, it has been found that the effect of changing (M) over bar (w) on the spinodal is much bigger than that of changing (M) over bar (n) and the extrema of the spinodal increases with the rise of the weight-average molecular weight of the polymer in the solutions with upper critical solution temperature (UCST). However, the effect of polydispersity on the spinodal can be neglected for the polymer with a considerably high weight-average molecular weight. A more simple expression of the spinodal for the polydisperse polymer solution in the framework of SLLFT was also derived under the assumption of upsilon(*)=upsilon(1)(*)=upsilon(2)(*) and (1/r(1)(0))-(1/r(2i)(0))-->(1/r(1)(0)).

DYNAMIC SCALING AND FRACTAL BEHAVIOR OF SPINODAL PHASE-SEPARATION IN POLYMER MIXTURES OF POLY(METHYL METHACRYLATE) WITH POLY(STYRENE-CO-ACRYLONITRILE)

Dynamic scaling and fractal behaviour of spinodal phase separation is studied in a binary polymer mixture of poly(methyl methacrylate) (PMMA) and poly(styrene-co-acrylonitrile) (SAN). In the later stages of spinodal phase separation, a simple dynamic scaling law was found for the scattering function S(q,t):S(q,t) approximately q(m)-3S approximately (q/q(m)). The possibility of using fractal theory to describe the complex morphology of spinodal phase separation is discussed. In phase separation, morphology exhibits strong self-similarity. The two-dimensional image obtained by optical microscopy can be analysed within the framework of fractal concepts. The results give a fractal dimension of 1.64. This implies that the fractal structure may be the reason for the dynamic scaling behaviour of the structure function.

DYNAMIC SCALING OF THE STRUCTURE-FUNCTION FOR SPINODAL DECOMPOSITION IN CRITICAL AND NONCRITICAL MIXTURES OF POLY(VINYL ACETATE) POLY(METHYL METHACRYLATE)

The dynamics of phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by using a time-resolved light-scattering technique. In the later stages of spinodal decomposition, a simple dynamic scaling law was found for the scattering function S(q, t)(S(q, t) approximately I(q, t)): S(q, t)q(m)-3 S approximately (q/q(m)). The scaling function determined experimentally was in good agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X8) for critical concentration, and approximately in agreement with that predicted by Furukawa, S approximately (X) approximately X2/(3 + X6) for non-critical mixtures. The light-scattering invariant shows that the later stages of the spinodal decomposition were undergoing domain ripening.

FRACTAL BEHAVIOR OF SPINODAL DECOMPOSITION IN POLYMER BLENDS

Fractal behaviour of ramified domains in the late stage of spinodal phase separation in a binary polymer blend of poly(vinyl acetate) with poly(methyl methacrylate) was investigated by optical microscopic method. In the late stage of the spinodal decomposition, the fractal dimension D is about 1.64. It implies that some anomalous properties of irregular structure probably may be explained by fractal concepts.

Comment on "Kinetics of spinodal decomposition in the ising model with vacancy diffusion"

In a recent paper [Phys. Rev. B 50, 3477 (1994)], P. Fratzl and O. Penrose present the results of the Monte Carlo simulation of the spinodal decomposition problem (phase separation) using the vacancy dynamics mechanism. They observe that the t1/3 growth regime is reached faster than when using the standard Kawasaki dynamics. In this Comment we provide a simple explanation for the phenomenon based on the role of interface diffusion, which they claim is irrelevant for the observed behavior.

Morphology induced spinodal decomposition at the surface of symmetric diblock copolymer films

Atomic force microscopy is used to study the ordering dynamics of symmetric diblock copolymer films. The films order to form a lamellar structure which results in a frustration when the film thickness is incommensurate with the lamellae. By probing the morphology of incommensurate films in the early ordering stages, we discover an intermediate phase of lamellae arranged perpendicular to the film surface. This morphology is accompanied by a continuous growth in amplitude of the film surface topography with a characteristic wavelength, indicative of a spinodal process. Using selfconsistent field theory, we show that the observation of perpendicular lamellae suggests an intermediate state with parallel lamellae at the substrate and perpendicular lamellae at the free surface. The calculations confirm that the intermediate state is unstable to thickness fluctuations, thereby driving the spinodal growth of surface structures.

Memory effect and fast spinodal decomposition

We consider the modification of the Cahn-Hilliard equation when a time delay process through a memory function is taken into account. We then study the process of spinodal decomposition in fast phase transitions associated with a conserved order parameter. The introduced memory effect plays an important role to obtain a finite group velocity. Then, we discuss the constraint for the parameters to satisfy causality. The memory effect is seen to affect the dynamics of phase transition at short times and have the effect of delaying, in a significant way, the process of rapid growth of the order parameter that follows a quench into the spinodal region.

Spinodal decomposition in pure-gauge QCD

Spinodal decomposition in a model of pure-gauge SU(2) theory that incorporates a deconfinement phase transition is investigated by means of real-time lattice simulations of the fully nonlinear Ginzburg-Landau equation. Results are compared with a Glauber dynamical evolution using Monte Carlo simulations of pure-gauge lattice QCD. © 2005 American Institute of Physics.