Spinodal ordering

Fig. 1. Equilibrium phase diagram T, c)=iT/Tc,c) for the alloy model used in Ref.. Solid lines boundaries of the disordered (a) and homogeneously ordered (6) fields areas c, d and e corre.spond to the two-phase region. Dashed line i.s the ordering spinodal separating the metastable disordered area c from the. spinodal decompo.sition area d. Dot-dashed line is the conditional spinodal that separate.s the area d from the ordered metastable area e.

Fig. 2 illustrates the ordering process after a quench of a disordered alloy below the ordering spinodal. As it was mentioned by AC, the primary ordered domains are formed after few atomic exchanges A.t 1, while further evolution corresponds to the growth of these domains. Fig. 3 shows that in the absence of APBs the microstructure evolution under spinodal decomposition with ordering is similar to that for disordered... 

Fig. 5.a A homogeneous monolayer confined by two external interfaces I and II ordering spinodal waves along z, and morphologies resulting from the spinodal decomposition, b Bilayer equilibrium structure [93]. c Equilibrium structure with two-dimensional domains [60]. d Exemplary transient morphology [94]... 

Figure A2.5.16. The coexistence curve, = KI(2R) versus mole fraction v for a simple mixture. Also shown as an abscissa is the order parameter s, which makes the diagram equally applicable to order-disorder phenomena in solids and to ferromagnetism. The dotted curve is the spinodal.

Figure A3.3.2 A schematic phase diagram for a typical binary mixture showmg stable, unstable and metastable regions according to a van der Waals mean field description. The coexistence curve (outer curve) and the spinodal curve (iimer curve) meet at the (upper) critical pomt. A critical quench corresponds to a sudden decrease in temperature along a constant order parameter (concentration) path passing through the critical point. Other constant order parameter paths ending within tire coexistence curve are called off-critical quenches.

Figure A3.3.5 Tliemiodynamic force as a fiuictioii of the order parameter. Three equilibrium isodiemis (fiill curves) are shown according to a mean field description. For T < J., the isothemi has a van der Waals loop, from which the use of the Maxwell equal area constmction leads to the horizontal dashed line for the equilibrium isothemi. Associated coexistence curve (dotted curve) and spinodal curve (dashed line) are also shown. The spinodal curve is the locus of extrema of the various van der Waals loops for T < T. The states within the spinodal curve are themiodynaniically unstable, and those between the spinodal and coexistence...

In the examples given below, the physical effects are described of an order-disorder transformation which does not change the overall composition, the separation of an inter-metallic compound from a solid solution the range of which decreases as the temperature decreases, and die separation of an alloy into two phases by spinodal decomposition. 

Phase transitions in two-dimensional (adsorbed) layers have been reviewed. For the multicomponent Widom-Rowlinson model the minimum number of components was found that is necessary to stabilize the non-trivial crystal phase. The effect of elastic interaction on the structures of an alloy during the process of spinodal decomposition is analyzed and results in configurations similar to those found in experiments. Fluids and molecules adsorbed on substrate surfaces often have phase transitions at low temperatures where quantum effects have to be considered. Examples are layers of H2, D2, N2, and CO molecules on graphite substrates. We review the PIMC approach, to such phenomena, clarify certain experimentally observed anomahes in H2 and D2 layers and give predictions for the order of the N2 herringbone transition. Dynamical quantum phenomena in fluids are also analyzed via PIMC. Comparisons with the results of approximate analytical theories demonstrate the importance of the PIMC approach to phase transitions, where quantum effects play a role. 

FIG. 4 Qualitative phase diagram close to a first-order irreversible phase transition. The solid line shows the dependence of the coverage of A species ( a) on the partial pressure (Ta). Just at the critical point F2a one has a discontinuity in (dashed line) which indicates coexistence between a reactive state with no large A clusters and an A rich phase (hkely a large A cluster). The dotted fine shows a metastability loop where Fas and F s are the upper and lower spinodal points, respectively. Between F2A and Fas the reactive state is unstable and is displaced by the A rich phase. In contrast, between F s and F2A the reactive state displaces the A rich phase. 

Short-time Brownian motion was simulated and compared with experiments [108]. The structural evolution and dynamics [109] and the translational and bond-orientational order [110] were simulated with Brownian dynamics (BD) for dense binary colloidal mixtures. The short-time dynamics was investigated through the velocity autocorrelation function [111] and an algebraic decay of velocity fluctuation in a confined liquid was found [112]. Dissipative particle dynamics [113] is an attempt to bridge the gap between atomistic and mesoscopic simulation. Colloidal adsorption was simulated with BD [114]. The hydrodynamic forces, usually friction forces, are found to be able to enhance the self-diffusion of colloidal particles [115]. A novel MC approach to the dynamics of fluids was proposed in Ref. 116. Spinodal decomposition [117] in binary fluids was simulated. BD simulations for hard spherocylinders in the isotropic [118] and in the nematic phase [119] were done. A two-site Yukawa system [120] was studied with... 

Fig. 3. Temporal evolution of Cj under spinodal decomposition of a single domain ordered state, at T = 0.42, c = 0.325, and following t (a) 500, (b) 2000, (c) 3000, and (d) 10000. The grey level in Figs. 3-5 linearly varies with Ci between Cj = 0 and c = 1.

Since the prefactor in Eq. (17) is a universal constant of order unity, the barrier AF / kaT is large only very close to the coexistence curve, i.e. for 5v / v /coex, while for larger 5v / the smallness of the barrier implies a very grad il transition from nucleation to spinodal decomposition.Conversely, for N x 1 where Eq. (16) holds the transition is very sharp since the barrier stays large right up to the spinodal for qo. 

The ultimate limit of metastability is reached in reality when AF /kaTc is of order unity. Thus the width over which the spinodal singularities are rounded can be estimated from AF /kaTc oc 1 as... 

Introduction. After we have discussed examples of uncorrelated but polydisperse particle systems we now turn to materials in which there is more structure - discrete scattering indicates correlation among the domains. In order to establish such correlation, various structure evolution mechanisms are possible. They range from a stochastic volume-filling mechanism over spinodal decomposition, nucleation-and-growth mechanisms to more complex interplays that may become palpable as experimental and evaluation technique is advancing. 

Fig. 8 Phase diagram for PI-fc-PEO system. Only equilibrium phases are shown, which are obtained on cooling from high temperatures. ODT and OOT temperatures were identified by SAXS and rheology. Values of /AT were obtained using /AT = 65/T + 0.125. Dashed line spinodal line in mean-field prediction. Note the pronounced asymmetry of phase diagram with ordered phases shifted parallel to composition axis. Asymmetric appearance can be accounted for by conformational asymmetry of segments. Adopted from [53]...

In what follows we will discuss systems with internal surfaces, ordered surfaces, topological transformations, and dynamical scaling. In Section II we shall show specific examples of mesoscopic systems with special attention devoted to the surfaces in the system—that is, periodic surfaces in surfactant systems, periodic surfaces in diblock copolymers, bicontinuous disordered interfaces in spinodally decomposing blends, ordered charge density wave patterns in electron liquids, and dissipative structures in reaction-diffusion systems. In Section III we will present the detailed theory of morphological measures the Euler characteristic, the Gaussian and mean curvatures, and so on. In fact, Sections II and III can be read independently because Section II shows specific models while Section III is devoted to the numerical and analytical computations of the surface characteristics. In a sense, Section III is robust that is, the methods presented in Section III apply to a variety of systems, not only the systems shown as examples in Section II. Brief conclusions are presented in Section IV. 

The systems undergoing phase transitions (like spinodal decomposition) often exhibit scaling phenomena [ 1—4] that is, a morphological pattern of the domains at earlier times looks statistically similar to a pattern at later times apart from the global change of scale implied by the growth of L(f)—the domain size. Quantitatively it means, for example, that the correlation function of the order parameter (density, concentration, magnetization, etc.)... 

We present an improved model for the flocculation of a dispersion of hard spheres in the presence of non-adsorbing polymer. The pair potential is derived from a recent theory for interacting polymer near a flat surface, and is a function of the depletion thickness. This thickness is of the order of the radius of gyration in dilute polymer solutions but decreases when the coils in solution begin to overlap. Flocculation occurs when the osmotic attraction energy, which is a consequence of the depletion, outweighs the loss in configurational entropy of the dispersed particles. Our analysis differs from that of De Hek and Vrij with respect to the dependence of the depletion thickness on the polymer concentration (i.e., we do not consider the polymer coils to be hard spheres) and to the stability criterion used (binodal, not spinodal phase separation conditions). 

For sub-critical isotherms (T < Tc), the parts of the isotherm where (dp/dV)T < 0 become unphysical, since this implies that the thermodynamic system has negative compressibility. At the particular reduced volumes where (dp/dV)T =0, (spinodal points that correspond to those discussed for solutions in the previous section. This breakdown of the van der Waals equation of state can be bypassed by allowing the system to become heterogeneous at equilibrium. The two phases formed at T[Pg.141]

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