Spinodal

The unstable situation caused when a spread him begins to dewet the surface has been studied [32, 33]. IDewetting generally proceeds from hole formation or retraction of the him edge [32] and hole formation can be a nucleation process or spinodal decomposition [34]. Brochart-Wyart and de Gennes provide a nice... 

The T, p coexistence curve can be calculated numerically to any desired precision and is shown in figure A2.5.10. The spinodal curve (shown dotted) satisfies the equation... 

Figure A2.5.10. Phase diagram for the van der Waals fluid, shown as reduced temperature versus reduced density p. . The region under the smooth coexistence curve is a two-phase liquid-gas region as indicated by the horizontal tie-lines. The critical point at the top of the curve has the coordinates (1,1). The dashed line is the diameter, and the dotted curve is the spinodal curve.

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...

For initial post-quench states in the metastable region between the classical spinodal and coexistence curves,... 

In figure A3.3.9 the early-time results of the interface fonnation are shown for = 0.48. The classical spinodal corresponds to 0.58. Interface motion can be simply monitored by defining the domain boundary as the location where i = 0. Surface tension smooths the domain boundaries as time increases. Large interconnected clusters begin to break apart into small circular droplets around t = 160. This is because the quadratic nonlinearity eventually outpaces the cubic one when off-criticality is large, as is the case here. 

Gonnella G, Orlandini E and Yeomans J M 1997 Spinodal decomposition to a lamellar phase effect of hydrodynamic flow Phys. Rev. Lett. 78 1695... 

Binder K 1983 Collective diffusion, nucleation, and spinodal decomposition in polymer mixtures J. Chem. Phys. 79 6387... 

Figure C2.1.10. (a) Gibbs energy of mixing as a function of the volume fraction of polymer A for a symmetric binary polymer mixture = Ag = N. The curves are obtained from equation (C2.1.9 ). (b) Phase diagram of a symmetric polymer mixture = Ag = A. The full curve is the binodal and delimits the homogeneous region from that of the two-phase stmcture. The broken curve is the spinodal.

Therefore, the locus of the values ( ) with a vanishing second derivative of A delimits the region of the miscibility gap in which spinodal decomposition occurs. This locus is referred to as the spinodal (figure C2.1.10 (bl). The length scale of the concentration fluctuations at the beginning of the separation process is controlled by... 

Verhaegh NAM, Asnaghi D, Lekkerkerker FI N W, Giglio M and Cipelletti L 1997 Transient gelation by spinodal decomposition in colloid-polymer mixtures Phys/ca A 242 104-18... 

Above the solution treatment temperature (ca 1250°C), the alloy is single phase with a bcc crystal stmcture. During cooling to ca 750—850°C, the sohd solution decomposes spinodally into two other bcc phases a and lattice parameter composition. The matrix a-phase is rich in Ni and Al and weakly magnetic as compared with which is rich in Fe and Co. The a -phase tends to be rod-like in the (100) dkection and ca 10 nm in diameter and ca 100 nm long. As the temperature is decreased, segregation of the elements becomes mote pronounced and the difference between the saturation polarizations of the two phases increases. 

ALnico 5, with added ductihty. The very Low Co alloys, however, require extremely long he at-treatment times because of the decreased kinetics of the spinodal decomposition. Deformation aged 23%Cr—23%Co—2%Cu exhibits (BH) of 78 kJ/m (9.75MG - Oe) (85). 

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. 

The kinetics of spinodal decomposition is complicated by the fact that the new phases which are formed must have different molar volumes from one another, and so tire interfacial energy plays a role in the rate of decomposition. Anotlrer important consideration is that the transformation must involve the appearance of concenuation gradients in the alloy, and drerefore the analysis above is incorrect if it is assumed that phase separation occurs to yield equilibrium phases of constant composition. An example of a binary alloy which shows this feature is the gold-nickel system, which begins to decompose below 810°C. 

Figure 6.5 The appearence of spinodal decomposition as the temperature is lowered from a range of complete solubility, to the separation of two phases. In the range of composition between the inflection points, the equilibrium spinodal phases should begin to separate...

Lipson (1943, 1944), who had examined a copper-nickeMron ternary alloy. A few years ago, on an occasion in honour of Mats Hillert, Cahn (1991) mapped out in masterly fashion the history of the spinodal concept and its establishment as a widespread alternative mechanism to classical nucleation in phase transformations, specially of the solid-solid variety. An excellent, up-to-date account of the present status of the theory of spinodal decomposition and its relation to experiment and to other branches of physics is by Binder (1991). The Hillert/Cahn/Hilliard theory has also proved particularly useful to modern polymer physicists concerned with structure control in polymer blends, since that theory was first applied to these materials in 1979 (see outline by Kyu 1993). 

Thermodynamics and kinetics of phase separation of polymer mixtures have benefited greatly from theories of spinodal decomposition and of classical nucleation. In fact, the best documented tests of the theory of spinodal decomposition have been performed on polymer mixtures. 

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