Two phase range

Examination of Bevan s careful work on the Ce02 a. system shows that the cell dimensions of the intermediate phases differ significantly in the adjoining two-phase ranges. This implies a significant, if small, composition range at the temperatures at which equilibrium was frozen into the crystal lattice (Table I). 

Fig. 12 Reduced vapor pressure of chloroform above solutions of PEO at 25°C as a function of the weight fraction w of the polymer [52]. The three composition ranges are labeled I, II, and III. The dotted line extrapolates the behavior of the homogeneous mixtures into the two-phase range...

An important parameter in phase behavior of polymer systems is the chemical composition of the chains. For example, in Schmitt el al. s work on the miscibility of poly(methylmethacrylate) and poly(styrene-co-acrylo-nitrile) [82] it was found that a minute change in the chemical composition of the statistical copolymer splits the single lower-critical miscibility gap into two and adds an upper consolute two-phase range. 

With a further increase in the temperature the gas composition moves to the right until it reaches v = 1/2 at the phase boundary, at which point all the liquid is gone. (This is called the dew point because, when the gas is cooled, this is the first point at which drops of liquid appear.) An unportant feature of this behaviour is that the transition from liquid to gas occurs gradually over a nonzero range of temperature, unlike the situation shown for a one-component system in figure A2.5.1. Thus the two-phase region is bounded by a dew-point curve and a bubble-point curve. 

Biopolymer Extraction. Research interests involving new techniques for separation of biochemicals from fermentation broth and cell culture media have increased as biotechnology has grown. Most separation methods are limited to small-scale appHcations but recendy solvent extraction has been studied as a potential technique for continuous and large-scale production and the use of two-phase aqueous systems has received increasing attention (259). A range of enzymes have favorable partition properties in a system based on a PGE—dextran—salt solution (97) ... 

Nylon-6. Nylon-6—clay nanometer composites using montmorillonite clay intercalated with 12-aminolauric acid have been produced (37,38). When mixed with S-caprolactam and polymerized at 100°C for 30 min, a nylon clay—hybrid (NCH) was produced. Transmission electron microscopy (tern) and x-ray diffraction of the NCH confirm both the intercalation and molecular level of mixing between the two phases. The benefits of such materials over ordinary nylon-6 or nonmolecularly mixed, clay-reinforced nylon-6 include increased heat distortion temperature, elastic modulus, tensile strength, and dynamic elastic modulus throughout the —150 to 250°C temperature range. 

Rates of nitration determined over a range of temperatures in two-phase dispersions have been used to calculate energies of activation from 59—75 kj/mol (14—18 kcal/mol). Such energies of activation must be considered as only apparent, since the tme kinetic rate constants, NO2 concentrations, and interfacial area all change as temperature is increased. 

Polyphase Alloys. The two-phase alloys have a rather wide range of properties resulting from variations within the stmcture. If the second phase is distributed in critical depression, the hardness and strength are at a maximum and the ductility is at a moderate level. Tensile strength may be 415—825 MPa (60,000—120,000 psi) yield strength, 170—585 MPa (25,000—85,000 psi) and elongation, 10—40%. 

Preparation of Dispersion. The reduction process is a two-phase reaction between soluble reducing agent and insoluble dye particles, and therefore the rate of reduction is influenced by the particle size distribution of the dye dispersion. The smaller the particle size the greater the surface area and hence the more rapid the reduction process. However, if the particles are too small, migration will occur in continuous dyeing. It is therefore extremely important to control the size and range of particle size and this is a closely guarded piece of dyestuff manufacturers know-how. 

In the simplest emulsions just described, the final separation is into two Hquid phases upon destabilization. The majority of emulsions are of this kind, but in some cases the emulsion is divided into more than two phases. One obvious reason for such a behavior is the presence of a material that does not dissolve in the oil or the water. One such case is the presence of soHd particles, which is common in emulsions for food, pharmaceuticals, and cosmetics. Another less trivial reason is that the surfactant associates with the water and/or the oil to form a colloidal stmcture that spontaneously separates from the two hquid phases. This colloidal stmcture may be an isotropic Hquid or may be a semisoHd phase, a Hquid crystal, with long-range order. 

Flammable liquids are considered particularly static-prone if their elec trical conductivity is within the range of 0.1 to 10 pS/m. If no particulates or immiscible liquid are present, these prodlic ts are considered safe when their conductivity has been raised to 50 pS/m or higher. Blending operations or other two-phase mixing may cause such a high rate of charging that a conductivity of at least 1000 pS/m is needed for safe charge dissipation (British Standard 5958, part 1, Control of Undesirable Static Electricity, para. 8, 1991). 

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. 

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...

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