Melting phase

Transamidation is an important process in the melt phase for polyamides because it is usually the process by which an equiUbrium molecular weight distribution is reestabUshed and, in the case of the melt blending of two or more polyamides to form a copolymer, it is the process by which randomi2ation of the individual monomers along the chain is effected. In the soHd phase, chain mobiUty is restricted and equiUbrium in either case often is not achieved. 

Polyamides, like other macromolecules, degrade as a result of mechanical stress either in the melt phase, in solution, or in the soHd state (124). Degradation in the fluid state is usually detected via a change in viscosity or molecular weight distribution (125). However, in the soHd state it is possible to observe the free radicals formed as a result of polymer chains breaking under the appHed stress. If the polymer is protected from oxygen, then alkyl radicals can be observed (126). However, if the sample is exposed to air then the radicals react with oxygen in a manner similar to thermo- and photooxidation. These reactions lead to the formation of microcracks, embrittlement, and fracture, which can eventually result in failure of the fiber, film, or plastic article. 

Figure 7 Schematic diagram of the free enthalpy-temperature relationships for (o) orthorhombic, (h) hexagonal, and (m) melt phases. (From Ref. 85.)...

At lower temperatures (180-200°C) the material was processed without melting the LCP and a real composite structure with solid LCP fibers in the PP matrix was formed. When processing was done above the Tm of the LCP (280°C), all the material was molten during processing and a compositelike blend morphology was created in situ during cooling of the oriented melt phase. 

A further confirmation that mirrorlcss lasing is restricted to single domains comes from an experiment in which an Oocl-OPV5 film has been crystallized from the isotropic melt phase (above 204 "C). Melt crystallization resulted in the formation of large domains with dimensions up to several millimeters (see Fig. 16-29 C). Tlie normalized emission spectra for different excitation energies are shown in Figure 16-47. The excitation spot diameter was 1 mm in these ex-... 

Radical induced grafting may be carried out in solution, in the melt phase,292 29 or as a solid state process.296 This section will focus on melt phase grafting to polyolefin substrates but many of the considerations are generic. The direct grafting of monomers onto polymers, in particular polyolefins, in the melt phase by reactive extrusion has been widely studied. Most recently, the subject has been reviewed by Moad1 9 and by Russell.292 More details on reactive extrusion as a technique can be found in volumes edited by Xanthos," A1 Malaika and Baker et a 21 7 The process most often involves combining a frcc-radical initiator (most commonly a peroxide) and a monomer or macromonomer with the polyolefin as they are conveyed through the extruder. Monomers commonly used in this context include MAII (Section 7.6.4.1), maleimidc derivatives and malcate esters (Section 7.6.4.2), (meth)acrylic acid and (meth)acrylate esters (Section 7.6.43), S, AMS and derivatives (Section 7.6.4.4), vinylsilancs (Section 7.6.4.5) and vinyl oxazolines (Section 7.6.4.6). 

With a history of more than 25 years, the free radical-induced grafting of MAH onto polyolefin substrates is one of the most studied polyolefin modification processes.29 "29, 302 The process has been carried out in the melt phase, in various forms of extruders and batch mixers, and there are numerous patents covering various aspects of the process. It has also been carried out successfully in solution and in the solid state. The materials have a range of applications including their use as precursors to graft copolymers, either directly, or during the preparation of blends.297... 

Many studies on the melt phase grafting of GMA onto polyolefins... 

By using diamide units, melt phasing can be avoided and at the same time the crystallization rate is rapid. Surprisingly, diese segmented copolymers widi diamide units not only crystallize quickly but also have a high fracture strain... 

The diamine and the diacid form a PA salt that is soluble in water at elevated temperatures. The polymerization from the PA salt solution occurs in two or three stages. In the first stage a prepolymer is made. This step is carried out under pressure to prevent the evaporation of the more volatile diamine. In the second stage, a polymer is made in the melt phase at atmospheric or slightly reduced pressure. 

The phase diagram for the Sr-Au system shows three congruently melting phases, /3-SrAu (970°C), SrAu2 (1085°C) and SrAu, (1040°C) four phases formed in peritectic reactions are also observed, Sr Au (640°C), SrjAu (590°C), y-Srj Au (750°C) and 5-Sr,Au2, which has a limited stability range from the eutectoid (725°C) to the peritectic reaction (770°C). Independent structural investigations confirm the forma-... 

Because of the difficulty in explaining the observed U-series excesses by time-independent models, interpretations of how disequilibria are created have evolved into models based on residence times. In these models, a melt phase coexists with the solid mantle but moves relative to it due to a driving force, most typically buoyancy. The physical situation under ridges can be referred to as two-phase flow because both the solid and the liquid flow. McKenzie (1984) and Scott and Stevenson (1984, 1986) derived the equations describing flow in a viscously deforming porous media. McKenzie... 

Fig. 16. Variation in a stationary cycling state of catalyst temperature, S03, and complex concentrations in the melt phase and the concentration of gas phase species with time in a half cycle in the forward flow portion of a reactor operating under periodic reversal of flow direction with r = 40 min, SV = 900 h (Csodo = 6 vol%, (Co2)o = 15 vol%, Ta = 50°C. Curves 1, just after switching flow direction 2,1 min 3, 6.6 min 4, 13.3 min, and 5, 20 min after a switch in flow direction. (Figure adapted from Bunimovich et at., 1995, with permission, 1995 Elsevier Science Ltd.)...

C° total concentration of pyrosulfate and sulfate anions Cv concentration of biatomic vanadium complexes C3l concentration of S03 in the melt phase Cp specific heat (kcal/kg °C)... 

Sm specific surface are of the melt phase on bed volume basis (m 1) Sv volumetric specific surface area (m 1)... 

The fusion free energy of both chain ends can be calculated from the equilibrium condition Z = 1 in Eq. 4 by setting the chain length r = 2 in the melt phase. The additional contribution is thus given by... 

Fig. 23 The bonds that constitute crystalline domains must lie nearly parallel to the jy-axis with an angle 6 of less than 20°. Furthermore, the bonds must have at least three neighbors that satisfy 0.7a < Jr + r < 1.3a and ry < r0/2. Note that the crystalline stems deep inside the crystal (black spheres) have six neighbors, while those on the free sin-faces (hatched spheres) have four neighbors. The stems at the half-crystal site, or at the kink site, (white sphere) have three neighbors. Stems attached on the free surface, and those floating in the melt phase have less than three neighbors...

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