Phase-separation spinning

Phase separation spinning was reported in detail by Zwick [134]. This method allows spinning of fibers at winding speeds of 10-1000 m/min from solutions of polymer contents of 10-25%, with the use of modified melt-spinning equipment. T o realize phase separation, the concentration of the solution has to be chosen so that, on the way from the spinneret to the winder, and at a temperature between that of the spinneret and room temperature, the thin streams of polymer undergo phase separation into a concentrated gel, or pure polymer phase, and a solvent phase. 

Phase-separation spinning is concerned with the extrusion of polymers and solvent at high temperatures into a cooling zone. During the cooling process a phase separation occurs, usually accompanied by crystallization of the solvent. The polymers in the extruded filament form fibers during this process, while the solvent can be removed before or after drawing. 

Recently, due to increased interest in membrane raft domains, extensive attention has been paid to the cholesterol-dependent liquid-ordered phase in the membrane (Subczynski and Kusumi 2003). The pulse EPR spin-labeling DOT method detected two coexisting phases in the DMPC/cholesterol membranes the liquid-ordered and the liquid-disordered domains above the phase-transition temperature (Subczynski et al. 2007b). However, using the same method for DMPC/lutein (zeaxanthin) membranes, only the liquid-ordered-like phase was detected above the phase-transition temperature (Widomska, Wisniewska, and Subczynski, unpublished data). No significant differences were found in the effects of lutein and zeaxanthin on the lateral organization of lipid bilayer membranes. We can conclude that lutein and zeaxanthin—macular xanthophylls that parallel cholesterol in its function as a regulator of both membrane fluidity and hydrophobicity—cannot parallel the ability of cholesterol to induce liquid-ordered-disordered phase separation. 

A review of the application of ESR to the study of free radical polymerisation is given by Yamada and co-workers [146]. A survey of the application ESR spectroscopy spin label/probe methods in heterogeneous polymer systems is provided by Veksli and co-workers [147]. Spin probe methods allow the study of the MD of the polymer, its free volume, phase separation and phase morphology. 

Knight, D. P., Knight, M. M., and Vollrath, F. (2000). Beta transition and stress-induced phase separation in the spinning of spider dragline silk. Int. J. Biol. Macromol. 27, 205-210. 

Resist systems may be more complicated than just a single polymer in a single solvent. They may be composed of polymer, polymer/dye, or polymer/polymer combinations (where the small molecule dye or additional polymer increases the radiation sensitivity of the resist film) with one or more solvents. The more complicated polymer/dye or polymer/polymer systems have the added possibilities of phase separation or aggregation during the non-equilibrium casting process. Law (16 I investigated the effects of spin casting on a... 

Several modifications have been proposed for the basic HNN-COSY experiment. For example, frequency separations between amino and aromatic 15N resonances are typically in the range 100-130 ppm and therefore much larger than between imino 15N donor and aromatic 15N acceptor resonances. As has been pointed out by Majumdar and coworkers [33], such 15N frequency separations are too large to be covered effectively by the non-selective 15N pulses of the homonuclear HNN-COSY. They therefore designed a pseudo-heteronuclear H(N)N-COSY experiment, where selective 15N pulses excite the amino and aromatic 15N resonances separately to yield excellent sensitivity [33]. An inconvenience of this experiment is that the resonances corresponding to the amino 15N nuclei are not detected, and a separate spin-echo difference experiment was used to quantify the h2/NN values. A slightly improved version of this pseudo-heteronuclear H(N)N-COSY [35] remedies this problem by the use of phase-coherent 15N pulses such that both amino and aromatic 15N resonances can be detected in a single experiment. 

Fig. 2. Phase diagram describing lateral phase separations in the plane of bilayer membranes for binary mixtures of dielaidoylphosphatidylcholine (DEPC) and dipalmitoyl-phosphatidylcholine (DPPC). The two-phase region (F+S) represents an equilibrium between a homogeneous fluid solution F (La phase) and a solid solution phase S presumably having monoclinic symmetry (P(J. phase) in multilayers. This phase diagram is discussed in Refs. 19, 18, 4. The phase diagram was derived from studies of spin-label binding to the membranes.

When two polymeric systems are mixed together in a solvent and are spin-coated onto a substrate, phase separation sometimes occurs, as described for the application of poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor for a Novolak resin (4). There are two ways to improve the compatibility of polymer mixtures in addition to using a proper solvent modification of one or both components. The miscibility of poly(olefin sulfones) with Novolak resins is reported to be marginal. To improve miscibility, Fahrenholtz and Kwei prepared several alkyl-substituted phenol-formaldehyde Novolak resins (including 2-n-propylphenol, 2-r-butylphenol, 2-sec-butylphenol, and 2-phenylphenol). They discussed the compatibility in terms of increased specific interactions such as formation of hydrogen bonds between unlike polymers and decreased specific interactions by a bulky substituent, and also in terms of "polarity matches" (18). In these studies, 2-ethoxyethyl acetate was used as a solvent (4,18). Formation of charge transfer complexes between the Novolak resins and the poly (olefin sulfones) is also reported (6). 

For further enhancement of electron beam sensitivity, the chlorinated Novolak resin was studied using poly (2-methyl-1-pentene sulfone) as a dissolution inhibitor. The chlorinated Novolak resin mixed well with the polysulfone, and there was no phase separation observed when the films were spin-coated. With 13 wt% of the polysulfone, the chlorinated Novolak resist cast from a cellosolve acetate solution yielded fully developed images with R/Ra = 9.2 after exposure to 2 / 2. It gave fully developed images with R/R0 = 3.2 at a dose of 1 / 2, as shown in Figure 3. There are some problems with this resist system some cracking of the developed resist images... 

Trichlorodifluoroethane (HCFC-122) is a co-spin agent, which lowers the cloud-point pressure. The cloud-point pressure means the pressure at which a single phase liquid solution begins to phase separate. At temperatures above the critical point, there cannot be any liquid phase present and therefore a single phase, supercritical solution phase separates into a polymer-rich/spin fluid-rich, two-phase gaseous dispersion. 

Figure 5 shows the EPR spectra and intensity for the x=0.06 sample. It is seen that in contrast to the x <0.06 samples at x=0.06 only a single EPR line is observed and the temperature dependence of the signal intensity recovers an usual Curie-Weiss behavior. On the other hand there is still a substantial isotope effect on the EPR line. To understand the change of the EPR spectra at x=0.06, one should first comment on the observability of the phase separation in our EPR experiments. The main difference of the EPR signals from the hole-rich and hole-poor regions is the spin relaxation rate of the Cu... 

After phase separation, the sizes increase up to 100 nm. At the same time, trapped radicals were observed by electron spin resonance (esr) spectroscopy. 

As mentioned above, for finite forcing amplitudes one already has periodic A solutions in the range e < 0. But, when the system is quenched into the two-phase region with e > 0, where one may choose for reasons of simplicity e = 1, the spin-odal decomposition sets in and the late stage of the phase separation process depends on the forcing amplitude a. It is an interesting question, for which parameter combinations the systems ends up in a A solution that is locked to the periodicity of the external forcing, independent of the initial conditions before the quench. 

FIGURE 1.1. Schematic representation of a spin-coating experiment. Initially, the two polymers and the solvent are mixed. As the solvent evaporates during film formation, phase separation sets in resulting in a characteristic phase morphology in the final film (from [7]). 

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