Phase inversion processes, production

Strathmann, H., Production of microporous media by phase inversion processes. In Material Science of Synthetic Membranes, Lloyd, D.R., Ed., American Chemical Society, ACS Symposium Series 269, Washington, DC, 1985, p. 165. 

The role of phase inversion processes in the production of micro-porous aromatic polyamide membranes is discussed by Strathmann (25). Acknowledgments... 

Production of Mlcroporous Media by Phase Inversion Processes... 

The majority of todays membranes used in microfiitration, dialysis or ultrafiltration and reverse osmosis cire prepared from a homogeneous polymer solution by a technique referred to as phase inversion. Phase inversion can be achieved by solvent evaporation, non-solvent precipitation and thermcd gelation. Phase separation processes can not only be applied to a large number of polymers but also to glasses and metal alloys and the proper selection of the various process parameters leads to different membranes with defined structures and mass transport properties. In this paper the fundamentals of membrane preparation by phase inversion processes and the effect of different preparation parameters on membrane structures and transport properties are discussed, and problems utilizing phase inversion techniques for a large scale production of membranes are specified. 

Polymeric membranes are prepared from a variety of materials using several different production techniques. Table 5 summarizes a partial list of the various polymer materials used in the manufacture of cross-flow filters for both MF and UF applications. For microfiltration applications, typically symmetric membranes are used. Examples include polyethylene, polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE) membrane. These can be produced by stretching, molding and sintering finegrained and partially crystalline polymers. Polyester and polycarbonate membranes are made using irradiation and etching processes and polymers such as polypropylene, polyamide, cellulose acetate and polysulfone membranes are produced by the phase inversion process.f Jf f ... 

Disadvantages of the known porous polymeric membrane preparation processes are that they involve additional process steps after the formation of the fiber to come to a final product. It is therefore desirable to have a more efficient preparation process. A new method to prepare structures of any geometry (Figure 6.13c through f) and large variety of functionality was recently proposed [61]. The authors proposed to incorporate the functionality by dispersion of particles in a polymeric porous structure formed by phase inversion. A slurry of dissolved polymer and particulate material can be cast as a flat film or spun into a fiber and then solidified by a phase inversion process. This concept is nowadays commercialized by Mosaic Systems. The adsorber membranes prepared via this route contain particles tightly held together within a polymeric matrix of different shapes, which can be operated either in stack of microporous flat membranes or as a bundle of solid or hollow-fiber membranes. 

Data in this report are generated from both commercial and developmental flat-sheet CA membranes. CA manbranes are prepared by dissolving commercial grades of CA polymers into a solvenl/non-solvent mixture to give a highly viscous dope solution. After microfiltration a knife blade is used to spread the dope onto a woven nylon substrate. The commercial equipment utilized allows for a 1-m width to be cast. The thin dope film is quenched into a water bath to form the microporous structure by the phase inversion process. Membrane is washed with water and post-treated to give finished product in dry state as roll stock. 

The size of the cell walls (as studied by AFM) was influenced by the length of the polystyrene block in the copolymer for molecular masses larger than 50.000 the regularity in the structure gradually disappeared. The authors related the mechanism of formation of this structure to the classical phase inversion process for the production of polymeric membranes [139]. In a later work the authors reported on the possibility to monitor this honeycomb structure in different polymeric systems including polystyrene-block-poly(p-phenylene), star branched polystyrenes, polystyrene-block-poly-3-hexylthiophene, and polystyrenes with polar endgroups and polymer blends [140]. Possible applications for such fascinating structures are in the area of polymeric membranes and optical devices. 

The characteristics of an emulsion depend to a large extent on the physicochemical properties of the fluids involved, and also on the chemical additives used. Emulsifying surfactant products perform two functions. When they reduce surface tension, they help reduce the size of the bubbles and droplets. They also serve to stabilize the emulsion to prevent it from coalescing as soon as the stirring ceases. The first characteristic parameter of an emulsion is the volume fraction of each fluid. When a fluid is gradually incorporated into another which is being stirred, the incorporated fluid constitutes necessarily the dispersed phase and the receiving fluid the continuous phase, since the volume of the dispersed phase is smaller than that of the continuous phase. An inversion phenomenon may occur when the volumes of both phases become comparable. Surfactant additives also act to control phase inversion processes. 

If a linear mbber is used as a feedstock for the mass process (85), the mbber becomes insoluble in the mixture of monomers and SAN polymer which is formed in the reactors, and discrete mbber particles are formed. This is referred to as phase inversion since the continuous phase shifts from mbber to SAN. Grafting of some of the SAN onto the mbber particles occurs as in the emulsion process. Typically, the mass-produced mbber particles are larger (0.5 to 5 llm) than those of emulsion-based ABS (0.1 to 1 llm) and contain much larger internal occlusions of SAN polymer. The reaction recipe can include polymerization initiators, chain-transfer agents, and other additives. Diluents are sometimes used to reduce the viscosity of the monomer and polymer mixture to faciUtate processing at high conversion. The product from the reactor system is devolatilized to remove the unreacted monomers and is then pelletized. Equipment used for devolatilization includes single- and twin-screw extmders, and flash and thin film evaporators. Unreacted monomers are recovered for recycle to the reactors to improve the process yield. 

Phase Inversion Phase inversion is the process whereby a system changes from an oil-in-water emulsion to a water-in-oil emulsion, or vice versa (Figure 5). Phase inversion is an essential step in the manufacture of a number of important food products, including butter and margarine (1, 60, 85). In most other foods, phase inversion is undesirable because it has an adverse effect on the products appearance, texture, stability, and taste and should therefore be avoided. 

Flow induced phase inversion (FIPI) has been observed by the author and applied to intensive materials structuring such as agglomeration, microencapsulation, detergent processing, emulsification, and latex production from polymer melt emulsifica-A diagrammatic illustration of FIPI is shown in Fig. 4. When material A is mixed with material B, in the absence of any significant deformation, the type of dispersion obtained [(A-in-B) or (B-in-A)] is dictated by the thermodynamic state variables (TSVs) (concentration, viscosity of components, surface activity, temperature, and pressure). If the... 

In a novel process, FIPI was also applied to the emulsiflcation of polymer melts in water, thus providing an alternative method to emulsion polymerization for the production of latexes. " " In fact, some thermoplastic melts (such as polyethylene) cannot be obtained through the emulsion polymerization route hence, the present technique is an example of PI providing a novel product form. To achieve the emulsiflcation of thermoplastics, it is necessary to operate near or above 100°C and at elevated pressures, which necessitates the use of polymer processing equipment fitted with a MFCS mixer at the outlet. It was found that molecular surfactants could not be used to obtain the initial (water-in-polymer melt) emulsion. Instead, hydrophobically modified water-soluble polymers were used as the surface active material. After the phase inversion in the MFCS mixer, the resulting emulsion was diluted to the level required. This also freezes the molten latexes. The important attributes of FIPI emulsification include a low level of surfactant use, low temperature processing, production of submicrometer particles with a narrow size distribution, and production of novel products. 

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