Polymeric membranes phase separation process

The phase separation in polymeric systems is determined by thermodynamic and kinetic parameters, such as the chemical potentials and diffusivities of the individual components and the Gibb s free energy of mixing of the entire system. Identification and description of the phase separation process is the key to understanding the membrane formation mechanism, a necessity for optimizing membrane properties and structures. 

To prepare an asymmetric membrane, either the phase-inversion process (skin and support made of the same material) or a two-step process (barrier layer deposited on a porous substructure) is used. In the latter case, the barrier and support structures are usually made from different materials. Symmetric and asymmetric polymeric membranes can be prepared using the phase separation process. ° A precipitation/solidification process is used to transform a polymer solution into two phases (a polymer-rich solid and a polymer-lean liquid phase). The following techniques can be used to solidify the polymer ... 

Membranes used for the pressure driven separation processes, microfiltration (MF), ultrafiltration (UF) and reverse osmosis (RO), as well as those used for dialysis, are most commonly made of polymeric materials. Initially most such membranes were cellulosic in nature. These ate now being replaced by polyamide, polysulphone, polycarbonate and several other advanced polymers. These synthetic polymers have improved chemical stability and better resistance to microbial degradation. Membranes have most commonly been produced by a form of phase inversion known as immersion precipitation.11 This process has four main steps ... 

Phase separation controlled by diffusion exchange often results in a skin which is composed of a micellar assembly of nodules, as will be discussed below. When extremely hydrophobic polymers (e.g., modifled-PPO) are cast from dioxane into water (pg = p = p ) a dense polymer layer is formed at the solution s interface that somewhat resembles the type of layer formed by Interfacial polymerization. There is almost no inward contraction of the interfacial skin, and the coagulation process is controlled by diffusion through the dense, interfacial thin film. These result in an anisotropic membrane with a very fine "coral" structure (Figures 9 and 10). 

By far the majority of polymeric membranes, including UF membranes and porous supports for RO, NF or PV composite membranes, are produced via phase separation. The TIPS process is typically used to prepare membranes with a macroporous barrier, that is, for MF, or as support for liquid membranes and as gas-liquid contactors. In technical manufacturing, the NIPS process is most frequently applied, and membranes with anisotropic cross-section are obtained. Often,... 

Today the majority of polymeric porous flat membranes used in microfiltration, ultrafiltration, and dialysis are prepared from a homogenous polymer solution by the wet-phase inversion method [59-66]. This method involves casting of a polymer solution onto an inert support followed by immersion of the support with the cast film into a bath filled with a non-solvent for the polymer. The contact between the solvent and the non-solvent causes the solution to be phase separated. This process involves the use of organic solvents that must be expensively removed from the membrane with posttreatments, since residual solvents can cause potential problems for use in biomedical apphcations (i.e., dialysis). Moreover, long formation times and a limited versatihty (reduced possibUity to modulate cell size and membrane stmcture) characterize this process. 

Pervaporation have been considered an interesting alternative process for the current industrial options for aroma recovery, distillation, partial condensation, solvent extraction, adsorption, or a combination thereof. It is considered a basic unit operation with significant potential for the solution of various environmental and energetic processes (moderate temperatures). This separation process is based on a selective transport through a dense membrane (polymeric or ceramic) associated with a recovery of the permeate from the vapour phase. A feed liquid mixture contacts one side of a membrane the permeate is removed as a vapour from the other side. Transport through... 

Way, Noble and Bateman (49) review the historical development of immobilized liquid membranes and propose a number of structural and chemical guidelines for the selection of support materials. Structural factors to be considered include membrane geometry (to maximize surface area per unit volume), membrane thickness (<100 pm), porosity (>50 volume Z), mean pore size (<0.1)jm), pore size distribution (narrow) and tortuosity. The amount of liquid membrane phase available for transport In a membrane module Is proportional to membrane porosity, thickness and geometry. The length of the diffusion path, and therefore membrane productivity, is directly related to membrane thickness and tortuosity. The maximum operating pressure Is directly related to the minimum pore size and the ability of the liquid phase to wet the polymeric support material. Chemically the support must be Inert to all of the liquids which It encounters. Of course, final support selection also depends on the physical state of the mixture to be separated (liquid or gas), the chemical nature of the components to be separated (inert, ionic, polar, dispersive, etc.) as well as the operating conditions of the separation process (temperature and pressure). The discussions in this chapter by Way, Noble and Bateman should be applicable the development of immobilized or supported gas membranes (50). 

For many years polymeric membranes have been utilized widely for material separation without detailed characterization of the pore size and the pore size distribution. Most of the commercially available membranes are prepared by either a dry or a wet phase-inversion process. These membranes are formed by the phase separation of multicomponent polymer-solvent systems, the underlying principle being phase separation of the polymer solution. 

In the SLM process, like in all membrane processes, the membrane plays a key role in the transport and separation efficiency. The permeation rate and separation efficiency depends strongly on the type of liquids and supports used for SLM construction. However, the transport properties depend on the type of liquids used as a membrane phase the hquid membrane stability and mechanical stability depend, to a large extent, on the microstructure like pore shape, size, and tortuosity of the membrane used as a support. Therefore, many types of polymeric and inorganic microporous membrane supports are studied for the liquid membrane phase immobilization. 

Facilitated or carrier-mediated transport is a coupled transport process that combines a (chemical) coupling reaction with a diffusion process. The solute has first to react with the carrier to fonn a solute-carrier complex, which then diffuses through the membrane to finally release the solute at the permeate side. The overall process can be considered as a passive transport since the solute molecule is transported from a high to a low chemical potential. In the case of polymeric membranes the carrier can be chemically or physically bound to the solid matrix (Jixed carrier system), whereby the solute hops from one site to the other. Mobile carrier molecules have been incorporated in liquid membranes, which consist of a solid polymer matrix (support) and a liquid phase containing the carrier [2, 8], see Fig. 7.1. The state of the art of supported liquid membranes for gas separations will be discussed in detail in this chapter. 

Membrane separations involve the selective solubility in a thin polymeric membrane of a component in a mixture and/or the selective diffusion of that component through the membrane. In reverse osmosis (3) applications, which entail recovery of a solvent from dissolved solutes such as in desalination of brackish or polluted water, pressures sufficient to overcome both osmotic pressure and pressure drop through the membrane must be applied. In permeation (4), osmotic pressure effects are negligible and the upstream side of the membrane can be a gas or liquid mixture. Sometimes a phase transition is involved as in the process for dehydration of isopropanol shown in Fig. 1.8. In addition, polymeric liquid surfactant and immobilized-solvent membranes have been used. 

The formation of a porous structure results from phase separation (or phase inversion) mechanisms that are not limited to electrospraying. It is the process that controls membrane formation, as the solvent exchanges with a nonsolvent, polymer solution solidifies and polymeric device forms. The phase separation is fully investigated in fabrication of flat or hollow fiber membranes or in situ forming drug delivery systems. - Usually, quick evaporation of the solvent produces particles with porous or golf ball-shaped surfaces (Figure 22.26). 

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