Wet-phase inversion method

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. 

An integrally skinned asymmetric membrane with a porous skin layer (hereafter called substrate membrane) is prepared from a polymer solution by applying the dry-wet phase inversion method and dried according to the method described later, before being dipped into a bath containing a dilute solution of another polymer. When the membrane is taken out of the bath, a thin layer of coating solution is deposited on top of the substrate membrane. The solvent is then removed by evaporation, leaving a thin layer of the latter polymer on top of the substrate membrane. 

Membranes for vapor removal from air have a structure similar to the prism membrane, but they are prepared on a different principle.Aromatic PEI is used to produce a porous substrate membrane by the dry-wet phase inversion method. This polymer was chosen over PS/PES because of the higher durability of PEI to organic vapors. Unlike an asymmetric PS substrate for the prism membrane, the top layer of asymmetric PEI membrane has a large number of pores, the size of which is equivalent to those of UF membranes. When a layer of silicone rubber is coated on the top layer of the porous substrate membrane, the silicone rubber layer will govern the selectivity and the porous support will provide only mechanical strength to the composite membrane. Because the permeabilities of water and organic vapors through the silicone... 

In addition, PEEK-WC membranes have been prepared by using a phase inversion process with supercritical fluids. The supercritical fluid acts as a non-solvent. In comparison to the dry/wet phase inversion method, the supercritical fluid allows the cell size and the membrane morphology to modulate by changing the experimental conditions, such as polymer concentration, temperature, and pressure. A dry membrane can be obtained rapidly and without additional post-treatments. ... 

Membranes for vapor removal from air have a structure similar to the Prism membrane, but they are prepared on a different principle [22]. Aromatic poly(etherimide) is used to produce a porous substrate membrane by the dry-wet phase inversion method. This polymer was chosen over polysulfone/poly(ether sul-... 

Feng et al. [32] studied the morphology of the inner and outer surfaces of hollow fibers fabricated from poly(etherimide) by TM-AFM. The hollow fibers were fabricated by the dry-wet phase inversion method at two different bore fluid flow rates, 0.1 and 0.4 mLmin and their effect on the surface morphology was investigated. The average pore sizes on the inner surface were 39.8 and 81.9 nm, respectively, for 0.1 and 0.4 mLmin while those on the outer surface were 218.4 and 93.4, respectively, for 0.1 and 0.4 mLmin h It is interesting to note that the pore size increased with an increase in the bore fluid flow rate at the inner surface, while the opposite was the case at the outer surface. 

Membranes prepared by the dry-wet phase inversion method from glassy polymers are composed of polymeric spheres. 

The use of supercritical CO (SC CO ) as a nonsolvent to induce phase separation of polymer solution for the purpose of dry membranes has the following advantages in comparison with the traditional wet phase inversion method ... 

The majority of the commereial gas separation membranes are made by wet phase inversion method whieh results in an integrally skinned asymmetrie membrane. This method was first used by Loeb and Sourirajan to produee cellulose acetate membranes for desalination of sea water. An alternative method for making gas separation membranes uses an ultra-porous skinned asymmetric membrane over which a thin polymer film is deposited by either coating or by interfacial polymerization. This method was developed by Cadotte for the creation of in situ dense skin thin film composite membranes for water desalination. These membrane fabrication techniques were made commercially successful for gas separation membranes by a brilliant empirical discovery for in situ sealing of the tiny pinhole defects on the skin of the membrane. 

Recently, Mi et al. (2002) proposed a new method for the preparation of porous chitosan beads via a wet phase-inversion method. Delval et al. (2003) prepared porous crosslinked starch by generating gas bubbles within the material during S5mthesis. The size of sorbent particles has also been shown to be a key parameter in the control of sorption performances [30, 43, 166]. 

Another way of using PVA for UF membranes is by modifying PVA by controlling hydroxyl groups. In this way the pore structure can be easily adjusted by the method phase inversion. Otherwise, once PVA is a water -soluble polymer it is difficult to form porous UF membranes with an ideal morphological structure by the method of wet phase inversion directly when water is used as a coagulation bath. 

In an alternative approach, MIP membranes can be obtained by generating molec-ularly imprinted sites in a non-specific matrix of a synthetic or natural polymer material during polymer solidification. The recognition cavities are formed by the fixation of a polymer conformation adopted upon interaction with the template molecule. Phase inversion methods have used either the evaporation of polymer solvent (dry phase separation) or the precipitation of the pre-synthesised polymer (wet phase inversion process). The major difficulties of this method lay both in the appropriate process conditions allowing the formation of porous materials and recognition sites and in the stability of these sites after template removal due to the lack of chemical cross-linking. 

Phase inversion is a process in which a polymer is transformed from a liquid to a solid state. There are a number of methods to achieve phase inversion. Among others, the dry-wet phase inversion technique and the temperature induced phase separation (TIPS) are most commonly used in the industrial membrane manufacturing. The dry-wet phase inversion technique was applied by Loeb and Sourirajan in their development... 

Hydrophilic MF membranes can be made by the dry-wet phase inversion technique. The latter technique is also applicable in making PVDF membranes. On the other hand, other hydrophobic MF membranes are made by the TIPS technique. In particular, semicrystalline PE, PP, and PTFE are stretched parallel to the direction of film extrusion so that the crystalline regions are aligned to the direction of stretch, while the noncrystalline region is ruptured, forming long and narrow pores. Hydrophobic membranes do not allow penetration of water into the pore until the transmembrane pressure drop reaches a threshold pressure called liquid entry pressure of water. These membranes can therefore be used for membrane distillation. Tracketching method is applied to make MF membranes from PC. 

Kawakami et al. prepared dense and asymmetric membranes from 2,2 -bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and bis[4-(4-aminophen-oxy)phenyl]sulfone (APPS) by solvent evaporation (dense) and by the dry-wet phase inversion technique [47]. The surface morphology was studied by AFM. They reported that the solvent evaporation method adopted for the preparation of the dense membrane influenced the formation of nodules, while the dry-wet process in which solvent/nonsolvent exchange was involved determined the roughness of the skin layer. 

Wu et al. (1992) treated the surfaces of the hydrophilic porous membranes, such as cellulose acetate, by radiation graft polymerization of styrene to increase their hydrophobicity and to reach the MD membrane characteristics. Kong et al. (1992) employed a cellulose nitrate membrane modified via plasma polymerization of both vinyltrimethylsilicone and carbontetrafluoride and octafluorocyclobutane for the preparation of MD membranes. Fujii et al. (1992) prepared tubular membranes from PVDF polymer dopes by using the dry-jet wet-spinning technique. Ortiz de Zarate et al. (1995) and Tomaszewska (1996) reported on PVDF flat-sheet membranes prepared for MD by the phase inversion method. 

When disperse phase of the coarse emulsion wets the membrane wall and suitable surfactants are dissolved in both liquid phases, the process results in a phase inversion namely a coarse OAV emulsion is inverted into a fine W/O emulsion (Figure 6.1c), and vice versa (Suzuki et al, 1999). The main advantage of this method is that a fine emulsion can be easily prepared from a low concentration coarse emulsion at high rates. For polytetrafluoroethylene (PTFE) membrane filters with a mean pore size of 1 im, the maximum dispersed phase volume fraction in phase-inverted emulsions was 0.9 and 0.84 for O/W and W/O emulsions, respectively (Suzuki et al., 1999). Flow-induced phase-inversion (FIPI) phenomenon was observed earlier by Akay (1998) who used a multiple expansion-contraction static mixer (MECSM) consisting of a series of short capillaries with flow dividers. Hino et al. (2000) and Kawashima et al. (1991) inverted a W/O/W emulsion made up of liquid paraffin. Span 80 (a hydrophobic surfactant), and Tween 20 (a hydrophilic surfactant) into a W/ O emulsion by extrusion through polycarbonate membranes with a mean pore sizes of 3 and 8 im. Inside the membrane pores, surfactant molecules are oriented with their hydrophobic groups toward the wall surface and with hydro-phihc groups toward the solubilized water molecules as a result of a lamellar structure formed inside the pores. The structure ruptured at the pore outlets. 

For a more economical fabrication of microtubular SOFC with more reliability and flexibility in quality control, an advanced dry-jet wet extrusion technique, that is, a phase inversion-based co-extrusion process, followed by co-sintering and reduction processes was employed to fabricate a novel electroly te/anode dual-layer hollow fiber. Using the co-extrusion technique, one of the layers has to be thick in order to provide mechanical strength to the fiber, and in this design, the anode is chosen to be the thick layer due to the much lower ohmic losses (as shown in Figure 11.16). Use of co-extrusion has many advantages over conventional dry-jet wet extrusion methods such as simplified fabrication and better control over the manbrane structure. Furthermore, the risk of defects formation can be reduced and at the same time greater adhesion between the layers can be achieved. 

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