Ultrafiltration membranes phase-inversion process

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. 

Ultrafiltration membranes are usually asymmetric and are also made from a variety of materials but are primarily made by the phase inversion process. In the phase inversion process, a homogeneous liquid phase consisting of a polymer and a solvent is converted into a two-phase system. The polymer is precipitated as a solid phase (through a change in temperature, solvent evaporation or addition of a precipitant) and the liquid phase forms the pore system. UF membranes currently on the market are also made from a variety of materials, including polyvinylidene fluoride, polyacrylonitrile, polyethersulfone and polysulfone. 

The majority of polymer membranes used for microfiltration and ultrafiltration of liquids are prepared by the wet phase inversion process. Such membranes exhibit a typical asymmetric structure characterized by a thin dense surface layer and a thick microporous bulk. Poly(phthalazinone ether sulfone ketone) (PPESK) copolymers, c.f. Figure 7.10, show glass transition temperatures in the range of 263-305°C. The polymers show an outstanding chemical stability. They are soluble only in 98% H2SO4. Concentrated aqueous solutions of sodium chlorate, hydrogen peroxide, acetic acid, and nitric acid show no effect. ... 

The membrane can be a solid, a liquid, or a gel, and the bulk phases can be liquid, gas, or vapor. Membranes can be classified according to their structures. Homogeneous or symmetric membranes each have a structure that is the same across the thickness of the membrane. These membranes can be porous or have a rather dense uniform structure. Heterogeneous or asymmetric membranes can be categorized into three basic structures (1) integrally skinned asymmetric membrane with a porous skin layer, (2) integrally skinned asymmetric membrane with a dense skin layer, and (3) thin film composite membranes [13]. Porous asymmetric membranes are made by the phase inversion process [14,15] and are applied in dialysis, ultrafiltration, and microfiltration, whereas integrally skinned asymmetric membranes with a dense skin layer are applied in reverse osmosis and gas separation applications. 

When solvents are removed solely by evaporation, the membrane formation is known as a dry phase inversion process (Resting 1985). When the phase separation and structure formation are achieved by immersion of a cast membrane in a quench medium, the process is known as a wet phase inversion process (Heffelfinger 1978). The latter process is used to prepare asymmetric membranes for either microfiltration (Roesink 1989), ultrafiltration (Michaels 1971), reverse... 

Let us take polysulfone as an example. This is a polymer which is frequently used as a membrane material, both for microfiltration/ultrafiltration as well as a sublayer in composite membranes. These applications require an open porous structure, but in addition also asymmetric membranes with a dense nonporous top layer can also be obtained which are useful for pervaporation or gas separation applications. Some examples are given in table ni.S which clearly demonstrate the influence of various parameters on the membrane structure when the same system, DMAc/polysulfone(PSf), is employed in each case. How is it possible to obtain such different structures with one and the same system To understand this it is necessary to consider how each of the variables affects the phase inversion process. The ultimate structure arises through two mechanisms i) diffusion... 

In the previous section the thermodynamic and kinetic relationships have been given to describe membrane formation by phase inversion processes. These relationships contain various parameters which have a large impact on the diffusion and demixing processes and hence on the ultimate membrane morphology. It has been shown that two different types of membranes may be obtained, the porous membrane (microfiltration and ultrafiltration) and the nonporous membrane (pervaporation and gas separation), depending on the type of formation mechanism, i.e. instantaneous demixing or delayed onset of demixing, involved. 

Most of ultrafiltration membranes used commercially these days are prepared from polymeric materials by a phase inversion process. Some of these materials are listed below ... 

The study of dual-layer asyimnetric hollow-fiber membranes formed by the phase-inversion process started in the late 1980s. In 1987, Yanagimoto invented dual-layer asymmetric flat-sheet and hollow-fiber membranes to improve the antifouling properties of membranes for ultrafiltration and microfiltration (Yanagimoto, 1987, 1988). Since then, Kuzumoto and Nitta (1989) simultaneously extruded inner and outer dopes containing the same polymer but different solvents and additives to improve water permeability. Ekiner et al. (1992) disclosed the procedures for the fabrication of dual-layer hollow fibers for gas separation. Li et al. (2002) developed a delamination-fiee dual-layer asymmetric... 

Polymeric membranes utilized for nano- and ultrafiltration applications are usually produced by the phase inversion process. Unlike in reverse osmosis, there is no continuous thin dense skin on the membrane surface. The membrane, however, has a tighter pore surface than the bulk of the membrane to allow the desired separation. The bulk of the membrane is much more open, to provide membrane support while limiting the resistance to water flux. Polymers employed in these membranes include polysulfone, poly(ether sulfone), polyacrylonitrile, poly(vinylidene fluoride), aromatic polyamides, sulfonated poly(ether sulfone), and cellulose acetate. 

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 ... 

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. 

For many years, polymeric membranes have been widely utilized in practical appHca-tions without having precise information on their pore size and pore size distribution, despite the fact that most commercial membranes are prepared by the phase inversion technique, and the performance of those membranes is known to be governed by their pore characteristics in a complicated manner [1]. These pore characteristics are influenced both by the molecular characteristics of the polymer and by the preparative method [2]. Crudely, membranes applied for pressure-driven separation processes can be distinguished on the basis of pore diameter as reverse osmosis (RO, < 1 nm), dialysis (2-5 nm), ultrafiltration (UF, 2-100 nm), and microfiltration (MF, 100 nm to 2 J,m). Nanofiltration (NF) membranes are a relatively new class and have applications in a wide range of fields [3]. The pore sizes of NF lie between those of RO and UF membranes. 

Nanohybrid materials have been furthermore used for ultra-/nanofiltration applications. Nanofiltration is a pressure-driven membrane separation process and can be used for the production of drinking water as well as for the treatment of process and waste waters. Some apphcations are desalination of brackish water, water softening, removal of micropollutants, and retention of dyes. Ultrafiltration membranes based on polysulfones filled with zirconia nanoparticles are usually prepared via a phase-inversion technique and have been used since 1990 [328]. Various studies were done in order to assess the effect of the addition of Zr02 to polysulfone-based ultrafiltration membranes [329] and the influence of filler loading on the compaction and filtration properties of membranes. The results indicate that the elastic strain of the nanohybrid membranes decreases and the time-dependent strain... 

Membrane formation is generally a fast process and only polymers that are capable of crystallising rapidly fe.g.polyethylene, polypropylene, aliphatic polyamides) will exhibit an appreciable amount of crystallinity. Other semi-ciystalline polymers contain a low to veiy low crystalline content after membrane formation. For example, PPO (2, dimethylphenylene oxide) shows a broad melting endotherm at 245 C[24]. Ultrafiltration membranes derived from this polymer, prepared by phase inversion, hardly contain any crystalline material indicating that membrane formation was too fast to allow crystallisation. 

The information presented in Table 16.2 suggests PAN and PI are solvent-resistant polymers. Both polymers can be processed by the phase inversion technique. Polyimides are commonly used for integral asymmetric nanohltration (NF) membrane preparation and will be addressed in this section. PAN is mainly associated with the preparation of integral asymmetric ultrafiltration (UF) membranes and consequently serves as a support for composite NF membranes to be discussed in the next chapter. Pis are made by the reaction of diamines (DA) with dianhydrides to form the soluble polymer precursor known as poly(amic acid). This can then be processed into a useful shape by converting it into the final PI by cyclodehydration of the amic acid (imidization). Figure 16.1 shows the mechanism for the pyromeUitic dianhydride (PMDA) case. 

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