Microporous membrane materials

Table l. Commercially available microporous membrane materials used as separators in lithium-ion batteries. 

Topical microporous-membrane materials used in dialysis are hydrophilic, including cellulose, cellulose acetate, and various acid-resistant polyvinyl copolymers, typically less than 50 pm thick and with pore diameters of 15 to 100 A. Dialysis membranes can be thin because pressures on either side of the membrane are essentially equal. The most common membrane modules are plate-and-frame and hollow-fiber. Compact hollow-fiber hemodialyzers, which are widely used, typically contain several thousand 200-pm-diameter fibers with a wall thickness of 20-30 pm and a length of 10 to 30 cm (Seader and Henley, 2006). 

Ceramic, Metal, and Liquid Membranes. The discussion so far implies that membrane materials are organic polymers and, in fact, the vast majority of membranes used commercially are polymer based. However, interest in membranes formed from less conventional materials has increased. Ceramic membranes, a special class of microporous membranes, are being used in ultrafHtration and microfiltration appHcations, for which solvent resistance and thermal stabHity are required. Dense metal membranes, particularly palladium membranes, are being considered for the separation of hydrogen from gas mixtures, and supported or emulsified Hquid films are being developed for coupled and facHitated transport processes. 

Battery makers sometimes view separators with disdain the separator is needed but does not actively contribute to battery operation. Consequently, very little work (relative to that on electrode materials and electrolytes) is directed towards characterizing separators. In fact, development efforts are under way to displace microporous membranes as battery separators and instead to use gel electrolytes or polymer electrolytes. Polymer electrolytes, in particular, promise enhanced safety by elimi-... 

Isotropic fibrous materials, 11 176-177 Isotropic microporous membranes, 15 798 Isotropic moldings, 23 397 Isotropic pitch-based carbon fibers, 26 734-735... 

Membrane materials have to withstand a pressure difference and relatively high temperatures (500 °C and up). Microporous ceramic membranes have been... 

In summary, it may be stated that thin, microporous membranes offer by far the largest selectivities and reasonable fluxes in a wide range of temperatures, but the material processing is not yet fully understood and controlled (Uhlhorn 1990). 

Microporous membranes (pore radius less than 10 A) are ideal materials to be used as separators in membrane reactor processes. Microporous membranes also combine the high selectivities to certain components with high permeation rates. The high selectivities mean that maximum conversions (and thus equilibria shifts) higher than those achieved by porous membranes can be attained, while the high permeation rates allow for high reaction rates... 

To overcome the poor mechanical properties of polymer and gel polymer type electrolytes, microporous membranes impregnated with gel polymer electrolytes, such as PVdF. PVdF—HFP. and other gelling agents, have been developed as an electrolyte material for lithium batteries.Gel coated and/ or gel-filled separators have some characteristics that may be harder to achieve in the separator-free gel electrolytes. For example, they can offer much better protection against internal shorts when compared to gel electrolytes and can therefore help in reducing the overall thickness of the electrolyte layer. In addition the ability of some separators to shutdown... 

Various materials have been used as separators in zinc—bromine cells. Ideally a material is needed which allows the transport of zinc and bromide ions but does not allow the transport of aqueous bromine, polybromide ions, or complex phase structures. Ion selective membranes are more efficient at blocking transport then nonselective membranes.These membranes, however, are more expensive, less durable, and more difficult to handle then microporous membranes (e.g., Daramic membranes).The use of ion selective membranes can also produce problems with the balance of water between the positive and negative electrolyte flow loops. Thus, battery developers have only used nonselective microporous materials for the separator. 

Recently developed blood oxygenators are disposable, used only once, and can be presterilized and coated with anticoagulant (e.g., heparin) when they are constructed. Normally, membranes with high gas permeabilities, such as silicone rubber membranes, are used. In the case of microporous membranes, which are also used widely, the membrane materials themselves are not gas permeable, but gas-liquid interfaces are formed in the pores of the membrane. The blood does not leak from the pores for at least several hours, due to its surface tension. Composite membranes consisting of microporous polypropylene and silicone rubber have also been developed. 

In general, UHMWPE is difficult to process because the resin does not flow when melted. However, there are alternative techniques to process this material, i.e., sintering, compression molding, ram extrusion, or gel processing. Microporous membranes can be made... 

Although the literature of gas separation with microporous membranes is dominated by inorganic materials, polymer membranes have also been tried with some success. The polymers used are substituted polyacetylenes, which can have an extraordinarily high free volume, on the order of 25 vol %. The free volume is so high that the free volume elements in these polymers are probably interconnected. Membranes made from these polymers appear to function as finely microporous materials with pores in the 5 to 15 A diameter range [71,72], The two most... 

Figure 3.15 Polypropylene structures, (a) Type I open cell structure formed at low cooling rates, (b) Type II fine structure formed at high cooling rates [37]. Reprinted with permission from W.C. Hiatt, G.H. Vitzthum, K.B. Wagener, K. Gerlach and C. Josefiak, Microporous Membranes via Upper Critical Temperature Phase Separation, in Materials Science of Synthetic Membranes, D.R. Lloyd (ed.), ACS Symposium Series Number 269, Washington, DC. Copyright 1985, American Chemical Society and American Pharmaceutical Association...

D.R. Lloyd, J.W. Barlow and K.E. Kinzer, Microporous Membrane Formation via Thermally-induced Phase, in New Membrane Materials and Processes for Separation, K.K. Sirkar and D.R. Lloyd (eds), AIChE Symposium Series 261, AIChE, New York, NY, p. 84 (1988). 

Microporous membrane liquid-liquid extraction (MMLLE) is a two-phase extraction setup. In MMLLE procedures, the membrane material and format (FS and HF), extraction units, and system configurations are identical to those described in SLM (Section 4.4.1.2).63 The two-phase HF-MMLLE system is identical to that used in Section 4.4.3, although sometimes with minor differences. In contrast to three-phase SLM extraction, MMLLE employs a microporous membrane as a miniaturized barrier between two different phases (aqueous and organic). One of the phases is organic, filling both the membrane pores (thus making the membrane nonporous) and the compartment on one side of the membrane (acceptor side). The other phase is the aqueous sample on the other side of the membrane (donor side). In this way, the two-phase MMLLE system is highly suited to the extraction of hydrophobic compounds (log Ko/w > 4) and can thus be considered a technique complimentary to SLM in which polar analytes (2 < log Ko/w < 4) can be extracted. 

Applications in the chemical field, include extrusion of an oil phase containing a photographic hydrophobic material through a microporous membrane into water [89] and emulsification of low-viscosity paraffin wax in water [90],... 

Membranes used for separation are thin selective barriers. They may be selective on the basis of size and shape, chemical properties, or electrical charge of the materials to be separated. As discussed in previous sections, membranes that are microporous control separation predominantly by size discrimination, charge interaction, or a combination of both, while nonporous membranes rely on preferential sorption and molecular diffusion of individual species. This permeation selectivity may, in turn, originate from chemical similarity, specific complexation, and/or ionic interaction between the permeants and the membrane material, or specific recognition mechanisms such as bioaffinity. 

Considerable effort is being devoted to developing new polymeric membrane materials. A special type of oxygen-enrichment membrane has also been explored, which consists of a solvent immobilized within a microporous solid support (Fig. 7D). Dissolved in the liquid is a carrier... 

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