Polycarbonate membrane chemical etching

The scope of applications of MF has been broadened in recent years by the introduction of inert membranes, particularly polypropylene, polycarbonate, and Teflon . In general, these materials cannot be made by the methods developed for the cellulosics because of their insolubility. Both Teflon and pol)propylene MF membranes have been made by a controlled stretching procedure in which microtears are introduced Microporous polycarbonate membranes have been prepared by a unique radiation-track-etch method A thin polycarbonate film is exposed to ionizing radiation which leaves labile sites that can later be chemically etched to produce straight-throi channels. The pore size can be controlled by the etching conditions. The pores in these membranes, contrary to those in cellulosic membranes, are quite uniform in diameter. 

Martin and coworkers176 177 178 have used controlled pore-size membranes as templates to electrochemically grow fibrillar mats of CEPs. Similar structures have also been produced using nanoporous particle track-etched polycarbonate membranes with both ppyl79,180,181,182 and PAn183 via chemical and electrochemical techniques. The approach involves the oxidation of the monomer within the pores of a template. This is achieved electrochemically as illustrated in Figure 2.17. The electrode sub-... 

Polybutadiene/polycarbonate membranes with a pp-ethylenediamine layer had an increased gas permeability (in comparison with the unmodified one) due to surface etching. Their selectivity was closely connected with the chemical composition of the top layer. A high nitrogen content was required for high O2 selectivity (Ruaan et al. 1998). The presence of the amine groups on the membrane surface also enhanced the capacity for CO2/CH4 separation. The plasma-polymerized diisopropylamine on the surface of the composite membrane—porous polyimide (support)/ silicone (skin)— made the separation coefficient as high as 17 for a permeation rate of 4.5 X cmVcm sec cmHg (Matsuyama et al. 1994). 

The formation of nanostructured arrays of conjugated polymers by the utilization of nanoporous templates has been reported. The deposition of the polymer inside the pores can be achieved by filling the pores with a solution of polymer and evaporation of the solvent or by the direct synthesis of conjugated polymer inside the pores by chemical or electrochemical approaches. Porous templates were based on track-etched polycarbonate membranes [106-108] or alumina that is obtained by anodic aluminum oxidation (AAO) [109-lllj. Thus, periodic vertical channels with diameters between 20 and 120 nm are formed by first electrochemical oxidation and etching and then subsequent etching for pore widening (Figure 13.16). 

In developing these template synthetic methods, we made an interesting discovery. When these polymers are synthesized (either chemically or electrochemically) within the pores of the track-etched polycarbonate membranes, the polymer preferentially nucleates and grows on the pore walls [11,14,46]. As a result, polymeric tubules are obtained at short polymerization times (Fig. 16.2A). These tubular structures have been quite useful in our fundamental investigations of electronic conductivity in the template-synthesized materials (see below). In addition, tubular structures of this type have a number... 

Boehme et al. employed polycarbonate membrane filters as templates to synthesize ceria nanotubes by low-temperature deposition. The polycarbonate membranes were chemically etched by an NaOH solution, followed by an activation and sensitization process performed by aqueous SnClg, AgNOj and Co(NOa)2, Pd(N03>2, and Ag2S04. The final electroless deposition step used a Ce(III) and C2H10BN solution. Ceria nanotubes grew in the membrane channel and the template was easily removed by dichloromethane. 

Track-etched membranes are made by exposing thin films (mica, polycarbonate, etc) to fission fragments from a radiation source. The high energy particles chemically alter material in their path. The material is then dissolved by suitable reagents, leaving nearly cylindrical holes (19). 

Finally, track-etched MF membranes are made from polymers, such as polycarbonate and polyester, wherein electrons are bombarded onto the polymeric surface. This bombardment results in sensitized tracks, where chemical bonds in the polymeric backbone are broken. Subsequently, the irradiated film is placed in an etching bath (such as a basic solution), in which the damaged polymer in the tracks is preferentially etched from the film, thereby forming cylindrical pores. The residence time in the irradiator determines pore density, and residence time in the etching bath determines pore size. Membranes made by this process generally have cylindrical pores with very narrow pore-size distribution, albeit with low overall porosity. Furthermore, there always is the risk of a double hit, i.e., the etched pore becomes wider and could result in particulate penetration. Such filter membranes are often used in the electronic industry to filter high-purity water. 

Kim, K.J. et al., Chemical and elechical characterization of virgin and protein-fouled polycarbonate track-etched membranes by FTIR and sheaming-potential measurements,/. Membr. Sci., 134, 199, 1997. 

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