Polymeric membranes layer

Interfdci l Composite Membra.nes, A method of making asymmetric membranes involving interfacial polymerization was developed in the 1960s. This technique was used to produce reverse osmosis membranes with dramatically improved salt rejections and water fluxes compared to those prepared by the Loeb-Sourirajan process (28). In the interfacial polymerization method, an aqueous solution of a reactive prepolymer, such as polyamine, is first deposited in the pores of a microporous support membrane, typically a polysulfone ultrafUtration membrane. The amine-loaded support is then immersed in a water-immiscible solvent solution containing a reactant, for example, a diacid chloride in hexane. The amine and acid chloride then react at the interface of the two solutions to form a densely cross-linked, extremely thin membrane layer. This preparation method is shown schematically in Figure 15. The first membrane made was based on polyethylenimine cross-linked with toluene-2,4-diisocyanate (28). The process was later refined at FilmTec Corporation (29,30) and at UOP (31) in the United States, and at Nitto (32) in Japan. 

Interfacial polymerization membranes are less appHcable to gas separation because of the water swollen hydrogel that fills the pores of the support membrane. In reverse osmosis, this layer is highly water swollen and offers Httle resistance to water flow, but when the membrane is dried and used in gas separations the gel becomes a rigid glass with very low gas permeabiUty. This glassy polymer fills the membrane pores and, as a result, defect-free interfacial composite membranes usually have low gas fluxes, although their selectivities can be good. 

Ionophore-based solvent polymeric membranes were used as sensing layers for the development of LAPS selective for lithium [70], potassium and calcium ions [71]. Anion-selective LAPS for the determination of nitrate and sulfate ions were described [72],... 

The first and very simple solid contact polymeric sensors were proposed in the early 1970s by Cattrall and Freiser and comprised of a metal wire coated with an ion-selective polymeric membrane [94], These coated wire electrodes (CWEs) had similar sensitivity and selectivity and even somewhat better DLs than conventional ISEs, but suffered from severe potential drifts, resulting in poor reproducibility. The origin of the CWE potential instabilities is now believed to be the formation of a thin aqueous layer between membrane and metal [95], The dominating redox process in the layer is likely the reduction of dissolved oxygen, and the potential drift is mainly caused by pH and p02 changes in a sample. Additionally, the ionic composition of this layer may vary as a function of the sample composition, leading to additional potential instabilities. 

The only ceramic membranes of which results are published, are tubular microporous silica membranes provided by ECN (Petten, The Netherlands).[10] The membrane consists of several support layers of a- and y-alumina, and the selective top layer at the outer wall of the tube is made of amorphous silica (Figure 4.10).[24] The pore size lies between 0.5 and 0.8 nm. The membranes were used in homogeneous catalysis in supercritical carbon dioxide (see paragraph 4.6.1). No details about solvent and temperature influences are given but it is expected that these are less important than in the case of polymeric membranes. 

Characteristic microstructural properties of TiOj membranes produced in this way are given in Table 2.5. Mean pore diameters of 4-5 nm were obtained after heat treatment at T < 500°C. The pore size distribution was narrow in this case and the particle size in the membrane layer was about 5 nm. Anderson et al. (1988) discuss sol/gel chemistry and the formation of nonsupported titania membranes using the colloidal suspension synthesis of the type mentioned above. The particle size in the colloidal dispersion increased with the H/Ti ratio from 80 nm (H /Ti = 0.4, minimum gelling volume) to 140 nm (H /Ti " — 1.0). The membranes, thus prepared, had microstructural characteristics similar to those reported in Table 2.5 and are composed mainly of 20 nm anatase particles. Considerable problems were encountered in membrane synthesis with the polymeric gel route. Anderson et al. (1988) report that clear polymeric sols without precipitates could be produced using initial water concentrations up to 16 mole per mole Ti. Transparent gels could be obtained only when the molar ratio of H2O to Ti is < 4. Gels with up to 12 wt.% T1O2 could be produced provided a low pH is used (H /Ti + < 0.025). 

Buccal dosage forms can be of the reservoir or the matrix type. Formulations of the reservoir type are surrounded by a polymeric membrane, which controls the release rate. Reservoir systems present a constant release profile provided (1) that the polymeric membrane is rate limiting, and (2) that an excess amoimt of drug is present in the reservoir. Condition (1) may be achieved with a thicker membrane (i.e., rate controlling) and lower diffusivity in which case the rate of drug release is directly proportional to the polymer solubility and membrane diffusivity, and inversely proportional to membrane thickness. Condition (2) may be achieved, if the intrinsic thermodynamic activity of the drug is very low and the device has a thick hydrodynamic diffusion layer. In this case the release rate of the drug is directly proportional to solution solubility and solution diffusivity, and inversely proportional to the thickness of the hydrodynamic diffusion layer. 

Relationship Between Nodular and Rejecting Layers. Nodular formation was conceived by Maler and Scheuerman (14) and was shown to exist in the skin structure of anisotropic cellulose acetate membranes by Schultz and Asunmaa ( ), who ion etched the skin to discover an assembly of close-packed, 188 A in diameter spheres. Resting (15) has identified this kind of micellar structure in dry cellulose ester reverse osmosis membranes, and Panar, et al. (16) has identified their existence in the polyamide derivatives. Our work has shown that nodules exist in most polymeric membranes cast into a nonsolvent bath, where gelation at the interface is caused by initial depletion of solvent, as shown in Case B, which follows restricted Inward contraction of the interfacial zone. This leads to a dispersed phase of micelles within a continuous phase (designated as "polymer-poor phase") composed of a mixture of solvents, coagulant, and a dissolved fraction of the polymer. The formation of such a skin is delineated in the scheme shown in Figure 11. 

Most modern materials are formed empirically by solid-state methods. These methods generally involve more processing activity than chemical synthesis (for example, sintering of ceramic powders, modifying concrete by polymers, thermomechanical processing of alloys, layering polymeric membranes for... 

Description of the different mimetic systems will be the starting point of the presentation (Sect. 2). Preparation and characterization of monolayers (Langmuir films), Langmuir-Blodgett (LB) films, self-assembled (SA) mono-layers and multilayers, aqueous micelles, reversed micelles, microemulsions, surfactant vesicles, polymerized vesicles, polymeric vesicles, tubules, rods and related SA structures, bilayer lipid membranes (BLMs), cast multibilayers, polymers, polymeric membranes, and other systems will be delineated in sufficient detail to enable the neophyte to utilize these systems. Ample references will be provided to primary and secondary sources. 

It is typically on the order of several hundred nanometers. In practice the minimum thickness for polymeric membranes is 50gm or greater, which is far more than one would expect from (6.53). This is apparendy due to the fact that these membranes hydrate in the bulk, thus increasing the dielectric constant. They also form a hydrated layer at the solution/membrane interface (Li et al 1996) which affects their overall electrochemical properties and selectivities. Macroscopic ISEs use relatively thick membranes ( 500jU.m). In contrast, it is desirable to use thin membranes in the construction of asymmetric solid-state potentiometric ion sensors, in order to make their preparation compatible with the thin-layer preparation techniques. 

In ISFETS utilizing polymeric ion-selective membranes, it has been always assumed that these membranes are hydrophobic. Although they reject ions other than those for which they are designed to be selective, polymeric membranes allow permeation of electrically neutral species. Thus, it has been found that water penetrates into and through these membranes and forms a nonuniform concentration gradient just inside the polymer/solution interface (Li et al., 1996). This finding has set the practical limits on the minimum optimal thickness of ion-selective membranes on ISFETS. For most ISE membranes, that thickness is between 50-100 jttm. It also raises the issue of optimization of selectivity coefficients, because a partially hydrated selective layer is expected to have very different interactions with ions of different solvation energies. 

A typical PEFC, shown schematically in Fig. 1, consists of the anode and cathode compartments, separated by a proton conducting polymeric membrane. The anode and cathode sides each comprises of gas channel, gas diffusion layer (GDL) and catalyst layer (CL). Despite tremendous recent progress in enhancing the overall cell performance, a pivotal performance/durability limitation in PEFCs centers on liquid water transport and resulting flooding in the constituent components.1,2 Liquid water blocks the porous pathways in the CL and GDL thus causing hindered oxygen transport to the... 

Interfacial polymerization membranes. This type of anisotropic membrane is made by polymerizing an extremely thin layer of polymer at the surface of a microporous support polymer. 

An interesting group of composite membranes with very good properties is produced by condensation of furfuryl alcohol with sulfuric acid. The first membrane of this type was made by Cadotte at North Star Research and was known as the NS200 membrane [32], These membranes are not made by the interfacial composite process rather a polysulfone microporous support membrane is contacted first with an aqueous solution of furfuryl alcohol and then with sulfuric acid. The coated support is then heated to 140 °C. The furfuryl alcohol forms a polymerized, crosslinked layer on the polysulfone support the membrane is completely black. The chemistry of condensation and reaction is complex, but a possible polymerization scheme is shown in Figure 5.10. 

An important performance characteristic of passive samplers that operate in the TWA regime is the diffusion barrier that is inserted between the sampled medium and the sorption phase. This barrier is intended to control the rate of mass transfer of analyte molecules to the sorption phase. It is also used to define the selectivity of the sampler and prevent certain classes (e.g., polar or nonpolar compounds) of analytes, molecular sizes, or species from being sequestered. The resistance to mass transfer in a passive sampler is, however, seldom caused by a single barrier (e.g., a polymeric membrane), but equals the sum of the resistances posed by the individual media (e.g., aqueous boundary layer, biofilm, and membrane) through which analyte diffuses from the bulk water phase to the sorption phase.19 The individual resistances are equal to the reciprocal value of their respective mass transfer coefficients and are additive. They are directly proportional to the thickness of the barrier... 

Kemperman, A.J.B., Rolevink, H.H.M., Bargeman, D., Vandenboomgaard, T. and Strathmann, H. (1998) Stabilization of supported liquid membranes by interfadal polymerization top layers. Journal of Membrane Science, 138, 43. 

The greatest challenge in membrane extraction with a GC interface has been the slow permeation through the polymeric membrane and the aqueous boundary layer. The problem is much less in MIMS, where the vacuum in the mass spectrometer provides a high partial pressure gradient for mass transfer. The time required to complete permeation is referred to as lag time. In membrane extraction, the lag time can be significantly longer than the sample residence time in the membrane. An important reason is the bound-... 

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