Asymmetric films

Zeolite/polymer mixed-matrix membranes can be fabricated into dense film, asymmetric flat sheet, or asymmetric hollow fiber. Similar to commercial polymer membranes, mixed-matrix membranes need to have an asymmetric membrane geometry with a thin selective skin layer on a porous support layer to be commercially viable. The skin layer should be made from a zeohte/polymer mixed-matrix material to provide the membrane high selectivity, but the non-selective porous support layer can be made from the zeohte/polymer mixed-matrix material, a pure polymer membrane material, or an inorganic membrane material. 

J. Sasaki, K. Naruo, Kyoichi (Fuji Photo Film). Asymmetric microporous membrane containing a layer of minimum size pores below the surface thereof. US Patent 4933081, June 1990. 

Chemical properties of deposited monolayers have been studied in various ways. The degree of ionization of a substituted coumarin film deposited on quartz was determined as a function of the pH of a solution in contact with the film, from which comparison with Gouy-Chapman theory (see Section V-2) could be made [151]. Several studies have been made of the UV-induced polymerization of monolayers (as well as of multilayers) of diacetylene amphiphiles (see Refs. 168, 169). Excitation energy transfer has been observed in a mixed monolayer of donor and acceptor molecules in stearic acid [170]. Electrical properties have been of interest, particularly the possibility that a suitably asymmetric film might be a unidirectional conductor, that is, a rectifier (see Refs. 171, 172). Optical properties of interest include the ability to make planar optical waveguides of thick LB films [173, 174]. 

The seminal discovery that transformed membrane separation from a laboratory to an industrial process was the development, in the early 1960s, of the Loeb-Sourirajan process for making defect-free, high flux, asymmetric reverse osmosis membranes (5). These membranes consist of an ultrathin, selective surface film on a microporous support, which provides the mechanical strength. The flux of the first Loeb-Sourirajan reverse osmosis membrane was 10 times higher than that of any membrane then avaUable and made reverse osmosis practical. The work of Loeb and Sourirajan, and the timely infusion of large sums of research doUars from the U.S. Department of Interior, Office of Saline Water (OSW), resulted in the commercialization of reverse osmosis (qv) and was a primary factor in the development of ultrafiltration (qv) and microfiltration. The development of electro dialysis was also aided by OSW funding. 

Nonporous Dense Membranes. Nonporous, dense membranes consist of a dense film through which permeants are transported by diffusion under the driving force of a pressure, concentration, or electrical potential gradient. The separation of various components of a solution is related directiy to their relative transport rate within the membrane, which is determined by their diffusivity and solubiUty ia the membrane material. An important property of nonporous, dense membranes is that even permeants of similar size may be separated when their concentration ia the membrane material (ie, their solubiUty) differs significantly. Most gas separation, pervaporation, and reverse osmosis membranes use dense membranes to perform the separation. However, these membranes usually have an asymmetric stmcture to improve the flux. 

Because membranes appHcable to diverse separation problems are often made by the same general techniques, classification by end use appHcation or preparation method is difficult. The first part of this section is, therefore, organized by membrane stmcture preparation methods are described for symmetrical membranes, asymmetric membranes, ceramic and metal membranes, and Hquid membranes. The production of hollow-fine fiber membranes and membrane modules is then covered. Symmetrical membranes have a uniform stmcture throughout such membranes can be either dense films or microporous. 

LB films of 1,4,8,11,15,18-hexaoctyl-22,25-bis-(carboxypropyl)-phthalocyanine (2), an asymmetrically substituted phthalocyanine, were stable monolayers formed at the water—air interface that could be transferred onto hydrophilic siUca substrates (32—34). When a monolayer film of the phthalocyanine derivative was heated, there was a remarkable change in the optical spectmm. This, by comparison to the spectmm of the bulk material, indicated a phase transition from the low temperature herringbone packing, to a high temperature hexagonal packing. 

Cellulose acetate, the earhest reverse osmosis membrane, is still widely used. Asymmetric polyamide and thin-film composites of polyamide and several other polymers have also made gains in recent years whereas polysulfone is the most practical membrane material in ultrafiltration appHcations. 

M. F. Toney and S. Brennan. Structural Depth Profiling of Iron Oxide Thin Films using Grazing Incidence Asymmetric Bra X-ray DiflFraction. J. Appl. Phys. 65J 4763, 1989. 

The simplest and most widely used model to explain the response of organic photovoltaic devices under illumination is a metal-insulaior-metal (MIM) tunnel diode [55] with asymmetrical work-function metal electrodes (see Fig. 15-10). In forward bias, holes from the high work-function metal and electrons from the low work-function metal are injected into the organic semiconductor thin film. Because of the asymmetry of the work-functions for the two different metals, forward bias currents are orders of magnitude larger than reverse bias currents at low voltages. The expansion of the current transport model described above to a carrier generation term was not taken into account until now. 

Waveguiding inside the film is crucial mirrorlcss lasing has not been observed in annealed films of 100 nm thickness, a thickness which is below the cut-off value for waveguiding in this asymmetric layered structure. 

Numerous research activities have focused on the improvement of the protective films and the suppression of solvent cointercalation. Beside ethylene carbonate, significant improvements have been achieved with other film-forming electrolyte components such as C02 [156, 169-177], N20 [170, 177], S02 [155, 169, 177-179], S/ [170, 177, 180, 181], ethyl propyl carbonate [182], ethyl methyl carbonate [183, 184], and other asymmetric alkyl methyl carbonates [185], vinylpropylene carbonate [186], ethylene sulfite [187], S,S-dialkyl dithiocarbonates [188], vinylene carbonate [189], and chloroethylene carbonate [190-194] (which evolves C02 during reduction [195]). In many cases the suppression of solvent co-intercalation is due to the fact that the electrolyte components form effective SEI films already at potential which are positive relative to the potentials of solvent co-intercalation. An excess of DMC or DEC in the electrolyte inhibits PC co-intercalation into graphite, too [183]. 

Electrode surface, and dipole potential difference or potential dependence, 15 Electrode systems, unstable, with asymmetrical fluctuations, 255 Electrode-electrite interface, microwave power and its effect on, 439 Electrogenerated films, storage capacity, 321... 

Flade potential, 247 Flame-annealed gold surfaces and the work of Kolb, 81 Flat band potential, 483 Fluctuations asymmetrical and unstable systems, 255 controlling progress in pitting, 299 in pitting dissolution, 251 and corrosion processes, 217 during dissolution, 252 at electrodes, theory, 281 during film breakdown, 233 and mathematical expressions thereof, 276... 

Thus the formation of tilted analogues of the smectic A phases, i.e. monolayer Cl and bilayer C2, is possible for mesogens with relatively large electric quadrupoles. In the case of strongly sterically asymmetric molecules (e.g., zigzag shaped or dumbell shaped molecules, Fig. 3b) these quadrupolar interactions may be steric in origin. From this point of view observation of molecular tilt in the molecular dynamics simulations for a one-layer film of DOBAMBC in the absence of electrostatic interactions is not so surprising [106]. 

Microscopy methods based on nonlinear optical phenomena that provide chemical information are a recent development. Infrared snm-frequency microscopy has been demonstrated for LB films of arachidic acid, allowing for surface-specific imaging of the lateral distribution of a selected vibrational mode, the asymmetric methyl stretch [60]. The method is sensitive to the snrface distribntion of the functional gronp as well as to lateral variations in the gronp environmental and conformation. Second-harmonic generation (SHG) microscopy has also been demonstrated for both spread monolayers and LB films of dye molecules [61,62]. The method images the molecular density and orientation field with optical resolution, and local qnantitative information can be extracted. 

Zhao, J., Jiang, S., Ji, X., Lijia, L.An. and Jiang, B. (2005) Study of the time evolution of the surface morphology of thin asymmetric diblock copolymer films under solvent vapor. Polymer, 46, 6513-6521. 

The theory has been verified by voltammetric measurements using different hole diameters and by electrochemical simulations [13,15]. The plot of the half-wave potential versus log[(4d/7rr)-I-1] yielded a straight line with a slope of 60 mV (Fig. 3), but the experimental points deviated from the theory for small radii. Equations (3) to (5) show that the half-wave potential depends on the hole radius, the film thickness, the interface position within the hole, and the diffusion coefficient values. When d is rather large or the diffusion coefficient in the organic phase is very low, steady-state diffusion in the organic phase cannot be achieved because of the linear diffusion field within the microcylinder [Fig. 2(c)]. Although no analytical solution has been reported for non-steady-state IT across the microhole, the simulations reported in Ref. 13 showed that the diffusion field is asymmetrical, and concentration profiles are similar to those in micropipettes (see... 

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