Pore of polymers

Irradiation of heavy ions like An and Kr deposits a heavy damage along the ion track in polymer films. When some polymer films are irradiated with heavy ions and dipped in an alkaline aqueous solution, micropores are produced along the ion track. Since the shape and size of pores of polymers can be controlled by etching conditions and by the species of heavy ions, these polymer films are expected to be used for high-performance filters and ion detectors [92]. The development of the polymer filters and ion detectors are described as follows. 

FIGURE 18.1 Production of ion-track membranes (a) and electroplating of cooper nanowires within the pores of polymer membranes (b). 

The total volume of open pores Vp of the cryogels can easily be estimated through uptake of a poor solvent, such as acetone for PAAm or methanol for PIB cryogels. Since a poor solvent for polymer can only enter into the pores of polymer networks, Vp (milliliters of pores in 1 g of dry polymer network) can be calculated... 

The surface chemistry of electronically conducting polymers represents a virgin field. The surface electrochemical area, particularly study of the double layer and its interface (metallic or Schottky ) awaits development. Electrodekinetics has not been examined from the basic point of view. For example, it is not known to what degree diffusion and transport in the pores of polymer electrodes control the rate of electrode reactions. What is the order of magnitude of rate constants involved in various electrochemical reactions which have electronically conducting polymers as their substrate ... 

Khorasani, A.N. Molecular modeling of proton and water distribution in catalyst layer pores of polymer electrolyte fuel cells. Abstract MA2012-011059. 

Dobrev, D., Vetter, J., Angert, N. and Neumann, R. (1999) Electrochemical growth of copper single aystals in pores of polymer ion-track membranes. 

Two classes of micron-sized stationary phases have been encountered in this section silica particles and cross-linked polymer resin beads. Both materials are porous, with pore sizes ranging from approximately 50 to 4000 A for silica particles and from 50 to 1,000,000 A for divinylbenzene cross-linked polystyrene resins. In size-exclusion chromatography, also called molecular-exclusion or gel-permeation chromatography, separation is based on the solute s ability to enter into the pores of the column packing. Smaller solutes spend proportionally more time within the pores and, consequently, take longer to elute from the column. 

A detailed examination of the correlation between Vj and M is discussed in references on analytical chemistry such as Ref. 6. We shall only outline the problem, with particular emphasis on those aspects which overlap other topics in this book. To consider the origin of the calibration curve, we begin by picturing a narrow band of polymer solution being introduced at the top of a solvent-filled column. The volume of this solvent can be subdivided into two categories the stagnant solvent in the pores (subscript i for internal) and the interstitial liquid in the voids (subscript v) between the packing particles ... 

Figure 9.15 Schematic illustration of size exclusion in a cylindrical pore (a) for spherical particles of radius R and (b) for a flexible chain, showing allowed (solid) and forbidden (broken) conformations of polymer.

Membranes made by interfacial polymerization have a dense, highly cross-linked interfacial polymer layer formed on the surface of the support membrane at the interface of the two solutions. A less cross-linked, more permeable hydrogel layer forms under this surface layer and fills the pores of the support membrane. Because the dense cross-linked polymer layer can only form at the interface, it is extremely thin, on the order of 0.1 p.m or less, and the permeation flux is high. Because the polymer is highly cross-linked, its selectivity is also high. The first reverse osmosis membranes made this way were 5—10 times less salt-permeable than the best membranes with comparable water fluxes made by other techniques. 

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. 

Gels are viscoelastic bodies that have intercoimected pores of submicrometric dimensions. A gel typically consists of at least two phases, a soHd network that entraps a Hquid phase. The term gel embraces numerous combinations of substances, which can be classified into the following categories (2) (/) weU-ordered lamellar stmctures (2) covalent polymeric networks that are completely disordered (2) polymer networks formed through physical aggregation that are predominantly disordered and (4) particular disordered stmctures. 

Most photochromic compounds undergo large stmctural changes while being transformed from the uncolored to the colored form. This property has been used to examine the pore si2e of polymers by utili2ing the relationship of pore si2e and the kinetics of the photochromic response (46). 

In recent years there has been a renewed appreciation of potential beneficial effects of roughness on a macroscale. For example Morris and Shanahan worked with sintered steel substrates bonded with a polyurethane adhesive [61]. They observed much higher fracture energy for joints with sintered steel compared with those with fully dense steel, and ascribed this to the mechanical interlocking of polymer within the pores. Extra energy was required to extend and break these polymer fibrils. 

A. Milchev, K. Binder. Dynamics of polymer chains confined in slit-like pores. J Physique 7/5 21-31, 1996. 

The porosity of polymer beads is controlled by the ratio of diluents (poro-gen) to monomers in the organic phase. The increase in the ratio of diluents to monomer in the monomer mixture increases the porosity of polymer beads. The pore size can be manipulated by adjusting the ratio of nonsolvating and solvating diluents in the monomer mixture. The increase in the ratio of nonsolvating diluent (precipitant) in the monomer mixture increases the pore sizes and vice versa. 

Porosity and surface area are routinely measured by nitrogen absorption-desorption, mercury intrusion, and low-angle X ray. The electron microscope (EM) provides direct visual evidence of pore size and pore-size distribution. Thus, a combination of EM and conventional methods of pore-size measurement should provide reliable information on the pore structure of polymers. 

When a dilute solution of a polymer (c << c ) is equilibrated with a porous medium, some polymer chains are partitioned to the pore channels. The partition coefficient K, defined as the ratio of the polymer concentration in the pore to the one in the exterior solution, decreases with increasing MW of the polymer (7). This size exclusion principle has been used successfully in SEC to characterize the MW distribution of polymer samples (8). 

The partitioning principle is different at high concentrations c > c . Strong repulsions between solvated polymer chains increase the osmotic pressure of the solution to a level much higher when compared to an ideal solution of the same concentration (5). The high osmotic pressure of the solution exterior to the pore drives polymer chains into the pore channels at a higher proportion (4,9). Thus K increases as c increases. For a solution of monodisperse polymer, K approaches unity at sufficiently high concentrations, but never exceeds unity. 

The porous materials that offer the narrowest possible pore size distribution are those that have cylindrical pores of uniform diameter penetrating the entire medium without branching. Branching gives polymer molecules in the junctions extra conformational entropy. An agglomerate of tiny pieces of these porous materials, interlaced with larger voids (much larger than the pore size), should also be chosen. 

These replaceable cartridges or packs are the most commonly used however, there are cartridges of wire mesh, sintered or porous metal which can be removed, cleaned, and replaced. Usually, the fine pores of the metal become progressively plugged and the cartridges lose capacity. They are often used for filtering hot fluids, or polymers with suspended particles, pharmaceuticals, and foods (liquids). In the case of polymers and other applications a special solvent and blow-back cleaning system may be employed. 

Large yields of polymer seem to be obtained only when polymerization proceeds on the outer catalyst surface, because the transport of high molecular polyethylene from catalyst pores is impossible (112). The working part of the specific surface of the catalyst can be expected to increase with diminishing strength of links between catalyst particles (112). Therefore, to obtain a highly active catalyst a support with large pore volume should be used (e.g. silica with pore volume >1.5 cm8/g). 

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