Barriers/barrier layers diffusion through

A key factor determining the performance of ultrafiltration membranes is concentration polarization due to macromolecules retained at the membrane surface. In ultrafiltration, both solvent and macromolecules are carried to the membrane surface by the solution permeating the membrane. Because only the solvent and small solutes permeate the membrane, macromolecular solutes accumulate at the membrane surface. The rate at which the rejected macromolecules can diffuse away from the membrane surface into the bulk solution is relatively low. This means that the concentration of macromolecules at the surface can increase to the point that a gel layer of rejected macromolecules forms on the membrane surface, becoming a secondary barrier to flow through the membrane. In most ultrafiltration appHcations this secondary barrier is the principal resistance to flow through the membrane and dominates the membrane performance. 

A fundamental difference exists between the assumptions of the homogeneous and porous membrane models. For the homogeneous models, it is assumed that the membrane is nonporous, that is, transport takes place between the interstitial spaces of the polymer chains or polymer nodules, usually by diffusion. For the porous models, it is assumed that transport takes place through pores that mn the length of the membrane barrier layer. As a result, transport can occur by both diffusion and convection through the pores. Whereas both conceptual models have had some success in predicting RO separations, the question of whether an RO membrane is truly homogeneous, ie, has no pores, or is porous, is still a point of debate. No available technique can definitively answer this question. Two models, one nonporous and diffusion-based, the other pore-based, are discussed herein. 

In 1929 Pfeil" published a most interesting account of the way layered structures form and the manner in which they influence oxidation rates. From detailed studies of the growth and composition of scales he was able to show clearly how the formation of barrier layers reduced scale formation by hindering outward diffusion of iron through the scale. Naturally, this work had to be largely based on the study of scales of sufficient thickness so that the mechanism of the early stages of oxidation could not be studied in this way. Pfeil analysed the outer, middle and inner layers of scales formed... 

The characteristic feature of solid—solid reactions which controls, to some extent, the methods which can be applied to the investigation of their kinetics, is that the continuation of product formation requires the transportation of one or both reactants to a zone of interaction, perhaps through a coherent barrier layer of the product phase or as a monomolec-ular layer across surfaces. Since diffusion at phase boundaries may occur at temperatures appreciably below those required for bulk diffusion, the initial step in product formation may be rapidly completed on the attainment of reaction temperature. In such systems, there is no initial delay during nucleation and the initial processes, perhaps involving monomolec-ular films, are not readily identified. The subsequent growth of the product phase, the main reaction, is thereafter controlled by the diffusion of one or more species through the barrier layer. Microscopic observation is of little value where the phases present cannot be unambiguously identified and X-ray diffraction techniques are more fruitful. More recently, the considerable potential of electron microprobe analyses has been developed and exploited. 

If a diffusion barrier is required, then a titanium/nitride (Ti/TiN) is used. This counteracts the tendency of most metals to diffuse through a given structure, particularly if the layers are composed of several different t rpes of metals, connections. 

The sole purpose of the filter support and any applied extracellular matrix is simply to provide a surface for cell attachment and thus to provide mechanical support to the monolayer. However, the filter and matrix also can act as serial barriers to solute movement after diffusion through the cell monolayer. The important variables are the chemical composition of the filter, porosity, pore size, and overall thickness. In some cases, pore tortuosity also can be important. It is desired that the filter, with or without an added matrix, provide a favorable surface to which the cells can attach. However, in some cases these properties can also result in an attractive surface for nonspecific adsorption of the transported solute. In these instances, the appearance of the solute in the receiver compartment of the diffusion cell will not be a true reflection of its movement across the mono-layer. Such problems must be examined on a case-by-case basis. 

The chemical incorporated in a vehicle should reach the surface of the skin at a suitable rate and concentration. If the site of action lies in the deeper layers of the epidermis or below, the substance must cross the stratum comeum, if the skin is intact. Both processes, diffusion from the dosage form and diffusion through the skin barriers, are inextricably linked. They should be considered simultaneously and can be influenced by the choice of formulation. 

Mitrovic and Knezic (1979) also prepared ultrafiltration and reverse osmosis membranes by this technique. Their membranes were etched in 5% oxalic acid. The membranes had pores of the order of 100 nm, but only about 1.5 nm in the residual barrier layer (layer AB in Figure 2.15). The pores in the barrier layer were unstable in water and the permeability decreased during the experiments. Complete dehydration of alumina or phase transformation to a-alumina was necessary to stabilize the pore structure. The resulting membranes were found unsuitable for reverse osmosis but suitable for ultrafiltration after removing the barrier layer. Beside reverse osmosis and ultrafiltration measurements, some gas permeability data have also been reported on this type of membranes (Itaya et al. 1984). The water flux through a 50/im thick membrane is about 0.2mL/cm -h with a N2 flow about 6cmVcm -min-bar. The gas transport through the membrane was due to Knudsen diffusion mechanism, which is inversely proportional to the square root of molecular mass. 

Diffusion barriers are coatings that serve in that role specifically, protection against undesirable diffusion. One of the best examples is that of a 100- tm-thick electrode-posited copper layer that serves as an effective barrier against the diffusion of carbon. Another example is that of nickel and nickel alloys (notably, electrolessly deposited Ni-P) that block diffusion of copper into and through gold overplate. This is achieved by the deposition of a relatively thin Ni-P layer (less than 1 /mm) between the copper and its overlayer. Naturally, the effectiveness of the diffusion barrier increases with its thickness. Other factors in the effectiveness of a diffusion barrier... 

Beta-lactam antibiotics must pass through the outer layer of the cell in order to get the desired PBP to the surface of the membrane. In Gram-positive bacteria, the cell membrane is the only layer covering the cytoplasmic membrane. In a few types of this bacteria, there is a polysaccharide capsule on the outer side of the cell membrane. However, not one of the described structures can serve as a barrier for the diffusion of small molecules such as beta-lactams. Therefore, the idea that the cause of possible resistance is the inability of beta-lactam antibiotics to get the desired PBP is not likely to be a possible mechanism of resistance for Gram-positive bacteria. 

The decrease in the alpha factor to values below a = 1 can be due to a decrease in either kL or a or both. Two theories are commonly used to explain the reduction in kp. the barrier effect and the hydrodynamic effect. In the barrier theory, the presence of the surfactants at the phase interface creates an additional resistance to mass transfer due to diffusion through the surfactant layer. In the hydrodynamic theory, the layer of surfactant molecules at the gas-liquid interface depresses the hydrodynamic activity (Gurol and Nekouinaini, 1985). 

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