Diffusion silicone rubber

The accuracy of constant k has been evaluated by comparing the experimental values of 0(t) with the values deduced from Eq. (28) for contact times greater than 30 minutes shown in Table 1. Good agreement between both series of values justifies the simple model of diffusion of TCP in silicone rubber. 

This process involves the suspension of the biocatalyst in a monomer solution which is polymerized, and the enzymes are entrapped within the polymer lattice during the crosslinking process. This method differs from the covalent binding that the enzyme itself does not bind to the gel matrix. Due to the size of the biomolecule it will not diffuse out of the polymer network but small substrate or product molecules can transfer across or within it to ensure the continuous transformation. For sensing purposes, the polymer matrix can be formed directly on the surface of the fiber, or polymerized onto a transparent support (for instance, glass) that is then coupled to the fiber. The most popular matrices include polyacrylamide (Figure 5), silicone rubber, poly(vinyl alcohol), starch and polyurethane. 

The heat of permeation of chlorine in a silicone rubber membrane is —3 to — 5 kcal mol-1 while that of nitrogen is 1.0-1.5 kcal mol-1. Separation of these gases therefore is helped by low temperature. The flux of chlorine actually increases as temperature is lowered, reflecting the increased sorption. The flux of nitrogen decreases, reflecting the lower diffusivity. 

With polymeric phases containing a relatively thick silicon rubber layer inside the pores not only the reduction in pore diameter available for solute diffusion but also the mass transfer resistance in the alkyl polysi-... 

Figure 5.23 — Flow-through ionophore-based sensor for the determination of lithium in serum. (A) Mechanism involved in the sensor response (symbol meanings as in Fig. 5.20). (B) Diffuse reflectance flow-cell (a) upper stainless steel cell body (A) silicon rubber packing (c) quartz glass window (d) Teflon spacer (0.05 mm thickness) (e) hydrophobic surface mirror (/) lower stainless steel cell body. For details, see text. (Reproduced from [90] with permission of the American Chemical Society).

Several different membrane materials have been used, namely Teflon, polyethylene, and silicon rubber among others. It is possible to obtain some degree of selectivity by choosing the material of this membrane according to the conditions of the application. The diffusion through such a structure is more complicated. For radial geometry, the steady-state current is given as... 

Figure 2.20 Permeant diffusion coefficient as a function of permeant molecular weight in water, natural rubber, silicone rubber and polystyrene. Diffusion coefficients of solutes in polymers usually lie between the value in natural rubber, an extremely permeable polymer, and the value in polystyrene, an extremely impermeable material [28]...

Various analytical techniques make use of both porous and nonporous (semipermeable) membranes. For porous membranes, components are separated as a result of a sieving effect (size exclusion), that is, the membrane is permeable to molecules with diameters smaller than the membrane pore diameter. The selectivity of such a membrane is thus dependent on its pore diameter. The operation of nonporous membranes is based on differences in solubility and the diffusion coefficients of individual analytes in the membrane material. A porous membrane impregnated with a liquid or a membrane made of a monolithic material, such as silicone rubber, can be used as nonporous membranes. 

Table 4.2 illustrates the various selectivity factors for some typical rubbery polymers, that is, silicone rubber, poly(dimethyl siloxane), and natural rubber, polyiso-prene, and a glassy polymer, polysulfone. Here, we consider the important 02/N2 pair and several pairs involving C02 that will be our focus later. In all the cases, the solubility selectivity is greater than unity and there is not a large difference between rubbery and glassy polymers. For most of these pairs, the diffusion selectivity is greater than unity, but there are some exceptions for C02/02 and C02/N2 that reflect... 

Table 4.3 shows the permselectivity characteristics of pure, semicrystalline PEO films [76]. The selectivity characteristics for 02/N2 are rather similar to those for silicone rubber and natural rubber shown in Table 4.2. However, the values of permselectivity for C02 relative to the various light gases shown are all much higher than Table 4.2 shows for the rubbery polymers listed there and even for polysulfone except for C02/CH4. Comparison of the data in Tables 4.2 and 4.3 makes it clear that this high permselectivity of PEO stems from its high solubility selectivity for C02 versus other gases this is augmented by modest values of diffusivity selectivity. Data in Table 4.4 for the C02/N2 pair illustrate that this effect can be translated into various block-copolymer structures when the PEO content is high enough to ensure it is the continuous phase. In fact, nearly all these materials have higher permselectivity and solubility selectivity for C02/N2 than does pure PEO (see Table 4.3) however, the diffusion selectivity for these copolymers is much closer to, or even less than, unity than seen for pure PEO. Furthermore, the copolymers all have much higher absolute permeability coefficients than does PEO.

Membrane-reservoir systems based on solution-diffusion mechanism have been utilized in different forms for the controlled delivery of therapeutic agents. These systems including membrane devices, microcapsules, liposomes, and hollow fibres have been applied to a number of areas ranging from birth control, transdermal delivery, to cancer therapy. Various polymeric materials including silicone rubber, ethylene vinylacetate copolymers, polyurethanes, and hydrogels have been employed in the fabrication of such membrane-reservoir systems (13). 

Fillers such as silica In silicone rubber have the same effect as crystallinity, reducing polymer motion by physical crosslinking and increasing the tortuosity of the diffusion path (14,15). 

Paul and McSpadden studied the permeation of a red organic dye (Sudan III) in acetone through a silicone rubber membrane as shown in Figure 6.9. The partition coefficient of 0.148 has been independently determined for the dye in the membrane and in acetone by an extraction method. Calculate the diffusion coefficient and the solubility of the dye. Assume that the thickness and the diameter of the membrane are 0.15 cm and 8 mm, respectively. 

FIG. 18.3 Activation energy of diffusion as a function of Tg for 21 different polymers from low to high temperatures, ( ) odd numbers (O) even numbers 1. Silicone rubber 2. Butadiene rubber 3. Hydropol (hydrogenated polybutadiene = amorphous polyethylene) 4. Styrene/butadiene rubber 5. Natural rubber 6. Butadiene/acrylonitrile rubber (80/20) 7. Butyl rubber 8. Ethylene/propylene rubber 9. Chloro-prene rubber (neoprene) 10. Poly(oxy methylene) 11. Butadiene/acrylonitrile rubber (60/40) 12. Polypropylene 13. Methyl rubber 14. Poly(viny[ acetate) 15. Nylon-11 16. Poly(ethyl methacrylate) 17. Polyethylene terephthalate) 18. Poly(vinyl chloride) 19. Polystyrene 20. Poly (bisphenol A carbonate) 21. Poly(2,6 dimethyl-p.phenylene oxide). 

Here, an ISE in contact with a thin external layer of aqueous electrolyte (the filling solution ) is kept close to the glass membrane by an additional, outer membrane that is selectively permeable to the gas of interest. The arrangement for a CO2 electrode is shown in Fig. 34.4 in this case the outer membrane is made of C02-permeable silicone rubber. When CO2 gas in the sample selectively diffuses across the membrane and dissolves in the filling solution (in this case an aqueous NaHCOs/NaCl mixture), a change in pH occurs owing to the shift in the equilibrium ... 

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