Permeability gases

The situation is rather more complex in the case of a gas (assiuned to be non adsorbed by the membrane material) because compressibility and molecular effects, which predominate at low pressure, introduce a pressure dependence. Nevertheless the interpretation of results can yield more information than obtained with liquid media. 

The measurement of the permeability of non adsorbed gases is classically used to determine the range of pore size in membranes (macro, meso or micropores). Indeed by plotting the permeability as a function of gas pressure, a straight line is usually obtained whose slope gives an indication of the gas transport mechanism in the membrane. A quantitative description of pore structure can be attempted from the results. 

One method which is known under the name of permeametry [131] or Poiseuille-Knudsen method [124] is based on the law of gas permeability in a porous media in the two flow regimes molecular flow (Knudsen) and laminar or viscous flow (Poiseuille). According to Darcy s law, the gas flux through a membrane with a thickness / can be written as / = KAP/l, where K is the permeability coefficient and AP (AP = Pi - P2) the pressure difference across the membrane. If the membrane pore diameter is comparable to the mean free path of the permeating gas, K can be expressed as a stun of a viscous and a non-vis-cous term 

The modelling of gas permeation has been applied by several authors in the qualitative characterisation of porous structures of ceramic membranes [132-138]. Concerning the difficult case of gas transport analysis in microporous membranes, we have to notice the extensive works of A.B. Shelekhin et al. on glass membranes [139,14] as well as those more recent of R.S.A. de Lange et al. on sol-gel derived molecular sieve membranes [137,138]. The influence of errors in measured variables on the reliability of membrane structural parameters have been discussed in [136]. The accuracy of experimental data and the mutual relation between the resistance to gas flow of the separation layer and of the support are the limitations for the application of the permeation method. The interpretation of flux data must be further considered in heterogeneous media due to the effects of pore size distribution and pore connectivity. This can be conveniently done in terms of structure factors [5]. Furthermore the adsorption of gas is often considered as negligible in simple kinetic theories. Application of flow methods should always be critically examined with this in mind. 

As mentioned molds and cores must have a suitable permeability for gases, since upon casting of a hot liquid metal into a mold, moisture evaporates, the polymeric binder decomposes, and volatiles are formed. These must not harm the casting ingot and therefore should leave the mold via its porous network. Gas permeability is thus essential to avoid casting defects like blowholes and internal porosity, especially under the skin. Molds and cores bonded by RF aerogels have to be analyzed with respect to their permeability because 

A cylindrical chamber of volume Vc serves as a test volume. For the measurement, the test volume is evacuated to a preset pressure pdO) and the valve in front of the AeroSand piece is opened. Then the ambient pressure po, being measured, exists on one side of the sample and oti the other side initially the lower pressure p. The pressure difference drives a gas flow through the porous body. A vacuum gauge measures the pressure increase pdt) in the chamber with time. This pressure increase can be calculated to follow a law such as 

Od is the gas flow velocity through the porous body and dp/dr the applied pressure difference. A has the dimension of a squared length (see also Chap. 21). 

The theoretically predicted behavior was also confirmed by the experimentally measured pressure vs. time relation. It turned out that K is not a constant, but varies with pressure difference po — Pc(0). This is in contrast to the expectatimi that K is determined fuUy by the geometry of the porous body. Test measurements performed on sintered porous glass samples indicated that the permeability is indeed ccmstant and thus that the pressure difference dependence is a specialty of polymer-bonded sands, and aerogel-bonded sands are in this sense just a subclass. The polymer mixture does not bond aU sand grains perfectly 

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TABLE 10.5 Gas Permeability Constants (10 P) at 25°C for Polymers and Rubbers The gas permeability constant P is defined as... 

The gas permeability constant is the amount of gas expressed in cubic centimeters passed in 1 s through a 1-cm area of film when the pressure across a film thickness of 1 cm is 1 cmHg and the temperature is 25°C. All tabulated values are multiplied by 10 and are in units of seconds" (centimeters of Hg) k Other temperatures are indicated by exponents and are expressed in degrees Celsius. 

An extensive new Section 10 is devoted to polymers, rubbers, fats, oils, and waxes. A discussion of polymers and rubbers is followed by the formulas and key properties of plastic materials. Eor each member and type of the plastic families there is a tabulation of their physical, electrical, mechanical, and thermal properties and characteristics. A similar treatment is accorded the various types of rubber materials. Chemical resistance and gas permeability constants are also given for rubbers and plastics. The section concludes with various constants of fats, oils, and waxes. 

In one version of the urea electrode, shown in Figure 11.16, an NH3 electrode is modified by adding a dialysis membrane that physically traps a pH 7.0 buffered solution of urease between the dialysis membrane and the gas-permeable... 

One important application of amperometry is in the construction of chemical sensors. One of the first amperometric sensors to be developed was for dissolved O2 in blood, which was developed in 1956 by L. C. Clark. The design of the amperometric sensor is shown in Figure 11.38 and is similar to potentiometric membrane electrodes. A gas-permeable membrane is stretched across the end of the sensor and is separated from the working and counter electrodes by a thin solution of KCl. The working electrode is a Pt disk cathode, and an Ag ring anode is the... 

Potentiometric electrodes also can be designed to respond to molecules by incorporating a reaction producing an ion whose concentration can be determined using a traditional ion-selective electrode. Gas-sensing electrodes, for example, include a gas-permeable membrane that isolates the ion-selective electrode from the solution containing the analyte. Diffusion of a dissolved gas across the membrane alters the composition of the inner solution in a manner that can be followed with an ion-selective electrode. Enzyme electrodes operate in the same way. 

See Barrier POLYMERS for a discussion of units of gas permeability and WVTR. 

The principal packagiag use of PVC film is as a gas-permeable but water-vapor impermeable wrap for red meat, poultry, and produce. Sparkle and transparency, combined with the abiHty to transmit oxygen to maintain red-meat color, offer advantages in these appHcations. 

Gas Permeability. Crystalline PMP is relatively highly permeable to various organic and inorganic gases. Permeabilities to oxygen, nitrogen. 

The effect of copolymer composition on gas permeability is shown in Table 9. The inherent barrier in VDC copolymers can best be exploited by using films containing Htde or no plasticizers and as much VDC as possible. However, the permeabiUty of even completely amorphous copolymers, for example, 60% VDC—40% AN or 50% VDC—50% VC, is low compared to that of other polymers. The primary reason is that diffusion coefficients of molecules in VDC copolymers are very low. This factor, together with the low solubiUty of many gases in VDC copolymers and the high crystallinity, results in very low permeabiUty. PermeabiUty is affected by the kind and amounts of comonomer as well as crystallinity. A change from PVDC to 50 wt °/ VC or 40 wt % AN increases permeabiUty 10-fold, but has Httle effect on the solubiUty coefficient. 

Vinyl neopentanoate is used in the preparation of adhesives and binders (44—46), optical materials for plastic lenses (47), gas permeable membranes for oxygen enrichment (48), and in coating appHcations (49,50). 

The number of contact lens wearers has grown to an estimated 24 million in the United States and 50 million worldwide. Concurrendy, there has been a proliferation of contact lens manufacturers and products. The 1980s saw the widespread introduction of lens products made of more oxygen-permeable materials, ie, rigid gas-permeable (RGP) materials that made PMMA lenses virtually obsolete and high water content hydrogels that competed with HEMA-based lenses. 

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