Cellulose acetate, permeability

FIG. 22-76 Constant -cost lines as a function of permeability and selectivity for CO2/CH4, Cellulose-acetate membrane mscf is one thousand standard cubic feet, CouHesy VP R. Grace.)... 

Polymer blends have been categorized as (1) compatible, exhibiting only a single Tg, (2) mechanically compatible, exhibiting the Tg values of each component but with superior mechanical properties, and (3) incompatible, exhibiting the unenhanced properties of phase-separated materials (8). Based on the mechanical properties, it has been suggested that PCL-cellulose acetate butyrate blends are compatible (8). Dynamic mechanical measurements of the Tg of PCL-polylactic acid blends indicate that the compatability may depend on the ratios employed (65). Both of these blends have been used to control the permeability of delivery systems (vide infra). 

The predominant RO membranes used in water applications include cellulose polymers, thin film oomposites (TFCs) consisting of aromatic polyamides, and crosslinked polyetherurea. Cellulosic membranes are formed by immersion casting of 30 to 40 percent polymer lacquers on a web immersed in water. These lacquers include cellulose acetate, triacetate, and acetate-butyrate. TFCs are formed by interfacial polymerization that involves coating a microporous membrane substrate with an aqueous prepolymer solution and immersing in a water-immiscible solvent containing a reactant [Petersen, J. Memhr. Sol., 83, 81 (1993)]. The Dow FilmTec FT-30 membrane developed by Cadotte uses 1-3 diaminobenzene prepolymer crosslinked with 1-3 and 1-4 benzenedicarboxylic acid chlorides. These membranes have NaCl retention and water permeability claims. 

This technique has been applied to the concentration of organochlorine and organophosphorus insecticide [7,8] and various ethers, glycols amines, nitriles, hydrocarbons, and chlorinated hydrocarbons. Although this work was concerned with drinking water, it is a useful technique which may have application in seawater analysis. Cellulose acetate [9], ethyl cellulose acetate [6], and crosslinked polyethyleneinine [8] have been used as semi-permeable membranes. 

Membrane Specifications. At a specified operating temperature and pressure, a cellulose acetate membrane is completely specified in terms of its pure water permeability constant A and solute transport parameter D /k6 for a convenient reference solute such as sodium chloride. A single set of experimental data on (PWP), (PR), and f at known operating conditions is enough to obtain data on the specifying parameters A and (DAM/X6)jjg(. 2 at any given temperature and pressure. 

Of the existing flat-sheet RO membranes, cellulose acetate membranes of the Loeb-Sourirajan type give the best results because their open microporous substrate minimizes internal concentration polarization. Conventional interfacial composite membranes, despite their high water permeabilities and good salt rejections, are not suitable for PRO because of severe internal concentration polarization. 

Model of Deterioration Mechanisum, As acetyl content decreases due to hydrolysis or oxidation of ester bonding, solute permeability increases. Then concentration of solute( in this case sodium hypochlorite) in the membrane increases and the hydrolysis or oxidation rate increases and so on. It will be more reasonable to assume that hydrolysis or oxidation rate of cellulose acetate in the active surface layer may be accelerated by the action of the nascent oxygen generated from sodium hypochlorite. 

Chlorine is the oldest and most widespread method of water disinfection. In reverse osmosis systems, chlorine may be added to feedwater for control of micro-organisms and, in addition, to prevent membrane fouling by microbiological growth. According to Vos et al. [i,2], chlorine will attack cellulose diacetate membranes at concentrations above 50 ppm. Membranes were found to show a sharp increase in salt permeability and a decrease in strength after one week of continuous exposure. Under milder conditions (10 ppm chlorine for 15 days) no detectable change in performance was observed. Spatz and Friedlander [3] have also found cellulose acetate membranes to be resistant to chlorine when exposed to 1.5 ppm for three weeks. 

The rate of transmission of gases and vapors through polymeric films varies with the structure of both the diffusate molecule and the polymer. Polymers with polar groups, such as cellulose and cellulose acetate, are permeable to water vapor, but polymeric hydrocarbons, such as PIB, are essentially impervious to water vapor. 

The requirement of hydrophilicity in barrier materials has been widely accepted, but the mechanism by which it affects membrane performance, especially for the permselectivity, is not fully understood. Cellulose acetate and some kinds of polyamides and their analogues featured in the present review have both hydraulic permeability and permselectivity, while most highly hydrophilic materials have high permeability for water and show unselective permeation for ions and organic solutes. 

From the data in Table III. 1 it may be seen that cellophane and cellulose acetate have very large permeabilities to water also, the solubility of water in these materials is great, so they are clearly unsuited as moisture barriers. Of the elastomers listed, silicone rubber has the highest permeability to air. 

Additional semipermeable membrane—forming polymers are selected from the group consisting of acetaldehyde dimethyl cellulose acetate, cellulose acetate ethyl carbamate, cellulose dimethylamino acetate, semipermeable polyamides, semipermeable polyurethanes, or semipermeable sulfonated polystyrenes. Semipermeable cross-linked selectively permeable polymers formed by coprecipitation of a polyanion and a polycation also can be used for this purpose.22 23 Other polymer materials such as lightly cross-linked polystyrene derivatives, semipermeable cross-linked poly(sodium styrene sulfonate), and semipermeable poly (vinylbenzyltrimethyl ammonium chloride) may be considered.24,25... 

This so-called "active" layer has characteristics similar to those of cellulose acetate films but with a thickness of the order of 0.1 micrometer (jjm) or less, whereas the total membrane thickness may range from approximately 75 to 125 ym (see Figure 1). The major portion of the membrane is an open-pore sponge-like support structure through which the gases flow without restriction. The permeability and selectivity characteristics of these asymmetric membranes are functions of casting solution composition, film casting conditions and post-treatment, and are relatively independent of total membrane thickness. 

Other system variables that will have an effect on the separation process are temperature and relative humidity of the gas. Increasing the temperature raises most permeabilities by about 10 to 15% per 10°C and has little effect on separation factors. The effect of relative humidity is variable depending upon the membrane used. High relative humidities, greater than 95%, are generally detrimental due to membrane plasticization. Contamination with liquid water has been found to dramatically reduce membrane performance for cellulose acetate ... 

Finally, PSPs based on the OEP metal complexes in various cellulose derivative polymers also have been introduced. Cellulose derivative polymers such as ethyl cellulose, cellulose acetate etc., as shown in Fig. 9, also provide a mechanical strength to thin film. The oxygen permeability, diffusion constant, and solubility for oxygen for typical cellulose derivative polymers are listed in Table 1. Cellulose derivative polymer films with plasticizer tributyl phosphate (TBP) have large oxygen permeability. Cellulose acetate with TBP... 

Equation (4.9) shows that concentration polarization increases exponentially as the total volume flow Jv through the membrane increases. This is one of the reasons why modem spiral-wound reverse osmosis membrane modules are operated at low pressures. Modem membranes have two to five times the water permeability, at equivalent salt selectivities, of the first-generation cellulose acetate reverse osmosis membranes. If membrane modules containing these new membranes were operated at the same pressures as early cellulose acetate modules, two to five times the desalted water throughput could be achieved with the same... 

Figure 5.4 Permeabilities of cellulose acetate to water and sodium chloride as a function of acetyl content at 25 °C. Data from Lonsdale et al. [20]...

Figure 5.5 Water permeability as a function of sodium chloride permeability for membranes made from cellulose acetate of various degrees of acetylation. The expected rejection coefficients for these membranes, calculated for dilute salt solutions using Equation (5.6),...

There are two types of membranes, cellulosic and synthetic or polymeric ones. Cellulosic membranes can be in regenerated cellulose (cuprophan, Bioflux from Membrana, Germany) or modified cellulose (cellulose acetate or diacetate, from Asahi, triacetate cellulose from Baxter and Nipro, which has a high hydraulic permeability or Hemophan from Membrana). Cuprophan was originally the most common one, because of its low cost, but is no longer produced because of its lower biocompatibility and hydraulic permeability. A wide variety of polymeric membranes are now available with both high and medium hydraulic permeabilities. Only the Eval... 

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