Membrane structure casting solution

The concepts and techniques discussed by Cirkel and Okada are relevant with a view toward modifying the structure of solution cast Nafion membranes by manipulating counterion type, solvent, temperature, and other variables. 

It has been shown (, , 2.) that a membrane casting dope is a strongly structurlzed polymer solution, and that the morphology of the membrane surface layer can be correlated to the structure of the casting solution. The latter parameter affects the nature and details of the phase inversion process occuring in the upper part of the cast solution, in an incipient skin. Thus the solution structure is one of the factors responsible for the skin properties, and consequently for the performance of the ultimately formed asymmetric membrane. 

These have been investigated on both the casting solution structure and the asymmetric membrane properties. Two relevant parameters have been examined 1. The PA concentration in the fixed amount of additive, i.e. the additive quality, and 2. the additive content in the casting dope. 

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. 

Precipitation of the cast liquid polymer solution to form the anisotropic membrane can be achieved in several ways, as summarized in Table 3.1. Precipitation by immersion in a bath of water was the technique discovered by Loeb and Souri-rajan, but precipitation can also be caused by absorption of water from a humid atmosphere. A third method is to cast the film as a hot solution. As the cast film cools, a point is reached at which precipitation occurs to form a microporous structure this method is called thermal gelation. Finally, evaporation of one of the solvents in the casting solution can be used to cause precipitation. In this technique the casting solution consists of a polymer dissolved in a mixture of a volatile good solvent and a less volatile nonsolvent (typically water or alcohol). When a film of the solution is cast and allowed to evaporate, the volatile good solvent evaporates first, the film then becomes enriched in the nonvolatile nonsolvent, and finally precipitates. Many combinations of these processes have also been developed. For example, a cast film placed in a humid atmosphere can precipitate partly because of water vapor absorption but also because of evaporation of one of the more volatile components. 

Whitesides and coworkers describe the use of an elastomeric membrane to pattern proteins and cells on bacteriological polystyrene (PS), glass, and poly(dimethyl-siloxane) (PDMS) substrates [92], A patterned PDMS membrane was casted from lithographically structured photoresists and brought into close contact with the substrates (Fig. 6). When incubated with a solution of fibronectin (FN), adsorption of the cell-adhesion-mediating protein to the surface was restricted to the exposed areas. The membrane was peeled off and cells were seeded from a serum-free medium. Passivation to cell attachment of the untreated portions of the surface was achieved by adding 1% bovine serum albumin (BSA) to the cell-seeding medium, which... 

The relationship between separation properties and casting parameters depends on the membrane structure. According to the Bokhorst - Altena — Smolders theory of phase separation [ 8 ], when PS concentration in the casting solution is increased and the time of solvent evaporation is extended, pore diameter decreases, thus improving the selectivity of the membranes. However, the increase of temperature to a critical value accounts for the increase of pore diameter, which brings about a decrease of the separation factor value. Further increase in temperature brings about a rapid evaporation of the solvent to yield small pore diameter membranes characterized by better separation properties. 

Most UF membranes are asymmetric, having a thin separating layer or skin layer with small pores on one side of the membrane, and a much thicker layer with larger pores below the membrane which provides structural support with minimum flow resistance. Asymmetric membranes are manufactured by wet phase inversion casting. In this process, a casting solution of a polymer in a water-miscible solvent is spread in a thin layer onto a flat surface and then immersed in water. The water causes extraction of solvent and precipitation of the polymer as a porous flat sheet. The skin layer is formed on the upper surface that was in direct contact with water, and the underlying... 

Casting-solution and environmental variables permit far greater control over the ultimate structure and performance of phase inversion membranes than does the modification of a primary gel into a secondary gel by postformation treatments. Because the properties of the primary gel determine to a large extent those of its secondary counterpart, the former should be considered as more fundamental and important in discussing the effects of fabrication parameters such as casting-solution composition, upon performance. Once a primary gel has been formed, it may be utilized as such (particularly for low-pressure applications) or it may be subjected to various physical and/or chemical treatments for conversion into a more pressure-resistant secondary gel. 

Table IV. Rates of precipitation and structures of membranes prepared from a casting solution of 15 % polyamide in DMAc by precipita-...

Two different techniques have been employed for the precipitation of membranes from a polymer casting solution. In the first method, the precipitant is introduced from the vapor phase. In this case the precipitation is slow, and a more or less homogeneous structure is obtained without a dense skin on the top or bottom side of the polymer film. This structure can be understood when the concentration profiles of the polymer, the precipitant and the solvent during the precipitation process are considered. The significant feature in the vapor-phase precipitation process is the fact that the rate-limiting step for precipitant transport into the cast polymer solution is the slow diffusion in the vapor phase adjacent to the film surface. This leads to uniform and flat concentration profiles in the film. The concentration profiles of the precipitant at various times in the polymer film are shown schematically in Figure 13. 

---