Surface Coatings or Pore Modifications Prior to Applications

1 Surface Coatings or Pore Modifications Prior to Applications 

Membranes prepared by the majority of the established methods have limitations in their pore sizes. To make membranes with finer pore diameters suitable for more demanding separation and membrane reactor applications, a widely practiced technique is to modify the pores or the surface of an existing membrane structure which has already been made. This encompasses a variety of techniques. Some of them are based on gas or vapor phase reactions. Others modifications occur in liquid phase. Some progress having pore diameters in the molecular sieving range has been made. 

Gas/vapor phase modifications. Many inorganic membrane materials display functional groups that have chemical affinity to selected chemical agents. A well known example is a gamma-alumina membrane which has hydroxyl groups on the surfaces of the alumina crystallites. These hydroxyl groups present on the pore walls and the macroscopic surface of the membrane can act as the reactive sites for modifications of the pore structure with a chemical agent such as the diversified family of silane compounds (chloro- or alkoxy silanes). 

Miller and Kotos [1990] applied this concept to modifying gamma-alumina membranes. The pore sizes of these membranes are modified by using the U ifunctional silane, tridecafluro-l,l,2,2-tetrahydrooctyM-trichlorosilane (abbreviated as TDFS), which has three reactive chlorine atoms. The reaction between the silane and the available hydroxyl groups on the membrane surface leads to the formation of Al-O-Si bonds and the release of HCl. The release of HCl in combination with the pressure measurement can be used to monitor the reaction. 

Liquid phase modifications. Alternatively a porous membrane can be reduced in pore size by a liquid deposition prcx ess where the membrane is dipped into a solution or sol to form deposits inside the membrane pores. For example, a silicon nitride tube with a mean pore diameter of 0.35 pm is first immersed in a solution of aluminum alcoholate (aluminum isopropylate or 2 butylate) or chelate (aluminum tris(ethyl acetoacetate) or ethyl acetoacetate aluminum diisopropylate) in an organic solvent (hexane, cyclohexane, benzene, isopropanol, etc.). It is then treated with saturated water vapor to hydrolyze the alcoholate or chelate to form bochmite inside the pores, thus changing the pore diameter to as small as 20 nm [Mitsubishi Heavy Ind., 1984a and 1934b]. Upon calcining at 800X, boehmite transforms into transition-alumina. 

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