Metal membrane fabrication method

The most common methods for manufacturing thin metal membranes include rolled foil, drawn tubes, and films deposited onto porous substrates (ceramic or sintered metal). Usually, electroless plating or electrolytic plating are the methods used to deposit the permselective metal onto the porous substrates although vapor deposition methods have been the subject of much research effort However, to date, vapor deposition methods have not proven to be a superior membrane fabrication method. There are pros and cons to each of these methods, but commercial membrane modules have only succeeded using rolled foil and drawn tubular membranes. 

To control costs of membranes containing precious metals, such as Pd, and to improve their performance in a commercially viable configuration, considerable development effort has been focused on membrane fabrication methods. The most important factors to consider when selecting a fabrication method are H2 transport rates, selectivity, stability, and life. Three common approaches are discussed here free-standing thin foils, thin films on porous substrates, and composite membranes. 

Thicker, self-supporting, dense metal membranes are known. These are tubular and are usually commercially successful palladium-silver hydrogen separation membranes were of this type.21 Currently, Power and Energy, Inc. also fabricates this type of membrane, although planar membranes are more common due to easier fabrication and a greater variety of fabrication methods. 

Very little is known about the influence of grain growth, or crystallization if the membrane is composed of an amorphous alloy, on membrane durability. The as-fabricated permselective metal membrane will be polycrystalline or amorphous, depending on the alloy composition and fabrication method. Amorphous, or metallic glass, structures are far less common than are polycrystalline structures. Both amorphous and polycrystalline structures are quasi-stable, meaning that structures are kinetically stabilized and slow to rearrange to the thermodynamically favored structure. In both cases, this would be a single crystal of the metal. 

In the past, thin metal membranes have been fabricated by rolling between precision rollers, but potential for pinhole defects limits this method for Pd-alloy membranes to a current state of the art of 25 p,m (0.001 in.). Difficulty in controlling... 

For example, effective intermediate layers have been developed that create a smoother support surface to minimize defect density and reduce metallic interdiffusion. The following sections of this chapter examine the history, background, and applications of palladium membranes, including recent advances in fabrication methods and performance. 

Plutonium is so toxic that processing and fabrication are always done in sealed cells or glove boxes, but accidental dispersions of aerosol occur from time to time. Following combustion of Pu metal chips in a production area at Rocky Flats, Colorado, in 1964, airborne contamination was widespread. Alpha tracks from individual particles caught on membrane filters were detected on nuclear film, and the Pu content, and hence the particle size, was deduced (Fig. 5.2, curve E). The activity median diameter was 0.3 /urn (Mann Kirchner, 1967). The same method, used during normal operations in a production area at Los Alamos, gave activity median diameters in the range 0.15 to 0.65 /urn (Moss et al., 1961). However, when a spill occurred, followed by clean-up operations, the Pu particles were found to be associated with inert dust particles of mass median diameter 7 /urn. 

A method to form metal-SAM-metal nanowires with a diameter < 40 nm was developed by Mallouk and coworkers [51, 76]. The nanowires were produced by electrodeposition of Au or Pd into the nanopores of a polycarbonate membrane. A SAM was formed at the end of the wire and a second metal contact (Au, Ag or Pd) was deposited on top of this. The polycarbonate was subsequently dissolved in dichloromethane, which released a large quantity (1011 cm-2) of nanowires that could be aligned individually between pairs of lithographically fabricated metal electrodes. A schematic illustration of the nanowire molecular junctions is shown in Fig. 10.14. 

The third main class of separation methods, the use of micro-porous and non-porous membranes as semi-permeable barriers (see Figure 2c) is rapidly gaining popularity in industrial separation processes for application to difficult and highly selective separations. Membranes are usually fabricated from natural fibres, synthetic polymers, ceramics or metals, but they may also consist of liquid films. Solid membranes are fabricated into flat sheets, tubes, hollow fibres or spiral-wound sheets. For the micro-porous membranes, separation is effected by differing rates of diffusion through the pores, while for non-porous membranes, separation occurs because of differences in both the solubility in the membrane and the rate of diffusion through the membrane. Table 2 is a compilation of the more common industrial separation operations based on the use of a barrier. A more comprehensive table is given by Seader and Henley.1... 

Photolithographic methods, which play a key part in the fabrication of semiconductors, are potential candidates for the photo-patterning of small enzyme-immobilized membranes on a FET at its wafer stage. Ion-sensing FET devices with neutral carrier membranes sensitive to alkaline and alkaline earth metal... 

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