Dense metallic membranes effect

The manufacture of dense metal membranes or thin films can be effected by a number of processes casting/rolling, vapor deposition by physical and chemical means, electroplating (or electroforming) and electroless plating. By far, casting in combination with rolling is the predominant preparation and fabrication technique. It is noted that many of these processes have been demonstrated with palladium and its alloys because of their low oxidation propensity. Preparation of dense metal membranes is summarized in some detail as follows. 

The effect of reactant loss on membrane reactor performance was explained nicely in a study by Harold et al [5.25], who compared conversion during the cyclohexane dehydrogenation reaction in a PBMR equipped with different types of membranes. The results are shown in Fig. 5.4, which shows the cyclohexane conversion in the reactor as a function of the ratio of permeation to reaction rates (proportional to the ratio of a characteristic time for reaction in the packed bed to a characteristic time for transport through the membrane). Curves 1 and 2 correspond to mesoporous membranes with a Knudsen (H2/cyclohexane) separation factor. Curves 3 and 4 are for microporous membranes with a separation factor of 100, and curves 5 and 6 correspond to dense metal membranes with an infinite separation factor. The odd numbered curves correspond to using an inert sweep gas flow rate equal to the cyclohexane flow, whereas for the even numbered curves the sweep to cyclohexane flow ratio is 10. 

As explained in Chapter 5, the transport mechanism in dense crystalline materials is generally made up of incessant displacements of mobile atoms because of the so-called vacancy or interstitial mechanisms. In this sense, the solution-diffusion mechanism is the most commonly used physical model to describe gas transport through dense membranes. The solution-diffusion separation mechanism is based on both solubility and mobility of one species in an effective solid barrier [23-25], This mechanism can be described as follows first, a gas molecule is adsorbed, and in some cases dissociated, on the surface of one side of the membrane, it then dissolves in the membrane material, and thereafter diffuses through the membrane. Finally, in some cases it is associated and desorbs, and in other cases, it only desorbs on the other side of the membrane. For example, for hydrogen transport through a dense metal such as Pd, the H2 molecule has to split up after adsorption, and, thereafter, recombine after diffusing through the membrane on the other side (see Section 5.6.1). 

Enhancement in conversion by the usage of a membrane reactor has been demonstrated for many dehydrogenation reactions. Product selectivity of some hydrogenation and other reactions arc found to improve with a permselective membrane as part of the reactor. Several dense metal as well as solid elecu olyte membranes and porous metal as well as various oxide membranes have been discovered to be effective for the reaction performance. 

H2S can have significant effects on dense Pd membranes resulting in some instances in complete membrane failure in short periods of time. Short of replacing Pd with other metals, it is imclear at this point how one overcomes the problem of Pd sensitivity to sulphur and chloride impurities, which are unfortunately present in many industrial hydrocarbon streams. 

Strategies to solve this problem involve application of adsorptive porous layers on the dense membrane and of metal-oxide composites where the exchange reaction is catalysed by the metal. The study of these surface reactions and of ways to decrease their effect is important. 

Directed self-assembly shows promise in advanced lithography and a variety of other applications that have less complex requirements. For example, directed self-assembly could be used for enhancing etch selectivity, placing dopants in ordered arrays, or generating high-density, close-packed electrodes in capacitor arrays [6]. Additionally, the assembled nanostructures could be used for fabricating densely packed porous templates [12-14] or membranes [15, 16] at the nanoscale. Other potential applications of assembled block copolymer thin films include the fabrication of MOSFETs (metal-oxide-semiconductor field-effect transistors) [17], quantum dots [18], high surface area devices [19, 20], photovoltaic devices [21], and bit patterned media [22-24]. 

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