Membrane alloying

Figure 4. X-ray Mapping of Elemental Constituents within the micrsotructure of a V53-Ti26-Ni21 membrane alloy (a) V-Kal map, (b)Ti Kal map, and (c) Ni-Kal map.

C. Guizard, A. Julbe, A. Larbot and L. Cot, Nanostructures in sol-gel derived materials application to the elaboration of nanofiltration membranes. /. Alloys Compounds, 188 (1992) 8. 

N. I. Timofeev, F. N. Berseneva, V. M. Makarov, New palladium-based membrane alloys for separation of gas mixtures to generate ultrapure hydrogen, Int.]. Hydrogen Energy 1994, 39(11), 895-898. 

Other areas of corrosion concern are the membrane seals. If the seals are composed of flexible graphite, a preferred sealing material as discussed above, then corrosion by the common feed stream constituents is not a problem. However, with any metal seal - whether it be a brazed, welded, or soft-metal gasket seal - it is prudent to evaluate the potential for corrosion specifically at the seal. This evaluation is complicated by the fact that with brazed and welded seals, the metallurgy of the seal is influenced by the addition of the membrane alloy to the liquid braze alloy or weld pool. Experience has shown that welded seals to Pd—40Cu membranes, in which the membrane is welded to either Monel or 304L stainless steel, rapidly fail when subjected to 50 ppm hydrogen sulfide at 400 °C. 

The last two points are very important in membrane preparation for hydrogen separation because fabricating membrane alloys helps to overcome the problem of hydrogen embrittlement, while the nanostructured films may have unique size-dependent properties, e.g., a high hydrogen permeation [38]. 

Figure 5.6 SEM images of joint-like and nanoflower morphology (a-c) are alloyed samples at 150 W, 300 W and 400 W, respectively (d-f) are dealloyed samples (g-i) are deaUoyed and NaBH4treated samples and (j-k) are dealloyed and NaBH4treated samples on asymmetric membrane alloyed at 300 W [104].

Hydrogen permeation and chemical stability of In-doped SrCeo.gsTmo.osOs- membranes. /. Alloys Compd., 616, 142-147. 

Mechanical properties are very important for the reliability of both self-supported and composite Pd membranes. Alloying of Pd increases the mechanical strength, and, similar to other chemical-physical properties, the tensile strength of the Pd-Ag alloy, both in the worked and annealed state, is also maximum at a silver content around 25%-30%, as shown in Figure 13.3 [19]. A similar behavior is reported for the hardness versus silver content of the Pd alloy [19]. 

CPA. Copolymer alloy membranes (CPAs) are made by alloying high molecular weight polymeries, plasticizers, special stabilizers, biocides, and antioxidants with poly(vinyl chloride) (PVC). The membrane is typically reinforced with polyester and comes in finished thicknesses of 0.75—1.5 mm and widths of 1.5—1.8 m. The primary installation method is mechanically fastened, but some fully adhered systems are also possible. The CPA membranes can exhibit long-term flexibiHty by alleviating migration of the polymeric plasticizers, and are chemically resistant and compatible with many oils and greases, animal fats, asphalt, and coal-tar pitch. The physical characteristics of a CPA membrane have been described (15). 

BP. These nitrile alloy membranes are compounded from PVC, flexibilized by the addition of butadiene—acrylonitrile copolymers, PVC, and other proprietary ingredients. Typically reinforced with polyester scrim, NBP membranes are 1 mm thick and have a width of 1.5 m. They ate ptedominandy used in mechanically fastened roofing systems. NBP membranes exhibit excellent teat and puncture resistance as well as good weatherabihty, and remain flexible at low temperatures. They ate resistant to most chemicals but ate sensitive to aromatic hydrocarbons. The sheet is usually offered in light colors. The physical characteristics of NBP membranes have been described (15). 

Caleadered PVC has approximately 55% of the PVC/PVC alloy segmeat, PVC dispersioa coatiags usiag a reinforcement are 40%, and PVC extmsion with width limitations is about 5%. Almost all PVC membranes are reiaforced or supported with thicknesses from 1.2—2.4 mm (47—96) mils. Converters typically purchase roUstock ia 5—6 ft widths (1.5—1.8 m). Colors and designs are not common most manufacturers offer a soHd white, gray, or tan sheet. 

A.sahi Chemical EHD Processes. In the late 1960s, Asahi Chemical Industries in Japan developed an alternative electrolyte system for the electroreductive coupling of acrylonitrile. The catholyte in the Asahi divided cell process consisted of an emulsion of acrylonitrile and electrolysis products in a 10% aqueous solution of tetraethyl ammonium sulfate. The concentration of acrylonitrile in the aqueous phase for the original Monsanto process was 15—20 wt %, but the Asahi process uses only about 2 wt %. Asahi claims simpler separation and purification of the adiponitrile from the catholyte. A cation-exchange membrane is employed with dilute sulfuric acid in the anode compartment. The cathode is lead containing 6% antimony, and the anode is the same alloy but also contains 0.7% silver (45). The current efficiency is of 88—89%, with an adiponitrile selectivity of 91%. This process, started by Asahi in 1971, at Nobeoka City, Japan, is also operated by the RhcJ)ne Poulenc subsidiary, Rhodia, in Bra2il under Hcense from Asahi. 

Selective gas permeation has been known for generations, and the early use of p adium silver-alloy membranes achieved sporadic industrial use. Gas separation on a massive scale was used to separate from using porous (Knudsen flow) membranes. An upgrade of the membranes at Oak Ridge cost 1.5 billion. Polymeric membranes became economically viable about 1980, introducing the modern era of gas-separation membranes. Hg recoveiy was the first major apphcation, followed quickly by acid gas separation (CO9/CH4) and the production of No from air. 

Metallic Palladium films pass H9 readily, especially above 300°C. Ot for this separation is extremely high, and H9 produced by purification through certain Pd alloy membranes is uniquely pure. Pd alloys are used to overcome the ciystalline instability of pure Pd during heat-ing-coohng cycles. Economics limit this membrane to high-purity apphcations. 

The electrolyte is a perfluorosulfonic acid ionomer, commercially available under the trade name of Nafion . It is in the form of a membrane about 0.17 mm (0.007 in) thick, and the electrodes are bonded directly onto the surface. The elec trodes contain veiy finely divided platinum or platinum alloys supported on carbon powder or fibers. The bipolar plates are made of graphite or metal. 

The shell may be of metal (steel, alloy, or non-ferrous), plastic, wood or some combination which may require the addition of liners or inner layers of rubber, plastic or brick. The mechanical problems of attaching inner nozzles, supports and brick require considerable attention that is not an integral part of sizing the equipment. Figures 9-2A-C show a typical large steel brick-lined-membrane lined tower with corbeled brick support locations. In these towers, temperature and/or corrosive conditions usually dictate the internal lining, and the selection of the proper acid- (or alkali-) proof cements. 

Ruthenium, iridium and osmium Baths based on the complex anion (NRu2Clg(H20)2) are best for ruthenium electrodeposition. Being strongly acid, however, they attack the Ni-Fe or Co-Fe-V alloys used in reed switches. Reacting the complex with oxalic acid gives a solution from which ruthenium can be deposited at neutral pH. To maintain stability, it is necessary to operate the bath with an ion-selective membrane between the electrodes . 

Electro-catalysts which have various metal contents have been applied to the polymer electrolyte membrane fuel cell(PEMFC). For the PEMFCs, Pt based noble metals have been widely used. In case the pure hydrogen is supplied as anode fuel, the platinum only electrocatalysts show the best activity in PEMFC. But the severe activity degradation can occur even by ppm level CO containing fuels, i.e. hydrocarbon reformates[l-3]. To enhance the resistivity to the CO poison of electro-catalysts, various kinds of alloy catalysts have been suggested. Among them, Pt-Ru alloy catalyst has been considered one of the best catalyst in the aspect of CO tolerance[l-3]. 

The catalysts at the anode can be made less sensitive to CO poisoning by alloying platinum with other metals such as ruthenium, antimony or tin[N.M. Markovic and P.N. Ross, New Flectro catalysts for fuel cells CATTECH 4 (2001) 110]. There is a clear demand for better and cheaper catalysts. Another way to circumvent the CO problem is to use proton-exchange membranes that operate at higher temperatures, where CO desorbs. Such membranes have been developed, but are not at present commercially available. 

In addition, the filament reactor can contain a membrane-separation function by grouping threads of filaments around an inner empty reactor core, that guides the permeate and may also increase permeation by reaction. Thus, the tube reactor constructed in such a way comprises two concentric zones, separated by a permeable Pd/Ag alloy membrane in the form of a tube. The reaction takes place in the filament zone. One product such as hydrogen is removed via the membrane and... 

Significant (and even spectacular) results were contributed by the group of Norskov to the field of electrocatalysis [102-105]. Theoretical calculations led to the design of novel nanoparticulate anode catalysts for proton exchange membrane fuel cells (PEMFC) which are composed of trimetallic systems where which PtRu is alloyed with a third, non-noble metal such as Co, Ni, or W. Remarkably, the activity trends observed experimentally when using Pt-, PtRu-, PtRuNi-, and PtRuCo electrocatalysts corresponded exactly with the theoretical predictions (cf. Figure 5(a) and (b)) [102]. 

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