Preparation and characterisation of palladium composite membranes.

Keuler, Johan Nico (1997-12)

Thesis (MScEng (Process Engineering))--University of Stellenbosch, 1997.


This study focuses on the preparation and characterization of palladium-silver-nickel composite membranes. Electroless plating was used to deposit thin metal films on aluminazirconia membrane supports. Palladium conversion, in the electroless palladium plating process, was optimized with the aim of minimizing expensive palladium losses. The effect of deposition order on alloy composition and heat treatment on structural characteristics of the composite membrane was investigated. The inorganic support membranes were thoroughly cleaned and pretreated prior to plating to catalyze the surface. Factorial designs were used to obtain the maximum palladium conversion. Tetra amine palladium nitrate gave better solution stability and resulted in higher conversions than tetra amine palladium chloride. Buffer pH values of 9 to 11 caused little variation in palladium conversion. Moving outside this range resulted in a sharp decline in palladium conversion. At a pH of 9 to 11 the stabilizer is in the correct ionic form (EDTA3 and EDTA4,) to best stabilize the palladium ions, and hydrazine acts as a proper reducing agent. Significant interactions existed between the EDTA concentration (stabilizer) and hydrazine concentration (reducing agent) and between EDTA and temperature. The EDTA concentration was the most sensitive variable. A 27.5 g 10% tetra amine palladium nitrate solution per liter plating solution was used. Conversions exceeding 80% were obtained after three hours plating with 20 ml plating solution at the following conditions: temperatures from 71 to 77 DC, 40-60% molar excess hydrazine, EDTA:Pd-salt molar ratios between 30:1 and 40: 1 and buffer pH = 11. Silver plating rates for two hours plating of up to 2 mg/cm2 were obtained using a dilute silver nitrate solution with hydrazine as reducing agent. Electroless nickel plating was performed in a low temperature bath (40 DC) with nickel sulphate as source of metal ions and sodium hypophosphite as reducing agent. Metal films were fully characterized before and after heat treatment for 5 hours in a hydrogen atmosphere at 650 dc. Scanning electron microscopy (SEM) was used to analyze the surface structure. X-ray diffraction (XRD) patterns were taken to examine alloying and detect changes in the crystal structure .after heating. Energy dispersive X-ray maps (EDS) were used to visualize the diffusion process and particle induced X-ray emission (PIXE) was used to construct concentration profiles across the thickness of the metal films. Palladium deposits were dense, but columnlike, with a purity of 99.75%. Silver deposits were non-homogeneous, in other words it did not cover the entire substrate. The purity of the silver films was 99.5%. The nickel films were about 97% pure, very dense and defect free. When silver was deposited on palladium, the alloy penetrated more than 3 microns into the support and the palladium and silver concentrations varied across the thickness of the film after heating. By depositing palladium on silver, there was very little penetration into the support membrane pores (about 1 micron) and the palladium to silver ratio remained constant across the thickness of the film after heating. Silver-palladium-nickel alloy films call be prepared by first depositing silver, then palladium and finally nickel. During heat treatment, a counter diffusion process took place and the smaller nickel atoms penetrated into pores and defects that might be present in the palladium-silver solid solution. By adding more than 3% nickel, dense defect free films can be prepared, which is much thinner than conventional palladium-silver films. This method makes it possible to reduce the film thickness of dense, non-porous films to less than 5 microns, reducing fabrication cost and increasing the hydrogen flux through the film. Dense, non-porous palladium-silver films are usually in the range of 10-15 microns.

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