The electrodeposition of palladium-iron alloys
The main subject of the thesis is the investigation of palladium-iron alloy electrodeposition from aqueous solutions in general. Palladium-iron alloy deposits could be in principle a substitute for nickel or nickel-palladium deposits to avoid metal dermatitis. Nickel contact dermatitis is an especially sensitive allergy caused by decorative or functional use of nickel: it needs to be avoided in a number of applications. Electrochemical and chemical experiments have been carried out on several solutions with variable pH, salts and metal complexes to design a chemical and electrochemical stable electrolyte for palladium-iron alloy electrodeposition. Electrochemical measurements, physical and chemical analysis techniques, mechanical, optical, chemical and electrochemical measurements methods as well as different corrosion tests were used to describe the electrochemical processes and the properties of the palladium-iron deposits. Investigations have shown that from ammoniacal electrolytes electrodeposition in a wide range of composition is possible (pH = 7.5 - 10.5). Electrolyte consists of palladiurn as Pd(NH3)4CI2 and iron as iron(ill)-citrate. Composition of the deposited alloys depends mainly on the ratio of the metal ions in the electrolyte, while the effect of current density and electrolyte temperature is slight. Current efficiency depends on iron concentration in the electrolyte and is a maximum of ca. 85 %. Palladium-iron alloys with a higher content of palladium (>80.-%) show cracks because of the high internal stress (tensile stress) of those layers. Alloys with smaller content of palladium (<20 wt. -%) are less sensitive to cracking. Wear resistance and corrosion resistance of the palladium-iron alloys are similar or sometimes better to palladium, palladium-silver, palladium-cobalt or palladium-nickel deposits. Hardness of the palladium-iron layers increases with increasing iron content from 200 to 600 VHN. Contact resistance is low in the range of 0.5 to 1.5 mfl and barrier layer properties are excellent for gold and copper diffusion during services up to 160 degrees Celsius for 240 hours.