«STRUCTURE AND PROPERTIES OF ELECTRODEPOSITED NANOCRYSTALLINE NI AND NI-FE ALLOY CONTINUOUS FOILS by Jason Derek Giallonardo A thesis submitted in ...»
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CHAPTER 3 Experimental Methods
3.1. Introduction This chapter provides an overview of the experimental methods used during the course of this research. These methods were chosen based on their ability to provide the information necessary to meet the objectives of this study. The synthesis method used to produce the nanocrystalline Ni and Ni-Fe alloys is described. In addition, a brief description of the methods used for materials characterization, testing and analysis is given along with the specific details.
3.2. Synthesis of Continuous Nanocrystalline Ni and Ni-Fe Foils 3.2.1. Drum Plater There are a number of methods available to synthesize nanocrystalline materials including sputtering, laser ablation, inert gas condensation, high energy ball-milling, sol-gel deposition, and electrodeposition. As described in Chapter 2, electrodeposition allows for the ability to produce a large number of fully dense metals and metal alloys at high production rates and low capital investment in practically a single step process. One particular process is described by Palumbo et al. (2005), where a “drum plater” is used to produce foils in a continuous manner. Fig. 3.1 schematically shows a cross-sectional view of the drum plating apparatus. The drum, which is made of Ti (30 cm in diameter and 30 cm in length), acts as the cathode while the anode consisted of a Ti mesh basket filled with ValeInco Ni R-Rounds. The tank also contains a pump and filter system to remove fine
Cross-sectional schematic view of the drum plating apparatus (1) filled with an electrolyte (2). A rotating cathode in the shape of a drum (3) is electrically connected to a power supply (4). The drum is rotated by an electric motor (not shown) with a belt drive having a variable speed control. The anode (5) is conforming, as shown, and is also connected to the power supply (4). The foil (6) that is electrodeposited on the drum is pulled from the surface emerging from the electrolyte [Palumbo et al. (2005)].
particulate from the electrolyte that may produce defects by being co-deposited with the metal. An additional pump system is used to provide adequate agitation to the cathode in order to prevent mass transfer limiting effects during the electrodeposition process. A heater and temperature controller are also used to maintain the electrolyte temperature to within the prescribed working range. The power supply is equipped to deliver direct or pulsed current and is normally set to within the working ranges known to produce a nanostructured electrodeposit [El-Sherik and Erb (1995), Erb and El-Sherik (1994), Erb et al. (1995)]. When the power source supplies a constant current, the foil thickness may be controlled by adjusting the drum rotation speed.
3.2.2. Electrodeposited Nanocrystalline Ni Simple mechanisms used to describe the cathodic reactions during Ni plating (i.e., Ni2+ + 2e- → Ni ) do not take into consideration the existence of the NiOH+ ion that is usually present in considerable concentrations at the cathode due to pH change at the interface during the codeposition of H [Piatti et al. (1969)]. A detailed cathodic reaction mechanism for the electrodeposition of Ni has been proposed in several studies, e.g., Matulis and Slizys (1964) and Piatti et al. (1969), to have the following sequence,
where, the subscript ads refers to the NiOH+ ion in the adsorbed state. In the study by Piatti et al. (1969), it was concluded that Ni deposition depends strongly on the pH of the solution.
The electrodeposited nanocrystalline Ni foils were synthesized using the electrodeposition technique described in El-Sherik and Erb (1995), Erb and El-Sherik (1994), and Erb et al. (1995). A Watt’s type electrolyte was used for the production of the Ni samples consisting of primarily nickel sulfate (NiSO4·6H2O), nickel chloride (NiCl2·6H2O), boric acid (H3BO3), and proprietary additives supplied by Integran Technologies, Inc.
(Mississauga, Canada). The proprietary additives consisted of a grain refiner/stress reducer (Nanovate™ A24) and a wetting agent (Nanovate™ B16). The proprietary additives were mixtures of organic compounds. The nanocrystalline Ni samples were produced in the first electrolyte by varying the concentration of Nanovate™ A24 (0, 0.1, 1.0, 2.0 and 10 g/L).
Nanovate™ B16 (held constant at 5 mL/L) prevents the development of pits in the deposit
caused by gas bubbles forming on the cathode surface by lowering the surface tension of the solution. With a lowered surface tension any gas bubbles that are formed on the surface may easily detach from the cathode surface. All other chemical constituents in the electrolyte were also held constant. The pH for both solutions was kept within a range of 2.3-2.6 and the temperature at 58-62oC. The samples were plated to a thickness of 50 μm by adjusting the drum rotation speed to obtain a continuous foil that was collected on a spool.
3.2.3. Electrodeposited Nanocrystalline Ni-Fe The cathodic reaction mechanism for the electrodeposition of Ni-Fe is referred to as “anomalous”, meaning the less noble Fe deposits preferentially under most plating conditions [Brenner (1963), Dahms and Croll (1965)]. There have been numerous studies directed towards understanding the deposition mechanism, e.g., Romankiw (1987), Nichol and Philip (1976), Andricacos et al. (1989), Hessami and Tobias (1989), Matlosz (1993), Yin et al.
(1995), Yin (1997), Nakano et al. (2004). Most recently, Nakano et al. (2004) proposed a mechanism for the anomalous behaviour of the Ni-Fe electrodeposition process from sulfate solution at low pH by taking into the consideration the preferential adsorption of the FeOH+ ion due to the smaller dissociation constant of the FeOH+ compared with the NiOH+ during the multi-step cathodic reaction process. Nakano et al. (2004) provide a reaction mechanism for the Ni-Fe electrodeposition based on the assumption that the deposition of the Ni and Fe is preceded by the formation of metal hydroxide ions,
where, M is the metal (Ni or Fe). Since the dissociation constant of the FeOH+ ion is much lower than the NiOH+ ion, it is likely that during this series of cathodic reactions the concentration of the FeOH+ ion is much higher at the interface allowing for Fe to be preferentially deposited.
The electrodeposited nanocrystalline Ni-Fe foils were synthesized using the same electrodeposition technique as that of the Ni foils [El-Sherik and Erb (1995), Erb and ElSherik (1994), Erb et al. (1995)]. A modified Watt’s type electrolyte was also used for the production of the Ni-Fe foils consisting of primarily nickel sulfate (NiSO4·6H2O), nickel chloride (NiCl2·6H2O), ferrous sulfate (FeSO4·5H2O), boric acid (H3BO3), and proprietary additives supplied by Integran Technologies, Inc. (Mississauga, Canada). The same proprietary additives used to produce the nanocrystalline Ni foils were used in this electrolyte, i.e., Nanovate™ A24 and Nanovate™ B16. In addition to these, the electrolyte was formulated to also include a proprietary complexing agent (Nanovate™ C77). A complexing agent is commonly used in Ni-Fe alloy electroplating where its primary function is to form a ligand with Fe to prevent the precipitation of ferric compounds in the electrolyte [Brenner (1963)].
The nanocrystalline Ni-Fe samples with different Fe concentration were produced by varying the concentration of FeSO4·5H2O (4, 7, 9, and 13 g/L) in the electrolyte while the Nanovate™ A24 concentration was held constant at 2 g/L. All other chemical constituents in the electrolyte other than those mentioned were also held constant. The pH for the solution was kept within a range of 2.3-2.6 and the temperature at 58-62oC. The samples were plated
to a thickness of 50 μm by adjusting the drum rotation speed to obtain a continuous foil that was collected on a spool.