Compliant nanoporous gold is investigated with regards to its elastic modulus and deformation mechanisms. Samples are fabricated by dealloying AgAu alloys at elevated temperature and reduced dealloying potential compared with conventional methods in the literature. This procedure minimizes cracking and shrinkage that is typical from other dealloying methods. Furthermore, samples are found to be more compliant while immersed in water. Samples were tested in cyclic compression using a piezoelectric compression rig. Testing showed that the wet samples become stiffer upon drying and the effect is reversible with short drying times. This is attributed to microstructural effects as the ligament network becomes more connected as a result of drying, effectively shifting the dominant deformation mode from three-point bending to cantilever bending. At longer dry times, the effect is irreversible due to contact weld formation. Preliminary results on sputter deposited AgAuPt alloys show altered dealloying kinetics and crack formation.

Nanoporosity formation by selective dissolution of Ag-5 at. pct Au in perchloric acid has been investigated with regards to the mechanism of stress-corrosion cracking (SCC), film-induced cleavage in particular. It has been proven that dealloying of silver-gold systems containing low concentration of gold leads to the formation of a three dimensional nanoporous layer and that it can be carried out in a broad range of potentials and concentrations of a dealloying solution. Therefore, stress-corrosion cracking observed in these alloys may be caused, initiated or at least accompanied by the formation of nanoporosity resulting from dealloying. These results will have impact on the fabrication of cheaper nanomaterials where there is required large surface to volume ratio with gold as the outermost layer. Understanding the role of dealloying will also help us to design new materials of higher resistance against stress-corrosion cracking.

Compliant nanoporous gold is investigated with regards to its elastic modulus and deformation mechanisms. Samples are fabricated by dealloying AgAu alloys at elevated temperature and reduced dealloying potential compared with conventional methods in the literature. This procedure minimizes cracking and shrinkage that is typical from other dealloying methods. Furthermore, samples are found to be more compliant while immersed in water. Samples were tested in cyclic compression using a piezoelectric compression rig. Testing showed that the wet samples become stiffer upon drying and the effect is reversible with short drying times. This is attributed to microstructural effects as the ligament network becomes more connected as a result of drying, effectively shifting the dominant deformation mode from three-point bending to cantilever bending. At longer dry times, the effect is irreversible due to contact weld formation. Preliminary results on sputter deposited AgAuPt alloys show altered dealloying kinetics and crack formation.

Nanoporosity formation by selective dissolution of Ag-5 at. pct Au in perchloric acid has been investigated with regards to the mechanism of stress-corrosion cracking (SCC), film-induced cleavage in particular. It has been proven that dealloying of silver-gold systems containing low concentration of gold leads to the formation of a three dimensional nanoporous layer and that it can be carried out in a broad range of potentials and concentrations of a dealloying solution. Therefore, stress-corrosion cracking observed in these alloys may be caused, initiated or at least accompanied by the formation of nanoporosity resulting from dealloying. These results will have impact on the fabrication of cheaper nanomaterials where there is required large surface to volume ratio with gold as the outermost layer. Understanding the role of dealloying will also help us to design new materials of higher resistance against stress-corrosion cracking.

abstract: Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase. / Dissertation/Thesis / Ph.D. Materials Science and Engineering 2013

A study is presented on the synthesis and characterization of nanoporous AgPt and AgAu alloys after annealing and dealloying in 5% HClO4. Dealloying removes the less-noble atom from the alloy surface to produce nanoporous, highly-interconnected ligaments. Voltammetry of AgPt and AgAu shows the critical potential, Ec, at various potential scan rates. Potential hold current decay experiments on Ag-23Pt and Ag-23Au further show the intrinsic Ec to be 275 mV and 290 mV, respectively. Ec was governed by thermodynamic clustering in the alloys as opposed to dissolution-diffusion kinetic effects. EDX shows the starting 77Ag-23Pt material changes composition after dealloying to about 12Ag-88Pt. XRD indicates the presence of ordering in AgPt via a superlattice (100)-peak for a specific anneal treatment. EIS measurements done on as-annealed and dealloyed AgPt and AgAu samples show the onset of bulk porosity and show that capacitance increase is equal for both alloys at two different dealloying potentials.

A study is presented on the synthesis and characterization of nanoporous AgPt and AgAu alloys after annealing and dealloying in 5% HClO4. Dealloying removes the less-noble atom from the alloy surface to produce nanoporous, highly-interconnected ligaments. Voltammetry of AgPt and AgAu shows the critical potential, Ec, at various potential scan rates. Potential hold current decay experiments on Ag-23Pt and Ag-23Au further show the intrinsic Ec to be 275 mV and 290 mV, respectively. Ec was governed by thermodynamic clustering in the alloys as opposed to dissolution-diffusion kinetic effects. EDX shows the starting 77Ag-23Pt material changes composition after dealloying to about 12Ag-88Pt. XRD indicates the presence of ordering in AgPt via a superlattice (100)-peak for a specific anneal treatment. EIS measurements done on as-annealed and dealloyed AgPt and AgAu samples show the onset of bulk porosity and show that capacitance increase is equal for both alloys at two different dealloying potentials.

The processing and characterization of thin film metallic glasses (TFMGs) and bulk metallic glass foams (BMGFs), prepared by the dealloying corrosion process, have been studied. The TFMGs were fabricated by the co-sputtering with the Zr65Cu25Ti10 (wt%) alloy target and the pure Ta target. For BMG, there are two kinds of amorphous metallic powders adopted, namely, Zr53Cu30Ni9Al8, and Ti40Cu36Pd14Zr10. The Zr- and Ti-based powders were sintered at the temperature that Zr- and Ti-based powders overlap their supercooled regions. To fabricate the porous structure, these materials were selectively dissolved using electrochemical treatments in 0.1 M HNO3 solution. The glassy nature and the pore morphology of the corroded materials were confirmed by X-ray diffraction and scanning electron microscopy. In the current study, the pore size is about 10-30 £gm and the porosity volume faction is about 43%. By using different combinations of the powders size and volume fraction, the resulting pore size and porosity fraction can be upgraded to 200-500 £gm and 60-80%, respectively.

Nanostructured noble metals exhibit novel physical, mechanical and chemical behavior, and hold promise for applications such as gas sensing and electron emission. A strong emphasis was placed on the processing and characterization of these materials, in the form of nanoporous or nanocrystalline thin films. Palladium-based and osmium-ruthenium alloys were investigated in this dissertation research and will be presented as follows: (1) Preparation and Characterization of Nanoporous Metal Thin Films (2) Characterization of Osmium-Ruthenium Coatings Nanoporous palladium (np-Pd) thin films were prepared by dealloying co-sputtered palladium-nickel precursor alloys. Nanoporous structures were created with 3-D interconnected ligaments and open pores. Size of ligaments and pores was ~5 nm, achieved with a novel processing method developed in this study. Hydrogen cycling tests performed with np-Pd films demonstrated a significant improvement in sensitivity to hydrogen and response time for sensing. Effects of alloying element (Ni), film thickness, local stress and pore/ligament size on hydrogen cycling behavior were investigated in detail. Additionally, nanoporous gold and gold-palladium thin films were studied to clarify the evolution of microstructure during dealloying, including the formation of nanoporous structure and effects of substrate curvature on dealloying behavior. The results from this project have yielded a new understanding of dealloying as well as an ideal coating material for hydrogen sensing. Nanocrystalline osmium-ruthenium (Os-Ru) thin films were deposited on porous tungsten substrates with varied sputtering parameters. These parameters were mapped to microstructure, film texture and film composition in samples that were comparable to commercial devices. Using this map, Os-Ru films can be produced with higher stability during annealing and/or high-temperature operation. These results should lead to Os-Ru top coatings that increase the lifetime and emission performance of dispenser cathodes.

abstract: In this dissertation, micro-galvanic corrosion effects and passivation behavior of single-phase binary alloys have been studied in order to formulate new insights towards the development of “stainless-like” lightweight alloys. As a lightweight material of interest, Mg-xAl alloys were studied using aqueous free corrosion, atmospheric corrosion, dissolution rate kinetics, and ionic liquid dissolution. Polarization and “accelerated” free corrosion studies in aqueous chloride were used to characterize the corrosion behavior and morphology of alloys. Atmospheric corrosion experiments revealed surface roughness and pH evolution behavior in aqueous environment. Dissolution in absence of water using choline-chloride:urea ionic liquid allowed for a simpler dissolution mechanism to be observed, providing additional insights regarding surface mobility of Al. These results were compared with commercial alloy (AZ31B, AM60, and AZ91D) behavior to better elucidate effects associated with secondary phases and intermetallic particles often present in Mg alloys. Aqueous free corrosion, “accelerated” free corrosion and ionic liquid dissolution studies have confirmed Al surface enrichment in a variety of morphologies, including Al-rich platelet and Al nanowire formation. This behavior is attributed to the preferential dissolution of Al as the more “noble” element in the matrix. Inductively-coupled mass spectroscopy was used to measure first-order rate reaction constants for elemental Mg and Al dissolution in aqueous chloride environment to be kMg= 9.419 x 10-6 and kAl = 2.103 x 10-6 for future implementation in kinetic Monte Carlo simulations. To better understand how “stainless-like” passivation may be achieved, Ni-xCr alloys were studied using polarization and potential pulse experiments. The passivation potential, critical current density, and passivation current density were found to decay with increasing Cr composition. The measured average number of monolayers dissolved during passivation was found to be in good agreement with percolation theory, with a fitted 3-D percolation threshold of p_c^3D=0.118 compared with the theoretical value of 0.137. Using these results, possible approaches towards achieving passivation in other systems, including Mg-Al, are discussed. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018