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- All Subjects: corrosion
- Creators: Sieradzki, Karl
Description
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.
ContributorsAiello, Ashlee (Author) / Sieradzki, Karl (Thesis advisor) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2018
Description
In 2015, the United States consumed about 140.43 billion gallons of gasoline, resulting in the emission of over 1 billion metric tons of carbon dioxide, according to the U.S. Energy Information Administration. Despite continued efforts to develop more efficient engines and cleaner fuels, a major barrier to reducing energy consumption and CO2 production is the mass of the vehicle. Replacing traditional automotive materials such as iron and steel with lighter-weight materials is a big step toward improving fuel economy. Magnesium has great potential for use in the automotive industry because of its low density, about 78% less than the density of steel, and high strength-to-weight ratio. Using cast magnesium instead of steel can reduce the overall weight of a vehicle, improving performance and increasing fuel efficiency. However, magnesium’s high susceptibility to corrosion limits its feasibility as a substitute for traditional materials.
This project aimed to understand the effects of composition and phase distribution on the corrosion behavior of magnesium-aluminum (Mg-Al) alloys in an ionic liquid electrolyte. The purpose of studying corrosion in nonaqueous ILs is to determine the anodic dissolution behaviors of the alloy phases without the interference of side reactions that occur in aqueous electrolytes, such as di-oxygen or water reduction. Three commercial Mg-Al alloys were studied: AZ91D (9% Al), AM60 (6% Al), and AZ31B (3% Al). An annealed alloy containing solid-solution α-phase Mg-Al with 5 at% aluminum content (Mg5Al) was also used. The ionic liquid chosen for this project was 1:2 molar ratio choline-chloride:urea (cc-urea), a deep eutectic solvent. After potentiostatic corrosion in cc-urea, the magnesium alloys were found to form a high surface area porous morphology as corrosion duration increased. This morphology consists of aluminum-rich ridges formed by Al nanowires surrounding an aluminum-poor base area, but with an overall increase in surface Al composition, indicating selective dealloying of the Mg in cc-urea and redistribution of the Al on the surface. Further work will focus on the development of hydrophobic coatings using ionic liquids.
This project aimed to understand the effects of composition and phase distribution on the corrosion behavior of magnesium-aluminum (Mg-Al) alloys in an ionic liquid electrolyte. The purpose of studying corrosion in nonaqueous ILs is to determine the anodic dissolution behaviors of the alloy phases without the interference of side reactions that occur in aqueous electrolytes, such as di-oxygen or water reduction. Three commercial Mg-Al alloys were studied: AZ91D (9% Al), AM60 (6% Al), and AZ31B (3% Al). An annealed alloy containing solid-solution α-phase Mg-Al with 5 at% aluminum content (Mg5Al) was also used. The ionic liquid chosen for this project was 1:2 molar ratio choline-chloride:urea (cc-urea), a deep eutectic solvent. After potentiostatic corrosion in cc-urea, the magnesium alloys were found to form a high surface area porous morphology as corrosion duration increased. This morphology consists of aluminum-rich ridges formed by Al nanowires surrounding an aluminum-poor base area, but with an overall increase in surface Al composition, indicating selective dealloying of the Mg in cc-urea and redistribution of the Al on the surface. Further work will focus on the development of hydrophobic coatings using ionic liquids.
ContributorsWeiss, Anna Caroline (Author) / Sieradzki, Karl (Thesis director) / Chan, Candace (Committee member) / Materials Science and Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a corrosive environment under a tensile stress. Silver-gold can experience this type of brittle fracture for a range of compositions. The corrosion process in this alloy results in a bicontinuous nanoscale morphology composed of gold-rich ligaments and voids often referred to as nanoporous gold. Experiments have shown that monolithic nanoporous gold can sustain high speed cracks which can then be injected into parent-phase alloy. This work compares nanoporous gold created from ordered and disordered copper-gold using digital image analysis and electron backscatter diffraction. Nanoporous gold from both disordered copper-gold and silver-gold, and ordered copper-gold show that grain orientation and shape remain largely unchanged by the dealloying process. Comparing the morphology of the nanoporous gold from ordered and disordered copper-gold with digital image analysis, minimal differences are found between the two and it is concluded that they are not statistically significant. This reveals the robust nature of nanoporous gold morphology against small variations in surface diffusion and parent-phase crystal structure.
Then the corrosion penetration down the grain boundary is compared to the depth of crack injections in polycrystal silver-gold. Based on statistical comparison, the crack-injections penetrate into the parent-phase grain boundary beyond the corrosion-induced porosity. To compare crack injections to stress-corrosion cracking, single crystal silver-gold samples are employed. Due to the cleavage-like nature of the fracture surfaces, electron backscatter diffraction is possible and employed to compare the crystallography of stress-corrosion crack surfaces and crack-injection surfaces. From the crystallographic similarities of these fracture surfaces, it is concluded that stress-corrosion can occur via a series of crack-injection events. This relationship between crack injections and stress corrosion cracking is further examined using electrochemical data from polycrystal silver-gold samples during stress-corrosion cracking. The results support the idea that crack injection is a mechanism for stress-corrosion cracking.
Then the corrosion penetration down the grain boundary is compared to the depth of crack injections in polycrystal silver-gold. Based on statistical comparison, the crack-injections penetrate into the parent-phase grain boundary beyond the corrosion-induced porosity. To compare crack injections to stress-corrosion cracking, single crystal silver-gold samples are employed. Due to the cleavage-like nature of the fracture surfaces, electron backscatter diffraction is possible and employed to compare the crystallography of stress-corrosion crack surfaces and crack-injection surfaces. From the crystallographic similarities of these fracture surfaces, it is concluded that stress-corrosion can occur via a series of crack-injection events. This relationship between crack injections and stress corrosion cracking is further examined using electrochemical data from polycrystal silver-gold samples during stress-corrosion cracking. The results support the idea that crack injection is a mechanism for stress-corrosion cracking.
ContributorsKarasz, Erin (Author) / Sieradzki, Karl (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Peralta, Pedro (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2020