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- All Subjects: Materials Science
- Creators: Sieradzki, Karl
Description
This research focuses on the stress and structure evolution observed in-situ during the earliest stages of thin film growth in Cu on Au(111)-reconstruction. For the research, an ultra high vacuum-scanning tunneling microscopy (UHV-STM) system was modified to have the additional capabilities of in-situ deposition and in-situ stress evolution monitoring. The design and fabrication processes for the modifications are explained in detail. The deposition source enabled imaging during the deposition of Cu thin films, while also being columnar enough to avoid negatively impacting the function of the microscope. It was found that the stress-induced changes in piezo voltage occurred over a substantially longer time scale and larger piezo scale than used during imaging, allowing for the deconvolution of the two sources of piezo voltage change. The intrinsic stress evolution observed at the onset of Cu growth was tensile in character and reached a maximum of 0.19 N/m at approximately 0.8ML, with an average tensile slope of 1.0GPa. As the film thickness increased beyond 0.8 ML, the stress became less tensile as the observation of disordered stripe and trigon patterns of misfit dislocations began to appear. The transport of atoms from the surface of enlarged Cu islands into the strained layer played an important role in this stage, because they effectively reduce the activation barrier for the formation of the observed surface structures. A rich array of structures were observed in the work presented here including stripe, disordered stripe and trigon patterns co-existing in a single Cu layer. Heteroepitaxial systems in existing literature showed a uniform structure in the single layer. The non-uniform structures in the single layer of this work may be attributed to the room temperature Cu growth, which can kinetically limit uniform pattern formation. The development of the UHV-STM system with additional capabilities for this work is expected to contribute to research for the stress and structure relationships of many other heteroepitaxial systems.
ContributorsNah, Jungwoo (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Bennett, Peter (Committee member) / Arizona State University (Publisher)
Created2012
Description
Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.
ContributorsYang, Ting (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter A. (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2012
Description
The electrochemical behavior of nanoscale solids has become an important topic to applications, such as catalysis, sensing, and nano–electronic devices. The electrochemical behavior of elemental metal and alloy particles was studied in this work both theoretically and experimentally. A systematic thermodynamic derivation for the size–dependent Pourbaix Diagram for elemental metal particles is presented. The stability of Pt particles was studied by in situ electrochemical scanning tunneling microscopy (ECSTM). It is shown that small Pt particles dissolve at a lower potential than the corresponding bulk material. For the alloy particles, two size ranges of AuAg particles, ∼4 nm and ∼45 nm in diameter, were synthesized by co–reduction of the salts of Au and Ag from an aqueous phase. The alloy particles were dealloyed at a series of potential by chronoamperometry in acid, and the resulting morphology and composition were characterized by electron microscopy, energy dispersive X–ray spectroscopy (EDX). In the case of the smaller particles, only surface dealloying occurred yielding a core–shell structure. A porous structure was observed for the larger particles when the potential was larger than a critical value that was within 50 mV of the thermodynamic prediction.
ContributorsLi, Xiaoqian (Author) / Sieradzki, Karl (Thesis advisor) / Crozier, Peter (Committee member) / Buttry, Daniel (Committee member) / Friesen, Cody (Committee member) / Arizona State University (Publisher)
Created2012
Description
The increasing demand for structural materials with superior mechanical properties has provided a strong impetus to the discovery of novel materials, and innovations in processing techniques to improve the properties of existing materials. Methods like severe plastic deformation (SPD) and surface mechanical attrition treatment (SMAT) have led to significant enhancement in the strength of traditional structural materials like Al and Fe based alloys via microstructural refinement. However, the nanocrystalline materials produced using these techniques exhibit poor ductility due to the lack of effective strain hardening mechanisms, and as a result the well-known strength-ductility trade-off persists. To overcome this trade-off, researchers have proposed the concept of heterostructured materials, which are composed of domains ranging in size from a few nanometers to several micrometers. Over the last two decades, there has been intense research on the development of new methods to synthesize heterostructured materials. However, none of these methods is capable of providing precise control over key microstructural parameters such as average grain size, grain morphology, and volume fraction and connectivity of coarse and fine grains. Due to the lack of microstructural control, the relationship between these parameters and the deformation behavior of heterostructured materials cannot be investigated systematically, and hence designing heterostructured materials with optimized properties is currently infeasible. This work aims to address this scientific and technological challenge and is composed of two distinct but interrelated parts. The first part concerns the development of a broadly applicable synthesis method to produce heterostructured metallic films with precisely defined architectures. This method exploits two forms of film growth (epitaxial and Volmer-Weber) to generate heterostructured metallic films. The second part investigates the effect of different microstructural parameters on the deformation behavior of heterostructured metallic films with the aim of elucidating their structure-property relationships. Towards this end, freestanding heterostructured Fe films with different architectures were fabricated and uniaxially deformed using MEMS stages. The results from these experiments are presented and their implications for the mechanical properties of heterostructured materials is discussed.
ContributorsBerlia, Rohit (Author) / Rajagopalan, Jagannathan (Thesis advisor) / Sieradzki, Karl (Committee member) / Peralta, Pedro (Committee member) / Crozier, Peter (Committee member) / Solanki, Kiran (Committee member) / Arizona State University (Publisher)
Created2021
Description
As selenium and chromium are toxic even at low levels, it is very necessary to remove them from drinking water with proper ways. In this work, titanium dioxide based photocatalysts were mainly investigated in detail for their photoreduction ability towards selenate and chromate in aqueous environment. Firstly, photoreduction ability of layered double hydroxide (LDH) nanosheets with commercial TiO2 particle hybrid materials was investigated towards selenate or chromate. The results showed that commercial LDH/TiO2 (P90) composite, homemade LDH nanosheets/TiO2 (P90) composite and also in situ LDH/TiO2 (P25) composite all did not indicate significant improvement on photoreduction performance towards selenate or chromate. Secondly, TiO2 nanosheets material was synthesized with TiS2 as precursor via hydrothermal treatment. Morphology of TiO2 nanosheets were characterized by SEM, AFM and TEM. Photodegradation of MB (methylene blue) with TiO2 nanosheets was performed. In the future, first approach is to synthesize visible-light driven LDH photocatalyst NiFe-LDH nanosheets with TiO2 nanosheets hybrid material for selenate removal. Second approach is to use anion intercalation/insertion via electrochemical process to remove anions in drinking water.
ContributorsJing, Hangkun (Author) / Chan, Candace K. (Thesis advisor) / Sieradzki, Karl (Committee member) / Wang, Qinghua (Committee member) / Arizona State University (Publisher)
Created2018
Description
Stress corrosion cracking (SCC) is a materials degradation phenomena resulting from a combination of stress and a corrosive environment. Among the alphabet soup of proposed mechanism of SCC the most important are film-rupture, film-induced cleavage and hydrogen embrittlement.
This work examines various aspects of film-induced cleavage in gold alloys for which the operation of hydrogen embrittlement processes can be strictly ruled out on thermodynamic grounds. This is so because in such alloys SCC occurs under electrochemical conditions within which water is stable to hydrogen gas evolution. The alloy system examined in this work is AgAu since the corrosion processes in this system occur by a dealloying mechanism that results in the formation of nanoporous gold. The physics behind the dealloying process as well as the resulting formation of nanoporous gold is today well understood.
Two important aspects of the film-induced cleavage mechanism are examined in this work: dynamic fracture in monolithic nanoporous gold and crack injection. In crack injection there is a finite thickness dealloyed layer formed on a AgAu alloy sample and the question of whether or not a crack that nucleates within this layer can travel for some finite distance into the un-corroded parent phase alloy is addressed. Dynamic fracture tests were performed on single edge-notched monolithic nanoporous gold samples as well as “infinite strip” sample configurations for which the stress intensity remains constant over a significant portion of the crack length. High-speed photography was used to measure the crack velocity. In the dynamic fracture experiments cracks were observed to travel at speeds as large as 270 m/s corresponding to about 68% of the Raleigh wave velocity. Crack injection experiments were performed on single crystal Ag77Au23, polycrystalline Ag72Au28 and pure gold, all of which had thin nanoporous gold layers on the surface of samples. Through-thickness fracture was seen in both the single crystal and polycrystalline samples and there was an indication of ~ 1 μm injected cracks into pure gold. These results have important implications for the operation of the film-induced cleavage mechanism and represent a first step in the development of a fundamental model of SCC.
This work examines various aspects of film-induced cleavage in gold alloys for which the operation of hydrogen embrittlement processes can be strictly ruled out on thermodynamic grounds. This is so because in such alloys SCC occurs under electrochemical conditions within which water is stable to hydrogen gas evolution. The alloy system examined in this work is AgAu since the corrosion processes in this system occur by a dealloying mechanism that results in the formation of nanoporous gold. The physics behind the dealloying process as well as the resulting formation of nanoporous gold is today well understood.
Two important aspects of the film-induced cleavage mechanism are examined in this work: dynamic fracture in monolithic nanoporous gold and crack injection. In crack injection there is a finite thickness dealloyed layer formed on a AgAu alloy sample and the question of whether or not a crack that nucleates within this layer can travel for some finite distance into the un-corroded parent phase alloy is addressed. Dynamic fracture tests were performed on single edge-notched monolithic nanoporous gold samples as well as “infinite strip” sample configurations for which the stress intensity remains constant over a significant portion of the crack length. High-speed photography was used to measure the crack velocity. In the dynamic fracture experiments cracks were observed to travel at speeds as large as 270 m/s corresponding to about 68% of the Raleigh wave velocity. Crack injection experiments were performed on single crystal Ag77Au23, polycrystalline Ag72Au28 and pure gold, all of which had thin nanoporous gold layers on the surface of samples. Through-thickness fracture was seen in both the single crystal and polycrystalline samples and there was an indication of ~ 1 μm injected cracks into pure gold. These results have important implications for the operation of the film-induced cleavage mechanism and represent a first step in the development of a fundamental model of SCC.
ContributorsChen, Xiying (Author) / Sieradzki, Karl (Thesis advisor) / Jiao, Yang (Committee member) / Oswald, Jay (Committee member) / Crozier, Peter (Committee member) / Peralta, Pedro (Committee member) / Arizona State University (Publisher)
Created2016
Description
Because of their favorable ionic and/or electronic conductivity, non-stoichiometric oxides are utilized for energy storage, energy conversion, sensing, catalysis, gas separation, and information technologies, both potential and commercialized. Charge transport in these materials is influenced strongly by grain boundaries, which exhibit fluctuations in composition, chemistry and atomic structure within Ångstroms or nanometers. Here, studies are presented that elucidate the interplay between macroscopic electrical conductivity, microscopic character, and local composition and electronic structure of grain boundaries in polycrystalline ceria-based (CeO2) solid solutions. AC impedance spectroscopy is employed to measure macroscopic electrical conductivity of grain boundaries, and electron energy-loss spectroscopy (EELS) in the aberration-correction scanning transmission electron microscope (AC-STEM) is used to quantify local composition and electronic structure. Electron diffraction orientation imaging microscopy is employed to assess microscopic grain boundary character, and links these macro- and nanoscopic techniques across length scales.
A model system, CaxCe1-xO2-x-δ, is used to systematically investigate relationships between nominal Ca2+ concentration, grain boundary ionic conductivity, microscale character, and local solute concentration. Grain boundary conductivity varied by several orders of magnitude over the composition range, and assessment of grain boundary character highlighted the critical influence of local composition on conductivity. Ceria containing Gd3+ and Pr3+/4+ was also investigated following previous theoretical work predicting superior ionic conductivity relative to state-of-the-art GdxCe1-xO2-x/2-δ. The grain boundary conductivity was nearly 100 times greater than expected and a factor four enrichment of Pr concentration was observed at the grain boundary, which suggested electronic conduction that was cited as the origin of the enhanced conductivity. This finding inspired the development of two EELS-based experimental approaches to elucidate the effect of Pr enrichment on grain boundary conductivity. One employed ultra-high energy resolution (~10 meV) monochromated EELS to characterize Pr inter-bandgap electronic states. Alternatively, STEM nanodiffraction orientation imaging coupled with AC-STEM EELS was employed to estimate the composition of the entire grain boundary population in a polycrystalline material. These compositional data were the input to a thermodynamic model used to predict electrical properties of the grain boundary population. These results suggest improved DC ionic conduction and enhanced electronic conduction under AC conditions.
A model system, CaxCe1-xO2-x-δ, is used to systematically investigate relationships between nominal Ca2+ concentration, grain boundary ionic conductivity, microscale character, and local solute concentration. Grain boundary conductivity varied by several orders of magnitude over the composition range, and assessment of grain boundary character highlighted the critical influence of local composition on conductivity. Ceria containing Gd3+ and Pr3+/4+ was also investigated following previous theoretical work predicting superior ionic conductivity relative to state-of-the-art GdxCe1-xO2-x/2-δ. The grain boundary conductivity was nearly 100 times greater than expected and a factor four enrichment of Pr concentration was observed at the grain boundary, which suggested electronic conduction that was cited as the origin of the enhanced conductivity. This finding inspired the development of two EELS-based experimental approaches to elucidate the effect of Pr enrichment on grain boundary conductivity. One employed ultra-high energy resolution (~10 meV) monochromated EELS to characterize Pr inter-bandgap electronic states. Alternatively, STEM nanodiffraction orientation imaging coupled with AC-STEM EELS was employed to estimate the composition of the entire grain boundary population in a polycrystalline material. These compositional data were the input to a thermodynamic model used to predict electrical properties of the grain boundary population. These results suggest improved DC ionic conduction and enhanced electronic conduction under AC conditions.
ContributorsBowman, William John (Author) / Crozier, Peter A. (Thesis advisor) / Chan, Candace K. (Committee member) / McCartney, Martha (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2016
Description
Structural stability and performance of structural materials is important for energy production, whether renewable or non renewable, to have uninterrupted energy supply, that is economically feasible and safe. High temperature metallic materials used in the turbines of AORA, an Israel-based clean energy producer, often experience high temperature, high stress and foreign object damage (FOD). In this study, efforts were made to study the effects of FOD on the fatigue life of these materials and to understand their failure mechanisms. The foreign objects/debris recovered by AORA were characterized using Powder X-ray Diffraction (XRD) and Energy Dispersive Spectroscopy (EDS) to identify composition and phases. To perform foreign object damage experiment a gas gun was built and results of XRD and EDS were used to select particles to mimic FOD in lab experiments for two materials of interest to AORA: Hastelloy X and SS 347. Electron Backscattering Diffraction, hardness and tensile tests were also performed to characterize microstructure and mechanical properties. Fatigue tests using at high temperature were performed on dog bone samples with and without FOD and the fracture surfaces and well as the regions affected by FOD were analyzed using Scanning Electron Microscopy (SEM) to understand the failure mechanism. The findings of these study indicate that FOD is causing multiple secondary cracks at and around the impact sites, which can potentially grow to coalesce and remove pieces of material, and the multisite damage could also lead to lower fatigue lives, despite the fact that the FOD site was not always the most favorable for initiation of the fatal fatigue crack. It was also seen by the effect of FOD on fatigue life that SS 347 is more susceptible to FOD than Hastelloy X.
ContributorsDobaria, Nirmal (Author) / Peralta, Pedro (Thesis advisor) / Sieradzki, Karl (Committee member) / Solanki, Kiran (Committee member) / Arizona State University (Publisher)
Created2016
Description
There is a fundamental attractiveness about harnessing renewable energy in an age when sustainability is an ethical norm. Lithium ion batteries and hydrogen fuels are considered the most promising energy source instead of fossil fuels. This work describes the investigation of new cathode materials and devices architectures for lithium ion batteries, and photocatalysts for their usage in water splitting and waste water treatment.
LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks.
Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting.
Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties.
Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions.
LiCoO2 and LiNi1/3Mn1/3Co1/3O2 were exfoliated into nanosheets using electrochemical oxidation followed by intercalation of tetraethylammonium cations. The nanosheets were purified using dialysis and electrophoresis. The nanosheets were successfully restacked into functional cathode materials with microwave hydrothermal assistance, indicating that new cathodes can be obtained by reassembling nanosheets. This method can pave the way for the synthesis of materials with novel structures and electrochemical properties, as well as facilitate the fabrication of hybrid and composite structures from different nanosheets as building blocks.
Paper folding techniques are used in order to compact a Li-ion battery and increase its energy per footprint area. Full cells were prepared using Li4Ti5O12 and LiCoO2 powders deposited onto current collectors consisting of paper coated with carbon nanotubes. Folded cells showed higher areal capacities compared to the planar versions. Origami lithium-ion battery made in this method that can be deformed at an unprecedented high level, including folding, bending and twisting.
Spray pyrolysis was used to prepare films of AgInS2 with and without Sn as an extrinsic dopant. The photoelectrochemical performance of these films was evaluated after annealing under a N2 or S atmosphere with different amounts of the Sn dopant. Density Function Theory (DFT) was used to calculate the band structure of AgInS2 and understand the role of Sn doping in the observed properties.
Cr(VI) removal was investigated using multiple oxide photocatalyst and additives. The efficiency for Cr(VI) removal using these photocatalysts was investigated in synthetic neutral and alkaline water, as well as in cooling tower blowdown water. While sulfite alone can chemically reduce Cr(VI), sulfite in combination with a photocatalyst resulted in faster and complete removal of Cr(VI) in 10 min using a SO32−/Cr(VI) ratio >35 in pH ∼ 8 solutions.
ContributorsCheng, Qian (Author) / Chan, Candace Kay (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / He, Ximin (Committee member) / Arizona State University (Publisher)
Created2016
Description
This research examines several critical aspects of the so-called "film induced cleavage" model of stress corrosion cracking using silver-gold alloys as the parent-phase material. The model hypothesizes that the corrosion generates a brittle nanoporous film, which subsequently fractures forming a high-speed crack that is injected into the uncorroded parent-phase alloy. This high speed crack owing to its kinetic energy can penetrate beyond the corroded layer into the parent phase and thus effectively reducing strength of the parent phase. Silver-gold alloys provide an ideal system to study this effect, as hydrogen effect can be ruled out on thermodynamic basis. During corrosion of the silver-gold alloy, the less noble metal i.e. silver is removed from the system leaving behind a nanoporous gold (NPG) layer. In the case of polycrystalline material, this corrosion process proceeds deeper along the grain boundary than the matrix grain. All of the cracks with apparent penetration beyond the corroded (dealloyed) layer are intergranular. Our aim was to study the crack penetration depth along the grain boundary to ascertain whether the penetration occurs past the grain-boundary dealloyed depth. EDS and imaging in high-resolution aberration corrected scanning transmission electron microscope (STEM) and atom probe tomography (APT) have been used to evaluate the grain boundary corrosion depth.
The mechanical properties of monolithic NPG are also studied. The motivation behind this is two-fold. The crack injection depth depends on the speed of the crack formed in the nanoporous layer, which in turn depends on the mechanical properties of the NPG. Also NPG has potential applications in actuation, sensing and catalysis. The measured value of the Young's modulus of NPG with 40 nm ligament size and 28% density was ~ 2.5 GPa and the Poisson's ratio was ~ 0.20. The fracture stress was observed to be ~ 11-13 MPa. There was no significant change observed between these mechanical properties on oxidation of NPG at 1.4 V. The fracture toughness value for the NPG was ~ 10 J/m2. Also dynamic fracture tests showed that the NPG is capable of supporting crack velocities ~ 100 - 180 m/s.
The mechanical properties of monolithic NPG are also studied. The motivation behind this is two-fold. The crack injection depth depends on the speed of the crack formed in the nanoporous layer, which in turn depends on the mechanical properties of the NPG. Also NPG has potential applications in actuation, sensing and catalysis. The measured value of the Young's modulus of NPG with 40 nm ligament size and 28% density was ~ 2.5 GPa and the Poisson's ratio was ~ 0.20. The fracture stress was observed to be ~ 11-13 MPa. There was no significant change observed between these mechanical properties on oxidation of NPG at 1.4 V. The fracture toughness value for the NPG was ~ 10 J/m2. Also dynamic fracture tests showed that the NPG is capable of supporting crack velocities ~ 100 - 180 m/s.
ContributorsBadwe, Nilesh (Author) / Sieradzki, Karl (Thesis advisor) / Peralta, Pedro (Committee member) / Oswald, Jay (Committee member) / Mahajan, Ravi (Committee member) / Arizona State University (Publisher)
Created2014