Theses and Dissertations
This collection includes both ASU Theses and Dissertations, submitted by graduate students, and the Barrett, Honors College theses submitted by undergraduate students.
Displaying 61 - 64 of 64
Description
Nanoholes on the basal plane of graphene can provide abundant mass transport channels and chemically active sites for enhancing the electrochemical performance, making this material highly promising in applications such as supercapacitors, batteries, desalination, molecule or ion detection, and biosensing. However, the current solution-based chemical etching processes to manufacture these nanoholes commonly suffer from low process efficiency, scalability, and controllability, because conventional bulk heating cannot promote the etching reactions. Herein, a novel manufacturing method is developed to address this issue using microwave irradiation to facilitate and control the chemical etching of graphene. In this process, microwave irradiation induces selective heating of graphene in the aqueous solution due to an energy dissipation mechanism coupled with the dielectric and conduction losses. This strategy brings a remarkable reduction of processing time from hour-scale to minute-scale compared to the conventional approaches. By further incorporating microwave pretreatment, it is possible to control the population and area percentage of the in-plane nanoholes on graphene. Theoretical calculations reveal that the nanoholes emerge and grow by a repeating reduction–oxidation process occurring at the edge-sites atoms around vacancy defects on the graphene basal plane. The reduced holey graphene oxide sheets obtained via the microwave-assisted chemical etching method exhibit great potentials in supercapacitors and electrocatalysis. Excellent capacitive performance and electrocatalytic activity are observed in electrochemical measurements. The improvements against the non-holey counterpart are attributed to the enhanced kinetics involving ion diffusion and heterogeneous charge transfer.
ContributorsWang, Dini (Author) / Nian, Qiong (Thesis advisor) / Alford, Terry (Committee member) / Wang, Qing Hua (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
Description
Nanocrystalline (NC) materials are of great interest to researchers due to their multitude of properties such as exceptional strength and radiation resistance owing to their high fraction of grain boundaries that act as defect sinks for radiation-induced defects, provided they are microstructurally stable. In this dissertation, radiation effects in microstructurally stable bulk NC copper (Cu)- tantalum (Ta) alloys engineered with uniformly dispersed Ta nano-precipitates are systematically probed. Towards this, both ex-situ and in-situ irradiations using heavy (self) ion, helium ion, and concurrent dual ion beams (He+Au) followed by isochronal annealing inside TEM were utilized to understand radiation tolerance and underlying mechanisms of microstructure evolution in stable NC alloys. With systematic self-ion irradiation, the high density of tantalum nanoclusters in Cu-10at.%Ta were observed to act as stable sinks in suppressing radiation hardening, in addition to stabilizing the grain boundaries; while the large incoherent precipitates experienced ballistic mixing and dissolution at high doses. Interestingly, the alloy exhibited a microstructure self-healing mechanism, where with a moderate thermal input, this dissolved tantalum eventually re-precipitated, thus replenishing the sink density. The high stability of these tantalum nanoclusters is attributed to the high positive enthalpy of mixing of tantalum in copper which also acted as a critical driving force against atomic mixing to facilitate re-precipitation of tantalum nanoclusters. Furthermore, these nanoclusters proved to be effective trapping sites for helium, thus sequestering helium into isolated small bubbles and aid in increasing the overall swelling threshold of the alloy. The alloy was then compositionally optimized to reduce the density of large incoherent precipitates without compromising on the grain size and nanocluster density (Cu-3at.%Ta) which resulted in a consistent and more promising response to high dose self-ion irradiation. In-situ helium and dual beam irradiation coupled with isochronal annealing till 723 K, also revealed a comparable microstructural stability and enhanced ability of Cu-3Ta in controlling bubble growth and suppressing swelling compared to Cu-10Ta indicating a promising improvement in radiation tolerance in the optimized composition. Overall, this work helps advancing the current understanding of radiation tolerance in stable nanocrystalline alloys and aid developing design strategies for engineering radiation tolerant materials with stable interfaces.
ContributorsSrinivasan, Soundarya (Author) / Solanki, Kiran (Thesis advisor) / Peralta, Pedro (Committee member) / Alford, Terry (Committee member) / Darling, Kristopher (Committee member) / Arizona State University (Publisher)
Created2021
Description
Organic materials have emerged as an attractive component of electronics over the past few decades, particularly in the development of efficient and stable organic light-emitting diodes (OLEDs) and organic neuromorphic devices. The electrical, chemical, physical, and optical studies of organic materials and their corresponding devices have been conducted for efficient and stable electronics. The development of efficient and stable deep blue OLED devices remains a challenge that has obstructed the progress of large-scale OLED commercialization. One approach was taken to achieve a deep blue emitter through a color tuning strategy. A new complex, PtNONS56-dtb, was designed and synthesized by controlling the energy gap between T1 and T2 energy states to achieve narrowed and blueshifted emission spectra. This emitter material showed an emission spectrum at 460 nm with a FWHM of 59 nm at room temperature in PMMA, and the PtNONS56-dtb-based device exhibited a peak EQE of 8.5% with CIE coordinates of (0.14, 0.27).
A newly developed host and electron blocking materials were demonstrated to achieve efficient and stable OLED devices. The indolocarbazole-based materials were designed to have good hole mobility and high triplet energy. BCN34 as an electron blocking material achieved the estimated LT80 of 12509 h at 1000 cd m-2 with a peak EQE of 30.3% in devices employing Pd3O3 emitter. Additionally, a device with bi-layer emissive layer structure, using BCN34 and CBP as host materials doped with PtN3N emitter, achieved a peak EQE of 16.5% with the LT97 of 351 h at 1000 cd m-2. A new neuromorphic device using Ru(bpy)3(PF6)2 as an active layer was designed to emulate the short-term characteristics of a biological synapse. This memristive device showed a similar operational mechanism with biological synapse through the movement of ions and electronic charges. Furthermore, the performance of the device showed tunability by adding salt. Ultimately, the device with 2% LiClO4 salt shows similar timescales to short-term plasticity characteristics of biological synapses.
ContributorsShin, Samuel (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Alford, Terry (Committee member) / Arizona State University (Publisher)
Created2021
Description
Protein crystallization is a technique for the formation of three-dimensional protein crystals, which is widely utilized by scientists, engineers, and researchers. Protein crystallography allows for protein structures and functions to be studied. As proteins play a central role in biological systems and life itself, a deeper understanding of their structure-function properties is crucial to elucidating fundamental behaviors, such as protein folding in addition to the role that they play in emerging fields, such as, tissue engineering with application to the emerging field of regenerative medicine. However, a significant limitation toward achieving further advancements in this field is that in order to determine detailed structure of proteins from protein crystals, high-quality and larger size protein crystals are needed. Because it is difficult to produce adequate size, high-quality crystals, it remains difficult to determine the structure of many proteins. However, a new method using a microgravity environment to crystallize proteins has proven effective through various studies conducted on the International Space Station (ISS). In the presence of microgravity, free convection is essentially absent in the bulk solution where crystallization occurs, thus allowing for purely random Brownian motion to exist which favors the nucleation and growth of high-quality protein crystals. Many studies from the ISS to date have demonstrated that growing protein crystals in a microgravity environment produces larger and higher-quality crystals. This method provides new opportunities for better structure identification and analysis of proteins. Although there remains many more limitations and challenges in the field, microgravity protein crystallization holds many opportunities for the future of biotechnology and scientific development. The objective of this thesis was to study the crystallization of hen egg white lysozyme (HEWL) and determine the effects of both unit and microgravity on growth/size and quality of HEWL. Through preliminary trials using a universal ground-based reduced-gravity system, the crystallization of HEWL in a simulated microgravity environment was successfully conducted and the results reported are promising. The utility of continuous, scalable ground-based, microgravity platforms for studies on a wide range of material systems and behavior, such as, protein crystallization, has significant implications regarding its impact on many industries, including drug development as well as regenerative medicine.
ContributorsTran, Amanda Marie (Author) / Pizziconi, Vincent (Thesis director) / Alford, Terry (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2020-12