Materials Science & Engineering Theses and Dissertations

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    The Determination of Preferred Orientation in Rolled Electrical Steels Using Single Diffraction of Neutrons
    (1963) Eugenio, Manuel; Duffey, Dick; Nuclear Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, MD)
    Preferred orientation in rolled electrical steels has been determined using single diffraction of neutrons from the University of Maryland pool-type nuclear reactor (DMR) operating at 10 KW thermal . X-rays are used extensively to determine preferred orientations in metallic wires and rolled sheets, but X-rays suffer the disadvantage of high absorption and cannot be used effectively on thick samples without chemical or mechanical treatment which ultimately results in the destruction of the samples. The use of reactor neutrons for this purpose is believed to offer particular advantages such as the use of thicker samples and wider beams. To this end, neutrons from the UMR were scattered directly from metallic sheet samples to obtain diffraction patterns from which preferred orientations of the crystallographic axes could be deduced. The neutron diffraction data were obtained in the form of : 1) Maxwellian curves; and 2) rocking curves. To obtain the first type of curve, the sample and neutron detector were rotated at a 1-to-2 angular ratio, respectively, and the diffraction pattern was essentially the Maxwellian neutron energy distribution. From the maximum of the Maxwellian curve, the crystallographic plane mainly responsible for the reflection was calculated; from this, the main orientation was deduced. For the second type of curve, the sample was rocked back and forth, with the neutron detector fixed, and the resulting pattern was used to infer the variation of a given crystallographic direction about its main orientation. The results of this study, particularly on grain-oriented and cube-textured silicon-iron (Si-Fe) alloy sheets demonstrate that single diffraction techniques can be used to determine preferred orientation in highly oriented materials. The results on Si-Fe sheets described as non-oriented indicate the possibility that these techniques may be applicable to ordinary rolled metallic sheets, which are not highly oriented.
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    Functionalized Thin-Film Shape Memory Alloys for Novel MEMS Applications
    (2023) Curtis , Sabrina M.; Takeuchi, Ichiro; Quandt, Eckhard; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Nickel-titanium (NiTi) shape memory alloy (SMA) films are already implemented into microelectromechanical system (MEMS) devices such as sensors, actuators, and implantable medical devices. In this thesis, I used DC magnetron sputter deposition to study the influence of film composition, microstructure, and annealing conditions on the stability of the phase transformation for the NiTi-based SMA thin films TiNiCu, TiNiCuCo, and TiNiHf. SMAs are a type of smart material that can undergo stress or temperature-induced solid-to-solid phase transformation between two different crystalline phases. In NiTi-based SMAs, the two phases are known as martensite with a monoclinic crystalline structure and austenite with a cubic crystal structure. The temperature-induced phase transformations can be used to switch between the martensite and austenite phases, and thus switch between two sets of material properties in the SMA. For example, in NiTi-based SMAs the Young’s modulus, electrical resistivity, and coefficient of thermal expansion of the austenite phase are typically 2X larger than that of the martensite phase. The transformation temperatures, recovery strains, enthalpy of transformation, and fatigue properties of NiTi SMAs can be tuned by alloying NiTi with other elements like copper (Cu), cobalt (Co), and hafnium (Hf). For example, certain compositions of sputtered TiNiCu and TiNiCuCo are known to be ultra-low fatigue SMAs, able to reversibly undergo the phase transformation for 10+ million cycles without degradation in the mechanical or thermal properties. The primary focus of this thesis was the integration of these sputtered NiTi-based SMA thin-films into the following four novel MEMS devices: 1) TiNiCu for magneoelectric sensors, 2) TiNiHf for bistable actuators, 3) TiNiCuCo for stretchable electronics and 4) thin-film SMA stretchable auxetic structures for wearable and implantable medical devices. The shape memory effect was observed in TiNiCu and TiNiHf films when the film thickness and lateral dimensions are downscaled to micro and nano dimensions. In the research publication “Integration of AlN piezoelectric thin films on ultralow fatigue TiNiCu shape memory alloys.”, I showed the reproducibility of the thermal-induced phase transformation of Ti50Ni35Cu15 is attractive for integration into MEMS devices that require a high cycle lifetime. I showed how the SMA’s phase transformation can be used to tune the resonant of bending cantilever-type sensors like magnetoelectric sensors. I also demonstrated excellent thin-film piezoelectric and shape memory alloy properties for 2 μm AlN/ 5 μm TiNiCu films composites deposited onto silicon substrates. The large work densities and high strength-to-weight ratio offered by SMAs are attractive for the development of micro and nano actuators. The thermal induced phase transformation between martensite and austenite is also used to develop bi-directional micro-actuators with TiNiHf/Si and TiNiHf/SiO2/Si composites. In another research publication, “TiNiHf/SiO2/Si shape memory film composites for bi-directional micro actuation”, I demonstrated the influence of film thickness and substrate on the phase transformation properties of TiNiHf thin-films. Ti40.4Ni48Hf11.6 films with thicknesses as low as 220 nm on SiO2/Si substrates can undergo the phase transformation with high transformation temperatures (As > 100 °C) and a wide thermal hysteresis (ΔT > 50 °C). In this publication, we explain how the wide hysteresis and high transformation temperature obtained in TiNiHf films can be used to develop micro and nano-scale bistable actuators based on PMMA/TiNiHf/Si composites. Even though thin-film NiTi-based SMAs are known to reversibly recover superelastic strains of up to 8%, surprisingly, they have not yet been exploited in the growing field of stretchable electronics. In the technical article “Thin-Film Superelastic Alloys for Stretchable Electronics” I demonstrate the first experimental and numerical studies of freestanding thin-film superelastic TiNiCuCo structured into a serpentine geometry for use as stretchable electrical interconnects. Fabricated electropolished serpentine structures were demonstrated to have low fatigue after cycling external strains between 30% - 50% for 100,000 cycles. The electrical resistivity of the austenite phase of a Ti53.3Ni30.9Cu12.9Co2.9 thin-film at room temperature was measured to be 5.43 × 10-7 Ω m, which is larger than reported measurements for copper thin-films (1.87 × 10-8 Ω m). Expanding upon this work, in the conference proceedings paper “Auxetic Superelastic TiNiCuCo Sputtered Thin-Films for Stretchable Electronics”, I present a new platform for functionalized wearable electronics and implantable medical devices based on superelastic thin-film SMA substrates structured into novel stretchable auxetic geometries. Since thin-film SMAs are conductive, the structured substrate itself could serve as the current collector for such stretchable and flexible devices, or a more conductive electrode can be deposited on top of the stretchable auxetic SMA substrate. Overall, the results discussed in this doctoral thesis look to the future of harnessing the functional properties of thin-film sputtered SMAs for novel uses in next-generation MEMS devices.
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    (2023) Guerin, Steven James; Al-Sheikhly, Mohamad I; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    Nuclear power plants (NPPs) are complex engineering systems, with malfunctions having enormous potential to lead to widespread and extreme impacts on society and the environment as a whole. Their safe operation depends on a multitude of factors such as intelligent planning, proper design, quality components, high-level safety operations, and economic viability. Due to requiring high temperature and high pressure of an NPP’s cooling fluid, one of the main concerns for further developing safe operating conditions and evaluating component lifetimes is improving our understanding on the issue of corrosion in nuclear systems. In the U.S., all commercially operated Pressurized Water nuclear Reactors (PWRs) are light-water reactors wherein their coolant waters can reach temperatures up to 350 °C. According to a report in 2005 in association with the U.S. Federal Highway Administration, an annual cost of $4.2 billion was directly attributed to corrosion in NPPs in 1998, out of a total $6.9 billion in the electrical utilities industry (Koch, et al., 2005). Boron is added into commercial PWR primary water in the form of boric acid as a soluble chemical neutron “shim” in order to compensate for fuel burnup and allow smooth long-term reactivity control. After a boron nucleus captures a thermal neutron and becomes unstable, the energy of the recoil ions resulting from its fission accounts for up to 33 % of the total dose to the primary water. This event is an important source for H2 and corrosive H2O2, so its product yields must be accurately included in models of the cooling water radiation chemistry. H2 produced in water from the 10B(n,α)7Li fission reaction has been measured up to 300 °C to aid in quantification of the corrosive H2O2 from the same reaction. Thermal energy neutrons from the Rhode Island Nuclear Science Center 2 MW reactor interacted with boric acid contained in N2O-saturated water in temperature-controlled high-pressure cells made from tubing of either titanium or zirconium alloy. After exposure for a minimum of one hour, the solution samples were extracted and sparged with argon. The H2 entrained by the sparging gas was sampled with a small mass spectrometer. A small amount of sodium was included in the boric acid solution so that after sparging, samples could be collected for 24Na activation measurements in a gamma spectrometer to determine the neutron exposure and thus the total energy deposited in solution. The G-value (µmol/J) for H2 production was obtained for water at a pressure of 25 MPa, over a temperature range from 20 °C to 300 °C. These results have been complemented with Monte Carlo N-Particle® (MCNP®) simulations in collaboration with the National Institute of Standards and Technology, and have been compared with previous experimental results at room temperature and simulated results up to 350 °C. Additionally, boric acid has thus far been accepted as a chemically nondisruptive additive, as it was confirmed long ago to have extremely low reactivity with the two main reactive species produced in reactor primary water by radiolysis, the solvated aqueous electron and the hydroxyl radical (e(aq)- and •OH). However, at the Electric Power Research Institute standard desired pH of 7.3 and the operational temperature of 350 °C, approximately 22% of the boron added in PWR primary water exists in the chemical form of the conjugate base, borate, not boric acid. Although borate was previously confirmed to have no appreciable reactions with e(aq)-, it was not adequately studied for reactions with •OH prior to this work. We have observed a clearly apparent reaction between borate and •OH. Current chemistry models are completely ignorant on both the existence of the resultant species and its reactions. The chemical reaction of [B(OH)4]- (borate) with •OH along with cross-reactions of the product species have been studied up to 200 °C to determine those reactions’ rate constants and the products’ spectra. The University of Notre Dame Radiation Laboratory’s 8 MeV electron linear accelerator (LINAC) was configured to perform pulse radiolysis with pulse widths between 4ns to 20ns providing doses between 5.5 Gy and 62 Gy. High-energy electrons from the LINAC interact with the borated solution which has been N2O-saturated and is continuously flowed through a 316 stainless-steel optical cell. The cell temperature was adjusted by resistive-heating silicon cartridges, and pressure was controlled by two syringe pumps to prevent boiling. The cell had two fused silica windows for transmitting light from a xenon arc lamp through the solution and out to a multichromatic spectrophotometer system. Time-resolved spectral data was obtained over nano- and micro-second timeframes, for wavelengths ranging from the deep UV and into the infrared spectrum (250 nm to 820 nm). The reaction rates and products’ spectra were then obtained by analyzing the data using computational aids, namely IGOR Pro by Wavemetrics and KinTek Explorer by KinTek Corp. The product species of the reaction between borate and •OH is conjectured to be •[BO(OH)3]-, on the basis of ab initio calculations, which likely reacts with boric acid or borate to form a polymer radical.
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    Development of Low-Cost Autonomous Systems
    (2023) Saar, Logan Miles; Takeuchi, Ichiro; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    A central challenge of materials discovery for improved technologies arises from the increasing compositional, processing, and structural complexity involved when synthesizing hitherto unexplored material systems. Traditional Edisonian and combinatorial high-throughput methods have not been able to keep up with the exponential growth in potential materials and relevant property metrics. Autonomously operated Self-Driving Labs (SDLs) - guided by the optimal experiment design sub-field of machine learning, known as active learning - have arisen as promising candidates for intelligently searching these high-dimensional search spaces. In the fields of biology, pharmacology, and chemistry, these SDLs have allowed for expedited experimental discovery of new drugs, catalysts, and more. However, in material science, highly specialized workflows and bespoke robotics have limited the impact of SDLs and contributed to their exorbitant costs. In order to equip the next generation workforce of scientists and advanced manufacturers with the skills needed to coexist with, improve, and understand the benefits and limitations of these autonomous systems, a low-cost and modular SDL must be available to them. This thesis describes the development of such a system and its implementation in an undergraduate and graduate machine learning for materials science course. The low-cost SDL system developed is shown to be affordable for primary through graduate level adoption, and provides a hands-on method for simultaneously teaching active learning, robotics, measurement science, programming, and teamwork: all necessary skills for an autonomous compatible workforce. A novel hypothesis generation and validation active learning scheme is also demonstrated in the discovery of simple composition/acidity relationships.
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    Pyrolysis of 3D Printed Photopolymers: Characterization and Process Development
    (2023) Tyler, Joshua Bixler; Cumings, John; Material Science and Engineering; Digital Repository at the University of Maryland; University of Maryland (College Park, Md.)
    3D printing has shown to be instrumental in the development of complex structures that have been previously unobtainable through traditional manufacturing processes. Photopolymers have been used in lithography-based 3D printing techniques for decades and have shown to be easily printed from the micro to macro scales. The thermal decomposition, or pyrolysis, of patterned photopolymers of microscale and mesoscale has been shown to create carbon devices such as carbon micro electromechanical systems (MEMS) and electrodes. In this dissertation, I present the characterization of pyrolyzed photopolymers 3D printed via stereolithography (SLA) and two-photon polymerization (2PP). Furthermore, processes in which to bolster the material properties of the pyrolyzed materials was examined.First, I study the effects of increasing the pyrolysis temperature on 2PP photopolymers and how this changes the electrical conductivity and microstructure of the material. From this it was shown the ability to vary the conductivity of 3D printed and pyrolyzed glassy carbon parts by up to 500X through only the temperature of pyrolysis, including reaching conductivities an order of magnitude higher than previously reported work. By extending the characterization of pyrolyzed photopolymers to SLA photopolymers I am able to further develop a generalized understanding of the electrical and microstructural properties of pyrolyzed 3D printed photopolymers. Further, demonstrate a metric in which to understand the deformation of the material during pyrolysis and perform an electrical and microstructural study of the material. Secondly, I investigate increasing the electrical and mechanical properties of pyrolyzed photopolymers through metals deposition via electroplating. In doing so I introduce a novel technique on which to electrodeposit on the surface of pyrolyzed SLA and 2PP 3D printed parts. Metallizing these pyrolyzed samples showed to increase both the electrical conductivity and ultimate strength of both pyrolyzed photopolymers. Lastly, I looked at increasing the stiffness of the pyrolyzed photopolymers through the addition of hBN filler into the precursor photopolymer. In doing so I examine the manufacturing of the composite hBN containing photopolymers for 3D printing with SLA and 2PP systems. Following 3D printing and pyrolysis of the hBN/photopolymer composite compositional and microstructural analysis is performed. Mechanical testing of the pyrolyzed composites shows that a slight increase in the stiffness of the material is observed. I have shown the ability to control the electrical conductivity and microstructure of pyrolyzed 3D printed photopolymers through pyrolysis temperature. Through the addition of metals via electroplating I demonstrate a process by which to increase the electrical conductivity and ultimate strength of pyrolyzed photopolymers and through the addition of hBN into the precursor photopolymer I have shown a way to increase the stiffness of the pyrolyzed materials. These processes have already demonstrated the ability to 3D printed electrical devices and have laid out a groundwork for future development of 3D printed electronics, energy-storage devices, and shielding.