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(2021)ThesisImprovements in liquid lithium-ion battery electrolytes using of metal organic frameworks (MOFs) as a functional decoration on polymer membrane separators were investigated using a combination of experimental and theoretical methods. Zirconium-based MOF UiO-66 was introduced to the polymer support using the mixed matrix membrane (MMM) method. The method allowed the one-step manufacture of a robust, mechanically pliable polymer-MOF membrane composite of high MOF loading. MOF-MMMs imparted improved electrochemical behaviours such as a widened potential operating window, near-unity transference number, and increased presence of solid electrolyte interphase (SEI) components crucial to battery performance. Density functional theory (DFT) calculations were also performed to provide insights regarding electrolyte solvation in the presence of MOF. A simple dip-coating technique was utilised to modify the surface of the MOF-MMMs with polydopamine (PDA) for further improvement of the electrochemical properties. Increased transference numbers, as well as stability during rate cycling, were observed with the resulting PDA-MMM owing to the improved electrode/electrolyte interface. However, surface analyses using x-ray photoelectron spectroscopy (XPS) showed that there are reduced amounts vital SEI components compared to the original MOF-MMM support. The last section further explores the versatility of UiO-66 and tackled the preparation of gel polymer electrolytes (GPEs) decorated with UiO-66 via phase inversion technique. Using the phase inversion method, the fabricated GPE contained pores from both polymer substrate and the intrinsic pores of the 3D nanomaterial for improvement of electrochemical properties. It was demonstrated in this work that the MOF GPE is equally inert and suitable in ether or carbonate-based electrolytes. Overall, this study demonstrated the versatility of UiO-66 metal organic frameworks for use as a functional nanofiller for electrolyte membranes. With the use of inexpensive membrane fabrication methods, the composites obtained are viable for lithium-metal battery applications. Similarly, insights drawn can provide a springboard towards future study of MOF-based electrolytes.
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(2021)ThesisMultiferroic BiFe0.5Cr0.5O3 (BFCO) in which ferroelectric and magnetic orders coexist has gained research interest owing to its potential applications, e.g., spintronic and resistive random-access memory. Moreover, multiferroics possess a narrower bandgap compared to typical ferroelectrics, extending their application to photovoltaic devices. In contrast to the conventional semiconductors, the polarization-induced electric field facilitates the photoexcited charge separation, leading to an above-bandgap photovoltage in ferroelectrics. Nevertheless, a long-standing issue is the relatively low absorption of visible light. Thus, it is essential but challenging to tune their bandgap without compromising ferroelectricity. This thesis explores structural phase transition in the epitaxial BFCO films grown on SrRuO3 buffered (001) SrTiO3 substrate via Laser Molecular Beam Epitaxy (LMBE). Reciprocal space mapping result shows strain relaxation mechanism is not solely by the formation of misfit dislocation but also by changing the crystal symmetry, transitioning from tetragonal-like to a monoclinically distorted phase as the thickness increases. The crystallographic evolution is also coupled with bandgap modulation, confirming that BFCO structure and its physical properties are strongly intertwined. Using spectroscopic ellipsometry, the slight redshift of the bandgap distinguishes the absorption process of the T-like BFCO layer from that of monoclinically distorted structure, further confirmed by spectral photocurrent measurement via conductive-atomic force microscopy. The preparation of pure phase BFCO film with a robust polarization is of paramount importance for practical application. Yet, similar to the parental bismuth ferrite, BFCO suffers from poor electrical leakage performance. We report a three-order of magnitude suppression in the leakage current for the BFCO film through judicious adjustment of the growth rate. Scanning probe microscopy (PFM, AFM and c-AFM) results reveal that both microstructure and ferroelectric properties can be tuned by lowering the growth rate, ensuing realization of the room-temperature ferroelectric polarization comparable to the ab-initio predicted value. This thesis provides a facile strategy to tailor the structure-property of epitaxial BFCO film and its functional response for emerging optoelectronic devices.
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(2022)ThesisThis thesis focuses on the development and applications of magnetic resonance electrical properties tomography (MREPT), which is an emerging imaging modality to noninvasively obtain the electrical properties of tissues, such as conductivity and permittivity. Chapter 2 describes the general information about human research ethics, MRI scanner, MR sequence and the method of phase-based MREPT implemented in this thesis. Chapter 3 examines the repeatability of phase-based MREPT in the brain conductivity measurement using balanced fast field echo (bFFE) and turbo spin echo (TSE) sequences, and investigate the effects of compressed SENSE, whole-head B_1 shimming and video watching during scan on the measurement precision. Chapter 4 investigates the conductivity signal in response to short-duration visual stimulus, compares the signal and functional activation pathway with that of BOLD, and tests the consistency of functional conductivity imaging (funCI) with visual stimulation across participants. Chapter 5 extends the use of functional conductivity imaging to somatosensory stimulation and trigeminal nerve stimulation to evaluate the consistency of functional conductivity activation across different types of stimuli. In addition, visual adaptation experiment is performed to test if the repetition suppression effect can be observed using funCI. Chapter 6 explores if resting state conductivity networks can be reliably constructed using resting state funCI, evaluates the consistency of persistent homology architectures, and compares the links between nodes in the whole brain. Chapter 7 investigates the feasibility of prostate conductivity imaging using MREPT, and distinctive features in the conductivity distribution between healthy participants and participants with suspected abnormalities.
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(2022)ThesisTwo-dimensional transition metal dichalcogenide (TMD) nanocrystals (NCs) exhibit unique optical and electrocatalytic properties. However, the growth of uniform and high-quality NCs of monolayer TMD remains a challenge. Until now, most of them are synthesized via solution-based hydrothermal process or ultrasonic exfoliation method, in which the capping ligands introduced from organic solution often quench the optical and electrocatalytic properties of TMD NCs. Moreover, it is difficult to homogeneously disperse the solution-based TMD NCs on a substrate for device fabrication since the dispersed NCs can easily aggregate. Here, we put forward a novel CVD method to grow closely-spaced TMD NCs and explored the growth mechanism and attempts on the size control. Their applications acting as electrocatalysts and adhesion layer for Au film deposition have been also well displayed. Through the whole chapters of this thesis, the following aspects are highlighted: 1. MoS2 and other TMD nanocrystals have been grown on the c-plane sapphire. The surface oxygen vacancies determine the density of TMD nanocrystals. The MoS2 nanocrystals demonstrate excellent hydrogen evolution reaction and surface-enhanced Raman scattering performance owing to the abundant edges. 2. Deep insights into the growth of MoS2 nanograins have been explored. The surface step edges and lattice structures of the underlying sapphire substrates have a significant influence on the growth behaviors. The step edges could modulate the aggregation of MoS2 nanograins to form unidirectional triangular islands. The Raman spectra of MoS2 demonstrate a linear relationship with the crystal size of MoS2. 3. The orientation of sapphire substrate has an of importance effect on the critical size of MoS2 nanocrystals. The MoS2 nanocrystals have the smallest size on the r-plane sapphire, besides, the MoS2 on r-plane sapphire demonstrates the sintering-resistance feature, which is attributed to the edge-pinning effect when MoS2 edges are anchored on the sapphire surface. 4. The MoS2 nanocrystalline layer was utilized as the adhesion layer for Au film depositing on a sapphire substrate. The Au films on MoS2 displayed superior transmittance and electrical conductivity as well as outstanding thermal stability, which lay in the strong binding of Au film with MoS2 nanocrystalline layer.
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(2023)ThesisBiodegradable implant materials are more appropriate for temporary support applications compared with their inert counterparts since the former requires no removal surgery because they naturally degrade and eventually dissolve completely during healing. Iron and its alloys are a possible substitute for the commercial magnesium biodegradable implants because of their superior mechanical properties and slower corrosion rates. The addition of manganese and silicon in iron imparts another interesting property to the material–the shape memory effect. There is copious research on the structure and properties of the biodegradable face centred cubic (FCC) Fe-30Mn-6Si shape memory alloy (SMA) that exhibits the reversible FCC austenite to hexagonal close packed (HCP) ε-martensite transformation. However, recent advances in additive manufacturing of metals, brought by the development of the laser powder bed fusion (LPBF) technique, warrant the need for an investigation on the adaptability of the technique in fabricating this alloy composition. The LPBF technique is limited by the need for specialty raw material powder, and this thesis extends the application of the technique in fabricating the Fe-30Mn-6Si shape memory alloy (SMA) from homogenised powder precursors. More so, LPBF processing of Fe-30Mn-6Si alloy from either pre-alloyed powder or blended powder has not been reported. To successfully fabricate a Fe-30Mn-6Si LPBF product, the influence of key LPBF processing parameters on product quality was identified as a major challenge. This was addressed by investigating the influence of laser power, laser scan speed, laser re-scanning, and their equivalent input energy on the relative density and defect formation. A relative density of over 99% with few processing defects was achieved using the optimised parameters of 175 W laser power, 400 mm/s scan speed, and no re-scanning. The influence of these parameters on the solidification microstructure was also investigated using key techniques, such as X-ray diffraction (XRD) and scanning electron microscopy (SEM) in conjunction with energy dispersive spectroscopy (EDS) and electron backscatter diffraction (EBSD). Further, the simulated thermal profile of the melt pool region as a function of process parameters via single scan track experiments was calculated using the finite element method (FEM). These data were used to explain the key microstructural features observed in the as-solidified microstructure of the LPBF alloy as a function of the processing parameters. The mechanical properties of the LPBF alloy were then assessed by hardness and tensile testing and then compared with a reference alloy produced by arc melting. The hardness of the LPBF as-built alloy was ∼20% higher than the reference alloy. To identify the factors affecting the increased hardness of the former, the influence of grain size and morphology, crystallographic texture, phase constituents (mainly austenite and martensite), and residual strain were investigated. The hardness of the reference alloy was affected mainly by the grain size and residual strain, but for the LPBF-built alloy, the relative volume fractions of austenite and martensite strongly influenced the hardness. Meanwhile, the tensile properties of the LPBF alloy, such as the yield stress, ultimate tensile stress, and ductility, were adversely affected by the internal defects present, such that high temperature homogenisation and hot isostatic pressing (HIP) post-process treatments were investigated to improve these properties. The homogenisation and HIP treatments increased both the tensile strength and ductility of the LPBF-built alloy. Homogenisation altered the grain morphology by promoting recrystallisation and grain growth, and this increased the tensile strength by ∼80%. The hardness, however, decreased due to a reduction in the volume fraction of HCP martensite in the FCC austenitic microstructure. HIP retained some of the columnar microstructure generated by the LPBF process, marginally increased the density, and increased the tensile strength by ∼65%. The improvement in tensile properties through these post-process treatments allowed for the measurement of LPBF alloy’s shape memory behaviour, whereby a tensile recovery strain of 2% was achieved for the HIP-treated alloy. Finally, the biocorrosion behaviour of the LPBF-processed and HIP-treated alloy was investigated, whereby the in vitro corrosion potential and current density of the alloy were determined to be -769 mV and 5.6 μA/cm2, respectively, indicating a reasonable corrosion rate for this material. Overall, this thesis enabled the first demonstration of the shape memory effect in an LPBF-built Fe-based alloy fabricated from homogenised powder, an alloy which also exhibits biodegradable properties.
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(2022)ThesisIncreasing population and resource demands, a changing hydroclimate, and increasing risks of extreme events means that sustainable water management is more important now than ever before. Water planners are increasingly recognising that short instrumental records are insufficient to understand fully natural trends and variability in climate. High resolution paleoclimate proxies, like tree rings, can provide long time series of observations prior to the instrumental period, to better understand instrumental and pre-instrumental variability, the occurrence, trends, and drivers of extreme events, and provide insights into possible future hydroclimatic scenarios. However, tree-ring proxies are not evenly distributed in the landscape, and the South Pacific has very few high-resolution paleoclimate proxies to develop detailed reconstructions of climate variability. This thesis explores whether the relationships between tree-ring proxies in regions with strong teleconnections to the Pacific (i.e., ‘remote’ tree rings) can be exploited to reconstruct hydroclimatic indices across eastern Australia and the South Pacific Islands. Methods for hydroclimatic reconstruction are investigated, considering the unique challenges of the region: strong inter-annual and inter-decadal variability, very short data records, data gaps, and potential non-stationarities in climate teleconnections. Existing methods for tree-ring reconstructions have been successfully applied in the South Pacific (Chapter 2); however, overcoming the challenges posed by very short and non-continuous records required adaptations to existing methods (Chapter 3) and the development of new methods (Chapter 5). In the final two chapters, the thesis focuses on how catchment-scale tree-ring reconstructions can be most useful to water managers. In these chapters, methods of identifying, explaining, and representing extreme event frequency, return periods, and trends are explored, as are methods for using paleoclimate data along with climate model projections to help contextualise future risks of climate change. Overall, this thesis highlights the enormous potential of remote tree-rings for improving our understanding of past climate in the South Pacific. The reconstructions consistently demonstrate that the instrumental period underestimates the full range of natural climate variability and shows how century-long records provided by tree rings can help us better understand past climate drivers, contextualise the instrumental period, and refine estimates of future climate risks. This thesis builds upon a growing body of work that demonstrates the considerable value of tree-ring based reconstructions for current and future water resource decision making, most notably in remote regions that are highly vulnerable to climate change but where there are limited instrumental records. Maximising the potential of tree-ring data for water management will require ongoing collaboration between dendrochronologists and water managers.
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(2022)ThesisMultijunction solar cells based on silicon are predicted to achieve an efficiency of 40-45% for a top cell with a band gap of 1.6-1.9 eV. However, there are currently no known materials with suitable band gaps able to deliver high efficiencies. Two classes of materials that have been proposed for top cells are alloys of CuGaSe2 and alloyed oxide perovskites. CuGaSe2 has a suitable band gap (1.68 eV) for a top cell on silicon, but the maximum efficiency achieved is only 11%, while that of the closely-related CuInGaSe2 (band gap 1.14 eV) is 23.35%. The low efficiency of CuGaSe2 has been attributed to anti-site defects. Therefore, suppressing this defect formation is critical to achieving higher efficiencies. On the other hand, most oxide perovskites have band gaps that are too high (>2 eV) to be used as top cells on silicon, hence strategies such as alloying are required to lower their band gaps. In this work, the effects of alloying CuGaSe2 with Ag, Na, K, Al, In, La and S were investigated using Density Functional Theory (DFT) calculations. The band gaps of the alloyed compounds and formation energies of anti-site defects were calculated to find alloying elements that can increase the defect formation energy but maintain the band gap. CuGaSe2 alloyed with Al at 50at% showed the highest increase (compared to unalloyed CuGaSe2) in the defect formation energy (by ~0.20 eV) followed by Na (~0.15 eV) and S (~0.10 eV), both at 50at%. However, the band gap of the Al alloy (~2.15 eV) is too high for a top cell, while those of Na (~1.95 eV) and S (~1.91 eV) are slightly above the upper limit. Thus, alloying with these elements is not an ideal route towards significantly increasing the formation energy of anti-site defects while maintaining the band gap of CuGaSe2. However, some of the factors that influence the defect formation energy are identified, potentially leading to design rules for future work. Defect formation energies were found to be higher in structures with more positively charged Ga and negatively charged Se atoms. Analysis of bond lengths revealed a positive correlation between shorter Ga and Se bonds and higher defect formation energies. Band gaps of various alloyed oxide perovskites were calculated using DFT. BiFeO3 was alloyed with Y and Sb; LaFeO3 with Cr and Sb and YFeO3 with Bi and Sb. YFeO3 alloyed with Sb at 50at%, was found to have a band gap of 1.4-2.1 eV (depending on the basis set used) which is in the range for a top cell.
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(2022)ThesisThere has been a rapid-growing market and academic enthusiasm for small wearable molecular diagnostic platforms driven by the growing demand for continuous monitoring of human health. Wearable devices need to be portable, stretchable, and ideally re-configurable to be able to work for different analytes. Such flexible physiological monitoring devices which are non-invasive or minimally-invasive represent the next frontier of biomedical diagnostics. They may make it possible to predict and prevent diseases or facilitate treatment by diagnosing diseases at the initial stages. However, there are many problems that restrict further applications of these devices. Firstly, there are a limited number of bio-materials which are highly flexible, biocompatible and have anti-fouling properties; such biomaterials are needed as substrates for wearable devices. Secondly, traditional biosensors used in wearable devices focus on the detection of physical signals (such as heartbeat) and small chemical molecules, e.g. Na+, K+. These are not sufficient to provide in depth health information which requires sensing of large molecules such as proteins, ideally in real time, which is currently challenging. This provides a motivation to develop highly sensitive wearable biosensors for the detection of large molecules in sweat. This thesis centres on the development of a bio-material based wearable device for continuous detection of crucial analytes in human sweat. To achieve this target, our first aim was to design a highly bio-compatible flexible material as a substrate for wearable devices. A tough and anti-fouling three-network hydrogel has been prepared by integrating a zwitterionic polymer network into a robust double-network hydrogel. Secondly, to fill the gap between technological development of continuous and non-invasive detection of different analytes in human sweat, a patterned sweat-based biosensor was created for the detection of key biomolecules. This sensor was produced by placing specific aptamers or enzymes on flexible working electrodes. In addition, nanotechnology methods have been applied to refine the bio-sensing interface to further increase the sensitivity of our sensors. Finally, a sample collection chip has been combined with our high sensitivity sensors to fabricate a wearable device for sweat bio-sensing purposes. Future research may involve integration of a commercially available wireless signal readout module with this wearable biosensing device. The outcomes of this work may provide new insights for the development of wearable devices for continuous measurement of a spectrum of analytes in sweat, as an important step towards point-of-care diagnostics
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(2022)ThesisOver the past two decades, Bismuth ferrite (BiFeO3, BFO) thin films have attracted significant attention on account of their attractive multifunctional properties, ranging from room-temperature multiferroicity to robust high Curie temperature (Tc), large switchable spontaneous polarization (Ps) and enhanced electromechanical response, and ability to generate photovoltaic current etc. In particular, the past decade has seen huge efforts devoted to engineering the phase structure of BFO films to achieve a morphotropic phase boundary -(MPB)-like materials system with excellent ferroelectric properties and high electromechanical response. In this thesis, strain engineering and site engineering are applied to tailor the phase composition of epitaxial BFO films through a chemical solution deposition (CSD) method. The compressive epitaxial strain provided by the lattice misfit between the film and the lanthanum aluminate (LaAlO3, LAO) substrate can stabilize a tetragonal-like (T’) phase. The chemical pressure produced by the A-site substitution of smaller Sm element can induce a ferroelectric rhombohedral (R) to paraelectric orthorhombic (O) phase transition. The coexistence of these diverse polymorphs of BFO is expected to generate an MPB effect, where a maximum electromechanical property usually reports. The thesis first employs the misfit strain engineering (BFO films grown on LAO substrates) to tune the phase fraction in mixed-phase (rhombohedral-like (R’)-T’ coexistence) BFO films by altering the synthesis parameters via the CSD method. It shows that the T’-phase fraction ranging from 10% to 35% is achieved by decreasing the spin-coated layers from four to one layer. In a two-layer configuration, the T’-phase fraction is further found that can be varied from 8% to 38% by changing the precursor concentration and heating treatment parameters. The mixed-phase BFO films show a typical polydomain structure with a polarization-orientation dependent conduction behavior whereby poled-up (polarization pointing away from the lower electrode) domains have higher conductivity. An optimized film with a T’-phase fraction of ~ 28% shows the lowest leakage current of <0.1 A/cm2 up to field strengths of 500 kV/cm. Upon increasing electric field, the mixed-phase film shows an interface-limited Schottky emission to bulk-limited space-charge-limited-conduction (SCLC) mechanism predominate leakage current transition. The thesis then applies site engineering (A-site substitution with Sm) to tailor the phase structure of BFO films deposited on strontium titanate (SrTiO3, STO, the lattice parameter is similar to that of BFO) substrates. The role of the Sm on the precursor gelation chemistry is first studied. It is found that the electronegativity of the cation species in metal nitrates affects the reaction rate of the hydrolysis reaction and esterification reaction. The structural investigation of the crystalline films shows that the phase transition occurs at x = 0.10 with paraelectric O phase and antipolar phase appearance. The domain contrast of as-grown BFO/BSFO (BSFO: Bi1-xSmxFeO3) films reduces gradually with the increase of the Sm composition. More importantly, Sm introduction greatly improves the ferroelectric properties of BFO films. At an Sm ratio of 0.14, a fully developed polarization hysteresis loop is achieved. When the Sm ratio is increased to 0.15, an electric-field-induced distorted double hysteresis loop is observed. Then strain engineering and site engineering are combined to construct a complex phase configuration in BSFO films. A structural evolution from T’-R’ to T’-R’-O, and then to T’-O phases is demonstrated with the increase of the Sm ratio. The synergetic effects of misfit strain and chemical pressure drive the phase transition composition to a higher value of 0.14 compared to that of strain-free BSFO/LSMO//STO (LSMO: La0.67Sr0.33MnO3) films at 0.10. Likewise, Sm doping in the A-site leads to the decrease of the piezoresponse force microscopy (PFM) amplitude. While an enhanced domain switching behavior is attained at MPB. The ferroelectric properties show a transition from a single ferroelectric square-shaped to a slightly distorted double hysteresis loop with the Sm3+ doping content increasing from 0.14 to 0.16. The investigation of the resistive switching behavior shows an interesting transition of the current flow under the external bias from “high resistance state (HRS)-> low resistance state (LRS)->HRS->LRS” to “HRS->LRS->LRS->HRS”. This thesis provides a comprehensive understanding of the effects of epitaxial strain or/and chemical pressure on the phase composition of BFO films and their multifunctional properties. The appealing physical properties induced by the structure evolution promote the seeking of novel phase structure of perovskite oxides in thin-film form.
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(2022)ThesisDissolved organic carbon is stored and processed in groundwater in three ways. It is stored on minerals by adsorption, it is biologically processed through biodegradation, and it also undergoes a process to return to groundwater called desorption. This biophysiochemical research shows that the groundwater system is therefore a vital part of the global carbon cycle and carbon sink. This research fills a gap in the existing understanding of how to calculate the global carbon budget, as does not yet include the dissolved organic carbon that is stored in groundwater. This thesis exclusively explores processes determining dissolved organic carbon character and concentration in groundwater in different geological environments. This is new, useful knowledge to describe the biophysiochemical process. This research did not examine human interference in adding carbon to groundwater. This research found how dissolved organic carbon is stored and processed in groundwater due to biodegradation and desorption, and how it is adsorbed onto sediment surface. This research explored the characteristics and concentration of Dissolved organic carbon in groundwater by using Liquid Chromatography-Organic Carbon Detection, and other techniques, to examine dissolved organic carbon in terms of its fractions: humic substances, hydrophobic organic carbon, biopolymers, building blocks (BB), low molecular weight neutrals and low molecular weight acids. There were several key findings. First, the results showed that both semi-arid inland low sedimentary organic carbon environments – i.e., Maules Creek and Wellington – were a carbon source; while the high rainfall temperate coastal peatland environment of Anna Bay was a carbon sink. Secondly, another key finding was that dissolved organic carbon was not processed as a whole chemical compound, but it was processed by its fractions where each fraction was processed distinctly. For example, humic substances were only adsorbed/desorbed in groundwater; while low molecular weight neutrals were only consumed by microbes in the biodegradation process in groundwater.