The depletion of natural resources has long been a concern since the rapid increase in energy consumption in recent years. The gradual increase of pollution worldwide accompanied by energy generation process also started to post threats to the environment. With the evolution of technology and materials, power generation and energy storage with significant improved efficiency can be made possible, and further benefits the reduction of degree of pollution generated. In this research, synthesis, processing, characterization and application of nano materials towards energy generation and energy storage devices are studied. In chapter 2, superior corrosion resistance properties of HVOF thermal spray of TiC and TiB2 coatings on 304H stainless steel, 430, and P91 steels were reported. The coatings successfully served at a protection layer by limiting oxygen penetration, sulfur attack, and decreased the formation of pits and cracks on the substrates at 750°C for up to 800 hours. In chapter 3, continuous smooth TiC nanofibers were successfully synthesized by carbothermal reduction of electrospun titanium based nanofibers. XRD and HR-TEM analysis results indicated the synthesized nanofibers were composed of high purity TiC. Electric conductivity of a single fiber was in the 2.00×10^5 range. Symmetrical cyclic voltammetry curve further indicated good electrochemical properties of the fibers. In addition, the TiC nanofibers also exhibited excellent sintering properties over TiC or TiB2 nanoparticles. Studies on morphology and electrochemical properties of MnOx nanofiber and nanoparticles is reported in chapter 4. MnOx, MnOx/SnO2, and MnOx/CNT nanofibers synthesized using electrospinning method showed specific capacitance of 166.12 F/g, 182 F/g for, and 472 F/g at scan rate of 10mV/s. Analysis results also showed positive impact of conductivity and fiber morphology on the electrochemical properties of the fibers. morphology and electrochemical properties of the MnOx nanoparticles synthesized using solvents with different polarity with gelation pH of 8.5, 9.0 and 10.0 were also studied. Analysis results show the impact of particle sized and morphology on the electrochemical properties. Highest specific capacitance measured for the synthesized nanoparticles was 231.38F/g@10mV/s and 165.13F/g@10mV/s for methanol and mixture of methanol and propanol based MnOx respectively. Effect of solvent polarity of the manganese sol on MnOx formation and phase transformation temperature is also shown in the chapter.

The research of this dissertation is formulated in two fields, i.e., the theoretical and computational studies of circumferential wrinkling on soft nanofibers and the swelling mechanics study of a bi-layered spherical hydrogel containing a hard core. Continuous polymer nanofibers have been massively produced by means of the low-cost, top-down electrospinning technique. As a unique surface instability phenomenon, surface wrinkling in circumferential direction is commonly observed on soft nanofibers in electrospinning. In this study, a theoretical continuum mechanics model is developed to explore the mechanisms of circumferential wrinkling on soft nanofibers under uniaxial stretching. The model is able to examine the effects of elastic properties, surface energy, and fiber radius on the critical axial stretch to trigger circumferential wrinkling and to discover the threshold fiber radius to initiate spontaneous wrinkling. In addition, nonlinear finite element method (FEM) is further adopted to predict the critical mismatch strain to evoke circumferential wrinkling in core-shell polymer nanofibers containing a hard core, as a powerful computational tool to simulate controllable wrinkling on soft nanofibers via co-electrospinning polymer nanofibers incorporated with nanoparticles as the core. The studies provide rational understanding of surface wrinkling in polymer nanofibers and technical approaches to actively tune surface morphologies of polymer nanofibers for particular applications, e.g. high-grade filtration, oil-water separation, polymer nanocomposites, wound dressing, tissue scaffolding, drug delivery, and renewable energy harvesting, conversion, and storage, etc. Furthermore, hydrogels are made of cross-linked polymer chains that can swell significantly when imbibing water and exhibit inhomogeneous deformation, stress, and, water concentration fields when the swelling is constrained. In this study, a continuum mechanics field theory is adopted to study the swelling behavior of a bi-layered spherical hydrogel containing a hard core. The problem is reduced into a two-point boundary value problem of a 2nd-order nonlinear ordinary differential equation (ODE) and solved numerically. Effects of material properties on the deformation, stress, and water concentration fields of the hydrogel are examined. The study offers a rational route to design and regulate hydrogels with tailorable swelling behavior for practical applications in drug delivery, leakage blocking, etc.

The global spread of COIVD-19, as well as the worsening air pollution throughout the world have brought tremendous attention into the development of materials that can efficiently capture particulate matter (PM). Traditional filters made from fabric, glass fibers, or melt blown fibers exhibit a low efficiency at removing sub-micrometer and nanoscale particles. Additionally, they exhibit limited performance in high humidity, high temperature environments. We suggest that the high porosity of filters composed of nanofibers could provide minimal obstruction to air flow, while their high tortuosity and surface area-to-volume ratio presents an excellent platform for particle capture. Electrospinning is a simple and well-studied process to produce randomly accumulated nano- and micro-scale diameter fibers. The main advantages of electrospun nanofibers include their tunable fiber morphology and diameter under specific electrospinning parameters, as well as the ease of post-process modification. Studies have demonstrated its promising applications ranging from tissue engineering, water purification to wearable electronics. Giving the tunable aspect of the process, various polymers were electrospun with different morphology and fiber diameter which all demonstrated high particle removal efficiency. Cellulose was chosen as the base material for our study since it is the most abundant biopolymer and its affinity for further chemical modification. In this study, the removal of nanoscale particles via in-house fabricated cellulose nanofilters is significantly enhanced by chemically functionalizing the fibers’ surface via the deposition of the bio-inspired glue polydopamine (PDA) and the polycation poly(diallyldimethylammonium chloride) (PDADMAC). Nanofilters were electrospun from cellulose acetate solutions before being regenerated to cellulose via an alkaline treatment. Cellulose nanofilters were then functionalized using only PDA or the codeposition of PDA with PDADMAC. Scanning electron microscope (SEM), Fourier transform infrared spectrometer (FTIR), and high-resolution X-ray photoelectron spectroscopy (XPS) were used to characterize the nanofilters. The effects of filter packing density, filter layering, and surface functionalization on their performance, i.e., their filtration efficiency, most penetrating particle size (MPPS), performance in a high humidity environment, and filter pressure drop were investigated. Furthermore, by introducing hydrophilic and hydrophobic nanofibers within a composite filter structure, the performance of the composite filter remained unchanged even in high humidity.

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Polymer nanofibers are gaining importance due to their wide applicability in diverse fields, such as tissue engineering, fuel cells, photonics and sensors. For these applications, manufacturing aligned polymer nanofibers with precisely controlled morphology and well characterized mechanical properties in a bottom up configuration is essential. In this work, we developed an isodiametric design space for fabrication of aligned polystyrene nanofibers (diameter 60-800nm) using non-electrospinning Spinneret based Tunable Engineered Parameter (STEP) technique. By adjusting the processing parameters such as relative humidity, solvent volatility and polarity, porous polymer tubes are demonstrated having large specific surface areas. Combining STEP with sol-gel process, aligned inorganic nanofibers, such as Titanium Oxide (TiO2) with varied morphologies can be conveniently obtained. Mechanical properties of aligned polymer nanofibers (diameter from 50nm to several hundred nanometers) with fixed-fixed boundary conditions were estimated using a lateral force microscope (LFM). We find that the tension in the fiber caused during fabrication process scales with fiber diameter and it dominates fiber stiffness. Our studies demonstrate isotropic arrangement of polymer chains in the fibers and anisotropic arrangement in the necking region for fibers undergone deformation. Finally, this study demonstrates development of force sensors capable of measuring single cell forces, which scale with the fiber structural stiffness. The ability to measure cell forces during cell division, migration and apoptosis provides new insights in cell mechanobiology. / Ph. D.