Doctor of Philosophy

dissertationThis thesis describes the development of novel silica and hybrid nanoporous membranes. Nanoporous membranes are widely used in various applications. This thesis focuses on their potential applications in the energy area, such as fuel cells and lithium batteries, and in separations and ultrafiltration. We use silica colloidal spheres and polymer-modified silica spheres to prepare the membranes in a time-, cost- and materialefficient manner. First, we prepared novel silica nanoporous membranes by pressing silica colloidal spheres followed by sintering. The pore size, the thickness, and the area of the membrane are precisely controlled by experiment parameters. The resulting membranes are mechanically and thermally durable, crack-free, and capable of size-selective transport. Next, to demonstrate the utility of the pressed membranes, described above, the proton-conductive pore-filled silica colloidal membranes were prepared and the fuel cells were constructed using these membranes. We modified these membranes by filling the membrane pores with surface-attached proton-conductive polymer brushes and prepared membrane-electrode assemblies to test fuel cell performance. We studied the proton conductivity and fuel cell performance as a function of the amount of sulfonic groups in the membrane. We also prepared and characterized reversible hybrid nanoporous membranes, self-assembled from solution containing polymer-modified silica colloidal spheres. Here we applied the new concept of noncovalent membranes, where the material is held together via noncovalent interactions of polymer brushes. This enables so-called reversible assembly of the membranes, in which membrane can be assembled in one solvent and dissolved in other. This approach provides advantages in recycling and reusing of the material. This work is one of the first of its kind and it opens a whole new area of research on reversible membranes made of polymer-modified nanoparticles. Finally, we applied our approach for preparation of both pore-filled and reversible self-assembled silica membranes to develop new SPE material for lithium rechargeable batteries. We successfully prepared ion-conductive SPE from each of the materials and demonstrated the proof-of-concept for these approaches. Overall, in this thesis, we introduce unique approaches where we combine simple materials with novel yet easy preparation and modification methods to obtain new functional nanoporous membranes with desired properties

Shear-Induced Alignment of Anisotropic Nanoparticles in a Single-Droplet Oscillatory Microfluidic Platform

Flow-induced alignment of shape-anisotropic colloidal particles is of great importance in fundamental research and in the fabrication of structurally anisotropic materials; however, rheo-optical studies of shear-induced particle orientation are time- and labor-intensive and require complicated experimental setups. We report a single-droplet oscillatory microfluidic strategy integrated with in-line polarized light imaging as a strategy for studies of shear-induced alignment of rod-shape nanoparticles. Using an oscillating droplet of an aqueous isotropic suspension of cellulose nanocrystals (CNCs), we explore the effect of the shear rate and suspension viscosity on the flow-induced CNC alignment and subsequent relaxation to the isotropic state. The proposed microfluidic strategy enables high-throughput studies of shear-induced orientations in structured liquid under precisely controlled experimental conditions. The results of such studies can be used in the development of structure-anisotropic materials

Injectable Shear-Thinning Fluorescent Hydrogel Formed by Cellulose Nanocrystals and Graphene Quantum Dots

In the search for new building blocks of nanofibrillar hydrogels, cellulose nanocrystals (CNCs) have attracted great interest because of their sustainability, biocompatibility, ease of surface functionalization, and mechanical strength. Making these hydrogels fluorescent extends the range of their applications in tissue engineering, bioimaging, and biosensing. We report the preparation and properties of a multifunctional hydrogel formed by CNCs and graphene quantum dots (GQDs). We show that although CNCs and GQDs are both negatively charged, hydrogen bonding and hydrophobic interactions overcome the electrostatic repulsion between these nanoparticles and yield a physically cross-linked hydrogel with tunable mechanical properties. Owing to their shear-thinning behavior, the CNC-GQD hydrogels were used as an injectable material in 3D printing. The hydrogels were fluorescent and had an anisotropic nanofibrillar structure. The combination of these advantageous properties makes this hybrid hydrogel a promising material and fosters the development of new manufacturing methods such as 3D printing

Line Emission Mapper (LEM): Probing the physics of cosmic ecosystems

The Line Emission Mapper (LEM) is an X-ray Probe for the 2030s that will answer the outstanding questions of the Universe's structure formation. It will also provide transformative new observing capabilities for every area of astrophysics, and to heliophysics and planetary physics as well. LEM's main goal is a comprehensive look at the physics of galaxy formation, including stellar and black-hole feedback and flows of baryonic matter into and out of galaxies. These processes are best studied in X-rays, and emission-line mapping is the pressing need in this area. LEM will use a large microcalorimeter array/IFU, covering a 30x30' field with 10" angular resolution, to map the soft X-ray line emission from objects that constitute galactic ecosystems. These include supernova remnants, star-forming regions, superbubbles, galactic outflows (such as the Fermi/eROSITA bubbles in the Milky Way and their analogs in other galaxies), the Circumgalactic Medium in the Milky Way and other galaxies, and the Intergalactic Medium at the outskirts and beyond the confines of galaxies and clusters. LEM's 1-2 eV spectral resolution in the 0.2-2 keV band will make it possible to disentangle the faintest emission lines in those objects from the bright Milky Way foreground, providing groundbreaking measurements of the physics of these plasmas, from temperatures, densities, chemical composition to gas dynamics. While LEM's main focus is on galaxy formation, it will provide transformative capability for all classes of astrophysical objects, from the Earth's magnetosphere, planets and comets to the interstellar medium and X-ray binaries in nearby galaxies, AGN, and cooling gas in galaxy clusters. In addition to pointed observations, LEM will perform a shallow all-sky survey that will dramatically expand the discovery space