Four silicon nitride powder blends vary in starting powder characteristics, glass chemistry, and phase composition. This work focuses on how these properties influence densification behavior, microstructural development, and the resulting mechanical performance of dense ceramics. Previous work completed on alpha-rich, low oxide containing (8 wt%), and fine silicon nitride powder (GS-44) showed high hardness equiaxed with grained ceramic. GS-44 served as an excellent precursor for the matrix phase material in graphene reinforced composites, which resulted in 235% increase in toughness and high hardness retention [1] with the addition of 1.5 vol% graphene. As the GS-44 powder is no longer in production, investigative work into other commercial powders and customization of powder blends was initiated. Commercial blends were selected based on availability, high alpha content, fine particle size, and additive chemistry (Al2O3, MgO, and Y2O3). The objective was to understand which powder characteristics led to a ceramic design that contained high hardness, strength, and toughness properties in order to increase the use of silicon nitride in extreme temperature environments. One such example is aerospace and structural applications that require a high-performance material that is lightweight and good thermal stability. Strong covalent bonding in silicon nitride make densification of powders extremely difficult; thereby, sintering additives are necessary to promote liquid phase sintering processes. Compaction of ceramic powders was carried out using a spark plasma sintering (SPS) furnace by utilizing a pulsed direct current through a conductive graphite die that encapsulates the sample powder. SPS was preferred over other conventional sintering methods owing to its high heating rate and short dwell times at the sintering target temperature. Thus, SPS provides superior control for tailoring the final silicon nitride properties by producing a hard alpha-phase and tough beta-phase microstructures. The custom blend developed had an appreciable amount of media wear included during the milling process that increased the additive content. Development of the custom blend was used to understand the effect of a larger additive content. Commercial GS-44 blend was used as the control to track the effect of adjusting specific surface area and oxide content in silicon nitride powder systems (HCS-M, C-R3, and UA-SN). The mechanical results for the four matrix systems, showed that toughness increased with grain coarsening and minimization of alumina content in beta silicon nitride. Based on these findings it is important to determine tradeoffs (i.e. balance of high hardness, toughness, and strength) to engineer an optimal ceramic that can be used for structural and aerospace applications.

Silicon nitride thin films are of interest in the biomedical engineering field due to their biocompatibility and favorable tribological properties. Evaluation and understanding of the properties of these films under diverse loading and failure conditions is a necessary prerequisite to their use in biomedical devices. Three wafers of silicon nitride-coated silicon were obtained from Lawrence Livermore National Laboratory and used to create 96 samples. Samples were subjected to nanoindentation testing to evaluate the mechanical properties of the film. Samples were subjected to nanoimpact testing to compare the damage resistance of the film to separate nanoimpact types. Samples were subjected to nanoscratch testing to evaluate the consistency of the critical load of the film. Results showed that there were no significant differences in the mechanical properties of the film across the tested groups. There was a significant difference observed in the rate of damage to the film between pendulum oscillation nanoimpact testing and sample oscillation nanoimpact testing, with the former causing more damage with all experiment variables controlled for. Results showed that the critical load measure for the film was significantly different between different nanoscratch test parameters. The conclusions from this study will support future work for in vitro and in vivo testing of ceramic thin films for biomedical applications.

Over the past decades, integrated photonics has revolutionized the way we generate and manipulate light, employing micro- and nanoscale structures to shrink full optical systems into chips smaller than a fingernail. By leveraging the infrastructure of semiconductor foundries and fabrication processes, the development and deployment of integrated photonic technologies has been greatly accelerated. The main focus has been in applications for infrared light, such as optical interconnects and communication. Nevertheless, photonic integrated circuits (PICs) have quickly found applications in many other fields, including sensing, ranging, imaging, quantum technologies, biomedicine, spectroscopy, microwave generation, astrophysics, and displays. However, many of these technologies require light at visible wavelengths, where PIC technology is still in its infancy. Visible-light photonics presents several additional and stricter challenges when compared the infrared portion of the spectrum. First, laser sources are not as developed or available. Second, the sensitivity of devices to fabrication variations and the coupling losses are intensified. Third, the range of transparent materials available for waveguiding is more limited, and their technology is not as mature. Lastly, techniques that work well in the infrared spectrum are not as effective in the visible range due to the remarkably different material properties in this spectral window.In this thesis, we explore integrated photonics in the visible spectrum and focus on solving two of its main challenges: the lack of high-performance laser sources, and the high losses of PICs. We develop a low loss, high-confinement silicon nitride (SiN) platform and use it to demonstrate high-performance visible-light lasers from near-ultraviolet (near-UV) to near-infrared (near-IR), to probe the limits of absorption and scattering across the visible spectrum, and to generate multi-octave frequency combs with simultaneous infrared and visible light of all colors of the rainbow. Since our SiN platform is compatible with current photonic foundries, our work lays the foundation for fully-integrated, dense and scalable visible-light PIC systems that combine high-performance lasers and ultra-low loss devices. We envision such chip-scale platform to not only transform existing technologies, but to also enable a whole new generation of applications that have so far been impossible, causing tremendous impact in science, medicine and industry.

Small scale renewable energy harvesting is an attractive solution to the growing need for power in remote technological applications. For this purpose, localized thermal gradients on-chip—created via radiative cooling—could be exploited to produce microscale renewable heat engines running on environmental heat. This could allow self-powering in small scale portable applications, thus reducing the need for non-renewable sources of electricity and hazardous batteries. In this work, we demonstrate the creation of a local thermal gradient on-chip by radiative cooling of a 90 nm thick freestanding silicon nitride nanomechanical resonator integrated on a silicon substrate at ambient temperature. The reduction in temperature of the thin film is inferred by tracking its mechanical resonance frequency, under high vacuum, using an optical fiber interferometer. Experiments were conducted on 15 different days during fall and summer months, resulting in successful radiative cooling in each case. Maximum temperature drops of 9.3 K and 7.1 K are demonstrated during the day and night, respectively, in close correspondence with our heat transfer model. Future improvements to the experimental setup could enhance the temperature reduction to 48 K for the same membrane, while emissivity engineering potentially yields a maximum theoretical cooling of 67 K with an ideal emitter. This thesis first elaborates a literature review on the field of radiative cooling, along with a theoretical review of relevant thermal radiation concepts. Then, a heat transfer model of the radiative cooling experiment is detailed, followed by the experimental method, apparatus, and procedures. Finally, the experimental and theoretical results are presented, along with future work and concluding remarks.

No description available.

Reaction sintered silicon nitride (RSSN) was studied as a substitute coating material on the carbon-carbon material (RCC) presently used as a heat shield on the space shuttle, and on advanced carbon-carbon (ACC), a later development. On RCC, RSSN showed potential in a 538°C (1000°F) screening test in which silicon carbide coated material exhibits its highest oxidation rate; RSSN afforded less protection to ACC because of a larger thermal expansion mismatch. Organosilicon densification and metallic silicon sealing methods were studied as means of further increasing the oxidation resistance of the coating, and some improvement was noted when these methods were employed. / Master of Science

Silicon nitride (Si₃N₄) has the potential for use in various high-performance applications. However, surface defects such as voids/pits are commonly present on as processed Si₃N₄. When subjected to external forces, fracture originates at such flaws. To reduce or eliminate surface flaws, machining operations are required which constitute a major proportion of production costs. In order to offer an inexpensive alternative to machining and also to enhance the room temperature flexural strength of as fired Si₃N₄, low expansion glaze coatings of lithium aluminosilicate (LAS) and magnesium aluminosilicate (MAS) compositions were developed. Homogeneous and crack-free glaze coatings were successfully formed on as processed Si₃N₄. This ensured formation of compressive surface stresses on the as fired Si₃N₄ which, in turn, led to the reduction of the effects of surface flaws. When compared to the uncoated as fired Si₃N₄, both the glaze coatings helped achieve greater flexural strength. Analyses of the two glazes indicated better strength for the MAS coating compared to the LAS. Wear tests revealed that the MAS glaze exhibited higher wear resistance than the LAS glaze. These differences were attributed to the ability of the magnesium aluminosilicate glaze to achieve greater surface smoothness and better adherence to the substrate than the lithium aluminosilicate. / Master of Science

The breast cancer susceptibility protein, BRCA1, is a tumor suppressor that helps maintain genomic integrity. Changes in BRCA1 that effect DNA repair processes can fuel cancer induction. The Kelly lab, at the Virginia Tech Carilion Research Institute, has recently developed a new methodology that employs silicon nitride (SiN) microchips to isolate BRCA1 assemblies from the nuclear material of breast cancer cells. These microchips are coated with adaptor proteins that include antibodies against target proteins of interest. The adaptor proteins are added in sequential steps to the coated microchips, followed by an aliquot of sample containing the protein of interest, such as BRCA1. The Kelly lab, partnered with Protochips Inc., developed these devices as a robust, tunable platform to monitor molecular processes, and refer to them as 'Cryo-SiN' in cryo-Electron Microscopy (EM) imaging. We are currently using Cryo-SiN to recruit BRCA1 protein assemblies to the microchip surface under mild conditions, while simultaneously preparing them for cryogenic preservation and EM imaging. This strategy presents a viable alternative to antibody affinity columns that require stringent elution steps to obtain protein complexes from the column. Another advantage of the microchip strategy is that it requires only a 30-minute nuclear extraction, a 60-minute enrichment procedure, and a 5-minute microchip capture step--a total of 95 minutes from initially lysing the cells to plunge-freezing the EM specimens. Therefore, these novel approaches represent a major departure from classical separation procedures that often require days to complete, during which time active protein assemblies can readily dissociate or become inactive. Overall, our use of BRCA1-specific microchips may reveal changes in the BRCA1 architecture during various stages of cancer progression--a major gap in knowledge that persists in cancer research. / M. S. / Modern advances in the imaging technology used for cryogenic electron microscopy (cryo-EM) have offered researchers an extraordinary view into the world of biology at the nanoscale. Supplemental to these technical innovations is the development of tunable substrates based on functional new materials that revolutionize the sequestering of biological components from human cells, such as protein complexes formed in breast cancer cells. New developments of novel viewing substrates, given traditional electron microscopy viewing grids have remained unchanged for decades, is the logical next step into the future of enhanced cryo-EM imaging. Tunable microchip substrates, made using recently enhanced micro-engineering techniques, are currently under development for use in cryo-EM imaging. In this work I have examined these microchip substrates for their capacity to streamline the isolation of biomolecules such as the protein most prominently cited in breast cancer, known as the breast cancer susceptibility protein (BRCA1). Utilizing these novel microchip substrates in the Kelly Lab, I have collected and analyzed data containing BRCA1 proteins, formed in human breast cancer cells, toward the development of 3-dimensional protein structures that allow us to peer into the structure-function relationships of these proteins. New and exciting Cryo-EM data, collected using these newly developed microchips, has the potential to reveal obscure disease mechanisms being propagated at the molecular level in modern clinical practice, such as breast cancer.

A new material system was developed for fabricating the combustion engine of an unmanned aerial vehicle. The material system consisted of a mixture of nanoscale and microscale particles of silicon nitride. Magnesia and yttria were used as sintering additives. The powders were mixed with a paraffin binder system. The binder-powder was analyzed for its properties and molding attributes. The study involved several steps of the development and processing. These steps include torque rheometery analysis, mixing scale-up, property measurements of binder-powder, injection molding, binder removal, sintering, scanning electron microscopy analysis and mechanical properties measurements. Simulations of the injection molding process were conducted to assess the feasibility of manufacturing a ceramic engine and to determine its optimal process parameters. The model building required for the simulation was based on flow and solidification behavior data compiled for the binder-powder mixture. The simulations were performed using the Moldfow software package. A design of experiments approach was set up in order to gain an understanding of critical process parameters as well as identifying a feasible process window. Quality criteria were then analyzed in order to determine the optimal production parameters. The study resulted in the successful development of design parameters that will enable fabrication of silicon nitride engine components by powder injection molding. / Graduation date: 2012

An environmentally friendly, and contamination free process for etching and cleaning semiconductors is critical to future of the IC industry. Under the right conditions, water has the ability to meet these requirements. Water becomes more reactive as a function of temperature in part because the number of hydronium and hydroxyl ions increase. As water approaches its boiling point, the concentration of these species increases over seven times their concentrations at room temperature. At 150 °C, when the liquid state is maintained, these concentrations increase 15 times over room temperature. Due to its enhanced reactivity, high temperature water (HTW) has been studied as an etch and clean of thermally grown SiO2, Si3N4, and low-k films. High temperature deuterium oxide (HT-D2O) behaves similarly to HTW; however, it dissociates an order of magnitude less than HTW resulting in an equivalent reduction in reactive species. This allowed for the effects of reactive specie concentration on etch rate to be studied, providing valuable insight into how HTW compares to other high temperature wet etching processes such as hot phosphoric acid (HPA). Characterization was conducted using Fourier transform infrared spectroscopy (FTIR) to determine chemical changes due to etching, spectroscopic ellipsometry to determine film thickness, profilometry to measure thickness change across the samples, scanning electron microscopy (SEM), contact angle to measure changes in wetting behavior, and UV-Vis spectroscopy to measure dissolved silica in post etch water. HTW has demonstrated the ability to effective etch both SiO2 and Si3N4, HT-D2O also showed similar etch rates of Si3N4 indicating that a threshold reactive specie concentration is needed to maximize etch rate at a given temperature and additional reactive species do not further increase the etch rate. Because HTW has no hazardous byproducts, high temperature water could become a more environmentally friendly etchant of SiO2 and Si3N4 thin films.