This paper studies the geometrically non-linear bending behavior of functionally graded beams subjected to buckling loads using the finite element method. The computational model is based on an improved first-order shear deformation theory for beams with five independent variables. The abstract finite element formulation is derived by means of the principle of virtual work. High-order nodal-spectral interpolation functions were utilized to approximate the field variables which minimizes the locking problem. The incremental/iterative solution technique of Newton's type is implemented to solve the nonlinear equations. The model is verified with benchmark problems available in the literature. The objective is to investigate the effect of volume fraction variation in the response of functionally graded beams made of ceramics and metals. As expected, the results show that transverse deflections vary significantly depending on the ceramic and metal combination. / Revisión por pares

Replacing organic liquid electrolytes with nonflammable solid electrolytes can improve safety, offer higher volumetric and gravimetric energy densities, and lower the cost of lithium-ion batteries. However, today’s all-solid-state batteries suffer from low Li-ion conductivity in the electrolyte, slow Li-ion transport across the electrolyte/electrode interface, and slow solid-state Li-ion diffusion within the electrode. Defect chemistry is critical to understanding ionic conductivity and predicting the charge transport through heterogeneous solid interfaces. The goal of this dissertation is to analyze and improve solid state materials for energy storage applications by understanding their defect structure and transport properties. I have investigated defect chemistry of cubic Li7La3Zr2O12 (c-LLZO), one of the most promising candidate solid electrolytes for all-solid-state lithium batteries. By combining conductivity measurements with defect modeling, I constructed a defect diagram of c-LLZO featuring the intrinsic formation of lithium vacancy-hole pairs. The findings provided insights into tailoring single-phase mixed lithium-ion/electron conducting materials for emerging ionic devices, i.e., composite cathodes requiring both fast electronic and ionic paths in solid-state batteries. I suggested that oxygen vacancies could increase the Li-ion conductivity by reducing the amount of electron holes bound with lithium vacancies. Using a simpler but also attractive solid electrolyte Li2ZrO3 (LZO) as an example, I significantly improved Li-ion conductivity by creating extra oxygen vacancies via cation doping. In particular, Fe-doped LZO shows the highest Li-ion conductivity reported for the family of LZO compounds, reaching 3.3 mS/cm at 300 °C. This study brought attentions to the long-neglected oxygen vacancy defects in lithium-ion conductors and revealed their critical role in promoting Li-ion transport. More importantly, it established a novel defect engineering strategy for designing Li-oxide based solid electrolytes for all-solid-state batteries. I surface-modified LiNi0.6Co0.2Mn0.2O2 cathode material with a LZO coating prepared under dry air and oxygen, and systematically investigated the effect of coating atmosphere on their transport properties and electrochemical behaviors. The LZO coating prepared in oxygen is largely amorphous. It not only provided surface protection against the electrolyte corrosion but also enabled faster lithium-ion transport. Additionally, oxygen atmosphere facilitated Zr diffusion from the surface coating to the bulk of LiNi0.6Co0.2Mn0.2O2, which stabilized the crystal structure and enhanced lithium ion diffusion. Consequently, LiNi0.6Co0.2Mn0.2O2 cathodes coated with Li2ZrO3 in oxygen achieved a significant improvement in high-voltage cycling stability and high-rate performance.

The efficacy of dispersed reduced graphene oxide (rGO) as a nucleation site for the growth of mesophase in an isotropic pitch was investigated and quantified in this study. Concentrations of rGO were systematically tested in an isotropic petroleum and coal-tar pitch during thermal treatments and compared to pitch without rGO. The mesophase content of each thermally treated pitch was quantified by polarized light point counting. Further characterization of softening temperature and insolubles were quantified. Additionally, the pitches with and without rGO were melt spun, graphitized, and tensile tested to determine the effects of rGO on graphitized fiber mechanical properties and fiber morphology.

A piezoelectric microspeaker device that could be used in a variety of acoustic applications was designed and fabricated using a thin film ZnO layer that was reactively DC sputtered onto a single crystalline n-type silicon substrate. When tested the microspeaker did not produce sound due to complications in the etching process, the thickness of the diaphragms, and clamping effects. Instead, a characterization approach was taken and the structural, optical, electrical, and piezoelectric properties of the ZnO were investigated. Scanning electron microscopy, x-ray diffraction, and atomic force microscopy were utilized to discover the ZnO’s structural properties. Using the XRD and SEM, the as-sputtered ZnO films were found to have highly c-axis oriented columnar crystals. Optical properties were determined from the reflectance spectrums obtained from a Filmetrics F20 reflectometer and were used to determine the film thickness, the optical constants, and the optical band gap of the ZnO thin films. Using a four-point probe, the as-sputtered ZnO films were found to be highly resistive and insulative, mainly due to voided growth boundaries between the crystals. To improve electrical conductivity and piezoelectric response, ZnO samples were annealed at varying temperatures in a nitrogen environment. The annealing process successfully increased the electrical conductivity and piezoelectric properties of the films. The local piezoelectric properties of the ZnO were discovered with an Asylum MFP-3D and a piezoresponse force microscopy (PFM) technique called DART-PFM. The ZnO films that were sputtered with 70 watts and an argon to oxygen gas ratio of 2:1 were found to have the highest d33 piezoelectric coefficients. The ZnO sample that was annealed at 600°C for 30 minutes had the highest overall d33 value of 4.0 pm/V, which means that the 600°C annealed ZnO films would have the best chance of making a functional microspeaker.

The dissertation is split into two parts. The first part will be focused on changes in material properties found at the nanoscale, as miscibility and electronic structure can change significantly with size. The formation of classically-immiscible bimetallic nanoparticles (BNPs) becomes favorable at the nanoscale and novel catalytic properties can emerge from the bimetallic alloying. The formation of alloyed and non-alloyed BNPs is achieved through pulse laser ablation (PLA) and a significant increase in catalytic activity is observed for both. Recently discovered, the increased activity in the non-alloyed BNPs, deemed multicomponent photocatalysis, is examined and the proposed mechanism discussed. The second part of the talk will focus on thermal barrier coatings (TBCs), which are advanced, multi-layered coatings used to protect materials in high temperature environments. MCrAlY (M=Ni, Co) bond coats deposited via atmospheric plasma spray (APS) are intrinsically rough and initially the roughness provides a high surface area platform for the mechanical interlocking of the yttria stabilized zirconia (YSZ) top coat, which provides the bulk of the thermal insulation. After high temperature exposure, a protective oxide scale forms at the top coat/bond coat interface however the convex asperities of the bond coat can grow non-α-Al2O3 type oxides that can be detrimental for coating lifetime. A surface modification technique that removes the asperities while leaving intact the concavities is used to examine the role that roughness distribution has on 1100°C APS coating lifetime. Lastly, recent work validating a modelling strategy for evaluating 900°C TBC lifetimes, which can typically surpass 25 kh, is presented. Differences in coating-substrate interdiffusion behavior over 5-20 kh of 900°C exposure are discussed and reproduced with Thermo- Calc/DICTRA for three superalloys (1483, 247, X4) deposited with high velocity oxy fuel (HVOF) NiCoCrAlY coatings.

Borides and carbides of tantalum and hafnium are of great interest due to their ultrahigh temperature applications. Properties of these ceramics including oxidation resistance and mechanical properties might be further improved through solid solution/composite formation. Synthesis of single-phase TaxHf1-xC and TaxHf1-xB2 solid solution powders including nanopowders via carbothermal reduction (CTR) is complicated due to noticeable difference in reactivity of parent oxides with carbon, and also the low solubility of those oxides in each other. Moreover, for TaC-HfC system the solid solution may go through phase separation due to the presence of a miscibility gap at temperatures below 887°C.In this study, a method of low-cost aqueous solution processing followed by CTR was used to synthesize TaxHf1-xC and TaxHf1-xB2 solid solution powders. In fact, method was first used to synthesize boron carbide (B4C) powders as it paves the way for a detailed study on the synthesis of TaxHf1-xC and TaxHf1-xB2 solid solutions powders considering the fact that B4C contains both carbon and boron in its structure. Particular emphasis was given to investigate the influences of starting compositions and processing conditions on phase separation during the formation of both carbide and boride phase(s). It was found that individual TaC-HfC and TaB2-HfB2 phases always form quickly but separately during the CTR process (e.g., at 1600 °C within a few minutes). Those carbides and borides remain phase-separated unless heated to much higher temperatures for long time due to the slow inter-diffusion between them. It was also found that for TaxHf1-xC applying a DC electric field through the use of spark plasma sintering (SPS) system significantly accelerates the inter-diffusion of Ta and Hf leading to formation of a single-phase TaxHf1-xC solid solution at 1600 °C for 15 minutes. On the other hand, for borides alkali metal reduction reaction (AMR) method appears to be an excellent alternative to CTR-based method for formation of a single-phase TaxHf1-xB2 solid solution. In this method, chlorides of tantalum and hafnium are directly reduced using sodium borohydride (NaBH4) giving rise to formation of a single-phase Ta0.5Hf0.5B2 solid solution nanopowders in one step at much lower temperatures (e.g., 700 °C) by avoiding the oxides formation and the associated phase separation of individual borides as observed in the CTR-based process.

Abstract not available

Nanoscale surfaces were examined in order to determine the influence of surface curvature on polymer behavior at polymer-ceramic interfaces, as well as the influence of nanoparticles in cellulosic media. Poly(methyl methacrylate) and block copolymers thereof were adsorbed onto porous alumina substrates of various pore sizes in order to determine how polymer and copolymer adsorption behavior at nanoscale surfaces differs from adsorption onto flat surfaces. It was determined that chain density on concave surfaces dramatically decreases as curvature increases in much the same way that it does on convex surfaces (e.g. on the surface of nanoparticles), and physical models are provided to explain this similarity. Diblock copolymer adsorption is observed to vary dramatically with solvent quality and block asymmetry and can be correlated with the surface curvature very similarly to the adsorptive behavior of homopolymers on those same surfaces. The addition of nanoparticles to cellulosic media was investigated as a means to significantly modify the properties of cellulosic composites with minimal additions of nanoparticles. Although cellulose is among the most abundant polymers on earth, its primary uses are limited to bulk commodity goods, such as paper and textiles. This work demonstrates a simple means to control cellulosic fluid viscosity, thereby increasing the versatility of these biopolymers in additional applications with higher value-added potential. The formation of iron-cellulosic nanocomposites by the in-situ thermolysis of metal carbonyls to form metallic nanoparticles was performed and was analyzed by viscometry among other techniques. It was determined that the nanocomposites that were formed exhibited significantly increased viscosity, up to the point of gelation. Additionally, an introduction to the expansive field of nanocomposites is provided, including how and why composite properties change abruptly as filler size approaches the nanoscale. An extensive background on this diverse field as it relates to the current work is provided with an emphasis on cellulosic nanocomposites and the dependence of curvature on polymer-surface interactions. A detailed account of the experimental work relevant to this work is provided, including materials and characterization methods. Future work is proposed for both cellulosic nanocomposites as well as for curvature-dependent polymer adsorption. Finally, conclusions are drawn from the entire work and its implications to the greater field of nanocomposites.

Boron carbide (B₄C) is a non-oxide ceramic in the same class of nonmetallic hard materials as silicon carbide and diamond. The high hardness, high elastic modulus and low density of B₄C make it a nearly ideal material for personnel and vehicular armor. B₄C plates formed via hot-pressing are currently issued to U.S. soldiers and have exhibited excellent performance; however, hot-pressed articles contain inherent processing defects and are limited to simple geometries such as low-curvature plates. Recent advances in the pressureless sintering of B₄C have produced theoretically-dense and complex-shape articles that also exhibit superior ballistic performance. However, the cost of this material is currently high due to the powder shape, size, and size distribution that are required, which limits the economic feasibility of producing such a product. Additionally, the low fracture toughness of pure boron carbide may have resulted in historically lower transition velocities (the projectile velocity range at which armor begins to fail) than competing silicon carbide ceramics in high-velocity long-rod tungsten penetrator tests. Lower fracture toughness also limits multi-hit protection capability. Consequently, these requirements motivated research into methods for improving the densification and fracture toughness of inexpensive boron carbide composites that could result in the development of a superior armor material that would also be cost-competitive with other high-performance ceramics. The primary objective of this research was to study the effect of titanium and carbon additives on the sintering and mechanical properties of inexpensive B₄C powders. The boron carbide powder examined in this study was a submicron (0.6 μm median particle size) boron carbide powder produced by H.C. Starck GmbH via a jet milling process. A carbon source in the form ofphenolic resin, and titanium additives in the form of 32 nm and 0.9 μm TiO₂ powders were selected. Parametric studies of sintering behavior were performed via high-temperature dilatometry in order to measure the in-situ sample contraction and thereby measure the influence of the additives and their amounts on the overall densification rate. Additionally, broad composition and sintering/post-HIPing studies followed by characterization and mechanical testing elucidated the effects of these additives on sample densification, microstructure development, and mechanical properties such as Vickers hardness and microindentation fracture toughness. Based upon this research, a process has been developed for the sintering of boron carbide that yielded end products with high relative densities (i.e., 100%, or theoretical density), microstructures with a fine (∼2-3 μm) grain size, and high Vickers microindentation hardness values. In addition to possessing these improved physical properties, the costs of producing this material were substantially lower (by a factor of 5 or more) than recently patented work on the pressureless sintering and post-HIPing of phase-pure boron carbide powder. This recently patented work developed out of our laboratory utilized an optimized powder distribution and yielded samples with high relative densities and high hardness values. The current work employed the use of titanium and carbon additives in specific ratios to activate the sintering of boron carbide powder possessing an approximately mono-modal particle size distribution. Upon heating to high temperatures, these additives produced fine-scale TiO ₂ and graphite inclusions that served to hinder grain growth and substantially improve overall sintered and post-HIPed densities when added in sufficient concentrations. The fine boron carbide grain size manifested as a result of these second phase inclusions caused a substantial increase in hardness; the highest hardness specimen yielded a hardness value (2884.5 kg/mm²) approaching that of phase-pure and theoretically-dense boron carbide (2939 kg/mm²). Additionally, the same high-hardness composition exhibited a noticeably higher fracture toughness (3.04 MPa•m¹/²) compared to phase-pure boron carbide (2.42 MPa• m¹/²), representing a 25.6% improvement. A potential consequence of this study would be the development of a superior armor material that is sufficiently affordable, allowing it to be incorporated into the general soldier’s armor chassis.

Zirconium diboride (ZrB₂) is a ceramic material possessing ultra-high melting temperatures. As such, this compound could be useful in the construction of thermal protection systems for aerospace applications. This work addresses a primary shortcoming of this material, namely its propensity to destructively oxidize at high temperatures, as well as secondary issues concerning its heat transport properties.To characterize and improve oxidation properties, thermogravimetric studies were per- formed using a specially constructed experimental setup. ZrB₂-SiC two-phase ceramic composites were isothermally oxidized for ∼90 min in flowing air in the range 1500-1900°C. Specimens with 30 mol% SiC formed distinctive reaction product layers which were highly protective; 28 mol% SiC - 6 mol% TaB₂ performed similarly. At higher temperatures, specimens containing lower amounts of SiC were shown to be non-protective, whereas specimens containing greater amounts of SiC produced unstable oxide layers due to gas evolution. Oxide coating thicknesses calculated from weight loss data were consistent with those measured from SEM micrographs. In order to characterize one aspect of the materials' heat transport properties, the thermal diffusivities of ZrB₂-SiC composites were measured using the laser flash technique. These were converted to thermal conductivities using temperature dependent specific heat and density data; thermal conductivity decreased with increasing temperature over the range 25-2000°C. The composition with the highest SiC content showed the highest thermal conductivity at room temperature, but the lowest at temperatures in excess of ∼400°C, because of the greater temperature sensitivity of the thermal conductivity of the SiC phase, as compared to more electrically-conductive ZrB₂. Subsequent finite difference calculations were good predictors of multi-phase thermal conductvities for the compositions examined. The thermal conductivities of pure ZrB₂ as a function of temperature were back-calculated from the experimental results for the multi-phase materials, and literature thermal conductivities of the other two phases. This established a relatively constant thermal conductivity of 88-104 W/m·K over the evaluated temperature range. Further heat transport characterization was performed using pre-oxidized, directly resistively heated ZrB₂-30 mol% SiC ribbon specimens under the observation of a spectral radiometer. The ribbons were heated and held at specific temperatures over the range 1100- 1330°C in flowing Ar, and normal spectral emittance values were recorded over the 1-6 μm range with a resolution of 10 nm. The normal spectral emittance was shown to decrease with loss of the borosilicate layer over the course of the data collection time periods. This change was measured and compensated for to produce traces showing the emittance of the oxidized composition rising from ∼0.7 to ∼0.9 over the range of wavelengths measured.