Elevated temperature mechanical properties of zirconium diboride based ceramics

Research presented in this dissertation focused on the mechanical behavior of ZrB₂ based ceramic at elevated temperatures. Flexure strength, fracture toughness, and elastic modulus were measured at temperatures up to 2300ºC for three compositions: monolithic ZrB₂ (Z); ZrB₂ - 30 vol% SiC - 2 vol% B₄ C (ZS); and ZrB₂ - 10 vol% ZrC (ZC). In argon, Z, ZS, and ZC had strengths of 210 (at 2300ºC), 260 (at 2200ºC), and 295 MPa (at 2300ºC), the highest temperatures tested for each composition. Fractography was used extensively to characterize the strength limiting flaws as a function of temperature. Strength of ZS in argon was controlled by the SiC cluster size up to 1800ºC, and the formation of B-O-C-N phases that bridged SiC clusters above 2000ºC. For ZC, surface flaws introduced during specimen preparation were the source of critical flaws in the material up to 1400ºC, sub-critical crack growth of surface flaws between 1600 and 2000ºC, and microvoid coalescence above 2000ºC. It was also shown that thermal annealing at either 1400, 1500, or 1600ºC improves the strength and modulus of ZS at temperatures between 800ºC and 1600ºC. Heat treatment at 1400ºC for 10 hours produced the largest improvement in strength, 430 MPa at 1600ºC versus 380 MPa for the as processed material. As a whole, the research pointed to several key microstructural features currently limiting the mechanical properties at the highest temperatures. In particular, removal of unfavorable secondary phases, and improved control over microstructure, should be promising methods to improve the elevated temperature properties of ZrB₂ ceramics. --Abstract, page iv

Processing and Mechanical Properties of Hot-Pressed Zirconium Diboride – Zirconium Carbide Ceramics

ZrB2 was mixed with 0.5 wt% carbon and up to 10 vol% ZrC and densified by hot-pressing at 2000 °C. All compositions were \u3e 99.8% dense following hot-pressing. The dense ceramics contained 1–1.5 vol% less ZrC than the nominal ZrC addition and had between 0.5 and 1 vol% residual carbon. Grain sizes for the ZrB2 phase decreased from 10.1 µm for 2.5 vol% ZrC to 4.2 µm for 10 vol% ZrC, while the ZrC cluster size increased from 1.3 µm to 2.2 µm over the same composition range. Elastic modulus was ~505 GPa and toughness was ~2.6 MPa·m½ for all compositions. Vickers hardness increased from 14.1 to 15.3 GPa as ZrC increased from 2.5 to 10 vol%. Flexure strength increased from 395 MPa for 2.5 vol% ZrC to 615 MPa for 10 vol% ZrC. Griffith-type analysis suggests ZrB2 grain pullout from machining as the strength limiting flaw for all compositions

Pressureless Sintering of Zirconium Diboride with Carbon and Boron Carbide Nanopowder

Zirconium diboride ceramics with and without carbon and boron carbide nano powder additives were prepared by ball milling with ZrB2 grinding media and pressureless sintering. Additions of up to 1 wt% nano-B4C and 0.5 wt% C were made to the ZrB2 powder. The materials were then sintered between 1800 and 2300 °C for between 90 and 360 min in an Ar/10H2 atmosphere. After sintering at 2200 °C for 90 min, densities ranged from 88.3 to 90.7% for the ZrB2 with 0–1.0% nano-B4C addition. Carbon additions of 0.5 wt% and nano-B4C additions from 0 to 1.0 wt% resulted in densities ranging from 90.9 to 91.9% after sintering at 2100 °C for 90 min. Grain size ranged from 16.6 to 21.7 μm for ZrB2 with nano-B4C content increasing from 0 to 1.0 wt%, sintered at 2200 °C. For the ZrB2 with 0.5 wt% C, increasing the nano-B4C content from 0 to 1.0 wt% resulted in a decrease in grain size from 25.4 to 18.5 μm. The densities achieved in this study were lower than previous pressureless sintering studies of ZrB2 that used WC-6Co grinding media, presumably due to the absence of WC and Co that can also act as sintering aids

Elevated Temperature Thermal Properties of ZrB2-B4C Ceramics

The elevated temperature thermal properties of zirconium diboride ceramics containing boron carbide additions of up to 15 vol% were investigated using a combined experimental and modeling approach. The addition of B4C led to a decrease in the ZrB2 grain size from 22 µm for nominally pure ZrB2 to 5.4 µm for ZrB2 containing 15 vol% B4C. The measured room temperature thermal conductivity decreased from 93 W/m·K for nominally pure ZrB2 to 80 W/m·K for ZrB2 containing 15 vol% B4C. The thermal conductivity also decreased as temperature increased. For nominally pure ZrB2, the thermal conductivity was 67 W/m·K at 2000 °C compared to 55 W/m·K for ZrB2 containing 15 vol% B4C. A model was developed to describe the effects of grain size and the second phase additions on thermal conductivity from room temperature to 2000 °C. Differences between model predictions and measured values were less than 2 W/m·K at 25 °C for nominally pure ZrB2 and less than 6 W/m·K when 15 vol% B4C was added

Direct observation of membrane insertion by enveloped virus matrix proteins by phosphate displacement

Enveloped virus release is driven by poorly understood proteins that are functional analogs of the coat protein assemblies that mediate intracellular vesicle trafficking. We used differential electron density mapping to detect membrane integration by membrane-bending proteins from five virus families. This demonstrates that virus matrix proteins replace an unexpectedly large portion of the lipid content of the inner membrane face, a generalized feature likely to play a role in reshaping cellular membranes

Surface and lightning sources of nitrogen oxides over the United States: Magnitudes, chemical evolution, and outflow

We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/ flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export

Surface and Lightning Sources of Nitrogen Oxides over the United States: Magnitudes, Chemical Evolution, and Outflow

We use observations from two aircraft during the ICARTT campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of regional sources, chemical evolution, and export of NOx. The boundary layer NOx data provide top-down verification of a 50% decrease in power plant and industry NOx emissions over the eastern United States between 1999 and 2004. Observed NOx concentrations at 8–12 km altitude were 0.55 ± 0.36 ppbv, much larger than in previous U.S. aircraft campaigns (ELCHEM, SUCCESS, SONEX) though consistent with data from the NOXAR program aboard commercial aircraft. We show that regional lightning is the dominant source of this upper tropospheric NOx and increases upper tropospheric ozone by 10 ppbv. Simulating ICARTT upper tropospheric NOx observations with GEOS-Chem requires a factor of 4 increase in modeled NOx yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, for reasons that are unclear. A NOy-CO correlation analysis of the fraction f of North American NOx emissions vented to the free troposphere as NOy (sum of NOx and its oxidation products) shows observed f = 16 ± 10% and modeled f = 14 ± 9%, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NOy export efficiency and speciation, supporting previous model estimates of a large U.S. anthropogenic contribution to global tropospheric ozone through PAN export.Earth and Planetary SciencesEngineering and Applied Science

Classifying Complications: Assessing Adult Spinal Deformity 2-Year Surgical Outcomes.

STUDY DESIGN: Retrospective review of prospective database. OBJECTIVE: Complication rates for adult spinal deformity (ASD) surgery vary widely because there is no accepted system for categorization. Our objective was to identify the impact of complication occurrence, minor-major complication, and Clavien-Dindo complication classification (Cc) on clinical variables and patient-reported outcomes. METHODS: Complications in surgical ASD patients with complete baseline and 2-year data were considered intraoperatively, perioperatively (\u3c6 \u3eweeks), and postoperatively (\u3e6 weeks). Primary outcome measures were complication timing and severity according to 3 scales: complication presence (yes/no), minor-major, and Cc score. Secondary outcomes were surgical outcomes (estimated blood loss [EBL], length of stay [LOS], reoperation) and health-related quality of life (HRQL) scores. Univariate analyses determined complication presence, type, and Cc grade impact on operative variables and on HRQL scores. RESULTS: Of 167 patients, 30.5% (n = 51) had intraoperative, 48.5% (n = 81) had perioperative, and 58.7% (n = 98) had postoperative complications. Major intraoperative complications were associated with increased EBL ( CONCLUSION: The Cc Scale was most useful in predicting changes in patient outcomes; at 2 years, patients with raised perioperative Cc scores and postoperative complications saw reduced HRQL improvement. Intraoperative and perioperative complications were associated with worse short-term surgical and inpatient outcomes

External validation of the RISC, RISC-Malawi, and PERCH clinical prediction rules to identify risk of death in children hospitalized with pneumonia

From Crossref journal articles via Jisc Publications RouterBackground Existing scores to identify children at risk of hospitalized pneumonia-related mortality lack broad external validation. Our objective was to externally validate three such risk scores. Methods We applied the Respiratory Index of Severity in Children (RISC) for HIV-negative children, the RISC-Malawi, and the Pneumonia Etiology Research for Child Health (PERCH) scores to hospitalized children in the Pneumonia REsearch Partnerships to Assess WHO REcommendations (PREPARE) data set. The PREPARE data set includes pooled data from 41 studies on pediatric pneumonia from across the world. We calculated test characteristics and the area under the curve (AUC) for each of these clinical prediction rules. Results The RISC score for HIV-negative children was applied to 3574 children 0-24 months and demonstrated poor discriminatory ability (AUC = 0.66, 95% confidence interval (CI) = 0.58-0.73) in the identification of children at risk of hospitalized pneumonia-related mortality. The RISC-Malawi score had fair discriminatory value (AUC = 0.75, 95% CI = 0.74-0.77) among 17 864 children 2-59 months. The PERCH score was applied to 732 children 1-59 months and also demonstrated poor discriminatory value (AUC = 0.55, 95% CI = 0.37-0.73). Conclusions In a large external application of the RISC, RISC-Malawi, and PERCH scores, a substantial number of children were misclassified for their risk of hospitalized pneumonia-related mortality. Although pneumonia risk scores have performed well among the cohorts in which they were derived, their performance diminished when externally applied. A generalizable risk assessment tool with higher sensitivity and specificity to identify children at risk of hospitalized pneumonia-related mortality may be needed. Such a generalizable risk assessment tool would need context-specific validation prior to implementation in that setting.11pubpub