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At least 685 records · Page 38

Additive Manufacturing of C/C-SiC Ceramic Matrix Composites by Automated Fiber Placement of Continuous Fiber Tow in Polymer with Pyrolysis and Reactive Silicon Melt Infiltration

An additive manufacturing process for fabricating ceramic matrix composites has been developed based on the C/C-SiC system. Automated fiber placement of the continuous carbon fibers in a polyether ether ketone matrix was performed to consolidate the carbon fibers into a printed preform. Pyrolysis was performed to convert the polymer matrix to porous carbon, and then Si was introduced by reactive melt infiltration to convert a portion of the carbon matrix to silicon carbide. The densities and microstructures were characterized after each step during the processing, and the mechanical properties were measured. The C/C-SiC composites exhibited a porosity of 10–20%, characteristic flexural strength of 234.91 MPa, and Weibull modulus of 3.21. The composites displayed toughness via a significant displacement to failure.

36 MATERIALS SCIENCE↗

Convective transport of reactive constituents to the tropical and mid-latitude tropopause region: I. Observations

Measurements of ozone, reactive carbon and nitrogen, and other trace constituents from flights of the NASA WB-57F aircraft in the upper troposphere and lower stratosphere reveal that convection in the tropics can present a complex mix of surface-emitted constituents right up to the altitude of the lapse rate tropopause. At higher latitudes over the southern US, the strongest transport signal, in terms of constituent mixing ratios, occurred in the potential temperature range of 340-350K or approximately over the altitude range of 9-11km. Weaker convective signals were also seen up to near the tropopause. There was no evidence of convective transport directly into the lower stratosphere from these flights. $CPY 2003 Elsevier Ltd. All rights reserved.

Transport signals↗

Fish oil increases mitochondrial phospholipid unsaturation, upregulating reactive oxygen species and apoptosis in rat colonocytes

We have shown that a combination of fish oil (high in n-3 fatty acids) with the butyrate-producing fiber pectin, upregulates apoptosis in colon cells exposed to the carcinogen azoxymethane, protecting against colon tumor development. We now hypothesize that n-3 fatty acids prime the colonocytes such that butyrate can initiate apoptosis. To test this, 30 Sprague-Dawley rats were provided with diets differing in the fatty acid composition (corn oil, fish oil or a purified fatty acid ethyl ester diet). Intact colon crypts were exposed ex vivo to butyrate, and analyzed for reactive oxygen species (ROS), mitochondrial membrane potential (MMP), translocation of cytochrome C to the cytosol, and caspase-3 activity (early events in apoptosis). The fatty acid composition of the three major mitochondrial phospholipids was also determined, and an unsaturation index calculated. The unsaturation index in cardiolipin was correlated with ROS levels (R = 0.99; P = 0.02). When colon crypts from fish oil and FAEE-fed rats were exposed to butyrate, MMP decreased (P = 0.041); and translocation of cytochrome C to the cytosol (P = 0.037) and caspase-3 activation increased (P = 0.032). The data suggest that fish oil may prime the colonocytes for butyrate-induced apoptosis by enhancing the unsaturation of mitochondrial phospholipids, especially cardiolipin, resulting in an increase in ROS and initiating apoptotic cascade.

Non-NASA Center↗

Absence of diurnal variation of C-reactive protein concentrations in healthy human subjects

BACKGROUND: The concentration of C-reactive protein (CRP) in otherwise healthy subjects has been shown to predict future risk of myocardial infarction and stroke. CRP is synthesized by the liver in response to interleukin-6, the serum concentration of which is subject to diurnal variation. METHODS: To examine the existence of a time-of-day effect for baseline CRP values, we determined CRP concentrations in hourly blood samples drawn from healthy subjects (10 males, 3 females; age range, 21-35 years) during a baseline day in a controlled environment (8 h of nighttime sleep). RESULTS: Overall CRP concentrations were low, with only three subjects having CRP concentrations >2 mg/L. Comparison of raw data showed stability of CRP concentrations throughout the 24 h studied. When compared with cutoff values of CRP quintile derived from population-based studies, misclassification of greater than one quintile did not occur as a result of diurnal variation in any of the subjects studied. Nonparametric ANOVA comparing different time points showed no significant differences for both raw and z-transformed data. Analysis for rhythmic diurnal variation using a method fitting a cosine curve to the group data was negative. CONCLUSIONS: Our data show that baseline CRP concentrations are not subject to time-of-day variation and thus help to explain why CRP concentrations are a better predictor of vascular risk than interleukin-6. Determination of CRP for cardiovascular risk prediction may be performed without concern for diurnal variation.

Non-NASA Center↗

Mutagenicity of arsenic in mammalian cells: role of reactive oxygen species

Arsenite, the trivalent form of arsenic present in the environment, is a known human carcinogen that lacked mutagenic activity in bacterial and standard mammalian cell mutation assays. We show herein that when evaluated in an assay (AL cell assay), in which both intragenic and multilocus mutations are detectable, that arsenite is in fact a strong dose-dependent mutagen and that it induces mostly large deletion mutations. Cotreatment of cells with the oxygen radical scavenger dimethyl sulfoxide significantly reduces the mutagenicity of arsenite. Thus, the carcinogenicity of arsenite can be explained at least in part by it being a mutagen that depends on reactive oxygen species for its activity.

Non-NASA Center↗

Concept Demonstration of Dopant Selective Reactive Etching (DSRIE) in Silicon Carbide

Accurate quantification of combustor pressure dynamics for the primary purpose of experimental validation of computational fluid dynamics (CFD) codes requires the use of robust, reliable and sensitive pressure sensors that can resolve sub--pound-per-square-inch pressure levels in high temperature environments (i.e., combustor). The state of the art microfabricated piezoresistive silicon carbide (SiC) pressure sensors that we have developed are capable of operating reliably at 600 degrees Centigrade. This technology was used in support of the ARMD ISRP-ERA (NASA's Aeronautics Research Mission Directorate, Integrated System Research Project - Environmentally Responsible Aviation) program to quantify combustor thermoacoustic instabilities. The results showed that while the SiC pressure sensors survived the high temperature and measured instabilities, the diaphragm (force collector) was not thin enough to be sensitive in resolving sub-pound-per-square-inch pressures; 30 meters is the thinnest diaphragm achievable with conventional reactive ion etching (RIE) processes. Therefore, this precludes its use for sub-pound-per-square-inch pressure measurement with high fidelity. In order to effectively resolve sub-pound-per-square-inch pressures, a thinner more sensitive diaphragm (10 meters) is needed. To achieve this would require a new and innovative fabrication process technique.

static↗

Optical and Electrical Properties of Reactively Sputtered TiN, ZrN, and HfN Thin Films

Thin films of titanium, zirconium, and hafnium nitride are prepared by DC magnetron reactive sputtering at room temperature on fused silica, optical glass, and silicon substrates. Deposition parameters are investigated in order to obtain stoichiometric films. The optical and electrical properties of the films as a function of nitrogen partial pressure are determined. The results show that an inverse correlation exists between the optical reflectance and the electrical resistivity of the films. Ellipsometer data for all three films show that their refractive index in the visible spectrum is decreased by increasing the film thickness while the extinction coefficient is unchanged. Thin films of TiN have the lowest room temperature resistivity relative to ZrN and HfN thin films.

Reactive↗

Reactive Transport and Mass Balance Modeling of the Stimson Sedimentary Formation and Altered Fracture Zones Constrain Diagenetic Conditions at Gale Crater, Mars

On a planet as cold and dry as present-day Mars, evidence of multiple aqueous episodes offers an intriguing view into very different past environments. Fluvial, lacustrine, and eolian depositional environments are being investigated by the Mars Science Laboratory Curiosityin Gale crater, Mars. Geochemical and mineralogical observations of these sedimentary rocks suggest diagenetic processes affected the sediments. Here, we analyze diagenesis of the Stimson formation eolian parent material, which caused loss of olivine and formation of magnetite. Additional, later alteration in fracture zones resulted in preferential dissolution of pyroxene and precipitation of secondary amorphous silica and Ca sulfate. The ability to compare the unaltered parent material with the reacted material allows constraints to be placed on the characteristics of the altering solutions. In this work we use a combination of a mass balance approach calculating the fraction of a mobile element lost or gained, τ, with fundamental geochemical kinetics and thermodynamics in the reactive transport code CrunchFlow to examine the characteristics of multiple stages of aqueous alteration at Gale crater, Mars. Our model results indicate that early diagenesis of the Stimson sedimentary formation is consistent with leaching of an eolian deposit by a near-neutral solution, and that formation of the altered fracture zones is consistent with a very acidic, high sulfate solution containing Ca, P and Si. These results indicate a range of past aqueous conditions occurring at Gale crater, Mars, with important implications for past Martian climate and environments.

Gale crater↗

Effect of Aromaticity on Soot Formation: A Reactive Molecular Dynamics Study

This study investigates the formation of soot from n-dodecane and its blend with m-xylene under pyrolytic and low-oxygen conditions with reactive molecular dynamics (MD) simulations. ReaxFF force field is used to simulate the interactions of fuel and oxygen molecules at engine-relevant conditions (2500-3500 K and 70-75 bar). Fuel molecules with carbon atom density of 0.03 g/cm 3 are dispersed into a cube and constant temperature simulations are carried out with a Nosé-Hoover thermostat. Pyrolysis of n-dodecane and the chemical pathway towards the formation of aromatic hydrocarbons are investigated. The initial pyrolysis rate of n-dodecane is observed to be slightly higher with the addition of aromatic compounds and oxygen. While the first aromatics formed from the decomposed n-dodecane are phenyl radicals at 2500 K, decomposition of the aliphatic fuel compound is observed to be necessary to build a carbon cluster, and eventually soot. Morphological properties of the created soot particles are also analyzed. The maturity, size and aromatics content of the soot particle are slightly affected with the addition of m-xylene and oxygen at 3500 K within the 3 ns simulation time possibly due the formation of larger and more condensed aromatic rings, resulting in larger soot molecules. The outcomes of this study provide important insights into the formation mechanism of soot and its morphological characteristics depending on varying fuel concentrations at pyrolysis and low oxygen engine conditions. Results of this analysis will further contribute to the understanding of contrail formation on generated soot particles originated from the combustion of different chemical components with particle chemistry matching companion experiments.

soot formation↗

High-burnup Experiments in Reactivity Initiated Accidents (HERA)

HERA is a joint experimental program (JEEP) operating within the Nuclear Energy Agency’s (NEA’s) framework for irradiation experiments (FIDES). HERA is dedicated to the understanding of light water reactor (LWR) fuel performance at high burnup under reactivity-initiated accidents (RIA). During RIAs the fuel cladding can be breached by one of two mechanisms; pellet-cladding mechanical interaction or high temperature balloon and rupture. Pellet-cladding mechanical interaction (PCMI) failure occurs in the early phase of an RIA transient where the fuel pellet expands rapidly into the cladding prior to any meaningful heat transfer from the pellet to the cladding. This results in high stresses in the cladding resulting in crack propagation through the base Zircaloy metal and axially along the cladding tube. Failure by PCMI is a brittle failure mode and occurs at low cladding strains, approximately 2% hoop strain. If the cladding survives the PCMI phase of the transient, it may still fail due to ballooning and rupture induced by extended exposure to high temperature. Thermal transport from the fuel pin to the coolant is significantly reduced if a transition to film boiling on the cladding surface occurs. This result in both a rapid increase in fuel temperature, which drives fission gas release, and a spike in cladding temperature, which results in loss of mechanical strength. If the internal pressure of the fuel rod is greater than the system pressure the cladding can inelastically deform and eventually rupture. Failure by swelling and rupture occurs at larger strains, generally greater than 5% hoop strain. While PCMI failures are generally seen as more limiting, the dominance of one failure mode over the other can be affected by both the cladding material conditions, and the transient evolution.

(HERA)↗

Transforming Energy Through Computational Excellence: Bringing Low Mach Number Reactive Flow Simulations at the Exascale

PeleLMeX's unique capabilities are allowing for reactive flow modeling at unprecedented scales and a reasonable time and cost. The code is currently being extended to tackle more practical, design-oriented simulations by implementing Large Eddy Simulation and data-driven chemical models, providing a fast but accurate tool for engineers considering the emergence of GPU-accelerated platforms. These extensions are critical for enabling the physical insight required to design the next generation of combustion devices as a key component of a renewable energy future.

MATHEMATICS AND COMPUTING↗

Applications of Similarity Analysis of Reactivity-initiated Accident Experiments in TREAT

Experimental testing capabilities have been created to perform reactivity-initiated accident experiments in the Transient Reactor Test Facility for fuel safety testing of Accident Tolerant Fuel concepts and to extend the burnup limits for our current light water reactor fuel designs. Completely prototypic test conditions are not possible and compromises naturally have to be made. To date, the representativity of the small scale safety testing to a similar event in a commercial reactor is made by comparing a few specific phenomena of interest. The goal of this work is to apply similarity analysis as another metric to judge the representativity of in-pile safety tests to full-scaled accident scenario.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-burnup Experiments in Reactivity Initiated Accidents (HERA)

HERA is a joint experimental program (JEEP) operating within the Nuclear Energy Agency’s (NEA’s) framework for irradiation experiments (FIDES). HERA is dedicated to the understanding of light water reactor (LWR) fuel performance at high burnup under reactivity-initiated accidents (RIA). During RIAs the fuel cladding can be breached by one of two mechanisms; pellet-cladding mechanical interaction or high temperature balloon and rupture. Pellet-cladding mechanical interaction (PCMI) failure occurs in the early phase of an RIA transient where the fuel pellet expands rapidly into the cladding prior to any meaningful heat transfer from the pellet to the cladding. This results in high stresses in the cladding resulting in crack propagation through the base Zircaloy metal and axially along the cladding tube. Failure by PCMI is a brittle failure mode and occurs at low cladding strains, approximately 2% hoop strain. If the cladding survives the PCMI phase of the transient, it may still fail due to ballooning and rupture induced by extended exposure to high temperature. Thermal transport from the fuel pin to the coolant is significantly reduced if a transition to film boiling on the cladding surface occurs. This result in both a rapid increase in fuel temperature, which drives fission gas release, and a spike in cladding temperature, which results in loss of mechanical strength. If the internal pressure of the fuel rod is greater than the system pressure the cladding can inelastically deform and eventually rupture. Failure by swelling and rupture occurs at larger strains, generally greater than 5% hoop strain. While PCMI failures are generally seen as more limiting, the dominance of one failure mode over the other can be affected by both the cladding material conditions, and the transient evolution.

(HERA)↗

A Reactive Inkjet Printing Process for Fabricating Biodegradable Conductive Zinc Structures

A novel reactive inkjet printing (RIJ) process for fabricating environmentally benign, conductive zinc structures on biodegradable substrates is reported. A precursor consisting of oxidized zinc microparticles is formulated into a viscous ink for high‐resolution, high‐repeatability screen printing. A single RIJ process is performed to selectively dispense an acid‐based oxide etching agent onto the screen‐printed zinc ink to significantly improve its electrical conductivity, up to 4 × 10 4 S m −1 . The RIJ process enables precise control of the amount of deposited etching agent, allowing control of conductivity and avoiding damage caused by excessive acid exposure. The RIJ process deposits the etching agent selectively on the screen‐printed, water‐soluble zinc patterns, thus preserving the print fidelity by avoiding ink smearing that can occur when using a blanket treatment such as submersion. A printed biodegradable antenna with a minimum feature size of 500 μm for use with a batteryless radio frequency identification (RFID) chip is fabricated as demonstration. Due to the higher ink conductivity and improved pattern fidelity, the antenna fabricated by the RIJ process shows a ≈2.2× increase in reading distance compared with a similar antenna that is screen printed and activated using a drop‐casting process.

Sui, Yongkun↗

Grain‐Boundary‐Rich Noble Metal Nanoparticle Assemblies: Synthesis, Characterization, and Reactivity

Abstract Here, a comprehensive study on the synthesis, characterization, and reactivity of grain‐boundary (GB)‐rich noble metal nanoparticle (NP) assemblies is presented. A facile and scalable synthesis of Pt, Pd, Au, Ag, and Rh NP assemblies is developed, in which NPs are predominantly connected via Σ3 (111) twin GBs, forming a network. Driven by water electrolysis, the random collisions and oriented attachment of colloidal NPs in solution lead to the formation of Σ3 (111) twin boundaries and some highly mismatched GBs. This synthetic method also provides convenient control over the GB density without altering the crystallite size or GB type by varying the NP collision frequency. The structural characterization reveals the presence of localized tensile strain at the GB sites. The ultrahigh activity of GB‐rich Pt NP assembly toward catalytic hydrogen oxidation in air is demonstrated, enabling room‐temperature catalytic hydrogen sensing for the first time. Finally, density functional theory calculations reveal that the strained Σ3(111) twin boundary facilitates oxygen dissociation, drastically enhancing the hydrogen oxidation rate via the dissociative pathway. This reported large‐scale synthesis of the Σ3 (111) twin GB‐rich structures enables the development of a broad range of high‐performance GB‐rich catalysts.

Geng, Xin↗

Reactive Carbide‐Based Synthesis and Microstructure of NASICON Sodium Metal All Solid‐State Electrolyte

Reactive carbide precursor-based synthesis of NASICON-type NZSP (Na 1+x Zr 2 Si x P 3-x O 12 ) solid-state electrolyte (SSE) is demonstrated, in contrast to the established oxide-based approach. Exothermic decomposition of ZrC and SiC in air homogenizes microstructure, yielding 98% compact density after conventional sintering at 1200 °C. Quantitative stereology demonstrates that significant microstructural differences are present. Compacts of carbide-derived Carb-NZSP are 98% dense with a secondary zirconium oxide (ZrO 2 ) volume fraction of 0.2% ± 0.3%, versus 93% dense and 3% ± 1% for oxide-derived baseline. For Carb-NZSP, the secondary glassy phosphate phase is agglomerated, while for baseline, it is dispersed and percolated. Electrochemical testing combined with post-mortem analysis demonstrates how microstructural control of secondary phases is critical for dendrite suppression: Carb-NZSP critical current density (CCD) is 3.1 ± 0.8 mA cm −2 at 0.1 mAh cm −2 , versus 1.0 ± 0.7 mA cm −2 at 0.1 mAh cm −2 . Cryogenic focused ion beam (cryo-FIB) analysis demonstrates that in both materials, the porous 2D sheet-like sodium metal dendrites propagate around and subsume NZSP grains, likely following a path enriched with glassy phase and with porosity. Dendrites also flow around isolated zirconia particles. Phase field simulation reveals deflection of dendrites by mechanically tough zirconia, while brittle glassy phase accelerates dendrite growth, especially when finely distributed.

36 MATERIALS SCIENCE↗

Boron Phosphide Films by Reactive Sputtering: Searching for a P‐Type Transparent Conductor

Abstract With an indirect band gap in the visible and a direct band gap at a much higher energy, boron phosphide (BP) holds promise as an unconventional p‐type transparent conductor. This work reports on reactive sputtering of amorphous BP films, their partial crystallization in a P‐containing annealing atmosphere, and extrinsic doping by C and Si. The highest hole concentration to date for p‐type BP (5 × 10 20 cm −3 ) is achieved using C doping under B‐rich conditions. Furthermore, bipolar doping is confirmed to be feasible in BP. An anneal temperature of at least 1000 °C is necessary for crystallization and dopant activation. Hole mobilities are low and indirect optical transitions are stronger than that predicted by theory. Low crystalline quality probably plays a role in both cases. High figures of merit for transparent conductors might be achievable in extrinsically doped BP films with improved crystalline quality.

36 MATERIALS SCIENCE↗