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At least 181 records · Page 10

Additive manufacturing of continuous carbon fiber-reinforced SiC ceramic composite with multiple fiber bundles by an extrusion-based technique

Due to the high cost, complex preparation process and difficulty in structural design, the traditional methods for carbon fiber-reinforced SiC ceramic composite preparation have great limitations. This paper presents a technique for the additive manufacturing multiple continuous carbon fiber bundle-reinforced SiC ceramic composite with core-shell structure using an extrusion-based technique. A conventional nozzle system was modified to print simultaneously a water-based SiC paste with continuous carbon fibers. Different levels of binder contents were investigated to optimize the stickiness, viscosity, thixotropy and viscoelasticity of the paste. After sintering, SiC whiskers were generated on the surface of fiber, which is conjectured to be due to the reaction between SiO and carbon fiber at high temperature. The continuous carbon fiber-reinforced SiC ceramic composite exhibited non-brittle fracture. In conclusion, the flexural strength of the additively manufactured Cf/SiC composites improved from 162 MPa with no fiber bundles to a maximum of 219 MPa with three fiber bundles.

36 MATERIALS SCIENCE↗

Cast Aluminum Alloys for High Temperature Applications Using Nanoparticles Al2O3 and Al3-X Compounds (X = Ti, V, Zr)

In this paper, the effect of nanoparticles Al2O3 and Al3-X compounds (X = Ti, V, Zr) on the improvement of mechanical properties of aluminum alloys for elevated temperature applications is presented. These nanoparticles were selected based on their low cost, chemical stability and low diffusions rates in aluminum at high temperatures. The strengthening mechanism at high temperature for aluminum alloy is based on the mechanical blocking of dislocation movements by these nanoparticles. For Al2O3 nanoparticles, the test samples were prepared from special Al2O3 preforms, which were produced using ceramic injection molding process and then pressure infiltrated by molten aluminum. In another method, Al2O3 nanoparticles can also be homogeneously mixed with fine aluminum powder and consolidated into test samples through hot pressing and sintering. With the Al3-X nanoparticles, the test samples are produced as precipitates from in-situ reactions with molten aluminum using conventional permanent mold or die casting techniques. It is found that cast aluminum alloy using nanoparticles Al3-X is the most cost effective method to produce high strength aluminum alloys for high temperature applications in comparison to nanoparticles Al2O3. Furthermore, significant mechanical properties retention in high temperature environment could be achieved with Al3-X nanoparticles, resulting in tensile strength of nearly 3 times higher than most 300- series conventional cast aluminum alloys tested at 600 F.

Lee, Jonathan A.↗

Mechanistic Insights into Nonoxidative Ethanol Dehydrogenation on NiCu Single-Atom Alloys

Ethanol dehydrogenation presents a promising pathway towards the production of acetaldehyde, a valuable building block in chemicals production. Under non-oxidative conditions, the reaction is facilitated by supported Cu nanoparticles which afford reasonable activity and high selectivity. The stability issues associated with Cu nanoparticle sintering can be addressed by the addition of small amounts of Ni, which further boost reactivity while retaining selectivity. Despite the promise of NiCu single-atom alloys for non-oxidative ethanol dehydrogenation, little is known about the role of each component and the pathway of this mechanistically complex process. Herein, kinetic investigations from reactor tests identify C-H bond scission as the rate limiting step, while 1-hydroxyethyl is detected as the intermediate via IR spectroscopy. Temperature program desorption studies are employed to examine the effect of Ni coverage and to demonstrate that Ni atoms activate ethanol selectively at lower temperatures, resulting in higher acetaldehyde yield than pure Cu. Temperature program desorption experiments also reveal the spillover of intermediates from the Ni atom to neighboring Cu sites as a relevant step in the reaction pathway. Density functional theory calculations are used to investigate the 2 reaction energetics and to confirm that C-H bond scission is the initial reaction step, while a clear effect of H 2 partial pressure on the reaction pathway is realized. Further, counter to the expected behavior that all reaction steps take place on the Ni atoms, our degree of rate control analysis reveals that a mechanism involving spillover of the 1-hydroxyethyl intermediate from the Ni atom to the Cu surface, where it will dehydrogenate further, is more likely. Furthermore, our combined kinetic, spectroscopic, and theoretical approach sheds light on this complex reaction mechanism and represents a promising method for the understanding and designing of highly active, selective, and stable single-atom alloys for other multistep catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Combustion synthesis of ceramic-metal composite materials - The TiC-Al2O3-Al system

Combustion synthesis was applied for producing ceramic-metal composites with reduced levels of porosity, by allowing an excess amount of liquid metal, generated by the exothermic reaction during synthesis, to infiltrate the pores. It is shown that this method, when applied to TiC-Al2O3 system, led to a decreased level of porosity in the resulting TiC-Al2O3-Al product, as compared with that of TiC-Al2O3 system. This in situ procedure is more efficient than the two-stage conventional processes (i.e., sintering followed by liquid metal infiltration), although there are limitations with respect to total penetration of the liquid metal and maintaining a stable propagation of the combustion reaction.

Feng, H. J.↗

CO-oxidation catalysts: Low-temperature CO oxidation over Noble-Metal Reducible Oxide (NMRO) catalysts

Oxidation of CO to CO2 is an important reaction technologically and environmentally and a complex and interesting reaction scientifically. In most cases, the reaction is carried out in order to remove CO as an environmental hazard. A major application of heterogeneous catalysts is catalytic oxidation of CO in the exhaust of combustion devices. The reaction over catalysts in exhaust gas is fast and often mass-transfer-limited since exhaust gases are hot and O2/CO ratios are high. The main challenges to catalyst designers are to control thermal sintering and chemical poisoning of the active materials. The effect of the noble metal on the oxide is discussed, followed by the effect of the oxide on the noble metal, the interaction of the noble metal and oxide to form unique catalytic sites, and the possible ways in which the CO oxidation reaction is catalyzed by the NMRO materials.

Herz, Richard K.↗

Polymer Entrapment Flash Pyrolysis for the Preparation of Nanoscale Iridium-Free Oxygen Evolution Electrocatalysts

This paper describes the use of a new polymer entrapment flash pyrolysis (PEFP) method for making nanoscale yttrium ruthenate (Y 2 Ru 2 O 7-δ ) electrocatalysts. Here, this approach effectively reduced the synthesis temperature of phase-pure pyrochlore catalysts from 1000 °C to 550 °C, and greatly suppressed the sintering of catalyst particles. The supported nanocrystalline Y 2 Ru 2 O 7-δ catalysts showed enhanced activity towards oxygen evolution reaction (OER) in acidic electrolyte and were stable at 1.50 V for the comparative study (>20 h) under the current density of 10 mA/cm 2 geo in chronopotentiometry testing. This is equivalent to an overpotential value of 270 mV, about half of that of the reference IrO 2 catalyst. X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analysis showed that the high-surface-area Y 2 Ru 2 O 7-δ catalyst had an oxygen-deficient structure. This study provides a route to the synthesis of fine ceramic (or oxide)-based electrocatalysts for making high-performing electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formation of porous surface layers in reaction bonded silicon nitride during processing

An effort was undertaken to determine if the formation of the generally observed layer of large porosity adjacent to the as-nitride surfaces of reaction bonded silicon nitrides could be prevented during processing. Isostatically pressed test bars were prepared from wet vibratory milled Si powder. Sintering and nitriding were each done under three different conditions:(1) bars directly exposed to the furnance atmosphere; (2) bars packed in Si powder; (3) bars packed in Si3N4 powder. Packing the bars in either Si of Si3N4 powder during sintering retarded formation of the layer of large porosity. Only packing the bars in Si prevented formation of the layer during nitridation. The strongest bars (316 MPa) were those sintered in Si and nitrided in Si3N4 despite their having a layer of large surface porosity; failure initiated at very large pores and inclusions. The alpha/beta ratio was found to be directly proportional to the oxygen content; a possible explanation for this relationship is discussed.

Shaw, N. J.↗

A Conceptual Design Study of a High Temperature Solar Thermal Receiver

A conceptual design was made for a solar thermal receiver capable of operation in the 1095 to 1650 C (2000 to 3000 F) temperature range. This receiver is designed for use with a two-axis paraboloidal concentrator in the 25 to 150 kW sub t power range, and is intended for industrial process heat, Brayton engines, or chemical/fuels reactions. Three concepts were analyzed parametrically. One was selected for conceptual design. Its key feature is a helical coiled tube of sintered silicon nitride which serves as the heat exchanger between the incident solar radiation and the working fluid. A mechanical design of this concept was prepared, and both thermal and stress analysis performed. The analysis showed good performance, low potential cost in mass production, and adaptability to both Brayton cycle engines and chemical/fuels production.

Robertson, C. S.↗

Exploring Mars for Evidence of Habitable Environments and Life

The climate of Mars has been more similar to that of Earth than has the climate of any other planet in our Solar System. But Mars still provides a valuable alternative example of how planetary processes and environments can affect the potential presence of life elsewhere. For example, although Mars also differentiated very early into a core, mantle and crust, it then evolved mostly if not completely without plate tectonics and has lost most of its early atmosphere. The Martian crust has been more stable than that of Earth, thus it has probably preserved a more complete record of its earliest history. Orbital observations determined that near-surface water was once pervasive. Orbiters have identified the following diverse aqueous sedimentary deposits: layered phyllosilicates, phyllosilicates in intracrater fans, plains sediments potentially harboring evaporitic minerals, deep phyllosilicates, carbonate-bearing deposits, intracrater clay-sulfate deposits, Meridiani-type layered deposits, valles-type layered deposits, hydrated silica-bearing deposits, and gypsum plains. These features, together with evidence of more vigorous past geologic activity, indicate that early climates were wetter and perhaps also somewhat warmer. The denser atmosphere that was required for liquid water to be stable on the surface also provided more substantial protection from radiation. Whereas ancient climates might have favored habitable environments at least in some localities, clearly much of the Martian surface for most of its history has been markedly less favorable for life. The combination of dry conditions, oxidizing surface environments and typically low rates of sedimentation are not conducive to the preservation of evidence of ancient environments and any biota. Thus a strategy is required whereby candidate sites are first identified and then characterized for their potential to preserve evidence of past habitable environments. Rovers are then sent to explore the most promising candidates. The Mars Exploration Rover (MER) Opportunity revealed that water once flowed to the surface across the vast Meridiani plains, creating saline lakes whose waters were roiled by ancient winds that also sculptured their salt deposits into sand dunes. Opportunity then drove more than 30 km to explore even older deposits on a crater rim. MER Spirit found evidence that thermal waters (heated by volcanism or by impacts?) altered rocks to create sulfate salts, and siliceous sinters. These discoveries indicate that an early hydrological cycle apparently sustained precipitation, streams and lakes. Liquid water participated in rock weathering reactions, such as iron and sulfur oxidation, that created distinctive weathering regimes. Volcanism, impacts, groundwater and ice interacted at least locally. Redox chemical energy from volcanism, hydrothermal activity and weathering of crustal materials would have been available for any life. Thus conditions might have supported life in the past, at least locally. The main objective of the Mars Science Laboratory (MSL) Curiosity rover is to determine the extent to which Gale crater hosted environments capable of supporting microbial life. The rover has already found stream gravels as well as sediments that might have been deposited in an ancient lake. The rover is now traversing to Mt. Sharp, a 5 km-high mound that is located on the crater floor and that exhibits layered sedimentary rocks having diverse minerals (sulfates and clays) that apparently formed in the presence of liquid water. This rock sequence was deposited over an extended time period in diverse potentially habitable watery environments. Curiosity is poised to characterize a a well-preserved rock record of hundreds of millions of years of diverse environments and profound climate change.

layered phyllosilicates↗

Densification of the entropy stabilized oxide (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O

The first entropy-stabilized oxide, (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O, was reported in 2015. Initial studies synthesized this material using solid state processing and were limited to densities < 80%. Here, we report a straightforward solid state route to sinter samples to densities up to 98% of the theoretical by identifying the role of oxygen and promoting the resulting mechanisms in densification. Previous works have studied effects of cation stoichiometry on the entropy-driven reaction to form a single phase, but few have explored the associated effects of anion stoichiometry and/or redox chemistry on both phase stability and densification. We demonstrate here that tuning heating rate and pO 2 during heating of initially-homogeneous calcined powders can enhance densifying diffusion processes and enable reliable sintering of dense (Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 )O samples.

MATERIALS SCIENCE↗

Chemically Inert Hydrocarbon-Based Slurries for Rapid Laser Sintering of Thin Proton-Conducting Ceramics

The process of rapid laser sintering of thin BaZrO 3 –BaCeO 3 -based proton-conducting electrolytes is being developed for easy fabrication of ceramic fuel cells and electrolyzers. However, cracks on the electrolytes caused by volume change due to chemical reactions between the basic ceramic constituents and the polar solvents during wet processing has been problematic. In order to address this issue, the use of chemically inert saturated-hydrocarbon-based slurries comprised of hexadecane, polybutene, and a long-chain saturated fatty acid were investigated in this work. By optimizing slurry composition and laser sintering conditions, a 20 mm long, 4 mm wide, 13.5-μm-thick and 97%-dense BaCe 0.7 Zr 0.1 Y 0.07 Sm 0.13 O 3-d membrane showing proton conductivity on the order of 10 –4 S•cm –1 at 600 °C was successfully prepared in just three seconds by laser sintering. As a result, the use of saturated-hydrocarbon-based slurries will facilitate wet processing and rapid laser sintering of proton-conducting ceramic electrolytes.

36 MATERIALS SCIENCE↗

Cyclic moisture reactivation of calcium sorbents for long duration thermochemical energy storage

The transition to a flexible and reliable energy infrastructure, using electro-thermal energy generation technologies such as geothermal, concentrated solar power, and nuclear, usually demands simultaneous advancement of thermal energy storage (TES) to support on-demand electricity generation and industrial applications while mitigating the inherent intermittency of renewable energy sources and power outages from direct energy generation. Among TES technologies, thermochemical energy storage (TCES) based on calcium looping emerges as a compelling high-power energy storage candidate due to its high reaction enthalpy, compatibility with elevated operating temperatures, and abundance of low-cost materials. However, the long-term durability of calcium-based sorbents for TCES is hindered by surface sintering and particle aggregation, leading to performance degradation over repeated thermal cycles. This study explores a moisture hydration-based strategy to regenerate a degraded calcium sorbent and mitigate performance degradation for long duration TCES. The addition of moisture transforms calcium oxide into calcium hydroxide and produces intercalation water layers, associated with a regenerated surface area and reduced calcium oxide crystallite size. Both these effects are beneficial in restoring the sorbents' reactivity for carbonization. Additionally, an optimized hydration-assisted reactivation protocol balances the recovered energy storage capacity with heating penalty required for moisture removal from hydrated samples, resulting in an enhanced energy storage capacity up to 176% compared to benchmark sorbents that undergo cycling without reactivation after 60 cycles. In conclusion, these results highlight the potential of hydration-assisted reactivation to enhance the long-term performance of TCES, providing an effective pathway to advancing electro-thermal storage technologies.

36 MATERIALS SCIENCE↗

Raspberry colloid-templated approach for the synthesis of palladium-based oxidation catalysts with enhanced hydrothermal stability and low-temperature activity

It is becoming increasingly urgent to develop and utilize novel, more efficient and stable materials for mobile and stationary emission control applications as the deleterious consequences of anthropogenic air pollution are becoming more evident and pressing. Tightening regulations, particularly related to automotive exhaust treatment, together with continued improvements in engine design, that result in lowering the engine operating temperatures and inadvertently lead to the release of an overwhelming proportion of pollutants during the cold start, present new challenges for materials design, specifically for oxidation catalysts. In particular, improvements in the low-temperature activity while maintaining catalyst stability at high temperatures are required from the next-generation catalyst. Typical catalysts for removal of pollutants from automotive exhaust streams incorporate platinum group metals (PGMs). They tend to be inefficient at low temperatures (below 250 °C), thus accounting for the cold start problem, yet sinter and lose their activity at high temperatures that are frequently encountered during catalyst operation. High PGM loadings are often employed to compensate for catalyst inefficiencies and fast degradation, ultimately resulting in high-cost catalytic converters. Here, we have developed a new approach for the design and formation of catalytic materials that allows for both significantly more efficient PGM incorporation and improved overall catalyst performance at reduced PGM loadings. The method provides control over the composition and geometry of the support through self-assembly of sacrificial composite template — “raspberry” polymeric colloids decorated with catalytic particles — accompanied by infiltration with metal-oxide precursor and subsequent removal of the colloids. This method simultaneously structures the porous network and organizes the catalytic particles within it. Uniquely, the resulting catalytic particles are partially embedded in the support matrix and partially exposed to the pore interior, producing catalytic sites that are both stable and accessible. Herein, the feasibility of this novel and versatile approach for automotive catalytic conversion is demonstrated: the studies include testing alumina-based raspberry-colloid-templated (RCT) catalysts containing Pd nanoparticles (RCT Pd/Al2O3) for oxidation of propane and carbon monoxide under simulated diesel exhaust conditions and hydrothermal aging at 800 °C for 50 h in the simulated stream. The RCT Pd/Al2O3 catalysts exhibit exceptional activity toward CO oxidation, reduced reaction onset temperature, and high stability to elevated temperatures (demonstrated through prolonged exposure to temperatures up to 950 °C) and reactive gas streams, without migration, sintering or loss of the precious metal NPs. Notably, the novel catalyst shows the same or slightly better performance than the commercial catalysts even when the PGM load is reduced by ~80 % compared to the commercial counterparts. These results provide confidence for the utilization of the RCT approach for the fabrication of robust nanostructured catalysts for next-generation, energy-efficient catalytic converters with improved performance at low and high temperatures and reduced costs. The RCT methodology is, in addition, highly generalizable, and can thus be applied for the design of a wide range of catalytic systems in the automotive sector and beyond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling Heterogeneous Catalysis with Organic Monolayers on Metal Oxides

A key theme of heterogeneous catalysis research is achieving control of the environment surrounding the active site to precisely steer the reactivity toward desired reaction products. One method toward this goal has been the use of organic ligands or self-assembled monolayers (SAMs) on metal nanoparticles. Metal-bound SAMs are typically employed to improve catalyst selectivity but often decrease the reaction rate as a result of site blocking from the ligands. Recently, the use of metal oxide-bound organic modifiers such as organophosphonic acid (PA) SAMs has shown promise as an additional method for tuning reactions on metal oxide surfaces as well as modifying oxide-supported metal catalysts. In this Account, we summarize recent approaches to enhance catalyst performance with oxide-bound monolayers. These approaches include (1) modification of metal oxide catalysts to tune surface reactions, (2) formation of SAMs on the oxide component of supported metal catalysts to modify sites at the metal–support interface, and (3) enhancement of catalyst performance (e.g., stability) through modification of sites remote from the active sites. Further, both the headgroups and organic tail groups of PA SAMs or other ligands can influence reactions on metal oxide surfaces. Binding of the headgroup can selectively poison certain active sites, altering the selectivity in a manner analogous to metal-bound ligands (at the expense of active site quantity). Moreover, tail groups can be functionalized to interact favorably with reactants and intermediates, for instance through dipole–dipole interactions. On supported metal catalysts like Pt/Al 2 O 3 , PA SAMs can selectively form on the oxide support. This selective deposition allows for modification of the metal–support interface with minimal blockage of metal sites. PA headgroups were shown to provide tunable acid sites at the interface, dramatically improving hydrodeoxygenation rates of various alcohols. Additionally, organic tail functionality was used to activate or stabilize specific reactants at the interface, such as with the use of amine-functionalized PAs to stabilize chemisorption of CO 2 during the reverse water gas shift reaction. PAs have also been found to affect the electronic properties of bulk metal sites through long-range electron withdrawal via the oxide, providing an additional avenue to tune catalytic behavior. Finally, organic modifiers were shown to enhance catalytic performance without directly modifying the active site. For instance, in biphasic liquid environments the modification of catalyst particles with hydrophobic or hydrophilic SAMs shifts the selectivity of multipath reactions on the basis of the hydrophobicities of different intermediates and products. As another “long-range” effect, the deposition of ligands on oxide supports improved catalyst stability through both improved resistance to sintering and suppression of active site poisoning. The recent contributions discussed in this Account demonstrate the versatility and significant potential for the approach of modifying catalysts with oxide-bound organic monolayers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reductive catalytic fractionation of agricultural residue and energy crop lignin and application of lignin oil as antimicrobials

Cheap and abundant waste from bioethanol and agricultural processing industries are an alluring alternative feedstock for biorefineries. In this work, we employ reductive catalytic fractionation (RCF) to depolymerize, over Ru/C powder and Ru/Al 2 O 3 pellets, five herbaceous biomass feedstocks, namely corn stover, miscanthus, switchgrass, sugarcane bagasse, and wheat straw into phenolic monomers with high yields (~40 wt.% based on total (Klason + acid soluble) lignin and > 50 wt.% when stabilized using aldehydes), leaving behind a carbohydrate pulp residue. Interestingly, a polar solvent is sufficient to solubilize and fragment the lignin polymer into monomers without any catalyst. Here, contrary to woody biomass, where the monomer yields are positively correlated with the S-content of lignin, principal component analysis indicates that the monomer yields from herbaceous biomass depend on the content of lignin crosslinker – ferulate. Using NMR, we further identify α – 6 C-C linked oligomers formed from condensation reactions, explaining the unexpected low monomer yields of high β-O-4 herbaceous biomass. Recyclability experiments indicate that catalyst deactivation occurs through sintering, leaching, and fouling. Lignin oil from herbaceous biomass exhibits bacteriostatic effects against Staphylococcus aureus, highlighting a potential application in functional food development and as food or feed preservative.

09 BIOMASS FUELS↗

Methanol carbonylation to acetaldehyde on Au particles supported by single-layer MoS 2 grown on silica

Homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold are found to isolate the reaction of methanol with carbon monoxide, the fundamental step toward higher alcohols, from an array of possible surface reactions. Active surfaces were prepared from homogenous single-layer MoS 2 films coated with sub-single layer amounts of gold. These gold atoms formed clusters on the MoS2 surface. A gas mixture of carbon monoxide (CO) and methanol (CH 3 OH) was partially converted to acetaldehyde (CH 3 CHO) under mild process conditions (308 kPa and 393 K). This carbonylation of methanol to a C 2 species is a critical step toward the formation of higher alcohols. Density functional theory modeling of critical steps of the catalytic process identify a viable reaction pathway. Imaging and spectroscopic methods revealed that the single layer of MoS 2 facilitated formation of nanoscale gold islands, which appear to sinter through Ostwald ripening. Here, the formation of acetaldehyde by the catalytic carbonylation of methanol over supported gold clusters is an important step toward realizing controlled production of useful molecules from low carbon-count precursors.

2D catalyst↗

Synthesis and Flash Sintering of (Hf1-xZrx)B2 Solid Solution Fine Powders

Fine powders of (Hf1-xZrx)B2 solid solution were synthesized by two methods. In the first one, solution-based processing of HfCl4, ZrCl4, sucrose and H3BO3 was carried out followed by heat treatment (e.g., at 1500 °C for 1 h) in Argon to achieve the carbothermal reduction (CTR) reaction to form the boride solid solution. In the second one, called boron hydride reduction (BHR) method, HfCl4, ZrCl4 and NaBH4 were directly mixed in a glove box followed by heat treatment in Argon at elevated temperatures from 700 to 1500 °C. In addition, the powders synthesized via both methods were flash sintered without sample preheating in a homemade setup. The synthesized powders as well as the flash sintered bulk ceramics were characterized using different techniques including XRD, SEM, EDS, TEM, TGA-DSC, and Vickers hardness test to reveal the inter-relationships between starting materials composition, processing conditions, and the resulting materials microstructure and physical/chemical properties.

Belisario, Jose↗