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At least 685 records · Page 38

Mono-C,O-chelated bromo- and triflatosilanes with an amino acid moiety: salts or covalently bonded complexes?

Derivatives of the amino acids sarcosine and proline – triflates TsN(Me)CH{sub 2}C(O)N(Me)-CH{sub 2}SiMe{sub 2}OTf and Ns–Pro–N(Me)CH2SiMe2OTf (Ns is 4-NO{sub 2}C{sub 6}H{sub 4}SO{sub 2}) – were synthesized by the reaction of trimethylsilyl triflate with halosilanes prepared previously. Bromide NsNHCH(Me)C(O)N(Me)CH2SiMe2Br was synthesized by the cleavage of the Si–O–Si moiety of the appropriate disiloxane with excess acetyl bromide. The X-ray diffraction study of these compounds and of the previously characterized bromide TsN(Ac)CH{sub 2}C(O)N(Me) CH{sub 2}SiMe{sub 2}Br showed that the Si–O coordination bond lengths in the triflates are 1.7692(14)– 1.8623(14) Å. The interatomic distances between the bromine and silicon atoms are 2.7095(8) and 2.9704(7) Å, which indicates that these bonds are weak. To elucidate the nature of Si…X bonding (X = OTf, Br), the topological analysis of electron density was performed and {sup 29}Si NMR chemical shifts were calculated. The interatomic Si…X interaction in triflate TsN(Me)CH{sub 2}C(O)- N(Me)CH{sub 2}SiMe{sub 2}OTf and bromide TsN(Ac)CH{sub 2}C(O)N(Me)CH{sub 2}SiMe{sub 2}Br is weak. In triflate Ns–Pro–N(Me)CH{sub 2}SiMe{sub 2}OTf and bromide NsNHCH(Me)C(O)N(Me) CH{sub 2} SiMe{sub 2}Br, the Si…X interaction is significantly stronger and corresponds to a weak coordination bond. Hence, the tosylates can be considered as salts, whereas the para-nitrobenzenesulfonyl derivatives are monochelated five-coordinate silicon complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural-Phase States of Fe–Cu and Fe–Ag Bimetallic Particles Produced by Electric Explosion of Two Wires

X-ray phase analysis, transmission electron microscopy, and X-ray microanalysis were used to examine the structural-phase states of Fe–Cu and Fe–Ag bimetallic nanoparticles. The nanoparticles were obtained by the electric explosion of two twisted metal wires in argon atmosphere. It was demonstrated that the nanoparticles have the structure of Janus particles. Presence of the Janus particle structure in the samples indicates formation of binary melt under conditions of combined electric explosion of two wires. Phases based on supersaturated solid solutions were not found in the examined samples. The data obtained allow arguing that it is possible to achieve uniform mixing of the two-wire explosion products under the described experiment conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Mechanism of Ball Milling Effect on Carbothermic Reduction of Industrial Magnesia by Coke

Mechanical milling always improves the chemical reaction rate in the metallurgy process. The experiment proved that ball milling treatment on raw materials, including industrial magnesia, metallurgical coke, and fluoride calcium, could increase greatly the reaction rate of magnesia. The reaction samples and residues were analyzed by particle size measurement, X-ray diffraction (XRD) analysis, Raman spectroscopy analysis, scanning electron microscope (SEM), and transmission electron microscope (TEM). The results suggested that the positive effect of ball milling on the reaction rate came from three aspects. Ball milling could decrease magnesia particle size and peel coke into graphite sheets to enlarge their contact surface. Meanwhile, ball milling could slightly destroy the crystal grain surface of magnesia and decrease the crystallization of graphite. The nanometer-scale magnesia particles and graphite sheets would stably and strongly attract together after a longer time ball milling. The possible evolution of the particles during ball milling was given, which explained the mechanism of the ball milling effect on the carbothermic reduction of industrial magnesia by coke.

36 MATERIALS SCIENCE↗

Behavior of Ga, In, Sn, and Te in Copper Matte Smelting

The distributions of Ga, In, Sn, and Te between copper-iron mattes and silica-saturated iron silicate slags over a wide range of matte grades 55 to 75 pct Cu were determined at 1300 °C using a gas-phase equilibration-quenching technique and direct phase composition analysis by Electron Probe X-ray Microanalysis and Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry. Alumina from aluminum, a typical minor element of electric and electronic copper scrap, and lime were adopted as slag modifiers for increasing the trace element recoveries. Gallium and tin were distributed predominantly in the slag, indium preferred sulfide matte at low matte grades and slag at high, whereas tellurium strongly favored the sulfide matte in particular in high matte grades. The slag modifiers alumina and lime had a minor impact on the distribution coefficients of gallium and tin, but for indium and tellurium the distribution coefficients were more strongly affected by the basic oxides. The strong tendencies of tin and tellurium to vaporize at the experimental temperature were confirmed.

36 MATERIALS SCIENCE↗

Formation and Decomposition Process of the Filled Skutterudite Sm{sub y}(Fe{sub x}Ni{sub 1−x}){sub 4}Sb{sub 12} (0.40 ≤ x ≤ 1) as Revealed by Differential Thermal Analysis

Filled skutterudites are among the most promising thermoelectric materials, and the obtainment of monophasic samples is crucial for the study of their transport properties. In this work, a differential thermal analysis study was performed on samples belonging to the Sm{sub y}(Fe{sub x}Ni{sub 1-x}){sub 4}Sb{sub 12} system with the aim to determine the most proper annealing temperature to possibly obtain skutterudite monophasic samples, and to study the effect of Sm addition on the thermodynamics of the Fe-Ni-Sb system. Samples were prepared through the traditional procedure consisting in melting–quenching–annealing the starting elements. DTA analyses were carried out on annealed samples, and results were interpreted using the Fe{sub 25}Sb{sub 75}-Ni{sub 25}Sb{sub 75} pseudobinary phase diagram taken from the literature as a starting point. They reveal that 870 K is the best annealing temperature, being the formation of a liquid phase just above this point; moreover, the Sm introduction results in widening the one-phase skutterudite stability region toward both higher temperatures and higher Fe concentrations compared with the Sm-free system.

36 MATERIALS SCIENCE↗

Effects of Vanadium on Modification of Iron-Rich Intermetallics and Mechanical Properties in A356 Cast Alloys with 1.5 wt.% Fe

Formation of Fe-rich intermetallics and mechanical properties of vanadium-modified A356 cast alloys with 1.5 wt.% Fe were investigated using image analysis, scanning electron microscopy, differential scanning calorimetry, and a tensile test. The results showed that V content has no apparent influence on α-Al grain size in A356 alloys with high Fe content. Also, 0.8 wt.% V is beneficial for improving mechanical properties in A356 cast alloys with high Fe content. Specifically, these results can be attributed to the formation of Chinese script or block α-Fe phases, refined needle-like β-Fe (Al{sub 5}FeSi), and decreased porosities. An excessive amount of V deteriorates mechanical properties of alloys because it leads to VSi{sub 2} formation, large sized iron-rich intermetallics, and increased porosities.

36 MATERIALS SCIENCE↗

Effect of Ca and Sm Combined Addition on the Microstructure and Elevated-Temperature Mechanical Properties of Mg-6Al Alloys

In the present study, the microstructure and elevated-temperature mechanical properties of Mg-6Al, Mg-6Al-4Ca, Mg-6Al-4Sm and Mg-6Al-2Ca-2Sm alloys were investigated. The experimental results showed that the microstructure and elevated-temperature mechanical property of Mg-6Al alloy changed obviously with the different elements addition. By analyzing the results of optical microscope, x-ray diffraction analysis, scanning electron microscope, and transmission electron microscope, it could be determined that there was only Mg{sub 17}Al{sub 12} phase in Mg-6Al alloy, there were Al{sub 2}Ca and (Mg, Al){sub 2}Ca phases in Mg-6Al-4Ca alloy, there were Al{sub 2}Sm and Mg{sub 17}Al{sub 12} phases in Mg-6Al-4Sm alloy, and there were (Mg, Al){sub 2}Ca, Al{sub 2}Ca and Al{sub 2}Sm phases in Mg-6Al-2Ca-2Sm alloy. In addition, the addition of alloying elements including Ca and Sm, especially the composite addition, could significantly improve the tensile properties of Mg-6Al alloy. Compared to Mg-6Al alloy, the tensile strengths of Mg-6Al-2Ca-2Sm alloy at 448, 473 and 498 K were enhanced by 50.32, 87.92, and 94.99%, respectively. Furthermore, when the stretching temperatures were 448 and 473 K, the fracture pattern of Mg-6Al-2Ca-2Sm alloy was the mixture of intergranular fracture and trans-crystalline fracture. However, when the stretching temperature was 498 K, the fracture pattern of Mg-6Al-2Ca-2Sm alloy was the intergranular fracture.

36 MATERIALS SCIENCE↗

Creep Behavior of Friction Stir Processed Haynes 282

Haynes 282 is a nickel-based superalloy designed for use in hot sections of turbines for aircraft and power generation. In these applications, elevated temperature creep performance is critical. To that end, creep behavior of friction stir processed material was carried out to investigate the high-temperature performance of this alloy. Friction stir processing of Haynes 282 was successfully completed, and the processed region was found to be defect-free. Various mechanical property characterization approaches were carried out in post-heat treated condition. Transverse tensile samples repeatedly failed in the base metal indicating 100% joint efficiency. Creep property evaluation was completed at 760 °C and at various stress levels. The creep-rupture lifetime of the processed material was similar to the base metal. Detailed electron microscopy analysis of the failed sample was carried out to understand the microstructural evolution in various locations of the sample during creep.

creep↗

Effect of Aluminizing on the High-Temperature Oxidation Behavior of an Alumina-Forming Austenitic Stainless Steel

Due to their excellent oxidation resistance and creep resistance at elevated temperatures, alumina forming austenitic (AFA) stainless steels have emerged as potential alloys for high temperature applications. In this study, a Reactive Air Aluminizing (RAA) method was used to aluminize the surface of AFA25 stainless steel. The high temperature oxidation behavior of both as-received and aluminized AFA25 was investigated at 850 °C in dry air. The mass gain per unit area was higher for the aluminized AFA25 than for the as-received material. X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDXS), performed on the oxide scales following the high temperature oxidation tests, confirmed the formation of alumina scale on both as-received and aluminized AFA. However, the aluminized alloy exhibited a thicker alumina scale on the surface, as well as more extensive penetration of the scale into the subsurface region of the alloy.

Rashidi, S.↗

High temperature microstructural stability and recrystallization mechanisms in 14YWT alloys

In-situ neutron diffraction experiments were performed on room temperature compressed 14YWT nanostructured ferritic alloys at 1100°C and 1150°C to understand their thermally activated static recrystallization mechanisms. The existence of high density of Y-Ti-O rich nano-oxides (<5 nm) shift the recrystallization temperature up due to Zener pinning of the grain boundaries, making these materials attractive for high temperature applications. This study serves to quantify the texture evolution in-situ and understand the effect of particles on the recrystallization mechanisms in 14YWT alloys. We have shown, both experimentally and theoretically, that there is considerable recovery in the 20% compressed sample after 6.5 h annealing at 1100°C while recrystallization occurs within an hour of annealing at 1100°C and 1150°C in the 60% compressed samples. Moreover, the 60% compressed samples show {112}<110> and {112}<111> texture components during annealing, in contrast to the conventional recrystallization textures in body centered cubic alloys. Furthermore, nano-oxide size, shape, density and distribution are considerably different in unrecrystallized and abnormally grown grains. Transmission electron microscopy analysis shows that oxide particles having a size between 5 and 30 nm play a critical role for recrystallization mechanisms in 14YWT nanostructured ferritic alloys.

36 MATERIALS SCIENCE↗

Source and distribution of naturally occurring arsenic in groundwater from Alberta’s Southern Oil Sands Regions

Arsenic (As) concentrations as high as 179 μg/L have been observed in shallow groundwater in the Alberta’s Southern Oil Sand Regions. The geology of this area of Alberta includes a thick cover (up to 200 m) of unconsolidated glacial deposits, with a number of regional interglacial sand and gravel aquifers, underlain by marine shale. Arsenic concentrations observed in 216 unconsolidated sediment samples ranged from 1 and 17 ppm. A survey of over 800 water wells sampled for As in the area found that 50% of the wells contained As concentrations exceeding drinking water guidelines of 10 μg/L. Higher As concentrations in groundwater were associated with reducing conditions. Measurements of As speciation from 175 groundwater samples indicate that As(III) was the dominant species in 74% of the wells. Speciation model calculations showed that the majority of groundwater samples were undersaturated with respect to ferrihydrite, suggesting that reductive dissolution of Fe-oxyhydroxides may be the source of some As in groundwater. Detailed mineralogical characterization of sediment samples collected from two formations revealed the presence of fresh framboidal pyrite in the deeper unoxidized sediments. Electron microprobe analysis employing wavelength dispersive spectrometry indicated that the framboidal pyrite had variable As content with an average As concentration of 530 ppm, reaching up to 1840 ppm. In contrast, the oxidized sediments did not contain framboidal pyrite, but exhibited spheroidal Fe-oxyhydroxide grains with elevated As concentrations. The habit and composition suggest that these Fe-oxyhydroxide grains in the oxidized sediment were an alteration product of former framboidal pyrite grains. X-ray absorption near edge spectroscopy (XANES) indicated that the oxidized sediments are dominated by As(V) species having spectral features similar to those of goethite or ferrihydrite with adsorbed As, suggesting that Fe-oxyhydroxides are the dominant As carriers. XANES spectra collected on unoxidized sediment samples, in contrast, indicated the presence of a reduced As species (As(-I)) characteristic of arsenopyrite and arsenian pyrite. The results of the mineralogical analyses indicate that the oxidation of framboidal pyrite during weathering may be the source of As released to shallow aquifers in this region.

58 GEOSCIENCES↗

Carbon nanotube coated metal mesh: Bridging nanoscale and macroscale

A novel hybrid structure has been developed by growing carbon nanotubes (CNTs) on a metal mesh that functions as a literally unlimitedly extendable backbone. This hybrid material structure provides a new approach of extending CNTs’ advantageous properties such as ultrahigh thermal and electrical conductivities, high sensitivity to gases, and distinctive wettability for different liquids with chemical inertness to macroscale—otherwise available only in nano- and microscales. In this feasibility work, CNTs were grown on a Type 316 stainless steel (SS) mesh by self-catalytical chemical vapor deposition (CVD) without the need of an externally added catalyst or catalyst support. For the radially aligned and entangled CNT forest on the SS mesh, the average CNT diameter is around 50 nm, while the length varies from 20 to 25 µm. High-resolution transmission electron microscopy analysis revealed the multiwall structure of the CNTs with >30 rolled-up graphitic sheets. Raman spectra of the CNTs showed a dominant G band, indicating a well-ordered graphitic nanostructure. Being highly hydrophobic with a water contact angle of ∼145° and oleophilic, the CNT-coated SS mesh could be used in fluid separation and organic contaminant removal from water. Moreover, CNTs are recognized for their exceptional thermal conductivity and the CNT-coated mesh offers a supportive structure with directly connected CNTs for efficient heat transfer. Proof of concept has been achieved for the CNT-coated mesh’s potentials as a liquid filter and an thermal interface material (TIM). Specifically, the CNT-coated mesh demonstrated the capability of capturing water from a water-organic mixture with a 100 % efficiency while allowing organic liquids to pass through the filter. Furthermore, when used as a TIM, the CNT-coated mesh reduced the interfacial thermal impedance by >30 %.

Carbon nanotubes (CNTS)↗

Effect of nanostructured carbon support on copper electrocatalytic activity toward CO 2 electroreduction to hydrocarbon fuels

The effect of support on electrocatalytic activity of Cu nanoparticles (NPs) towards CO 2 electroreduction to hydrocarbon fuels (CH 4 and C 2 H 4 ) is investigated for three types of nanostructured carbons: single wall carbon nanotubes (SWNT), graphene (GP) and onion-like carbon (OLC). Cu/SWNT, Cu/GP and Cu/OLC composite catalysts are synthesized and characterized by X-Ray diffraction analysis, transmission electron microscopy and electrochemical surface area measurements. Electrocatalytic activities of the synthesized materials, as measured in an electrochemical cell connected to a gas chromatograph, are compared to that of Cu NPs supported on Vulcan carbon. All four catalysts demonstrate higher activity towards C 2 H 4 generation vs CH 4 , with production of the latter mostly suppressed on Cu NPs supported on nanostructured substrates. Onset potentials for C 2 H 4 vs CH 4 generation are shifted positively by 200 mV for Cu/SWNT, Cu/GP, and Cu/OLC catalysts. The Cu/OLC catalyst is found to be superior to the other two nanostructured catalysts in terms of stability, activity and selectivity towards C 2 H 4 generation. Its faradaic efficiency reached 60% at -1.8 V vs Ag/AgCl. The enhanced activity and stability of Cu/OLC catalyst can be attributed to the unique catalyst design, wherein a shell of OLC surrounds the Cu NPs such that the outer layer acts as a filter that protects the Cu surface from adsorption of undesirable species, enhances its electrocatalytic performance, and improves its viability in CO 2 electroreduction reaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Degradation mechanism of blended cement pastes in sulfate-bearing environments under applied electric fields: Sulfate attack vs. decalcification

Applied electric fields, the reason behind stray currents, accelerate the ingress of sulfate into cementitious materials. To identify mitigation approaches, this study investigates the effects of slag and fly ash on sodium sulfate attacks of cement pastes under a constant electric current. The mineralogical alterations induced by the attacks were analyzed using X-ray diffractometry, thermogravimetric analysis, scanning electron microscopy, and thermodynamic modeling. The dissolution of aluminates in the slag and fly ash induced a monosulfate-rich area (>~20 mm from the cathode surface) to form next to the ettringite-rich area on the sample surface (<~20 mm). This effect reduced the availability of SO 4 2– in the pore solution, thereby hindering the penetration of sulfate. Meanwhile, the consumption of portlandite by the pozzolanic reaction lowered the decalcification resistance of the materials. This produced a wide area that endured the decomposition of portlandite and carbonate-AFm. Altogether, blending 30% fly ash did not improve the resistance of the material to either sulfate attacks or decalcification; blending 50% slag can effectively mitigate sulfate ingress, though decalcification may become a governing mechanism in the degradation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Roles of Mn and Co in Ni-rich layered oxide cathodes synthesized utilizing a Taylor Vortex Reactor

It is reported that layered oxides, composed of nickel, manganese, and cobalt (NMC), are sought after as cathode materials which provide improved energy density, cycle life, and safety in commercial lithium ion batteries (LIBs). Increasing Ni contents higher than 80% can provide even higher practical discharge capacities >200 mAh/g and similar to ~4 V discharge potential vs Li/Li + , making them promising cathodes for next generation LIBs. However, rapid capacity fade during cycling and heat-related safety concerns are delaying their successful transition to industry. We report systematic performance optimization of LiNiO 2 , LiNi 0.9 Mn 0.1 O 2 , and LiNi 0.9 Co 0.1 O 2 high Ni layered oxide cathodes synthesized by utilizing a Taylor Vortex Reactor. Co-free LiNi 0.9 Mn 0.1 O 2 cathode showed 200 mAh/g highest discharge capacity at 0.1 C rate with 84% retention after 103 cycles at 0.3C rate while LiNi 0.9 Co 0.1 O 2 cathode showed higher initial but poor cycle life (225 mAh/g highest discharge capacity at 0.1C rate with only 56% capacity retention after 103 cycles at 0.3 C rate. Synchrotron based X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS) and focused ion beam (FIB) imaging of pristine and cycled cathodes after 103 cycles provided important information on degradation mechanism. The roles of Mn and Co on layered structure formation, charge balance, cationic mixing, and electrochemical performance were elucidated using the crystallographic information from XRD refinement and electronic state analysis from XAS providing valuable information to design future Ni-rich layered oxide cathodes.

25 ENERGY STORAGE↗

Petrogenesis, alteration, and shock history of intermediate shergottite Northwest Africa 7042: Evidence for hydrous magmatism on Mars?

We report Northwest Africa (NWA) 7042 is an intermediate, permafic shergottite consisting of two generations of zoned olivine (early olivine Fo 41-76 , and late-stage olivine Fo 46-56 ), complexly zoned pyroxene (En 35-64 Fs 22-46 Wo 5-34 ), maskelynitized feldspar and shock melt (An 5-30 Ab 16-61 Or 1-47 ), and accessory merrillite, apatite, ilmenite, titanomagnetite, Fe-Cr-Ti spinels, pyrrhotite, and baddeleyite. The olivine grains have been pervasively altered resulting in orange-brown stained cores with dark-brown margins, surrounded by significantly less altered overgrowth rims. This textural relationship suggests that the alteration of the cores took place at magmatic temperatures prior to crystallization of the rims on Mars. While this type of olivine alteration is rare in shergottites, it is similar to deuterically altered olivine in basalts and gabbros on Earth, caused by residual water-rich magmatic fluids. Launch-generated shock veins in NWA 7042 crosscut and displace several of the altered olivine grains indicating that the alteration occurred before ejection of the meteorite from Mars. However, NWA 7042 has also been subjected to extensive terrestrial weathering, with terrestrial calcite/barite veins occurring throughout the sample. Transmission electron microscopy analysis of the olivine alteration also reveals an absence of high-temperature phases typically associated with hydrous deuteric alteration on Earth, complicating our interpretation. The potential presence of deuterically altered olivine in NWA 7042 has significant implications, as it is the third martian meteorite where deuteric alteration of olivine has been observed (the others being NWA 10416, ALH 77005). The different mantle sources for the parental melts of these three meteorites would suggest many, if not all martian mantle reservoirs have the potential to produce water-rich magmas.

58 GEOSCIENCES↗

W-ZrC composites prepared by reactive melt infiltration of Zr 2 Cu alloy into binder jet 3D printed WC preforms

W-ZrC composites were successfully prepared by reactive melt infiltration (RMI) of stoichiometric and excess amounts of Zr 2 Cu into sintered and un-sintered WC preforms made from binder jet 3D printing. The focus of this work was to study the conversion of reactant powders and liquid infiltrant with varying preform density and infiltrant amount by controlling the processing time to reach high conversion yield while understanding the phase composition, microstructure, and hardness. To investigate the effect of time, the reactive melt infiltration was conducted at 1400 °C for 2, 4 and 8 h in a furnace with 96% Ar - 4% H2 gas atmosphere. The increase in reaction time from 2 to 8 h increased the W and W 2 C phase contents and decreased the ZrC phase content when using sintered WC preforms. Samples prepared from un-sintered WC preforms exhibited improved reactive melt infiltration compared to sintered samples, and there was no detectable W 2 C phase and nearly full consumption of WC. Similar to sintered WC samples, the content of W and ZrC phases increased with the increase in time from 2 to 8 h. The interfaces and phases at reaction interfaces were investigated using electron diffraction analysis and S/TEM-EDS to understand material stability; the phases were identified and consistent with XRD analysis. Additionally, there was no Cu present at the interfaces. Increasing the amount of infiltrant led to better reactive melt infiltration. In general, the hardness increased with reaction time and the highest Vickers hardness was found in the W-ZrC sample formed from sintered WC reacted with excess Zr 2 Cu. Finally, this research addresses the critical comparison of sintering and RMI time and shows that by using un-sintered samples for 8 h we are able to achieve W-ZrC composites with fewer undesired phases.

36 MATERIALS SCIENCE↗