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At least 37 records · Page 2

Atomically Dispersed Platinum in Surface and Subsurface Sites on MgO Have Contrasting Catalytic Properties for CO Oxidation

Atomically dispersed metals on metal oxide supports are a rapidly growing class of catalysts. Developing an understanding of where and how the metals are bonded to the supports is challenging because support surfaces are heterogeneous, and most reports lack a detailed consideration of these points. In this work, we report two atomically dispersed CO oxidation catalysts having markedly different metal–support interactions: platinum in the first layer of crystalline MgO powder and platinum in the second layer of this support. Structural models have been determined on the basis of data and computations, including those determined by extended X-ray absorption fine structure and X-ray absorption near edge structure spectroscopies, infrared spectroscopy of adsorbed CO, and scanning transmission electron microscopy. The data demonstrate the transformation of surface to subsurface platinum as the temperature of sample calcination increased. Catalyst performance data demonstrate the lower activity but greater stability of the subsurface platinum than of the surface platinum.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalysts Prepared from Atomically Dispersed Ce(III) on MgO Rival Bulk Ceria for CO Oxidation

Atomically dispersed cerium catalysts on an inert, crystalline MgO powder support were prepared by using both Ce(III) and Ce(IV) precursors. The materials were used as catalysts for CO oxidation in a once-through flow reactor and characterized by atomic-resolution scanning transmission electron microscopy, X-ray absorption near edge structure spectroscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction, among other techniques, before and after catalysis. The most active catalysts, formed from the precursor incorporating Ce(III), displayed a performance similar to that reported for bulk ceria under comparable conditions. The catalyst provided stable time-on-stream performance for as long as it was kept on stream, two days, increasing slightly in activity as the atomically dispersed cerium ions were transformed into ceria nanodomains represented as CeO x and having increased reducibility on the MgO support. Furthermore, the results suggest how highly dispersed supported ceria catalysts with low cerium loadings can be prepared and may pave the way to improved efficiencies of cerium utilization in oxidation catalysis.

36 MATERIALS SCIENCE↗

A direct process for preparing semi-crystalline polyimides

The invention is a direct process for preparing semi-crystalline polyimides. This process comprises the steps of: providing a polar aprotic solvent, adding a dianhydride and a diamine to the solvent to form a mixture, stirring the mixture at ambient temperature, and adding glacial acetic acid to the mixture to provide a ratio of polar aprotic solvent to glacial acetic acid which ranges from about 90 to 10 to about 75 to 25 by volume to form a solution. The solution was heated to a range from about 110 C to about 140 C to form a polyimide precipitate. The polyimide precipitate was recovered as a semi-crystalline polyimide powder.

Chang, Alice C.↗

Direct process for preparing semi-crystalline polyimides

The invention is a direct process for preparing semi-crystalline polyimides. This process comprises the steps of: providing a polar aprotic solvent, adding a dianhydride and a diamine to the solvent to form a mixture, stirring the mixture at ambient temperature, and adding glacial acetic acid to the mixture to provide a ratio of polar aprotic solvent to glacial acetic acid which ranges from about 90 to 10 to about 75 to 25 by volume to form a solution. The solution was heated to a range from about 110.degree. C. to about 140.degree. C. to form a polyimide precipitate. The polyimide precipitate was recovered as a semi-crystalline polyimide powder.

Chang, Alice C.↗

Effect of Composition on the Phase Structure and Magnetic Properties of Ball-Milled LaFe11.71-xMnxSi1.29H1.6 Magnetocaloric Powders

Magnetocaloric alloys are an important class of materials that enable non-vapor compression cycles. One promising candidate for magnetocaloric systems is LaFeMnSi, thanks to a combination of factors including low-cost constituents and a useful curie temperature, although control of the constituents’ phase distribution can be challenging. In this paper, the effects of composition and high energy ball milling on the particle morphology and phase stability of LaFe11.71-xMnxSi1.29H1.6 magnetocaloric powders were investigated. The powders were characterized with optical microscopy, dynamic light scattering, X-ray diffraction (XRD), and differential scanning calorimetry (DSC). It was found that the powders retained most of their original magnetocaloric phase during milling, although milling reduced the degree of crystallinity in the powder. Furthermore, some oxide phases (<1 weight percent) were present in the as-received and milled powders, which indicates that no significant contamination of the powders occurred during milling. Finally, the results indicated that the Curie temperature drops as Fe content decreases (Mn content increases). In all of the powders, milling led to an increase in the Curie temperature of ~3–6 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental studies and applications of vanadium oxides.

The electrical and electrochemical properties of V-5 and V-7 vanadium oxides were investigated. The effects of pressure, temperature and moisture on the bulk resistivity of the oxides in powder, sintered, and crystalline form were determined, and the static and dynamic volt-ampere characteristics were obtained. Sintered samples tested showed better electrical stability than the compressed powder samples. Two types of commercially available vanadium pentoxide were heat-treated to obtain various crystalline oxide forms which were mounted on alumina substrates and terminated by thick-film conductors for making electrical connections. Indications are that these materials could have applications as sensors, critical-temperature resistors, high-speed switches, and temperature-compensation elements in hybrid microelectronic circuits.

Williams, L., Jr.↗

Heats of immersion of titania powders in primer solutions

The oxide layer present on titanium alloys can play an important role in determining the strength and durability of adhesive bonds. Here, three titania powders in different crystalline phases, rutile-R1, anatase-A1, and anatase-A2, are characterized by several techniques. These include microelectrophoresis, X-ray diffractometry, surface area pore volume analysis, X-ray photoelectron spectroscopy, and measurements of the heats of immersion. Of the three powders, R1 has the highest heat of immersion in water, while the interaction between water and A1 powder is low. Experimental data also suggest a specific preferential interaction of polyphenylquinoxaline with anatase.

Siriwardane, R.↗

Chemically Derived Dense Alumina-Zirconia Composites for Improved Mechanical and Wear Erosion Properties

As a result of this funded project high purity Zirconia-Toughened Alumina (ZTA) ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and rheological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. This improved materials should have enhanced properties such strength, toughness, and wear resistance for advanced structural applications, for example engine components in high technology aerospace applications.

Source record↗

Characterization of the Sol-Gel Transition for Zirconia-Toughened Alumina Precursors

High purity ZTA ceramic powders with and without yttria were produced using metal alkoxide precursors. ZTA ceramic powders with varying volume percents of zirconia were prepared (7, 15, and 22%). Aluminum tri-sec butoxide, zirconium propoxide, and yttrium isopropoxide were the reagents used. Synthesis conditions were varied to control the hydrolysis and the aging conditions for the sol to gel transition. FTIR analysis and theological characterization were used to follow the structural evolution during the sol to gel transition. The greater extent of hydrolysis and the build-up of structure measured from viscoelastic properties were consistent. Heat treatment was conducted to produce submicron grain fully crystalline ZTA ceramic powders. In all experimental cases a-alumina and tetragonal zirconia phases were confirmed even in the absence of yttria.

Moeti, I.↗

Solid state polymerization and crystallography of polyimide precursors

Although the production of crystallinity in a polymeric system has historically led to commerically useful properties, the polyimides, prized for their high temperature characteristics, as customarily synthesized by melt or solution casting, are amorphous. It is shown that polymide containing residual crystallinity can be synthesized by isothermal annealing of crystals of the salt of the diisopropyl ester of pyromellitic acid and phenylene diamine. The reaction is topochemical in that the geometry of the polymer product is dependent upon that of the crystalline precursor. Infrared spectroscopy reveals the presence of imide absorption in the polymer, while powder diffractometry suggests residual crystallinity. Single crystal X-ray analysis of the monomer yields a structure of chains of alternating acid and base suggesting that the monomer is amenable to polymerization with a minimum of geometrical disruption.

Wakelyn, N. T.↗

Thermoplastic matrix composites - LARC-TPI, polyimidesulfone and their blends

Composites were fabricated from unidirectional unsized AS-4 carbon fiber and two baseline polyimides: benzophenone dianhydride-3,3'-diaminodiphenylsulfone (PISO2) and benzophenone dianhydride-3,3'-diaminobenzophenone (LARC-TPI). In addition, each polymer solution prior to prepregging was doped with various amounts of crystalline LARC-TPI powder to enhance melt flow during press molding. The 2:1, 1:1, and 1:2 ratios of crystalline to amorphous resin, respectively, were studied in the LARC-TPI system and the 1:2 ratio in the PISO2 system. Matrix characterization, prepreg fabrication/characterization and composite fabrication and physical/mechanical properties are described. The latter include three point short beam shear and flexure, dry and wet, as well as fracture toughness properties in selected compositions.

Johnston, Norman J.↗

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al2O3-2SiO2). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al2O3, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al203-2Si02). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al203, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

Design and characterization of hierarchical aluminosilicate composite materials for Cs entrapment: Adsorption efficiency tied to microstructure

The growing quantity of nuclear waste and the serious threats to the environment challenge researchers to innovate and target new waste form technologies. In the past decades, considerable efforts have been devoted to developing highly selective sorbents followed by safe disposal with the assurance of chemical stability and robust retention performance. Zeolite-containing geopolymers are regarded as a possible 2-in-1 material able to both capture and sequester elements such as Cs in bed fixed column application perspective. Here, these composites show promise for combining extraction properties of zeolite powder due to its crystalline structure (high capacity and selective adsorption), with the tunable microstructure and the shaping feasibility of the geopolymer binder. For the development of materials devoted to Cs immobilization, porous zeolite/geopolymer composites were prepared by dispersing NaY zeolite particles in a geopolymer binder. The influence of the structural properties of such composites on their ability to entrap a large amount of Cs by an ionic exchange process was notably studied. Composites' compositions, porosities, morphologies and crystallinity were analyzed by scanning electron microscopy coupled with energy dispersive x-ray spectroscopy (SEM-EDX), x-ray diffraction analysis (XRD) and nitrogen adsorption/desorption studies. Experimental Cs sorption in batch mode was used to follow the ionic exchange phenomenon in these materials. Along with 5 wt% amount of zeolite in geopolymer improves the Cs adsorption performance offering multiple new adsorption sites. Additionally, the geopolymer mesopores are beneficial facilitating the access of Cs and its role as a binder is advantageous to tailor granular hierarchical structure for safer industrial application.

36 MATERIALS SCIENCE↗

Evaluation of high temperature structural adhesives for extended service, phase 5

The evaluation of 3 experimental polymers from NASA-Langley and a commercially produced polymer from Mitsui Toatsu Chemicals as high temperature structural adhesives is presented. A polyphenylquinoxaline (PPQ), polyimide (STPI/LaRC-2), and a polyarylene ether (PAE-SO2) were evaluated as metal-to-metal adhesives. Lap shear, crack extension, and climbing drum peel specimens were fabricated from all three polymers and tested after thermal, combined thermal/humidity, and stressed hydraulic fluid (Skydrol) exposure. The fourth polymer, LARC-TPI was evaluated as an adhesive for titanium honeycomb sandwich structure. All three experimental polymers performed well as metal-to-metal adhesives from 219 K (-65 F) to 505 K (450 F), including humidity exposure. Structural adhesive strength was also maintained at 505 K for a minimum of 3000 hours. LaRC-TPI was evaluated as a high temperature (505 K) adhesive for titanium honeycomb sandwich structure. The LaRC-TPI bonding process development concentrated on improving the honeycomb core-to-skin bond. The most promising approach of those evaluated combined a LaRC-TPI polymer solution with a semi-crystalline LaRC-TPI powder for adhesive film fabrication and fillet formation.

Hendricks, C. L.↗

Processing Bi-Pb-Sr-Ca-Cu-O superconductors from amorphous state

Researchers produced superconducting ceramics of the Bi-Pb-Sr-Ca-Cu-O system started from a glass. To form the glass, the mixed oxide powder was melted at 1200 C in air. The liquid was quenched rapidly by pouring it onto an aluminum plate and rapidly pressing with another plate. The quenched compound was in the form of black amorphous solid, whose x-ray powder pattern has no crystalline peaks. After heat treatment at high temperatures, the glass crystallized into a superconductor. The crystalline phases in the superconductor identified using x-ray diffraction patterns. These phases were that associated with the superconducting phases of T(sub c) = 80 K (Bi2Ca1Sr2Cu2Ox) and of T(sub c) = 110 K (Bi2Ca2Sr2Cu3Ox). The dc resistivity and the ac susceptibility of these superconductors were studied.

Chiang, C. K.↗

Applications of diamond films and related materials; Proceedings of the 1st International Conference, Auburn, AL, Aug. 17-22, 1991

The present conference discusses the nucleation and growth of diamond from hydrocarbons, the cutting tool performance of CVD thick-film diamond, the characterization of CVD diamond grinding powder, industrial applications of crystalline diamond-coated tools, standardized SEM tribometry of diamond-coated substrates, residual stress in CVD diamond films, the optical properties of CVD diamond films, polycrystalline diamond films for optical applications, and diamond growth on ferrous metals. Also discussed are ion beam-irradiation smoothing of diamond films, electronic circuits on diamond substrates, diamond-laminated surfaces for evaporative spray cooling, electron devices based on the unique properties of diamond, diamond cold cathodes, thin-film diamond microstructure applications, Schottky diodes from flame-grown diamond, diamond films for thermionic applications, methods of diamond nucleation and selective deposition, high-rate/large-area diamond film production, halogen-assisted diamond growth, the economics of diamond technology, and the optical and mechanical properties of diamondlike films.

Tzeng, Yonhua↗