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At least 19 records

Direct atomic-scale observation of layer-by-layer oxide growth during magnesium oxidation

The atomic-scale oxide growth dynamics are directly revealed by in situ high resolution transmission electron microscopy during the oxidation of Mg surface. The oxidation process is characterized by the layer-by-layer growth of magnesium oxide (MgO) nanocrystal via the adatom process. Consistently, the nucleated MgO crystals exhibit faceted surface morphology as enclosed by (200) lattice planes. It is believed that the relatively lower surface energies of (200) lattice planes should play important roles, governing the growth mechanism. These results facilitate the understanding of the nanoscale oxide growth mechanism that will have an important impact on the development of magnesium or magnesium alloys with improved resistance to oxidation.

36 MATERIALS SCIENCE↗

Effect of Composition and Local Environment on CO 2 Adsorption on Nickel and Magnesium Oxide Solid Solutions

CO 2 adsorption energies on the (100) surfaces of a nickel oxide doped with Mg, magnesium oxide doped with Ni, and their 50:50 solid solution were calculated using density functional theory. The composition and atomic arrangement of the adsorption site was varied to understand how the local environment affects CO 2 adsorption and the basicity of the surfaces at the atomic level. The dispersive and electronic contributions to the adsorption energies were quantified, and the results indicate that the variation of the adsorption energy with adsorption site configuration and metal composition is dominated by electronic interactions. Interestingly, for magnesium oxide doped with nickel, a single substitution can create stronger CO 2 binding sites, which implies stronger basic sites, even though nickel oxide is less basic than magnesium oxide. The effect of double substitution at the binding site can be reasonably approximated by summing the effects of single substitutions. Furthermore, this work provides guidance for the preparation of metal oxides with tailored Lewis basicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rhodium pair-sites on magnesium oxide: Synthesis, characterization, and catalysis of ethylene hydrogenation

Supported rhodium acetate dimers were prepared by the reaction of Rh2(OAc)4 (OAc is acetate) with highly dehydroxylated MgO powder and characterized by extended X-ray absorption fine structure and infrared (IR) spectra, which show that the supported species were well represented as Rh2(OAc)3, with each Rh atom on average bonded to one oxygen atom of the MgO surface. Aberration-corrected scanning transmission electron microscopy gave images of Rh atoms in pairs on the MgO. The supported rhodium dimers were probed with a pulse of CO, and the IR spectra indicate a Rh(II) species with weakly bonded carbonyl ligands; the sharpness of the νCO band indicates highly uniform surface species. Further treatment in CO led to breakup of the rhodium dimers into mononuclear species; such fragmentation took place in other treatment gases as well, with the degree of fragmentation decreasing in the order CO > C2H4 > helium. The fragmentation is inferred on the basis of IR spectra to have proceeded through intermediate Rh2 species without acetate ligands. In contrast, rhodium dimers were reduced and not fragmented in the presence of H2 at 353 K, but at higher temperatures the rhodium aggregated to give larger clusters. The supported species catalyzed ethylene hydrogenation at 298 K and 1 bar at a H2 to ethylene molar ratio of 4; after 27 h of catalysis in a once-through flow reactor, acetate ligands were removed from the dimers, and some of them fragmented, as shown by IR spectroscopy. The intermediate dirhodium species without acetate ligands are two or three orders of magnitude more active as catalysts than the supported mononuclear rhodium species or those present predominantly as Rh2(OAc)3, respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of corrosive solutions on microhardness and chemistry of magnesium oxide /001/ surfaces

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted on cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved to specimen size along the /001/ surface, and indentations were made on the cleaved surface in corrosive solutions containing HCl, NaOH, or HNO3 and in water without exposing the specimen to any other environment. The results indicated that chloride (such as MgCl2) and sodium films are formed on the magnesium oxide surface as a result of interactions between an HCl-containing solution and a cleaved magnesium oxide surface. The chloride films soften the magnesium oxide surface. In this case microhardness is strongly influenced by the pH value of the solution. The lower the pH, the lower the microhardness. Sodium films, which are formed on the magnesium oxide surface exposed to an NaOH containing solution, do not soften the magnesium oxide surface.

Ishigaki, H.↗

Hydrothermal synthesis and characterization under dynamic conditions of cobalt oxide nanoparticles supported over magnesium oxide nano-plates

Here, a nano-catalyst comprised of oxidized Co NPs supported on MgO nano-plates was synthesized via a hydrothermal co-precipitation strategy and calcination in O 2 and subsequently in H 2 at 250 °C. Spectro-microscopy characterization was performed by scanning transmission electron microscopy, electron energy loss spectroscopy and scanning X-ray transmission microscopy. Surface measurements under H 2 and H 2 + CO atmospheres were obtained by ambient pressure X-ray photoelectron spectroscopy and in situ X-ray absorption spectroscopy in the 225–480 °C range. These measurements at the atomic and microscopic levels demonstrated that the oxidized Co nanoparticles uniformly decorated the MgO nano-plates. The surfaces are enriched with Co, and with a mixture of Co(OH) 2 and CoO under H 2 and H 2 + CO atmospheres. Under a H 2 atmosphere, the outermost surfaces were composed of (lattice) O 2- , CO 3 2- and OH - . No inorganic carbonates were observed in the bulk. Chemisorbed CO, likely on the oxidized Co surfaces, was observed at the expense of O 2- under 300 mTorr H 2 + CO (2:1) at 225 °C. Gas phase CO 2 was detected under 32 Torr H 2 + CO (2:1) at 225 °C upon prolonged reaction time, and was attributed to a surface chemical reaction between O 2- and chemisorbed CO. Furthermore, sp 3 like carbon species were detected on the otherwise carbon free surface in H 2 + CO, which remained on the surface under the subsequent reaction conditions. The formation of sp 3 like hydrocarbons was ascribed to a surface catalytic reaction between the chemisorbed CO and OH - as the apparent hydrogen source.

36 MATERIALS SCIENCE↗

A Double-Blind Placebo-Controlled Randomized Clinical Trial With Magnesium Oxide to Reduce Intrafraction Prostate Motion for Prostate Cancer Radiotherapy

Purpose: To investigate whether magnesium oxide during external-beam radiotherapy for prostate cancer reduces intrafraction prostate motion in a double-blind, placebo-controlled randomized trial. Methods and Materials: At the Department of Radiotherapy, prostate cancer patients scheduled for intensity-modulated radiotherapy (77 Gy in 35 fractions) using fiducial marker-based position verification were randomly assigned to receive magnesium oxide (500 mg twice a day) or placebo during radiotherapy. The primary outcome was the proportion of patients with clinically relevant intrafraction prostate motion, defined as the proportion of patients who demonstrated in {>=}50% of the fractions an intrafraction motion outside a range of 2 mm. Secondary outcome measures included quality of life and acute toxicity. Results: In total, 46 patients per treatment arm were enrolled. The primary endpoint did not show a statistically significant difference between the treatment arms with a percentage of patients with clinically relevant intrafraction motion of 83% in the magnesium oxide arm as compared with 80% in the placebo arm (p = 1.00). Concerning the secondary endpoints, exploratory analyses demonstrated a trend towards worsened quality of life and slightly more toxicity in the magnesium oxide arm than in the placebo arm; however, these differences were not statistically significant. Conclusions: Magnesium oxide is not effective in reducing the intrafraction prostate motion during external-beam radiotherapy, and therefore there is no indication to use it in clinical practice for this purpose.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Influence of mineral oil and additives on microhardness and surface chemistry of magnesium oxide (001) surface

X-ray photoelectron spectroscopy analyses and hardness experiments were conducted with cleaved magnesium oxide /001/ surfaces. The magnesium oxide bulk crystals were cleaved into specimens along the /001/ surface, and indentations were made on the cleaved surface in laboratory air, in nitrogen gas, or in degassed mineral oil with and without an additive while not exposing specimen surface to any other environment. The various additives examined contained sulfur, phosphorus, chlorine, or oleic acid. The sulfur-containing additive exhibited the highest hardness and smallest dislocation patterns evidencing plastic deformation; the chlorine-containing additive exhibited the lowest hardness and largest dislocation patterns evidencing plastic deformation. Hydrocarbon and chloride (MgCl2) films formed on the magnesium oxide surface. A chloride film was responsible for the lowest measured hardness.

Miyoshi, K.↗

The analysis of magnesium oxide hydration in three-phase reaction system

In order to investigate the magnesium oxide hydration process in gas–liquid–solid (three-phase) reaction system, magnesium hydroxide was prepared by magnesium oxide hydration in liquid–solid (two-phase) and three-phase reaction systems. A semi-empirical model and the classical shrinking core model were used to fit the experimental data. The fitting result shows that both models describe well the hydration process of three-phase system, while only the semi-empirical model right for the hydration process of two-phase system. The characterization of the hydration product using X-Ray diffraction (XRD) and scanning electron microscope (SEM) was performed. The XRD and SEM show hydration process in the two-phase system follows common dissolution/precipitation mechanism. While in the three-phase system, the hydration process undergo MgO dissolution, Mg(OH){sub 2} precipitation, Mg(OH){sub 2} peeling off from MgO particle and leaving behind fresh MgO surface. - Graphical abstract: There was existence of a peeling-off process in the gas–liquid–solid (three-phase) MgO hydration system. - Highlights: • Magnesium oxide hydration in gas–liquid–solid system was investigated. • The experimental data in three-phase system could be fitted well by two models. • The morphology analysis suggested that there was existence of a peel-off process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental evidence for a phase transition in magnesium oxide at exoplanet pressures

Here, magnesium oxide, an important component of the Earth’s mantle, has been extensively studied in the pressure and temperature range found within the Earth. However,much less is known about its behavior under conditions appropriate for newly-discovered super-Earth planets, where pressures can exceed 1000 GPa (10 Mbar). It is widely believed that MgO will follow the rocksalt (B1) to cesium chloride (B2) transformation pathway commonly found for many alkali halides, alkaline earth oxides and various other ionic compounds. Static compression experiments have determined the structure of MgO to 250 GPa but have been unable to reach pressures necessary to induce the predicted transformation, resulting in large uncertainties regarding its properties under conditions relevant to super-Earths and other large planets. Here we report new dynamic x-ray diffraction measurements of ramp-compressed MgO to 900 GPa.We report evidence for the B2 phase beginning near 600 GPa, remaining stable on further compression to 900 GPa, the highest pressure diffraction data ever collected.

58 GEOSCIENCES↗

Effect of magnesium oxide content on oxidation behavior of some superalloy-base cermets

The effect of increasing magnesium oxide (MgO) content on the cyclic oxidation resistance of hot-pressed cermets of MgO in NiCrAlY, MgO in Hoskins-875, MgO in Inconel-702, and MgO in Hastelloy-X was investigated. The cermets with magnesium oxide levels of 5, 10, 20, and 40 vol percent were examined. The cyclic oxidation behavior of these cermets at 1100 and 1200 C in still air was determined by a thermogravimetric method supplemented by X-ray diffraction analysis and light and electron microscopy. In all instances, MgO prevented grain growth in the metallic phase. No evidence of oxidation along interphase boundaries was detected. Cermets of MgO in NiCrAlY and MgO in Hoskins-875 were superior to cermets of MgO in Inconel-702 and MgO in Hastelloy-X. Their oxidation resistance was degraded only when the MgO content was 40 vol percent. The oxidation behavior of MgO-in-Inconel-702 powder cermets containing 5- and 10-vol percent MgO was approximately similar to that of pure Inconel-702 compacts. The 20- and 40-vol percent MgO content reduced the oxidation resistance of MgO-in-Inconel-702 powder cermets relative to that of pure Inconel-702.

Zaplatynsky, I.↗