Nucleation of isolated PO4 units on CeO2 driven by high temperatures and the effect on its oxygen storage and release properties

The chemical nature of P-containing species of varying concentration present in CeO₂ after impregnation with (NH₄)₂HPO₄ and calcination at 1273 K, and their effects on the oxygen storage and release (OSR) properties of ceria are reported for the first time. The samples were characterized by different techniques and the results were compared with those recently reported on the same samples but calcined at 873 K. When P-containing ceria solids were calcined at 1273 K, CePO₄ (monazite) was the predominant P-containing species on the surface of ceria, confirming previous studies that showed that monazite exists for those samples in which the surface P loading (P atoms per nm⁻²) is larger than 5.5. For lower surface P concentrations, isolated orthophosphate units are present at the surface and within the subsurface region of the solid. Severe sintering of CeO₂ after calcination at 1273 K resulted in P concentrations >5.5 P atoms·nm⁻² in all samples. Isolated PO₄ units that could initially be present in the samples calcined at 873 K nucleated and CePO₄ was formed when samples were calcined at 1273 K. OSR properties of CeO₂ deteriorated progressively when P loading increased due to the presence of larger crystals of the very stable Ce(III) phase of CePO₄ at the surface of the P-containing ceria solids.     

Catalytic removal of SO2, NO and HCl from incineration flue gas over activated carbon-supported metal oxides

Activated carbon-supported copper, iron, or vanadium oxide catalysts were exposed to incineration flue gas to investigate the simultaneous catalytic oxidation of sulfur dioxide/hydrogen chloride and selective catalytic reduction of nitrogen oxide by carbon monoxide. The results show that AC-supported catalysts exhibit higher activities for SO₂ and HCl oxidation than traditional γ-Al₂O₃-supported catalysts and the iron and vanadium catalysts act as catalysts instead of sorbents, and can decompose sulfate with evolution of SO₃ and then regenerate for more SO₂ adsorption to take place. The AC-supported catalysts also display a high activity for NO reduction with CO generated from a flue gas incineration process and the presence of SO₂ in the incineration flue gas can significantly promote catalytic activity. Using CO as the reducing agent for NO reduction is more effective than using NH₃, because NH₃ may be partially oxidized in the presence of excess O₂ (12 vol%. in the incineration flue gas used) to form N₂, which can decrease the overall extent of NO reduction.     

DSC and synchrotron-radiation X-ray diffraction studies on crystallization and polymorphic behavior of palm stearin in bulk and oil-in-water emulsion states

The crystallization and polymorphic behavior of palm stearin (PS) in a bulk state and in oil-in-water (O/W) emulsion droplets (average diameter, 1.7±0.3 μm) was observed by using DSC, optical microscopy, and in situ X-ray diffraction with synchrotron radiation (SR-XRD). For the bulk sample the DSC measurements revealed three main exothermic peaks at approximately 31 (large), 21 (small) and 3°C (medium) on cooling, and broad endothermic peaks at approximate −3 (small), 8, 15 to 25 (medium), and 37 and 53°C upon heating. The SR-XRD patterns taken during cooling from 60 to −5°C clarified that the DSC exothermic peaks around 31 and 3°C corresponded to crystallization of the α form of high-melting and low-melting fractions, respectively, and that the occurrence of β′ corresponded to the small exothermic peak around 21°C. The XR-XRD patterns taken during heating from −5 to 60°C demonstrated that the DSC endothermic peaks corresponded to the following transformation processes: melting of α of the low-melting fraction (−3°C), melt-mediated transformation from α to ∇′ (15–25°C), melting of β′ (36°C), and melting of β (53°C) of the high-melting fraction. As for the O/W emulsion sample, the DSC and SR-XRD measurements during the cooling and heating processes exhibited basically the same behavior as that of PS in the bulk state, except that β′ did not crystallize during the cooling process, and the temperatures of crystallization of α, melt-mediated α→β′→β transformation, and melting of β were lower in the emulsion droplets than in the bulk state.     

Structure of Atomic and Molecular Adsorbates on Low-Miller-Index ZnO Surfaces Using X-ray Absorption Spectroscopy

We review our X-ray absorption spectroscopy studies of adsorbate geometries on the O-terminated (000 ) and Zn-terminated (0001) basel faces, as well as the non-polar (10 0) prism face of ZnO. Studies employing near-edge X-ray absorption fine-structure (NEXAFS) and surface X-ray absorption fine-structure (SEXAFS) are included.     

Strain-induced ordering of microdomain structures in polystyrene-block-polybutadiene-block-polystyrene triblock copolymers cross-linked in the disordered state

Strain-induced ordering of microdomain structures in cross-linked polystyrene-block-polybutadiene-block-polystyrene (SBS) triblock copolymers was examined by the small-angle X-ray scattering technique. To stretch the SBS samples at elevated temperature above the glass transition temperature of polystyrene, polybutadiene blocks were chemically cross-linked in the disordered state. The initial morphology was disorder-like or bicontinuous due to incompletion of microphase separation in the presence of the chemical cross-links. When the cross-linked SBS samples were mechanically stretched at 130 °C and were further annealed for 24 h under a stretched state, the random domain structures ordered gradually and lamellar-like regularity was finally attained. It was found that the ordering proceeded more for the case of the higher strain.     

Adhesive Bonding of Oil-Contaminated Steel Substrates

Durability of adhesive bonds formed by curing epoxies against oil-contaminated steel substrates using amidoamine curing agents was determined during exposure to boiling water. The most durable bonds were obtained using amidoamine curing agents with relatively low amine numbers and by blending silane coupling agents such as γ-glycidoxypropyltrimethoxysilane (γ-GPS) and N-(2-aminoethyl)-3-aminopropyltrimethoxy silane (AAMS) into the adhesives. When X-ray photoelectron spectroscopy (XPS) was used to characterize the failure surfaces of the adhesive joints after exposure to boiling water, it was determined that adhesives prepared using amidoamine curing agents with low amine numbers were able to displace the oil from the steel surface but adhesives prepared with amidoamine curing agents with high amine numbers were not. Results obtained from XPS also showed that the amino groups on the substrate fracture surfaces of joints prepared using curing agents with low amine numbers were protonated whereas the amino groups in the bulk adhesive were not, indicating that there was a chemical interaction between the curing agent and the hydrated surface of the substrate. It was also shown using infrared spectroscopy that the amidoamine curing agents formed salts with calcium compounds in the oil.     

Hydration Study of the System Ca3Al2O6–CaSO4· 2H2O–Ca(OH)2–H2O with and without Citric Acid

Hydration occurring in the system Ca₃Al₂O₆–CaSO₄· 2H₂O–Ca(OH)₂–H₂O has been studied at different temperatures and it was found that the reactions are diffusion controlled. The kinetic data obeyed Jander's equation and the rate of reaction increased with increasing temperature. X-ray diffraction studies and calorimetric measurements show that when gypsum is consumed, ettringite is converted into monosulfate. The rate of this conversion also increased with the increasing temperature and decreased in the presence of citric acid. Spectroscopic studies showed that there was some interaction between citric acid and the cement and that the product of hydration is of colloidal nature. Zeta potential measurements show that retardation of Ca₃Al₂O₆ hydration in the presence of gypsum and Ca(OH)₂ is not due to SO²⁻₄ adsorption. Electrical conductivity and thermoelectric potential measurements of solid Ca₃Al₂O₆ show that Ca₃Al₂O₆ is an n -type semiconductor and contains defects. The retardation of Ca₃Al₂O₆ may be due to poisoning of reaction sites by gypsum and Ca(OH)_2.     

MDX1060型X-荧光分析仪的应用与实践

甘肃祁连山水泥股份有限公司从英国牛津仪器公司引进的MDX1060型X-荧光分析仪于2001年11月投入使用，经过2年的调试和维护，掌握了影响其测试稳定性和准确性的各种因素(包括样品制备质量、设备维护技术、工作曲线和测试操作水平等)及其克服这些因素影响的技术措施，从而实现了该公司生产原材料和生科、熟料化学组成CaO，SiO2，Al2O3，Fe2O3，MgO，SO3，K2O和Na2O的快速准确测定，为提高生料配料质量和熟料质量提供了可靠的技术参数。     

Equilibrium and dynamics of acetylene sorption in multiwalled carbon nanotubes

Multiwalled carbon nanotubes (MWCNT) were characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), and by adsorption of N₂ and acetylene. The dynamics of acetylene sorption was studied by frequency response spectroscopy. The average tube dimension and the shell number were determined from a statistical evaluation of the TEM images. This value agreed with that obtained from XRD via the Scherrer equation only if a shape factor of 0.49 was used. The diffusion of acetylene in the nanotubes of the MWCNT sample was found to be the rate-controlling step of the sorption process. Relationships between the tube dimensions and the equilibrium and dynamic sorption properties were demonstrated.     

Carbon-encapsulated Fe nanoparticles from detonation-induced pyrolysis of ferrocene

Carbon-encapsulated Fe nanoparticles with size between 5 and 20 nm were synthesized via a picric acid-detonation-induced pyrolysis of ferrocene, which is characterized by a self-heating and extremely fast process. The nanoparticles exhibit well-constructed core-shell structures, with bcc-Fe cores and graphitic shells. The graphitic shells can protect effectively the cores against the attack of HNO₃ solution. The formation of the core-shell nanoparticles can be selectively controlled by adjusting the composition of the picric acid-ferrocene mixture, which determines C/Fe atomic ratio of the reaction system. The core-shell nanoparticles are preferably formed at low C/Fe atomic ratios, while tubular structures are formed at high C/Fe ratio. The possible pathway for the carbon-encapsulated Fe nanoparticles formation is discussed briefly.