Preparation, Characterisation and Catalytic Behaviour of a New TeVMoO Crystalline Phase

TeM_xMo_1.7O mixed oxides (M = V and/or Nb; x = 0-1.7) have been prepared by calcination of the corresponding salts at 600 °C in an atmosphere of N₂. A new crystalline phase, with a Te/V/Mo atomic ratio of 1/0.2-1.5/1.7, has been isolated and characterised by XRD and IR spectroscopy. This phase is observed in the TeVMo or TeVNbMo mixed oxide but not in the TeNbMo mixed oxide. The new crystalline phase shows an XRD pattern similar to Sb₄Mo₁₀O₃₁ and probably corresponds to the M1 phase recently proposed by Aouine et al. (Chem. Commun. 1180, 2001) to be present in the active and selective MoVTeNbO catalysts. Although these catalysts present a very low activity in the propane oxidation, they are active and selective in the oxidation of propene to acrolein and/or acrylic acid. However, the product distribution depends on the catalyst composition. Acrolein or acrylic acid can be selectively obtained from propene on Nb-free or Nb-containing TeVMo catalysts, respectively. The presence of both V and Nb, in addition to Mo and Te, appears to be important in the formation of acrylic acid from propene.     

Evolution of grain structure in thin film reactions

In this paper, we examine, both experimentally and theoretically, the kinetics of formation and microstructure of product phases in thin film reactions, using the Nb/Al and Ti/Al systems as our prototypes. The results of calorimetry and microscopy studies are interpreted using simple kinetic and morphology models. In particular, the kinetic models employed here focus on the nucleation and growth components of the phase formation process and the morphology models provide a starting point for the classification of product grain structures. An erratum to this article is available at .     

Superconductivity and magnetism in niobium doped YBa2Cu3O7 Related high Tc ceramics

Magnetic characterization has been performed on the members of the cuprateniobate RBa₂Cu₂NbO₈ (R = Pr, Nd, and La) series and R_1.5Ce_0.5Sr₂Cu₂NbO₁₀ (R = Pr, Eu, Nd, and Sm) series. The PrBCNO samples show a signature in the magnetization of a magnetic ordering at 12K. The PrCSCNO sample is nonsuperconducting and shows two distinct orderings at 17K and 53K. No such magnetic phase transition is observed down to 2K in the Nd and La based RBCNO materials or the Nd, Sm, and Eu based RCSCNO materials. Measurements of the lower critical field curve, dc irreversibility line, and critical curent densities are reported for each of the superconducting NdCSCNO, SmCSCNO, and EuCSCNO compounds.     

Thermogravimetric Study of the M-Co-O System: I, M = Ta and Nb at 1200°C

Phase equilibria in the Ta-Co-O and Nb-Co-O systems have been studied at 1200°C at oxygen partial pressures from 10^−0.68 to 10^−13.50 atm for the former and from 10^−0.68 to 10^−13.30 atm for the latter. In both systems, M₂CoO₆ and M₂Co₄O₉ are stable ternary compounds under the experimental conditions, and a new phase, Nb₅Co₂O₁₄, has been identified. The Ta-Co-O system is simple, whereas the Nb-Co-O system is somewhat more complicated because of the extra phase. The lattice constants of the ternary compounds have been determined and compared with previous values. The standard Gibbs energies of reactions have been determined using oxygen partial pressures in equilibrium with three solid phases.     

0.91Pb(Zn1/3Nb2/3)O3-0.09PbTiO3的析晶行为及助溶剂法生长

研究了0.91Pb(znl/3Nb2/3)O3-0.09PbTiO3(PZNT91/9,摩尔分数)在不同组分和配比熔盐中的析晶行为及其对晶体生长的影响。发现B2O3,PbF2等助溶剂不利于钙钛矿相的析出;而BaTiO3-PbO复合体系虽然能够促进钙钛矿相析出,但晶体析出量很少;只有适当比例的。PbO助溶剂比较适合于生长具有铁电性的钙钛矿相PZNT91/9单晶。助溶剂法生长的工艺参数为:溶质与PbO助溶剂的摩尔比为l:l,泡料温度1 150-1 200℃,泡料时间10 h,晶体生长时降温速度0.8-2℃/h,当温度降到900℃时停止生长,以50℃/h快速冷却至室温。所得晶体为琥珀色,最大尺寸达φ30 mm×15 mm,其压电系数和机电偶合系数分别为2000 pc/N和0.92。     

Development of the Acidity of Zirconia-Supported Niobia Catalysts

A series of NbO _x /ZrO₂ catalysts containing up to 2.67wt Nb (ca. 80 nominal surface coverage) was prepared by incipient wetness impregnation from niobium oxalate and oxalic acid solution. The structure of the catalysts was monitored by X-ray diffraction and Raman spectroscopy. The results indicated the presence of a surface Nb phase. No evidence for the formation of crystalline Nb₂O₅ species was found. The development of the acidity as a function of Nb loading was monitored by adsorption of a basic probe molecule followed by infrared spectroscopy. The results indicated the appearance of Brnsted acid sites for a threshold of Nb loading. The abundance of Brnsted acid sites correlated well with the isopropanol dehydration activity. The overall behavior was very similar to that reported earlier for the WO _x /ZrO₂ system.     

Oxidation and intergranular disintegration of the aluminides NiAl and NbAl3 and phases in the system Nb-Ni-Al

The oxidation behavior is very different for an aluminide with a wide homogeneity range such as -NiAl than for a line compound such as NbAl ₃.Oxidation of -NiAl at temperatures 1273 K leads to a slow-growing -alumina layer. The metal phase beneath the scale remains as -NiAl; however, cavity formation is observed. The cavity formation may be favored by sulphur surface segregation. Oxidation of NbAl ₃ at temperatures 1273 K initially leads to -Al ₂O₃,but the Al depletion causes the formation of Nb ₂ Al beneath the oxide layer. Cracking of the Al ₂O₃ layer opens Nb ₂ Al to the atmosphere, which oxidizes rapidly to Nb ₂O₅ and NbAlO₄.After consumption of the Nb ₂ Al, a layer of Al ₂O₃ formed again on the NbAl ₃ phase, but failure of the alumina and the fast growth of the other oxides occur as a repeated process. Thus, NbAl ₃ exhibited rapid linear oxidation kinetics. Multiphase alloys in the system Nb-Ni-Al generally behave better than NbAl ₃,and the low oxidation rates of -NiAl can be approached. In the temperature range below 1273 K, with a maximum at 1000 K, both NiAl and NbAl ₃ show the pest phenomenon, an intergranular disintegration. Preceding the disintegration, oxygen diffuses into the grain boundaries of the material and Al ₂O₃ is formed at the grain boundaries, beginning from the surface region. NiAl is susceptible only in a very limited range of oxygen pressures and temperatures, whereas NbAl ₃ is much more susceptible.     

Growth characteristics and kinetics of niobium carbide coating obtained on AISI 52100 by thermal-reactive diffusion technique

Niobium carbide coating was produced by thermal-reactive diffusion technique on AISI 52100 steel in salt bath at 1 123 K, 1 173 K, and 1 223 K for 1, 2, 4, and 6 hours. The salt consisted of borax, sodium fl uoride, boron carbide, and niobium pentoxide. The presence of NbC phase on the steel surface was confi rmed by X-ray diffraction analysis. Microscopic observation showed that niobium carbide coating formed on the substrate was smooth and compact. There was a distinct and fl at interface between the coating and substrate. The micro-hardness of niobium carbide coating was 2892±145HV. The thickness of coating ranged from 1.6 μm to 14μm. The forming kinetics of niobium carbide coating was revealed. Moreover, a contour diagram derived from experimental data was graphed for correct selection of process parameters. Some mathematical equations were built for predicting the coating thickness with predetermined processing temperature and time. The results showed that these mathematical equations are very practical as well as the kinetics equation.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.