Studies on vacuum pyrolysis of ammonium perchlorate and ammonium perchlorate/polystyrene propellant in the presence of transition metal oxides

Vacuum pyrolysis of ammonium perchlorate (AP) and ammonium perchlorate/polystyrene (PS) propellant has been studied by differential thermal analysis (DTA) in order to observe the effect of transition metal oxides on sublimation. Sublimation and decomposition being competitive processes, their proportions depend on the pressure of the pyrolysis chamber. The enthalpies for complete decomposition and complete sublimation are available from the literature and by using these data together with DTA area measurements, the extents of sublimation and decomposition have been calculated for AP and the propellant system. The effect of the metal ions on the extent and rate of sublimation depends on their nature. For AP the extent of sublimation increases with a decrease in particle size. For the propellants the powder sublimes more readily than the bulk material, but in the presence of metal ions the bulk material sublimes more readily than the powder. To substantiate this finding, the effect of MnO2 on AP sublimation as a function of particle size was examined, and it was observed that the extent of sublimation decreases as the particle size decreases.

The role of transition metal oxides in the decomposition and explosion of arylammonium perchlorates

The influence of MnO2, CuO, and NiO on the thermal decomposition and explosivity of arylammonium perchlorates has been studied by differential thermal analysis (DTA) and explosive sensitivity measurements. The metal oxides considerably sensitize both decomposition and explosion and the sensitizing effect is in the order NiO < CuO < MnO2. The accelerated decomposition or explosion seems to occur via the formation of an intermediate, metal perchlorate arylamine complex. The experimental evidence for the mechanism put forward has been included.

Mechanistic studies on the pyrolysis and combustion of polystyrene/ammonium perchlorate propellants in the presence of transition metal oxides

The effect of transition metal oxides (Fe2O3, MnO2, Ni2O3 and Co2O3) on polystyrene/ammonium perchlorate propellant systems has been examined. The mechanism of action of the oxides in increasing the burning rate was examined by studying the effect of the oxides on the thermal decomposition and combustion of the oxidizer and the propellant. It has been concluded that one of the mechanisms by which the oxides act is by promoting the charge-transfer process, which is indicated by the enhancement of the electron-transfer process in ammonium perchlorate and by the correlation between the redox potential of the metal ions and the corresponding burning rates of the propellant.

Noble Metal Ionic Catalysts

Because of growing environmental concerns and increasingly stringent regulations governing auto emissions, new more efficient exhaust catalysts are needed to reduce the amount of pollutants released from internal combustion engines. To accomplish this goal, the major pollutants in exhaust-CO, NOx, and unburned hydrocarbons-need to be fully converted to CO2, N-2, and H2O. Most exhaust catalysts contain nanocrystalline noble metals (Pt, Pd, Rh) dispersed on oxide supports such as Al2O3 or SiO2 promoted by CeO2. However, in conventional catalysts, only the surface atoms of the noble metal particles serve as adsorption sites, and even in 4-6 nm metal particles, only 1/4 to 1/5 of the total noble metal atoms are utilized for catalytic conversion. The complete dispersion of noble metals can be achieved only as ions within an oxide support. In this Account, we describe a novel solution to this dispersion problem: a new solution combustion method for synthesizing dispersed noble metal ionic catalysts. We have synthesized nanocrystalline, single-phase Ce1-xMxO2-delta and Ce1-x-yTiyMxO2-delta (M = Pt, Pd, Rh; x = 0,01-0.02, delta approximate to x, y = 0.15-0.25) oxides in fluorite structure, In these oxide catalysts, pt(2+), Pd2+, or Rh3+ ions are substituted only to the extent of 1-2% of Ce4+ ion. Lower-valent noble metal ion substitution in CeO2 creates oxygen vacancies. Reducing molecules (CO, H-2, NH3) are adsorbed onto electron-deficient noble metal ions, while oxidizing (02, NO) molecules are absorbed onto electron-rich oxide ion vacancy sites. The rates of CO and hydrocarbon oxidation and NOx reduction (with >80% N-2 selectivity) are 15-30 times higher in the presence of these ionic catalysts than when the same amount of noble metal loaded on an oxide support is used. Catalysts with palladium ion dispersed in CeO2 or Ce1-xTixO2 were far superior to Pt or Rh ionic catalysts. Therefore, we have demonstrated that the more expensive Pt and Rh metals are not necessary in exhaust catalysts. We have also grown these nanocrystalline ionic catalysts on ceramic cordierite and have reproduced the results we observed in powder material on the honeycomb catalytic converter. Oxygen in a CeO2 lattice is activated by the substitution of Ti ion, as well as noble metal ions. Because this substitution creates longer Ti-O and M-O bonds relative to the average Ce-O bond within the lattice, the materials facilitate high oxygen storage and release. The interaction among M-0/Mn+, Ce4+/Ce3+, and Ti4+/Ti3+ redox couples leads to the promoting action of CeO2, activation of lattice oxygen and high oxygen storage capacity, metal support interaction, and high rates of catalytic activity in exhaust catalysis.

Metal Auger Intensity Ratios in Transition Metals and Their Compounds

Metal Auger intensity ratios of the type Z(CVV)/I(CC'V) and Z(CVV)/Z(CC'C"), where C, C' and C" denote core levels and V stands for a valence level, are shown to increase progressively with the number of valence electrons in the metal in the case of second-row transition metals and their oxides. Metal Auger intensity ratios in chalcogenides of transition metals can be correlated by taking the effective atomic charge on the metal into consideration. The possible use of metal Auger intensity ratios in the study of surface oxidation of second-row transition metals is illustrated in the case of zirconium.

Structures of mannose-6-phosphate isomerase from Salmonella typhimurium bound to metal atoms and substrate: implications for catalytic mechanism

Mannose-6-phosphate isomerase (MPI) catalyzes the inter-conversion of mannose 6-phosphate and fructose 6-phosphate. X-ray crystal structures of MPI from Salmonella typhimurium in the apo form (with no metal bound) and in the holo form (with bound Zn2+) and two other structures with yttrium bound at an inhibitory site and complexed with Zn2+ and fructose 6-phosphate (F6P) were determined in order to gain insights into the structure and the isomerization mechanism. Isomerization involves acid/base catalysis with proton transfer between the C1 and C2 atoms of the substrate. His99, Lys132, His131 and Asp270 are close to the substrate and are likely to be the residues involved in proton transfer. The interactions observed at the active site suggest that the ring-opening step is probably catalyzed by His99 and Asp270. An active-site loop consisting of residues 130-133 undergoes conformational changes upon substrate binding. Zn2+ binding induces structural order in the loop consisting of residues 50-54. The metal atom appears to play a role in substrate binding and is probably also important for maintaining the architecture of the active site. Isomerization probably follows the previously suggested cis-enediol mechanism.

An elegant direct route for the preparation of pyridinium, ammonium and alkali metal hexafluorotitanates (IV)

Pyridinium hexafluorotitanate (IV) has been prepared by a one step procedure. Addition of titanium tetrachloride to pyridinium poly(hydrogen fluoride) yields nearly quantitative amounts of pyridinium hexafluorotitanate(IV). Making use of pyridinium hexafluorotitanate as precursor, ammonium and alkali metal (Na, K, Rb, and Cs) hexafluorotitanates have been prepared in good yields. These salts have been characterised by IR, N.M.R. (1H, 13C and 19F), X-ray powder diffraction data and chemical analysis.

Pyridinium poly(hydrogen fluoride). A versatile fluorinating reagent preparation and characterization of nonmetal and metal complex fluoro salts

Abstract is not available.

Small nickel metal particles in Ni---Al2O3 metal-ceramic composites

Magnetic measurements have been used in combination with transmission electron microscopy to investigate small nickel metal particles in metal-ceramic composites. Estimates of the average number of atoms in the particles are given for nonmagnetic samples with low Ni content.

Low cycle fatigue behaviour of a low interstitial Ni-base superalloy

The low cycle fatigue behaviour of precipitation strengthened nickel-base superalloy 720Li containing a low concentration of interstitial carbon and boron was studied at 25, 400 and 650 degrees C. Cyclic stress response at all temperatures was stable under fully reversed constant total strain amplitude (Delta epsilon/2) when Delta epsilon/2 <= 0.6%. At Delta epsilon/2 > 0.6%, cyclic hardening was followed by softening, until fracture at 25 and 650 degrees C. At 400 degrees C, however, cyclic stress plateaued after initial hardening. Dislocation-dislocation interactions and precipitate shearing were the micromechanisms responsible for the cyclic hardening and softening, respectively. The number of reversals to failure vs. plastic strain amplitude plot exhibits a bilinear Coffin-Manson relation. Transmission electron microscopy substructures revealed that planar slip was the major deformation mode under the conditions examined. However, differences in its distribution were observed to be the cause for the bilinearity in fatigue lives. The presence of fine deformation twins at low Delta epsilon/2 at 650 degrees C suggests the role of twinning in homogenization of cyclic deformation.

Synthesis and Characterisation of Metal Hydrazine Nitrate, Azide and Perchlorate Complexes

Metal hydrazine nitrate complexes of the type M(N2H4)Nn (NO3)2 where M = Mg, n = 2; M = Mn, Fe, Co, Ni, Zn and Cd and n = 3; metal dihydrazine azide complexes of the type M(N2H4)2 (N3)2 where M = Mg, Co, Ni and Zn; and Mg(N2H4)2 (C1O4)2 have been prepared by dissolving the respective metal powders in the solution of corresponding ammonium salts (NO3, N3 and C1O4) in hydrazine hydrate. These hydrazine complexes were also prepared by the conventional method involving the addition of alcoholic hydrazine hydrate to the aqueous solution of metal salts. The hydrazine complexes have been characterised by chemical analysis, infrared spectra and differential thermal analysis (DTA). Impact sensitivities of hydrazine complexes were determined by the drop weight method. The reactivity of these hydrazine complexes does not change with the method of preparation.

Automated estimation of fatigue crack length and closure/opening stress

An experimental technique is proposed for the estimation of crack length as well as crack closure/opening stress during fatigue crack growth. A specially designed, single cantilever, crack opening displacement gauge is used to monitor these variables during fatigue crack propagation testing. The technique was experimentally validated through electronfractography.

Doping Dependence of Semiconductor-Metal Transition in InP at High Pressures

The resistivity of selenium-doped n-InP single crystal layers grown by liquid-phase epitaxy with electron concentrations varying from 6.7 x 10$^18$ to 1.8 x 10$^20$ cm$^{-3}$ has been measured as a function of hydrostatic pressure up to 10 GPa. Semiconductor-metal transitions were observed in each case with a change in resistivity by two to three orders of magnitude. The transition pressure p$_c$ decreased monotonically from 7.24 to 5.90 GPa with increasing doping concentration n according to the relation $p_c = p_o [1 - k(n/n_m)^a]$, where n$_m$ is the concentration (per cubic centimetre) of phosphorus donor sites in InP atoms, p$_o$ is the transition pressure at low doping concentrations, k is a constant and $\alpha$ is an exponent found experimentally to be 0.637. The decrease in p$_c$ is considered to be due to increasing internal stress developed at high concentrations of ionized donors. The high-pressure metallic phase had a resistivity (2.02-6.47) x 10$^{-7}$ $\Omega$ cm, with a positive temperature coefficient dependent on doping.