Temperature dependence of the cation distribution in nickel aluminate (NiAl2O4) spinel: a powder XRD study

NiAl₂O₄ is a largely inverse spinel, which in detail shows increasing randomisation with temperature of Ni and Al between the octahedral and tetrahedral cation sites of the spinel structure. We have used powder XRD to determine this cation distribution in various samples of NiAl₂O₄ quenched after annealing between 700 and 1400° C. The inversion parameter (x) can be measured with a precision of ± 0.004 (one standard deviation), and a comparison of different methods of synthesis, X-ray diffraction and refinement techniques, suggests a probable accuracy of better than 0.01. The results are supported by some preliminary single crystal refinements on flux-grown samples.Below 800° C the rate of cation ordering becomes very slow, and, despite reaching an apparently steady state, it is doubtful if our samples attained complete internal equilibrium. Above 1250° C the cation redistribution becomes so fast that the quenching method becomes unreliable. Between 800 and 1250° C inclusive, the degree of inversion changes smoothly from 0.87 at 800° C to 0.79 at 1250° C, and is accompanied by linear changes in u, the oxygen parameter, from 0.2555 to 0.2563 (±0.0002), and a₀, the lattice parameter, from 8.0462 to 8.0522 Å (±0.0002 Å).     

Biochemische Abbaubarkeit ausgewählter alicyclischer Verbindungen

Thirteen alicyclic compounds (C₅… C₇) are examined for their biochemical degradability in a laboratory activating tank and in two respirometers (Warburg, Sapromat). The tests were performed with adapted and nonadapted activated sludge. In addition, the COD was determined by three different methods. With the exception of cycloheptane (BOD < 25% of the BOD_theor.), six compounds prove to be easily degradable (BOD > 45% of the BOD_theor.) and six compounds prove to be degradable (BOD 45… 25% of the BOD_theor.).     

Thermodynamics of Co3O4: a possible electron spin unpairing transition in Co3+

The free energy of the reaction: $$Co_3 O_4 \rightleftarrows 3C_O O + \tfrac{1}{2}O_2$$ has been studied between 890 and 1,240 K using an e.m.f. technique. There is a phase transition in Co₃O₄ at 1,120±20 K which is accompanied by a large change in entropy (～47 JK^?1 mol^?1 of Co₃O₄), and a rapid increase in unit cell volume and in electical conductivity. This is interpreted to be due to a partial change in electronic spin states in Co^{3 +} from the spin-paired (low spin) configuration observed at room temperature to the spin-unpaired (high spin) state. The transition is probably not first order.     

Intergrowth of pyroxene and pyroxenoid; chain periodicity faults in pyroxene

Intergrowth of clinopyroxenes (augite, A) and pyroxenoids (Fe-rhodonite and pyroxferroite, Pxo) was observed by transmission electron microscopy. The following orientation relationship was found: (001)_Pxo is parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)_{\text{A}}\) and \([1\bar 10]_{Pxo}\) is parallel to [011]_A. This relationship can be explained by similarities of the structures of clinopyroxenes and pyroxenoids. It contradicts a suggestion based on structural arguments of Koto et al. (1976). Chain periodicity faults parallel to \((1\mathop {\bar 1}\limits^ + \bar 1)\) are also observed in pure clinopyroxenes.     

Structure of the upper mantle in the Northeastern Atlantic close to the azores-gibraltar ridge from surface-wave and body-wave observations

Phase velocities of teleseismic Rayleigh waves have been measured in the central North Atlantic on both sides of the Azores-Gibraltar Ridge (AGR) by means of a specially designed long-period station network. The dispersion data obtained were regionalized and then subjected to a “hedgehog” inversion, which gives a set of upper mantle models compatible with the observational data within specified error bounds.Reasonable model solutions were selected by using regional body-wave observations, such as P_n- and S_n-wave velocities determined from earthquakes along the AGR. The S_(itn) velocities measured indicate that the shear-wave velocity in the mantle part of the lithosphere is much higher on the northern side of the AGR. Strongly negative P-wave residuals in this area indicate faster seismic propagation than implied by the Jeffreys-Bullen travel-time tables, while propagation is much slower in the Gulf of Cadiz area. Furthermore the residuals show a clear difference for paths through oceanic and continental domains and suggest that the transition between these two domains extends much further into the ocean on the southern side of the AGR than on the northern side.The proposed model for the structure of the upper mantle in that region shows that there exists a pronounced velocity contrast across the AGR. Thickening of the lithospheric plate with increasing plate age is indicated to the south of the ridge. The greatest thickness is reached close to the continental margin within a zone about 500 km wide, whose velocity close to the Canary Islands and Madeira is significantly lower, probably due to the well-known volcanic activity there. These observations together with the travel time residuals reveal that this zone seems to be of a transitional nature somewhere between a continental and oceanic structure.