Authors:R. Frost, J. Bouzaid, A. Musumeci, J. Kloprogge, and W. Martens
stability and thermal decomposition pathways for synthetic iowaite have been
determined using thermogravimetry in conjunction with evolved gas mass spectrometry.
Chemical analysis showed the formula of the synthesised iowaite to be Mg6.27Fe1.73(Cl)1.07(OH)16(CO3)0.336.1H2O
and X-ray diffraction confirms the layered structure. Dehydration of the iowaite
occurred at 35 and 79C. Dehydroxylation occurred at 254 and 291C.
Both steps were associated with the loss of CO2. Hydrogen
chloride gas was evolved in two steps at 368 and 434C. The products of
the thermal decomposition were MgO and a spinel MgFe2O4.
Experimentally it was found to be difficult to eliminate CO2
from inclusion in the interlayer during the synthesis of the iowaite compound
and in this way the synthesised iowaite resembled the natural mineral.
Authors:L. Gonsalves, V. Verenkar, and S. Mojumdar
A good precursor is foremost in the preparation of nanosized metal or mixed metal oxides. In the present study a novel precursor,
cobalt zinc fumarato-hydrazinate Co0.5Zn0.5Fe2(C4H2O4)3·6N2H4 has been prepared which decompose at a much lower temperature to give nanosized mixed-metal oxides. X-ray investigations,
confirms the formation of single spinel phase. The FTIR spectra show N-N stretching vibration at 965 cm−1 which confirms the bidentate bridging hydrazine. The thermal decomposition of the precursor has been studied by isothermal,
thermogravimetric and differential scanning calorimetric analysis. The precursor shows two-step dehydrazination followed by
decarboxylation to form Co0.5Zn0.5Fe2O4, the chemical analysis of the sample is corroborative of this.
From a model for isothermal oxidation kinetics in nanosized ferrite spinels based on a diffusion-induced stress effect, the
authors present a modeling of the DTG curves for the oxidation of Fe2+ and Mo3+ cations on octahedral sites of a molybdenum ferrite. This has been made by considering that the chemical diffusion coefficient
is given by the relation
Mössbauer effect technique has been used for the comparative study of Cu1−xZnxFe2O4 and Cu1−xCdxFe2O4 (x = 0.0−1.0) ferrites. Both Zn2+ and Cd2+ cations are divalent, non-magnetic ions with different ionic radii. With the substitution of these non-magnetic cations the
average internal magnetic field decreases and paramagnetic behavior is dominated at x = 0.7 in both series. It is observed that the occupancy of Cu2+ ions for tetrahedral site is not constant for all compositions but fluctuate between 8–15%. It is also found that Cu2+ ions have more preference for tetrahedral site in Cu-Zn system as compared to the Cu-Cd system. Zn2+ and Cd2+ both ions occupy tetrahedral site completely and form normal spinels for x = 1.0.
Authors:K. Barcova, M. Mashlan, R. Zboril, and P. Martinec
The transformation mechanism of Fe cations in natural olivine after thermal treatments in air has been studied using mainly57Fe Mössbauer spectroscopy. -Fe2O3 nanoparticles appear as the primary Fe3+ phase in Mössbauer spectra of olivine samples heated at 600-900 °C. These nanoparticles are thermally unstable and they are transformed to -Fe2O3 with the increase of heating time. Another transformation mechanism of iron related with the complete decomposition of olivine structure has been observed at temperatures of 1000 °C and higher. The mixed oxide MgFe2O4 with the spinel structure and enstatite MgSiO3 were identified as iron-bearing decomposition products.
Authors:J. M. Bouzaid, R. L. Frost, A. W. Musumeci, and W. N. Martens
stability and thermal decomposition pathways for synthetic woodallite have
been determined using thermogravimetry in conjunction with evolved gas mass
spectrometry. Chemical analysis showed the formula of the synthesised woodallite
to be Mg6.28Cr1.72Cl(OH)16(CO3)0.36⋅8.3H2O and X-ray diffraction confirms the layered
LDH structure. Dehydration of the woodallite occurred at 65C. Dehydroxylation
occurred at 302 and 338C. Both steps were associated with the loss of
carbonate. Hydrogen chloride gas was evolved over a wide temperature range
centred on 507C. The products of the thermal decomposition were MgO and
a spinel MgCr2O4. Experimentally
it was found to be difficult to eliminate CO2 from
inclusion in the interlayer during the synthesis of the woodallite compound
and in this way the synthesised woodallite resembled the natural mineral.
Kinetics of oxidation of Fe-Cr steel containing 25 wt.-percent Cr was studied as a function of temperature (1023–1173 K) for
up to 480 h in flowing air, which corresponds to SOFC cathode environment operating conditions. The oxidation process was
found to be a parabolic, suggesting that the diffusion of ionic defects in the scale is the slowest, rate determining step
and it occurs predominantly by short-circuit diffusion paths. Comparison of the determined activation energy of oxidation
of the studied steel with literature data indicates that at 1098–1173 K the chromia scale grows by the outward solid-state
diffusion of chromium interstitials, whereas at 1023–1098 K — through a significant contribution of counter-current oxygen/chromium
diffusion along Cr2O3 grain boundaries. The oxide scales were composed mainly of Cr2O3 with a continuous thin Mn1.5Cr1.5O4 spinel layer on top of the chromia scale. The oxidation test results on Fe-25Cr steel demonstrate the applicability of the
commercial type DIN 50049 stainless steel as interconnect for SOFC.
Authors:Szabolcs Harangi, Sonia Tonarini, Orlando Vaselli, and Piero Manetti
In Central Europe, Early Cretaceous alkaline igneous rocks (lamprophyres, basanites, phonolites) occur in the Moravian-Silesian Beskidy area (northern Czech Republic and southern Poland) and in the Mecsek-Alföld Zone (southern Hungary). Presently they are located at about 400 km distance of each other. These alkaline igneous rocks show close similarities in their mineral, chemical, and bulk rock compositional data, implying similar petrogenesis and suggesting that these two regions could have been much closer during the Early Cretaceous; they could belong to the same rift zone in the European continental margin. Their trace element distribution and Sr and Nd isotopic ratios suggest that the parental magmas derived from an enriched, HIMU OIB-like asthenospheric mantle by different degrees (3-6%) of partial melting at the depth of spinel-garnet transitional and garnet stabilization zone (about 60-80 km depth). This mantle source appears to be akin to that thought to have supplied the Tertiary to Quaternary alkaline mafic magmas in Europe (EAR=European Asthenospheric Reservoir). This may imply that this EAR-type mantle reservoir could have been present beneath Europe at least since the Early Cretaceous. It could reside at the base of the upper mantle (670 km discontinuity) supplying upwelling hot mantle fingers, or it may represent a long-lasting, polluted (HIMU+depleted MORB mantle) upper mantle at shallow depth beneath Europe.
Thermal analysis complimented with evolved gas mass spectrometry has been applied to hydrotalcites containing carbonate prepared
by coprecipitation and with varying divalent/trivalent cation ratios. The resulting materials were characterised by XRD, and
TG/DTG to determine the stability of the hydrotalcites synthesised. Hydrotalcites of formula Mg4(Fe,Al)2(OH)12(CO3)·4H2O, Mg6(Fe,Al)2(OH)16(CO3)·5H2O, and Mg8(Fe,Al)2(OH)20(CO3)·8H2O were formed by intercalation with the carbonate anion as a function of the divalent/trivalent cationic ratio.
XRD showed slight variations in the d-spacing between the hydrotalcites. The thermal decomposition of carbonate hydrotalcites
consists of two decomposition steps between 300 and 400°C, attributed to the simultaneous dehydroxylation and decarbonation
of the hydrotalcite lattice. Water loss ascribed to dehydroxylation occurs in two decomposition steps, where the first step
is due to the partial dehydroxylation of the lattice, while the second step is due to the loss of water interacting with the
interlayer anions. Dehydroxylation results in the collapse of the hydrotalcite structure to that of its corresponding metal
oxides and spinels, including MgO, MgAl2O4, and MgFeAlO4.
A series of samples in the system Ni0.65Zn0.35CuxFe2−xO4 (x=0.0, 0.1, 0.2, 0.3, 0.4 and 0.5) were prepared by the usual ceramic technique. X-ray analysis showed that they were cubic spinel (single phase). Young's modulus, the dielectric loss and the change in capacitance under mechanical stress were measured for the samples. Young's modulus decreased with increasing Cu content. This is due to the fact that Cu2+ ions entered the lattice substitutionally for Fe3+ ions at the octahedral sites, creating lattice vacancies gave rise to lattice strain.