Influence of iron on the synthesis and stability of yttrium silicate apatite

The stability of yttrium silicate apatite has been investigated by studying the influence of iron as a “stabilising cation” and also by using different synthesis routes. The formation of apatite in samples has been followed by X-ray diffraction and by ²⁹Si MAS NMR spectroscopy. The apatite phase appears to be stable at high temperatures (≈1700 °C) especially when heated in a nitrogen atmosphere; it can also occur in a metastable state when heated in air at lower temperatures; ≈1600 °C if prepared from a Y₂O₃SiO₂ mixture or in the range 950 °C <T< 1150 °C if synthesised by the sol–gel process. Longer heat-treatments result in its decomposition into Y₂Si₂O₇ and Y₂SiO₅. Iron appears to have two roles depending on the temperature; it stabilises the apatite phase at high temperatures when produced by the sol–gel route and catalyses the decomposition of sol–gel derived apatite at low temperatures.     

Oxidation Behaviour of A Boron Carbide Based Material in Dry and Wet Oxygen

The oxidation behaviour of a B₄C based material was investigated in a dry atmosphere O₂(20 vol.%)-CO₂(5 vol.%)-He and also in the presence of moisture H₂O (2.3 vol%) as boron oxide is very sensitive to water vapour. The mass changes of samples consisting of a chemical vapour deposit of B₄C on silicon nitride substrates were continuously monitored in the range 500–1000°C during isothermal experiments of 20 h. The stability of boron oxide formed by oxidation of B₄C was also studied in dry and wet atmospheres to explain the kinetic curves. In both atmospheres, oxidation is diffusion controlled at 700 and 800°C and enhanced by water vapour. At 900°C and higher temperatures, boron oxide volatilisation and consumption by reaction with water vapour modifies the properties of the oxide film and the material is no more protected. At 600°C, B₄C oxidation is weak but the process remains diffusion controlled in dry conditions as boron oxide volatilisation is negligible. However, in the presence of water vapour, B₂O₃ consumption rate is significant and mass losses corresponding to this consumption and to the combustion of the excess carbon are observed. This revised version was published online in August 2006 with corrections to the Cover Date.     

High-temperature oxidation behaviour of low-entropy alloy to medium- and high-entropy alloys

The high-temperature oxidation behaviour of CoCrNi, CoCrNiMn, and CoCrNiMnFe equimolar alloys was investigated. All three alloys have a single-phase face-centred cubic structure. Thermogravimetric analyses (TGA) were conducted at temperatures ranging from 800 to 1000 °C for 24 h in dry air. The kinetic curves of the oxidation were measured by TGA, and the microstructure and chemical element distribution in different regions of the specimens were analysed. The oxidation kinetics of the three alloys followed the two-stage parabolic rate law, with rate constants generally increasing with increasing temperature. CoCrNi displayed the highest resistance to oxidation, followed by CoCrNiMnFe and CoCrNiMn exhibiting the least resistance to oxidation. The addition of Mn to CoCrNi increased the oxidation rate. The oxidation resistance of CoCrNiMn was enhanced by the addition of Fe. Less Mn Content and the formation of more Cr₂O₃ were responsible for the reduction in the oxidation rates of CoCrNiMnFe. The calculated activation energies of CoCrNiMn and CoCrNiMnFe at 800, 850 and 900 °C were 108 and 137 kJ mol^?1, respectively, and are comparable to that of Mn diffusion in Mn oxides. The diffusion of Mn through the oxides at 800–900 °C is considered to be the rate-limiting process. The intense diffusion of Cr at 1000 °C contributed to the formation of CrMn_1.5O₄ spinel with Mn in the outer layer of CoCrNiMn and Cr₂O₃ in the outer layer of CoCrNiMn.     

Heat capacity of pure and doped V2O3 single crystals

Heat capacities have been measured for single crystals of V₂O₃, either pure or doped with 1 and 1.4 mole% Cr₂O₃ and Al₂O₃ over the temperature range 100–700°K. V₂O₃ undergoes a fairly sharp transition at low temperatures (～170°K) but fails to exhibit any thermal anomaly above 300°K. The thermal behavior of (M_xV_1?x)₂O₃, M = Cr, Al, is manifested by two transitions: one at low temperatures, 170–180°K for x = 0.01 and 180–190°K for x = 0.014, and the other at high temperatures. For x = 0.01, the high-temperature (HT) anomaly extended over the range 325–345°K (Cr-doped V₂O₃) and 345–365°K (Al-doped V₂O₃), respectively. The corresponding ranges for x = 0.014 were found to be 260–280°K and 270–290°K, respectively. Further, the HT anomaly was characterized by a large hysteresis (～50°K). The values of lattice heat capacity of pure and doped V₂O₃ were, however, found to be almost the same and could be empirically represented by the Debye (D)?Einstein (E) function $\text{D}\text{(}\text{580}\text{T}\text{) + 4}\text{E}\text{(}\text{θ}\text{T}\text{)}$ with θ values 430°K (T = 100–230°K) and 465°K (T > 230°K), respectively. Further, the enthalpy change ΔH associated with the HT anomaly in doped V₂O₃ (80 ≤ ΔH ≤ 510 J/mole) was 5–10 times smaller than the ΔH corresponding to the lower-temperature transition. The results cited here appear incompatible with the Mott transition model that has been invoked to explain the HT anomaly.     

Reactions between YBa2Cu3O7−δ and La2O3 and SrCO3

Solid state reactions at 925°C between the high-T _c ceramic superconductor YBa₂Cu₃O_7?δ and La₂O₃ and SrCO₃, respectively, mixed in various molar ratiosr=MeO_n/YBa₂Cu₃O_7?δ, were studied using X-ray powder diffraction and scanning electron microscopy. The reaction between YBa₂Cu₃O_7?δ and La₂O₃ yielded (La_1?xBa_x)₂CuO_4?δ, withx≈0.075?0.10. La_2?xBa_1+xCu₂O_6?δ, withx≈0.2?0.25 and La-doped (Y_1?xLa_x)₂BaCuO₅, withx≈0.10?0.15. Forr=3.0, Y-doped La₂BaCuO₅ resulted also. The reaction between YBa₂Cu₃O_7?δ and SrCO₃ yielded (Sr_1?zBa_z)₂CuO₃, withz≈0.1, Y₂(Ba_1?zSr_z)CuO₅, withz=0.1?0.15, and a nonsuperconducting compound with an approximate composition of Y(Ba_0.5Sr_0.5)₅Cu_3.5O_10±δ. At values ofr≤2.0, unsubstituted YBa₂Cu₃O_7?delta was found in the reaction products.     

Thermal Characterization and Physico-Chemical Properties of Fe2O3−Mn2O3/Al2O3 Systems

The effect of ferric and manganese oxides dopants on thermal and physicochemical properties of Mn-oxide/Al₂O₃ and Fe₂O₃/Al₂O₃ systems has been studied separately. The pure and doped mixed solids were thermally treated at 400–1000°C. Pyrolysis of pure and doped mixed solids was investigated via thermal analysis (TG-DTG) techniques. The thermal products were characterized using XRD-analysis. The results revealed that pure ferric nitrate decomposes into Fe₂O₃ at 350°C and shows thermal stability up to1000°C. Crystalline Fe₃O₄ and Mn₃O₄phases were detected for some doped solids precalcined at 1000°C. Crystalline γ-Al₂O₃ phase was detected for all solids preheated up to 800°C. Ferric and manganese oxides enhanced the formation of α-Al₂O₃ phase at1000°C. Crystalline MnAl₂O₄ and MnFe₂O₄ phases were formed at 1000°C as a result of solid–solid interaction processes. The catalytic behavior of the thermal products was tested using the decomposition of H₂O₂ reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

Oxidation resistance of LnSiON powders (Ln=Y,Gd and La)

For application of LnSiON (Ln=Y, Gd and La) oxynitride materials, e.g. as host-lattices for lamp phosphors, oxidation resistance up to about 600 °C in air is a prerequisite. In this study we prepared LnSiON (Ln=Y, Gd and La) powders by solid state reaction and observed via TGA/DTA-experiments that most compounds are oxidation resistant up to 600 °C in air. The stability in air at high temperatures increases going from Ln₅(SiO₄)₃N, Ln₄Si₂O₇N₂, LnSiO₂N, Ln₂Si₃O₃N₄ to Ln₃Si₈O₄N₁₁. This is explained by an increasing cross-linking between the siliconoxygennitrogen tetrahedra in this sequence. For the lattices with less cross-linking between the siliconoxygennitrogen tetrahedra we observed that the oxidation resistance decreases slightly going from Y and Gd to La. For these lattices, also, an additional weight gain was observed during the oxidation reaction, which was higher than expected for complete oxidation. The additional weight gain was ascribed to an intermediate phase in which nitrogen retention takes place.     

DTA-untersuchung der Umwandlungen des Amorphen Schwefels

DTA was applied to investigate amorphous sulfur samples remelted at different temperaturesT _f. For the sample remelted atT _f<159 °C, an exothermic process I occurs in the range 30–40°C. Transformation of orthorhombic to monoclinic sulfur, melting and polymerization ofS ₈ rings was observed at higher temperatures. For the sample remelted atT _f > 159 °C, a new, fast exothermic process II occurs at ambient temperature, followed by an exothermic process III at slightly higher temperature. The next, also exothermic process IV is detected in the vicinity of the melting point. The heats of the thermal effects for all the above-mentioned processes, and the part of sulfur insoluble in CS₂, were determined. An attempt was made to evaluate the mechanism of the transformations.     

Kinetics and mechanism of carbon monoxide oxidation on the supported metal complex catalyst PdCl<Subscript>2</Subscript>-CuCl<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The kinetics of carbon monoxide oxidation with atmospheric oxygen on a PdCl₂-CuCl₂/γ-Al₂O₃ catalyst was studied at T = 27°C and an N₂-O₂-CO mixture pressure of 1 atm. The catalyst was prepared by cold impregnation. Three groups of mechanistic hypotheses are considered, and two of them are demonstrated to be consistent with kinetic data, although they differ in the roles of water and oxygen in carbon monoxide oxidation.     

Contributionàl'étude du système formépar l'étain,le soufre et l'iode. Mise enévidence des deux variétés de l'iodosulfure stanneux Sn2SI2: Comportement thermique etétude structurale

We have found a new compound Mn₈O₁₀Cl₃. It is prepared by oxidation of anhydrous or hydrated MnCl₂ in streaming (N₂ + O₂) at temperatures less than 680°C. At room temperature the compound is tetragonal, a = b = 9.2898 Å, c = 13.0247 Å. The more symmetric space group is $\text{I4}\text{mmm}$. Mn₈O₁₀Cl₃ becomes cubic at 360°C with the c-axis as cubic parameter. In air, DTA and GTA have shown that Mn₈O₁₀Cl₃ is transformed at 580°C into Mn₂O₃ which gives Mn₃O₄ at 960°C. The exact formula has been determined only by crystal structure analysis.     

Beiträge zum Chemischen Transport oxidischer Metallverbindungen. II. Bemerkungen zum Transport von α-Fe2O3 über monomeres Eisen(III)-chlorid

Transport of α? Fe₂O₃ with HCl via monomeric iron(III) chloride according to Fe₂O_3(s) + 6 HCl_(g) = 2FeCl_3(g) + 3 H₂O_(g); T₂ → T₁ between T₂ = 1000°C and T₁ = 800°C in the region of diffusion produced crystals which contained, in dependence of total pressure, different amounts of divalent iron. By addition of oxygen to the transport gas stoichiometric crystals of hematite by otherwise unchanged conditions were obtained. The necessary amount of oxygen was calculated from the phase diagram Fe? O, and an explanation of the gas phase reactions is given. Dependence of the transport rate of hematite on total pressure in the region of diffusion (0.009 to 6 atm) is reported.     

Recativity of solid silicon with hydrogen under conditions of a low pressure plasma

The reactivity of solid silicon with a dydrogen has been studied in a temperature range between about 10°C and ≈540°C at discharge currents up to ≈420 mA and a pressure of ≈0.13 mbar (0.1 torr). At a given current the reaction rate displays a pronounced maximum at a temperature T₁ ? 60°C and it approaches zero at T₂ ? 300°C; both T₁ and T₂ d pending on the discharge current. Consequently, chemical transport of silicon is possible in temperature as well as plasma gradients.     

Preparation of HPEEK by Oligomer A2+B3 Approach

A series of hyperbranched poly(ether ether ketones) with different chain length between branching point (L) were prepared using a A₂+B₃ methodology, in which the A₂ is hydroxyl‐terminated PEEK oligomer. The L affects the properties of the polymers such as the inherent viscosity, the degree of crystallinity, the thermal properties of the polymers etc. The polymer with a L₂≈8 had T _g (122.4°C), T _c (200.2°C), and broad T _m (247.4°C). With the increment of L, up to the point L₂≈20 and L₂≈35, the polymers become semi‐crystalline, with a melting point of 300.9°C and 317.9°C, respectively. Their wide angle X‐ray scattering (WAXS) pattern indicated that their crystal structure is exactly the same as that of the linear homopolymer.     

Preparation and TG—DTA analysis of manganese silicon nitride

Manganese silicon nitride was prepared quantitatively as a precipitated phase by treating a Mn; Si-alloy (Mn: 1.84 w/o, Si: 1.12 w/o) in a mixture of 2% NH₃ and H₂ at 700°C. Nitriding was carried out in situ in a thermobalance and the nitrogen uptake was recorded as a function of time. The nitride phase was isolated and investigated by means of the combined TG-DTG-DTA technique both in an atmosphere of nitrogen at 25–1600°C and in a mixture of Ar+O₂ (p_O2 = 0.20 atm) at 25–1000°C. In the nitrogen atmosphere MnSiN₂ appears to be stable up to 1000°C. Oxidising the nitride in the Ar/O₂ mixture caused three distinct exothermic processes to occur at characteristic temperatures. The final oxidation products as identified by diffractometry and IR-spectroscopy are manganese oxide silicate (braunite) and silicon dioxide.     

High pressure and high temperature investigations in the system MgOSiO2H2O

The system MgOSiO₂H₂O was investigated at pressures between 40 and 95 kbar and at temperatures between 500 and 1400°C. The reaction products were examined by X-ray, optical and thermal analysis techniques and the density of phase A discovered by Ringwood and Major was also measured. It was found that phase A was hydrated and its chemical formula was H₆Mg₇Si₂O₁₄. When the $\text{Mg}\text{Si}$ ratio of the system is 2, phase A + clinoenstatite, and forsterite are stable at temperatures lower and higher than a boundary curve T (°C) = 10P (kbar), respectively. When the $\text{Mg}\text{Si}$ ratio of the system is 3, phase A + phase D (which is completely different from the phases, A, B and C discovered by Ringwood and Major, and any other known phases of magnesium silicate) and phase D + brucite are stable at temperatures lower and higher than a boundary curve T(°C) = 10P (kbar) + 200. Phase A has approximately an hexagonal symmetry and the space group and the lattice parameters are determined as P6₃ or $\text{P6}{}_3\text{m}$ and a = 7.866(2) Å and c = 9.600(3) Å, respectively. The measured density is 2.96 ± 0.02 g/cm³. The optical observations show that phase A is biaxial positive crystal with refractive indices α = 1.638 ± 0.001, β = 1.640 ± 0.002, and γ = 1.649 ± 0.001. Some interpretation is given on the inconsistency between the symmetry determined by the X-ray diffraction and the optical observation. The new phase D belongs to the space group $\text{P2}{}_1\text{c}$ with lattice parameters a = 7.914(2)Å, b = 4.752(1) Å, c = 10.350(2) Å and β = 108.71(5)° and is a biaxial crystal with refractive indices α = 1.630 ± 0.002, β = 1.642 ± 0.002 and γ = 1.658 ± 0.001.     

Effects of doping with CeO2 and calcination temperature on physicochemical properties of the NiO/Al2O3 system

The effects of doping with CeO₂ and calcination temperature on the physicochemical properties of the NiO/Al₂O₃ system have been investigated using DTA, XRD, nitrogen adsorption measurements at −196°C and decomposition of H₂O₂ at 30–50°C. The pure and variously doped solids were subjected to heat treatment at 300, 400, 700, 900 and 1000°C. The results revealed that the specific surface areas increased with increasing calcination temperature from 300 to 400°C and with doping of the system with CeO₂. The pure and variously doped solids calcined at 300 and 400°C consisted of poorly crystalline NiO dispersed on γ-Al₂O₃. Heating at 700°C resulted in formation of well crystalline NiO and γ-Al₂O₃ phases beside CeO₂ for the doped solids. Crystalline NiAl₂O₄ phase was formed starting from 900°C. The degree of crystallinity of NiAl₂O₄ increased with increasing the calcination temperature from 900 to 1000°C. An opposite effect was observed upon doping with CeO₂. The NiO/Al₂O₃ system calcined at 300 and 400°C has catalytic activity higher than individual NiO obtained at the same calcination temperatures. The catalytic activity of NiO/Al₂O₃ system increased, progressively, with increasing the amount of CeO₂ dopant and decreased with increasing the calcination temperature.     

Survey of the phase formation in the Yb2O3Ga2O3MO and Yb2O3Cr2O3MO systems in air at high temperatures (M: Co,Ni, Cu,and Zn)

The phase relations in the Yb₂O₃Ga₂O₃CoO system at 1300 and 1200°C, the Yb₂O₃Ga₂O₃NiO system at 1300 and 1200°C, the Yb₂O₃Ga₂O₃CuO system at 1000°C and the Yb₂O₃Ga₂O₃ZnO system at 1350 and 1200°C, the Yb₂O₃Cr₂O₃CoO system at 1300 and 1200°C, the Yb₂O₃Cr₂O₃NiO system at 1300 and 1200°C, the Yb₂O₃Cr₂O₃CuO system at 1000°C, and the Yb₂O₃Cr₂O₃ZnO system at 1300 and 1200°C were determined in air by means of a classical quenching method. YbGaCoO₄ (a = 3.4165(1) and c = 25.081(2) Å), YbGaCuO₄ (a = 3.4601(4) and c = 24.172(6) Å), and YbGaZnO₄ (a = 3.4153(5) and c = 25.093(7) Å), which are isostructural with YbFe₂O₄ (space group: $\text{R}\text{3}\text{m, a = 3.455(1)}$ and c = 25.109(2) Å, were obtained as stable phases. In the Yb₂O₃Ga₂O₃NiO system and the Yb₂O₃Cr₂O₃MO system (M: Co, Ni, Cu, and Zn), no ternary stable phases existed.     

Excellent complete conversion activity for methane and CO of Pd/TiO2-Zr0.5Al0.5O1.75 catalyst used in lean-burn natural gas vehicles

Palladium catalysts are supported on TiO₂, ZrO₂, Al₂O₃, Zr_0.5Al_0.5O_1.75 and TiO₂-Zr_0.5Al_0.5O_1.75 prepared by co-precipitation method, respectively. Catalytic activities for methane and CO oxidation are evaluated in a gas mixture that simulated the exhaust from lean-burn natural gas vehicles (NGVs). Pd/TiO₂-Zr_0.5Al_0.5O_1.75 performs the best catalytic activity among the tested five catalysts. For CH₄, the light-off temperature (T₅₀) is 254 °C, and the complete conversion temperature (T₉₀) is 280 °C; for CO, T₅₀ is 84 °C, and T₉₀ was 96 °C. Various techniques, including N₂ adsorption-desorption, X-ray diffraction (XRD), H₂-temperature-programmed reduction (H₂-TPR), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM) are employed to characterize the effect of supports on the physicochemical properties of prepared catalysts. N₂ adsorption-desorption and SEM show that TiO₂-Zr_0.5Al_0.5O_1.75 expresses uniform nano-particles and large meso-pore diameters of 26 nm. H₂-TPR and XRD indicate that PdO is well dispersed on the supports and strongly interacted with each other. The results of XPS show that the electron density around PdO and the proportion of active oxygen on TiO₂-Zr_0.5Al_0.5O_1.75 are maxima among the five supports.     

Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si₃N₄ and Si₂N₂O are formed as the nitridation products in the samples. Fibroid and short columnar Si₃N₄ are detected in the samples. The formation mechanisms of Si₃N₄ and Si₂N₂O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O₂ in N₂ atmosphere, forming a thin film of SiO₂ on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO₂ film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO₂ film will crack, and N₂ is infiltrated into the central section of the sample through cracks, generating Si₂N₂O and short columnar Si₃N₄ in situ. At the same time, metastable SiO(g) reacts with N₂ and form fibroid Si₃N₄. In the regions where the oxygen partial pressure is high, Si₃N₄ is oxidized into Si₂N₂O.     

Synthesis and Crystal Structure of the Nitridosilicates Ca5[Si2N6] and Ca7[NbSi2N9]

Ca₅[Si₂N₆] and Ca₇[NbSi₂N₉] were obtained by reaction of Ca₃N₂, Ca₂N and Si₃N₄ (with addition of niobium powder in case of Ca₇[NbSi₂N₉]) in closed tantalum ampoules at temperatures at 1060 °C and 1000 °C, respectively. Ca₅[Si₂N₆] is monoclinic C2/c with a = 983.6(2) pm, b = 605.2(1) pm, c = 1275.7(3), β = 100.20(3)° and Z = 4 crystallising homotypically to Ba₅[Si₂N₆]. The crystal structure contains pairs of edgesharing SiN₄ tetrahedra forming isolated nitridosilicate anions of [Si₂N₆]^10?. Ca₇[NbSi₂N₉] is monoclinic P2₁/m with a = 605.1(1), b = 994.6(2), c = 899.7(2), β = 92.10(1)°, Z = 2 and crystallises in an hitherto unknown structure type. Ca₇[NbSi₂N₉] contains isolated anions [NbSi₂N₉]^14? which are composed of two edgesharing SiN₄ tetrahedra and an edge‐sharing NbN₅ pyramid. So far, such a pseudotrisilicate unit has not been observed in the family of silicates.