High temperature oxidation of HP40 alloy under H2–H2O and air atmospheres: a surface study

In the present work, high temperature oxidation of HP40 alloy was carried out at 1050 °C under H₂–H₂O and air atmospheres; the influence of atmosphere on surface morphology and composition was studied. Octahedral crystals with considerable spalled regions are present on the surface of alloy oxidized under air, the oxide scale composes of MnCr₂O₄, Cr₂O₃ and (Fe, Ni)Cr₂O₄ and spalled regions exhibit base alloy and SiO₂‐rich regions. The surface of alloy oxidized under H₂–H₂O is fully covered by small granular crystals and blade‐type structures without spallation, and the oxide scale composes of MnCr₂O₄ and Cr₂O₃. Moreover, X‐ray photoelectron spectroscopy analysis shows considerable difference in chemical valence states of Mn, Cr and O elements on both alloy surfaces, and hydroxyl compounds exist on the alloy oxidized under H₂–H₂O atmosphere. Copyright © 2017 John Wiley & Sons, Ltd.     

A novel spinel coating on cobalt‐based Superalloy GH605 via an in‐situ oxidation approach

Cr‐Mn‐O spinel coating was prepared on the surface of cobalt‐based superalloy GH605 via an in‐situ oxidation method in H₂O‐H₂ environment. The composition, morphology, and chemical value state of the oxide spinel coatings were investigated by SEM, EDS, XRD, Raman spectra, and XPS. It indicated that the morphology of coating varied with oxidation temperature, and granular surface appeared when oxidation temperature increased to 1100°C. The formed Cr‐Mn‐O spinel coating was composed of Cr₂O₃ and MnCr₂O₄, and the thickness increased significantly with oxidation temperature. In the coating, Cr element existed in the state of Cr³⁺ ions and Cr⁶⁺ ions, while Mn element only existed in the form of Mn²⁺ ions.     

Surface Characterization and the Gas Response of a Mixed,Fe2O3?Fe2(MoO4)3, Oxide to Low Concentrations of H2S in Air

The preparation and H₂S sensing potential of thick‐films of a mixed oxide, Fe₂O₃? Fe₂(MoO₄)₃, were investigated. A Fourier‐transform infrared (FTIR) study confirmed the existence of sulfur species at the surface after the interaction of H₂S gas with the mixed oxide. The starting material, β‐FeMoO₄, was synthesized by a solvothermal method, followed by supercritical drying. Heat treatment of this material (oxidation) above 500 °C resulted in the formation of Fe₂O₃? Fe₂(MoO₄)₃ mixed oxide, where Fe₂O₃ was a by‐product. An increase in the conductivity of the films in the presence of H₂S gas (concentration range 1–20 ppm in air) was observed with the simultaneous formation of water and sulfide ions at 225 °C. An improvement of the H₂S sensing potential is obtained, using an intermediate short heat treatment at higher temperature (500 °C) in the beginning of recovery (desorption) phase. This intermediate high temperature, used before every expected exposure to H₂S gas, may contribute the formation of an initial surface coverage of O^2?.     

Preparation of nanocrystalline BiFeO3 and kinetics of thermal process of precursor

The Bi₂Fe₂(C₂O₄)₅·5H₂O was synthesized by solid-state reaction at low heat using Bi(NO₃)₃·5H₂O, FeSO₄·7H₂O, and Na₂C₂O₄ as raw materials. The nanocrystalline BiFeO₃ was obtained by calcining Bi₂Fe₂(C₂O₄)₅·5H₂O at 600 °C in air. The precursor and its calcined products were characterized by thermogravimetry and differential scanning calorimetry, FT-IR, X-ray powder diffraction, and vibrating sample magnetometer. The data showed that highly crystallized BiFeO₃ with hexagonal structure [space group R3c(161)] was obtained when the precursor was calcined at 600 °C in air for 1.5 h. The thermal process of the precursor in air experienced five steps which involved, at first, the dehydration of an adsorption water molecule, then dehydration of four crystal water molecules, decomposition of FeC₂O₄ into Fe₂O₃, decomposition of Bi₂(C₂O₄)₃ into Bi₂O₃, and at last, reaction of Bi₂O₃ and Fe₂O₃ into hexagonal BiFeO₃. Based on Starink equation, the values of the activation energies associated with the thermal process of Bi₂Fe₂(C₂O₄)₅·5H₂O were determined. Besides, the most probable mechanism functions and thermodynamic functions (ΔS ^≠, ΔH ^≠, and ΔG ^≠) of thermal processes of Bi₂Fe₂(C₂O₄)₅·5H₂O were also determined.     

New synthesis method for M(II) chromites/silica nanocomposites by thermal decomposition of some precursors formed inside the silica gels

In this article, we present a new method for the obtaining of ZnCr₂O₄ and MgCr₂O₄ embedded in silica matrix. This method consists in the formation of Cr(III), Zn(II) and Cr(III), Mg(II) hydroxycarboxylate/carboxylate compounds, during the redox reaction between the nitrate ion and diol (1,3-propanediol), uniformly dispersed in the pores of hybrid gels. The thermal decomposition of these precursors leads to a mixture of corresponding metal oxides. The gels were synthesized starting from mixtures of Cr(NO₃)₃·9H₂O, Zn(NO₃)₂·6H₂O and Cr(NO₃)₃·9H₂O, Mg(NO₃)₂·6H₂O with tetraethyl orthosilicate and 1,3-propanediol for final compositions 50% ZnCr₂O₄/50% SiO₂ and 50% MgCr₂O₄/50% SiO₂. The obtained gels have been thermally treated at 140?°C, when the redox reaction nitrates-diol took place with formation of the precursors within the xerogels pores. The thermal decomposition of all precursors took place up to 300?°C, with formation of oxides mixtures (Cr₂O_3?+?x and ZnO) and (Cr₂O_3?+?x and MgO), respectively. At 400?°C, Cr₂O_3?+?x turn to Cr₂O₃ which reacts with ZnO forming ZnCr₂O₄/SiO₂. Starting with 400?°C, Cr₂O₃ reacts with MgO to an intermediary phase MgCrO₄, which decomposes with the formation of MgCr₂O₄/SiO₂. The formation of the precursors inside the silica matrix and the evolution of the crystalline phases were studied by thermal analysis, FT-IR spectrometry, XRD, and TEM.     

Thermal decomposition of chromium(III) nitrate(V) nanohydrate

Thermal decomposition of Cr(NO₃)₃·9H₂O in helium and in synthetic air was studied by means of TG, DTA, EGA and XRD analysis. The dehydration occurs together with decomposition of nitrate(V) groups. Eight distinct stages of reaction were found. Intermediate products of decomposition are hydroxy- and oxynitrates containing chromium in hexa- and trivalent states. The process carried out in helium leads to at about 260°C and in air is formed at about 200°C. The final product of decomposition (>450°C) is Cr₂O₃, both in helium and in air. This revised version was published online in July 2006 with corrections to the Cover Date.     

The decomposition of the oxalate precursor and the stability and reduction of the YBa2Cu4O8 superconductor studied by TG coupled with FTIR and by XRD

The 124 superconductor YBa₂Cu₄O₈ was prepared from the oxalate precursor Y₂(C₂O₄)₃. ·4BaC₂O₄·8CuC₂O₄·xH₂O at one atmosphere oxygen pressure. In O₂ the precursor decomposes in one step at 300°C and more gradually (300°–600°C) in Ar. The stability of the superconductor is strongly dependent on the gas atmosphere: in O₂ and in air there is no significant weight change as long as the temperature does not exceed 800°C, whereas in a 1% O₂-99%N₂ mixture decomposition starts at about 670°C with the formation of CuO and YBa₂Cu₃O_x withx<7. The reduction of YBa₂Cu₄O₈ in a 5% H₂-95% Ar mixture takes place in at least four major steps with formation of products such as Y₂O₃, BaO, Cu₂O, Cu, BaY₂O₄ and Ba₄Y₂O₇.     

Preparation of magnetic nanocrystalline Mn0.5Mg0.5Fe2O4 and kinetics of thermal decomposition of precursor

The spinel Mn_0.5Mg_0.5Fe₂O₄ was obtained via calcining Mn_0.5Mg_0.5Fe₂(C₂O₄)₃·5H₂O above 400 °C in air. The precursor and its calcined products were characterized by thermogravimetry and differential scanning calorimetry, Fourier transform FT-IR, X-ray powder diffraction, scanning electron microscopy, energy dispersive X-ray spectrometer, and vibrating sample magnetometer. The results showed that Mn_0.5Mg_0.5Fe₂O₄ obtained at 600 °C had a specific saturation magnetization of 46.2 emu g^–1. The thermal decomposition of Mn_0.5Mg_0.5Fe₂(C₂O₄)₃·5H₂O below 450 °C experienced two steps which involved, at first, the dehydration of five water molecules and then decomposition of Mn_0.5Mg_0.5Fe₂(C₂O₄)₃ into spinel Mn_0.5Mg_0.5Fe₂O₄ in air. Based on Starink equation, the values of the activation energies associated with the thermal decomposition of Mn_0.5Mg_0.5Fe₂(C₂O₄)₃·5H₂O were determined.     

Thermolysis mechanism of chromium nitrate nonahydrate and computerized modeling of intermediate products

Thermal decomposition of chromium nitrate nonahydrate was studied by thermal analysis, differential scanning calorimetry, infrared spectroscopy, and high temperature X-ray diffraction, so that mass losses were related to the exactly coincident endothermic effects and vibrational energy levels of the evolved gases. The thermal decomposition of chromium nitrate is a complex process, which begins with the simultaneous dehydration and concurrent condensation of 4 mol of the initial monomer Cr(NO₃)₃·9H₂O. Soon after that, the resulting product Cr₄N₁₂O₃₆·31H₂O gradually loses water and azeotrope HNO₃ + H₂O, and is transformed into tetrameric oxynitrate Cr₄N₄O₁₆. At higher temperatures, the tetramer loses N₂O₃ and O₂ and a simultaneous oxidation of Cr(III) to Cr(IV) occurs. The resulting composition at this stage is chromium dioxide dimer Cr₄O₈. Finally, at 447 °C the unstable dimer loses oxygen and is transformed into 2Cr₂O₃. The models of intermediate amorphous compounds represent a reasonably good approximation to the real structures and a proper interpretation of experimental data.     

DTA,TG studies of catalytic oxidation of carbon particles over M2 III O3 (MIII=Al,Cr, Fe,Ni)

Carbonizate as a model soot has been submitted to oxidation using Al₂O₃, Cr₂O₃, Ni₂O₃ and Fe₂O₃ as catalysts in the temperature range from RT up to 1000°C. The results obtained indicate that Fe₂O₃ is the most active catalyst in soot oxidation. However, all the catalysts examined are active in transformation of carbonizate components. It has been shown that DTA and TG methods can be used as fast methods testing the carbonizate oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal Investigations of M[La(C2O4)3]⋅xH2O (M=Cr(III) and Co(III))

The complexes M[La(C₂O₄)₃]⋅xH₂O (x=10 for M=Cr(III) and x=7 forM=Co(III)) have been synthesized and their thermal stability was investigated. The complexes were characterized by elemental analysis, IR, reflectance and powder X-ray diffraction (XRD) studies. Thermal investigations using TG, DTG and DTA techniques in air of chromium(III)tris(oxalato)lanthanum(III)decahydrate, Cr[La(C₂O₄)₃]⋅10H₂O showed the complex decomposition pattern in air. The compound released all the ten molecules of water within ∼170°C, followed by decomposition to a mixture of oxides and carbides of chromium and lanthanum, i.e. CrO₂, Cr₂O₃, Cr₃O₄, Cr₃C₂, La₂O₃, La₂C₃, LaCO, LaCrO_x (2<x<3) and C at ∼1000°C through the intermediate formation of several compounds of chromium and lanthanum at ∼374, ∼430 and ∼550°C. Thecobalt(III)tris(oxalato)lanthanum(III)heptahydrate, Co[La(C₂O₄)₃]⋅7H₂O becomes anhydrous around 225°C, followed by decomposition to Co₃O₄, La₂(CO₃)₃ and C at ∼340°C and several other mixture species of cobalt and lanthanum at∼485°C. The end products were identified to be LaCoO₃, Co₃O₄, La₂O₃, La₂C₃, Co₃C, LaCO and C at ∼ 2>1000°C. DSC studies in nitrogen of both the compounds showed several distinct steps of decomposition along with ΔH and ΔSvalues. IR and powder XRD studies have identified some of the intermediate species. The tentative mechanisms for the decomposition in air are proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

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.     

Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.     

Monolithic FeO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for ammonia oxidation and nitrous oxide decomposition

(1.2–8.3)%FeO_х/Al₂O₃ monolith catalysts have been prepared by impregnating alumina with aqueous solutions of iron(III) nitrate and oxalate and have been tested in NH₃ oxidation and in the selective decomposition of N₂O in mixtures resulting from ammonia oxidation over a Pt–Rh gauze pack under conditions of nitric acid synthesis (800–900°C). In the case of the support calcined at 1200°C, the catalyst is dominated by bulk Fe₂O₃ particles localized on the Al₂O₃ surface. The activity of these samples in both reactions decreases with a decreasing active component content, thus limiting the potential of Fe₂(C₂O₄)₃ · 5H₂O, an environmentally friendlier but poorly soluble compound, as a substitute for Fe(NO₃)₃ · 9H₂O. Decreasing the support calcination temperature to 1000°C or below leads to the formation of a highly defective Fe–Al–O solid solution in the (1.2–2.7)%FeO_х/Al₂O₃ catalysts. The surface layers of the solid solution are enriched with iron ions or stabilize ultrafine FeO_х particles. The catalytic activity of these samples in both reactions is close to the activities measured for ~8%FeO_х/Al₂O₃ samples prepared using iron nitrate.     

A New Route to Crystalline Salts of the Hydrolytic Dimer of Chromium(III)

Crystalline salts of the hydrolytic dimer of Cr(III), [Cr₂(μ-OH)₂(H₂O)₈]X₄·n H₂O (X = p-toluenesulfonate (tos) or mesitylene-2-sulfonate (dmtos)) have been prepared in good yields via a simple two-step procedure: H⁺ oxidation of Cr metal to give Cr²⁺ (T ≈? 70°) followed by O₂ oxidation, of Cr²⁺ to give the dimer (T ≈? 25°). The mechanism of conversion of Cr²⁺ into the dimer is discussed.     

The effect of calcination on morphology of phosphate coating and microstructure of sintered iron phosphated powder

Carbonyl iron powder was coated with phosphate layer using phosphating precipitation method. The phosphated powder was dried at 60 °C for 2 h in air and heat treated by calcination at 400 and 800 °C for 3 h in air. Cylindrical specimens density of ~6.5 g.cm^?3 based on iron phosphated powder calcined at 400 °C were sintered at 820, 900, 1110 °C in N₂ + 10%H₂ atmosphere and 1240 °C in vacuum for 30 min. The morphology and phase composition of the phosphate coating and sintered compacts were studied by scanning electron microscopy, atomic force microscopy (AFM) and X‐ray diffraction (XRD) analysis. Gelatinous morphology of dried phosphate coating (thickness of ~100 nm) containing nanoparticles of iron oxyhydroxides and hydrated iron phosphate was observed. From XRD, diffractogram indicated the presence of goethite α‐FeOOH, lepidocrocite γ‐FeOOH and ludlamite Fe₃(PO₄)₂.4H₂O. The calcined phosphate coating (thickness of ~ 400 nm) contained non‐homogeneous consistency of α‐Fe₂O₃ layer on iron particles, an inter‐layer of amorphous FePO₄ and Fe₃O₄ top layer. The transformation to crystalline FePO₄ structure occurred during calcination at 800 °C with the presence of α‐Fe₂O₃ forming a light top zone (rough morphology). The microstructure of compacts sintered in solid state at temperatures up to 900 °C has retained composite network character. A fundamental change in microstructure due to the liquid phase sintering occurred after sintering at temperatures of 1100 and 1240 °C. It was confirmed that the microstructure complex consists of spheroidized α‐Fe and α‐Fe₂O₃ phases surrounded by solidified liquid phase consisting various phosphate compounds. Copyright © 2013 John Wiley & Sons, Ltd.     

The effect of water vapor on the oxidation behavior of 9%Cr steels in simulated combustion gases

The effect of the O₂ and H₂O content on the oxidation behavior of the 9%Cr steel P91 was studied in the temperature range of 600–800 °C. The oxidation rates under the various experimental conditions were determined by in-situ thermogravimetry. In dry oxygen a protective scale growth occurs with an oxidation rate controlled by diffusion in the scale. In presence of water vapor, after an incubation period, the scales become non-protective, as a result of a change of the oxidation limiting process. The water vapor effect is especially apparent in the temperature range of 600–700 °C, whereas at higher temperatures hardly any effect was found. The destruction of the protective scale by water vapor does not only depend on the H₂O content but also on the H₂O/O₂-ratio. Received: 15 July 1997 / Revised: 5 February 1998 / Accepted: 10 February 1998     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

The obtaining of NiCr2O4 nanoparticles by unconventional synthesis methods

This paper presents a study regarding the obtaining of NiCr₂O₄ by two new unconventional synthesis methods: (i) the first method is based on the formation of Cr(III) and Ni(II) carboxylate-type precursors in the redox reaction between the nitrate ion and 1,3-propanediol. The thermal decomposition of these complex combinations, at ~300 °C, leads to an oxide mixture of Cr₂O_3+x and NiO, with advanced homogeneity, small particles and high reactivity. On heating this mixture at 500 °C, Cr₂O₃ reacts with NiO to form NiCr₂O₄, which was evidenced by FT-IR and X-ray diffractometry (XRD) analysis; (ii) the second method starts from a mechanical mixture of (NH₄)₂Cr₂O₇ and Ni(NO₃)₂·6H₂O. On heating this mixture, a violent decomposition at 240 °C with formation of an oxides mixture (Cr₂O₃ + CrO₃) and NiO takes place. On thermal treatment up to 500 °C, an intermediary phase NiCrO₄ is formed, which by decomposition at ~700 °C leads to NiCr₂O₄, evidenced by FT-IR and XRD analysis. NiCr₂O₄ is formed, in both cases, starting with a temperature higher than 400 °C, when the non-stoichiometric chromium oxide (Cr₂O_3+x ) loses the oxygen excess and turns to stoichiometric chromium oxide (Cr₂O₃), which further reacts with NiO.     

Sensing characteristics of mixed-potential-type zirconia-based sensor using laminated-oxide sensing electrode

A planar sensor was fabricated using a yttria-stabilized zirconia (YSZ) plate and laminated-oxide sensing electrode (SE) aiming for selective detection of NO₂ at high temperature. The NO₂ sensing characteristics as well as the cross-sensitivity to various gases were examined in the temperature range of 700–900 °C under the wet condition (5 vol.% H₂O). It was found that the sensor attached with the laminated hetero-oxide layer (Cr₂O₃/NiO (+WO₃)) could detect NO₂ selectively at 895 °C. It was speculated that the additional oxide layer (Cr₂O₃) placed on the NiO (+WO₃) layer acted as a catalyst for the oxidation of CO, hydrocarbons and NO, and then led to better NO₂ selectivity.