MoO3 Evaporation Studies from Binary Systems towards Choice of Mo Precursors in EAF

The evaporation rate of molybdenum oxide from mixtures with CaO or MgO was studied in the temperature range 300‐1573 K. The investigations were carried out using high temperature X‐ray diffraction and thermogravimetry. Further, additions of these precursors to molten steel in the laboratory scale and the Mo yield achieved were determined. The X‐ray studies show that the calcium molybdate is formed from the oxide mixture in the temperature interval 773‐873 K, which precedes the beginning of evaporation of MoO₃. Results of thermogravimetric studies with mixtures CaO and MgO with MoO₃ as well as the compounds CaMoO₄ and MgMoO₄ confirm the above results. Addition of various molybdenum precursors, viz. the mixtures of carbon with pure MoO₃, CaMoO₄ and MgMoO₄, as well as oxide mixtures (CaO + MoO₃, MgO + MoO₃) show that the highest yield was observed for CaMoO₄ + C and MoO₃ + C mixtures, while MgO + C + MoO₃ mixture showed much lower yield.     

Fe2MoO4 as a Precursor Material for Mo Alloying in Steel (Part II): Up‐Scaling Test

The Mo yield when using three different alloying mixtures (MoO₃ +C; MoO₃ +C + FeO_x; and MoO₃+ C + CaO) was tested both in laboratory experiments (16 g and 0.5 kg scale) and industrial trials (3 ton scale). The alloying is based on in‐situ formation of compounds of Mo in the mixtures from molybdenite concentrate with industrial grade Fe₂O₃. Thermogravimetry (TGA) and X‐ray diffraction (XRD) analyses were performed to identify the reduction steps and final products of the alloying mixtures. At least two steps of mass change were discovered during the reduction of all tested mixtures by carbon. The Mo yield for MoO₃ + C mixture is 93% which was confirmed by both laboratory and industrial experiments. The Mo yield for MoO₃ + C + CaO mixture is around 92% during 16 g scale laboratory and 3 ton scale industrial tests. The best results were obtained in the case of the mixture which contained FeO_x, MoO₃ and C, resulting in the Mo yield up to 98% at all the experiment scale levels. It was found that the combination of both lower evaporation and fast reduction by carbon of the mixture along with further dissolution in steel are necessary to provide high Mo yield during steel alloying. The calculated mass balance of 3 ton trial heats showed that only a small part of initial Mo amount (8–13 ppm) has gone into slag.     

Effect of Thermal Aging on Ductile-Brittle Transition Temperature of Modified 9Cr-1Mo Steel Evaluated with Reference Temperature Approach Under Dynamic Loading Condition

The effect of thermal aging on the ductile-brittle transition behavior has been assessed for a modified 9Cr-1Mo steel (P91) using the reference temperature approach under dynamic loading condition (T ₀ ^dy ). The steel in normalized and tempered (NT) condition and in different levels of subsequent cold work (CW) was subjected to thermal aging at temperatures of 873 K and 923 K (600 °C and 650 °C) for 5000 and 10,000 hours. For the NT and all the cold work conditions of the starting material, a drastic increase in T ₀ ^dy has been noticed after aging at 923 K (650 °C) for 10,000 h. A moderate increase was observed for the NT steel aged at 873 K (600 °C) for 5000 hours and for the 10 pct CW steel aged at 873 K (600 °C) for 10,000 h. A detailed transmission electron microscope (TEM) study of the embrittled materials aged at 923 K (650 °C)/10,000 hours and 873 K (600 °C)/10,000 hours has indicated presence of hexagonal Laves phase of Fe₂(Mo,Nb) type with different size and spatial distributions. The increase in the T ₀ ^dy is attributed to the embrittling effect of a network of Laves phase precipitates along the grain boundaries.     

Thermodynamic studies of oxygen behavior in tantalum-based alloys

An experimental study of equilibrium thermodynamic properties of oxygen in pure tantalum and tantalum alloyed with V, Nb or Mo was made by EMF measurements on solid electrolytic cells over the temperature range of 873–1373 K (600–1100°C). The solubility of oxygen in pure tantalum in equilibrium with Ta₂O₅ was determined to be C_s = 12.4exp[−(16 kJ/mol)/(RT)] over the experimental temperature range. It was concluded that oxygen obeys Henry's law for concentrations up to the terminal solubility in tantalum for the temperature range 873–1373 K (600–1100°C). The oxygen activity coefficient increased with Mo content in TaMo alloys and decreased with V content in TaV alloys. The equilibrium results showed virtually no change in thermodynamic behavior of the oxygen solution by adding Nb to TaO alloys. The positive deviation of the oxygen activity coefficient in TaMo alloys is evidence of a repulsive interaction between molybdenum and oxygen atoms. The interaction energy was calculated assuming that the interaction extends to third nearest neighbors. It may, in fact, extend to fourth or higher neighboring shells of atoms.     

Activities of Phosphorus in Copper‐Iron Liquid Alloys Saturated with Copper‐Iron Solid Solutions

In order to determine the activities of phosphorus and iron in liquid {Cu‐Fe‐P} alloys, the two coexisting phases of liquid {Cu‐Fe‐P} alloys + <Cu‐Fe‐P> solid solutions were brought into equilibrium with a mixture of Al₂O₃ + AlPO₄ + Fe_xAl₂O₄ at temperatures of 1416K and 1526K. The oxygen partial pressures were measured with the aid of a solid‐oxide galvanic cell of the type: (+)Mo / Mo + MoO₂/ ZrO₂(MgO) / {Cu‐Fe‐P} + <Cu‐Fe‐P> + <Al₂O₃> + <AlPO₄> + <FeAl₂O₄> / Fe(‐) The equilibrium reactions underlying the experiments can be expressed by 2[P]_cu + (5/2) (O₂) + <Al₂O₃> = 2 <AlPO₄> and x[Fe]_Cu + (1/2) (O₂) + <Al₂O₃> = <Fe_xAl₂O₄> The Henrian activity coefficient referred to 1 wt pct solution in pure liquid copper could be well expressed by the formula log f_P° = (4.46±0.40) ‐ (8.67±0.59)/(T/K). The iron activities referred to pure solid iron could be formulated as log a_Fe =‐ (0.37 ± 0.12) + (500 ±200) /(T/K).     

A thermodynamic study of SrO + FexO and BaO + FexO liquid slags by disposable electrochemical oxygen probes

An electrochemical technique involving magnesia-stabilized zirconia as the solid electrolyte and a mixture of Mo + MoO₂ as the reference electrode for the measurements of the activities of Fe_xO in the SrO + Fe_xO and BaO + Fe_xO systems at 1673 K. Measurement of oxygen potentials established at the slag electrode by disposable solid state cells. Expression of the thermodynamic properties of SrO + Fe_xO and BaO + Fe_xO by the binary subregular model.     

Influence of Manganese Oxide and Silica on the Morphological Structure of Hematite Compacts

Dry compacts of pure Fe₂O₃ and Fe₂O₃ doped with either (2–6 mass%) MnO₂, (2.5–7.5 mass%) SiO₂ or with both (2–6% MnO₂ + 7.5% SiO₂) were indurated at 1373 K for 6 hours and physically and chemically characterized. The fired compacts were isothermally reduced with pure CO gas at 1073–1373 K. The O₂‐weight loss was continuously recorded as a function of time using TGA technique. The external volume of pure and doped compacts was measured at different reduction conditions and the volume change was calculated. The structural changes accompanying the reduction process were visually and microscopically examined and the different phases were identified by X‐ray diffraction analysis. After firing, manganese ferrite (MnFe₂O₄) phase was identified in MnO₂‐doped compacts. In pure Fe₂O₃ compacts, the external volume of compacts was increased with reduction temperature, showing a maximum swelling value at 1198 K. Catastrophic swelling was observed in MnO₂‐doped Fe₂O₃ compacts, the volume change increased with MnO₂ content showing catastrophic swelling in compacts containing 6%MnO₂ at 1248 K. The catastrophic swelling was attributed to the formation of dense metallic iron whiskers and plates in a highly porous structure. Unlike in MnO₂‐doped samples, no considerable volume changes were detected in SiO₂‐doped Fe₂O₃ and (MnO₂ + SiO₂)‐doped Fe₂O₃ compacts where the presence of silica greatly hindered the swelling phenomenon at all reduction temperatures.     

Age hardening and mechanical properties of a 2400 MPa grade cobalt-free maraging steel

The age hardening kinetics in the temperature range of 713 to 813 K of a 2400 MPa grade cobalt-free maraging steel (Fe-(18.8 ∼ 19.1) pct Ni-(4.4 ∼ 5.4) pct Mo-2.6 pct Ti, wt pct) has been studied. Study of microstructure and mechanical properties showed that a high number of Ni₃Ti and Fe₂(Mo,Ti) precipitates were formed during the ageing process, which resulted in high strength and relatively low fracture toughness. Ni₃Ti was the main precipitation phase. Fractography has shown ductile failure of tensile and fracture toughness specimens. Thermodynamic calculations showed that the equilibrium phases are Ni₃Ti, Fe₂(Mo,Ti), ferrite, and austenite.     

Thermoanalysis of the combined Fe3O4-reduction and CH4-reforming processes

The chemical equilibrium composition of the system Fe₃O₄ + 4CH₄, at 1300 K and 1 atm consists of solid Fe and a 2:1 gas mixture of H₂ and CO. Thermogravimetric (TG) analysis combined with gas Chromatographic measurements was conducted on the reduction of Fe₃O₄ (powder, 2-μm mean particle size) with 2.3, 5, 10, and 20 pct CH₄ in Ar, at 1273, 1373, 1473, and 1573 K. The reduction proceeded in two stages, from Fe₃O_{4 to FeO, and finally to Fe. CR}, conversion and H₂ yield increased with temperature, while the overall reaction rate increased with temperature and CH4 concentration. C (gr) deposition, due to the cracking of CR,, was observed. By applying a topochemical model for spherical particles of unchanging size, the reaction mechanism was found to be mostly controlled by gas boundary layer diffusion. The apparent activation energy reached a maximum at 30 pct reduction extent and decreased monotonically until completion. When compared with the results using instead either H₂ or CO as reducing gas, the reduction achieved completion faster using CH₄, at temperatures above 1373 K.     

Electrochemical Measurements of Oxygen Potentials in the Slag System CaO‐P2O5‐SiO2‐FexO

The liquidus compositions of the four‐phase assemblages in the quaternary system of CaO‐P₂O₅‐SiO₂‐Fe_xO were determined at 1473 and 1573 K by employing electron probe microanalysis. Measurements were also made on the Fe_xO activities at temperatures between 1373K and 1699K by employing an electrochemical technique involving stabilized zirconia electrolyte.     

Reactions of zinc calcium oxysulfide with metallic iron and its sulfide

Mixtures of zinc calcium oxysulfide with metallic iron or its sulfide are heated at 873–1373 K, and the products are studied by X-ray diffraction, electron-probe microanalysis, and chemical analysis. In the case of CaZnSO with FeS, the reaction gives a continuous series of Ca(Fe _x Zn_{1 ? x} )SO solid solutions and, eventually, iron calcium oxysulfide. The degree of the reaction depends on the CaZnSO/FeS ratio and the heating temperature. Heating of CaZnSO with Fe above 1173 K results in zinc-vapor evolution and solid solutions with variable Ca(Fe _x Zn_{1 ? x} )SO compositions. The degree of zinc sublimation is determined by the amount of introduced metallic iron and the roasting time and temperature.     

The Activities of FexO in {CaO‐SiO2‐Al2O3‐MgO‐FexO} Slags at 1723 K

In Japanese steelworks, hot metal is now produced by scrap melting process. With this process removal of sulphur is very much handicapped because of very high sulphur levels (0.04 to 0.09 pct by weight) and relatively low tapping temperatures (1623 to 1723 K). In order to overcome such disadvantages, the authors explored on the phase diagrams of {CaO‐SiO₂‐Al₂O₃‐MgO} slags, and this research revealed that those slags at 35 wt%‐Al₂O₃ would be good candidates as reagents for the removal of sulphur from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, activities of Fe_xO were determined by using solid‐state electrochemical cells incorporating MgO‐stabilized zirconia and Mo + MoO₂ reference electrode.     

Volume Changes of Iron Oxide Compacts under Isothermal Reduction Conditions

Compacts made from chemically grade Fe₂O₃ were fired at 1473K for 6 hrs. The fired compacts were isothermally reduced either by hydrogen or carbon monoxide at 1073–1373K. The O₂ weight‐loss resulting from the reduction process was continuously recorded as a function of time using TGA technique, whereas the volume change at different reduction conditions was measured by displacement method. Porosity measurements, microscopic examination and X‐ray diffraction analysis were used to characterize the fired and reduced products. The rate of reduction at both the initial and final stages was increased with temperature. The reduction mechanism deduced from the correlations between apparent activation energy values, structure of partially reduced compacts and application of gas‐solid reaction models revealed the reduction rate (dr/dt) at both the initial and final stages. At early stages, the reduction was controlled by a combined effect of gaseous diffusion and interfacial chemical reaction mechanism, while at the final stages the interfacial chemical reaction was the rate determining step. In H₂ reduction, maximum swelling (80%) was obtained at 1373K, which was attributed to the formation of metallic iron plates. In CO reduction, catastrophic swelling (255%) was obtained at 1198K due to the formation of metallic iron plates and whiskers.     

Activities of titanium in molten copper at dilute concentrations measured by solid- state electrochemical cells at 1373 K

In order to obtain the activities of titanium in molten copper at dilute concentrations,i.e., between 5 x 10^-6 and 3.4 x 10^-3 titanium mole fractions, liquid copper was brought into equilibrium with molten {CaCl₂ + Ti₂O₃} slag saturated with Ti₂O₃ (s) at 1373 K and the equilibrium oxygen partial pressures were measured by means of a solid-oxide galvanic cell of the type Mo/Mo + MoO₂/ZrO₂(MgO)/(Cu + Ti)_alloy + Ti₂O₃ + CaCl₂ + Ti₂O_{3 slag}/Mo The free energy change for the dissolution of solid titanium in molten copper at infinite dilution referred to 1 wt pet was determined as Ti (s) = Ti(1 wt pet in Cu) ΔG°/J = -86,100 ± 8900 at 1373 K     

Microwave Absorption Characteristics of Conventionally Heated Nonstoichiometric Ferrous Oxide

The temperature dependence of the microwave absorption of conventionally heated nonstoichiometric ferrous oxide (Fe_0.925O) was characterized via the cavity perturbation technique between 294 K and 1373 K (21 °C and 1100 °C). The complex relative permittivity and permeability of the heated Fe_0.925O sample slightly change with temperature from 294 K to 473 K (21 °C to 200 °C). The dramatic variations of permittivity and permeability of the sample from 473 K to 823 K (200 °C to 550 °C) are partially attributed to the formation of magnetite (Fe₃O₄) and metal iron (Fe) from the thermal decomposition of Fe_0.925O, as confirmed by the high-temperature X-ray diffraction (HT-XRD). At higher temperatures up to 1373 K (1100 °C), it is found that Fe_0.925O regenerates and remains as a stable phase with high permittivity. Since the permittivity dominates the microwave absorption of Fe_0.925O above 823 K (550 °C), resulting in shallow microwave penetration depth (~0.11 and ~0.015 m at 915 and 2450 MHz, respectively), the regenerated nonstoichiometric ferrous oxide exhibits useful microwave absorption capability in the temperature range of 823 K to1373 K (550 °C to 1100 °C).     

Chemical potentials of components of the system CaO + P2O5 + FexO at 1673 K

Electromotive force (emf) measurements were conducted with a solid oxide galvanic cell of the type Mo/Mo + MoO₂/ZrO₂ (MgO)/Fe (s) + Fe_xO (in slag)/Ag/Fe at 1673 K in order to obtain the activities of Fe_xO in CaO + P₂O₅ + Fe_xO ternary slags. By using the Gibbs-Duhem integration, the activities of P₂O₅ and CaO were also obtained.     

Phase transformations during tempering of the Fe-15Cr-1Mo martensites containing nitrogen or carbon

Hardness measurements, dilatometry, internal friction measurements, Mössbauer spectroscopy and transmission electron microscopy are utilized in order to study the effect of tempering on the microstructure of a stainless martensitic steel containing 15% Cr, 1% Mo and 0.6% N. A similar carbon steel containing 15% Cr, 1% Mo and 0.6% C is used for comparison. Tempering of alloy Fe-15Cr-1Mo-0.6N in the low temperature range of 353-473 K leads to formation of hexagonal ?-nitride (Fe,Cr)₂N, which is followed by precipitation of the orthorombic ?-nitride (Fe,Cr)₂N at temperatures of 573-773 K. The hexagonal nitride Cr₂N is precipitated at 923 K and preferably formed at grain boundaries. The alloy Fe-15Cr-1Mo-0.6C shows the expected tempering behaviour. ?-carbide (Fe,Cr)₂C and cementite (Fe,Cr)₃C are precipitated during low temperature ageing, followed by the formation of Cr₇C₃ carbides after the temperature has risen to 873 K. With a similar interstitial content the amount of retained austenite in the nitrogen martensite is nearly twice as high as in the carbon one. Furthermore, the thermal stability of the retained austenite of the nitrogen alloy is substantially higher than that of the carbon steel.     

Reduction kinetics of Fe<Subscript>2</Subscript>MoO<Subscript>4</Subscript> fine powder by hydrogen in a fluidized bed

Iron molybdate (Fe₂MoO₄) powders with an average particle size of 100 μm were reduced by hydrogen using a fluidized-bed batch reactor in the temperature range of 923 to 1173 K. The extent of the reaction was followed as a function of time by gas chromatography. The fluidizing-gas velocity was set at about 1.5 times the minimum fluidization velocity. The ratio of the height of the static bed to its diameter is about 1. Under the prevailing experimental conditions, it was found that the chemical reaction was the rate-controlling factor. The activation energy for this process was 158±17 kJ/mol. The crystal size of the Fe₂Mo powder produced at lower temperatures was in the nanometer range, indicating the possibility of mass production of alloys and intermetallics in the nanorange, using a fluidized bed.     

Effect of alloying additions on the structure and mechanical properties of Fe<Subscript>3</Subscript>Al -1C intermetallic alloy

Effect of titanium and nickel on the structure and properties of Fe₃Al intermetallic alloy containing about 1.0wt.% C have been investigated. The composition of the alloying element was substituted for Iron. The alloys were prepared by melting commercial grade raw materials iron, aluminum, titanium or nickel in air induction furnace with flux cover (AIMFC). Further these ingots were refined by electroslag refining (ESR) process. These ingots could be successfully hot-worked using conventional hot-forging and hot-rolling techniques. The hot-worked material was sound and free from cracks. ESR hot-rolled alloys were examined using optical microscopy, X-ray diffraction (XRD), scanning electron micrograph (SEM) to understand the microstructure of these alloys. The electron probe micro analysis (EPMA) studies were carried out to determine the matrix and precipitate compositions and to identify the phases present in the alloys. The base alloy and the alloy containing Ni exhibited a two-phase microstructure of Fe₃AlC_0.5 precipitates in Fe₃Al matrix. The alloy containing Ti exhibits three-phase microstructure, the additional phase being TiC precipitate. Ti addition resulted in no improvement in strength at room temperature and at 873 K whereas Ni addition has resulted in greater improvement in strength at room temperature and at 873 K and also improved the creep life significantly from 66 hrs to 111 hrs.