Selective Oxidation and Sub‐Surface Phase Transformation of TWIP Steel during Continuous Annealing

The selective oxidation of Twinning Induced Plasticity (TWIP) steel during annealing at 800 °C in a N₂ + 10%H₂ gas atmosphere with a dew point of ?17 °C and ?3 °C was investigated by means of high resolution transmission electron microscopy of cross‐sectional samples. The annealing resulted in the selective oxidation of Mn and Si and the austenite‐to‐ferrite phase transformation of the sub‐surface region. In the low dew point atmosphere, the annealing resulted in the formation of a MnO layer at the surface. Crystalline c –xMnO · SiO₂ (x ≥ 2) particles and amorphous a –xMnO · SiO₂ (x < 0.9) particles were found at the interface between the MnO layer and the steel matrix. In a narrow zone of the sub‐surface, the Mn depletion resulted in the transformation of the initial austenite. In the high dew point atmosphere, a thicker MnO layer was formed on the surface and no mixed manganese‐silicon oxides particles were observed at the MnO/steel matrix interface. In the sub‐surface, Mn was significantly depleted in the range of 2–3 µm below the surface and the initial austenite in this zone was transformed to ferrite. MnO particles were found at the grain boundaries and in the interior of grains.     

Kirkendall Void Formation During Selective Oxidation

The selective oxidation of high Mn austenitic steel was investigated by transmission electron microscopy. The annealing resulted in a MnO surface layer and a Mn-depleted ferritic layer. At the MnO/steel interface, voids were formed between the a-xMnO.SiO₂ and c-MnO.Al₂O₃ layers. This is the first time that void formation is observed during selective oxidation of steel. The Kirkendall voids grow and develop characteristic void surfaces because of the fast diffusion of MnO on the void surface.     

Thermodynamics of manganese distribution between liquid iron and the CaO–Al2O3–SiO2–FeO–MnO system

The thermodynamics of distribution of constituents between liquid iron and the CaO–Al₂O₃–SiO₂–FeO–MnO system at 1600°C was studied using electrochemical indication of the equilibrium partial pressure of oxygen in both phases. The results show that oxidation potential of the Fe(l)–CaO–Al₂O₃–SiO₂–FeO–MnO system, expressed in terms of log p(O₂), is directly proportional to log (x(MnO) · x(FeO)/w| Mn |). Manganese distribution coefficient, L'_mn, in intersection CaO/Al₂O₃ = 1 decreases with increasing slag basicity expressed in terms of activity a(CaO) or 1/γ(MnO). Experimentally determined equilibrium constant K_Mn/Fe is equal to 2.7 for 1600°C. The number of exchanged electrons between Fe-O-Mn-Si electrode and the slag approaches the theoretical value.     

Thermodynamics of Composition Control of CaO‐MnO‐Al2O3‐SiO2 Inclusions in Tire Cord Steel

The effect of oxide component content on the low melting point zone (simplified as LMP) in the CaO‐MnO‐Al₂O₃‐SiO₂ system has been analysed by FactSage. The contents of [Si], [Mn], [O] and [Al] in liquid steel which are in equilibrium with the LMP inclusions in the CaO‐MnO‐Al₂O₃‐SiO₂ system have been calculated. The results show that the CaO‐MnO‐Al₂O₃‐SiO₂ system has the largest LMP zone (below 1400°C) when the Al₂O₃ content is 20% or the CaO content is 15%, and that the LMP zone becomes wider with increase in SiO₂ and MnO contents (within the range of 0~25%). To obtain LMP inclusions (below 1400°C), [Si] and [Mn] can be controlled within a wide range, but [Al] and [O] must be controlled within the range of 0.5~5 ppm and 50~120 ppm, respectively.     

Formation of Inclusion in Ti–Al Killed Low C–Mn Steel

The formation of inclusion in Ti–Al complex deoxidized C–Mn steel was investigated. When Al content in steel is very low ([Al]=0.0005%), for 0.003%<[Ti]<0.007%, the inclusion is the Al₂O₃–SiO₂–MnO–TiO_x composite inclusion; for [Ti]≥0.009%, the inclusion is TiO_x in the steel. When [Ti]=0.005%, [Al]<0.001%, the inclusion is the Al₂O₃–SiO₂–MnO–TiO_x composite inclusion; while [Al]>0.006%, inclusions would be pure Al₂O₃. The experimental results agree with the thermodynamics conclusions.     

Effects of Al content on non-metallic inclusion evolution in Fe–16Mn–xAl–0.6C high Mn TWIP steel

In the present study, the effects of Al content on the evolution of inclusions formed in Fe–16Mn–xAl–0.6C high Mn TWIP steels were investigated experimentally and discussed based on the thermodynamic calculation with FactSage. The results showed that with the increase of Al content from 0.002 to 2.1?wt-% in the steels, the evolution route of the main oxide inclusions is MnO?→?Al₂O₃?→?MgAl₂O₄?→?MgO, the main sulphide inclusion is changed from MnS to MgS, and the dominant stable inclusion changes along the route of MnO?→?Al₂O₃/MnS?→?MnS?→?AlN. The main inclusion types in thermodynamic calculation results with FactSage are consistent with the observed results in the present experimental steels.     

Formation and Evolution Mechanism of the Inclusions of Al2O3·SiO2·CaO and Al2O3·SiO2·CaO·MgO in Seamless Steel Tube Steel

Herein, the formation and evolution mechanism of inclusions of Al₂O₃·SiO₂·CaO and Al₂O₃·SiO₂·CaO·MgO in seamless steel tube steel are investigated. In the long strip defects on the longitudinal cross section of the steel tube after the rolling bar piercing, the defect is mainly formed by Al₂O₃·SiO₂·CaO·MgO inclusions and Al₂O₃·SiO₂·CaO·inclusions dotted with·CaS inclusions after the rolling. The typical inclusions in the different steelmaking stages are mainly composed of CaS, Al₂O₃·(SiO₂), CaO·(SiO₂), MnS·(TiN), Al₂O₃·SiO₂·CaO·(CaS)·(MnS), Al₂O₃·SiO₂·CaO·MgO·(MnO), Al₂O₃·SiO₂·CaO·MgO·(CaS)·(MnS), etc. In the billet, the average sizes of Al₂O₃·SiO₂·CaO-based and Al₂O₃·SiO₂·CaO·MgO-based inclusions are much larger than those of the other types of inclusions. Part of SiO₂ in the deoxidized products SiO₂ can be reduced by [Al], resulting in the formation of the Al₂O₃·SiO₂ composite inclusions. The SiO₂ in Al₂O₃·SiO₂ inclusions can continuously be reduced by the dissolved [Ca] to form the Al₂O₃·SiO₂·CaO composite inclusions. The SiO₂ in the Al₂O₃·SiO₂·CaO inclusions can be reduced by the dissolved [Mg] to form the Al₂O₃·SiO₂·CaO·MgO composite inclusions. Another formation process of Al₂O₃·SiO₂·CaO·MgO inclusions is the entrapment of ladle slag in the vacuum degassing (VD) stage, due to the strong agitation of the rising Ar bubbles in the vacuum condition of the VD stage.     

Phase equilibrium data and liquidus for the system “MnO”-CaO-(Al2O3 + SiO2) at Al2O3/SiO2 = 0.41

Phase-equilibrium data and the liquidus for the system “MnO”-CaO-(Al₂O₃-SiO₂) at a manganese-rich alloy saturation have been determined in the temperature range from 1423 to 1723 K. The results are presented in the form of a pseudoternary section “MnO”-CaO-(Al₂O₃ + SiO₂) with an Al₂O₃/SiO₂ weight ratio of 0.41. The following primary phases are present in the range of conditions investigated: 3Al₂O₃·2SiO₂; SiO₂; MnO·Al₂O₃·2SiO₂; (Mn,Ca)O·SiO₂; 2(Mn,Ca)O·SiO₂; MnO·Al₂O₃; (Mn,Ca)O; α-2CaO·SiO₂; α′-2CaO·SiO₂; 2CaO·Al₂O₃·SiO₂; CaO·SiO₂, and CaO·Al₂O₃·2SiO₂. The presence of alumina in this system is shown to have a significant effect on the liquidus compared to the system “MnO”-CaO-SiO₂, leading to the stabilization of the anorthite and gehlenite phases.     

A Reaction Between High Mn-High Al Steel and CaO-SiO2-Type Molten Mold Flux: Part I. Composition Evolution in Molten Mold Flux

In order to elucidate the reaction mechanism between high Mn-high Al steel such as twin-induced plasticity steel and molten mold flux composed mainly of CaO-SiO₂ during continuous casting process, a series of laboratory-scale experiments were carried out in the present study. Molten steel and molten flux were brought to react in a refractory crucible in a temperature range between 1713 K to 1823 K (1440 °C to 1550 °C) and composition evolution in the steel and the flux was analyzed using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and electron probe microanalysis. The amount of SiO₂ in the flux was significantly reduced by Al in the steel; thus, Al₂O₃ was accumulated in the flux as a result of a chemical reaction, 4[Al] + 3(SiO₂) = 3[Si] + 2(Al₂O₃). In order to find a major factor which governs the reaction, a number of factors ((pct CaO/pct SiO₂), (pct Al₂O₃), [pct Al], [pct Si], and temperature) were varied in the experiments. It was found that the above chemical reaction was mostly governed by [pct Al] in the molten steel. Temperature had a mild effect on the reaction. On the other hand, (pct CaO/pct SiO₂), (pct Al₂O₃), and [pct Si] did not show any noticeable effect on the reaction. Apart from the above reaction, the following reactions are also thought to happen simultaneously: 2[Mn] + (SiO₂) = [Si] + 2(MnO) and 2[Fe] + (SiO₂) = [Si] + 2(FeO). These oxide components were subsequently reduced by Al in the molten steel. Na₂O in the molten flux was gradually decreased and the decrease was accelerated by increasing [pct Al] and temperature. Possible reactions affecting the Al₂O₃ accumulation are summarized.     

Activities in MnO-SiO2-AI2O3 slags and deoxidation equilibria of Mn and Si

The activities of MnO and SiO₂ along the liquidus line in the MnO-SiO₂-Al₂O₃-Fe_tO (1.2 to 6.7 mass pct) system were determined at 1823 and 1873 K by using a slag-metal equilibration technique. On the basis of the re-evaluated MnO iso-activity curves, the SiO₂ and Al₂O₃ iso-activity curves were determined by using the ternary Gibbs-Duhem relation. The control of inclusions composition in Si-Mn killed steels is discussed based on the equilibria between inclusion and steel with respect to Si, Mn, Al, and O.     

Atomizing molten metals — a review

Abstract

Data from the literature were used to construct activity diagrams for the systems Mn–Fe–C, MnO–CaO–SiO₂ and CaO–Al₂O₃–SiO₂ with 10% MnO. Assuming that the reduction temperature is close to slag melting point, the MnO content required to obtain a 75% Mn alloy can be found. One can also calculate the Si content corresponding to the slag composition. Fixing the allowable %Si it is found that the slag will contain more than 25% MnO in the MnO–CaO–SiO₂ system. The effect of CO pressure is minor. If it is practical to add Al₂O₃ to the slag, its melting point can be lowered sufficiently to obtain slags with 10% MnO in the CaO–Al₂O₃–SiO₂ system while keeping Si in the metal low.

Résumé

Des données de la littérature ont été employées pour construire les diagrammes d'activité des systèmes Mn–Fe–C, MnO–CaO–SiO₂, et CaO–Al₂O₃–SiO₂ it 10% de MnO. En admettant que la température de la zone de réduction est proche de celle de fusion du laitier, on trouve la teneur en MnO nécessaire pour obtenir l'alliage à 75% de Mn. La quantité de Si réduit a également été déterminée. Le calcul montre qu'en fixant la teneur finale silicium à moins de 0.5% la teneur en MnO doit être supérieure à 25% . dans les laitiers MnO–CaO–SiO₂. La pression de CO n'a guere d'effet. S'il est pratique d'ajouter du Al₂O₃ au laitier pour en abaisser le point de fusion on peut obtenir avec un laiter it 10 % de MnO un alliage pour lequelle Si ne dépasse pas les bornes permises.     

Control of the manganese-oxygen reaction in pure iron melts

EMF sensor measurements using ZrO₂(CaO) or ThO₂(Y₂O₃) plug-type sensors with a Cr-Cr₂O₃ reference were performed to redetermine the Mn-O equilibrium reaction. In these experiments a strong effect of deoxidation of manganese was ascertained at saturation with solid deoxidation products. The measuring interval of the sensors at MnO saturation was limited to about 12 min due to chemical corrosion of the used Al₂O₃ sheaths. In the case of double saturation with solid MnO · Al₂O₃ (MA) and Al₂O₃ (A) the sensors could be used as long as desirable. Moreover, the combined deoxidation of the iron melt with Mn and Al was investigated. An auxiliary electrode at the tip of the sensor ensured rapid saturation of the iron melt with solid MnO or MnO · Al₂O₃ + Al₂O₃.     

Phase equilibrium studies in the “MnO”-Al2O3-SiO2 system

Phase relations and the liquidus surface in the system “MnO”-Al₂O₃-SiO₂ at manganese-rich alloy saturation have been investigated in the temperature range from 1373 to 1773 K. This system contains the primary-phase fields of tridymite and cristobalite (SiO₂); mullite (3Al₂O₃·2SiO₂); corundum (Al₂O₃); galaxite (MnO·Al₂O₃); manganosite (MnO); tephroite (2MnO·SiO₂); rhodonite (MnO·SiO₂); spessartine (3MnO·Al₂O₃·SiO₂); and the compound MnO·Al₂O₃·2SiO₂.     

Effect of Al2O3–SiO2–MnO inclusions on precipitation of MnS in Si–Mn-killed 304 stainless steels

Laboratory experiments and thermodynamic calculation were conducted to investigate the precipitation of MnS inclusions in Si–Mn-killed 304 stainless steels with various Al and S concentrations. Three types of MnS-contained inclusions were detected: MnS phase dissolved in the MnO–SiO₂ inclusion, the Al₂O₃-rich core phase surrounded by a MnS out layer, and the individual MnS. In steel with less than 0.001% Al, the liquid SiO₂–MnO-rich inclusions can hardly influence the precipitation of MnS inclusions during the cooling process of 304 stainless steels. With the increase of Al in steel, more solid Al₂O₃-rich inclusions are formed, which can act as nucleation agents for MnS inclusions and dramatically promote the precipitation of MnS inclusions during the cooling process of Si–Mn-killed 304 stainless steels.     

Critical assessment of activity coefficients of oxides in molten binary and ternary silicates,aluminates and aluminosilicates

Critical assessment is made of the activity coefficients of CaO, MgO, MnO, FeO, Al₂O₃ and SiO₂ in molten silicates, aluminates and aluminosilicates. In this assessment due consideration is given to the consistency of the free energies of formation of the interoxide compounds derived from the oxide activity data, compared with those derived from the compiled thermochemical data. For most oxides, it is found that by using an empirical formulation of the melt composition in ternary systems, the composition dependence of the oxide activity coefficient, γOX, can be represented by a single curve. For example, over a wide composition range in the FeO‐CaO‐SiO₂ system, the log(γCaO) is a single function of the melt composition in mol fraction as (?SiO₂ + 0.3xFeO); this relation being similar to that in the binary CaO‐SiO₂ melts. Therefore, with respect to γCaO, this ternary system is reduced to a pseudo binary system as xCaO ‐ (?SiO₂ + 0.3xFeO). With respect to γCaO, the ternary system CaO‐Al₂O₃‐SiO₂ is reduced to a pseudo binary system as xCaO ‐ (?SiO₂ + 0.4 xAl₂O₃). With γSiO₂, this ternary system is reduced to a pseudo binary system as (?CaO + xAl₂O₃) ‐ xSiO₂.     

Reduction of MnO from molten slags with liquid steel of high carbon content

This work estimated the reduction of MnO in slags of the CaO‐SiO₂‐FeO‐CaF₂‐MnO system and liquid steel with the initial composition (mass contents) 0.75 %Mn, 0.16 % Si and 0.5 to 2.0 % C, as an alternative to introducing Mn to the steel melt. The slag basicities (CaO/SiO₂) In the experiments were 2 and 3. MnO was obtained from manganese ore. The experiments were carried out in an open 10 kg induction furnace using Al₂O₃‐based refractory at 1873 K. The oxygen potential was measured throughout the experiments with a galvanic cell (ZrO₂‐solid electrolyte with a Cr/Cr₂O₃ reference electrode). The MnO reaction mechanism was analysed in terms of the slag basicity, the silicon and the initial carbon contents in the melt. The rate and the degree of MnO reduction were found to increase with the increasing of initial carbon content; however, the effect of slag basicity was less important. A kinetic analysis of the process was performed using a coupled reaction model.     

Activities of SiO2 and Al2O3 and activity coefficients of FetO and MnO in CaO-SiO2-Al2O3-MgO slags

The activities of SiO₂ and Al₂O₃ in CaO-SiO₂-Al₂O₃-MgO slags were determined at 1873 K along the liquidus lines saturated with 2CaO · SiO₂, 2(Mg,Ca)O · SiO₂, MgO, and MgO · Al₂O₃ phases using a slag-metal equilibration technique. Based on these and previous results obtained in ternary and quaternary slags, the isoactivity lines of SiO₂ and Al₂O₃ over the liquid region on the 0, 10, 20, 30, and 40 mass pct Al₂O₃ planes and those on the 10 and 20 mass pct MgO planes were determined. The activity coefficients of Fe _t O and MnO, the phase boundary, and the solubility of MgO were also determined.     

Characteristics analysis of inclusion of 60Si2Mn–Cr spring steel via experiments and thermodynamic calculations

A plant trial of the production of 60Si2Mn–Cr spring steel using silicon–manganese combined with aluminium to deoxidise was performed, and the characteristics of inclusions during ladle furnace refining, calcium treatment and in billets were investigated by scanning electron microscope–energy dispersive spectroscopy and thermodynamic calculations. The formation mechanisms of oxide and CaS inclusions are discussed. The experimental observation and thermodynamic analysis showed that calcium treatment cannot entirely modify large-size MgO·Al₂O₃ spinel inclusions into homogeneous CaO–MgO–Al₂O₃ inclusions, but formed a liquid xCaO·yAl₂O₃ layer on its surface. When the Al content was 0.05 mass%, [Mg], [Ca] and [O] in molten steel could be controlled at 2.7～5 ppm, 2.5～8 ppm and 4.1～5.2 ppm, respectively, to achieve inclusions in the low melting point region. A large amount of CaS was generated in the present process due to a higher sulphur concentration in the molten steel and an excessive amount of Ca–Si wire. To avoid/reduce its formation, the sulphur concentration should be controlled to below 70 ppm.     

Activity of MnO in MnO‐CaO‐MgO‐SiO2‐Al2O3 Slags at 1500 °C

A thermodynamic study was made on the MnO‐CaO‐MgO‐SiO₂‐Al₂O₃ slags that are typical of the production of ferromanganese in submerged arc furnaces. The Al₂O₃ content of the slags was kept constant at 5 per cent by mass. The activity‐composition relationship in Pt‐Mn binary alloys were re‐determined for calibration purposes at 1300, 1400 and 1500°C and po₂ values between 5.40×10^?6 and 4.54×10^?13 atm. A linear regression equation was derived to predict the activity coefficients of manganese, in Pt‐Mn alloys at 1500°C. The effect of concentration, basicity ratio and CaO‐to‐MgO ratio on MnO activities in above mentioned complex slags was investigated at 1500 °C and at two different po₂ values of 4.76×10^?7 and 5.80×10^?8 atm. It was found that a_Mno values increase with increasing MnO, and tend to increase with an increasing CaO‐to‐MgO ratio. The a_MnO values also increase with increasing basicity ratio. The activity coefficient of MnO increases with an increase in its mole fraction in the slag. Quadratic multivariable regression model equations which represent the activity data successfully and which can be used to predict the MnO activities in the compositional range of this study were developed. The MnO activity data was interpreted in terms of a slag model which describes the thermodynamic properties of the slag successfully.     

Dissolution Behavior of Mg from Magnesia-Chromite Refractory into Al-killed Molten Steel

Magnesia-chromite refractory materials are widely employed in steel production, and are considered a potential MgO source for the generation of MgO·Al₂O₃ spinel inclusions in steel melts. In this study, a square magnesia-chromite refractory rod was immersed into molten steel of various compositions held in an Al₂O₃ crucibles. As the immersion time was extended, Mg and Cr gradually dissolved from the magnesia-chromite refractory, and the Mg and Cr contents of the steel melts increased. However, it was found that the inclusions in the steel melts remained as almost pure Al₂O₃ because the Mg content of the steel melts was low, approximately 1 ppm. On the surface of the magnesia-chromite refractory, an MgO·Al₂O₃ spinel layer with a variable composition was formed, and the thickness of the MgO·Al₂O₃ spinel layer increased with the immersion time and the Al content of the steel melts. At the rod interface, the formed layer consisted of MgO-saturated MgO·Al₂O₃ spinel. The MgO content decreased along the thickness direction of the layer, and at the steel melts interface, the formed layer consisted of Al₂O₃-saturated MgO·Al₂O₃ spinel. Therefore, the low content of Mg in steel melts and the unchanged inclusions were because of the equilibrium between Al₂O₃-saturated MgO·Al₂O₃ layer and Al₂O₃. In addition, the effects of the Al and Cr contents of the steel melts on the dissolution of Mg from the magnesia-chromite refractory are insignificant.