Effect of Mg on the evolution of non-metallic inclusions in Mn–Si–Ti deoxidised steel during solidification: experiments and thermodynamic calculations

Abstract

The effects of Mg on the evolution of non-metallic inclusions in Mn–Si–Ti deoxidised steels during solidification were investigated in a study based on experiments and thermodynamic calculations. The inclusions were composed of the MgO–MnO–Ti₂O₃–TiO₂ oxide, MnS, and TiN. With the increase of Mg concentration in steels, the phases of oxide inclusions were changed, in the order of pseudobrookite (Ti₃O₅–MnTi₂O₅), ilmenite (MgTiO₃–MnTiO₃–Ti₂O₃), spinel (Mg₂TiO₄–MgTi₂O₄–Mn₂TiO₄–MnTi₂O₄) and MgO. Thermodynamic calculations for inclusion evolutions were in good agreement with the experimental results.     

Catalyst effects in heterogeneous nucleation of acicular ferrite

The present investigation is concerned with basic studies of the mechanisms of acicular ferrite (AF)’formation in low-alloy steel weld metal. It is confirmed experimentally that different types of orientation relationships exist between AF and specific cubic inclusion constituent phases(i.e., γ-Al₂ MnOAl₂O₃, and TiN). Since the majority of these falls within the Bain orientation region, it is concluded that the associated reduction of the energy barrier to nucleation is the primary cause for the ferrite nucleus to develop orientation relationships with both the substrate and the austenite. Theoretical calculations show that about 12 pct of the inclusions will contain a cubic phase that lies within the Bain region purely by chance if they are randomly orientated in space. This intrinsic density of heterogeneous nucleation sites is sufficiently high to promote the formation of fine, interlocking AF laths in the weld metal during they- to- a transformation.     

Hybrid Laser-Arc Welding of X90 Pipeline Steel: Effect of Laser Power on Microstructure and Mechanical Properties

In this work, hybrid laser-arc welding process was applied to X90 pipeline steel which has wide potential applications in the future pipeline project. The effect of different laser power (1.0, 1.5 and 2.5 kW) on microstructure and mechanical properties of weld joints was investigated. It has been found that a macroscopic morphology of “wine cup like” is observed in the weld joint with increasing laser power, where fusion zone (FZ) and heat-affected zone (HAZ) can be clearly identified. The FZ microstructure mainly includes massive ferrite, acicular ferrite (AF), and increased laser power resulting in a decrease in AF content. The HAZ consists of coarse-grained HAZ (CGHAZ), fine-grained HAZ (FGHAZ) and mixed-grained HAZ (MGHAZ). The hardness ranging from the weld center to base metal decreases and then increases, and the effect of laser power on hardness is not significant. The increased laser power leads to an evident decrease in the ultimate tensile strength and impact toughness of weld joint. The highest ultimate tensile strength and impact energy are 815 MPa, 239.1 J respectively at a laser power of 1.0 kW. A number of inclusions are observed at the bottom of dimples, which may be the (Ti,Mn)₂O₃ particles.     

Effect of cooling after welding on microstructure and mechanical properties of 12 Pct Cr steel weld metals

The microstructure of three 12 pct cr steel weld metals with different nickel and nitrogen contents was studied in as-welded condition and after postweld heat treatment with and without intercooling. Tensile strength and impact toughness of the weld metals were investigated in different postweld heat treatment conditions. In weld metals heat treated without intercooling, austenite decomposed by a eutectoid reaction that resulted in M₂₃C₆ aggregates around retained δ-ferrite. Two morphologies of M₂N and MN precipitates were found in a low-dislocation α-ferrite. It was concluded that these phases were also transformed from austenite. In weld metals heat treated with intercooling, M₂₃C₆ precipitates were smaller and more homogeneously distributed. Different MN precipitates were found in the tempered martensite. The fracture mode of the weld metals at room temperature was mainly transgranular cleavage with some fibrous fracture. Intercooling treatment improved Charpy impact toughness of the 12 pct Cr steel weld metals substantially. It was found that the important microstructural factors affecting the impact toughness of the weld metals which were heat treated without intercooling were the sizes of the α-ferrite grains, nonmetallic inclusions, and M₂₃C₆ aggregates. For the weld metals heat treated with intercooling, the factors which affect the toughness of the weld metals were the sizes of martensite packets and nonmetallic inclusions.     

The origin of transformation textures in steel weld metals containing acicular ferrite

The present investigation is concerned with basic studies of the development of transformation textures in steel weld metals, using the electron backscattering pattern (EBSP) technique. It is shown that the acicular ferrite (AF) plates exhibit an orientation relationship with both the austenite and the prior delta ferrite columnar grains in which they grow. The observed orientation relationship lies within the Bain orientation region and can be described by three texture components,i.e., a 〈100〉 component and two complementary 〈111〉 components. Each of these texture components is orientated approximately parallel with the original cell/dendrite growth direction. Measurements of the spatial misorientation between neighboring plates confirm that the morphology of AF in low-alloy steel weld metals bears a close resemblance to upper bainite.     

Study of a titaniferous magnetite chlorination at high temperature

The chlorination of a titaniferous magnetite with low content in Ti and Fe has been studied between 1273 and 2273 K. Most of the hercynite and ilmenite initially present are decomposed during the gas-solid phase reaction between 1273 and 1823 K. Considerable ilmenite decomposition and FeCl₃evolution already occur at 1273 K, leaving a residue consisting of TiO₂, Fe₂O₃-TiO₂ (pseudobrookite), and about 50 pct of each of the Cr and Mg initially present. X-ray diffractograms shown the formation of Al₂TiO₅ which contributes to the stabilization of TiO₂ up to 1773 K, above which temperature significant decomposition of Al₂TiO₅ is observed. At the melting point of the titaniferous magnetite sample (around 1823 K), the presence of both solid and liquid phases result in a considerable decrease in the chlorination rate. In this respect, heating the sample under helium up to the melting point, so that liquid and solid phases are obtained at equilibrium, yields two structures replacing the magnetite present just prior to melting. One of these structures is of the spinel Fe₂TiO₄ type, while the other is a combination of the spinel types MgAl₂O₄, FeAl₂O₄, and MgCr₂O₄. When the sample is chlorinated, a high proportion of the initial Cr (90 pct) and Ti (80 pct) are found in the chlorination residue at the early stages of fusion, together with 13 pct of the initial Fe. Chlorination of the liquid phase between 1823 and 2273 K shows a steady decrease of Ti and Cr in the chlorination residue, associated with an increase of Fe content.     

Modification and Minimization of Spinel(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>·<Emphasis Type="Italic">x</Emphasis>MgO) Inclusions Formed in Ti-Added Steel Melts

High-melting-point inclusions such as spinel(Al₂O₃·xMgO) are known to promote clogging of the submerged entry nozzle (SEN) in a continuous caster mold. In particular, Ti-alloyed steels can have severe nozzle clogging problems, which are detrimental to the slab surface quality. In this work, the thermodynamic role of Ti in steels and the effect of Ca and Ti addition to the molten austenitic stainless steel deoxidized with Al on the formation of Al₂O₃·xMgO spinel inclusions were investigated. The sequence of Ca and Ti additions after Al deoxidation was also investigated. The inclusion chemistry and morphology according to the order of Ca and Ti are discussed from the standpoint of spinel formation. The thermodynamic interaction parameter of Mg with respect to the Ti alloying element was determined. The element of Ti in steels could contribute to enhancing the spinel formation, because Ti accelerates Mg dissolution from the MgO containing refractory walls or slags because of its high thermodynamic affinity for Mg ( e_\textMg^\textTi = - 0. 9 3 3). ( {e_{\text{Mg}}^{\text{Ti}} = - 0. 9 3 3}). Even though Ti also induces Ca dissolution from the CaO-containing refractory walls or slags because of its thermodynamic affinity for Ca ( e_\textCa^\textTi = - 0.119 ), \left( {e_{\text{Ca}}^{\text{Ti}} = - 0.119} \right), dissolved Ca plays a role in favoring the formation of calcium aluminate inclusions, which are more stable thermodynamically in an Al-deoxidized steel. The inclusion content of steel samples was analyzed to improve the understanding of fundamentals of Al₂O₃·xMgO spinel inclusion formation. The optimum processing conditions for Ca treatment and Ti addition in austenitic stainless steel melts to achieve the minimized spinel formation and the maximized Ti-alloying yield is discussed.     

Molybdenum-Nitride Precipitation in Recrystallized and Cold-Rolled Fe-1 at. pct Mo Alloy

Nitriding of recrystallized and cold-rolled Fe-1 at. pct Mo alloy at 853 K (580 °C) in a NH₃/H₂ gas mixture leads to the formation of cubic nanometer-sized Mo₂N-type precipitate platelets. These platelets obey a Baker–Nutting orientation relationship with the ferrite matrix. After prolonged nitriding, micrometer-sized colonies of lamellae consisting of a hexagonal MoN-type nitride and ferrite develop in a discontinuous precipitation reaction. These nitride lamellae have a Burgers-type orientation relationship with the ferrite lamellae. As compared to the recrystallized specimens, in the cold-rolled specimens, the precipitation of the initial Mo₂N-type platelets occurs much faster and moreover leads to incoherently diffracting precipitates; upon continued nitriding, a much earlier but only partially occurring transition of Mo₂N-type to MoN-type precipitates is observed. The results indicate that incorporation of iron in the nitrides can occur, if at all, only up till a negligible level, thereby invalidating earlier data.     

Study of inclusions in a failed aero-engine component

The cause of the fatigue failure in the retaining ring of the compressor region of an aero-engine turbine was found to be the presence of a high concentration of nonmetallic inclusions. The results of chemical analysis were used to estimate the phases present. The most frequently observed inclusions were spinel solid solutions of the type MO · N₂O₃, where M=Fe, Mn, or Mg and N=Cr or Al. The detrimental inclusions were corundum, calcium aluminates, cristobalite, and silicates. The most detrimental phases were traced on the surfaces of the specimens fractured using impact loading; the comparison is being made with the polished surfaces and the tensile specimen fracture surfaces. The inclusions in the failed retaining ring were compared with the ones in a similar component obtained from a used engine. In the case of the latter, a large number of fine and elongated (Mn, Cr, Fe)S inclusions were present along with spinels. The nondeformable, rigid oxide particles are considered more undesirable than the sulfides as far as fatigue life of the component is concerned. It has been reported that the presence of sulfides may eliminate the stresses due to oxides.     

Addition of Dispersoid Titanium Oxide Inclusions in Steel and Their Influence on Grain Refinement

In this article, the addition of dispersoid titanium oxide inclusions into liquid steel, the effect of additions on the inclusions found in the steel and on grain refinement, and acicular ferrite formation were studied. Different TiO₂-containing materials and addition procedures into liquid steel were tested in experimental heats to obtain inclusions that promote grain refinement and acicular ferrite formation in C-Mn-Cr steel. Different additives with metallic Ti and TiO₂ were added into the steel melt just before casting or into the mold during casting to create Ti-containing inclusions. The aluminum content in steel was lowered by an addition of iron oxide. The samples taken from steel melts and ingots were studied with a scanning electron microscope to find inclusions and to analyze them. Thermodynamic calculations showed that the Al content should be low (<50 ppm) to obtain Ti oxide dominating inclusions, whereas Al₂O₃ were formed at higher Al contents. When TiO₂ was added late before casting, the oxide inclusions were Ti oxides and were mixed with Ti, Al, and Mn oxides. Small inclusions around 1 μm were detected in the samples with TiO _x or TiN as the main component. It could be concluded that the additions resulted in a clearly higher number and in a smaller size of TiO _x inclusions than just by adding metallic Ti. Selected samples were brought for subsequent hot rolling and heat-treatment experiments to find out the grain-refining effect and the eventual formation of acicular ferrite. Grain refinement was observed clearly, but the presence of acicular ferrite could not be confirmed definitely.     

Étude de la valorisation de la magnétite titanifère de la région de Magpie,Québec: Partie II — Composition et structure de la fonte et de la scorie obtenues par fusion réductrice d'un concentré magnétique

Abstract

A magnetic concentrate from Magpie titaniferous iron ore has been smelted in a pilot scale arc furnace. A pig iron containing most of the chromium and vanadium of the ore has been obtained, while the titanium remained in the slag. The main phases occurring in this slag are a pseudobrookite-type solid solution, a spinel and several silicates. The composition of pseudobrookite depends on the reducing conditions and can reach 90% TiO₂. The spinel composition is on the MgAl₂O₄ side of the MgAl₂O₄-Mg₂TiO₄ solid solution.

Résumé

Des essais de fusion réductrice au four électrique en présence de carbone, ont été réalisés sur un concentré magnétique du minerai de Magpie. Ce traitement permet d'obtenir une fonte contenant la plus grande partie du chrome et du vanadium, et une scorie titanifere. Cette dernière est constituée d'une pseudobrookite, d'un spinelle et de silicates. La pseudobrookite est une solution solide de composition variable suivant le degré de réduction et titrant plus de 90% en TiO₂. Le spinelle est de composition voisine de MgAl₂O₄.     

In situ observation of austenite grain growth and transformation temperature in coarse grain heat affected zone of Ce-alloyed weld metal

Laser scanning confocal microscopy(LSCM) was used to study the inhibition of austenite grain growth by the inclusions and the effect of cerium on the trend of acicular ferrite(AF) and ferrite side plate(FSP) transformation temperature in coarse grain heat affected zone(CGHAZ) of Ce-alloyed weld metals. The results showed there were lots of tiny cerium oxides and sulfides inclusions in the CGHAZ of Ce-alloyed weld metals. When the concentration of Ce was 0.021%, the volume fraction of inclusions in weld metal CGHAZ was higher and the inclusion size was smaller, therefore austenite grain size was smaller with the increase of hightemperature residence time. Cerium tended to segregate at austenite grain boundaries, so FSP transformation temperature decreased and FSP transformation was suppressed. On the contrary, AF transformation temperature increased because AF transformation was promoted in CGHAZ of the Ce-alloyed weld metal, especially when the concentration of Ce was 0.021%.     

Inclusion evolution during refining and continuous casting of 316L stainless steel

The formation and characteristics of non-metallic inclusions in 316L stainless steel produced by the AOD (argon oxygen decarburization)–ladle furnace–continuous casting process were investigated. The morphology and composition of inclusions changed significantly during the refining and casting processes. After de-oxidation with Si/Mn additions, spherical complex inclusions mainly consisting of calcium silicates were observed. The contents of MgO and Al₂O₃ in these inclusions continuously increased as the steel moved from the AOD through ladle processing to the tundish. As the temperature decreased from the tundish through to solidification, harmful crystals of MgO/Al₂O₃ spinel were precipitated within the steel melt as well as within the calcium silicate matrix of existing inclusions. The results obtained from thermodynamic calculations carried out using FactSage? commercial software agreed well with the information derived from evaluation of the industrial samples enabling recommendations to be made for the avoidance of detrimental spinel inclusions.     

Inclusion phases and the nucleation of acicular ferrite in submerged arc welds in high strength low alloy steels

Series of submerged arc welds of HSLA steel made with three different fluxes and metallic additions of Ti, Mo, and Cr have been examined to study the inclusions and their role in the nucleation of acicular ferrite. Inclusion phases and compositions have been analyzed by electron diffraction and X-ray microanalysis. These analyses have shown that the inclusions contained many different compounds, the proportions of each depending upon both the flux and metallic additions. Six inclusion phases have been identified: galaxite (Al₂O₃ ⋅ MnO), a titanium-rich compound (probably TiO), a copper sulfide, a manganese sulfide, a silica, and an aluminum-rich phase. No correlation was found between the amount of acicular ferrite in the weld metal and either average inclusion composition or individual inclusion phases. No epitaxial relationships between inclusions and adjacent ferrite grains could be identified. It has been concluded that inclusions nucleate acicular ferrite by acting as inert substrates according to the classical theory of heterogeneous nucleation. Because most inclusions are multi-phase and are touched by several ferrite grains, it has also been concluded that each inclusion can nucleate several ferrite grains, due to local regions of high surface energy on the inclusion.     

Hydrolytic stripping of single and mixed metal-versatic solutions

Hydrolytic stripping is the process whereby metal ions in a loaded solvent extractant are directly precipitated as oxides or hydroxides by hydrolysis with water, typically at 130° to 200 °C. Hydrolytic stripping tests were carried out in sealed tubes at 200 °C on Versatic 10 solutions of Mg, Ca, Sr, Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Zn, and Cd, singly and in mixtures. Single solutions of Fe, Ni, Cu, Mg, and Mn precipitated αFe₂O₃, Ni(OH)₂, CuO + Cu₂O, Mg(OH)₂, and γMn₂O₃, respectively, during testing. Several mixtures of iron with other metals precipitated magnetic spinel ferrites, MFe₂O₄. No other combinations of metals formed crystallographically distinctive mixed oxides.     

Thermodynamics on the formation of spinel (MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) inclusion in liquid iron containing chromium

The stability diagram of MgO, spinel solid solution (MgO·(Al _X Cr_1−X )₂O₃), and sesquioxide solid solution ((Al _Y Cr_1−Y )₂O₃) as a function of Mg, Al, and O contents at a constant chromium content (18 mass pct) in liquid iron is drawn at 1873 K. The interaction parameters between Mg and other solutes (Al, Cr, Ni, Ti, Si, and C) are determined by the experimental method, which assures equilibrium between Mg vapor and liquid iron, were applied to calculate the diagram. Titanium deoxidation is not recommended for the prevention of spinel formation, because Ti accelerates Mg dissolution from refractory or slag due to its high affinity for Mg (e _Mg ^Ti = − 0.64). The standard Gibbs free energies of formation for the three inclusions (periclase, spinel, and sesquioxide solid solutions) and the tielines between two solid solutions were calculated with the aid of the regular solution model and the thermochemical F*A*C*T database computing system, respectively. The phase stability regions and oxygen content in steel for the current Fe-Mg-Al-Cr (18 mass pct)-O system are compared with those of the previous non-Cr system. Detailed information on the spinel composition according to Mg and Al contents is also available from the present stability diagram.     

Microstructural Evolution of the Interface Between Pure Titanium and Low Melting Point Zr-Ti-Ni(Cu) Filler Metals

Low melting point Zr-based filler metals with melting point depressants (MPDs) such as Cu and Ni elements are used for titanium brazing. However, the phase transition of the filler metals in the titanium joint needs to be explained, since the main element of Zr in the filler metals differs from that of the parent titanium alloys. In addition, since the MPDs easily form brittle intermetallics, that deteriorate joint properties, the phase evolution they cause needs to be studied. Zr-based filler metals having Cu content from 0 to 12 at. pct and Ni content from 12 to 24 at. pct with a melting temperature range of 1062 K to 1082 K (789 °C to 809 °C) were wetting-tested on a titanium plate to investigate the phase transformation and evolution at the interface between the titanium plate and the filler metals. In the interface, the alloys system with Zr, Zr₂Ni, and (Ti,Zr)₂Ni phases was easily changed to a Ti-based alloy system with Ti, Ti₂Ni, and (Ti,Zr)₂Ni phases, by the local melting of parent titanium. The dissolution depths of the parent metal were increased with increasing Ni content in the filler metals because Ni has a faster diffusion rate than Cu. Instead, slow diffusion of Cu into titanium substrate leads to the accumulation of Cu at the molten zone of the interface, which could form undesirable Ti _x Cu _y intermetallics. This study confirmed that Zr-based filler metals are compatible with the parent titanium metal with the minimum content of MPDs.     

Investigation of Oxide Inclusions and Primary Carbonitrides in Inconel 718 Superalloy Refined through Electroslag Remelting Process

The effect of remelting atmosphere and calcium treatment during electroslag remelting (ESR) of Inconel 718 superalloy on the oxide inclusions and primary carbonitrides was investigated. The results show that after ESR refining combined with calcium treatment, the original oxide inclusions in the electrode, mainly MgO·Al₂O₃ spinels and some MgO inclusions, were modified to CaO-Al₂O₃ system inclusions or the inclusions of MgO·Al₂O₃ spinel core surrounded by CaO-MgO-Al₂O₃ system inclusion layer. Without the calcium treatment in ESR process, all the oxide inclusions in superalloy ingots are MgO·Al₂O₃ spinels. All the oxide inclusions in ESR ingots act as the nucleation site for carbonitride (Nb,Ti)CN with two-layer structure precipitation, except for those with a single (Nb,Ti)CN layer containing a small amount of Ti and N in the ingot refined by a proper amount of calcium addition in ESR process. The carbonitrides (Nb,Ti)CN formed directly on the oxide inclusion have a small amount of Nb and C as well as a relatively fixed atomic ratio of Nb/Ti (about 0.6:1). There is a Nb-rich and C-rich (Nb,Ti)CN layer on the pre-existing (Nb,Ti)CN formed on the oxide inclusion. The size of the observed carbonitrides is in the range of 5 ??m to 15 ??m. The calcium treatment in the ESR process has a significant effect on the morphology of carbonitrides in superalloy ingot due to modification of oxide inclusions by Ca-treatment resulting in the change of precipitation and growth conditions for carbonitrides. The morphologies of carbonitrides were changed from clustered block or single octahedral to skeleton-like after calcium treatment.     

Effects of FeO and CaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al₂O₃) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al₂O₃ spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al₂O₃ spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al₂O₃ inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al₂O₃ spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.