Thermo‐elastic Homogenization of 3‐D Steel Microstructure Simulated by the Phase‐field Method

A multi‐scale approach based on the asymptotic homogenization method of periodic material structures is applied here to determine the effective thermo‐elastic properties of 3D steel microstructures, which have been calculated by phase‐field simulations. A multiphase‐field model, coupled to thermodynamic databases, is used to evaluate the microstructure evolution during the austenite to ferrite phase transformation of low carbon Fe‐C‐Mn steel. In order to derive effective mechanical properties, geometrical information about the grains, their phase properties and crystallographic orientations are transferred to the homogenization tool. Effective cubic Young and shear modules and Poisson coefficients are predicted for different ferrite volume fractions. Moreover, the volume change is derived as function of the phase fractions, leading to a calculated dilatometer curve. The effects of the thermal shrinkage and the volume expansion caused by the phase transformation are taken into account.     

Galvannealing of (High‐)Manganese‐Alloyed TRIP‐ and X‐IP®‐Steel

In this study the influence of Mn on galvannealed coatings of 1.7% Mn‐1.5% Al TRIP‐ and 23% Mn X‐IP®‐steels was investigated. It is shown that the external selective oxides like Mn, Al and Si of the TRIP steel which occur after annealing at 800 °C for 60 s at a dew point (DP) of ‐25 °C (5% H₂) hamper the Fe/Zn‐reaction during subsequent galvannealing. Preoxidation was beneficially utilized to increase the surface‐reactivity of the TRIP steel under the same dew point conditions. The influence of Mn on the steel alloy was investigated by using a 23% Mn containing X‐IP®‐steel which was bright annealed at 1100 °C for 60 s at DP ‐50 °C (5% H₂) to obtain a mainly oxide free surface prior to hot dip galvanizing (hdg) and subsequent galvannealing. As well known from the literature Mn alloyed to the liquid zinc melt stabilizes δ‐phase at lower temperatures by participating in the Fe‐Zn‐phase reactions, it was expected that the metallic Mn of the X‐IP®‐steel increases the Fe/Zn‐reactivity in the same manner. The approximation of the effective diffusion coefficient (D_eff(Fe)) during galvannealing was found to be higher than compared to a low alloyed steel reference. Contrary to the expectation no increased Fe/Zn‐reaction was found by microscopic investigations. Residual η‐ and ζ‐phase fractions prove a hampered Fe/Zn‐reaction. As explanation for the observed hampered Fe/Zn‐reaction the lower Fe‐content of the high‐Mn‐alloyed X‐IP®‐steel was suggested as the dominating factor for galvannealing.     

Composition Control of CaO‐MgO‐Al2O3‐SiO2 Inclusions in Tire Cord Steel ‐ a Thermodynamic Analysis

The effect of oxide component content on the low melting point zone (LMP) in the CaO‐MgO‐Al₂O₃‐SiO₂ system has been analysed using FactSage software. The contents of dissolved elements [Si], [Mg], [O] and [Al] in liquid steel in equilibrium with the LMP inclusions in the CaO‐MgO‐Al₂O₃‐SiO₂ system have been calculated. The results show that the CaO‐MgO‐Al₂O₃‐SiO₂ system has the largest LMP zone (below 1400°C) when the Al₂O₃ content is 20% or the MgO content is 10%. The LMP zone becomes wide with the increase in CaO content (within the range of 0~30 mass%) and the decrease in SiO₂ (from 25 to 5 mass%). To obtain the LMP (below 1400°C) inclusions, the [Mg], [Al] and [O] contents must be controlled within the range of 0.2~2 ppm, 1.0~2.0 ppm and 60~100 ppm, respectively.     

Reoxidation of Ni‐ and Ni‐Fe‐Alloys by Al2O3‐SiO2 Refractory Materials

Reactions at the refractory/melt interface during ingot casting of Ni‐ and Ni‐Fe‐alloys were studied. The casts were performed using different alumino‐silicate bricks as refractory materials. Samples taken from the casting channel before and after casting were investigated using light and scanning electron microscopy with XPS. Thermodynamic calculations were performed with FactSage and the results were compared with the results from industrial tests. After the melt has infiltrated the surface layer of the bricks, refractory corrosion starts with an attack of Mn and Mg of the melt on SiO₂ and Fe₂O₃ of the refractory bonding matrix. Despite the presence of elements with higher oxygen affinity in the melt, low‐melting alumino‐silicate phases are predominantly built by the reaction with Mn and Mg. In a second step this liquid phase either traps non‐metallic inclusions from the melt or, at higher contents of Zr, Ti, Mg, Y etc. in the melt, causes massive reoxidation and inclusion formation. The refractory materials investigated show an increasing trend for reoxidation with an increasing amount of SiO₂ in glassy phases of the refractory bonding matrix. By the use of a refractory material with higher mullite content in the bonding matrix or by use of alumina bricks a strong reoxidation of the melt and intense inclusion formation can be avoided. These observations are also valid for other alloys with higher contents of elements with high affinity to oxygen.     

Micro Semi‐solid Manufacturing ‐ A New Technological Approach towards Miniaturisation

One of the most important prerequisites to meet the increasing demand for efficient technologies for micro‐part production is constituted by the ability to overcome existing process limitations by new innovative technological approaches. By the introduction of a new process variant based on a hybrid material condition between solid and liquid state, such an approach is presented. This micro semi‐solid manufacturing technology, so‐called Micro‐Thixoforming, was initiated, on the one hand, by being aware of the technological limits of existing micro‐forming and micro‐casting processes and, on the other hand, by a comprehensive understanding of the special rheological mechanisms of metallic materials in semi‐solid state finally establishing the desired potential to follow the trend towards miniaturisation with drastically reduced process restrictions. However, this promising potential can only be successfully exploited when the initial idea, which is based on phenomenological considerations, can be transferred to a process technology with sufficient practical relevance. Therefore, the presented new integrated process concept for Micro‐Thixoforming is particularly characterised by the application of unconventional solutions for the main process steps: raw material conditioning, thermal pre‐processing, semi‐solid forming and thermal post‐processing. To give an indication of the innovative character of the chosen practical solutions liquid metal jet technology, LASER‐induced plasma shockwaves and high pressure water jet should be mentioned. However, what is even more important in this context is the ability not only to realise a process concept but, beyond that, to recognise the further potential regarding new strategies for material design arising from the availability of this process. Such a strategy e.g. consists of utilising the well‐known segregation effect, which notably often is negatively associated with semi‐solid forming. However, for the envisaged technological approach, controlled segregation aims at a defined adjustment of functionally graded properties for the produced micro part.     

Viscosities of the Quaternary Al2O3‐CaO‐MgO‐SiO2 Slags

Viscosities of some quaternary slags in the Al₂O₃‐CaO‐MgO‐SiO₂ system were measured using the rotating cylinder method. Eight different slag compositions were selected. These slag compositions ranging in the high basicity region were directly related to the secondary steel making operations. The measurements were carried out in the temperature range of 1720 to 1910 K. Viscosities in this system and its sub‐systems were expressed as a function of temperature and composition based on the viscosity model developed earlier at KTH. The iso‐viscosity contours in the Al₂O₃‐CaO‐MgO‐SiO₂ system relevant to ladle slags were calculated at 1823 K and 1873 K for 5 mass% MgO and 10 mass% MgO sections. The predicted results showed good agreement with experimental values and the literature data.     

Sulphide Capacities of CaO‐SiO2‐Al2O3‐MgO Slags

In Japanese steelworks, hot metal is now being produced by a scrap melting process. With this process, removals 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 handicaps, the authors explored on the respective phase diagrams. These explorations revealed that {CaO‐SiO₂‐Al₂O₃‐MgO} slags with Al₂O₃ contents of 30‐ to 35‐pct by weight would be good candidates as reagents for sulphur removal from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, sulphide capacities were determined through gas/slag equilibrium technique. The experimental results suggest that there would be, at least, a “window” to remove sulphur from high sulphur hot metal as relatively low temperatures.     

The Effect of MgO on the Viscosity of the CaO‐SiO2‐20 wt%Al2O3‐MgO Slag System

The viscosities of CaO‐SiO₂‐20 wt%Al₂O₃‐MgO slags (CaO/SiO₂ = 1.0–1.2, wt%MgO = 5–13) were measured to estimate the effect of MgO on the viscous behaviour at elevated temperatures. The slag viscosity at 1773 K decreased with increasing MgO contents, which was typical of a basic oxide component at relatively low basicity (CaO/SiO₂) of 1.0. The FT‐IR spectroscopic analysis of the slag structure seems to verify this behaviour. However, an unexpected contradiction with the temperature dependence was observed above 10 wt%MgO and above CaO/SiO₂ of 1.2. Although the apparent activation energy was expected to decrease with additions of the basic oxide component MgO, the apparent activation energy increased. This unexpected behaviour seems to be related to the change in the primary phase field correlating to the phase diagram corresponding to the slag composition. Therefore, in order to understand the viscosity at both high Al₂O₃ and MgO, not only should the typical depolymerization of the slag structure with high MgO content be considered but also the primary phases of which the molten slag originates.     

Transformation Conditions ‐ Microstructures ‐ Mechanical Properties Relationship in 0.60%C Hypoeutectoid Steel

The relationship between transformation conditions, microstructures and mechanical properties were investigated on a 0.60%C hypoeutectoid steel, which has predominantly pearlitic microstructure. The steel had been austenized at 850‐1050 °C and then isothermally transformed at 570‐660 °C. Afterwards, the microstructures were analyzed by optical microscope, scanning electron microscope, and quantitative metallography. And the mechanical properties were determined. The results indicated that the interlamellar spacing, the pearlitic colony size and the proeutectoid ferrite content follow a linear relationship with the reciprocal of the undercooling, and the strength, the hardness and the toughness follow a Hall‐Petch type of relationship with the inverse of the square root of the interlamellar spacing. Besides, the stress condition should be taken into account during analyzing the effect of the interlamellar spacing on the mechanical properties. The results have been explained on the basis of transformation conditions ‐ microsturctures ‐ mechanical properties ralationship.     

Water Capacity Model of Al2O3‐CaO‐MgO‐SiO2 Quaternary Slag System

The focus of the present work was to develop a water capacity model for the quaternary slag system Al₂O₃‐CaO‐MgO‐SiO₂. In the model, a silicate melt was considered to consist of two ion groupings, viz. cation grouping and oxygen ion. The water capacity of a melt is supposed to depend on the interactions between the cations in the presence of oxygen ions. These interactions were determined on the basis of the experimentally measured water solubility data. Only binary interactions were employed in the model. For the system CaO‐SiO₂, disagreement in the literature data was found. Since the interaction between Ca²⁺ and Si⁴⁺ would play an important role, experiments were carried out to determine the water capacities of some CaO‐SiO₂ slags. For this purpose a thermogravimetric method was employed. Iso‐lines of water capacities at constant MgO contents were predicted by the model and compared with the experimental data from literature. The model calculations agreed well with the experimental results.     

Effects of Influencing Factors on Distribution Behaviors of Vanadium between Hot Metal and FeO‐SiO2‐MnO (‐TiO2) Slag System

The distribution behavior of vanadium between a hot metal and a FeO‐SiO₂‐MnO (‐TiO₂) slag system was studied under laboratory conditions, together with the effects of influencing factors such as temperature, slag composition, the ratio of slag to hot metal, and the initial Si and/or Ti content in hot metal. The results suggested that in a ternary FeO‐SiO₂‐MnO slag system, with an increase in temperature and an increase in the SiO₂ content of slag, the extraction ratio ($\eta _{V} $ ), distribution ratio of V ($L_{V} $ ) and the vanadium capacity of the slag ($C_{VO_{3} {}^{3{-} } } $ ) decreased, while the effect of MnO content in slag showed a different tendency under different situations. For both high and low ratios of slag to hot metal, the extraction ratio of V reached its maximum value under slag compositions of 13%–25% MnO and 10%–24% SiO₂, which correspond to the regions with lower melting point and lower viscosity of the slag. In a quaternary FeO‐SiO₂‐MnO‐TiO₂ slag system,$\eta _{V} $ ,$L_{V} $ , and $C_{VO_{3} {}^{3{-} } } $ decreased, while the activity coefficient of V₂O₃ increased, as the TiO₂ content increased. Further, the data suggested that under laboratory conditions the effects of influencing factors on the extraction ratio of V from hot metal decreased in the following order: final slag composition > temperature > initial Si and/or Ti content in hot metal.     

Mechanical Behavior of Deformation‐Induced α′‐Martensite and Flow Curve Modeling of a Cast CrMnNi TRIP‐Steel

For the modeling of the mechanical behavior of a two phase alloy with the rule of mixture (RM), the flow stress of both phases is needed. In order to obtain these information for the α′‐martensite in high alloyed TRIP‐steels, compression tests at cryogenic temperatures were performed to create a fully deformation‐induced martensitic microstructure. This martensitic material condition was subsequently tested under compressive loading at ?60, 20, and 100°C and at strain rates of 10^?3, 10⁰, and 10³ s^?1 to determine the mechanical properties. The α′‐martensite possesses high strength and surprisingly good ductility up to 60% of compressive strain. Using the flow stress behavior of the α′‐martensite and that of the stable austenitic steel AISI 316L, the flow stress behavior of the high alloyed CrMnNi TRIP‐steel is modeled successfully using a special RM proposed by Narutani et al.     

In‐Situ Measurement of CO‐ and CO2‐Concentrations in BOF Off‐Gas

Improvement of the efficiency and productivity of steelmaking requires accurate and real‐time process information to precisely adjust the tapping conditions. The response time of BOF process control systems is commonly depending on the time needed for off‐gas sampling and analysis. A FTIR based measurement system was adapted and installed at an industrial steel converter of ArcelorMittal España S.A. in Aviles. An advanced data interpretation routine based on the quantum mechanical fundamentals of remote infrared (IR) spectroscopy was developed to enable precise determination of the {CO}‐ and {CO₂}‐concentrations, resp. their ratio, in the off‐gas. The results of the industrial measurement showed the ability of the FTIR based system for real‐time measurement of temperature, {CO}‐ and {CO₂}‐concentrations in the hot and dusty off‐gas. The influence of dust at the chosen defined optical path lengths in the IR wavelengths region can be neglected, but the collector lens clean has to be kept clean.     

Iron‐Rich Iron‐Aluminium‐Molybdenum Alloys with Strengthening Intermetallic μ phase and R phase Precipitates

Single‐phase and two‐phase ternary Fe‐Al‐Mo alloys with Al contents of usually 10 ‐16 at.% and Mo contents up to 42 at.% have been studied with respect to hardness at room temperature, yield stress and fracture strain at room temperature and higher temperatures up to 1000 °C and oxidation at temperatures of 400 ‐ 1000 °C. Thse alloys are strengthened by precipitation of the metastable R phase and/or the stable m phase depending on composition and heat treatment; both are hard and brittle intermetallic phases. The yield stress as well as the brittle‐to‐ductile transition temperature increases with increasing Mo content to reach yield stresses above 1400 MPa with, however, fracture strains below 1 % at temperatures below 800 °C. The observed short‐term oxidation is similar to that of other Fe‐Al alloys.     

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.     

Influence of Manganese and Nickel on the α´ Martensite Transformation Temperatures of High Alloyed Cr‐Mn‐Ni Steels

The martensite start temperature (M_s), the martensite austenite re‐transformation start temperature (A_s) and the re‐transformation finish temperature (A_f) of six high alloyed Cr‐Mn‐Ni steels with varying Ni and Mn contents in the wrought and as‐cast state were studied. The aim of this investigation is the development of the relationships between the M_s, A_s, A_f, T₀ temperatures and the chemical composition of a new type of Cr‐Mn‐Ni steels. The investigations show that the M_s, A_s and A_f temperatures decrease with increasing nickel and manganese contents. The A_f temperature depends on the amount of martensite. Regression equations for the transformation temperatures are given. The experimental results are based on dilatometer tests and microstructure investigations.