D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... 681–686 SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY SECONDARY METALLURGY TRAJNOSTNE IN STRATE[KE MEHKOMAGNETNE Fe-Si-Al ZLITINE, IZDELANE S POSTOPKI SEKUNDARNE METALURGIJE Darja Steiner Petrovi~ Institute of Metals and Technology, Lepi pot 11, Ljubljana, Slovenia Prejem rokopisa – received: 2023-12-11; sprejem za objavo – accepted for publication: 2023-12-15 doi:10.17222/mit.2023.1072 In Slovenia, Fe-Si-Al alloys for non-oriented, silicon-steel sheets are designed and manufactured in a sustainable manner. Fer- rous scrap is recycled, and, therefore, CO 2 emissions are greatly reduced. However, sustainable technologies based on secondary metallurgy have many limitations. Impurities that cannot be effectively removed from the steel melt increase the complexity of the material’s behavior during processing and use. One of the most contaminating elements is copper (Cu). In this review, the focus is on phenomena related to the Cu impurity during the specific steps of the metallurgical processing of selected Fe-Si-Al alloys. The identified challenges concerning the efficiency of some technological phases related to the presence of Cu in Fe-Si-Al, non-oriented electrical steels might motivate further (inter)disciplinary research, basic or applied. In order to follow the set goals of the EU and achieve climate neutrality by 2050, silicon electrical steels produced with sustainable circular-econ- omy approaches must be recognized as a strategic material for the EU. Keywords: silicon steel, secondary metallurgy, impurities, copper, magnetic losses, EU Green Deal V Sloveniji so zlitine Fe-Si-Al za neorientirane silicijeve jeklene plo~evine zasnovane in izdelane na trajnosten na~in. V postopkih sekundarne metalurgije recikliramo jekleni odpad, s ~imer se znatno zmanj{ajo emisije CO 2. Vendar pa imajo trajnostne tehnologije, ki temeljijo na sekundarni metalurgiji, {tevilne omejitve. Ne~isto~e, ki jih ni mogo~e u~inkovito odstraniti iz jeklene taline, znatno pove~ajo kompleksnost obna{anja materiala med predelavo v kon~ni proizvod in v njegovi rabi. Ena najbolj obremenilnih ne~isto~ je baker (Cu). V pregledu je poseben poudarek namenjen pojavom, ki so povezani z ne~isto~o bakrom in u~inkovitostjo posameznih proizvodnih faz v izdelavi Fe-Si-Al neorientiranih elektroplo~evin. Identificirani izzivi, povezani s prisotnostjo bakra v zlitinah Fe-Si-Al lahko motivirajo nadaljnje (inter)disciplinarne raziskave, bodisi temeljne bodisi aplikativne. Da bi sledili zastavljenim ciljem EU in dosegli podnebno nevtralnost EU do leta 2050, bi morala biti silicijeva elektro jekla, proizvedena s pristopi trajnostnega kro`nega gospodarstva, prepoznana kot strate{ki material. Klju~ne besede: silicijevo jeklo, sekundarna metalurgija, ne~isto~e, baker, magnetne izgube, Evropski zeleni dogovor 1 INTRODUCTION The synthesis and processing of metallic materials is the largest single source of greenhouse-gas emissions in the world. 1 Metals production accounts for 40 % of all industrial greenhouse-gas emissions, 10% of global en- ergy consumption, 3.2 billion tonnes of minerals mined, and several billion tonnes of by-products every year. Therefore, metals must become more sustainable. 1 The European Green Deal is the EU’s new growth strategy, aiming to transform the EU into a fairer and more pros- perous society, with a modern, resource-efficient and competitive economy, with no net emissions of green- house gases by mid-century. 2 Specific priority topics of the EU Green Deal have been defined, i.e., Clean En- ergy, Circular Economy, Efficient Renovations, Sustain- able Mobility, Sustainable Food, Preserving Biodiversity, all of which contribute to climate action and zero-pollu- tion ambitions. However, achieving a climate-neutral and circular economy requires the full mobilisation of indus- try. All industrial value chains will have a key role to play. To meet the EU’s energy and climate targets for 2030, EU countries need to establish integrated national energy and climate plans that outline how the EU coun- tries intend to address five areas: energy efficiency, renewables, greenhouse-gas-emission reductions, inter- connections, and research and innovation. Therefore, the whole industry value chains along with the research and innovation sector will have a key role to play. 2 Becoming the world’s first climate-neutral continent by 2050 is a once-in-a-lifetime opportunity to modernise the EU’s economy and society towards a sustainable future. The purpose of the article is to present the role of the soft-magnetic material silicon steel and give an overview of the state of the key challenges related to the material produced via circular-economy routes. Since silicon steels are designed and manufactured in a sustainable manner also in Slovenia, a special focus is dedicated to the phenomena related to Cu impurity during the specific steps of the metallurgical processing of selected Fe-Si-Al alloys. Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686 681 UDK 669.14.018.583 ISSN 1580-2949 Original scientific article/Izvirni znanstveni ~lanek MTAEC9, 57(6)681(2023) *Corresponding author's e-mail: darja.steiner@imt.si (Darja Steiner Petrovi~) 2 SOFT-MAGNETIC SILICON STEELS Soft-ferromagnetic materials are alloys that magnet- ise and demagnetise with low hysteresis losses. 3,4 A mag- netic material is considered "soft" when its coercive field strength is of the order of or lower than the earth’s mag- netic field (about 40 A/m). A soft-magnetic material can be employed as an efficient flux multiplier in a large va- riety of devices, including transformers, generators, and motors, to be used in the generation, distribution, and conversion of electrical energy, and a wide array of appa- ratus, from household appliances to scientific equip- ment. 5 Silicon steels are the most important soft-mag- netic material occupying most of the soft-magnetic mar- ket. Almost 97 % of soft-magnetic materials produced today are silicon electrical steels made of Fe-Si or Fe-Si-Al alloys. Over 12 million tons are produced annu- ally, around 80 % of which are non-oriented (NO) grades, the remainder being grain-oriented (GO) silicon steels. In electrical machines NO grades are used almost exclusively. 6,7 The development of new classes of high-specific-power electrical machines and drives is constantly required. 8 In Slovenia, non-oriented electrical steels are pro- duced by SIJ Acroni d.o.o., Jesenice. 9 Their SIWATT brand includes non-oriented electrical steel that is essen- tial for the economical production, conversion, distribu- tion and use of electricity. Various grades of Fe-Si-Al electrical steels under SIWATT are characterised by magnetising ability, high magnetic permeability and low losses and are built into the magnetic cores of electric motors and generators. For the optimal design of the soft-magnetic material ex-ante material’s characterization is necessary, includ- ing a definition of the chemical composition of the steel along with extensive thermodynamic and microstructure modellings, and magnetic-loss prediction. Ex-post chem- ical, mechanical, metallographic and magnetic character- ization analyses are dedicated to the optimization of the material’s properties. These generally include analyses of the steel’s chemical composition and purity, mechani- cal tests, microstructure analysis and grain-size measure- ments, the texture characterization and the magnetic-loss measurements. Many of their properties derive from an interplay of processing, microstructure, and chemistry, on scales that reach from manufacturing dimensions. This turns research on magnetic materials not only a multi-physics and multi-scale problem, but also requires close collaboration between characterization, processing, and theory. 3 3 THE METALURGY OF SILICON STEELS PRODUCED USING CIRCULAR-ECONOMY ROUTES The accumulation of impurities in the recycling of steel impacts the quality of secondary steel. Understand- ing impurity levels is crucial in the context of the prolif- eration of circular-economy policies, expected high recy- cling rates, and the growth of scrap consumption. 10 The complexity of the materials’ behaviour, and conse- quently, the metallurgical processing of silicon steels for magnetic applications increases with the complexity of steels’ chemical composition. Si being a ferrite stabilizer increases the ferrite phase fraction of Fe. 11 The addition of Si to iron brings notable changes in the physical, me- chanical and magnetic properties of the Fe. The most no- table effect regards the electrical resistivity. Alloying with Al instead of Si leads to similar physical and struc- tural effects, while not causing material embrittlement. However, Al is very reactive and prone to oxide forma- tion, but it brings an increase in magnetostriction. 5 When circular-economy approaches are involved, i.e., second- ary-metallurgy routes, the steel’s cleanliness becomes an important factor for silicon steels that are to be further processed into grain-oriented or non-oriented electrical steel sheets and coils. In the electric-arc-furnace (EAF) steelmaking process, the main raw material is ferrous scrap, and an inspection of its quality is the first crucial step in producing clean steel. Ferrous scrap is the most recycled material in the world, and through its utiliza- D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... 682 Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686 Figure 2: Rotor magnetic cores for electric motors 9 Figure 1: Coils of soft-magnetic Fe-Si-Al steel (SIWATT brand of SIJ Acroni d.o.o., Jesenice, Slovenia) 9 tion, CO 2 emissions can be significantly reduced. Ac- cording to the statistical data of The World Steel Associ- ation, 12 the imports and exports of scrap rose globally to >200 million metric tonnes in total, and that value is still increasing. However, efforts must be focused on the overall chemical composition of the steel. Since different qualities of scrap steel are used, the contents of impurity elements Cu, Sn, Sb, As, Ti, etc. can vary, and the con- trol of the residual elements must be appropriate. 13,14 It is well known that the Cu content constantly increases in secondary steels. The first cross-national comparison of impurity accumulation in recycled steel 10 has shown that the content of Cu impurity was higher in Western Europe and Japan than in Ukraine, Vietnam, and China. The main sources of copper contamination are automotive scrap, waste electric and electronic equipment (WEEE) and demolition waste. Cu is mixed with cut metal scrap during shredding and is difficult to separate, unless done manually. This scrap is not fully separated from copper parts in electric motors and electrical wires. Another Cu source is scrap with a high Cu content, like rebars and stainless steel. Because information on the type of con- sumed scrap in all investigated countries was not avail- able, the variation of the Cu content between countries was considered only in terms of the separation practices during recycling. 10 4 CHALLENGES CONCERNING COPPER IMPURITY Impurities that cannot be effectively removed from the steel melt increase the complexity of the material’s behavior. One of the most contaminating elements in secondary steels is copper (Cu). 4.1 Decarburization The decarburization of industrial cold-rolled sheets made of Fe-Si-Al steels produced by secondary metal- lurgy is performed by annealing in a wet gas mixture at temperatures around 850 °C. The principal reaction that controls the decarburization 7,15,16 is equation (1): [C] Fe +H 2 O(g) = CO(g) + H 2 (g) (1) The exact technological parameters depend mainly on the chemical composition of the steel and are carried out according to prescribed technological methods. The decarburization is determined by the chemical reactions between the gas mixture and the carbon at the steel’s sur- face. The temperature of the annealing, the composition of the gas mixture and the chemical composition of the steel are the influencing parameters that determine the kinetics and the mechanism of decarburization. The decarburization process of steel consists of several steps, among which is the diffusion of carbon to the steel sur- face among the most influential ones. One of our previ- ous studies shows that the carbon surface segregation in the Fe-1.8Si-0.5Al alloys was hindered by the presence of larger amounts of copper (e.g, up to 0.6 w/% Cu) in the steel. Carbon diffusion within the matrix of silicon steel is considered the rate-limiting step in the early stages of decarburization. 17 Elucidating the effectiveness of this metallurgical process in complex alloy systems such as secondary Fe-Si-Al steel is of utmost importance. 4.2 Magnetic properties The core loss of the non-oriented electrical steel is defined as the dissipation of electrical energy in the form of heat during magnetization by an alternating current. In spite of the fact that the core-loss prediction in laminated magnetic circuits has generated relentless scientific re- search efforts, the almost forty-year-old Statistical The- ory of Losses is still prevailing in this domain. 18 Since modern electrical energy conversion exposes laminated magnetic circuits to higher frequencies and larger excita- tion fields, novel models for core-loss prediction are pro- D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686 683 Figure 3: Carbon surface segregation in Fe-1.8 w/%Si-0.5 w/%Al alloys with different contents of Cu (0.3 w/%Cu and 0.6 w/%Cu, respectively) after annealing in vacuum posed. 18–22 Numerous parameters, including the chemical composition and the production technology, influence the magnetic properties of the electrical steel. 23 Increased core loss could also result from the increased cumulative (total) value of the impurity elements in the steel. Impu- rities can have a synergy effect on the deterioration of the magnetic properties. Their elevated contents mean a larger number of inclusions and precipitates. 7,24–26 An investigation of four different grades of fully-fin- ished, non-oriented, electrical steels manufactured of secondary Fe-Si-Al alloys, with the silicon content from 1.0 to 2.5 w/% has shown that the slope of the total mag- netic losses curve with increasing frequency is deter- mined by the rate of magnetic domains mobility. The higher is the density of magnetic domains, the smaller is their mobility. The complexity of the magnetic domains and their surroundings is decreasing with increasing con- tent of alloying elements. The rate of magnetic domains mobility is affected by the number of non-metallic inclu- sions and precipitates, which hinder the movement of magnetic domains and eddy currents, which produce losses and limit the mobility of domain walls. 27 4.3 Magnetic aging A necessary condition for obtaining high-quality electrical steel is a minimal amount of magnetic ag- ing. 28,29 Therefore, the electrical steel must be free of car- bon and contain only small quantities of nitrogen. A low carbon content is important because the carbon that is in the form of -carbide at temperatures above 150 °C is eliminated within the crystal grains, and with the nitrides acting as a barrier to the movement of Bloch walls, there is a substantial deterioration in the electromagnetic prop- erties. This process is called magnetic aging. In terms of the magnetic aging of non-oriented electrical steel of dif- ferent qualities in reference to Si content, at temperatures of 225 °C and 300 °C, the most significant impact comes from the carbon content in the steel. To prevent magnetic aging associated with the precipitation of carbides, pre- dominantly Fe 3 C and -carbide Fe 2.4 C, the decarburi- zation of the cold-rolled steel sheets is a very important processing step. 7 Various iron carbides precipitate and degrade the magnetic properties by interfering with mag- netic domain-wall motion. The slow precipitation of car- bides during service can cause a substantial increase in the core losses. A study on the magnetic aging 30 of Fe-Si-Al alloys produced using secondary metallurgy has shown that the extent of the magnetic aging was af- fected by the copper content. The results indicate that the proportion of magnetic aging decreases with increasing copper content in samples. 30 In general, the mobility and rotation of the magnetic domains are affected by the non-metallic inclusions and precipitates, which consti- tute barriers to the movement of the magnetic domains. To clearly determine the role of copper precipitates on the magnetic behavior, final magnetic properties and magnetic aging of non-oriented electrical steels, further studies are needed. 5 POTENTIAL RESEARCH TOPICS ON THE SUSTAINABILITY OF METALS Recently, Raabe has proposed several novel direc- tions for a potential basic research on the direct D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... 684 Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686 Figure 5: Epstein tester for measurements of magnetic properties of soft-magnetic silicon steels 9 Figure 4: Instrument for measurements of magnetic properties of soft-magnetic silicon steels 9 – MPG 200D Brockhaus Messtechnik sustainability of metals, 1 some of them being: (i) effi- ciency of metallurgical processes, (ii) recycling of well-sorted scrap, (iii) the nanoscrap recycling from complex modern products (microelectronics and cata- lysts), (iv) a deep understanding of all impurity and con- taminant effects in the entire spectrum of alloys, scrap, reductants, by-products, waste products and minerals, (v) multi-element and high-quality recycling, (vi) material- and recycling-oriented product design, etc. Based on this, metallurgical sustainability can be expected to break down into a large spectrum of different disciplines and branches. 1 6 SUMMARY Ferrous scrap is the most recycled material in the world, and through its utilization CO 2 emissions can be greatly reduced. In order to follow the set goals of the EU and achieve climate neutrality by 2050, silicon elec- trical steels produced with sustainable circular-economy approaches must be recognized as a strategic material for the EU. Therefore, the soft-magnetic silicon steels are strategic not only in the economic, but also in the social sense. Sustainable technologies based on the secondary metallurgy that recycles steel scrap have many limita- tions. Impurities that cannot be effectively removed from the steel melt increase the complexity of the material and its behavior. One of the most contaminating element in secondary Fe-Si-Al alloy is copper (Cu). The identified challenges concerning the unexplained mechanisms and efficiency of some metallurgical processes related to the presence of Cu in Fe-Si-Al steels (e.g., decarburization, magnetic domains mobility, magnetic aging, etc.) may motivate further (inter)disciplinary research, basic or ap- plied. 6 REFERENCES 1 D. Raabe, Materials Science behind Sustainable Metals and Alloys, Chemical Reviews 123 (2023), 2436–2608, doi:10.1021/acs. chemrev.2c00799 2 https://commission.europa.eu/strategy-and-policy/priorities-2019- 2024/european-green-deal_en, 8. 12. 2023 3 https://www.mpie.de/4673836/magnetic-materials, 8. 12. 2023 4 B. D. Cullity, C. D. Graham, Introduction to Magnetic Materials, 2 nd ed., Wiley – IEEE Press, New Jersey 2008, 317–325 5 F. Fiorillo, G. Bertotti, C. Appino, M. Pasquale, Soft Magnetic Mate- rials, in Wiley Encyclopedia of Electrical and Electronics Engi- neering, (2016), 1–42, doi:10.1002/047134608X.W4504.pub2 6 A. Krings, A. Boglietti, A. Cavagnino and S. Sprague, Soft Magnetic Material Status and Trends in Electric Machines, IEEE Trans Indus- trial Electronics, 64 (2017) 3, 2405–2414, doi:10.1109/TIE.2016. 2613844 7 D. Steiner Petrovi~, Non-oriented electrical steel sheets - a review, Mater. Tehnol., 44 (2010) 6, 317–325 8 A. El-Refaie, M. Osama, High Specific Power Electrical Machines: A System Perspective, CES TEMS 3 (2019), 88–93, doi:10.1109/ ICEMS.2017.8055931 9 https://sij.acroni.si/en/, 8. 12. 2023 10 D. Panasiuk, I. Daigo, T. Hoshino, H. Hayashi, E. Yamasue, D.H. Tran, B. Sprecher, F. Shi, V. Shatokha, International comparison of impurities mixing and accumulation in steel scrap, Journal of Indus- trial Ecology, 26 (2022) 1040–1050, doi:10.1111/jiec.13246 11 T. B. Massalski, Binary Alloy Phase Diagrams, ASM, Materials Park, Ohio 1991, 1772 12 Steel Statistical Yearbook 2018; The World Steel Association: Brussels, Belgium, 2019; Available online: https://www.world- steel.org/en/dam/jcr:e5a8eda5-4b46-4892-856b-00908b5ab492/SSY _2018.pdf, 8. 12. 2023 13 A. Martinelli Miranda, P. S. Assis, G. A. Brooks, M.A. Rhamdhani, A. Fontana, A. King, G. Sanders, G. P. Da Costa Moreira, Moni- toring of less-common residual elements in scrap feeds for EAF steelmaking, Ironmaking and Steelmaking 46 (2019), 598–608, doi:10.1080/03019233.2019.1601851 14 D. Steiner Petrovi~, Kinetics of Arsenic Surface Segregation in Scrap-Based Silicon Electrical Steel. Metals, 11 (2021)1 , doi:10.3390/met11010001 15 N. Birks, Decarburization, The Iron and Steel Institute, London 1970, 1–11 16 D. Steiner Petrovi~, M. Jenko, V. Dole~ek, The influence of Copper on the decarburization and recrystallization of Fe-Si-Al alloys, Ma- ter. Tehnol., 40 (2006) 1, 13–16 17 L. Wen, L. Ai, L. Hong, Y. Zhou, G. Zhu, C. Sun, Diffusion Behavior of Carbon and Silicon in the Process of Preparing Silicon Steel Using Solid-State Decarburization, Processes 11 (2023), 3176, doi:10.3390/ pr11113176 18 B. Ducharne, G. Sebald, Fractional derivatives for the core losses prediction: State of the art and beyond, Journal of Magnetism and Magnetic Materials, 563 (2022) 169961, doi:10.1016/j.jmmm.2022. 169961 19 J. Füzer, S. Dobák, I. Petryshynets, P. Kollár, F. Ková~, J. Slota, Cor- relation between Cutting Clearance, Deformation Texture, and Mag- netic Loss Prediction in Non-Oriented Electrical Steels, Materials, 14 (2021), 6893, doi:10.3390/ma14226893 20 G. Novak, J. Koko{ar, M. Bricelj, M. Bizjak, D. Steiner Petrovi~, A. Nagode, Improved Model Based on the Modified Steinmetz Equation for Predicting the Magnetic Losses in Non-Oriented Electrical Steels That is Valid for Elevated Temperatures and Frequencies, IEEE Transactions on Magnetics, 53 (2017) 10, 1–5, doi: 10.1109/TMAG. 2017.2726500 21 G. Novak, J. Koko{ar, A. Nagode and D. Steiner Petrovi~, Core-Loss Prediction for Non-Oriented Electrical Steels Based on the Steinmetz Equation Using Fixed Coefficients With a Wide Frequency Range of Validity, IEEE Transactions on Magnetics, 51 (2015) 4, 1–7, doi:10.1109/TMAG.2014.2354317 22 G. Novak, J. Kokosar, A. Nagode, D. Steiner Petrovic, Correlation between the excess losses and the relative permeability in fully fin- ished non-oriented electrical steels, Mater. Tehnol., 48 (2014)6 , 997–1001 23 M. Dems, Z. Gmyrek, K. Komeza, The Influence of Cutting Tech- nology on Magnetic Properties of Non-Oriented Electrical Steel—Review State of the Art, Energies 16 (2023), 4299, doi:10.3390/en16114299 24 D.Steiner Petrovi~, M. Jenko, A HRAES study of the morphology of non-metallic inclusions in non-oriented electrical steel containing Cu and Se, Vacuum, 71 (2003) 1–2, 33–40, doi:10.1016/S0042- 207X(02)00710-8 25 M. Wu, Y. Zeng, Effect of copper precipitates on the stability of microstructures and magnetic properties of non-oriented electrical steels, Journal of Magnetism and Magnetic Materials, 391 (2015) 96–100, doi:10.1016/j.jmmm.2015.04.085 26 D. Steiner Petrovi~, M. Jenko, A. Jakli~, A. ^op, Correlation of Tita- nium content and core loss in non-oriented electrical steel sheets, Metalurgija, 49 (2010) 1, 37–40 D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686 685 27 G. Novak, Designing of electromagnetic properties of non-oriented electrical steel, PhD Thesis, University of Ljubljana, Faculty of Nat- ural Sciences, Ljubljana 2015, 1–172 28 A. J. Moses, Energy efficient electrical steels: Magnetic performance prediction and optimization, Scripta Materialia, 67 (2012)6 , 560–565, doi:10.1016/j.scriptamat.2012.02.027 29 M. F. de Campos, M. Emura, F. J. G. Landgraf, Consequences of magnetic aging for iron losses in electrical steels, Journal of Magne- tism and Magnetic Materials, 304 (2006), 2, e593–e595, doi:10.1016/j.jmmm.2006.02.185 30 A. Kofol, Magnetic aging of non-oriented electrical steels, MSc The- sis, University of Ljubljana, Faculty of Natural Sciences, Ljubljana 2016, 1–130 D. STEINER PETROVI^: SUSTAINABLE AND STRATEGIC SOFT-MAGNETIC Fe-Si-Al ALLOYS PRODUCED BY ... 686 Materiali in tehnologije / Materials and technology 57 (2023) 6, 681–686