Study on the mechanism of external current inhibiting the adsorption of rare earth inclusions in molten steel by aluminum and magnesium refractory

Study on the mechanism of external current inhibiting the adsorption of rare earth inclusions in molten steel by aluminum and magnesium refractory | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Study on the mechanism of external current inhibiting the adsorption of rare earth inclusions in molten steel by aluminum and magnesium refractory Xiaonan Zheng, Diqiang Luo, Chaobin Lai, Hebin Wang, Chao Pan This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-8876255/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract This study aims to reveal the intrinsic mechanism by which external positive charge inhibits the adsorption of rare earth Y-based inclusions (Y, Y₂O₃, Y₂O₂S) on MgO and Al₂O₃ refractory surfaces, thereby providing a theoretical foundation for the active control of nozzle clogging during the continuous casting of rare earth steels. To this end, first-principles calculations based on density functional theory were employed, integrated with partial density of states analysis, charge density difference visualization, and high-temperature thermodynamic evaluations. The adsorption behaviors under neutral and positively charged states (+ 2, + 4) were systematically compared. The results demonstrate that external positive charge suppresses interfacial adsorption through a triple mechanism. Electronically, it disrupts the energy alignment and orbital hybridization between O-p and Y-d states, leading to significant attenuation of interfacial covalent bonding. Electrostatically, the net positive background reverses the local interfacial environment from electrostatic affinity to repulsion, establishing a physical barrier that hinders adsorbate approach. Thermodynamically, the Gibbs free energy change ΔG increases markedly under charged conditions, reflecting a quantifiable and universal reduction in adsorption spontaneity across all adsorbates and substrates. These findings clarify the mechanism of external charge inhibiting the adsorption of rare earth inclusions in molten steel by refractory. Metallurgy rare earth steel nozzle clogging applied current adsorption inhibition mechanism Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Introduction Rare earth has the functions of purifying inclusions, refining microstructure and strengthening properties in steel[ 1 – 3 ]. It is the key microalloying element for preparing high strength and toughness weathering steel[ 4 – 6 ].However, rare earth Y and its inclusions (Y 2 O 3 , Y 2 O 2 S) are adsorbed and deposited on the inner wall of Al 2 O 3 and MgO nozzles, which can block the flow channel within a few hours, resulting in the interruption of continuous casting[ 7 , 8 ]. According to statistics, the loss of a single accident is hundreds of thousands of yuan, and the annual loss of rare earth steel is more than ten million yuan[ 9 ]. With the increasing demand for rare earth microalloying in high-speed rail and nuclear power steels, this problem has evolved into a common technical problem that restricts the stable production of high-end steels[ 10 , 11 ]. The traditional protection strategies include alloy modification[ 12 – 13 ], coating protection[ 15 – 18 ] and flow field optimization[ 19 , 20 ]. Although these methods are effective, they are all ' off-line ' passive defense. The protection ability cannot be changed after the nozzle is installed, which can not be adjusted in real time according to the change of steel grade, and it is more difficult to intervene actively in the germination stage of blockage. In the face of the fluctuation of rare earth addition and the acceleration of smelting rhythm, traditional technology is not enough. Impressed current control technology provides a transformative solution for this[ 21 ]. Only by applying a weak current, a ' protective layer ' that can respond dynamically can be established on the nozzle wall to achieve millisecond-level, continuous and reversible active regulation of adsorption strength[ 22 ]. This is an anti-blocking technical path with real-time, reversible and quantitative adjustment potential[ 23 ]. However, its core scientific problem-how the current changes the interface adsorption from the electronic structure level-is still a ' black box '[ 24 ]. How do electrons transfer ? How to reconstruct the track ? How to cut off the bond ? How to weaken the thermodynamic driving force ? The unclear inhibition mechanism makes the electrochemical anti-blocking technology stay in the empirical exploration stage for a long time, and it is impossible to form a predictable and designable engineering scheme. In this paper, the microscopic mechanism of ' current inhibition interface adsorption ' was revealed from the cross-validation of electronic structure and thermodynamics. The triple inhibition mechanism of 'orbital hybridization attenuation-electrostatic environment repulsion-inhibition of chemical reaction ' was found. The nozzle anti-blocking technology is advanced from experience trial and error to a new scientific stage of mechanism design.The research results provide an urgent theoretical foundation for the development of electrochemical anti-nodulation nozzle for rare earth steel continuous casting. Computational details We used the DFT as implemented in the Vienna Ab initio simulation package (VASP) in all calculations. The exchange-correlation potential is described by using the generalized gradient approximation of Perdew-Burke-Ernzerhof (GGA-PBE). The projector augmented-wave (PAW) method is employed to treat interactions between ion cores and valence electrons. The plane-wave cutoff energy was fixed to 450 eV. A Γ-centered 5×5×5, for Al 2 O 3 and MgO bulks. A Monkhorst-Pack k-mesh with a 2×2×1 k-point grid was used for structural optimization. Given structural models were relaxed until the Hellmann-Feynman forces smaller than − 0.02 eV/Å and the change in energy smaller than 10 − 5 eV was attained. The 15 Å vacuum layer was normally added to the surface to eliminate the artificial interactions between periodic images. Grimme’s DFT-D3 methodology was used to describe the dispersion interactions among all the atoms in adsorption models. The adsorption energy (Eads) of species is calculated by: Eads = E(system)-E(catalyst) -E(species) where E(system), E(catalyst), and E(species) are the total energy of the optimized system with adsorbed species, the isolated catalyst, and species, respectively. The Gibbs free energy change is defined as: ΔG = ΔE + ΔZPE – TΔS where ΔE is the electronic energy calculated with VASP, ΔZPE and ΔS are the zero-point energy difference and the entropy change between the products and reactants, respectively, and T is the temperature (1473.15 -1873.15 K).The PBE functional and PAW pseudopotential method are used in the calculation, and the DFT-D3 Grime method is considered for van der Waals correction. The charge density difference (CDD) was computed as: Δ ρ = ρ total − ρ substrate − ρ adsorbat where ρ total is the charge density of the fully relaxed adsorption system, ρ substrate and ρ adsorbat are the charge densities of the isolated substrate and adsorbate. with all three components calculated in the identical supercell and fixed atomic coordinates. For charged systems (+ 2, + 4), the total electron number was reduced via the NELECT tag, and the same NELECT value was enforced for the total, substrate, and adsorbate calculations to guarantee the validity of the CDD analysis. Isosurface plots were generated using VESTA at ± 0.001 e/ų. The PDOS projections onto atomic orbitals (O-p, Y-d, Y-s) were extracted from the self-consistent charge densities using the LORBIT = 11 tag, which projects the wavefunctions onto spherical harmonics within the PAW spheres. All PDOS curves were broadened by a Gaussian smearing with a width of 0.05 eV. The Fermi level was aligned to zero energy for all systems. For charged systems (+ 2, + 4), the same NELECT settings as in the charge density difference calculations were consistently applied to ensure the comparability of the electronic structures under identical charge backgrounds. The orbital-projected PDOS spectra were visualized to identify the energy match, peak mirroring, and hybridization characteristics between Y-d/Y-s and O-p orbitals across different charge states. Results and Discussions Firstly, the adsorption behavior of Y atom, Y₂O₃ and Y₂O₂S species on the MgO(001) and Al₂O₃(001) substrate surfaces was systematically investigated via first-principles calculations. Three distinct high-symmetry adsorption sites were evaluated on each substrate: the hollow (H) site located above the surface oxygen anion, the bridge (B) site situated at the midpoint of the Mg–O or Al–O bond, and the top (T) site directly above the surface Mg or Al cation. The initial adsorption configurations for each adsorbate at these sites were constructed with an initial vertical separation of 30 Å between the adsorbate and the outmost substrate layer, ensuring negligible spurious interaction prior to relaxation. Full structural optimization was performed without any symmetry constraints, allowing all atomic degrees of freedom to relax until the residual forces converged below 0.02 eV/Å. The initial and fully relaxed configurations for all adsorption systems are illustrated in Fig. 1 . A comparative analysis of the geometric evolution before and after relaxation reveals a consistent and site-selective migration tendency: adsorbates initially positioned at the bridge (B) and top (T) sites spontaneously migrate toward the hollow (H) site during optimization, ultimately residing at or in close proximity to the O-top hollow position. This relaxation behavior is observed across all adsorbate types (Y, Y₂O₃, Y₂O₂S) and both substrate compositions (MgO, Al₂O₃), indicating a **strong thermodynamic preference** for the H-site configuration. The driving force underlying this preferential adsorption can be attributed to the **maximization of orbital overlap** between the Y‑centered orbitals (4d/5s) and the unsaturated p orbitals of the surface oxygen anions at the hollow site, which provides a multi-coordination environment and facilitates more effective charge transfer and covalent bonding. In contrast, the bridge and top sites offer fewer nearest-neighbor oxygen ligands and less favorable orbital alignment, resulting in weaker interfacial interaction and metastable character. Consequently, the hollow site is identified as the energetically most stable adsorption configuration for all investigated Y‑based inclusions on MgO and Al₂O₃ surfaces. The average distance between (Y, Y₂O₃, Y₂O₂S) and (MgO, Al 2 O 3 ) surface in steel increases monotonically with the increase of forward applied current, and the change is nonlinear. Except for the adsorption of Y atoms by Al 2 O 3 , they all show the characteristics of ' rapid weakening → gradual saturation '. When the external positive charge reaches + 4, the distance between some atoms and the surface is greater than 3.5 Å, which exceeds the geometric gap between oxides dominated by van der Waals interaction. It shows that the adsorption gradually changes from chemical adsorption dominated by chemical bonds to physical adsorption dominated by physical adsorption and tends to the limit, and finally forms repulsive phenomenon far away from the surface of the material. Moderately increasing the positive charge can effectively inhibit the adsorption of(Y, Y₂O₃, Y₂O₂S) species on (MgO, Al 2 O 3 ). The main suppression effect has been achieved in the smaller current interval, and the current revenue continues to increase. The adsorption energy changes of MgO and Al 2 O 3 on Y, Y 2 O 3 and Y 2 O 2 S show a significant performance gap. When adsorbing Y atoms in steel, the increase of surface charge of Al 2 O 3 and MgO will significantly reduce the adsorption capacity of Y. Especially in the case of high surface charge + 0, the adsorption energy of Al 2 O 3 to Y is close to − 19 eV / mol, which is much higher than that in the case of surface charge + 4. MgO also shows a decrease in adsorption strength under high surface charge, but the change is gentle. When adsorbing Y 2 O 3 and Y 2 O 2 S inclusions in steel : with the increase of charge, the adsorption energy of MgO and Al 2 O 3 changes gently. The adsorption degree of Al 2 O 3 on Y 2 O 3 and Y 2 O 2 S inclusions is always slightly higher than that of MgO. The increase of surface charge may cause the increase of the potential barrier of the surface itself, which leads to the weakening of the electrostatic binding force on the adsorbate, and also changes the interaction between the surface atoms and the adsorbed molecules. For Al 2O 3, the increase of positive charge may lead to the weakening of the interaction between alumina and Y on the surface, thus reducing the adsorption energy. When MgO and Al 2 O 3 adsorb Y 2 O 3 and Y 2 O 2 S, the increase of surface charge does not significantly affect their adsorption energy, indicating that the surface interaction of MgO and Al 2 O 3 on these adsorbates is relatively stable and is not easily affected by the change of surface charge. Al 2 O 3 shows a larger change than MgO, which may be related to its higher surface chemical activity.。 Figure 5 and Fig. 6 show the effect of applied current on the enthalpy ( H ) and entropy ( S ) of the adsorption process with temperature. In the temperature range of 1473 K-1873 K, the enthalpy and entropy of all adsorption systems increased linearly with the increase of temperature, but the change rate of entropy was relatively flat. In the temperature range above 1473 K, the effect of temperature fluctuation on the adsorption entropy change is limited. The dominant control variable of interface adsorption behavior is no longer temperature, but non-thermodynamic factors such as interface chemical potential, charge state and cluster size. By studying and comparing the change rules of the free energy of the adsorption system under different external charge states, it is found that the Gibbs free energy change ( ΔG ) of the adsorption reaction in the positive charge (+ 2, + 4 ) state is significantly greater than that in the uncharged ( 0 ) state, regardless of whether the substrate is MgO or Al 2 O 3 for Y 2 O 3 , Y 2 O 2 S or a single Y atom adsorption system, regardless of the substrate is MgO or Al 2 O 3 . This result has a clear and unified thermodynamic meaning : the external positive charge reduces the quantification of the spontaneous driving force of the adsorption reaction, and the interface adsorption equilibrium moves towards the direction of dissociation, that is, the external charge has a universal inhibitory effect on the adsorption behavior of Y-type inclusions on the oxide surface. The external positive charge induces a systematic reduction in the electron cloud density of oxygen atoms on the substrate surface, thereby significantly diminishing their nucleophilicity. This electronic depletion indicate that the cyan dissipation regions—which represent electron loss from the substrate—contract progressively as the applied positive charge increases from 0 to + 2 and + 4. This contraction provides direct visual evidence that the overall positive charge background fundamentally weakens the substrate’s intrinsic capability to “donate” electrons to the adsorbate at the source. In the neutral state, the spontaneous directional transfer of electrons from surface oxygen atoms to Y-based adsorbates constitutes the essential driving force for interfacial charge redistribution and covalent bond formation. However, the imposition of a net positive charge effectively raises the ionization potential of the substrate, suppresses its electron-donating propensity, and disrupts this native charge transfer channel. Consequently, the formation of interfacial chemical bonds. This source-level suppression of electron donation is fundamentally distinct from merely increasing the energetic barrier for adsorption; rather, it dismantles the electronic prerequisite for bonding itself. The progressive shrinkage of the cyan dissipation region thus serves as a compelling real-space fingerprint of the progressive passivation of substrate reactivity. Furthermore, this phenomenon corroborates the thermodynamic observation that ΔG becomes less negative with increasing charge: the diminished exothermicity originates precisely from this suppression of charge transfer, which reduces the covalent bonding contribution to the adsorption energy. In essence, the applied positive charge functions as an “electron blockade”, throttling the substrate’s ability to engage in the electronic exchange that underpins interfacial bonding. As shown in Fig. 10 and Fig. 11 , In the environment with an applied charge of 0, there are obvious PDOS peaks between the O atom O-p on the surface of the material and the adsorbed Y atom Y-d. The peak shape of the two shows mirror symmetry and synchronous fluctuation, indicating that there is a strong Y-d / O-p orbital hybridization, forming a clear bonding state E > 0, showing that the interface has strong covalent bonding characteristics. In the environment with an external charge of + 2, In the E < 0 region ( occupied state ), the number and amplitude of the peaks increase, indicating that the original hybrid band appears localization and energy level splitting, the electron effective mass increases, and the covalent bond begins to weaken.In the E > 0 region ( unoccupied state ), the number and amplitude of the peaks decrease, indicating that the antibonding state is partially emptied and the contribution of the Y-d orbital to the conduction band is weakened. At the same time, The Y-s orbital is activated and the overlap with the O-p orbital increases, indicating that the increase of the positive charge increases the effective nuclear charge of the Y atom, and the Y-s orbital energy level decreases and begins to participate in the bonding, suggesting the transition of the bonding mode. The energy gap changes initially, and the main peak spacing near E = 0 begins to narrow. As the applied charge continues to increase, the peak of the Y-d orbital continues to decrease. It shows that the electron localization is more obvious, but the energy matching is worse, the hybridization intensity is weakened sharply, and the old chemical bond tends to break. In the E > 0 region ( unoccupied state ), the peak of the Y-d orbital continues to decrease and no longer dominates the antibonding state.In the relationship between Y-s and O-p, the fluctuation of the energy lines of the two is close to synchronization, indicating that Y-s / O-p hybridization has been fully established and become the main bonding mode, forming a new stable chemical bond.The energy gap changes significantly, and the main peak spacing near E = 0 is significantly reduced, mainly due to the ' overall left shift of the right peak ( conduction band bottom ) ', including the new Y-s peak, which leads to the systematic narrowing of the band gap, and the conduction band bottom moves down due to the formation of new anti-bonding states ( Y-s / O-p ).The external positive charge selectively reduces the s-orbital energy level of Y atom by increasing the effective nuclear charge of Y atom, and induces the hybridization and recombination of Y-s and O-p orbitals to form a lower energy s-p hybrid antibonding state. Conclusion In this study, through the analysis of partial density of states, charge density difference diagram and high temperature thermodynamics, the core inhibition path of ' external charge → orbital hybridization attenuation → Electrostatic environment repulsion → inhibition of chemical reaction path → enthalpy degradation → adsorption driving force loss ' is revealed from three aspects of electronic structure, bonding essence and macroscopic thermodynamics. External charge fundamentally severs the electronic basis of interfacial bonding.In the neutral state, Y-d and O-p orbitals exhibit strong energy matching and peak mirroring, forming covalent bonds. Applied positive charge sharply shrinks PDOS overlap, weakens orbital hybridization, passivates surface oxygen nucleophilicity, and reduces charge transfer, actively undermining bonding and eliminating the driving force for adsorption. External charge reverses the interfacial electrostatic environment from affinity to repulsion.Charge density difference reveals directional electron transfer from substrate to adsorbate under neutral conditions. Applied positive charge imposes a net positive background, generating strong Coulomb repulsion toward cationic Y-species and reducing oxygen anionicity. This electrostatic reversal creates an energy barrier prior to interface contact. Applied charge significantly amplifies thermodynamic resistance. ΔG increases markedly with positive charge, indicating systematic attenuation of adsorption spontaneity. The origin lies in enthalpy degradation: external charge fundamentally disrupts interfacial bond strength, depriving adsorption of its core energetic driving force. At 1473–1873 K, this bond destruction overwhelmingly dominates, completely suppressing any entropic benefit. This enthalpy-centered mechanism—termed bond enthalpy deterioration—is the fundamental origin of charge-induced adsorption inhibition. Declarations Acknowledgements This work was supported by the National Science Foundation of China (Grant Nos.2022YFC2905200,52374337) ,the Jiangxi Provincial Natural Science Foundation (Grant Nos.2025BAC200310,20232BAB204002),and the Doctoral Scientific Research Foundation of Jiangxi University of Science and Technology No. 205200100601. Contributions XJ: Conceptualization, Methodology, Writing—Review & Editing; DL: Data Curation, Software; CL: Supervision;HW:Project administration;CB:Project administration. Corresponding author Correspondence to Chaobin Lai. Conflict of interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-8876255","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":591173375,"identity":"5d47a3ec-bceb-4625-a16e-24b53c1426ee","order_by":0,"name":"Xiaonan Zheng","email":"","orcid":"https://orcid.org/0009-0002-2678-5961","institution":"Jiangxi University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Xiaonan","middleName":"","lastName":"Zheng","suffix":""},{"id":591173376,"identity":"0593b825-67e4-4117-8620-47357752a58f","order_by":1,"name":"Diqiang Luo","email":"","orcid":"","institution":"Jiangxi 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Wang","email":"","orcid":"","institution":"Jiangxi University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Hebin","middleName":"","lastName":"Wang","suffix":""},{"id":591173379,"identity":"461df18a-1287-4f07-a00a-20f7e78d7b23","order_by":4,"name":"Chao Pan","email":"","orcid":"","institution":"Jiangxi University of Science and Technology","correspondingAuthor":false,"prefix":"","firstName":"Chao","middleName":"","lastName":"Pan","suffix":""}],"badges":[],"createdAt":"2026-02-14 02:19:58","currentVersionCode":1,"declarations":{"humanSubjects":false,"vertebrateSubjects":false,"conflictsOfInterestStatement":false,"humanSubjectEthicalGuidelines":false,"humanSubjectConsent":false,"humanSubjectClinicalTrial":false,"humanSubjectCaseReport":false,"vertebrateSubjectEthicalGuidelines":false},"doi":"10.21203/rs.3.rs-8876255/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-8876255/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":105727593,"identity":"9e154311-e454-4774-8e60-60798452f7f1","added_by":"auto","created_at":"2026-03-30 10:52:56","extension":"jpeg","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":716722,"visible":true,"origin":"","legend":"\u003cp\u003eStructural shape of stable adsorption of Y, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS on ( 001 ) surface of MgO\u003c/p\u003e","description":"","filename":"floatimage1.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/dbf3863c1e21ab082447b645.jpeg"},{"id":102962999,"identity":"5bb7b14d-7eda-4b53-850a-2d524ff68c62","added_by":"auto","created_at":"2026-02-19 04:12:43","extension":"jpeg","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":735437,"visible":true,"origin":"","legend":"\u003cp\u003eStructural shape of stable adsorption of Y, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS on ( 001 ) surface of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"floatimage2.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/ae6193f2cf3b9e418107f19e.jpeg"},{"id":102962980,"identity":"5ec728e9-7cb2-46cf-8ed7-997b6ccc23c5","added_by":"auto","created_at":"2026-02-19 04:12:34","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":194961,"visible":true,"origin":"","legend":"\u003cp\u003eThe average distance between adsorbate atoms and material surface\u003c/p\u003e","description":"","filename":"floatimage3.png","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/f775d8e0feee15e7df8952ac.png"},{"id":102962838,"identity":"9d459517-bef9-4f7e-a209-f953ea3f181b","added_by":"auto","created_at":"2026-02-19 04:11:37","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":307756,"visible":true,"origin":"","legend":"\u003cp\u003eAdsorption energies of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e for Y, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS\u003c/p\u003e","description":"","filename":"floatimage4.png","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/0983e6b04f8d541db2fe733a.png"},{"id":102817714,"identity":"0da54419-dd27-4796-93ad-5d753e8e22c7","added_by":"auto","created_at":"2026-02-17 06:29:26","extension":"jpeg","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":378635,"visible":true,"origin":"","legend":"\u003cp\u003eThe enthalpy-temperature and size-dependent curves of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorption systems\u003c/p\u003e","description":"","filename":"floatimage5.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/398ffbc7a27adb905df1956f.jpeg"},{"id":102817718,"identity":"e35baf69-76ed-43ca-8b19-6a204948d01a","added_by":"auto","created_at":"2026-02-17 06:29:26","extension":"jpeg","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":374516,"visible":true,"origin":"","legend":"\u003cp\u003eThe temperature dependence of entropy of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorption systems\u003c/p\u003e","description":"","filename":"floatimage6.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/37d88f3401f38b44d8726bd5.jpeg"},{"id":102963259,"identity":"506dcc1b-78b2-4e03-9e98-2d24aa790864","added_by":"auto","created_at":"2026-02-19 04:14:51","extension":"jpeg","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":347552,"visible":true,"origin":"","legend":"\u003cp\u003eThe temperature dependence of absolute Gibbs free energy of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorption systems\u003c/p\u003e","description":"","filename":"floatimage7.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/c80d7ea16e7b3c905f84461b.jpeg"},{"id":102962506,"identity":"67f530b8-188e-492d-aef2-eaafd7225855","added_by":"auto","created_at":"2026-02-19 04:09:31","extension":"jpeg","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":417371,"visible":true,"origin":"","legend":"\u003cp\u003eThe charge density change of MgO adsorption system, yellow ( electron accumulation ) and cyan ( electron dissipation )\u003c/p\u003e","description":"","filename":"floatimage8.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/1f193c6d29a9f8d4fc853964.jpeg"},{"id":102817724,"identity":"016e19b0-75bc-460f-b502-7221a6bf30ad","added_by":"auto","created_at":"2026-02-17 06:29:26","extension":"jpeg","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":415112,"visible":true,"origin":"","legend":"\u003cp\u003eThe charge density change of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorption system, yellow ( electron accumulation ) and cyan ( electron dissipation )\u003c/p\u003e","description":"","filename":"floatimage9.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/ce33e89d8792983e96d148c1.jpeg"},{"id":102817721,"identity":"863fff30-d894-4e83-a7e9-5bc9f3d49b6b","added_by":"auto","created_at":"2026-02-17 06:29:26","extension":"jpeg","order_by":10,"title":"Figure 10","display":"","copyAsset":false,"role":"figure","size":747984,"visible":true,"origin":"","legend":"\u003cp\u003ePartial density of states of MgO adsorption system\u003c/p\u003e","description":"","filename":"floatimage10.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/f737470a8aea9c91616049ce.jpeg"},{"id":103049242,"identity":"1dd730c3-d101-42b3-906b-bcd3bacf574a","added_by":"auto","created_at":"2026-02-20 07:38:52","extension":"jpeg","order_by":11,"title":"Figure 11","display":"","copyAsset":false,"role":"figure","size":750423,"visible":true,"origin":"","legend":"\u003cp\u003ePartial density of states of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorption system\u003c/p\u003e","description":"","filename":"floatimage11.jpeg","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/fcae7be1e08d8ac4dc43041f.jpeg"},{"id":105752108,"identity":"b030e80b-9a75-4604-be62-bdf1e902253c","added_by":"auto","created_at":"2026-03-30 15:54:53","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":5836337,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-8876255/v1/bbd9b09d-96d9-4211-99f1-e38a9b4cecfa.pdf"}],"financialInterests":"The authors declare no competing interests.","formattedTitle":"\u003cp\u003eStudy on the mechanism of external current inhibiting the adsorption of rare earth inclusions in molten steel by aluminum and magnesium refractory\u003c/p\u003e","fulltext":[{"header":"Introduction","content":"\u003cp\u003eRare earth has the functions of purifying inclusions, refining microstructure and strengthening properties in steel[\u003cspan additionalcitationids=\"CR2\" citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e–\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. It is the key microalloying element for preparing high strength and toughness weathering steel[\u003cspan additionalcitationids=\"CR5\" citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e–\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e].However, rare earth Y and its inclusions (Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS) are adsorbed and deposited on the inner wall of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and MgO nozzles, which can block the flow channel within a few hours, resulting in the interruption of continuous casting[\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e, \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e]. According to statistics, the loss of a single accident is hundreds of thousands of yuan, and the annual loss of rare earth steel is more than ten million yuan[\u003cspan citationid=\"CR9\" class=\"CitationRef\"\u003e9\u003c/span\u003e]. With the increasing demand for rare earth microalloying in high-speed rail and nuclear power steels, this problem has evolved into a common technical problem that restricts the stable production of high-end steels[\u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e10\u003c/span\u003e, \u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. The traditional protection strategies include alloy modification[\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e–\u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e], coating protection[\u003cspan additionalcitationids=\"CR16 CR17\" citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e–\u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e] and flow field optimization[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Although these methods are effective, they are all ' off-line ' passive defense. The protection ability cannot be changed after the nozzle is installed, which can not be adjusted in real time according to the change of steel grade, and it is more difficult to intervene actively in the germination stage of blockage. In the face of the fluctuation of rare earth addition and the acceleration of smelting rhythm, traditional technology is not enough.\u003c/p\u003e \u003cp\u003eImpressed current control technology provides a transformative solution for this[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e]. Only by applying a weak current, a ' protective layer ' that can respond dynamically can be established on the nozzle wall to achieve millisecond-level, continuous and reversible active regulation of adsorption strength[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e]. This is an anti-blocking technical path with real-time, reversible and quantitative adjustment potential[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e]. However, its core scientific problem-how the current changes the interface adsorption from the electronic structure level-is still a ' black box '[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e]. How do electrons transfer ? How to reconstruct the track ? How to cut off the bond ? How to weaken the thermodynamic driving force ? The unclear inhibition mechanism makes the electrochemical anti-blocking technology stay in the empirical exploration stage for a long time, and it is impossible to form a predictable and designable engineering scheme.\u003c/p\u003e \u003cp\u003eIn this paper, the microscopic mechanism of ' current inhibition interface adsorption ' was revealed from the cross-validation of electronic structure and thermodynamics. The triple inhibition mechanism of 'orbital hybridization attenuation-electrostatic environment repulsion-inhibition of chemical reaction ' was found. The nozzle anti-blocking technology is advanced from experience trial and error to a new scientific stage of mechanism design.The research results provide an urgent theoretical foundation for the development of electrochemical anti-nodulation nozzle for rare earth steel continuous casting.\u003c/p\u003e "},{"header":"Computational details","content":"\u003cp\u003eWe used the DFT as implemented in the Vienna Ab initio simulation package (VASP) in all calculations. The exchange-correlation potential is described by using the generalized gradient approximation of Perdew-Burke-Ernzerhof (GGA-PBE). The projector augmented-wave (PAW) method is employed to treat interactions between ion cores and valence electrons. The plane-wave cutoff energy was fixed to 450 eV. A Γ-centered 5×5×5, for Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and MgO bulks. A Monkhorst-Pack k-mesh with a 2×2×1 k-point grid was used for structural optimization. Given structural models were relaxed until the Hellmann-Feynman forces smaller than − 0.02 eV/Å and the change in energy smaller than 10 − 5 eV was attained. The 15 Å vacuum layer was normally added to the surface to eliminate the artificial interactions between periodic images. Grimme’s DFT-D3 methodology was used to describe the dispersion interactions among all the atoms in adsorption models.\u003c/p\u003e\u003cp\u003eThe adsorption energy (Eads) of species is calculated by:\u003c/p\u003e\u003cp\u003eEads = E(system)-E(catalyst) -E(species)\u003c/p\u003e\u003cp\u003ewhere E(system), E(catalyst), and E(species) are the total energy of the optimized system with adsorbed species, the isolated catalyst, and species, respectively.\u003c/p\u003e\u003cp\u003eThe Gibbs free energy change is defined as:\u003c/p\u003e\u003ch3\u003eΔG = ΔE + ΔZPE – TΔS\u003c/h3\u003e\u003cp\u003ewhere ΔE is the electronic energy calculated with VASP, ΔZPE and ΔS are the zero-point energy difference and the entropy change between the products and reactants, respectively, and T is the temperature (1473.15 -1873.15 K).The PBE functional and PAW pseudopotential method are used in the calculation, and the DFT-D3 Grime method is considered for van der Waals correction.\u003c/p\u003e\u003cp\u003eThe charge density difference (CDD) was computed as:\u003c/p\u003e\u003ch2\u003eΔ\u003cem\u003eρ\u003c/em\u003e = \u003cem\u003eρ\u003c/em\u003e\u003csub\u003etotal\u003c/sub\u003e − \u003cem\u003eρ\u003c/em\u003e\u003csub\u003esubstrate\u003c/sub\u003e − \u003cem\u003eρ\u003c/em\u003e\u003csub\u003eadsorbat\u003c/sub\u003e\u003c/h2\u003e\u003cp\u003ewhere \u003cem\u003eρ\u003c/em\u003e\u003csub\u003etotal\u003c/sub\u003e is the charge density of the fully relaxed adsorption system, \u003cem\u003eρ\u003c/em\u003e\u003csub\u003esubstrate\u003c/sub\u003e and \u003cem\u003eρ\u003c/em\u003e\u003csub\u003eadsorbat\u003c/sub\u003e are the charge densities of the isolated substrate and adsorbate.\u003c/p\u003e\u003cp\u003ewith all three components calculated in the identical supercell and fixed atomic coordinates. For charged systems (+ 2, + 4), the total electron number was reduced via the NELECT tag, and the same NELECT value was enforced for the total, substrate, and adsorbate calculations to guarantee the validity of the CDD analysis. Isosurface plots were generated using VESTA at ± 0.001\u0026nbsp;e/ų.\u003c/p\u003e\u003cp\u003eThe PDOS projections onto atomic orbitals (O-p, Y-d, Y-s) were extracted from the self-consistent charge densities using the LORBIT = 11 tag, which projects the wavefunctions onto spherical harmonics within the PAW spheres. All PDOS curves were broadened by a Gaussian smearing with a width of 0.05 eV. The Fermi level was aligned to zero energy for all systems. For charged systems (+ 2, + 4), the same NELECT settings as in the charge density difference calculations were consistently applied to ensure the comparability of the electronic structures under identical charge backgrounds. The orbital-projected PDOS spectra were visualized to identify the energy match, peak mirroring, and hybridization characteristics between Y-d/Y-s and O-p orbitals across different charge states.\u003c/p\u003e"},{"header":"Results and Discussions","content":"\u003cp\u003eFirstly, the adsorption behavior of Y atom, Y₂O₃ and Y₂O₂S species on the MgO(001) and Al₂O₃(001) substrate surfaces was systematically investigated via first-principles calculations. Three distinct high-symmetry adsorption sites were evaluated on each substrate: the hollow (H) site located above the surface oxygen anion, the bridge (B) site situated at the midpoint of the Mg–O or Al–O bond, and the top (T) site directly above the surface Mg or Al cation. The initial adsorption configurations for each adsorbate at these sites were constructed with an initial vertical separation of 30 Å between the adsorbate and the outmost substrate layer, ensuring negligible spurious interaction prior to relaxation. Full structural optimization was performed without any symmetry constraints, allowing all atomic degrees of freedom to relax until the residual forces converged below 0.02 eV/Å. The initial and fully relaxed configurations for all adsorption systems are illustrated in Fig.\u0026nbsp;\u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e.\u003c/p\u003e\u003cp\u003eA comparative analysis of the geometric evolution before and after relaxation reveals a consistent and site-selective migration tendency: adsorbates initially positioned at the bridge (B) and top (T) sites spontaneously migrate toward the hollow (H) site during optimization, ultimately residing at or in close proximity to the O-top hollow position. This relaxation behavior is observed across all adsorbate types (Y, Y₂O₃, Y₂O₂S) and both substrate compositions (MgO, Al₂O₃), indicating a **strong thermodynamic preference** for the H-site configuration. The driving force underlying this preferential adsorption can be attributed to the **maximization of orbital overlap** between the Y‑centered orbitals (4d/5s) and the unsaturated p orbitals of the surface oxygen anions at the hollow site, which provides a multi-coordination environment and facilitates more effective charge transfer and covalent bonding. In contrast, the bridge and top sites offer fewer nearest-neighbor oxygen ligands and less favorable orbital alignment, resulting in weaker interfacial interaction and metastable character.\u003c/p\u003e\u003cp\u003eConsequently, the hollow site is identified as the energetically most stable adsorption configuration for all investigated Y‑based inclusions on MgO and Al₂O₃ surfaces.\u003c/p\u003e\u003cp\u003eThe average distance between (Y, Y₂O₃, Y₂O₂S) and (MgO, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e) surface in steel increases monotonically with the increase of forward applied current, and the change is nonlinear. Except for the adsorption of Y atoms by Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, they all show the characteristics of ' rapid weakening → gradual saturation '. When the external positive charge reaches + 4, the distance between some atoms and the surface is greater than 3.5 Å, which exceeds the geometric gap between oxides dominated by van der Waals interaction. It shows that the adsorption gradually changes from chemical adsorption dominated by chemical bonds to physical adsorption dominated by physical adsorption and tends to the limit, and finally forms repulsive phenomenon far away from the surface of the material.\u003c/p\u003e\u003cp\u003eModerately increasing the positive charge can effectively inhibit the adsorption of(Y, Y₂O₃, Y₂O₂S) species on (MgO, Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e). The main suppression effect has been achieved in the smaller current interval, and the current revenue continues to increase.\u003c/p\u003e\u003cp\u003eThe adsorption energy changes of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on Y, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS show a significant performance gap. When adsorbing Y atoms in steel, the increase of surface charge of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and MgO will significantly reduce the adsorption capacity of Y. Especially in the case of high surface charge + 0, the adsorption energy of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e to Y is close to − 19 eV / mol, which is much higher than that in the case of surface charge + 4. MgO also shows a decrease in adsorption strength under high surface charge, but the change is gentle. When adsorbing Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS inclusions in steel : with the increase of charge, the adsorption energy of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e changes gently. The adsorption degree of Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS inclusions is always slightly higher than that of MgO.\u003c/p\u003e\u003cp\u003eThe increase of surface charge may cause the increase of the potential barrier of the surface itself, which leads to the weakening of the electrostatic binding force on the adsorbate, and also changes the interaction between the surface atoms and the adsorbed molecules. For Al 2O 3, the increase of positive charge may lead to the weakening of the interaction between alumina and Y on the surface, thus reducing the adsorption energy. When MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e adsorb Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e and Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS, the increase of surface charge does not significantly affect their adsorption energy, indicating that the surface interaction of MgO and Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e on these adsorbates is relatively stable and is not easily affected by the change of surface charge. Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e shows a larger change than MgO, which may be related to its higher surface chemical activity.。\u003c/p\u003e\u003cp\u003eFigure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e show the effect of applied current on the enthalpy ( H ) and entropy ( S ) of the adsorption process with temperature. In the temperature range of 1473 K-1873 K, the enthalpy and entropy of all adsorption systems increased linearly with the increase of temperature, but the change rate of entropy was relatively flat. In the temperature range above 1473 K, the effect of temperature fluctuation on the adsorption entropy change is limited. The dominant control variable of interface adsorption behavior is no longer temperature, but non-thermodynamic factors such as interface chemical potential, charge state and cluster size. By studying and comparing the change rules of the free energy of the adsorption system under different external charge states, it is found that the Gibbs free energy change ( ΔG ) of the adsorption reaction in the positive charge (+ 2, + 4 ) state is significantly greater than that in the uncharged ( 0 ) state, regardless of whether the substrate is MgO or Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e for Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e, Y\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e2\u003c/sub\u003eS or a single Y atom adsorption system, regardless of the substrate is MgO or Al\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e3\u003c/sub\u003e. This result has a clear and unified thermodynamic meaning : the external positive charge reduces the quantification of the spontaneous driving force of the adsorption reaction, and the interface adsorption equilibrium moves towards the direction of dissociation, that is, the external charge has a universal inhibitory effect on the adsorption behavior of Y-type inclusions on the oxide surface.\u003c/p\u003e\u003cp\u003eThe external positive charge induces a systematic reduction in the electron cloud density of oxygen atoms on the substrate surface, thereby significantly diminishing their nucleophilicity. This electronic depletion indicate that the cyan dissipation regions—which represent electron loss from the substrate—contract progressively as the applied positive charge increases from 0 to + 2 and + 4. This contraction provides direct visual evidence that the overall positive charge background fundamentally weakens the substrate’s intrinsic capability to “donate” electrons to the adsorbate at the source. In the neutral state, the spontaneous directional transfer of electrons from surface oxygen atoms to Y-based adsorbates constitutes the essential driving force for interfacial charge redistribution and covalent bond formation.\u003c/p\u003e\u003cp\u003eHowever, the imposition of a net positive charge effectively raises the ionization potential of the substrate, suppresses its electron-donating propensity, and disrupts this native charge transfer channel. Consequently, the formation of interfacial chemical bonds. This source-level suppression of electron donation is fundamentally distinct from merely increasing the energetic barrier for adsorption; rather, it dismantles the electronic prerequisite for bonding itself. The progressive shrinkage of the cyan dissipation region thus serves as a compelling real-space fingerprint of the progressive passivation of substrate reactivity. Furthermore, this phenomenon corroborates the thermodynamic observation that ΔG becomes less negative with increasing charge: the diminished exothermicity originates precisely from this suppression of charge transfer, which reduces the covalent bonding contribution to the adsorption energy. In essence, the applied positive charge functions as an “electron blockade”, throttling the substrate’s ability to engage in the electronic exchange that underpins interfacial bonding.\u003c/p\u003e\u003cp\u003eAs shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig10\" class=\"InternalRef\"\u003e10\u003c/span\u003e and Fig.\u0026nbsp;\u003cspan refid=\"Fig11\" class=\"InternalRef\"\u003e11\u003c/span\u003e, In the environment with an applied charge of 0, there are obvious PDOS peaks between the O atom O-p on the surface of the material and the adsorbed Y atom Y-d. The peak shape of the two shows mirror symmetry and synchronous fluctuation, indicating that there is a strong Y-d / O-p orbital hybridization, forming a clear bonding state E \u0026gt; 0, showing that the interface has strong covalent bonding characteristics.\u003c/p\u003e\u003cp\u003eIn the environment with an external charge of + 2, In the E \u0026lt; 0 region ( occupied state ), the number and amplitude of the peaks increase, indicating that the original hybrid band appears localization and energy level splitting, the electron effective mass increases, and the covalent bond begins to weaken.In the E \u0026gt; 0 region ( unoccupied state ), the number and amplitude of the peaks decrease, indicating that the antibonding state is partially emptied and the contribution of the Y-d orbital to the conduction band is weakened. At the same time, The Y-s orbital is activated and the overlap with the O-p orbital increases, indicating that the increase of the positive charge increases the effective nuclear charge of the Y atom, and the Y-s orbital energy level decreases and begins to participate in the bonding, suggesting the transition of the bonding mode. The energy gap changes initially, and the main peak spacing near E = 0 begins to narrow.\u003c/p\u003e\u003cp\u003eAs the applied charge continues to increase, the peak of the Y-d orbital continues to decrease. It shows that the electron localization is more obvious, but the energy matching is worse, the hybridization intensity is weakened sharply, and the old chemical bond tends to break. In the E \u0026gt; 0 region ( unoccupied state ), the peak of the Y-d orbital continues to decrease and no longer dominates the antibonding state.In the relationship between Y-s and O-p, the fluctuation of the energy lines of the two is close to synchronization, indicating that Y-s / O-p hybridization has been fully established and become the main bonding mode, forming a new stable chemical bond.The energy gap changes significantly, and the main peak spacing near E = 0 is significantly reduced, mainly due to the ' overall left shift of the right peak ( conduction band bottom ) ', including the new Y-s peak, which leads to the systematic narrowing of the band gap, and the conduction band bottom moves down due to the formation of new anti-bonding states ( Y-s / O-p ).The external positive charge selectively reduces the s-orbital energy level of Y atom by increasing the effective nuclear charge of Y atom, and induces the hybridization and recombination of Y-s and O-p orbitals to form a lower energy s-p hybrid antibonding state.\u003c/p\u003e"},{"header":"Conclusion","content":"\u003cp\u003eIn this study, through the analysis of partial density of states, charge density difference diagram and high temperature thermodynamics, the core inhibition path of ' external charge \u0026rarr; orbital hybridization attenuation \u0026rarr; Electrostatic environment repulsion \u0026rarr; inhibition of chemical reaction path \u0026rarr; enthalpy degradation \u0026rarr; adsorption driving force loss ' is revealed from three aspects of electronic structure, bonding essence and macroscopic thermodynamics.\u003c/p\u003e \u003cp\u003e \u003col\u003e \u003cspan\u003e \u003cli\u003e \u003cp\u003eExternal charge fundamentally severs the electronic basis of interfacial bonding.In the neutral state, Y-d and O-p orbitals exhibit strong energy matching and peak mirroring, forming covalent bonds. Applied positive charge sharply shrinks PDOS overlap, weakens orbital hybridization, passivates surface oxygen nucleophilicity, and reduces charge transfer, actively undermining bonding and eliminating the driving force for adsorption.\u003c/p\u003e \u003c/li\u003e \u003c/span\u003e \u003cspan\u003e \u003cli\u003e \u003cp\u003eExternal charge reverses the interfacial electrostatic environment from affinity to repulsion.Charge density difference reveals directional electron transfer from substrate to adsorbate under neutral conditions. Applied positive charge imposes a net positive background, generating strong Coulomb repulsion toward cationic Y-species and reducing oxygen anionicity. This electrostatic reversal creates an energy barrier prior to interface contact.\u003c/p\u003e \u003c/li\u003e \u003c/span\u003e \u003cspan\u003e \u003cli\u003e \u003cp\u003eApplied charge significantly amplifies thermodynamic resistance. ΔG increases markedly with positive charge, indicating systematic attenuation of adsorption spontaneity. The origin lies in enthalpy degradation: external charge fundamentally disrupts interfacial bond strength, depriving adsorption of its core energetic driving force. At 1473\u0026ndash;1873 K, this bond destruction overwhelmingly dominates, completely suppressing any entropic benefit. This enthalpy-centered mechanism\u0026mdash;termed bond enthalpy deterioration\u0026mdash;is the fundamental origin of charge-induced adsorption inhibition.\u003c/p\u003e \u003c/li\u003e \u003c/span\u003e \u003c/ol\u003e \u003c/p\u003e"},{"header":"Declarations","content":"\u003ch2\u003eAcknowledgements\u003c/h2\u003e \u003cp\u003eThis work was supported by the National Science Foundation of China (Grant Nos.2022YFC2905200,52374337) ,the Jiangxi Provincial Natural Science Foundation (Grant Nos.2025BAC200310,20232BAB204002),and the Doctoral Scientific Research Foundation of Jiangxi University of Science and Technology No. 205200100601.\u003c/p\u003e \u003cp\u003eContributions\u003c/p\u003e \u003cp\u003eXJ: Conceptualization, Methodology, Writing\u0026mdash;Review \u0026amp; Editing; DL: Data Curation, Software; CL: Supervision;HW:Project administration;CB:Project administration.\u003c/p\u003e \u003cp\u003eCorresponding author\u003c/p\u003e \u003cp\u003eCorrespondence to Chaobin Lai.\u003c/p\u003e \u003cp\u003eConflict of interest\u003c/p\u003e \u003cp\u003eThe authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eGong A (2024) The role of rare earths on steel and rare earth steel corrosion mechanism of research progress.Coatings14. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi:10.3390/coatings14040465\u003c/span\u003e\u003cspan address=\"https://doi:10.3390/coatings14040465\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e \u003cli\u003e\u003cspan\u003eMeng Z, Li GQ, Yuan C et al (2024) Comparative study on interaction between rare earth oxide refractories and rare earth treated stee. 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J Mater Sci 57:6988\u0026ndash;7000. \u003cspan class=\"ExternalRef\"\u003e\u003cspan class=\"RefSource\"\u003ehttps://doi.org/10.1007/s10853-022-07091-1\u003c/span\u003e\u003cspan address=\"10.1007/s10853-022-07091-1\" targettype=\"DOI\" class=\"RefTarget\"\u003e\u003c/span\u003e\u003c/span\u003e\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[{"identity":"21798e32-6a58-4bdd-9fa1-a5f2f9081f7c","identifier":"10.13039/501100001809","name":"National Natural Science Foundation of China","awardNumber":"2022YFC2905200","order_by":0},{"identity":"4ee9fd59-eab1-4be6-b973-0041b5d18f1c","identifier":"10.13039/501100001809","name":"National Natural Science Foundation of China","awardNumber":"52374337","order_by":1},{"identity":"d72884f9-820c-4f53-903a-3a4ea252e780","identifier":"10.13039/501100004479","name":"Natural Science Foundation of Jiangxi Province","awardNumber":"2025BAC200310","order_by":2},{"identity":"490de542-8025-4fea-b6de-3106fed6e4e2","identifier":"10.13039/501100004479","name":"Natural Science Foundation of Jiangxi Province","awardNumber":"20232BAB204002","order_by":3},{"identity":"5646b769-3ae8-475f-b974-1e6683d04aea","identifier":"10.13039/501100008254","name":"Jiangxi University of Science and Technology","awardNumber":"205200100601","order_by":4}],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":true,"hideJournal":true,"highlight":"","institution":"Jiangxi University of Science and Technology","isAcceptedByJournal":false,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"rare earth steel, nozzle clogging, applied current, adsorption, inhibition mechanism","lastPublishedDoi":"10.21203/rs.3.rs-8876255/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-8876255/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis study aims to reveal the intrinsic mechanism by which external positive charge inhibits the adsorption of rare earth Y-based inclusions (Y, Y₂O₃, Y₂O₂S) on MgO and Al₂O₃ refractory surfaces, thereby providing a theoretical foundation for the active control of nozzle clogging during the continuous casting of rare earth steels. To this end, first-principles calculations based on density functional theory were employed, integrated with partial density of states analysis, charge density difference visualization, and high-temperature thermodynamic evaluations. The adsorption behaviors under neutral and positively charged states (+\u0026thinsp;2, +\u0026thinsp;4) were systematically compared. The results demonstrate that external positive charge suppresses interfacial adsorption through a triple mechanism. Electronically, it disrupts the energy alignment and orbital hybridization between O-p and Y-d states, leading to significant attenuation of interfacial covalent bonding. Electrostatically, the net positive background reverses the local interfacial environment from electrostatic affinity to repulsion, establishing a physical barrier that hinders adsorbate approach. Thermodynamically, the Gibbs free energy change ΔG increases markedly under charged conditions, reflecting a quantifiable and universal reduction in adsorption spontaneity across all adsorbates and substrates. These findings clarify the mechanism of external charge inhibiting the adsorption of rare earth inclusions in molten steel by refractory.\u003c/p\u003e","manuscriptTitle":"Study on the mechanism of external current inhibiting the adsorption of rare earth inclusions in molten steel by aluminum and magnesium refractory","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2026-02-17 06:29:21","doi":"10.21203/rs.3.rs-8876255/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"166cb7e9-299a-4d43-aa2c-e734796393ee","owner":[],"postedDate":"February 17th, 2026","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[{"id":62914492,"name":"Metallurgy"}],"tags":[],"updatedAt":"2026-02-17T06:29:21+00:00","versionOfRecord":[],"versionCreatedAt":"2026-02-17 06:29:21","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-8876255","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-8876255","identity":"rs-8876255","version":["v1"]},"buildId":"XKTyCvWXoU3ODBz1xrDgd","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}