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At least 343 records · Page 19

Effect of surface steps on chemical ordering in the subsurface of Cu(Au) solid solutions

Atomic steps are typically assumed to only influence surface phenomena of solids. In contrast, in this paper we show, using in-situ atomic-resolution electron microscopy observations and atomistic modeling, the pronounced effect from surface stepsin inducing compositional and structural evolution in the subsurface of a Cu(Au) solid solution. We find that Au surface segregation results in a stacked sequence of Cu-Au ordered phases in the subsurface. The presence of a monatomic step at the surface induces the formation of an anti-phase boundary that extends from the surface step to deeper layers by maintaining the same composition profile associated with each terrace. The bunching of surface steps induces chemical disordering of the Cu-Au ordered phases in the subsurface region of the bunched steps. These results demonstrate the instant propagation of surface dynamics of atomic steps into the subsurface region and can find broader applicability in utilizing surface defects to tune the composition and structure in the subsurface of alloys.

36 MATERIALS SCIENCE↗

Hydride-Containing Eight-Electron Pt/Ag Superatoms: Structure, Bonding, and Multi-NMR Studies

Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of the superatom core, but no accurate location of the hydride could be experimentally proved, so far. Here, we report herein a hydride-doped eight-electron platinum/silver alloy nanocluster in which the position of four-coordinated hydride was determined by neutron diffraction for the first time. X-ray structures of [PtHAg 19 (dtp/desp) 12 ] (dtp = S 2 P(O n Pr) 2 , 1; dsep = Se 2 P(O i Pr) 2 , 2) describe a central platinum hydride (PtH) unit encapsulated within a distorted Ag 12 icosahedron, the resulting (PtH)@Ag 12 core being stabilized by an outer sphere made up of 7 capping silver atoms and 12 dichalcogenolates. Solid-state structures of 1 and 2 differ somewhat in the spatial configuration of their outer spheres, resulting in overall different symmetries, C 1 and C 3 , respectively. Whereas the multi-NMR spectra of 2 in solution at 173 K reveal that the structure of C 3 symmetry is the predominant one, 1 H and 195 Pt NMR spectra of 1 at the same temperature disclose the presence of isomers of both C 1 and C 3 symmetry. DFT calculations found both isomers to be very close in energy, supporting the fact that they co-exist in solution. They also show that the [PtH@Ag 12 ] 5+ kernel can be viewed as a closed-shell superatomic core, the μ4-hydride electron contributing to its eight-electron count. On the other hand, the 1s(H) orbital contributes only moderately to the superatomic orbitals, being mainly involved in the building of a Pt–H bonding electron pair with the 5d z 2 (Pt) orbital.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crystal growth and evolution of magnetism in the EuCuP-EuCuAs solid solution

The hexagonal EuMX (M = Cu, Ag, Au; X = P, As, Sb, Bi) compounds host interesting electronic and magnetic properties, with seemingly intertwined topology and transport properties. One key feature of such behavior is the nature of the ordered magnetic structure. In EuCuAs, a topological Hall effect is caused by a conical spin structure that emerges when a field is applied within the easy-plane (H ⊥ c) of the helical ground state that exists below the Neel temperature of T N = 14 K. On the other hand, EuCuP is an easy-axis ferromagnet with a Curie temperature T C near 31 K. Here, in this study, we investigate the evolution of the magnetic properties in EuCuAs 1-x P x single crystals with 0.16 ≤ x ≤ 0.75. Crystals grown by cooling slowly in a Sn flux possessed macroscale inhomogeneity of As/P, particularly for arsenic-rich crystals. However, growth in a Sn flux via an isothermal dwell at 600 °C produced crystals that were homogeneous within the resolution of the probes utilized to investigate these crystals. The unit cell volumes, Curie-Weiss temperatures, and magnetic transitions trend linearly with composition and the magnetic anisotropy is reduced in the alloys. The magnetization data of crystals with x = 0.16 and 0.24 indicate an easy-plane antiferromagnetic ground state while ferromagneticlike behavior is observed for crystals with x ≥ 0.41. The temperature-dependent magnetization data possess multiple transitions for compositions near EuCuAs 0.75 P 0.25 , revealing a competition of ground states in this arsenic-rich region of the phase diagram. Neutron diffraction data for EuCuP are also presented as a follow up to previous results that revealed a two-step transition at T C ; the observed data were consistent with ferromagnetic order at T = 5K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu 30 H 18 {E 2 P(OR) 2 } 12 ] (E=S or Se; R= n Pr, i Pr or i Bu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Here, we describe the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu 30 H 18 {S 2 P(O n Pr) 2 } 12 ] ( 1 H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1 H reveals an unprecedented central Cu 12 hollow icosahedron. Six faces of this icosahedron are capped by Cu 3 triangles, the whole Cu 30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S 6 symmetry. The locations of the 18 hydrides in 1 H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ 3 -H, interstitial μ 4 -H (seesaw) and μ 5 -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1 H NMR spectrum of 1 H are in line with their coordination environment in the solid state, retaining the S 6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu 30 H 18 {Se 2 P(OR) 2 } 12 ] ( 2 H : R= i Pr 3 H : R= i Bu) were synthesized from their sulfur relative 1 H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1 H – 3 H . In addition, the reaction of 1 H with [Pd(PPh 3 ) 2 Cl 2 ] in the presence of terminal alkynes led to the formation of new bimetallic Cu–Pd alloy clusters [PdCu 14 H 2 {S 2 P(O n Pr) 2 } 6 (C≡CR) 6 ] ( 4 : R=Ph; 5 : R = C 6 H 4 F).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overcoming time and complexity limitations in molecular dynamics investigations of equilibrium melting

Abstract A hybrid Monte-Carlo molecular-dynamics method for determining solidus and liquidus compositions in multicomponent systems is presented that overcomes both the time limitations in conventional molecular dynamics that prevent the evolution of distinct solid and liquid compositions via diffusion and the complexity challenge that prevents use of thermodynamic assessment in systems of many components. This hybrid method is validated in the Cu–Ni system against an independent assessment of solidus and liquidus compositions based on the regular solution model. Strategies for efficient mapping of different phase diagrams, based on the thermodynamic parameter T 0 , the temperature at which two phases of the composition X 0 have equal free energies, are presented and then demonstrated for the copper-nickel fully miscible system and the gold–silicon eutectic system. A calculation of the solidus and liquidus sampled during the equilibrium melting of equiatomic CrMnFeCoNi is performed, indicating that this method has potential to be extended to the study of many component alloys.

Au-Si↗

Taming Metal–Solid Electrolyte Interface Instability via Metal Strain Hardening

Abstract Solid-state lithium metal batteries have emerged as a promising technology for electric vehicles due to their high specific energy and safety potential. Obtaining intimate contact between Li and electrolyte during cell fabrication, however, remains challenging. Adequate fabrication pressure is required to promote close contact, but this pressure can cause Li deformation and penetration into the electrolyte, resulting in poor battery performance. Here, a strategy for addressing this problem is presented by incorporating 3 at% Mg into Li. Unlike pure Li which obeys the Voce hardening law and allows unconstrained deformation, Li–Mg alloy follows the Swift hardening law and strengthens with strain under compression stress. Because of the constrained deformation of Li–Mg, intimate contact with solid electrolytes is possible even at high fabrication pressure (50–65 MPa), resulting in high critical current densities. These findings underscore the importance of understanding Li metal deformation properties to improve solid-state battery performance.

25 ENERGY STORAGE↗

Toward High Conversion Efficiency of Thermoelectric Modules through Synergistical Optimization of Layered Materials

Abstract Waste‐heat electricity generation using high‐efficiency solid‐state conversion technology can significantly decrease dependence on fossil fuels. Here, a synergistical optimization of layered half‐Heusler (hH) materials and module to improve thermoelectric conversion efficiency is reported. This is realized by manufacturing multiple thermoelectric materials with major compositional variations and temperature‐gradient‐coupled carrier distribution by one‐step spark plasma sintering. This strategy provides a solution to overcome the intrinsic concomitants of the conventional segmented architecture that only considers the matching of the figure of merit ( zT ) with the temperature gradient. The current design is dedicated to temperature‐gradient‐coupled resistivity and compatibility matching, optimum zT matching, and reducing contact resistance sources. By enhancing the quality factor of the materials by Sb‐vapor‐pressure‐induced annealing, a superior zT of 1.47 at 973 K is achieved for (Nb, Hf)FeSb hH alloys. Along with the low‐temperature high‐ zT hH alloys of (Nb, Ta, Ti, V)FeSb, the single stage layered hH modules are developed with efficiencies of ≈15.2% and ≈13.5% for the single‐leg and unicouple thermoelectric modules, respectively, under Δ T of 670 K. Therefore, this work has a transformative impact on the design and development of next‐generation thermoelectric generators for any thermoelectric material families.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Transformation of a ceramic precursor to a biomedical (metallic) alloy: Part I – sinterability of Ta 2 O 5 and TiO 2 mixed oxides

Mixed Ta 2 O 5 – TiO 2 binary system was studied by a combination of differential thermal analysis (DTA), scanning electron microscopy-energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and in situ high temperature X-ray diffraction (HT-XRD) techniques. Different compositions of the mixed oxide powders were fabricated by ball–milling the powdered compositions, pelletizing the homogenized composite powders, and heating the green pellets in air at different temperatures for fixed time intervals. The sintered pellets were evaluated and characterized with respect to porosity, morphology, and phase distribution. DTA runs of the un-sintered powders indicated the onset temperatures for both exothermic and endothermic changes in the binary system. Significant amount of sintering was observed to take place at temperatures higher than 900 °C. Both room and high temperature X-ray diffraction patterns exhibited consistency in phase formation. A ternary compound (TaTiO 4 ) and a ternary solid solution (Ti 0.33 Ta 0.67 O 2 ) were observed to form in both room and high temperatures in addition to the respective binary phases (Ta 2 O 5 and TiO 2 ). A sintering temperature in the range 900–1000 °C was observed to be adequate to achieve the requisite mechanical strength and optimum internal porosity (40–48%) for subsequent electrochemical polarization experiments.

36 MATERIALS SCIENCE↗

Electrolyte design for LiF-rich solid–electrolyte interfaces to enable high-performance microsized alloy anodes for batteries

Lithium batteries with Si, Al or Bi microsized (>10 µm) particle anodes promise a high capacity, ease of production, low cost and low environmental impact, yet they suffer from fast degradation and a low Coulombic efficiency. In this paper, we demonstrate that a rationally designed electrolyte (2.0 M LiPF 6 in 1:1 v/v mixture of tetrahydrofuran and 2-methyltetrahydrofuran) enables 100 cycles of full cells that contain microsized Si, Al and Bi anodes with commercial LiFePO 4 and LiNi 0.8 Co 0.15 Al 0.05 O 2 cathodes. Alloy anodes with areal capacities of more than 2.5 mAh cm -2 achieved >300 cycles with a high initial Coulombic efficiency of >90% and average Coulombic efficiency of >99.9%. These improvements are facilitated by the formation of a high-modulus LiF–organic bilayer interphase, in which LiF possesses a high interfacial energy with the alloy anode to accommodate plastic deformation of the lithiated alloy during cycling. Lastly, this work provides a simple yet practical solution to current battery technology without any binder modification or special fabrication methods.

25 ENERGY STORAGE↗

Precipitate growth kinetics under inhomogeneous concentration fields using a phase-field model

We investigate precipitation dynamics in the presence of a local solute gradient using phase-field simulations. During the homogenization heat treatment of the solidified Inconel 718 alloy, high Nb concentration within the Laves phases or at the core of the secondary arms results in Nb diffusion into the γ matrix. The volume fraction and spatial distribution of precipitation during subsequent annealing can be controlled by tailoring the Nb concentration gradient in the matrix during homogenization. We use a surrogate Ni-Fe-Nb alloy for Inconel 718 to explore the growth dynamics of δ precipitates related to the local Nb concentration levels. The simulations indicate that in the presence of a Nb concentration gradient the growth rate of δ precipitates is higher than in a matrix of uniform average Nb concentration. The higher growth rate is a result of the higher local thermodynamic driving force at the interface between the solute-rich matrix and the δ interface. Here, we propose a phenomenological model to describe the diffusion-controlled growth kinetics of the δ phase under a solute concentration gradient.

36 MATERIALS SCIENCE↗

Predicting phase behavior in high entropy and chemically complex alloys

The interest in high entropy alloys and other metallic compounds with four or more elements at near-equiatomic ratios has drawn attention to the ability to rapidly predict phase behavior of these complex materials, particularly where existing thermodynamic data are lacking. In this paper, we discuss aspects of this from the point of view of predicting without utilizing (or fitting) experimental data. Of particular interest are heuristic approaches that provide prediction of single-phase compositions, more rigorous approaches that tackle the thermodynamics from a more fundamental point of view, and simulation approaches that provide further insight into the behaviors. This paper covers cases of all three of these, in order to examine the strengths and weaknesses of each approach, and to indicate directions where these may be utilized and improved upon. Of particular interest is moving beyond “which composition may form a solid solution,” to recognizing the importance of underlying thermodynamic realities that affect the temperature- and composition-dependent transformations of these materials.

36 MATERIALS SCIENCE↗

Spectral-partitioned Kohn-Sham density functional theory

Here we introduce a general, variational scheme for systematic approximation of a given Kohn-Sham free-energy functional by partitioning the density matrix into distinct spectral domains, each of which may be spanned by an independent diagonal representation without requirement of mutual orthogonality. It is shown that by generalizing the entropic contribution to the free energy to allow for independent representations in each spectral domain, the free energy becomes an upper bound to the exact (unpartitioned) Kohn-Sham free energy, attaining this limit as the representations approach Kohn-Sham eigenfunctions. A numerical procedure is devised for calculation of the generalized entropy associated with spectral partitioning of the density matrix. The result is a powerful framework for Kohn-Sham calculations of systems whose occupied subspaces span multiple energy regimes. As a case in point, we apply the proposed framework to warm- and hot-dense matter described by finite-temperature density functional theory, where at high energies the density matrix is represented by that of the free-electron gas, while at low energies it is variationally optimized. We derive expressions for the spectral-partitioned Kohn-Sham Hamiltonian, atomic forces, and macroscopic stresses within the projector-augmented wave (PAW) and the norm-conserving pseudopotential methods. It is demonstrated that at high temperatures, spectral partitioning facilitates accurate calculations at dramatically reduced computational cost. Moreover, as temperature is increased, fewer exact Kohn-Sham states are required for a given accuracy, leading to further reductions in computational cost. Finally, it is shown that standard multiprojector expansions of electronic orbitals within atomic spheres in the PAW method lack sufficient completeness at high temperatures. Spectral partitioning provides a systematic solution for this fundamental problem.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Tailoring microstructures with mild magnetic-field processing: A case study of CuNiFe alloys

Combined experimental and computational investigations of the CuNiFe spinodal system confirm that application of a mild magnetic field during thermal treatment alters elemental redistribution and the resulting microstructure, relative to that obtained from zero-field annealing. Spinodal decomposition of a Cu 40 Ni 42 Fe 18 alloy was initiated during thermal treatment at 773 K, conducted either under zero field or modest (60 mT) magnetic f ield conditions for up to 200 h. Periodic (~10 nm) chemical modulations into Cu-rich and NiFe-rich regions were observed under both conditions, with the amplitude and wavelength of the segregated regions increasing with treatment time. However, magnetic field annealing resulted in a more than twofold increase in the amplitude of elemental modulations relative to zero-field conditions – consistent with enhanced diffusional f luxes during spinodal decomposition – while the modulation wavelength remained largely unaffected. These microstructural differences are reflected in various extrinsic magnetic properties. In parallel, first-principles DFT calculations indicate that long-range ferromagnetic order, as induced by an applied magnetic field, substantially alters the strength and nature of atomic interactions, enhancing the thermodynamic instability of the CuNiFe solid solution. Collectively, these results suggest that incorporating a mild (millitesla-level) magnetic field – distinct from the strong (tesla-level) fields commonly used in prior studies – during thermal processing has the potential to deliver enhanced control of microstructures for targeted engineering outcomes.

36 MATERIALS SCIENCE↗

Elucidating the reversible exsolution–dissolution behaviour of high-entropy oxides in crystalline and amorphous phases

High-entropy oxides (HEOs), as a subclass of high-entropy materials (HEMs), offer a versatile platform for catalysis by leveraging entropy-stabilized solid solutions with tunable compositions, lattice structures, and electronic properties. While exsolution–dissolution of metal species in crystalline HEOs has emerged as a promising strategy for reversible active sites regeneration, the dynamic behaviour of HEOs possessing amorphous nature remains under-explored, particularly the difference with crystalline counterparts. In this work, we systematically investigate the architecture-dependent exsolution–dissolution behavior of HEOs by comparing a crystalline-phase HEO (c-HEO) and an amorphous-phase HEO (a-HEO), both comprising Ni, Mg, Cu, Zn, and Co as principal metal elements. Using a combination of in situ variable-temperature X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electron microscopy, and in situ CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS), the structural evolution of the two HEO phases under redox conditions was elucidated. Both materials exhibit reversible exsolution of metallic species or alloys in reducing environments, followed by re-incorporation into the host lattice upon oxidation. Remarkably, the a-HEO demonstrates more facile and dynamic self-healing behavior, with alloy exsolution and dissolution occurring under milder conditions because of its enhanced reducibility and structural disorder. This study provides critical insights into the design of next-generation regenerable catalysts based on amorphous HEOs, highlighting the role of phase structure in governing reversible metal-site formation dynamics and catalytic performance.

Wang, Qingju [Univ. of Tennessee, Knoxville, TN (U↗

Visualizing temperature-dependent phase stability in high entropy alloys

High entropy alloys (HEAs) contain near equimolar amounts of five or more elements and are a compelling space for materials design. In the design of HEAs, great emphasis is placed on identifying thermodynamic conditions for single-phase and multi-phase stability regions, but this process is hindered by the difficulty of navigating stability relationships in high-component spaces. Traditional phase diagrams use barycentric coordinates to represent composition axes, which require ( N – 1) spatial dimensions to represent an N -component system, meaning that HEA systems with N > 4 components cannot be readily visualized. Here, we propose forgoing barycentric composition axes in favor of two energy axes: a formation-energy axis and a ‘reaction energy’ axis. These Inverse Hull Webs offer an information-dense 2D representation that successfully captures complex phase stability relationships in N ≥ 5 component systems. We use our proposed diagrams to visualize the transition of HEA solid-solutions from high-temperature stability to metastability upon quenching, and identify important thermodynamic features that are correlated with the persistence or decomposition of metastable HEAs.

Chemistry↗

Small-scale mechanical testing and characterization of fuel cladding chemical interaction between HT9 cladding and advanced U-based metallic fuel alloy

Fuel cladding chemical interactions (FCCI) occurred on the interface between the nuclear metal fuel and cladding is the primary cause of cladding wastage, weakening cladding mechanical integrity, and placing fuel and cladding at risk. Although the microstructural and phase information of FCCI has been fairly understood, mechanical properties remain less studied due to limited reaction volume. Here, through a combining of advanced electron microscopy characterizations and small-scale mechanical testing techniques, including indentation and micro-tensile testing, this study investigated the microscale mechanical properties of FCCI between the ferritic/martensitic (F/M) HT9 cladding and an advanced Uranium (U)-based metallic fuel irradiated at the Advanced Test Reactor to 2.2% FIMA with peak inner cladding temperature reached to 650 °C. Mechanical testing results show significant hardening and embrittlement in the FCCI region. The brittle fracture of FCCI specimen is mainly attributed to the formation of nano-crystallized intermetallic σ-FeCr phase. Whereas mechanical softening was revealed in the unreacted HT9 matrix due to irradiation-induced microstructural and microchemical evolution, specifically, the disappearance of martensitic lath structure and the formation of Fe 2 Mo Laves phase precipitation which consumed the solid solution strengthening Mo from the F/M HT9 matrix. Due to the achieved high cladding temperature, this fuel pin is of particular significance for revealing the high-temperature irradiation effect on the mechanical properties of HT9 cladding. Therefore, the outcomes of this study are expected to contribute to the development of multi-scale mechanical behavior modeling of HT9 cladding for Generation IV reactors which requires cladding to run at higher temperature (above 600 ?).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Plastic deformation of single crystals of the equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy in tension and compression from 10 K to 1273 K

In this report the plastic deformation behavior of single crystals of the quinary, equiatomic Cr-Mn-Fe-Co-Ni high-entropy alloy (HEA) with the face-centered cubic structure has been investigated in tension and compression as a function of crystal orientation and temperature from 10 K to 1373 K. The critical resolved shear stress (CRSS) for {111}<110> slip at room temperature is 42-45 MPa. It does not depend much on crystal orientation (i.e., the Schmid law holds true) and the sense (tension vs. compression) of the applied load. The CRSS for {111}<110> slip increases with the decrease in temperature, without showing any significant inertia effects at cryogenic temperatures below 77 K. Extrapolation from the measured yield stresses down to 10 K yields a CRSS value at 0 K of 168 MPa. At cryogenic temperatures, the measured strain-rate sensitivity of flow stress is consistent with a very small activation volume. The concept of stress equivalence holds true both for the temperature dependence of CRSS and the stress dependence of activation volume, indicating that solid-solution hardening is the major strengthening mechanism. Deformation twinning occurs at 77 K but not at room temperature, resulting in higher tensile elongation to failure at 77 K than at room temperature. Deformation twinning at 77 K occurs at a shear stress of 378 MPa on conjugate ($\bar1\bar11$) planes in the form of Lüders deformation after large plastic strain (about 85%) achieved by the stage I (easy glide) and stage II (linear work-hardening) deformation.

36 MATERIALS SCIENCE↗

Comparative Study of Zinc Cold-Spray Coating and Pre-treatments for Magnesium Alloys

Magnesium (Mg) alloys are appealing for automotive lightweighting owing to their high specific strength. However, their susceptibility to corrosion in harsh environments remains a major challenge. Conventional industrial pre-treatment coatings, including zinc phosphate, chromate conversion, and non-chromate conversion, often exhibit discontinuities and microcracks, leading to localized corrosion near fasteners and parting lines. Here, this study investigates cold-sprayed zinc (Zn) coatings as a novel pre-treatment alternative for high-pressure die cast (HPDC) AZ91 Mg alloys, demonstrating significant improvements in wear and corrosion performance. Cold spray produces uniform and robust coatings, reducing wear rate by over 50% and reducing corrosion rate by over 99.3%, as measured by evolved hydrogen release, compared to traditional pre-treatments. Multimodal corrosion testing reveals that Zn cold-spray coatings form a protective layer during exposure, minimizing general and filiform corrosion, and exhibiting corrosion potential (E corr ) that is nobler by ~ 400 mV than the surfaces of both pre-treated and uncoated AZ91. Scalability of cold spray for selective application around multimaterial joints further strengthens their industrial viability. This work establishes Zn cold-spray coatings as highly effective pre-treatment solutions for the advancement of corrosion resistant Mg alloy components in automotive applications.

multimodal corrosion↗