Atomic Short-range Order Research Articles

Electron Concept of Hydrogen Embrittlement and Hydrogen-Increased Plasticity of Metals

Based on theoretical and experimental studies of hydrogen effect on the electron structure of iron, nickel and titanium, an electron concept is proposed for hydrogen embrittlement as well as for hydrogen-improved plasticity of engineering metallic materials. This concept implies a hydrogen-caused redistribution of valence electrons across their energy levels and an increase in the density of electron states at the Fermi level, causing a softening of the crystal lattice and, thereby, leading to a decrease in the specific energy of dislocations with consequent increase in their mobility. Innate phenomena in metallic solid solutions, namely, short-range atomic order in its two versions, short-range ordering and decomposition, are shown to be a precondition for the localization of plastic deformation. Hydrogen enhances merely this effect resulting in pseudo-brittle fracture. The role of hydrogen-induced superabundant vacancies in hydrogen-caused localization of plastic deformation and grain-boundary fracture in pure metals is discussed. Using the temperature- and strain-dependent internal friction, the enthalpies of hydrogen diffusion and hydrogen–dislocation binding are studied, and their controlling effect on the temperature- and strain-rate-dependent hydrogen embrittlement is demonstrated. Finally, a physical rationale is proposed for using hydrogen as a temporary alloying element in the technological processing of titanium alloys, and for a positive hydrogen effect on the fatigue life and plasticity of austenitic steels.

First-principles and cluster expansion study of the effect of magnetism on short-range order in Fe–Ni–Cr austenitic stainless steels

Short-range order (SRO), the regular and predictable arrangement of atoms over short distances, alters the mechanical properties of technologically relevant structural materials such as medium/high entropy alloys and austenitic stainless steels. In this study, we present a generalized spin cluster expansion (CE) model and show that magnetism is a primary factor influencing the level of SRO present in austenitic Fe–Ni–Cr alloys. The spin CE consists of a chemical cluster expansion combined with an Ising model for Fe–Ni–Cr austenitic alloys. It explicitly accounts for local magnetic exchange interactions, thereby capturing the effects of finite temperature magnetism on SRO. Model parameters are obtained by fitting to a first-principles data set comprising both chemically and magnetically diverse face-centered cubic configurations. The magnitude of the magnetic exchange interactions are found to be comparable to the chemical interactions. Compared to a conventional implicit magnetism CE built from only magnetic ground state configurations, the spin CE shows improved performance on several experimental benchmarks over a broad spectrum of compositions, particularly at higher temperatures due to the explicit treatment of magnetic disorder. We find that SRO is strongly influenced by alloy Cr content, since Cr atoms prefer to align antiferromagnetically with nearest neighbors but become magnetically frustrated with increasing Cr concentration. Using the spin CE, we predict that increasing the Cr concentration in typical austenitic stainless steels promotes the formation of SRO and increases order–disorder transition temperatures. This study underscores the significance of considering magnetic interactions explicitly when exploring the thermodynamic properties of complex transition metal alloys. It also highlights guidelines for customizing SRO through adjustments of alloy composition.

Competition between phase ordering and phase segregation in the TixNbMoTaW and TixVNbMoTaW refractory high-entropy alloys

Refractory high-entropy alloys are under consideration for applications where materials are subjected to high temperatures and levels of radiation, such as in the fusion power sector. However, at present, their scope is limited because they are highly brittle at room temperature. One suggested route to mitigate this issue is by alloying with Ti. In this theoretical study, using a computationally efficient linear-response theory based on density functional theory calculations of the electronic structure of the disordered alloys, we study the nature of atomic short-range order in these multi-component materials, as well as assessing their overall phase stability. Our analysis enables direct inference of phase transitions in addition to the extraction of an atomistic, pairwise model of the internal energy of an alloy suitable for study via, e.g., Monte Carlo simulations. Once Ti is added into either the NbMoTaW or VNbMoTaW system, we find that there is competition between chemical phase ordering and segregation. These results shed light on observed chemical inhomogeneity in experimental samples, as well as providing fundamental insight into the physics of these complex systems.

Hydrogen in metallic alloys ─ embrittlement and enhanced plasticity: a review

Abstract The evolution of ideas concerning the nature of hydrogen embrittlement of engineering metallic materials is described based on a number of the proposed hypotheses and corresponding experiments. The main attention is paid to two of them, namely hydrogen-enhanced decohesion (HEDE) and hydrogen-enhanced localized plasticity (HELP). Recent attempts to interconnect the both models as HELP + HEDE and HELP-mediated HEDE ones are also estimated. A conclusion is made that HELP model is preferential for understanding the entire array of experimental data with a caveat that it is necessary to consider the chemical nature of hydrogen atoms and view them not only as point defects. Based on the studies of hydrogen effect on the atomic interactions in iron, nickel, titanium, and its alloys, it is shown that the electron approach to HELP phenomenon adequately describes two competitive features of hydrogen behavior in metals: increased brittleness and enhanced plasticity. Due to the increase in the concentration of free electrons, hydrogen decreases the elasticity moduli, which causes the crystal lattice to soften. For this reason, the formation of hydrogen atmospheres around the dislocations decreases the start stress of dislocation sources, as well as line tension of emitted dislocations, enhancing thereby their mobility, and weakens repulsion between dislocations in their pile-ups. The range of temperatures and strain rates in which hydrogen embrittlement occurs is controlled by the enthalpies of hydrogen atoms’ diffusion and their binding to dislocations. The resulting consequences for mechanical properties depend on the short-range atomic order, SRO, which inherently occurs in the metallic solid solutions and localizes plastic deformation both in the cases of short-range atomic ordering and of short-range atomic decomposition. Hydrogen enhances slip localization because of its different solubility in the submicrovolumes of short-range decomposed solid solutions. If SRO is absent or not remarkably formed, the hydrogen-increased concentration of free electrons results in enhanced plasticity. Available positive hydrogen effects on the plasticity of titanium β-alloys and austenitic steels are presented and interpreted.

Study of the short-range order of Co-W alloys electrodeposited using pulse current

Pulsed electrodeposition modes allowed to obtain amorphous Co-W alloys. Using X-ray phase and spectral analysis methods, it was established that the deposition modes and the concentration of the amorphizing component (sodium tungstate salts) in an aqueous electrolyte solution affect the amorphization of alloys. The short-range atomic order was studied by X-ray diffraction analysis and the sizes of the regions of ordered arrangement of atoms were determined in X-ray amorphous Co-W alloys obtained by pulsed electrodeposition. The radial distribution function of atoms was analysed. The assumption is made that cobalt and tungsten atoms combine into configurations that are irregular polyhedrons.

Role of local atomic short-range order distribution in alloys: Why it matters in Si-Ge-Sn alloys

Role of local atomic short-range order distribution in alloys: Why it matters in Si-Ge-Sn alloys

Strain-driven anomalous elastic properties of GeSn thin films

Elastic strain engineering in the GeSn bandgap structure is an attractive area for designing novel material properties. The linear interpolation of the elastic constants of Ge and Sn is commonly used to estimate their respective values for Ge1−xSnx alloys. This work reveals that Young's modulus of Ge1−xSnx epitaxial layers has a non-monotonic dependence on Sn composition. It is shown that the decrease in the elastic modulus correlates with the increase in Sn content in pseudomorphically grown Ge1−xSnx-epilayers with Sn concentration in the range of 1–5 at. % and subcritical thicknesses. An anomalous increase in the elastic modulus is observed with the further increase in Sn content (12 at. %), which is also accompanied by an increase in in-plane tensile strain. Phase separation and a decrease in the elastic modulus are observed for Ge1−xSnx-epilayers grown above the critical thickness with Sn concentration ≥ 12 at. %. A correlation between the experimental elastic moduli and calculated elastic energies explains the complexity of strain-driven anomalous elastic properties of Ge1−xSnx-epilayers. The observed anomalous behavior of the Young's modulus for these GeSn epitaxial layers appears to be related to their recently predicted and observed short-range atomic order.

Orientation dependence of the effect of short-range ordering on the plastic deformation of a medium entropy alloy

Multi-principal-element alloys (also known as medium and high entropy alloys) offer a much larger and richer design space than conventional alloys, providing opportunities for discovering new functionalities and their governing physics. Some of these alloys exhibit an outstanding combination of high strength and ductility, linked to the activation of various deformation modes triggered by low-energy stacking faults. However, a pressing question remains: Is the plasticity of medium- and high-entropy alloys governed only by stacking fault energy, or does atomic short-range order (SRO) play a role? To answer this, we investigated how SRO affects the deformation in single-crystalline NiCoCr, with previous contradictory findings. First, we established unique experimental evidence for SRO formation in bulk single crystals using high-energy synchrotron transmission X-Ray Diffraction. By tuning the degree of SRO by aging at high temperatures, twinning density and strain-induced martensitic phase transformation can be significantly increased in the [110] and [111] orientations under tension, increasing the tensile ductility; yet, no increase was observed along the [001] orientation due to lack of TWinning-Induced Plasticity (TWIP) or TRansformation-Induced Plasticity (TRIP), indicating a strong crystallographic orientation dependence. Our first-principles thermodynamic calculations unequivocally show SRO exists and governs the observed microstructural evolution and deformation hardening behavior. Here we find direct proof that SRO triggers a simultaneous TWIP and TRIP in NiCoCr, a rare microstructural evolution path. Our findings establish that the interplay of SRO and plasticity could be exploited to alter deformation modes and yield unprecedented mechanical response in medium- and high-entropy alloys.

Direct evidence of the ultramicroporous structure of carbon molecular sieves

We utilize gas sorption experiments, neutron pair distribution function, and small-angle X-ray scattering studies on carbon molecular sieves (CMSs) to gain new insight into their ultramicroporous structure. CMS materials derived from the pyrolysis of PIM-1 (PIM = polymer of intrinsic microporosity) under an inert atmosphere (PIM-1-CMS) and H2 atmosphere (4% H2-PIM-1-CMS) were studied. Neutron total scattering studies of these materials reveal these CMS materials to be mainly graphene-like ribbons with short-range atomic ordering. Small-angle X-ray scattering and low angle diffraction peaks corroborate the presence of well-defined ultramicroporosity observed in carbon dioxide and cryogenic neon adsorption studies suggesting, expectedly, that these materials are non-graphitizing carbon structures. Our findings provide microscopic evidence of the non-graphitizing and ribbon-like structure of these CMS materials and suggest a possible hypothetical microporous structure.

Endothelial Cell Behavior and Nitric Oxide Production on a-C:H:SiOx-Coated Ti-6Al-4V Substrate.

This paper focuses on the surface modification of the Ti-6Al-4V alloy substrate via a-C:H:SiOx coating deposition. Research results concern the a-C:H:SiOx coating structure, investigated using transmission electron microscopy and in vitro endothelization to study the coating. Based on the analysis of the atomic radial distribution function, a model is proposed for the atomic short-range order structure of the a-C:H:SiOx coating, and chemical bonds (C-O, C-C, Si-C, Si-O, and Si-Si) are identified. It is shown that the a-C:H:SiOx coating does not possess prolonged cytotoxicity in relation to EA.hy926 endothelial cells. In vitro investigations showed that the adhesion, cell number, and nitric oxide production by EA.hy926 endothelial cells on the a-C:H:SiOx-coated Ti-6Al-4V substrate are significantly lower than those on the uncoated surface. The findings suggest that the a-C:H:SiOx coating can reduce the risk of endothelial cell hyperproliferation on implants and medical devices, including mechanical prosthetic heart valves, endovascular stents, and mechanical circulatory support devices.

Ferromagnetism of Nanometer Thick Sputtered Fe3GeTe2 Films in the Absence of Two-Dimensional Crystalline Order: Implications for Spintronics Applications

The discovery of ferromagnetism in two-dimensional (2D) monolayers has stimulated growing research interest in both spintronics and material science. However, these 2D ferromagnetic layers are mainly prepared through an incompatible approach for large-scale fabrication and integration, and moreover, a fundamental question of whether the observed ferromagnetism actually correlates with the 2D crystalline order has not been explored. Here, we choose a typical 2D ferromagnetic material, Fe3GeTe2, to address these two issues by investigating its ferromagnetism in an amorphous state. We have fabricated nanometer thick amorphous Fe3GeTe2 films approaching the monolayer thickness limit of crystallized Fe3GeTe2 (0.8 nm) through magnetron sputtering. Compared to crystallized Fe3GeTe2, we found that the basic ferromagnetic attributes, such as the Curie temperature which directly reflects magnetic exchange interactions and local anisotropic energy, do not change significantly in the amorphous states. This is attributed to the short-range atomic order, as confirmed by valence state analysis, being almost the same for both phases. The persistence of ferromagnetism in the ultrathin amorphous counterpart has also been confirmed through magnetoresistance measurements, where two unconventional switching dips arising from electrical transport within domain walls are clearly observed in the amorphous Fe3GeTe2 single layer. These results indicate that the long-range ferromagnetic order of crystallized Fe3GeTe2 may not correlate to the 2D crystalline order, and the corresponding ferromagnetic attributes can be utilized in an amorphous state which suits large-scale fabrication in a semiconductor technology-compatible manner for spintronics applications.

Local ordering in Ge/Ge–Sn semiconductor alloy core/shell nanowires revealed by extended x-ray absorption fine structure (EXAFS)

Short-range atomic order in semiconductor alloys is a relatively unexplored topic that may promote design of new materials with unexpected properties. Here, local atomic ordering is investigated in Ge–Sn alloys, a group-IV system that is attractive for its enhanced optoelectronic properties achievable via a direct gap for Sn concentrations exceeding ≈10 at. %. The substantial misfit strain imposed on Ge–Sn thin films during growth on bulk Si or Ge substrates can induce defect formation; however, misfit strain can be accommodated by growing Ge–Sn alloy films on Ge nanowires, which effectively act as elastically compliant substrates. In this work, Ge core/Ge1−xSnx (x ≈ 0.1) shell nanowires were characterized with extended x-ray absorption fine structure (EXAFS) to elucidate their local atomic environment. Simultaneous fitting of high-quality EXAFS data collected at both the Ge K-edge and the Sn K-edge reveals a large (≈ 40%) deficiency of Sn in the first coordination shell around a Sn atom relative to a random alloy, thereby providing the first direct experimental evidence of significant short-range order in this semiconductor alloy system. Comparison of path length data from the EXAFS measurements with density functional theory simulations provides alloy atomic structures consistent with this conclusion.

Short-range order and phase stability of CrCoNi explored with machine learning potentials

We present an analysis of temperature-dependent atomic short-range ordering and phase stability of the face-centered cubic CrCoNi medium-entropy alloy employing a combination of ab initio calculations and on-lattice machine learning interatomic potentials. Temperature-dependent properties are studied with canonical Monte Carlo simulations. At around 975 K a phase transition into an ordered $\mathrm{Cr}{(\mathrm{Ni},\mathrm{Co})}_{2}$ phase (${\mathrm{MoPt}}_{2}$-type) is found. This hitherto not reported state has an ordering energy twice as large than the ordered structures previously suggested. We show that magnetism is not responsible for the observed chemical ordering.

RF Magnetron Sputtering of Substituted Hydroxyapatite for Deposition of Biocoatings.

Functionalization of titanium (Ti)-based alloy implant surfaces by deposition of calcium phosphates (CaP) has been widely recognized. Substituted hydroxyapatites (HA) allow the coating properties to be tailored based on the use of different Ca substitutes. The formation of antibacterial CaP coatings with the incorporation of Zn or Cu by an RF magnetron sputtering is proposed. The influence of RF magnetron targets elemental composition and structure in the case of Zn-HA and Cu-HA, and the influence of substrate’s grain size, the substrate’s temperature during the deposition, and post-deposition heat treatment (HT) on the resulting coatings are represented. Sintering the targets at 1150 °C resulted in a noticeable structural change with an increase in cell volume and lattice parameters for substituted HA. The deposition rate of Cu-HA and Zn-HA was notably higher compared to stochiometric HA (10.5 and 10) nm/min vs. 9 ± 0.5 nm/min, respectively. At the substrate temperature below 100 °C, all deposited coatings were found to be amorphous with an atomic short-range order corresponding to the {300} plane of crystalline HA. All deposited coatings were found to be hyper-stochiometric with Ca/P ratios varying from 1.9 to 2.5. An increase in the substrate temperature to 200 °C resulted in the formation of equiaxed grain structure on both coarse-grained (CG) and nanostructured (NS) Ti. The use of NS Ti notably increased the scratch resistance of the deposited coatings from18 ± 1 N to 22 ± 2 N. Influence of HT in air or Ar atmosphere is also discussed. Thus, the deposition of Zn- or Cu-containing CaP is a complex process that could be fine-tuned using the obtained research results.

Compositional phase stability in medium-entropy and high-entropy Cantor-Wu alloys from an ab initio all-electron Landau-type theory and atomistic modeling

We describe implementation and analysis of a first-principles theory, derived in an earlier work, for the leading terms in an expansion of a Gibbs free energy of a multi-component alloy in terms of order parameters that characterize potential, compositional phases. The theory includes effects of rearranging charge and other electronics from changing atomic occupancies on lattice sites. As well as the rigorous description of atomic short-range order in the homogeneously disordered phase, pairwise interaction parameters suited for atomistic modelling in a multicomponent setting can be calculated. From our study of an indicative series of the Cantor-Wu alloys, NiCo, NiCoCr, NiCoFeCr, and NiCoFeMnCr, we find that the interactions are not approximated well either as pseudobinary or restricted to nearest neighbour range. Our computed order-disorder transition temperatures are low, consistent with experimental observations, and the nature of the ordering is dominated by correlations between Ni, Co, and Cr, while Fe and Mn interact weakly. Further atomistic modelling suggests that there is no true single-phase low-temperature ground state for these multicomponent systems. Instead the single-phase solid solution is kept stable to low temperatures by the large configurational entropy and the Fe, Mn dilution effects. The computationally cost-effectiveness of our method makes it a good candidate for further exploration of the space of multicomponent alloys.

Atomic Short-Range Order in a Cation-Deficient Perovskite Anode for Fast-Charging and Long-Life Lithium-Ion Batteries.

Perovskite-type oxides are widely used for energy conversion and storage, but their rate-inhibiting phase transition and large volume change hinder the applications of most perovskite-type oxides for high-rate electrochemical energy storage. Here, it is shown that a cation-deficient perovskite CeNb3 O9 (CNO) can store a sufficient amount of lithium at a high charge/discharge rate, even when the sizes of the synthesized particles are on the order of micrometers. At 60 C (15 A g-1 ), corresponding to a 1 min charge, the CNO anode delivers over 52.8% of its capacity. In addition, the CNO anode material exhibits 96.6% capacity retention after 2000 charge-discharge cycles at 50 C (12.5 A g-1 ), indicating exceptional long-term cycling stability at high rates. The excellent cycling performance is attributed to the formation of atomic short-range order, which significantly prevents local and long-range structural rearrangements, stabilizing the host structure and being responsible for the small volume evolution. Moreover, the extremely high rate capacity can be explained by the intrinsically large interstitial sites in multiple directions, intercalation pseudocapacitance, atomic short-range order, and cation-vacancy-enhanced 3D-conduction networks for lithium ions. These structural characteristics and mechanisms can be used to design advanced perovskite electrode materials for fast-charging and long-life lithium-ion batteries.

Electron Diffraction Study of Phase Formation in Nano Layers of Cu-=SUB=-2-=/SUB=-Te-In-=SUB=-2-=/SUB=-Te-=SUB=-3-=/SUB=-, Cu-In-Te Systems and Short-Range Atomic Order in Amorphous CuIn-=SUB=-5-=/SUB=-Te-=SUB=-8-=/SUB=- Films

It is shown that with the simultaneous and sequential deposition of films of the Cu2Te-In2Te3 system, as well as copper, indium, and tellurium of the highest purity used as starting materials, ~99.999%, taken in the ratio Cu : In : Te = 1 : 5 : 8, regardless of the deposition order ternary compounds of the compositions CuInTe2, CuIn3Te5, and CuIn5Te8 in the crystalline state are distinguished. During vacuum condensation of films on single-crystal substrates NaCl, KCl and amorphous celluloid cooled by liquid nitrogen to 203 K, the resulting films obtained both by co-evaporation of binary compounds of the Cu2Te-In2Te3 system and by the synthesis of thin layers applied by Cu, In, Te are amorphous. For the first time in nanosized amorphous films of the composition CuIn5Te8, crystallizing in the tetragonal system with the periods of unit cells a=6.162 Angstrem, c=12.291 Angstrem, obtained both under normal conditions and under the influence of an external electric field with a strength of 500 V · cm-1, the structure of the short-range atomic order is established --- the number of nearest neighbors --- coordination numbers and radius of coordination spheres. It was revealed that in amorphous CuIn5Te8 films obtained under the influence of an external electric field, in which the matrices consist of tetrahedral and octahedral environments of atoms, in opposite to films that are formed outside the field, the number of nearest neighbors remains unchanged, the radius of coordination spheres and interatomic distances are somewhat are shortened. Keywords: phase formation, elektronogram, radial distribution function of atoms (RDFA), coherent electron scattering.

Formation of Short-Range Atomic Order in Cu–Pd Alloys with a Low Palladium Content: Resistometric Study

Formation of Short-Range Atomic Order in Cu–Pd Alloys with a Low Palladium Content: Resistometric Study

(Invited) Understanding Electrocatalytic Pathways in Complex Organic and Inorganic Composites in Aqueous and Non Aqueous Environments

There are very few techniques that lend themselves to rigorous requirements, where the individual role of different transition metal components of nano-phasic materials can be investigated in both amorphous and crystalline forms. We have been at the forefront of various analytical techniques along with theoretical calculations, which enables the amount and specific adsorption site of species such as H, OH, O, CO, other C1 moieties and even anions such as bisulfate to be determined in situ on a metal surfaces using synchrotron XANES data. This technique, commonly called the ‘Delta Mu (∆μ) Technique’ can be taken in situ in both electrochemical cells and operating fuel cells, and can be obtained from a wide variety of transition metal surfaces and alloys, including non-Pt based metal electrocatalysts with element specificity. EXAFS data taken concurrently provide information on the changes in short range atomic order around the absorber atom thereby providing structural information such as bond distances and coordination numbers (thereby information on average cluster size, homogeneity and surface segregation etc.).In this presentation among other things we will show in-situ XAS study of group of (Metal-Nitrogen-Carbon) MNC catalysts from perspective of metal center. We will demonstrate the presence of ORR active bio-mimetic porphyrin-like FeNx functionalities (Fig.1), as well as other forms of the metal which indicate no catalytic activity. The XAS in-situ studies will be combined with electroanalytical evaluations using cyclic voltammetry (CV) and square wave voltammetry (SWV). Further the factors governing the ORR activity at MNC centers, such as the Lewis basicity of the carbon support and the accompanying changes in the redox potential of the metal center will be discussed. This part of the presentation will bring together electrochemistry and XAS spectroscopy (including ∆μ) on effect of pH (inner and outer sphere charge transfer) and aqueous vs. non aqueous electrolyte (concerted vs. non concerted charge transfer).

Tuning the magnetic phase diagram of Ni-Mn-Ga by Cr and Co substitution

Ni-Mn-based Heusler alloys have a high technical potential related to a large change of magnetization at the structural phase transition. These alloys show a subtle dependence of magnetic properties and structural phase stability on composition and substitution by 3d elements and although they have been extensively investigated, there are still ambiguities in the published results and their interpretation. To shed light on the large spread of reported properties, we perform a comprehensive study by means of density functional theory calculations. We focus on Cr and Co co-substitution whose benefit has been predicted previously for the expensive Ni-Mn-In-based alloy and study the more abundant iso-electronic counterpart Ni-Mn-Ga. We observe that substituting Ni partially by Co and/or Cr enhances the magnetization of the Heusler alloy and at the same time reduces the structural transition temperature. Thereby, Cr turns out to be more efficient to stabilize the ferromagnetic alignment of the Mn spins by strong antiferromagnetic interactions between Mn and Cr atoms. In a second step, we study Cr on the other sublattices and observe that an increase in the structural transition temperature is possible, but depends critically on the short-range order of Mn and Cr atoms. Based on our results, we are able to estimate composition dependent magnetic phase diagrams. In particular, we demonstrate that neither the atomic configuration with the lowest energy nor the results based on the coherent potential approximation are representative for materials with a homogeneous distribution of atoms and we also predict a simple method for fast screening of different concentrations which can be viewed as a blueprint for the study of high entropy alloys. Our results help to explain the large variation of experimentally found materials properties.