Complex Oxides Research Articles

Conductivity and chemical stability of co-doped LaScO3 ceramics

New materials based on LaScO3, namely, were synthesized by the solid-phase method. The structure of the resulting complex oxides was refined. The electrical properties of the undoped, mono- and co-doped samples were determined by varying the temperature T and pH2O. All substituted samples were found to have the conductivity of several orders of magnitude higher relative to the parent phase. The maximum conductivity was observed for the Ba2+/Mg2+-co-doped sample due to high concentration of oxygen vacancies The possibility of phase formation and its electrical properties are greatly influenced by geometric parameters such as the ratio of the radii of the host- and the dopant-ion, the free cell volume, the critical radius. It has been demonstrated that the nature of the dopant affects the porosity of the samples. The investigated phases demonstrate good chemical stability in a CO2-saturated atmosphere.

Charge-exchange-driven interfacial antiferromagnetic ground state in La0.8Sr0.2MnO3 ultrathin films

The evolution of the magnetic ground state of ultrathin 0–10 unit cells (uc) thick La0.8Sr0.2MnO3 films interfaced to an antiferromagnetic La0.45Sr0.55MnO3/SrTiO3(001) buffer layer was investigated with x-ray photoemission electron microscopy. For 0–3 uc La0.8Sr0.2MnO3, we observe antiferromagnetic domains but no ferromagnetic contrast, showing that nominally ferromagnetic La0.8Sr0.2MnO3 adopts the antiferromagnetic ground state of the buffer layer. For larger thicknesses, ferromagnetic domains emerge, confirming that the additional layers revert to the ferromagnetic ground state. We also observe a drastic increase in the complexity of the domain configuration between 3 and 5 uc, which we attribute to competing magnetic and electronic ground states in the system. We attribute the interfacial modified magnetic ground state to charge sharing at the interface due to the chemical potential mismatch, which leads to hole doping at the La0.8Sr0.2MnO3 interface. The present work sheds light on the impact of charge sharing at the interface of complex oxide materials, in particular on the magnetic and electronic states, and presents a strategy for modulating the electronic ground state properties at metallic interfaces.

High-temperature chlorination of different cobalt oxide phases using calcium chloride

ABSTRACT High-temperature chlorination method has been proposed for the recovery of value metals from industrial solid wastes. However, there are only a few reports about the effect of different occurrence states of value metals. The aim of this paper is to investigate the high-temperature chlorination of different cobalt (Co) phases using calcium chloride and phase evolution of Co oxide phases during high-temperature chlorination. Complex oxides of CoFe2O4, Co2SiO4, and CoAl2O4 were synthesised first. Concentrations of samples were measured by inductively coupled plasma-optical emission spectrometer (ICP-OES) after acid dissolution. Phases of calcines roasted at different times were detected by X-ray diffraction. The results showed that Co volatilisation percentages of different Co oxide phases at 1273 and 1373 K could be classified as CoO > Co2SiO4 > CoFe2O4 > CoAl2O4. Co volatilisation percentage decreased with the introduction of Al2O3 due to the generation of CoAl2O4 from the reaction between CoO and Al2O3. The phase evolution of different Co oxide phases during the high-temperature chlorination was described in detail.

Edge dislocation with [001] [formula omitted] induced positive magnetoresistance in BaTiO3/La0.66Sr0.33MnO3 heterostructure

The magnetoresistance (MR) effect holds immense potential for applications in various fields, including but not limited to storage and sensing. Manganese oxide has garnered significant attention due to its colossal magnetoresistance characteristics. Investigating the effects of the complex magnetic interactions on the magnetism and transport enables a better understanding of magnetic materials. La0.66Sr0.33MnO3 (LSMO) manganese oxides typically exhibiting negative MR as a result of magnetic field-induced spin order, while positive MR typically occurs in systems with spin-orbit coupling (SOC) or P-N junctions. In this work, the magnetic and transport properties of BaTiO3 (BTO)/LSMO heterostructure were studied. By introducing edge dislocation with [001] b→ (burgers vector) in BTO, the c-axis lattice constant is increased, resulting in positive MR in LSMO, which could be modulated by the magnetic field history and the annealing temperature. The nonlinear magnetic order induced by antiferromagnetism at the interface is proposed to cause the positive MR. Finally, the influence of ferroelectric layer on MR could be controlled by the ferroelectric BTO film. The increase in the large lattice constant and the observed variations in MR under magnetic field and annealing temperature provide valuable insights for further studies on the complex oxide.

Engineering Compounds for the Recovery of Critical Elements from Slags: Melt Characteristics of Li5AlO4, LiAlO2, and LiAl5O8.

Engineered artificial minerals (EnAMs) are the core of a new concept of designing scavenger compounds for the recovery of critical elements from slags. It requires a fundamental understanding of solidification from complex oxide melts. Ion diffusivity and viscosity play vital roles in this process. In the melt, phase separations and ion transport give rise to gradients/increments in composition and, with it, to ion diffusivity, temperature, and viscosity. Due to this complexity, solidification phenomena are yet not well understood. If the melt is understood as increments of simple composition on a microscopic level, then the properties of these are more easily accessible from models and experiments. Here, we obtain these data for three stoichiometric lithium aluminum oxides. LiAlO2 is a promising EnAM for the recovery of lithium from lithium-ion battery pyrometallurgical processing. It is obtained through the addition of aluminum to the recycling slag melt. The high temperature properties spanning from below to above the liquidus temperature of three stoichiometric Li-Al-Oxides: Li5AlO4, LiAlO2, and LiAl5O8 are determined using molecular dynamic simulations. The compounds are also synthesized via the sol-gel route. The Li+ ion exhibits the largest diffusivity. They are quite mobile already below the liquidus temperature, i.e., for LiAlO2 at T = 1700 K, the diffusion coefficient of the lithium ion equals D = 3.0 × 10-9 m2 s-1. The other ions Al3+ and O2- do not move considerably at that temperature. The diffusivity of Li+ is largest in the lithium-rich compound Li5AlO4 with D = 32 × 10-9 m2 s-1 at 2500 K. The lower the viscosity, the higher the lithium content. The Li5AlO4 exhibits a viscosity of η = 2.2 mPa s at 1328 K which matches well with the experimentally determined 2.5 mPa s at this temperature. The viscosity of LiAlO2 at 1800 K is more than two times higher. These data sets can help to describe the melts on a microscopic level and understand how the melt properties will change due to gradients in the Li/Al concentration.

Fluorite-pyrochlore-weberite phase transitions in a series of 20-component ultrahigh-entropy compositionally complex ceramics

A new series of 20-component fluorite-based compositionally complex oxides (20CCFBOxNb/Ta) with the general chemical formula (15RE1/15)2x+1(Ce1/3Zr1/3Hf1/3)3–3x(Nb1/2Ta1/2)xO8-δ (0 ≤ x ≤ 1, where 15RE1/15 = La1/15Pr1/15Nd1/15Sm1/15Eu1/15Gd1/15Tb1/15Dy1/15Y1/15Ho1/15Er1/15Tm1/15Yb1/15Lu1/15Sc1/15) are synthesized. Despite that the Gibbs phase rule allows for the existence of up to 20 phases at the thermodynamic equilibrium, 17 of the 20CCFBOxNb/Ta compositions synthesized in this study all possess single ultrahigh-entropy phases in fluorite, pyrochlore, or weberite structure, as shown by X-ray diffraction (XRD). Only < 1 vol% of secondary phases are observed in two compositions near the phase-transition points. With changing compositional variable x, this series of 20CCFBOxNb/Ta undergoes an abrupt fluorite-pyrochlore transition at x = ∼0.27 and an abrupt pyrochlore-weberite transition at x = ∼0.87. Careful characterization reveals abrupt changes of order parameters at both phase transitions. In addition, weberite short-range ordering can persist into the long-range pyrochlore phase, which leads to the lowest thermal conductivities.

Phase Equilibria, Crystal Structures, and Oxygen Nonstoichiometry of Complex Oxides Formed in the GdCoO3–SrCoO3–δ–SrFeO3–δ–GdFeO3 System

Phase Equilibria, Crystal Structures, and Oxygen Nonstoichiometry of Complex Oxides Formed in the GdCoO3–SrCoO3–δ–SrFeO3–δ–GdFeO3 System

Entropy-driven expansion of the thermodynamic stability of compositionally complex spinel oxides

High-entropy ceramics have sparked renewed interest in compositionally complex ceramics since the first introduction in 2015. The kaleidoscopic array of compositions and structures harnessed by this idea has unlocked an unprecedented opportunity to tailor materials for specific applications, including catalysis, thermal barriers, and electrochemical energy storage. Within the family of oxides, a competition exists between rock-salt and spinel structures. The rock-salt structure is highly symmetrical, consisting of a single cation sublattice, while the spinel structure offers more flexibility to accommodate various cations in two distinct sublattices. Herein, we aimed at stabilizing and expanding the thermal stability range of the spinel-structured oxide, successfully synthesizing novel, single-phase, compositionally complex materials by capitalizing on entropy stabilization, all while avoiding the ubiquitous use of nickel and chrome, notorious for their negative environmental impact. The right combination of cations resulted in the synthesis of a seven-metal oxide that is thermally stable up to the remarkable temperature of 1473 K.

Electronic Structure of Metallophlorins: Lessons from Iridium and Gold Phlorin Derivatives.

Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of 5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin. Theory and experiments concur that the phlorin derivatives exhibit substantially smaller HOMO-LUMO gaps, as reflected in a variety of observable properties. Thus, the experimentally studied Ir and Au complexes absorb strongly in the near-infrared (NIR), with absorption maxima at 806 and 770 nm, respectively. The two complexes are also weakly phosphorescent with emission maxima at 950 and 967 nm, respectively. They were also found to photosensitize singlet oxygen formation, with quantum yields of 40 and 28%, respectively. The near-infrared (NIR) absorption and emission are consonants with smaller electrochemical HOMO-LUMO gaps of ∼1.6 V, compared to values of ∼2.1 V, for electronically innocent porphyrins and corroles. Interestingly, both the first oxidation and reduction potentials of the Ir complex are some 600 mV shifted to more negative potentials relative to those of the Au complex, indicating an exceptionally electron-rich macrocycle in the case of the Ir complex.

Local Ordering, Distortion, and Redox Activity in (La0.75Sr0.25)(Mn0.25Fe0.25Co0.25Al0.25)O3 Investigated by a Computational Workflow for Compositionally Complex Perovskite Oxides.

Mixing multiple cations can result in a significant configurational entropy, offer a new compositional space with vast tunability, and introduce new computational challenges. For applications such as the two-step solar thermochemical hydrogen (STCH) generation techniques, we demonstrate that using density functional theory (DFT) combined with Metropolis Monte Carlo method (DFT-MC) can efficiently sample the possible cation configurations in compositionally complex perovskite oxide (CCPO) materials, with (La0.75Sr0.25)(Mn0.25Fe0.25Co0.25Al0.25)O3 as an example. In the presence of oxygen vacancies (VO), DFT-MC simulations reveal a significant increase of the local site preference of the cations (short-range ordering), compared to a more random mixing without VO. Co is found to be the redox-active element and the VO is the preferentially generated next to Co due to the stretched Co-O bonds. A clear definition of the vacancy formation energy (Evf) is proposed for CCPO in an ensemble of structures evolved in parallel from independent DFT-MC paths. By combining the distribution of Evf with VO interactions into a statistical model, the oxygen nonstoichiometry (δ), under the STCH thermal reduction and oxidation conditions, is predicted and compared with the experiments. Similar to the experiments, the predicted δ can be used to extract the enthalpy and entropy of reduction using the van't Hoff method, providing direct comparisons with the experimental results. This procedure provides a full predictive workflow for using DFT-MC to obtain possible local ordering or fully random structures, understand the redox activity of each element, and predict the thermodynamic properties of CCPOs, for computational screening and design of these CCPO materials at STCH conditions.

Ultra-high performance concrete with metal mine tailings and its properties: a review

Abstract Metal mine tailings (MMT) are a kind of industrial solid waste, with an increasing accumulation year by year, which has seriously damaged the ecological environment. Incorporating MMT in ultra-high performance concrete (UHPC) is an effective means to achieve green sustainable development, which can not only make wastes be resources and prevent pollution but also save raw material costs and reduce energy consumption. However, metal mine tailings contain complex and diverse metal oxides and other chemical substance and even contain certain radioactive elements and heavy metal ions. These factors can affect the corrosion resistance of UHPC, accelerate its aging and damage, and in addition may have serious impacts on the environment and human health. This paper summarizes the material properties of MMT and its application in UHPC; analyzes the effects of MMT as powder or fine aggregate on the workability, mechanical properties, durability, and leaching toxicity of UHPC; and elaborates the hydration products, interfacial transition zone, and pore structure of UHPC incorporating MMT (MMT-UHPC). Based on previous research results, the relationship between flowability, flexural strength, porosity, and compressive strength of MMT-UHPC is established.

Modeling from the first principles of the electronic properties of compositions of REE as precursors of high-temperature superconductors

Modeling of the first principles of the electronic properties of complex oxides of rare earth elements (BaY2O4, BaGd2O4, BaLu2O4) as precursors of high-temperature superconductors has been performed. The VASP software package was used as a modeling environment, in particular the method of coupled plane waves (PAW method), which allows us to obtain fairly accurate results for calculating the electron density and band structure. From the analysis of the obtained band energy structure, it follows that the studied REE oxides have a band gap width Eg = 3.29–3.84 eV, which is characteristic for dielectric materials. The studied compounds based on these rare earth elements selected from the yttrium (Y, La, Gd–Lu) and cerium (Ce–Eu) groups are characterized by an increase in Fermi energy and a decrease in the band gap as the atomic number (39, 64, 71) of the element in the periodic table increases. A method for modeling the quantum layers of the studied materials by simulating the restriction of the crystal structure along one of the coordinate axes is proposed. This representation approximates the model of the crystal lattice of REE oxides to the situation of analyzing a quantum layer whose thickness is equal to the size of the crystal cell along the specified axis. The rupture of atomic bonds in a crystal is simulated by increasing the distance between atomic layers along this axis to values at which the value of free energy is stabilized. In the quantum layer of rare earth element oxide (with its thickness close to 1 nm), a wider range of energy values is formed in which electrons are distributed than is observed in the continuous version, and the expansion of the electron distribution area extends to the energy levels of the band gap. This is explained by the fact that the geometric discretization of nanoscale structures determines the discreteness of the quantum-dimensional energy spectrum.

Novel 2DEG System at the HfO2/STO Interface.

Multifunctional integration in a single device has always been a hot research topic, especially for contradictory phenomena, one of which is the coexistence of ferroelectricity and metallicity. The complex oxide heterostructures, as symmetric breaking systems, provide a great possibility to incorporate different properties. Moreover, finding a series of oxide heterostructures to achieve this goal remains as a challenge. Here, taking the advantage of different physical phenomena, we use H2 plasma to pretreat the SrTiO3 (STO) substrate and then fabricate HfO2/STO heterostructures with it. The novel, well-repeatable metallic two-dimensional electron gas (2DEG) is directly obtained at the heterointerfaces without any further complex procedures, while the obvious ferroelectric-like behavior and Rashba spin-orbit coupling are also observed. The understanding of the mechanism, as well as the modified facile preparation procedure, would be meaningful for further development of ferroelectric metal in complex oxide heterostructures.

Transport properties of highly dense proton-conducting BaSn1−xInxO3−δ ceramics

Doped barium stannate belongs to the perovskite-structured complex oxides with proton transport capability. Such objects are of high interest in terms of their application in various protonic ceramic electrochemical cells. In the present work, In-doped barium stannate (BaSn1−xInxO3−δ, 0 ≤ x ≤ 0.4) materials were prepared and thoroughly characterized by structural, microstructural, and electrochemical techniques. The single-phase and high-dense ceramic materials were prepared by the conventional solid-state synthesis route over the entire doping range investigated. The chemical composition of these materials was found to be in close agreement with the nominal values, indicating no evaporation of Ba-, Sn-, or In-containing phases during sintering. The high-temperature electrochemical analysis showed that the ionic conductivity of BaSn1−xInxO3−δ gradually increases with increasing the In-content without reaching a concentration maximum, even for high dopant concentrations. The relatively high activation energy values indicate that this ionic conductivity is determined by oxygen-ionic transport, which, however, becomes predominantly protonic at reduced temperatures. The determination of bulk and grain boundary transport showed that both were improved with the In-doping. The possible reasons for these observations were discussed in detail in this work. Therefore, the obtained data are important for discovering the transport properties of stannates and their potential applications.

Distinct differences in surface transport between electrolyte-gated (110) and (001) SrTiO3

Electrolyte gating technology has been widely used as an effective tool to study novel physics at complex oxide surfaces and interfaces. Certain emergent phenomena reported in electro-gated SrTiO3 (STO) surfaces are particularly interesting. Here, we report on the disparate electron transport behaviors of electrolyte-gated STO (001) and (110) oriented surfaces. In contrast to the anomalous transport from an insulating state to a Kondo-like state and then metallic states on the (001) surface, with increasing carrier density, the (110) surface always behaves as an insulating state. A comparison study suggests that the oxygen vacancies and localized Ti3+ ions on the (001) surface are scatter carriers, but no such defects are found on the (110) surface. This suggests that these surfaces are intrinsically insulating, and the observed anomalous effects are likely induced by the Ti3+ ions and oxygen vacancies introduced during electrolyte gating. This work sheds light on complicated phenomena in electrolyte-gated STO-based systems.

Ultrafast Optically Induced Perturbation of Oxygen Octahedral Rotations in Multiferroic BiFeO3 Thin Films.

The functional properties of complex oxides, including magnetism and ferroelectricity, are closely linked to subtle structural distortions. Ultrafast optical excitations provide the means to manipulate structural features and ultimately to affect the functional properties of complex oxides with picosecond-scale precision. We report that the lattice expansion of multiferroic BiFeO3 following above-bandgap optical excitation leads to distortion of the oxygen octahedral rotation (OOR) pattern. The continuous coupling between OOR and strain was probed using time-resolved X-ray free-electron laser diffraction with femtosecond time resolution. Density functional theory calculations predict a relationship between the OOR and the elastic strain consistent with the experiment, demonstrating a route to employing this approach in a wider range of systems. Ultrafast control of the functional properties of BiFeO3 thin films is enabled by this approach because the OOR phenomena are related to ferroelectricity, and via the Fe-O-Fe bond angles, the superexchange interaction between Fe atoms.

Effect of Impact Force on the Impact-Sliding Wear of Titanium Alloy Drill Pipes against Steel Casings

Titanium alloys have been widely used for drill pipes in complex structural wells and ultra-deep wells because they can provide great benefits in cost and operation in drilling systems due to their excellent properties such as high strength, low density, exceptional corrosion resistance and inherent flexibility. However, their wear behaviors during drilling have not been well understood by the communities. In this work, the effect of the impact force on the wear performance of titanium alloy drill pipes against steel casings was investigated through using a modified wet impact-sliding pin-on-disk test system, in which ZSA-3 titanium alloy was used for the pins and J55 steel was for the disks. The tests were conducted under simulated drilling mud conditions. As the impact force increases, the coefficient of friction tends to become stable and fluctuates slightly, and thus the wear rate of the tribo-pairs decreases gradually. The wear mechanism of J55 steel disks presents a transition from plastic deformation to plastic deformation accompanied by adhesive wear, while that of the titanium alloy pins changes from the plowing effect with adhesive wear to plastic deformation and adhesive wear. In addition, complex oxides will be formed on the surfaces of the tribo-pairs due to the oxidation of Ti and Fe during the wear process. The present results could provide as a fundamental guide for the drilling engineers in related industries for reducing casing wear in the drilling environment.

Magnetic Interactions with Strain Gradient in Ultrathin Pr0.67Sr0.33MnO3 Films

Strain gradient is a normal phenomenon around a heterostructural interface in ultrathin film, and it is important to determine its effect on magnetic interactions to understand interfacial coupling. In this work, ultrathin Pr0.67Sr0.33MnO3 (PSMO) films on different substrates are studied. For PSMO film under different in-plane strain conditions, the saturated magnetization and Curie temperature can be qualitatively explained by double-exchange interaction and the Jahn–Teller distortion. However, the difference in the saturated magnetization with zero field cooling and 5 T field cooling is proportional to the strain gradient. Strain-gradient-induced structural disorder is proposed to enhance phonon–electron antiferromagnetic interactions and the corresponding antiferromagnetic-to-ferromagnetic phase transition via a strong magnetic field during the field cooling process. A non-monotonous structural transition of the MnO6 octahedral rotation can enlarge the strain gradient in PSMO film on a SrTiO3 substrate. This work demonstrates the existence of the flexomagnetic effect in ultrathin manganite film, which should be applicable to other complex oxide systems.

Patterning and epitaxy of large-area arrays of nanoscale complex oxide epitaxial heterostructures

A combination of block copolymer (BCP) lithography and solid-phase epitaxy can be employed to form large areas, on the order of square centimeters, of a high density of epitaxial crystalline complex oxide nanostructures. We have used BCP lithography with a poly(styrene-block-methyl methacrylate) (PS-b-PMMA) copolymer to template a nanohole array either directly on an (001)-oriented SrTiO3 (STO) single crystal substrate or on a 20 nm-thick Si3N4 layer deposited on the STO substrate. BCPs with the selected compositions assembled in a cylindrical phase with 16 nm diameter PMMA cylinders and a cylinder-to-cylinder spacing of 32 nm. The substrate was modified with an energetically non-preferential polymer layer to allow for the vertical alignment of the cylinders. The PMMA cylinders were removed using a subtractive process, leaving an array of cylindrical holes. For BCPs assembled on Si3N4/STO, the pattern was transferred to the Si3N4 layer using reactive ion etching, exposing the underlying STO substrate in the nanoholes. An amorphous LaAlO3 (LAO) layer was deposited on the patterned Si3N4/STO at room temperature. The amorphous LAO epitaxially crystallized within the nanoscale-patterned holes with fully relaxed lattice parameters through solid phase epitaxy, resulting in the formation of nanoscale LAO/STO epitaxial heterostructures.

Electrochemical charge storage performance of (Mn, Ni, Mo, Co, Fe)3O4 high entropy oxide nanoparticles produced via thermal plasma route

Highly complex high entropy metal oxides (HEOs) have several unique characteristics, such as more active sites and material stability that improve the electrochemical charge storage capacity. In this study, HEOs (Mn, Ni, Mo, Co, Fe)3O4 nanoparticles were synthesized using a thermal plasma route and its electrochemical energy storage performance was studied with two distinct electrolytes such as 1 M KOH and NaOH. The X-ray diffraction analysis revealed the phase pure spinel structured HEOs with crystalline size ranging from 13 to 29 nm. Scanning electron microscopy and electron dispersive X-ray spectroscopy results revealed the quasi-spherical morphology and uniform distribution of constitutional cations in the as-synthesized HEOs. The X-ray photoelectron spectroscopy results identified the oxidation states of cations in spinel HEOs. The charge/discharge studies of as-synthesized HEOs showed a specific capacitance of 215 F g-1 /26.9 mAh g-1 at a current density of 2 A g-1 in 1 M KOH electrolyte which is 156 % greater than 1 M NaOH electrolyte. Furthermore, a high capacitance retention of 91 % was achieved after completing 3000 cycles at 10 A g-1 current density which indicates that the HEOs have excellent charge/discharge reversibility. Electrochemical impedance spectroscopy revealed that the solution and charge transfer resistances of HEOs electrodes were 1.04 and 3.2 Ω, respectively. This novel synthesis strategy attempts to overcome the difficulties experienced by established methods for bulk manufacture of phase pure HEOs since thermal plasma method is a rapid and a single-step approach for the bulk production of nanomaterial.