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"Feste"
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Manufacture of optical ceramics based on two solid solutions of the AgBr - (TlBr0.46I0.54) system
2020
This work is devoted to the synthesis and the optical properties study of a new multicomponent heterophase ceramic based on two solid solutions of the AgBr - (TlBr0.46I0.54) system. Ceramics are transparent in the infrared range from 1.0 to 40.0 ÷ 50.0 μm, non-hygroscopic, are photo- and radiation-resistant, flexible, as a result of which various optical products are made from it by hot embossing.
Journal Article
Carbothermal shock synthesis of high-entropy-alloy nanoparticles
by
Rehwoldt, Miles
,
Hu, Liangbing
,
Yu, Daiwei
in
Alloying elements
,
Ammonia
,
Atmospheric chemistry
2018
Nanoparticles are useful in a wide range of applications such as catalysis, imaging, and energy storage. Yao et al. developed a method for making nanoparticles with up to eight different elements (see the Perspective by Skrabalak). The method relies on shocking metal salt-covered carbon nanofibers, followed by rapid quenching. The “carbothermal shock synthesis” can be tuned to select for nanoparticle size as well. The authors successfully created PtPdRhRuCe nanoparticles to catalyze ammonia oxidation. Science , this issue p. 1489 ; see also p. 1467 Shocking metal salts dispersed on carbon nanofibers produces nanoparticles composed of up to eight metals. The controllable incorporation of multiple immiscible elements into a single nanoparticle merits untold scientific and technological potential, yet remains a challenge using conventional synthetic techniques. We present a general route for alloying up to eight dissimilar elements into single-phase solid-solution nanoparticles, referred to as high-entropy-alloy nanoparticles (HEA-NPs), by thermally shocking precursor metal salt mixtures loaded onto carbon supports [temperature ~2000 kelvin (K), 55-millisecond duration, rate of ~10 5 K per second]. We synthesized a wide range of multicomponent nanoparticles with a desired chemistry (composition), size, and phase (solid solution, phase-separated) by controlling the carbothermal shock (CTS) parameters (substrate, temperature, shock duration, and heating/cooling rate). To prove utility, we synthesized quinary HEA-NPs as ammonia oxidation catalysts with ~100% conversion and >99% nitrogen oxide selectivity over prolonged operations.
Journal Article
Origin and hysteresis of lithium compositional spatiodynamics within battery primary particles
2016
The kinetics and uniformity of ion insertion reactions at the solid-liquid interface govern the rate capability and lifetime, respectively, of electrochemical devices such as Li-ion batteries. Using an operando x-ray microscopy platform that maps the dynamics of the Li composition and insertion rate in LixFePO₄, we found that nanoscale spatial variations in rate and in composition control the lithiation pathway at the subparticle length scale. Specifically, spatial variations in the insertion rate constant lead to the formation of nonuniform domains, and the composition dependence of the rate constant amplifies nonuniformities during delithiation but suppresses them during lithiation, and moreover stabilizes the solid solution during lithiation. This coupling of lithium composition and surface reaction rates controls the kinetics and uniformity during electrochemical ion insertion.
Journal Article
A molecular perovskite solid solution with piezoelectricity stronger than lead zirconate titanate
2019
Piezoelectric materials produce electricity when strained, making them ideal for different types of sensing applications. The most effective piezoelectric materials are ceramic solid solutions in which the piezoelectric effect is optimized at what are termed morphotropic phase boundaries (MPBs). Ceramics are not ideal for a variety of applications owing to some of their mechanical properties. We synthesized piezoelectric materials from a molecular perovskite (TMFM)ₓ(TMCM)1–x
CdCl₃ solid solution (TMFM, trimethylfluoromethyl ammonium; TMCM, trimethylchloromethyl ammonium, 0 ≤ x ≤ 1), in which the MPB exists between monoclinic and hexagonal phases. We found a composition for which the piezoelectric coefficient d
33 is ∼1540 picocoulombs per newton, comparable to high-performance piezoelectric ceramics. The material has potential applications for wearable piezoelectric devices.
Journal Article
Processing and Properties of High-Entropy Ultra-High Temperature Carbides
2018
Bulk equiatomic (Hf-Ta-Zr-Ti)C and (Hf-Ta-Zr-Nb)C high entropy Ultra-High Temperature Ceramic (UHTC) carbide compositions were fabricated by ball milling and Spark Plasma Sintering (SPS). It was found that the lattice parameter mismatch of the component monocarbides is a key factor for predicting single phase solid solution formation. The processing route was further optimised for the (Hf-Ta-Zr-Nb)C composition to produce a high purity, single phase, homogeneous, bulk high entropy material (99% density); revealing a vast new compositional space for the exploration of new UHTCs. One sample was observed to chemically decompose; indicating the presence of a miscibility gap. While this suggests the system is not thermodynamically stable to room temperature, it does reveal further potential for the development of new
in situ
formed UHTC nanocomposites. The optimised material was subjected to nanoindentation testing and directly compared to the constituent mono/binary carbides, revealing a significantly enhanced hardness (36.1 ± 1.6 GPa,) compared to the hardest monocarbide (HfC, 31.5 ± 1.3 GPa) and the binary (Hf-Ta)C (32.9 ± 1.8 GPa).
Journal Article
Entropic evidence for a Pomeranchuk effect in magic-angle graphene
by
Rozen, Asaf
,
Park, Jeong Min
,
Zondiner, Uri
in
136/117
,
639/766/119/2792/4128
,
639/766/119/995
2021
In the 1950s, Pomeranchuk
1
predicted that, counterintuitively, liquid
3
He may solidify on heating. This effect arises owing to high excess nuclear spin entropy in the solid phase, where the atoms are spatially localized. Here we find that an analogous effect occurs in magic-angle twisted bilayer graphene
2
–
6
. Using both local and global electronic entropy measurements, we show that near a filling of one electron per moiré unit cell, there is a marked increase in the electronic entropy to about 1
k
B
per unit cell (
k
B
is the Boltzmann constant). This large excess entropy is quenched by an in-plane magnetic field, pointing to its magnetic origin. A sharp drop in the compressibility as a function of the electron density, associated with a reset of the Fermi level back to the vicinity of the Dirac point, marks a clear boundary between two phases. We map this jump as a function of electron density, temperature and magnetic field. This reveals a phase diagram that is consistent with a Pomeranchuk-like temperature- and field-driven transition from a low-entropy electronic liquid to a high-entropy correlated state with nearly free magnetic moments. The correlated state features an unusual combination of seemingly contradictory properties, some associated with itinerant electrons—such as the absence of a thermodynamic gap, metallicity and a Dirac-like compressibility—and others associated with localized moments, such as a large entropy and its disappearance under a magnetic field. Moreover, the energy scales characterizing these two sets of properties are very different: whereas the compressibility jump has an onset at a temperature of about 30 kelvin, the bandwidth of magnetic excitations is about 3 kelvin or smaller. The hybrid nature of the present correlated state and the large separation of energy scales have implications for the thermodynamic and transport properties of the correlated states in twisted bilayer graphene.
Magic-angle graphene is found to have an exotic phase transition where, on heating, entropy is transferred from motional to magnetic degrees of freedom, analogously to the Pomeranchuk effect in
3
He.
Journal Article
Short-range order and its impact on the CrCoNi medium-entropy alloy
by
Zhao, Shiteng
,
Ritchie, Robert O.
,
Ding, Jun
in
639/301/1023/1026
,
639/301/930/328/2082
,
Alloy systems
2020
Traditional metallic alloys are mixtures of elements in which the atoms of minority species tend to be distributed randomly if they are below their solubility limit, or to form secondary phases if they are above it. The concept of multiple-principal-element alloys has recently expanded this view, as these materials are single-phase solid solutions of generally equiatomic mixtures of metallic elements. This group of materials has received much interest owing to their enhanced mechanical properties
1
–
5
. They are usually called medium-entropy alloys in ternary systems and high-entropy alloys in quaternary or quinary systems, alluding to their high degree of configurational entropy. However, the question has remained as to how random these solid solutions actually are, with the influence of short-range order being suggested in computational simulations but not seen experimentally
6
,
7
. Here we report the observation, using energy-filtered transmission electron microscopy, of structural features attributable to short-range order in the CrCoNi medium-entropy alloy. Increasing amounts of such order give rise to both higher stacking-fault energy and hardness. These findings suggest that the degree of local ordering at the nanometre scale can be tailored through thermomechanical processing, providing a new avenue for tuning the mechanical properties of medium- and high-entropy alloys.
Metal alloys consisting of three or more major elemental components show enhanced mechanical properties, which are now shown to be correlated with short-range order observed with electron microscopy.
Journal Article
Double transition-metal MXenes: Atomistic design of two-dimensional carbides and nitrides
by
Anasori, Babak
,
Wyatt, Brian C.
,
Nemani, Srinivasa Kartik
in
Applied and Technical Physics
,
Carbon nitride
,
Characterization and Evaluation of Materials
2020
MXenes are a large family of two-dimensional (2D) transition-metal carbides, nitrides, and carbonitrides. The MXene family has expanded since their original discovery in 2011, and has grown larger with the discovery of ordered double transition-metal (DTM) MXenes. These DTM MXenes differ from their counterpart mono-transition-metal (mono-M) MXenes, where two transition metals can occupy the metal sites. Ordered DTM MXenes are comprised of transition metals in either an in-plane or out-of-plane ordered structure. Additionally, some DTM MXenes are in the form of random solid solutions, which are defined by two randomly distributed transition metals throughout the 2D structure. Their different structures and array of transition-metal pairs provide the ability to tune DTM MXenes for specific optical, magnetic, electrochemical, thermoelectric, catalytic, or mechanical behavior. This degree of control over their composition and structure is unique in the field of 2D materials and offers a new avenue for application-driven design of functional nanomaterials. In this article, we review the synthesis, structure, and properties of DTM MXenes and provide an outlook for future research in this field.
Journal Article
Cation-disordered rocksalt-type high-entropy cathodes for Li-ion batteries
2021
High-entropy (HE) ceramics, by analogy with HE metallic alloys, are an emerging class of solid solutions composed of a large number of species. These materials offer the benefit of large compositional flexibility and can be used in a wide variety of applications, including thermoelectrics, catalysts, superionic conductors and battery electrodes. We show here that the HE concept can lead to very substantial improvements in performance in battery cathodes. Among lithium-ion cathodes, cation-disordered rocksalt (DRX)-type materials are an ideal platform within which to design HE materials because of their demonstrated chemical flexibility. By comparing a group of DRX cathodes containing two, four or six transition metal (TM) species, we show that short-range order systematically decreases, whereas energy density and rate capability systematically increase, as more TM cation species are mixed together, despite the total metal content remaining fixed. A DRX cathode with six TM species achieves 307 mAh g
−1
(955 Wh kg
−1
) at a low rate (20 mA g
−1
), and retains more than 170 mAh g
−1
when cycling at a high rate of 2,000 mA g
−1
. To facilitate further design in this HE DRX space, we also present a compatibility analysis of 23 different TM ions, and successfully synthesize a phase-pure HE DRX compound containing 12 TM species as a proof of concept.
High-entropy ceramics are solid solutions offering compositional flexibility and wide variety of applicability. High-entropy concepts are shown to lead to substantial performance improvement in cation-disordered rocksalt-type cathodes for Li-ion batteries.
Journal Article
A fracture-resistant high-entropy alloy for cryogenic applications
by
Hohenwarter, Anton
,
Ritchie, Robert O.
,
Gludovatz, Bernd
in
Alloying elements
,
Alloys
,
Aluminum
2014
High-entropy alloys are equiatomic, multi-element systems that can crystallize as a single phase, despite containing multiple elements with different crystal structures. A rationale for this is that the configurational entropy contribution to the total free energy in alloys with five or more major elements may stabilize the solid-solution state relative to multiphase microstructures.We examined a five-element high-entropy alloy, CrMnFeCoNi, which forms a single-phase face-centered cubic solid solution, and found it to have exceptional damage tolerance with tensile strengths above 1 GPa and fracture toughness values exceeding 200 MPa·m1/2. Furthermore, its mechanical properties actually improve at cryogenic temperatures; we attribute this to a transition from planar-slip dislocation activity at room temperature to deformation by mechanical nanotwinning with decreasing temperature, which results in continuous steady strain hardening.
Journal Article