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At least 631 records · Page 35

Stabilized copper selenide thermoelectric materials and methods of fabrication thereof

A thermoelectric composition is provided that includes a nanocomposite comprising a copper selenide (Cu 2 Se) matrix having a plurality of nanoinclusions comprising copper metal selenide (CuMSe 2 ) distributed therein. M may be selected from the group consisting of: indium (In), aluminum (Al), gallium (Ga), antimony (Sb), bismuth (Bi), and combinations thereof. The thermoelectric composition has an average figure of merit (ZT) of greater than or equal to about 1.5 at a temperature of less than or equal to about 850K (about 577° C.). Methods of making such a thermoelectric nanocomposite material by a sequential solid-state transformation of a CuSe2 precursor are also provided.

Poudeu-Poudeu, Pierre Ferdinand↗

Metal-ceramic composite powders

A process for manufacturing metal-ceramic composite material powder comprising ball milling metal powder and ceramic nanoparticles to yield a metal-ceramic composite powder comprising ceramic nanoparticles embedded in a metal matrix powder particles; wherein the ball milling is performed using a ceramic milling media and a milling vessel having a ceramic interior surface. Metal matrix nanocomposite powders comprising ceramic nanoparticles imbedded in metal matrix powder particles; wherein the metal matrix powder particles have a spherical shape; wherein there is uniform distribution the ceramic nanoparticles; wherein the nanocomposite powders have good flowability.

Chen, Lianyi↗

Axial flux motor

Provided is an axial flux motor including a rotor having a wound ribbon core, the wound ribbon core including a metal amorphous nanocomposite material. The axial flux motor further includes a stator assembly spaced apart from the rotor along a rotation axis of the rotor. The stator assembly includes a body including a metal amorphous nanocomposite material and a plurality of permanent magnets substantially free of rare-earth materials. The plurality of permanent magnets is arranged on the body of the stator assembly.

Simizu, Satoru↗

“Flower-like” LI 4 TI 5 O 12 -multiwalled carbon nanotube composite structures with performance as highrate anode-materials for Li-ion battery applications and methods of synthesis thereof

A method of fabricating nanocomposite anode material embodying a lithium titanate (LTO)-multi-walled carbon nanotube (MWNT) composite intended for use in a lithium-ion battery includes providing multi-walled carbon nanotube (MWNTs), including nanotube surfaces, onto which functional oxygenated carboxylic acid moieties are arranged, generating 3D flower-like, lithium titanate (LTO) microspheres, including thin nanosheets and anchoring the acid-functionalized MWNTs onto surfaces of the 3D LTO microspheres by π-π interaction strategy to realize the nanocomposite anode material.

Wong, Stanislaus S.↗

Morphology Control of Self-Assembled Three-Phase Au-BaTiO 3 –ZnO Hybrid Metamaterial for Tunable Optical Properties

Microstructural control in metal-dielectric hybrid metamaterials presents enormous opportunities in tailoring the physical properties including the magnetic and optical properties. In this paper, we demonstrate a strong tunability achieved in the microstructure of self-assembled ordered three-phase Au-BaTiO 3 –ZnO hybrid metamaterial along with its optical properties, grown by a pulsed laser deposition method. Varying the growth temperature, deposition frequency, and template thickness evolves the microstructure by tuning the Au and ZnO pillar geometry as well as the shape and size of the Au nanoparticles capping the ZnO nanowires. The three-phase hybrid metamaterials exhibit unique optical properties, including enhanced nonlinear optical properties, hyperbolic dispersion in the visible and near-infrared wavelength region, and tuned epsilon-near-zero (ENZ) wavelength upon varying the deposition parameters. This study suggests that the three-phase hybrid metamaterials present great potential in the microstructure and optical property tuning that can also be applied to other two-phase and three-phase nanocomposite systems.

36 MATERIALS SCIENCE↗

High-Resolution Three-Dimensional Sculpting of Two-Dimensional Graphene Oxide by E-Beam Direct Write

On demand switchable additive/subtractive patterning of 2D nanomaterials is an essential capability for developing new concepts of functional nanomaterials and their device realizations. Traditionally, this is performed via a multi-step process using photoresist coating and patterning by conventional photo or electron beam lithography, which is followed by bulk dry/wet etch or deposition. This limits the range of functionalities and structural topologies that can be achieved, as well as increases the complexity, cost, and possibility of contamination which are significant barriers to device fabrication from highly sensitive 2D materials. Focused electron beam induced processing (FEBIP) enables a material chemistry/site-specific, high-resolution multi-mode atomic scale processing and provides unprecedented opportunities for direct-write, single-step surface patterning of 2D nanomaterials with an in-situ imaging capability. It allows for realizing a rapid multi-scale/multi-mode approach, ranging from an atomic scale manipulation (e.g., via targeted defect introduction as an active site) to a large-area surface modification on nano and micro scales, including patterned doping and material removal/deposition with 2D (in-plane)/3D (out-of-plane) control. In this work, we report on a new capability of FEBIP for nanoscale patterning of graphene oxide via removal of oxygenated carbon moieties with no use of reactive gas required for etching complemented by carbon atom deposition using focused electron beam. The mechanism of experimentally observed phenomena is explored using the density functional theory (DFT) calculations, revealing that interactions of e-beam liberated reactive oxygen radicals with carbon atoms on graphene basal plane lead to creation of atomic vacancies in the material. The reaction by-products are volatile carbon di-oxides, which are dissociated and volatilized from the graphene oxide surface functional groups by interactions with an energetic focused electron beam. Along with selective “subtractive” patterning of graphene oxide, the same electron beam with increased irradiation doses can deposit out-of-plane 3D carbon nanostructures on top of or around the 2D etched pattern, thus forming a hybrid 2D/3D nanocomposite with feature control down to a few nanometers. Furthermore, this in-operando dual nanofabrication capability of FEBIP is unmatched by any other nanopatterning techniques and opens a new design window for forming 2D/3D complex nanostructures and functional nanodevices.

36 MATERIALS SCIENCE↗

Oxidation Driven Thin‐Film Solid‐State Metal Dealloying Forming Bicontinuous Nanostructures

Abstract Solid‐state metal dealloying (SSMD) is a promising method for fabricating nanoscale metallic composites and nanoporous metals across a range of materials. Thin‐film SSMD is particularly attractive due to its ability to create fine features via solid‐state interfacial reactions within a thin‐film geometry, which can be integrated into devices for various applications. This work examines a new dealloying couple, namely the Nb–Al alloy with the dealloying agent Sc, as previously predicted in the machine‐learning (ML) models. Prior ML predictions aimed to guide the design of nanoarchitectured materials through dealloying, relying on intuition‐driven discovery within a large parameter space. However, this work reveals that at the nanoscale, the involvement of oxygen in thin film processing may instead drive the dealloying process, resulting in the formation of bicontinuous nanostructures similar to those formed by metal‐agent dealloying. The phase evolution, as well as chemical and morphological changes, are closely analyzed using a combination of X‐ray absorption spectroscopy, diffraction, and scanning transmission electron microscopy to understand the mechanisms behind nanostructure formation. The findings suggest a potential pathway for utilizing oxygen to drive the formation of bicontinuous metal–metal oxide nanocomposites, paving the way for further development of functional nanoporous materials in diverse fields.

36 MATERIALS SCIENCE↗

Burning magnesium in carbon dioxide for highly effective phosphate removal

Magnesium oxide was found to have high-phosphate-affinity as an effective component to enhance the phosphate removal ability of common adsorbent materials. However, the currently prepared MgO-based hybrid adsorbents by conventional methods still suffer from the limited low loading of MgO and inferior removal performances, much far away from practical application. In this study, an ingenious carbon coated MgO nanocomposite is designed by directly burning magnesium in CO 2 , a well-known textbook reaction. X-ray diffraction analysis, scanning electron microscope and aberration-corrected high-resolution transmission electron microscope demonstrate the sample is well prepared. Consequently, the high content of nanosized MgO combined with defect-rich carbon layer brings unprecedented phosphate removal capacity of 1135.0 mg/g, removal rate of 99% and benign compatibility with coexisting anions and solution pH. Furthermore, the removal mechanism is also investigated in detail by characterizing the sample before and after adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Additionally, crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic K syn and ηsyn identifying the most likely elastic constants C 33 and C 13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E 11 =107 GPa and E 33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues.

36 MATERIALS SCIENCE↗

Toward a tunable fabrication of multifunctional iron-aluminum spinels via solution combustion synthesis: The effects of fuel, heating mode, and Fe:Al precursor ratio

The solid solutions of iron and aluminum spinels (hercynite, maghemite, magnetite, and γ-alumina) are promising materials for emerging technologies such as solar thermochemical fuel production and clean dehydrogenation of fossil fuels. Solution combustion synthesis (SCS) is an attractive technique for the fabrication of these materials as it has been used for synthesis of many nanoscale oxides. However, the design space of SCS is large with many synthesis parameters affecting the properties of the combustion products. To optimize the SCS of these materials, it is important to determine which parameters yield the best properties. In the present work, FeAlO x nanocomposites were obtained by SCS using iron nitrate and aluminum nitrate as precursors and oxidizers. Two fuels (citric acid and glycine), three Fe:Al molar ratios (1:2, 1:1, and 2:1) in the precursors, and three heating modes (hotplate, muffle furnace, and microwave oven) were compared. The products were characterized by X-ray diffraction analysis, scanning electron microscopy, Brunauer-Emmett-Teller surface area analysis, and laser diffraction particle size analysis. The fuel used had the largest impact on the combustion behavior and hence the material properties. The high combustion temperature of glycine allowed for the formation of an FeAl 2 O 4 /Fe 3 O 4 solid solution, while the lower-temperature combustion of citric acid yielded Al-substituted γ-Fe 2 O 3 with high amorphous content. With citric acid, the specific surface area as high as 200 m 2 /g was achieved. The effect of Fe:Al precursor ratio was clearly seen in variations of the lattice parameter, which demonstrated the ability to tune the phase composition. The heating mode had minor effects on material properties, but some differences were observed. As a result, all products obtained by SCS in a microwave oven had low specific surface areas compared to those obtained with a hotplate and a muffle furnace.

Alumina↗

Synthesis of bulk reactive Ni–Al composites using high pressure torsion

Self-propagating exothermic reactions, for instance in the nickel-aluminum (Ni-Al) system, have been widely studied to create high performance intermetallic compounds or for in-situ welding. Their easy ignition once the phase spacing is reduced below the micron scale, makes top-down methods like high-energy ball milling, ideal to fabricate such reactive nanostructures. A major drawback of ball milling is the need of a sintering step to form bulk pieces of the reactive material. However, this is not possible, as the targeted reactions would already proceed. Therefore, we investigate the ability of high pressure torsion as an alternative process, capable to produce bulk nanocomposites from powder mixtures. Severe straining of powder mixtures with a composition of 50 wt% Ni and 50 wt% Al enables fabrication of self-reactive bulk samples with microstructures similar to those obtained from ball milling or magnetron sputtering. Additionally, samples deformed at ambient temperature are highly reactive and can be ignited significantly below the Al melting point, finally predominantly consisting of Al 3 Ni 2 and Al 3 Ni, independent of the applied strain. Although the reaction proceeds first at the edge of the disk, the strain gradient present in the disks does not prevent reaction of the whole sample.

36 MATERIALS SCIENCE↗

Core-shell metallic alloy nanopillars-in-dielectric hybrid metamaterials with magneto-plasmonic coupling

Combining plasmonic and magnetic properties, namely magneto-plasmonic coupling, inspires great research interest and the search for magneto-plasmonic nanostructure becomes considerably critical. In this work, we designed a nanopillar-in-matrix structure with core–shell alloyed nanopillars for both BaTiO 3 (BTO)-Au 0.5 Co 0.5 (AuCo) and BTO-Au 0.25 Cu 0.25 Co 0.25 Ni 0.25 (AuCuCoNi) hybrid systems, i.e., ferromagnetic alloy cores (e.g., Co or CoNi) with plasmonic shells (e.g., Au or Au/Cu). These core–shell alloy nanopillars are uniformly embedded into a dielectric BTO matrix to form a vertically aligned nanocomposite (VAN) structure. Both hybrid systems present excellent epitaxial quality and interesting multi-functionality, e.g., high magnetic anisotropy, magneto-optical coupling response, tailorable plasmonic resonance wavelength, tunable hyperbolic properties and strong optical anisotropy. These alloyed nanopillars-in-matrix designs provide enormous potential for complex hybrid material designs with multi-functionality and demonstrate strong interface enabled magneto-plasmonic coupling along with plasmonic and magnetic performance.

36 MATERIALS SCIENCE↗

Topological structure enhanced nanostructure of high temperature polymer exhibiting more than ten times enhancement of dipolar response

Nanofillers in polymer composites will induce interface regions in the polymer with non-uniform nanostructures which can be approximated as multilayer shells surrounding nanofillers. This paper studies topological nanostructures in polymers that interface with one-dimensional (1-D) and zero-dimensional (0-D) nanofillers. This new class of dielectric polymer nanocomposites involves nanofillers at ultra-low volume loading (< 1 vol percent) that generate large dielectric enhancement. The results show that the dipolar response of polyetherimide, a high temperature dielectric polymer, is increased by more than ten times with ultra-low (0.75 vol %) loading of 1-D nanofillers. The results reveal that 1-D nanofillers induce cylindrical shell-topology in the polymer matrix which is more effective in enhancing the high dielectric constant interfacial region than the spherical shell-topology generated by 0-D fillers. Furthermore, the cylindrical shells generated by 1-D fillers provide much higher dielectric enhancement over a broader interfacial region in the polymer matrix, as compared to the spherical shells induced by 0-D nanofillers.

42 ENGINEERING↗

Critical Role of the Interfacial Layer in Associating Polymers with Microphase Separation

Polymers with dynamic (transient) bonds, often called associating polymers, have been attracting significant attention in recent years due to their unique viscoelastic properties, self-healing ability, and recyclability. Nevertheless, understanding the mechanisms and the factors controlling their macroscopic properties remains limited due to the higher complexity introduced by the dynamic bonds. Here in this study, small-angle X-ray scattering (SAXS), broadband dielectric spectroscopy (BDS), and rheology were applied to unravel the structure and dynamics of telechelic associating polymers with different molecular weights. SAXS measurements revealed phase separation of the functional end groups with an average cluster size of ~2–3 nm and the distance between clusters controlled by the chain length. Borrowing the interfacial layer model analysis of BDS data from the polymer nanocomposite field, we demonstrated the presence of an interfacial polymer layer with a thickness of ~0.7–0.9 nm surrounding these clusters. Rheological measurements showed quantitatively that the presence of the interfacial layer significantly alters the viscoelastic behavior of these materials, indicating the crucial role of the interfacial layer in defining the macroscopic mechanical properties of the studied telechelic materials. The presented results emphasize that phase separation of the functional groups in associating polymers leads to very significant changes of the viscoelastic properties, opening a promising avenue in the design of novel functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Using Nanofiller Assemblies to Control the Crystallization Kinetics of High-Density Polyethylene

Polyethylene-grafted nanoparticles (NPs) are organized into a variety of assemblies in a polydisperse polyethylene melt by tailoring the graft density and molecular weights of the graft chains. Under these conditions we systematically vary NP assemble state and study is consequences on crystal nucleation and growth rates. We find that the nucleation rate is suppressed below that of the unfilled polymer for good NP spatial dispersion. However, poorer dispersion, which leads to the formation of NP assemblies, can accelerate nucleation likely by providing multiple heterogenous sites due to topographical features. We find that a key parameter, the chain overcrowding in the brush, can predict these nucleation trends – in this language, the most enhanced nucleation rate is found when the grafts are the most overcrowded, and hence the least interpenetrated with the matrix chains. This result is consistent with one other literature result which utilized short crystallizable polyethylene glycol grafts in short PEO matrices. The growth kinetics were retarded for all nanocomposites, their temperature dependences were essentially equal to that for the pure polymer (in the absence of NPs) – the NPs thus do not affect secondary nucleation, indicating that the transport of the matrix to the growth front is the rate determining step. Thus, evidently the increase in matrix viscosity, or reduction in growth rates, is directly determined by the agglomeration state of the NPs. These results are consistent with past works with bare silica NPs in PEO, and with silica NPs grafted with amorphous chains in a PEO matrix, suggesting that growth kinetics in these systems apparently follow “universal” behavior. Additionally, there are initial hints that the ratio of the effective surface area of the NP clusters per unit matrix volume provides a unified description of the NP induced confinement that slows growth kinetics. Furthermore, our work thus shows that there is an evolving understanding of the role of NPs on crystallization kinetics, in particular crystal growth where trends appear to be independent of the grafts ability to crystallize.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermally Aged Li–Mn–O Cathode with Stabilized Hybrid Cation and Anion Redox

Though low-cost and environmentally friendly, Li–Mn–O cathodes suffer from low energy density. Although synthesized Li 4 Mn 5 O 12 -like overlithiated spinel cathode with reversible hybrid anion- and cation-redox (HACR) activities has a high initial capacity, it degrades rapidly due to oxygen loss and side-reaction-induced electrolyte decomposition. In this study, we develop a two-step heat treatment to promote local decomposition as Li 4 Mn 5 O 12 → 2LiMn 2 O 4 + Li 2 MnO 3 + 1/2 O 2 ↑, which releases near-surface reactive oxygen that is harmful to cycling stability. The produced nanocomposite delivers a high discharge capacity of 225 mAh/g and energy density of over 700 Wh/kg at active-material level at a current density of 100 mA/g between 1.8 to 4.7 V. Benefiting from suppressed oxygen loss and side reactions, 80% capacity retention is achieved after 214 cycles in half cells. With industrially acceptable electrolyte amount (6 g/Ah), full cells paired with Li 4 Ti 5 O 12 anode have a good retention over 100 cycles.

25 ENERGY STORAGE↗

High Thermoelectric Performance in 2D Sb 2 Te 3 and Bi 2 Te 3 Nanoplate Composites Enabled by Energy Carrier Filtering and Low Thermal Conductivity

Thermoelectrics are an important class of materials with great potential in alternative energy applications. In this study, two-dimensional (2D) nanoplates of the layered chalcogenides, Sb 2 Te 3 and Bi 2 Te 3 , are synthesized and composites of the two are investigated for their thermoelectric properties. The two materials, Sb 2 Te 3 and Bi 2 Te 3 , were synthesized as hexagonal, 2D nanoplates via a colloidal polyol route. The as-synthesized Sb 2 Te 3 and Bi 2 Te 3 vary drastically from one another in their lateral and vertical dimensions as revealed by scanning electron microscopy and atomic force microscopy. The single crystalline nanoplate nature is deduced by high-resolution transmission electron microscopy and selected area electron diffraction. Nanoplates have well-defined hexagonal facets as seen in the scanning and transmission electron microscopy images. The nanoplates were consolidated as an anisotropic nanostructured pellet via spark plasma sintering. Preferred orientation observed in the powder X-ray diffraction pattern and scanning electron microscopy images of the fractured pellets confirm the anisotropic structure of the nanoplates. Thermoelectric properties in the parallel and perpendicular directions were measured, revealing strong anisotropy with a significant reduction to thermal conductivity in the perpendicular direction due to increased phonon scattering at nanoplate interfaces. All compositions, except that of the 25% Bi 2 Te 3 nanoplate composite, behave as degenerate semiconductors with increasing electrical resistivity as the temperature increases. The Seebeck coefficient is also increased dramatically in the nanocomposites, the highest reaching 210 μV/K for 15% Bi 2 Te 3 . The increase in Seebeck is attributed to energy carrier filtering at the nanoplate interfaces. Overall, these enhanced thermoelectric properties lead to a drastic increase in the thermoelectric performance in the perpendicular direction, with zT ~ 1.26, for the 15% Bi 2 Te 3 nanoplate composite at 450 K.

36 MATERIALS SCIENCE↗