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At least 235 records · Page 13

Solid-State Welding of the Nanostructured Ferritic Alloy 14YWT Using a Capacitive Discharge Resistance Welding Technique

Joining nanostructured ferritic alloys (NFAs) has proved challenging, as the nano-oxides that provide superior strength, creep resistance, and radiation tolerance at high temperatures tend to agglomerate, redistribute, and coarsen during conventional fusion welding. In this study, capacitive discharge resistance welding (CDRW)—a solid-state variant of resistance welding—was used to join end caps and thin-walled cladding tubes of the NFA 14YWT. The resulting solid-state joints were found to be hermetically sealed and were characterized across the weld region using electron microscopy (macroscopic, microscopic, and nanometer scales) and nanoindentation. Microstructural evolution near the weld line was limited to narrow (~50–200 μm) thermo-mechanically affected zones (TMAZs) and to a reduction in pre-existing component textures. Dispersoid populations (i.e., nano-oxides and larger oxide particles) appeared unchanged by all but the highest energy and power CDRW condition, with this extreme producing only minor nano-oxide coarsening (~2 nm → ~5 nm Ø). Despite a minimal microstructural change, the TMAZs were found to be ~10% softer than the surrounding base material. These findings are considered in terms of past solid-state welding (SSW) efforts—cladding applications and NFA-like materials in particular—and in terms of strengthening mechanisms in NFAs and the potential impacts of localized temperature–strain conditions during SSW.

36 MATERIALS SCIENCE↗

A Scalable Solution Route to Porous Networks of Nanostructured Black Tungsten

This paper studied the feasibility of a new solution-processed method to manufacture black tungsten nanostructures by laser conversion of tungsten hexacarbonyl precursor on the Inconel 625 substrate under argon atmosphere at ambient pressure. The results show that sublimation of the precursor can be prevented if the decomposition temperature (>170 °C) is achieved using the laser heating method. Three different laser powers from 60–400 W were used to investigate the role of laser parameters on the conversion. It was found that lower laser power of 60 W resulted in a mixture of unconverted precursor and converted tungsten. Higher laser powers >200 W resulted in α-W (BCC) in one step without further heat treatment. Different oxygen concentrations from 0.5 ppm to 21 vol% were used in the laser canister to investigate the effect of oxygen concentration on the conversion. It was found that the hard vacuum (>10−4 torr) or hydrogen is not necessary to obtain α-W (BCC). The solar absorptance varied from 63–97%, depending on the amount of precursor deposited on the substrate and oxygen content in the laser canister. This solution-based laser conversion of tungsten precursor is a scalable method to manufacture tungsten coatings for high-temperature applications.

14 SOLAR ENERGY↗

Reactive Oxygen Ion Beam-Induced Deposition for Concurrent Purification of Platinum Nanostructures

Oxygen-focused ion beam induced deposition (O-FIBID) enables the direct-write fabrication of Pt nanostructures while simultaneously enhancing purity concurrently through reactive oxygen–deposit interactions. By systematically varying the dwell time, accelerating voltage, and precursor pressure, the Pt content and conductivity can be controlled. Under optimum conditions, the Pt content reached 63 at.%. Across the dwell-time range used for resistivity measurements, the Pt content increased from 20 to 33 at.%, while the resistivity decreased from 2.9 × 10 4 μΩ·cm to 1.2 × 10 3 μΩ·cm, which is consistent with enhanced percolation through Pt grains and the lower intrinsic resistivity of the purer Pt deposit. The simulation results support a purification mechanism driven by the beam-induced activation of implanted oxygen balanced against the preferential sputtering of Pt. These results demonstrate O-FIBID as a viable method for the nanoscale direct write of conductive Pt without post-processing, and some deviations from conventional FIBID wisdom are observed. These results serve as a foundation for exploring nascent, reactive focused ion beam-induced deposition processes.

deposit purification↗

Nanostructured Material Sensor Processing Using Microfabrication Technology

This presentation discusses the fabrication of microsensors based based on nanomaterials and microfabrication technology. In particular, is it shown that nanostructured materials can be incorporated into standard micro fabrication techniques yielding improved alignment and electrical contact in a microsensor platform. A nano templating technique is also shown which provides sensor structures with unique properties.

chemical sensors nanostructures nanomaterials micr↗

Formation and Consolidation of UN Nanostructures in U-Mo Fuel via Mechanical Alloying and Spark Plasma Sintering

Uranium-molybdenum (U-Mo) alloys show promise as a nuclear fuel system due to their high thermal conductivity and high fuel loading capability. However, U-Mo systems suffer from irradiation induced swelling ultimately affecting the cladding via mechanical and chemical interaction. To address these shortcomings, this thesis investigated the formation of uranium mononitride (UN) nanoparticles within a U-10Mo matrix. To promote the formation of UN, U-10Mo powders were mechanically alloyed under a high purity nitrogen cover gas (99.9995%) atmosphere. Variations were made in stainless steel milling media size, duration of milling, and number of times the milling jar was re-aerated with nitrogen gas. UN nanoparticulates were successfully formed within the U-Mo matrix and was characterized utilizing light element analysis, X-ray diffractometry, scanning and transmission-electron microscopy, electron energy loss spectroscopy, and atom probe tomography. Presence of the UN nanoparticles was found as early as 1-hour into the mechanical alloying process, and significant iron contamination found after 10-hours of milling. The U-Mo/UN powders were compacted using spark plasma sintering techniques in order to stabilize the nanostructure. U-Mo/UN compacts containing small amounts of neodymium and helium were analyzed to observe the defect migration tendencies of fission products within the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

On the Interplay between Size and Disorder in Suppressing Intercalation-Induced Phase Transitions in Pseudocapacitive Nanostructured MoS 2

Pseudocapacitors are an emerging class of energy storage materials that offer an attractive compromise between the energy density of batteries and power density of electric double-layer capacitors. Decreasing particle size and increasing surface area of battery materials is a common approach for introducing pseudocapacitive behavior and increasing power density. However, in many cases, as the crystal size is reduced, lattice disorder of unknown extent is also introduced, making it difficult to characterize the relative contribution of size and disorder to fast-charging performance. Here, in this work, a series of nanostructured MoS 2 materials are synthesized with different crystallite sizes and degrees of crystallinity to decouple the effects of size and disorder on charge/discharge kinetics. The extent and type of disorder in each material is quantified by total X-ray scattering experiments and pair distribution function analyses. Electrochemical characterization, including galvanostatic rate capability, cyclic voltammetry, and various kinetic analyses, are used to demonstrate that both decreasing particle size and introducing lattice disorder are effective strategies for increasing charge storage kinetics, and that the effects are additive. Finally, operando X-ray diffraction measurements show that both size and disorder can be used suppress first-order Li + intercalation-induced phase transitions, a key feature for enabling pseudocapacitive charge storage.

36 MATERIALS SCIENCE↗

Evaporative Assembly: Dual-Scale Nanostructures via Evaporative Assembly (Adv. Mater. Interfaces 7/2020)

In article number 1901954, Sunita Srivastava, Surita R. Bhatia, and co-workers demonstrate that evaporative assembly of functionalized nanoparticles can yield striking dual-scale hierarchical structures. Regular microscale stripes of nanoparticle monolayers with hexagonal nanoscale order are obtained on physically and chemically homogeneous substrates through evaporation of a suspension of DNAfunctionalized nanoparticles with a charged shell. The stripe width, spacing and nanoparticle ordering can be controlled by varying nanoparticle concentration and can be described by a simple analytical model. The results indicate that the interplay between “stick-slip” motion of the droplet contact line and Coulombic and steric nanoparticle interactions control the formation of the observed structures. Finally, this work demonstrates a simple cost-effective mask-free method for fabricating nanostructured 2D materials and metasurfaces for applications ranging from energy conversion/storage to optoelectronics and nanophotonics.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Hierarchical Thiospinel NiCo 2 S 4 /Polyaniline Hybrid Nanostructures as a Bifunctional Electrocatalyst for Highly Efficient and Durable Overall Water Splitting

The development of a nonprecious, stable, and highly effective electrocatalyst for decomposition of water into oxygen and hydrogen is vitally important for sustainable energy conversion, but it still remains challenging to replace the noble metal electrocatalysts with more economically viable alternatives. Here, in this paper, a polyaniline (PANI) decorated hierarchical nickel cobalt thiospinel (NiCo 2 S 4 ) hybrid catalyst (NCS-P) has been developed that shows enhanced dual catalytic activity for both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER) compared to pristine NiCo 2 S 4 (NCS). Benefiting from the conductive PANI coating, the hierarchical NCS-P nanostructure exhibits outstanding electrocatalytic activity in alkaline solution with low overpotentials of 273 ± 3 and 77 ± 4 mV at 10 mA cm -2 and low Tafel slopes of 42.2 and 68.5 mV dec -1 for OER and HER, respectively, which are better than those of the benchmark noble-metal-based RuO 2 and Pt/C.

36 MATERIALS SCIENCE↗

Auxetic Two‐Dimensional Nanostructures from DNA**

Abstract Architectured materials exhibit negative Poisson's ratios and enhanced mechanical properties compared with regular materials. Their auxetic behaviors emerge from periodic cellular structures regardless of the materials used. The majority of such metamaterials are constructed by top‐down approaches and macroscopic with unit cells of microns or larger. There are also molecular auxetics including natural crystals which are not designable. There is a gap from few nanometers to microns, which may be filled by biomolecular self‐assembly. Herein, we demonstrate two‐dimensional auxetic nanostructures using DNA origami. Structural reconfigurations are performed by two‐step DNA reactions and complemented by mechanical deformation studies using molecular dynamics simulations. We find that the auxetic behaviors are mostly defined by geometrical designs, yet the properties of the materials also play an important role. From elasticity theory, we introduce design principles for auxetic DNA metamaterials.

Li, Ruixin↗

Stable Thermotropic 3D and 2D Double Gyroid Nanostructures with Sub-2-nm Feature Size from Scalable Sugar–Polyolefin Conjugates

In this study, ultra-low molecular weight disaccharide–polyolefin conjugates with cellobiose, lactose and maltose head groups and atactic polypropene tails, such as 1, undergo a series of irreversible thermotropic order–order transitions with increasing temperature to provide nanostructured phases in the sequence: lamellar (L), hexagonal perforated lamellar (HPL), double gyroid (DG) and hexagonal cylindrical (C). The DG phase displays exceptional stability at ambient temperature and features two interpenetrating sugar domain networks having a sub-2-nm strut width and a lattice parameter, a DG , of 13.1 nm. The unique stability of this DG phase extends further within ultrathin films all the way down to the two-dimensional limit of 15 nm in which film thickness, l, is now less than the surface-oriented unit cell height, h DG . In addition to raising the fundamental question of what minimally constitutes a Schoen triply periodic minimal surface and DG lattice, these results serve to establish the class of sugar–polyolefin conjugates as a new material platform for nanoscience and nanotechnology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tubular Nanostructures from Large‐Pore 2D Covalent Organic Frameworks

Abstract The synthesis of a wavy mesoporous 2D covalent organic framework (COF) with a 6‐nm hexagonal pore lattice ( Joa‐COF‐1 ) is reported. This has been achieved by the synthesis of a terpyrenyl linker of approximately 2.7 nm in length and its subsequent condensation with a 3‐connected non‐planar cata‐hexabenzocoronene. Joa‐COF‐1 exists as non‐covalent tubular domains composed of π‐stacked 4 to 5 pores in 2D COF sections that can be separated by mild sonication, resulting in a family of tubular COF nanostructures that combine a 1D morphology with accessible mesopores.

Almarza, Joaquín [POLYMAT University of the Basque↗

Auxetic Two-Dimensional Nanostructures from DNA

Architectured materials exhibit negative Poisson's ratios and enhanced mechanical properties compared with regular materials. Their auxetic behaviors emerge from periodic cellular structures regardless of the materials used. The majority of such metamaterials are constructed by top-down approaches and macroscopic with unit cells of microns or larger. There are also molecular auxetics including natural crystals which are not designable. There is a gap from few nanometers to microns, which may be filled by biomolecular self-assembly. In this work, we demonstrate two-dimensional auxetic nanostructures using DNA origami. Structural reconfigurations are performed by two-step DNA reactions and complemented by mechanical deformation studies using molecular dynamics simulations. We find that the auxetic behaviors are mostly defined by geometrical designs, yet the properties of the materials also play an important role. From elasticity theory, we introduce design principles for auxetic DNA metamaterials.

59 BASIC BIOLOGICAL SCIENCES↗

Stable Thermotropic 3D and 2D Double Gyroid Nanostructures with Sub‐2‐nm Feature Size from Scalable Sugar–Polyolefin Conjugates

Abstract Ultra‐low molecular weight disaccharide–polyolefin conjugates with cellobiose, lactose and maltose head groups and atactic polypropene tails, such as 1 , undergo a series of irreversible thermotropic order–order transitions with increasing temperature to provide nanostructured phases in the sequence: lamellar ( L ), hexagonal perforated lamellar ( HPL ), double gyroid ( DG ) and hexagonal cylindrical ( C ). The DG phase displays exceptional stability at ambient temperature and features two interpenetrating sugar domain networks having a sub‐2‐nm strut width and a lattice parameter, a DG , of 13.1 nm. The unique stability of this DG phase extends further within ultrathin films all the way down to the two‐dimensional limit of 15 nm in which film thickness, l , is now less than the surface‐oriented unit cell height, h DG . In addition to raising the fundamental question of what minimally constitutes a Schoen triply periodic minimal surface and DG lattice, these results serve to establish the class of sugar–polyolefin conjugates as a new material platform for nanoscience and nanotechnology.

Nowak, Samantha R.↗

Tubular Nanostructures from Large‐Pore 2D Covalent Organic Frameworks

Abstract The synthesis of a wavy mesoporous 2D covalent organic framework (COF) with a 6‐nm hexagonal pore lattice ( Joa‐COF‐1 ) is reported. This has been achieved by the synthesis of a terpyrenyl linker of approximately 2.7 nm in length and its subsequent condensation with a 3‐connected non‐planar cata‐hexabenzocoronene. Joa‐COF‐1 exists as non‐covalent tubular domains composed of π‐stacked 4 to 5 pores in 2D COF sections that can be separated by mild sonication, resulting in a family of tubular COF nanostructures that combine a 1D morphology with accessible mesopores.

Almarza, Joaquín [POLYMAT University of the Basque↗

Creation of Multi-Principal Element Alloy NiCoCr Nanostructures via Nanosecond Laser-Induced Dewetting

The multi-principal element alloy nanoparticles (MPEA NPs), a new class of nanomaterials, present a highly rewarding opportunity to explore new or vastly different functional properties than the traditional mono/bi/multimetallic nanostructures due to their unique characteristics of atomic-level homogeneous mixing of constituent elements in the nanoconfinements. Here, in this paper, the successful creation of NiCoCr nanoparticles, a well-known MPEA system is reported, using ultrafast nanosecond laser-induced dewetting of alloy thin films. Nanoparticle formation occurs by spontaneously breaking the energetically unstable thin films in a melt state under laser-induced hydrodynamic instability and subsequently accumulating in a droplet shape via surface energy minimization. While NiCoCr alloy shows a stark contrast in physical properties compared to individual metallic constituents, i.e., Ni, Co, and Cr, yet the transient nature of the laser-driven process facilitates a homogeneous distribution of the constituents (Ni, Co, and Cr) in the nanoparticles. Using high-resolution chemical analysis and scanning nanodiffraction, the environmental stability and grain arrangement in the nanoparticles are further investigated. Thermal transport simulations reveal that the ultrashort (≈100 ns) melt-state lifetime of NiCoCr during the dewetting event helps retain the constituent elements in a single-phase solid solution with homogenous distribution and opens the pathway to create the unique MPEA nanoparticles with laser-induced dewetting process.

36 MATERIALS SCIENCE↗

Enhancement of Nanostructured Ferritic Alloy 14YWT Properties via Heat Treatment for Post-Consolidation Processing

The nanostructured ferritic alloy 14YWT is a promising candidate for in-core use in generation IV nuclear reactors, due to a dense dispersion of insoluble, ultrafine-scale Y-Ti-O nano-oxides, which provide a high degree of irradiation tolerance and thermal stability. This work investigates the effects of heat treatment on the workability of 14YWT, along with the effect of processing history on abnormal grain structures and radial microstructural uniformity. In this study, a 14YWT rod consolidated at 850 °C was heat treated in argon at 1100 °C, 1150 °C, 1200 °C, or 1250 °C for 1 or 8 hours and changes in mechanical properties and microstructure were examined using microhardness and electron backscattered diffraction (EBSD). Two distinct types of large abnormal grains were observed, each with unique processing origins, including one with high and the other with low strain energy. Consolidation via direct extrusion resulted in radial microstructural gradients, where the center of the rod was softer with larger grain sizes and lower strain energies. These gradients persisted and intensified throughout heat treatment. Based upon this work, the recommended heat treatment for increased workability with minimal microstructural change is 1150 °C for 1 hours.

36 MATERIALS SCIENCE↗

Geometrical quasi-ballistic effects on thermal transport in nanostructured devices

In this work, we employ thermoreflectance thermal imaging to directly measure the steady-state two-dimensional (2D) temperature field generated by nanostructured heat sources deposited on silicon substrate with different geometrical configurations and characteristic sizes down to 400nm. The analysis of the results using Fourier’s law not only breaks down as size scales down, but it also fails to capture the impact of the geometry of the heat source. The substrate effective Fourier thermal conductivities fitted to wire-shaped and circular-shaped structures with identical characteristic lengths are found to display up to 40% mismatch. Remarkably, a hydrodynamic heat transport model reproduces the observed temperature fields for all device sizes and shapes using just intrinsic Si parameters, i.e., a geometry and size-independent thermal conductivity and nonlocal length scale. The hydrodynamic model provides insight into the observed thermal response and of the contradictory Fourier predictions. We discuss the substantial Silicon hydrodynamic behavior at room temperature and contrast it to InGaAs, which shows less hydrodynamic effects due to dominant phonon-impurity scattering.

42 ENGINEERING↗

Rapid quantification of alcohol production in microorganisms based on nanostructure-initiator mass spectrometry (NIMS)

We described a mass spectrometry-based assay to rapidly quantify the production of primary alcohols directly from cell cultures. This novel assay used the combination of TEMPO-based oxidation chemistry and oxime ligation, followed by product analysis based on Nanostructure-Initiator Mass Spectrometry. This assay enables quantitative monitor both C5 to C18 alcohols as well as glucose and gluconate in the growth medium to support strain characterization and optimization. We find that this assay yields similar results to gas chromatography for isoprenol production but required much less acquisition time per sample. We applied this assay to gain new insights into P. Putida's utilization of alcohols and find that this strain largely could not grow on heptanol and octanol.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗