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At least 37 records · Page 2

Trapping and actively transporting single particles of arbitrary properties in low-pressure rf plasmas with and without a magnetic field

We report the experimental realization of optical trapping and controlled manipulations of single particles of arbitrary properties, e.g., nano- to micrometer in size, transparent spheres to strongly light absorbing nonspherical particles, in low-pressure rf plasmas. First, we show optical trapping and transport of single particles in an unmagnetized rf plasma. Then, we show similar observations in a weakly magnetized rf plasma. This is the first demonstration of actively transporting (pushing and pulling) light-absorbing, nonspherical single particles in plasmas. The result suggests that optically trapped, actively controlled, single plasma dust particles (not limited to those externally sampled spheres) could be an in situ micro-probe for dusty plasma and magnetized dusty plasma diagnostics.

Physics↗

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O 2 production prepared by layer-by-layer self-assembly

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor–chromophore–catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a Ru II (bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L) 2 ] (bda = 2,2'-bipyridine-6,6'-dicarboxylate) 2 , were linked by ALD by addition of the bridge precursors TiO 2 , ZrO 2 , and Al 2 O 3 as the bridging groups giving the assemblies, FTO|nanoITO|–MV 2+ –ALD MO 2 –RuP2 2+ –ALD M'O 2 –WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Single-Crystal Optical Actuation Generated by 100% SO 2 Linkage Photoisomerization in a Ruthenium-Based Coordination Complex

Single-crystal optical actuators are emerging as a new field of materials chemistry because of their wide-ranging potential applications, from light-induced molecular motors to photosensing technologies. Ruthenium-based coordination complexes that contain sulfur dioxide linkage photoisomers have shown particular promise as optical actuators, given that they may exhibit either optical switching or nano-optomechanical transduction in their single-crystal form. The type of single-crystal optical actuation observed in a specific compound within this family of complexes depends upon the nature of the ligand that lies trans to this SO 2 linkage photoisomer, since this governs the type and extent of photoisomer (η 2 -(OS)O or η 1 -OSO) that will form upon the application of light. We report the discovery of a new complex, trans-[Ru(SO 2 )(NH 3 ) 4 (3-iodopyridine)]tosylate 2 (1), which forms an η 1 -OSO photoisomer with 100% photoconversion upon the application of 505 nm light. The photoisomerization process in the ruthenium-based cation of 1 stimulates rotation and translation of the toluenic constituent of its neighboring anion, thereby affording nano-optomechnical transduction. We show that this η 1 -OSO photoisomer transitions to its more thermally stable η 2 -(OS)O photoisomer with an activation energy, E a , of 11(2) kJ/mol using thermally activated single-crystal optical absorption spectroscopy. The application of external light with different wavelengths to 1 is also shown to cause a variation in its optical absorption spectral characteristics. Here, this suggests that the photophysical properties of 1 may be tunable with light.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hierarchically porous and single Zn atom-embedded carbon molecular sieves for H2 separations

Abstract Hierarchically porous materials containing sub-nm ultramicropores with molecular sieving abilities and microcavities with high gas diffusivity may realize energy-efficient membranes for gas separations. However, rationally designing and constructing such pores into large-area membranes enabling efficient H 2 separations remains challenging. Here, we report the synthesis and utilization of hybrid carbon molecular sieve membranes with well-controlled nano- and micro-pores and single zinc atoms and clusters well-dispersed inside the nanopores via the carbonization of supramolecular mixed matrix materials containing amorphous and crystalline zeolitic imidazolate frameworks. Carbonization temperature is used to fine-tune pore sizes, achieving ultrahigh selectivity for H 2 /CO 2 (130), H 2 /CH 4 (2900), H 2 /N 2 (880), and H 2 /C 2 H 6 (7900) with stability against water vapor and physical aging during a continuous 120-h test.

42 ENGINEERING↗

Modification of Radiator Pigments by Atomic Layer Deposition (ALD)

The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. Other examples include the application of variable emittance coatings such as the use of VO2 to optimize radiator size, allowing for a decrease in heater power budget. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. Modification of these coatings can be accomplished during coating application preprocessing by using a deposition technique prevalent in the semiconductor micro processing industry called Atomic Layer Deposition (ALD). The preprocessing is rendered directly on the coating dry pigment before binding. ALD is a cost effective nano-manufacturing technique that allows for the conformal coating of substrates with atomic-level thickness control in a benign temperature and pressure environment. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano-structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. We have demonstrated a method for the ALD of In2O3 and ITO films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments (patent pending). The results indicate excellent growth of 4-22 nm thick films demonstrating an order of magnitude decrease in resistivity on the pigments.

ITO↗

Technology Development for the Modification of High Aspect Ratio Geometries for Thermal and Environmental Control

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗

Application and Development of Atomic Layer Deposition Techniques to Improve Thermo-Optical Coatings for Spacecraft Thermal Control and Advanced Optical Instruments

A key technology development driver in environmental control systems and next generation optics are discussed utilizing thin film development borrowed from the semiconductor industry. The optical and physical properties of spacecraft radiator coatings are dictated by orbital environmental conditions. For example, coatings must adequately dissipate charge buildup when orbital conditions, such as polar, geostationary or gravity neutral, result in surface charging. Current dissipation techniques include depositing a layer of ITO (indium tin oxide) on the radiator surface in a high temperature process. The application of these enhanced coatings must be such that the properties in question are tailored to mission-specific requirements. The multi-billion-dollar semiconductor industry has adopted Atomic Layer Deposition (ALD) for self-assembly and atomic-scale placement. ALD is a cost-effective nanoadditive-manufacturing technique that allows for the conformal coating of substrates with atomic control in a benign temperature and pressure environment. By using ALD, modification of these coatings can be accomplished during coating application preprocessing. The preprocessing is rendered directly on the coating dry pigment before binding. Through the introduction of paired precursor gases, thin films can be deposited on a myriad of substrates ranging from glass, polymers, aerogels, metals, powders, and other high aspect-ratio micro- and nano- structures. By providing atomic-level control, where single layers of atoms can be deposited, the fabrication of metal transparent films, precise nano-laminates, and coatings of nano-channels and pores is achievable. A method has been demonstrated for the ALD of In2O3 and films on a variety of substrates from Si(100) wafers, glass slides, and on Z93P pigments resulting in a direct spaceflight application. Results will be presented that verify the chemical composition of ALD pigments and charge dissipation properties when the pigment goes through its binding and coating process and we present early results of ALD for carbon nanotube formation and encapsulation.

Dwivedi, Vivek H.↗

Investigation of methane and ethane pyrolysis with highly active and durable iron-alumina catalyst to produce hydrogen and valuable nano carbons: Continuous fluidized bed tests and reaction rate analysis

The goal of this research work was to evaluate a novel iron-alumina catalyst for methane and ethane pyrolysis with high conversion rates to H 2 with a long life time to address two major issues reported with previous catalysts. Fluidized bed tests demonstrated continuous hydrogen production while collecting carbon containing fines. During the 230 h fluid bed test the methane conversion rate to hydrogen at 700 °C remained above 80% for 160 h while creating valuable nano carbons. Similarly high catalyst lifetimes with high methane conversions have not been reported before. Ethane was more active than methane for pyrolysis with 100% conversion to H 2 . Transmission electron microscopy and Raman analysis of the carbon showed single and multiwall nanotubes and conglomerate nano-fibers. Ethane did not impact the allotrope of carbon formed. TGA was used to create a data array that was used for kinetic analysis and reaction model parametric regressions. Ethane had a higher rate of pyrolysis that was 2.3–2.8 times that of methane. Ethane pyrolysis was found to be more sensitive to temperature with a higher activation energy of 62 kJ/mol as compared to methane at 43 kJ/mol. The frequency factor, A i , was significantly higher for ethane at 0.73 [[kmol/m 3 -sec]/[N/m2] n ] compared to 0.03 for methane on the same basis. Both gases had a functional partial pressure order dependence of ~0.6 based on the regression analysis.

08 HYDROGEN↗

Adaptive Fault Detection Based on Neural Networks and Multiple Sampling Points for Distribution Networks and Microgrids

Smart networks such as microgrid (MG) and active distribution networks (ADN) have been recently playing an important role in power system operation. The design and implementation of appropriate protection systems for such networks must be addressed, which imposes new technical challenges. This paper presents the implementation and validation aspects of an adaptive fault detection strategy based on neural networks (NNs) and multiple sampling points for ADN and MG. The solution is implemented on an edge device. Artificial NNs are used to derive a data-driven model that uses only local measurements to detect fault states of the network without the need for communication infrastructure. Multiple sampling points are used to derive a data-driven model, which allows the generalization considering the implementation in physical systems. The adaptive fault detector model is implemented on a Jetson Nano system, which is a single-board computer (SBC) with a small Graphic Processing Unit (GPU) intended to run machine learning loads at the edge. The proposed method is tested in a physical, real-life, low-voltage network located at Universidad del Norte, Colombia. This testing network is based on the IEEE-13 Node Test Feeder scaled down to 220 V. The validation in a simulation environment shows the accuracy and dependability above 99.6%, while the real-time tests show the accuracy and dependability of 95.5% and 100%, respectively. Without hard-to-derive parameters, the easy-to-implement embedded model highlights the potential for real-life applications.

42 ENGINEERING↗

Nano Sponges for Drug Delivery and Medicinal Applications

This invention is a means of delivering a drug, or payload, to cells using non-covalent associations of the payload with nano-engineered scaffolds; specifically, functionalized single-walled carbon nanotubes (SWNTs) and their derivatives where the payload is effectively sequestered by the nanotube's addends and then delivered to the site (often interior of a cell) of interest. Polyethylene glycol (PEG) and other water-soluble organic molecules have been shown to greatly enhance the solubility of SWNTs in water. PEG groups and other water-solubilizing addends can act to sequester (sponge) molecules and deliver them into cells. Using PEG that, when attached to the SWNTs, the SWNT/PEG matrix will enter cells has been demonstrated. This was visualized by the addition of fluorescein isothiocyanate (FITC) to the SWNT/PEG matrix. Control studies showed that both FITC alone and FITC/PEG did not enter the cells. These observations suggest that the FITC is highly associated with the SWNT/PEG matrix that brings the FITC into the cells, allowing visualization of SWNTs in cells. The FITC is not covalently attached, because extended dialysis in hot DMF will remove all fluorescence quickly (one week). However, prolonged dialysis in water (1-2 months) will only slowly diminish the fluorescence. This demonstrates that the SWNT/PEG matrix solubilizes the FITC by sequestering it from the surrounding water and into the more solubilizing organic environment of the SWNT/PEG matrix of this type. This can be extended for the sequestering of other molecules such as drugs with PEG and other surfactants.

Tour, James M.↗

New Technology for Microfabrication and Testing of a Thermoelectric Device for Generating Mobile Electrical Power

Thermoelectric (TE) power generation is an increasingly important power generation technology. Major advantages include: no moving parts, low-weight, modularity, covertness/silence, high power density, low amortized cost, and long service life with minimum or no required maintenance. Despite low efficiency of power generation, there are many specialized needs for electrical power that TE technologies can uniquely and successfully address. Recent advances in thermoelectric materials technology have rekindled acute interest in thermoelectric power generation. We have developed single crystalline n- and p- type PbTe crystals and are also, developing PbTe bulk nanocomposites using PbTe nano powders and emerging filed assisted sintering technology (FAST). We will discuss the materials requirements for efficient thermoelectric power generation using waste heat at intermediate temperature range (6500 to 8500 K). We will present our recent results on production of n- and p- type PbTe crystals and their thermoelectric characterization. Relative characteristics and performance of PbTe bulk single crystals and nano composites for thermoelectric power generation will be discussed.

Prasad, Narasimha S.↗

Two-Dimensional Molecular Charge Density Waves in Single-Layer-Thick Islands of a Dirac Fermion System

Charge density waves have been intensely studied in inorganic materials such as transition metal dichalcogenides however its counterpart in organic materials has yet to be explored in detail. Here we report the finding of a robust two dimensional charge density waves in molecular layers formed by α-(BEDT-TTF) 2 -I 3 on a Ag(111) surface. Low temperature scanning tunnelling microscopy images of a multi-layer thick α-(BEDT-TTF) 2 -I 3 on Ag(111) substrate reveal coexistence of 5a0 x 5a0 and √31 a0 x √31 a0 R9° charge density wave patterns commensurate with the underlying molecular lattice at 80 K. Both charge density wave patterns remain in nano-size molecular islands with just a single constituent molecular-layer thickness at 80 K and 5 K. Local tunneling spectroscopy measurements reveal the variation of the gap from 244 meV to 288 meV between the maximum and minimum charge density wave locations. Density functional theory calculations further confirm a vertical positioning of BEDT-TTF molecules in the molecular layer. While the observed charge density wave patterns are stable for the defect sites, they can be reversely switched for one molecular lattice site by means of inelastic tunnelling electron energy transfer with the electron energies exceeding 400 meV using a scanning tunneling microscope manipulation scheme.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Extinction-Based 3D Nano-Imaging of WS 2 on Gold

Broad band nano-extinction images recorded in the tip-enhanced optical spectroscopy geometry track the 3D topography of a single layer of WS 2 on Au substrate. The described nano-optical method is complementary to conventional AFM and offers additional information about the buried material-metal interface that is not accessible using conventional topographic imaging. Beyond 3D optical imaging, we observe large variations in the junction plasmon resonance on the nanoscale. The latter is important to understand and account for in tip-enhanced Raman and photoluminescence studies that target low-dimensional materials specifically. Further, our observations and (coherent) optical scattering-based method are also relevant to emerging efforts aimed at exploring strong coupling and Fano interferences in hybrid plasmonic-low dimensional quantum material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of the Nano-HEB Array for Low-Background Far-IR Applications

We present an overview of the recent progress made in the development of a far-IR array of ultrasensitive hot-electronnanobolometers (nano-HEB) made from thin titanium (Ti) films. We studied electrical noise, signal and noisebandwidth, single-photon detection, optical noise equivalent power (NEP), and a microwave SQUID (MSQUID) basedfrequency domain multiplexing (FDM) scheme. The obtained results demonstrate the very low electrical NEP down to1.5x10-(sup 2)? W/Hz(sup 1)/(sup 2) at 50 mK determined by the dominating phonon noise. The NEP increases with temperature as ~ T(sup 3)reaching ~ 10-(sup 1)? W/Hz(sup 1)/(sup 2) at the device critical temperature TC = 330-360 mK. Optical NEP = 8.6x10-(sup 1)? W/Hz(sup 1)/(sup 2) at 357mK and 1.4x10-(sup 1)? W/Hz(sup 1)/(sup 2) at 100 mK respectively, agree with thermal and electrical data. The optical couplingefficiency provided by a planar antenna was greater than 50%. Single 8-?m photons have been detected for the first timeusing a nano-HEB operating at 50-200 mK thus demonstrating a potential of these detectors for future photon-countingapplications in mid-IR and far-IR. In order to accommodate the relatively high detector speed (~ ?s at 300 mK, ~ 100 ?sat 100 mK), an MSQUID based FDM multiplexed readout with GHz carrier frequencies has been built. Both the readoutnoise ~ 2 pA/Hz(sup 1)/(sup 2) and the bandwidth > 150 kHz are suitable for nano-HEB detectors.

single-photon↗

Use of Functionalized Carbon Nanotubes for Covalent Attachment of Nanotubes to Silicon

The purpose of the invention is to covalently attach functionalized carbon nanotubes to silicon. This step allows for the introduction of carbon nanotubes onto all manner of silicon surfaces, and thereby introduction of carbon nano - tubes covalently into silicon-based devices, onto silicon particles, and onto silicon surfaces. Single-walled carbon nanotubes (SWNTs) dispersed as individuals in surfactant were functionalized. The nano - tube was first treated with 4-t-butylbenzenediazonium tetrafluoroborate to give increased solubility to the carbon nanotube; the second group attached to the sidewall of the nanotube has a silyl-protected terminal alkyne that is de-protected in situ. This gives a soluble carbon nanotube that has functional groups appended to the sidewall that can be attached covalently to silicon. This reaction was monitored by UV/vis/NJR to assure direct covalent functionalization.

Tour, James M.↗

Dislocation loop evolution and radiation hardening in nickel-based concentrated solid solution alloys

Effects of chemical composition, ion irradiation dose and temperature on unfaulting of irradiation induced Frank dislocation loops to perfect loops in two nickel based single-phase solid solution alloys, Ni–20Fe and NiFe–20Cr, have been studied. The fraction of Frank loops decreases with irradiation dose from 7.2 to 38.4 dpa at 500°C, but with more Frank loops remaining in the ternary alloy. However, perfect loops and dislocation networks become the dominant features of defects at 580°C in both alloys. The results indicate a thermally assisted loop unfaulting process that may be hindered by more sluggish defect motion in the alloy with more chemical components. Nano-indentation with both continuous stiffness method and single indentation method are used to measure radiation hardening. Loop unfaulting in both alloys irradiated at 580°C reduced radiation hardening while significant hardening is observed after irradiation at 500°C. The quasi-static single indentation method exhibits lower hardness results compared to continuous stiffness method, because dislocations induced from the cyclic loading in the latter method get relaxed and stabilized, resulting in higher resistance to the indenter.

36 MATERIALS SCIENCE↗

Correlation of optical properties with particle size, morphology, and polymorph of fine- and nano-particle formulations of titanium dioxide powders

Titanium dioxide (TiO 2 ) particulates are known to exhibit different visible and infrared optical properties compared to the bulk material, showing strong dependence on particle size, crystal structure, and morphology. In this study, the optical properties, sizes, and morphologies of TiO 2 particles from two different sources (nano and fine powders) having a) nominally different particle sizes and b) various crystal polymorph mixture fractions are compared using a combination of single particle mass spectrometry, optical spectroscopies, and aerosol characterization methods. The nano sample was found to be largely particles of the anatase polymorph (88% by mass), while the fine sample was found to consist largely of rutile particles (95% by mass). Two distinct particle morphologies (fractal and compact) were found in each powder sample and could be identified and separated in-situ based on particle aerodynamic properties. The attenuation of near-infrared, visible and ultraviolet light by TiO 2 particles shows strong dependence on particle morphology. Furthermore, while the fine particles were found to have larger near-infrared (675–800 nm) extinction coefficients by mass than the nanoparticles, the reverse was true in the ultraviolet and visible regions (370–675 nm). However, for polydisperse particles with different sizes and shapes, the optical behaviors are not straightforward to directly correlate to a combination of physical parameters.

Lockwood, Schuyler P. [Pacific Northwest National ↗

Elucidating metal–organic framework structures using synchrotron serial crystallography

Metal organic frameworks (MOFs) are porous crystalline materials that display a wide variety of physical and chemical properties. Their single crystal structure determination is often challenging because in most cases micro- or nano-sized crystals spontaneously form upon MOF synthesis, which cannot be recrystallized. The production of larger single crystals for structure determination involves optimizing, and thus modifying, the conditions of synthesis, in which success cannot be guaranteed. Failure to produce crystals suitable for single-crystal X-ray diffraction leaves the 3D structure of the MOF compound unknown, and scientists must resort to more challenging structure solution methods based on X-ray powder or electron diffraction data. These laborious tasks can be avoided by using serial crystallography techniques which merge data collected on many micro-crystals. Here, we report the application of three synchrotron serial crystallography methods. We call these “mesh”, “grid” and “mesh&collect” scans. “Still” images (no rotation) are collected in the mesh scan approach, whereas small rotational wedges are collected in the grid scan method. The third protocol, mesh&collect, combines the acquisition of still images and rotational wedges. Using these means, we determine the ab initio structure of benchmark MOFs, MIL-100(Fe) and ZIF-8, that differ largely in unit cell size. These methods are expected to be widely applicable and facilitate structure determination of many MOF microcrystalline systems.

36 MATERIALS SCIENCE↗