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At least 739 records · Page 41

Explosive welding technique for joining aluminum and steel tubes

Silver sheet is wrapped around aluminum portion of joint. Mylar powder box is wrapped over silver sheet. Explosion welds silver to aluminum. Stainless-steel tube is placed over silver-aluminum interface. Mylar powder box, covered with Mylar tape, is wrapped around steel member. Explosion welds steel to silver-aluminum interface.

Wakefield, M. E.↗

Effect of hard particle impacts on the atomic oxygen survivability of reflector surfaces with transparent protective overcoats

Silver mirror samples with protective coatings were subjected to a stream of 27 microns alumina particles to induce pinhole defects. The protective coating consisted of a layer of aluminum dioxide over silver followed by a layer of silicon dioxide over the alumina. Samples were prepared on both graphite-epoxy composite and fused quartz substrates. After exposure to the hard particle stream, the samples were exposed to an oxygen plasma environment in a laboratory plasma asher. The effects of both the hard particles and the oxygen plasma were documented by both reflectance measurements and scanning electron microscopy. The results indicated that oxidative damage to the silver reflecting layer continues beyond that of the erosively exposed silver. Oxidative undercutting of the silver layer and graphite-epoxy substrate continues in undamaged areas through adjacent, particle damaged defect sites. This may have implications for the use of such mirrors in a space station solar dynamic power system.

Gulino, D. A.↗

Effect of hard particle impacts on the atomic oxygen survivability of reflector surfaces with transparent protective overcoats

Silver mirror samples with protective coatings were subjected to a stream of 27 microns alumina particles to induce pinhole defects. The protective coating consisted of a layer of aluminum dioxide over silver followed by a layer of silicon dioxide over the alumina. Samples were prepared on both graphite-epoxy composite and fused quartz substrates. After exposure to the hard particle stream, the samples were exposed to an oxygen plasma environment in a laboratory plasma asher. The effects of both the hard particles and the oxygen plasma were documented by both reflectance measurements and scanning electron microscopy. The results indicated that oxidative damage to the silver reflecting layer continues beyond that of the erosively exposed silver. Oxidative undercutting of the silver layer and graphite-epoxy substrate continues in undamaged areas through adjacent, particle damaged defect sites. This may have implications for the use of such mirrors in a space station solar dynamic power system.

Gulino, Daniel A.↗

A comparison of ground-based and space flight data: Atomic oxygen reactions with boron nitride and silicon nitride

The effects of atomic oxygen on boron nitride (BN) and silicon nitride (Si3N4) have been studied in low Earth orbit (LEO) flight experiments and in a ground-based simulation facility at Los Alamos National Laboratory. Both the in-flight and ground-based experiments employed the materials coated over thin (approx 250 Angstrom) silver films whose electrical resistance was measured in situ to detect penetration of atomic oxygen through the BN and Si3N4 materials. In the presence of atomic oxygen, silver oxidizes to form silver oxide, which has a much higher electrical resistance than pure silver. Permeation of atomic oxygen through BN, as indicated by an increase in the electrical resistance of the silver underneath, was observed in both the in-flight and ground-based experiments. In contrast, no permeation of atomic oxygen through Si3N4 was observed in either the in-flight or ground-based experiments. The ground-based results show good qualitative correlation with the LEO flight results, thus validating the simulation fidelity of the ground-based facility in terms of reproducing LEO flight results.

Cross, J. B.↗

Using In-Situ Deposition of Metallic Thin Films on Mars to Monitor Atmospheric H20

We describe the use of a novel sensor, designed to characterize the reactive nature of the Martian atmosphere, to also characterize the instantaneous abundance of atmospheric H,O. The sensor deposits, in situ, a thin silver film onto a sapphire substrate and monitors oxidation by measuring resistance of the Ag film during both deposition and subsequent oxidation [1,2]. . The evaporation source is placed in the center of a hollow, open-ended tube. On flash heating the source, evaporated metallic silver rapidly reacts with oxidizing gases in the tube, depositing on the tube walls as a resisitive Ag oxide film. Unoxidized silver deposits over the Ag oxides, once the oxidizing gases in the vicinity of the source have been consumed. Since the ends of the tube are open, atmospheric gases in the tube cause a time delay as the evaporated silver initially reacts with the available O2, and H2O; once oxidizing gases in the tube are significantly depleted, a silver film closes the chemiresistor circuit. In principle this operation mode provides a repeatable measure of the variable H2O abundance, since O2, levels are constant in the atmosphere. To explore the utility of the instrument as an H2O sensor, predict its behavior, and identify possible failure modes, we developed a numerical model of the instrument, and exercised it for Mars conditions. The model predicts the behavior of the electrical circuit, the temperature dependence of resistivity for each component, and the resultant Joule heating. The model balances Joule heating against radiation, sensible heat loss to ambient CO2, and, latent heat loss from sublimating Ag. The flux of Ag atoms from the source is tracked continuously. In the gas phase, the number density of Ag, O2, and H2O is calculated, along with their reaction rates on collision. The model suggests that Ag substantially depletes H2O only near the center of the tube. The model supports the hypothesis that the onset of high conductivity between the A u electrodes is a function of the H2O abundance in the ambient gas, but only to a limit; when H2O abundances are buffered at or above 240K (an H2O abundance that would not have occurred on Mars), metallic Ag never deposits in excess of Ago, and the circuit does not close. A significant difference in the Mars simulation is that the Ag source sublimates more quickly, primarily because of differences in sensible heat fluxes from the source. This allows subsequent heating of the W filament used to support the Ag source. Had the originally-designed experimental sequence been carried out on Mars, the filament might have melted, making subsequent investigations impossible.

Zent, A. P.↗

Colorimetric Solid Phase Extraction (CSPE): Using Color to Monitor Spacecraft Water Quality

In August 2009, an experimental water quality monitoring kit based on Colorimetric Solid Phase Extraction (CSPE) technology was delivered to the International Space Station (ISS). The kit, called the Colorimetric Water Quality Monitoring Kit (CWQMK), was launched as a Station Development Test Objective (SDTO) experiment to evaluate the suitability of CSPE technology for routine use monitoring water quality on the ISS. CSPE is a sorption-spectrophotometric technique that combines colorimetric reagents, solid-phase extraction, and diffuse reflectance spectroscopy to quantify trace analytes in water samples. In CSPE, a known volume of sample is metered through a membrane disk that has been impregnated with an analyte-specific colorimetric reagent and any additives required to optimize the formation of the analyte-reagent complex. As the sample flows through the membrane disk, the target analyte is selectively extracted, concentrated, and complexed. Formation of the analyte-reagent complex causes a detectable change in the color of the membrane disk that is proportional to the amount of analyte present in the sample. The analyte is then quantified by measuring the color of the membrane disk surface using a hand-held diffuse reflectance spectrophotometer (DRS). The CWQMK provides the capability to measure the ionic silver (Ag +) and molecular iodine (I2) in water samples on-orbit. These analytes were selected for the evaluation of CSPE technology because they are the biocides used in the potable water storage and distribution systems on the ISS. Biocides are added to the potable water systems on spacecraft to inhibit microbial growth. On the United States (US) segment of the ISS molecular iodine serves as the biocide, while the Russian space agency utilizes silver as a biocide in their systems. In both cases, the biocides must be maintained at a level sufficient to control bacterial growth, but low enough to avoid any negative effects on crew health. For example, the presence of high levels of iodine in water can cause taste and odor issues that result in decreased water consumption by the crew. There are also concerns about potential impacts on thyroid function following exposure to high levels of iodine. With silver, there is a risk of developing argyria, an irreversible blue-gray discoloration of the skin, associated with long term consumption of water containing high concentrations of silver. The need to ensure that safe, effective levels of biocide are maintained in the potable water systems on the ISS provides a perfect platform for evaluating the suitability of CSPE technology for in-flight water quality monitoring. This paper provides an overview of CSPE technology and details on the silver and iodine methods used in the CWQMK. It also reports results obtained during in-flight analyses performed with the CWQMK and briefly discusses other potential applications for CSPE technology in both the spacecraft and terrestrial environments.

Gazda, Daniel B.↗

Fully Printed, Flexible, Phased Array Antenna for Lunar Surface Communication

NASAs future exploration missions focus on the manned exploration of the Moon, Mars, and beyond, which will rely heavily on the development of a reliable communications infrastructure from planetary surface-to-surface, surface-to-orbit, and back to Earth. Flexible antennas are highly desired in many scenarios. Active phased array antennas (active PAAs) with distributed control and processing electronics at the surface of an antenna aperture offer numerous advantages for radar communications. Large-area active PAAs on flexible substrates are of particular interest in NASA s space radars due to their efficient inflatable package that can be rolled up during transportation and deployed in space. Such an inflatable package significantly reduces stowage volume and mass. Because of these performance and packaging advantages, large-area inflatable active PAAs are highly desired in NASA s surface-to-orbit and surface-to-relay communications. To address the issues of flexible electronics, a room-temperature printing process of active phased-array antennas on a flexible Kapton substrate was developed. Field effect transistors (FETs) based on carbon nanotubes (CNTs), with many unique physical properties, were successfully proved feasible for the PAA system. This innovation is a new type of fully inkjet-printable, two-dimensional, high-frequency PAA on a flexible substrate at room temperature. The designed electronic circuit components, such as the FET switches in the phase shifter, metal interconnection lines, microstrip transmission lines, etc., are all printed using a special inkjet printer. Using the developed technology, entire 1x4, 2x2, and 4x4 PAA systems were developed, packaged, and demonstrated at 5.3 GHz. Several key solutions are addressed in this work to solve the fabrication issues. The source/drain contact is developed using droplets of silver ink printed on the source/drain areas prior to applying CNT thin-film. The wet silver ink droplets allow the silver to wet the CNT thin-film area and enable good contact with the source and drain contact after annealing. A passivation layer to protect the device channel is developed by bonding a thin Kapton film on top of the device channel. This film is also used as the media for transferring the aligned CNT thin-film on the device substrate. A simple and cost-effective technique to form multilayer metal interconnections on flexible substrate is developed and demonstrated. Contact vias are formed on the second substrate prior to bonding on the first substrate. Inkjet printing is used to fill the silver ink into the via structure. The printed silver ink penetrates through the vias to contact with the contact pads on the bottom layer. It is then annealed to form a good connection. One-dimensional and two-dimensional PAAs were fabricated and characterized. In these circuits, multilayer metal interconnects were used to make a complete PAA system.

Subbaraman, Harish↗

Process for the Production of Star Tracklng [Tracking] Reticles

A method for the production of reticles, particularly those for use in outer space, wherein the product is a quartz base coated with highly adherent layers of chromium, chromium-silver, and silver vacuum deposited through a mask, and then coated with an electrodeposit of copper from a copper sulfate solution followed by an electrodeposit of black chromium. The masks are produced by coating a beryllium-copper alloy substrate with a positive working photoresist, developing the photoresist according to a pattern to leave a positive mask, plating uncoated areas with gold, removing the photoresist, coating the substrate with a negative working photoresist, developing the negative working photoresist to expose the base metal of the pattern, and chemically etching the unplated side of the pattern to produce the mask. The mask produced is then used in the vacuum deposition of: (1) chromium metal on the surface of a quartz base to obtain a highly adherent quartz-chromium interface; (2) silver on the chromium deposit, during the final stage of chromium deposit, to produce a silver chromium alloy layer; and (3) silver onto the surface of the alloy layer. The coated quartz base is then coated by electroplating utilizing an acid copper deposit followed by a black chromium electrodeposit to produce the product of the present invention.

Smith, Wade O.↗

Nuclear Safety [Vol. 32, No. 1, January-March 1991]

Nuclear Safety is a review journal that covers significant developments in the field of nuclear safety. Its scope includes the analysis and control of hazards associated with nuclear energy, operations involving fissionable materials, and the products of nuclear fission and their effects on the environment. Primary emphasis is on safety in reactor design, construction, and operation; however, the safety aspects of the entire fuel cycle, including fuel fabrication, spent-fuel processing, nuclear waste disposal, handling of radioisotopes, and environmental effects of these operations, are also treated. Table of Contents for this issue follows. GENERAL SAFETY CONSIDERATIONS: 1 The Safety Review and Approval Process for Space Nuclear Power Sources, G. L. Bennett; 19 Report on the American Nuclear Society International Topical Meeting: "The Safety, Status, and Future of Non-Commercial Reactors and Irradiation Facilities", E. G. Silver; 35 Book Review: Fission Product Transport Processes in Reactor Accidents, Proceedings to the International Centre tor Heat and Mass Processes T. S. Kress; 38 Fast Reactor Technology in the 1990s: A Summary of the 1990 International Fast Reactor Safety Meeting, A. E. Levin; ACCIDENT ANALYSIS: 56 Effects of Chemical Phenomena on LWR Severe Accident Fission Product Behavior, A. P. Malinauskas and T. S. Kress; CONTROL AND INSTRUMENTATION: 65 Technical Note: Safety Parameter Display Systems—10 Years Later, R. J. Eckenrode; 68 Potential Application of Neural Networks to the Operation of Nuclear Power Plants, R. E. Uhrig; DESIGN FEATURES: 80 Twenty-First DOE/NRC Nuclear Air-Cleaning Conference, R. R. Bellamy, D. W. Moeller, and M. W. First; 91 Impact of an Apparent Radiation Embrittlement Rate on the Life Expectancy of PWR Vessel Supports, R. D. Cheverton, G. C. Robinson, W. E. Pennell, and R. K. Nanstad; ENVIRONMENTAL EFFECTS: 103 Technical Note: The Impact of Offsite Factors on the Safety Performance of Small Nuclear Power Plants, Yu. D. Baranaev and A. N. Viktorov; WASTE AND SPENT FUEL MANAGEMENT: 109 Activities Related to Waste Management, Compiled by E. G. Silver; OPERATING EXPERIENCES: 118 Reactor Shutdown Experience, Compiled by J. W. Cletcher; 121 Selected Safety-Related Events, Compiled by G. A. Murphy; 123 Operating U.S. Power Reactors, Compiled by E. G. Silver; RECENT DEVELOPMENTS: 140 General Administrative Activities, Compiled by E. G. Silver; 150 Reports, Standards, and Safety Guides, D. S. Queener; 155 Status of Power-Reactor Licensing Activities, Compiled by E. G. Silver; 157 Proposed Rule Changes as of Sept. 30, 1990; ANNOUNCEMENTS: 79 MIT Offers Summer Program on Nuclear Power Reactor Safety; 108 Harvard School of Public Health Offers Several Short Courses; 139 Short Course and Workshop on Nuclear Criticality Safety at University of New Mexico; 160 SCK/CEN Announces Training Course on Emergency Planning and Response; 161 The Authors; 164 Indexes to Nuclear Safety, Volume 31

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Unveiling 3D Morphology of Multiscale Micro-Nanosilver Sintering for Advanced Electronics Manufacturing by Ptychographic X-ray Nanotomography

The sintering processing–structure–property relationship of a multiscale silver materials is investigated: microparticles with nanofeatures, particularly on their three-dimensional (3D) morphology. The target application is to replace conventional lead-based solders in advanced electronic manufacturing. Unlike lead-based solders, silver powders are suited to satisfy increasingly demanding mechanical, electrical, and thermal requirements, meanwhile being free of health effect. Sintering the material at a low temperature and without applied pressure are desirable conditions, which results in a preferred use of silver nanoparticles, as nanofeatures have higher driving force to sinter with the decrease in particle size. However, nanosized powders present potential health/environmental effects. To address the trade-off between the benefits and shortcomings of nano-versus microparticles, this work studies a novel multiscale silver paste, namely micron-sized powders with nanosized features. To get quantitative 3D visualization of micro- and nanoscale features, ptychographic X-ray computed nanotomography is applied. The correlations between conditions (thermal aging, pressure, and substrate metallization), mechanical properties, and morphological parameters are established. Finally, using novel 3D X-ray nanoimaging technique, it is demonstrated that one can design multiscale materials while balancing complex demands required in advanced electronics manufacturing and research directions in materials design and characterization.

36 MATERIALS SCIENCE↗

Time-Resolved Evolution of the 3D Nanoporous Structure of Sintered Ag by X-Ray Nanotomography: Role of the Interface with a Copper Substrate

Here, the evolution of the nanoporous structure of cylindrical sintered silver samples during high temperature aging, ranging from 200 to 350 °C for 350 min, is studied through in situ computed X-ray tomography. Investigations are carried out for two types of specimens: pure sintered silver and specimens containing a silver-copper interface. It is shown that the overall pore evolution is driven by the evolution of very few large ones. The smaller pores, although being more numerous, do not really evolve before being absorbed by the few bigger ones. In pure silver, pore evolution is driven by diffusion (Ostwald ripening) but the presence of an interface promotes faster growth kinetics until the aging time reaches a threshold value, after which a deviation from Ostwald ripening occurs. The transition is a function of the aging temperature. This behavior is associated with the competition between elastic relaxation and surface energy minimization.

42 ENGINEERING↗

Overcoming Variability: A Reproducible Approach to SERS Detection of Nanodiamonds

Detonation nanodiamonds (DNDs) are formed at specific pressures and temperatures during explosions. Different explosives produce varied yields of DNDs within their detonation soot, with Composition B producing the highest yield. Raman spectroscopy (RS) is often used for the characterization of sp 2 - and sp 3 -hybridized carbon allotropes in carbonaceous materials because of distinct disorder and graphitic bands. Bulk diamond also gives a distinct Raman peak at 1332 cm –1 . Furthermore, as bulk diamond decreases in size to nanometer-sized species, the peak red-shifts and broadens, becoming increasingly difficult to detect with RS using visible excitations. Therefore, surface-enhanced Raman spectroscopy (SERS) was used to enhance the diamond peak of DNDs, enabling better detection and faster examination of DNDs within detonation soot. Previous literature of the SERS of DNDs delivered inconsistent results in spectral signatures and SERS substrates. Herein, refining of the methodology for the acquisition of SERS spectra of DNDs was achieved. Before any SERS experiments, the DNDs were first characterized with normal Raman (NR) and scanning electron microscopy. Two routes for SERS enhancement were evaluated: colloidal noble metal nanoparticles and evaporated silver films. Silver films produced the best signal enhancement of DNDs with the best signal-to-noise and peak enhancements observed at 20–30 nm thick silver films at 5% (∼300 μW) laser power. Consistent, reproducible SERS spectra were acquired of small aggregates of DNDs down to ∼500 nm. NR and SERS mapping analysis of DNDs before and after evaporation of silver films revealed the improvements in the detection capabilities of SERS compared with NR.

Carbon↗

Contactless Production Testing of Silicon Solar Cells

Critical cost reductions in silicon solar cells are made by minimizing silver usage in their metal contacts. The reason why is both clear and unavoidable—silver is not only expensive, but also a potential limiting resource for scale-up (the PV industry alone used 10.3 % of the global silver supply in 2020 [1]). The result is solar cells with vanishing electrical contact area that are extremely difficult to test prior to module manufacture, when they must be sorted for quality to maximize power output and reliability of the subsequent modules. This project developed a new measurement instrument that enables the transition to solar cells with very low silver content, including cell designs with both minimal busbars and no busbars at all to electrically contact. The resulting instrument at project completion demonstrated the ability to sort cells with comparable—or better—results than existing technology. Compared to existing cell-test instruments, the new tool has minimal contacting requirements, which lowers the maintenance costs and use of consumable parts. We demonstrated innovative, yet pragmatic, solutions for reporting a comprehensive set of measurement results useful for both cell sorting (going forward in the line for module manufacture) and process control (looking backward in the line to identify cell manufacturing issues from wafer to cell-test). In addition to the traditional current-voltage characterization at cell test—short circuit current, open-circuit voltage, power, efficiency and fill factor—the new tool maintains all the advanced parameter characterization of our existing product line such as a substrate doping measurement, carrier recombination (lifetime) analysis, and surface recombination analysis.

14 SOLAR ENERGY↗

BioWires: Conductive DNA Nanowires in a Computationally-Optimized, Synthetic Biological Platform for Nanoelectronic Fabrication

DNA is an ideal template for a biological nanowire-it has a linear structure several atoms thick; it possesses addressable nucleobase geometry that can be precisely defined; and it is massively scalable into branched networks. Until now, the drawback of DNA as a conducting nanowire been, simply put, its low conductance. To address this deficiency, we extensively characterize a chemical variant of canonical DNA that exploits the affinity of natural cytosine bases for silver ions. We successfully construct chains of single silver ions inside double-stranded DNA, confirm the basic dC-Ag+-dC bond geometry and kinetics, and show length-tunability dependent on mismatch distribution, ion availability and enzyme activity. An analysis of the absorbance spectra of natural DNA and silver-binding, poly-cytosine DNA demonstrates the heightened thermostability of the ion chain and its resistance to aqueous stresses such as precipitation, dialysis and forced reduction. These chemically critical traits lend themselves to an increase in electrical conductivity of over an order of magnitude for 11-base silver-paired duplexes over natural strands when assayed by STM break junction. We further construct and implement a genetic pathway in the E. coli bacterium for the biosynthesis of highly ionizable DNA sequences. Toward future circuits, we construct a model of transcription network architectures to determine the most efficient and robust connectivity for cell-based fabrication, and we perform sequence optimization with a genetic algorithm to identify oligonucleotides robust to changes in the base-pairing energy landscape. We propose that this system will serve as a synthetic biological fabrication platform for more complex DNA nanotechnology and nanoelectronics with applications to deep space and low resource environments.

DNA↗

Ammonia Permeation Through Inorganic Membranes

Moisture probes are used in the tritium facility to measure the moisture content of the gas stream. When tritium reacts with nitrogen to form ammonia, the ammonia gas damages the sensitive moisture probe. The gas stream tested during this experiment for moisture probe protection is composed of nitrogen and argon gas in conjunction with ammonia and water vapor. The gas stream is filtered through an inorganic membrane due to the high reactivity of tritium and a residual gas analyzer (RGA) is used to measure the ammonia and water vapor in the gas stream, as well as the permeability of nitrogen and argon through the inorganic membranes. The membranes tested were boron nitride and silver. The permeability was compared for each membrane at different pressures and flow rates. Fourier-transformed infrared spectroscopy (FT-IR) was used to compare the membranes before and after ammonia permeation. Ammonia gas is a byproduct formed from tritium gas reacting with nitrogen in the gas stream, similar to the Haber Process which occurs when hydrogen reacts with nitrogen [2]. The corrosive nature of ammonia damages metals and sensitive instruments such as moisture probes. Moisture probes are essential in various gas and liquid processes for measuring the moisture content of a gas. Membrane research has found that graphene oxide membranes successfully uptake ammonia from the gas stream at a humidity of approximately 30% at which point the pores pin closed, preventing gas permeation. Further research is being conducted to find an inorganic membrane that will prevent ammonia permeation thus circumventing damage to the sensitive moisture probe. The permeation measurements for argon and nitrogen gas and water and ammonia vapor were measured at various pressures of 800, 1000, 1200, 1500, 1800, and 2000 torr. The permeability average (PA) was calculated for each filter using a Barrer calculation. The average permeations for each filter were then compared. The gas composition was measured using the RGA Nitrogen was permeated through the membranes after ammonia permeation and a FT-IR spectrum was obtained. Boron Nitride: As the nitrogen pressure increased, the permeability of the membrane decreased from 800-1200 torr and remained relatively unchanged from 1200-2000 torr. The membrane exhibited a slight decrease in argon permeability from 800-1200 torr and a slight increase from 1500-2000 torr. The boron nitride membrane when permeated with ammonia and nitrogen prevented less ammonia permeation compared to the blank filter. The boron nitride filter demonstrated a decrease in permeability after ammonia permeation. Silver Membrane: When permeated with nitrogen alone, the membrane permeability decreased from 800 torr to 1200 torr. The permeability of the membrane showed little difference as pressure increased from 1200 torr. When permeated with argon, the same phenomenon occurred but on a much smaller scale. When compared to the blank and the boron nitride membranes the silver membrane exhibited significantly lower permeability. This may be in part due to the coating on the silver membrane and differences in pore size of the membranes. During permeation with ammonium hydroxide vapor and nitrogen, the partial pressure of the ammonia increased as compared to the blank membrane. The permeability before and after permeation with ammonia and nitrogen were compared. Permeability values suggested that after being permeated with the ammonia that the permeability for lower pressures increased slightly. There was no significant change in the FT-IR spectrums before and after permeation. Future work: Continue testing various inorganic membranes for ammonia permeation. Further research chemical separation of ammonia from the gas stream, which may prove difficult due to the high reactivity of tritium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synchrotron X‐Ray‐Driven Nitrogen Reduction on an AgCu Thin Film

Abstract Nitrogen (N 2 ) is an essential element for life, but kinetically stable N 2 in the atmosphere needs to be reduced to biologically available forms as a nutrient for organisms. Abiotic nitrogen fixation is critical to the origin of life on the early Earth, which is due to lightning or mineral‐based reduction. Here, synchrotron X‐ray‐induced silver nitrate formation on a silver copper (AgCu) thin‐film is reported. Time‐resolved X‐ray diffraction measurements show that under intense X‐ray exposure, initially formed silver oxides (AgOx) are quickly converted to silver nitrate (AgNO 3 ). Interestingly, AgNO 3 is first formed in its high‐temperature phase with a space group of R3cH , which gradually transforms to the room temperature phase with a space group of Pbca under continuous X‐ray irradiation. The result not only provides a new clue about the abiotic nitrogen reduction prior to life but also demonstrates a novel strategy of materials synthesis using synchrotron X‐rays.

Hui, Jian↗

Online ion mobility spectrometry of nanoparticle formation by non-thermal plasma conversion of metal salts in liquid aerosol droplets

The synthesis of nanoparticles by reaction of liquid aerosol droplets containing precursors in a flow-through, atmospheric-pressure, non-thermal plasma offers a continuous, scalable, substrate- and stabilizer-free approach for direct deposition into liquids or onto soft substrates. However, the combination of multiphase and non-equilibrium chemistry makes the process complicated and poorly understood. Here, we present ion mobility spectrometry measurements of liquid water droplets containing silver nitrate passing through an atmospheric-pressure dielectric barrier discharge reactor that allows us to monitor silver nanoparticle formation online for the first time. Mobility diameter distributions were obtained with the plasma on and off, and exhibited a shift, which was related to the degree of conversion of silver nitrate. The silver nanoparticles were also collected and characterized by UV–visible absorbance spectroscopy and transmission electron microscopy to support the online measurements. Importantly, negligible conversion was found when the water was removed by a diffusion dryer, suggesting that the key reducing species are in the liquid phase, such as solvated electrons. Finally, the study demonstrates how ion mobility spectrometry measurements can be applied to provide insight into this approach to nanoparticle synthesis.

42 ENGINEERING↗

Correlating structure, self-assembly chemistry and conductivity of trithiocyanuric acid on Au(111)

The majority of candidates for simple model molecular-electronic components consist of a conductive π-conjugated hydrocarbon linker attached to at least two anchoring groups, such as thiols or isocyanides. It has been found that select molecules self-assemble on gold surfaces, creating one-dimensional conductive structures that act as “molecular wires”. Furthermore, these oligomers can form molecular bridges between gold nanoparticles, leading to the creation of simple molecular-electronic devices. This raises the question whether other π-conjugated molecular linkers could exhibit similar behavior that might offer a broader range of candidates for fabricating electronic devices. Trithiocyanuric acid (1,3,5-triazine-2,4,6-trithiol, TTCA) provides a possible candidate. TTCA (C3N3(SH)3) can exist as a trithiol or as a trithione in which hydrogens transfer to the sulfurs so that they are present with three C=N groups within the ring. TTCA exists naturally in the trithione form but converts into a trithiol when adsorbed onto an Ag(111) where it is vertically oriented. The structure of TTCA adsorbed on Au(111) is studied here using reflection-absorption infrared spectroscopy (RAIRS) where it is found to remain as the trithione isomer, but changes orientation as the coverage increases. Scanning-tunneling microscopy (STM) reveals that TTCA oligomerizes on Au(111) to form chains and triangular structures. The influence on molecular conductivity due to the differences in the adsorbate's isomeric structure was investigated using devices comprising either silver or gold nanoparticles deposited in the gap between gold nanoelectrodes. Both devices were found to conduct when dosed with TTCA, but the devices fabricated using silver were about 13 time more conductive than those made from gold nanoparticles, consistent with the π-conjugated structure formed on silver but not on gold. This implies that oligomers form both on silver and on gold and potentially increases the range of molecule-metal combinations that might be used to fabricate molecular-electronic devices.

Molecular electronics↗