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At least 127 records · Page 7

Unraveling Interdiffusion Phenomena and the Role of Nanoscale Diffusion Barriers in the Copper–Gold System

Diffusion is one of the most fundamental concepts in materials science, playing a pivotal role in materials synthesis, forming, and degradation. Of particular importance is solid state interdiffusion of metals which defines the usable parameter space for material combinations in the form of alloys. This parameter space can be explored on the macroscopic scale by using diffusion couples. However, this method reaches its limit when going to low temperatures, small scales, and when testing ultrathin diffusion barriers. Therefore, this work transfers the principle of the diffusion couples to small scales by using core–shell nanowires and in situ heating. This allows us to delve into the interdiffusion dynamics of copper and gold, revealing the interplay between diffusion and the disorder–order phase transition. Our in situ TEM experiments in combination with chemical mapping reveal the interdiffusion coefficients of Cu and Au at low temperatures and highlight the impact of ordering processes on the diffusion behavior. The formation of ordered domains within the solid-solution is examined using high-resolution imaging and nanodiffraction including strain mapping. In addition, we examine the effectiveness of ultrathin Al 2 O 3 barrier layers to control interdiffusion of the diffusion couple. Our findings indicate that a 5 nm thick layer serves as an efficient diffusion barrier. Furthermore, this research provides valuable insights into the interdiffusion behavior of Cu and Au on the nanoscale, offering potential applications in the development of miniaturized integrated circuits and nanodevices.

alloys↗

At Extreme Strain Rates, Pure Metals Thermally Harden while Alloys Thermally Soften

When materials are deformed at extreme strain rates, >10 6 s -1 , a counterintuitive mechanical response is seen where the strength and hardness of pure metals increases with increasing temperature. This anti-thermal hardening is due to dislocations meeting resistance to their motion from phonons in the crystal lattice. However, here, using optically-driven microballistic impact testing to measure dynamic strength and hardness, we show that when the composition is systematically varied away from high purity, the mechanical response of metals transitions from phonon drag of dislocations back to thermally activated pinning of dislocations, even at the highest strain rates. This boundary from “hotter-is-stronger” to “hotter-is-softer” is observed and mapped for nickel, titanium and gold. Furthermore, the ability to tune between deformation mechanisms with very different temperature dependencies speaks to new directions for alloy design in extreme conditions.

Ballistic transport↗

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.↗

The solubility of gold in silicate melts: First results

The effects of oxygen fugacity and temperature on the solubility of Au in silicate melts were determined. Pd-Au alloys were equilibrated with silicate of anorthite-diopside eutectic composition at different T-fO2 conditions. The behavior of Au was found to be similar to that of Pd reported recently. Au solubilities for alloys with 30 to 40 at. percent Au decrease at 1400 C from 12 ppm in air to 160 ppb at a log fO2 = -8.7. The slope of the log(Me-solubility) vs. log(fO2) curve is close to 1/4 for Au and the simultaneously determined Pd suggesting a formal valence of Au and Pd of 1+. Near the IW buffer Pd and Au solubilities become even less dependent on fO2 perhaps reflecting the presence of some metallic Au and Pd.

Borisov, A.↗

Atmospheric-pressure ammonia synthesis on AuRu catalysts enabled by plasmon-controlled hydrogenation and nitrogen-species desorption

The Haber–Bosch process for ammonia synthesis contributes up to ~3% of global greenhouse gas emissions. Plasmonic catalysts strongly concentrate light and can alter the reaction intermediates via out-of-equilibrium processes, providing the potential for an alternative, less-energy-intensive pathway to synthesize ammonia. Here, in this study, we show that gold-ruthenium (AuRu) bimetallic nanoparticles can synthesize ammonia at room temperature and pressure using visible light. We create AuRu alloys with varying compositions and achieve ammonia production rates of ~60 μmol per gram of catalyst bed per hour. In situ infrared spectroscopy reveals that light accelerates the hydrogenation of nitrogen intermediates compared to conventional thermal catalysis. Through computational modelling, we demonstrate that photo-excited electrons enable associative hydrogenation pathways for nitrogen activation rather than direct nitrogen–nitrogen bond breaking. This light-assisted mechanism requires both hydrogen and light working together to overcome the nitrogen activation barrier, mimicking how biological enzymes produce ammonia naturally and providing fundamental insights for developing sustainable, energy-efficient chemical synthesis.

Yuan, Lin [Stanford Univ., CA (United States)] (OR↗

Mini-Brayton heat source assembly design study. Volume 2: Titan 3C mission

Major conclusions of the space shuttle heat source assembly study are reported that project a minimum weight design for a Titan 3 C synchronous orbit mission; requirements to recover the heat source in orbit are eliminated. This concept permits location of the heat source end enclosure supports and heat source assembly support housing in a low temperature region external to the insulation enclosure and considers titanium and beryllium alloys for these support elements. A high melting insulation blanket consisting of nickel foil coated with zirconia, or of gold foil separated with glass fiber layers, is selected to provide emergency cooling in the range 2000 to 2700 F to prevent the isotope heat source from reaching unsafe temperatures. A graphic view of the baseline heat source assembly is included.

Source record↗

Sputtered W-N diffusion barriers

The thermal stability of reactively sputtered tungsten-nitrogen alloy thin films is investigated for the application as diffusion barriers in silicon contact metallizations. The composition of W-N barriers is varied over a wide range including pure W. Aluminum, gold, and silver are used as low resistivity overlayers. Metallurgical interactions at temperatures ranging from 500 to 900 C are studied. Incorporating nitrogen into tungsten advantageously stabilizes all three systems. The overall failure takes place rapidly above critical temperatures that depend on both the metal overlayer and the microstructure of the barrier. In some cases, W-N alloys can effectively prevent interdiffusion at temperatures as high as 800 C for 30 min.

Kattelus, H. P.↗

Solubility of hydrogen in metals and its effect of pore-formation and embrittlement

The effect of alloying elements on hydrogen solubility were determined by evaluating solubility equations and interaction coefficients. The solubility of dry hydrogen at one atmosphere was investigated in liquid aluminum, Al-Ti, Al-Si, Al-Fe, liquid gold, Au-Cu, and Au-Pd. The design of rapid heating and high pressure casting furnaces used in meta foam experiments is discussed as well as the mechanism of precipitation of pores in melts, and the effect of hydrogen on the shrinkage porosity of Al-Cu and Al-Si alloys. Hydrogen embrittlement in iron base alloys is also examined.

Shahani, H. R.↗

Star tracking reticles

A method for the production of reticles, particularly those for use in outer space, where 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 is described. 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.

Smith, W. O.↗

Bondability of Al-Si thin film in thermosonic gold wire bonding

The bondability of two kinds of Al-Si thin films in thermosonic Au wire bonding was examined by means of microshear tests. One type of film was formed by sputtering an Al-2% Si alloy, and the other was formed by depositing an 0.05 micrometer-thick polysilicon layer on SiO2 by chemical vapor deposition (CVD) and then depositing a 1.2 micrometer-thick Al layer on them by evaporation. After heat-treatment at 450 deg for 30 min., Si in the Al-Si film crystallized. The grain size of the crystallized Si affects the thermosonic wire bondability, i.e., for Al-2% Si sputtered films, good bondability was obtained under relatively small (1.0 micrometer) grain size conditions. In the successive layer process, on the other hand, the grain size of crystallized Si varies with the polysilicon CVD temperature. The optimum CVD temp. was determined from the standpoint of bondability with respect to grain size.

Nakagawa, K.↗

Actuated Hybrid Mirror Telescope

The figure depicts the planned Actuated Hybrid Mirror Telescope (AHMT), which is intended to demonstrate a new approach to the design and construction of wide-aperture spaceborne telescopes for astronomy and Earth science. This technology is also appropriate for Earth-based telescopes. The new approach can be broadly summarized as using advanced lightweight mirrors that can be manufactured rapidly at relatively low cost. More specifically, it is planned to use precise replicated metallic nanolaminate mirrors to obtain the required high-quality optical finishes. Lightweight, dimensionally stable silicon carbide (SiC) structures will support the nanolaminate mirrors in the required surface figures. To enable diffraction- limited telescope performance, errors in surface figures will be corrected by use of mirror-shape-control actuators that will be energized, as needed, by a wave-front-sensing and control system. The concepts of nanolaminate materials and mirrors made from nanolaminate materials were discussed in several previous NASA Tech Briefs articles. Nanolaminates constitute a relatively new class of materials that can approach theoretical limits of stiffness and strength. Nanolaminate mirrors are synthesized by magnetron sputter deposition of metallic alloys and/or compounds on optically precise master surfaces to obtain optical-quality reflector surfaces backed by thin shell structures. As an integral part of the deposition process, a layer of gold that will constitute the reflective surface layer is deposited first, eliminating the need for a subsequent and separate reflective-coating process. The crystallographic textures of the nanolaminate will be controlled to optimize the performance of the mirror. The entire deposition process for making a nanolaminate mirror takes less than 100 hours, regardless of the mirror diameter. Each nanolaminate mirror will be bonded to its lightweight SiC supporting structure. The lightweight nanolaminate mirrors and SiC supporting structures will be fabricated from reusable master molds. The mirror-shape-control actuators will be low-power, high-capacitance lead magnesium niobate electrostrictive actuators that will be embedded in the SiC structures. The mode of operation of these actuators will be such that once power was applied, they will change in length and once power was removed, they will maintain dimensional stability to nanometer precision. This mode of operation will enable the use of low-power, minimally complex electronic control circuitry. The wave-front-sensing and control system will be designed and built according to a two-stage architecture. The first stage will be implemented by a Shack- Hartmann (SH) sensor subsystem, which will provide a large capture range. The second, higher-performance stage will be implemented by an image-based wave-front-sensing subsystem that will include a phase-retrieval camera (PRC), and will utilize phase retrieval and other techniques to measure wavefront error directly. Phase retrieval is a process in which multiple images of an unresolved object are iterated to estimate the phase of the optical system that acquired the images. The combination of SH and phase-retrieval sensors will afford the virtues of both a dynamic range of 105 and an accuracy of <10 nm.

Hickey, Gregory↗

Impact of Particle Size on the Vapor-Phase Oxidative Coupling of Methanol and Dimethylamine over Palladium–Gold Nanoparticles

Oxidative coupling of methanol and dimethylamine in the presence of O 2 in the vapor phase over dilute Pd in Au bimetallic catalysts occurs via the dissociation of O 2 on Pd and selective oxidation of methanol on Au. Here, we synthesize a series of silica-supported PdAu alloy nanoparticle catalysts of varied Pd:Au ratios with ~5 nm particle diameter and show that these catalysts have increased selectivity to dimethylformamide across all Pd:Au ratios (~95%), distinct from observations over larger PdAu nanoparticles (~15–25 nm diameter) of similar Pd:Au ratios. Small monometallic Pd particles are more selective than large monometallic Pd particles, and small Au nanoparticles are reactive and selective for oxidative coupling (while large Au nanoparticles are inactive). Rates per surface metal atom were similar over PdAu nanoparticles of all sizes and increased monotonically with increasing Pd content for the small nanoparticles. Further, apparent reaction kinetics demonstrate distinct apparent methanol reaction order and apparent activation energy relative to those reported over larger nanoparticles of similar Pd:Au ratios. Unlike larger PdAu nanoparticles, the rate of dimethylformamide formation is not promoted by cofed water over small PdAu nanoparticles. The results of the kinetic studies are used to propose a series of elementary steps, derive a plausible rate expression, and regress rate and equilibrium constants. These results suggest high coverages of surface methoxy species and low coverages of adsorbates derived from dimethylamine. Taken together, these results demonstrate the sensitivity of the rates, selectivities, and kinetics of oxidative coupling reactions to the size of bimetallic nanoparticles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Application of Nuclear Technology to Art Identification Problems: First Annual Report

Throughout the centuries, as man has become increasingly affluent, his interest in antiquities and objects of art, and the price he has been willing to pay for them, has increased. Inevitably, one result has been to attract the unscrupulous to the production and sale of counterfeit paintings, sculptures, and other works of art. The skill of forgers varies but often is highly sophisticated. However, dealers, museum curators, and other experts have also become more skillful in the detection of forgeries. Scientific tools of increasing sensitivity and sophistication have gradually been applied to the examination of the materials of art and archaeology. Such tools frequently support and render more reliable the judgment of the experts. The quality of forgeries may improve further as their makers become acquainted with the new methods of detection and in turn learn to circumvent or confound the methods. Therefore, the development of still more advanced methods of examination has great utility in the art world. This is particularly true if the ultimate effect is to make circumvention of the methods of examination so costly that the economic incentives for producing forgeries may be substantially reduced, if not eliminated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Overcoming time and complexity limitations in molecular dynamics investigations of equilibrium melting

Abstract A hybrid Monte-Carlo molecular-dynamics method for determining solidus and liquidus compositions in multicomponent systems is presented that overcomes both the time limitations in conventional molecular dynamics that prevent the evolution of distinct solid and liquid compositions via diffusion and the complexity challenge that prevents use of thermodynamic assessment in systems of many components. This hybrid method is validated in the Cu–Ni system against an independent assessment of solidus and liquidus compositions based on the regular solution model. Strategies for efficient mapping of different phase diagrams, based on the thermodynamic parameter T 0 , the temperature at which two phases of the composition X 0 have equal free energies, are presented and then demonstrated for the copper-nickel fully miscible system and the gold–silicon eutectic system. A calculation of the solidus and liquidus sampled during the equilibrium melting of equiatomic CrMnFeCoNi is performed, indicating that this method has potential to be extended to the study of many component alloys.

Au-Si↗

Analyses of Transistor Punchthrough Failures

The failure of two transistors in the Altitude Switch Assembly for the Solid Rocket Booster followed by two additional failures a year later presented a challenge to failure analysts. These devices had successfully worked for many years on numerous missions. There was no history of failures with this type of device. Extensive checks of the test procedures gave no indication for a source of the cause. The devices were manufactured more than twenty years ago and failure information on this lot date code was not readily available. External visual exam, radiography, PEID, and leak testing were performed with nominal results Electrical testing indicated nearly identical base-emitter and base-collector characteristics (both forward and reverse) with a low resistance short emitter to collector. These characteristics are indicative of a classic failure mechanism called punchthrough. In failure analysis punchthrough refers to an condition where a relatively low voltage pulse causes the device to conduct very hard producing localized areas of thermal runaway or "hot spots". At one or more of these hot spots, the excessive currents melt the silicon. Heavily doped emitter material diffuses through the base region to the collector forming a diffusion pipe shorting the emitter to base to collector. Upon cooling, an alloy junction forms between the pipe and the base region. Generally, the hot spot (punch-through site) is under the bond and no surface artifact is visible. The devices were delidded and the internal structures were examined microscopically. The gold emitter lead was melted on one device, but others had anomalies in the metallization around the in-tact emitter bonds. The SEM examination confirmed some anomalies to be cosmetic defects while other anomalies were artifacts of the punchthrough site. Subsequent to these analyses, the contractor determined that some irregular testing procedures occurred at the time of the failures heretofore unreported. These testing irregularities involved the use of a breakout box and were the likely cause of the failures. There was no evidence to suggest a generic failure mechanism was responsible for the failure of these transistors.

Nicolas, David P.↗

Nickel Accounting for the Psyche Spacecraft

(16) Psyche is a metallic asteroid located in the asteroid belt between Mars and Jupiter. The composition of Psyche is unknown, but the scientific community believes it is composed primarily of iron, nickel, and silicates. The Psyche mission will be the first space mission to study this asteroid in close proximity, and as such, determining the elemental composition of the asteroid is one of the primary objectives of this mission. The spacecraft measures this elemental composition using the Gamma Ray Spectrometer (GRS), which detects cosmic-ray induced gamma rays from Psyche’s surface. In addition to gamma rays from Psyche, the GRS will also detect background gamma rays from spacecraft material nearby the GRS. Because Ni is such a key element for achieving the mission science objectives, a special effort has been made to minimize background gamma rays from Ni, thus maximizing sensitivity to the Ni gamma rays from Psyche. The Psyche mission approached this potential Ni background issue with two methods, locating the GRS away from the spacecraft/source of Ni and setting a threshold requirement against the total Ni mass of the spacecraft. Verifying that the total amount of Ni on the spacecraft is within this threshold is thus a key part of ensuring the GRS can meet its science objectives. Ni alloys are commonly used on spacecraft, but the mass and location of elemental Ni is not typically accounted for. Ni can be found in many materials all over the spacecraft – in fasteners, optical assemblies, magnetic shields, electromagnetic interference (EMI) tape, under gold plating, in connectors, and so on. The task proved further challenging because of the distributed nature of the build of this spacecraft and the use of vendors external to JPL. While the analysis was atypical and source information difficult to cull, the approach described in this paper used tools and data available to the project in some form to achieve this goal. For Psyche, current analysis shows there is margin in meeting the Ni mass requirement. This paper explains the systematic approach used to accurately and precisely record Ni content on the Psyche spacecraft. While this approach was defined for Ni on the Psyche mission, it can be used for any future project with the need to accurately estimate the total mass of a single element or material on a spacecraft.

Cullinan, Joe↗