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Adsorption phenomena in noble metals rhodium, iridium, palladium, and gold - application of potentiostatic delta method
The formation of gold silicide on Au films evaporated onto Si(111) surfaces is studied by Auger electron spectroscopy (AES) and low-energy electron diffraction (LEED). Surface condition, film thickness, deposition temperature, annealing temperature, and heating rate during annealing are varied. Several oriented crystalline silicide layers are observed.
Sawed cross-section samples are rough polished at minimum pressure with 14 micron grit. After saw marks are polished away, polishing grit is changed to 0.05 micron. When smooth appearance is attained, surface is then chemically polished by hand in dust free room.
Our recent work on He, Ne, and Ar in Alpine gold samples has demonstrated that gold is extremely retentive for He and could thus, in principle, be used for U/Th-He-4 dating. For vein-type gold from Brusson, Northern Italy, we derived a U/Th-He-4 age of 36 Ma, in agreement with the K-Ar formation age of associated muscovites and biotites. However, in placer gold from the Napf area, Central Switzerland, we observed large excesses of both He-4 and radiogenic Ar-40 (Ar-40 sub rad, defined as Ar-40-295.5-Ar-.36). The gas release systematics indicate two distinct noble gas components, one of which is released below about 800 C and the other one at the melting point of gold (1064 C). We now present results of He and Xe measurements in a 1 g placer gold sample from the river Kruempelgraben, as well as He and Ar data for Brusson vein-type gold and for gold from the Lily Gold Mine, South Africa. We calculate reasonable U/Th-He-4 as well as U-Xe ages based on those gases which are released at approximately 800 C. Probably the low-temperature components represent in-situ-produced radiogenic He and fission Xe, whereas the gases evolving when gold melts have been trapped during gold formation. Therefore, only the low-temperature components are relevant for dating purposes.
The graded interface between an ion-plated film and a substrate is discussed as well as the friction and wear properties of ion-plated gold. X-ray photoelectron spectroscopy (XPS) depth profiling and microhardness depth profiling were used to investigate the interface. The friction and wear properties of ion-plated and vapor-deposited gold films were studied both in an ultra high vacuum system to maximize adhesion and in oil to minimize adhesion. The results indicate that the solubility of gold on the substrate material controls the depth of the graded interface. Thermal diffusion and chemical diffusion mechanisms are thought to be involved in the formation of the gold-nickel interface. In iron-gold graded interfaces the gold was primarily dispersed in the iron and thus formed a physically bonded interface. The hardness of the gold film was influenced by its depth and was also related to the composition gradient between the gold and the substrate. The graded nickel-gold interface exhibited the highest hardness because of an alloy hardening effect. The effects of film thickness on adhesion and friction were established.
The graded interface between an ion-plated film and a substrate is discussed as well as the friction and wear properties of ion-plated gold. X-ray photoelectron spectroscopy (XPS) depth profiling and microhardness depth profiling were used to investigate the interface. The friction and wear properties of ion-plated and vapor-deposited gold films were studied both in an ultra high vacuum system to maximize adhesion and in oil to minimize adhesion. The results indicate that the solubility of gold on the substrate material controls the depth of the graded interface. Thermal diffusion and chemical diffusion mechanisms are thought to be involved in the formation of the gold-nickel interface. In iron-gold graded interfaces the gold was primarily dispersed in the iron and thus formed a physically bonded interface. The hardness of the gold film was influenced by its depth and was also related to the composition gradient between the gold and the substrate. The graded nickel-gold interface exhibited the highest hardness because of an alloy hardening effect. The effects of film thickness on adhesion and friction were established.
In a first report on our investigations of noble gases in native gold we demonstrated that placer gold contains an excess of radiogenic (4)He and (40)Ar relative to the concentrations expected from in situ decay of U, Th, and K, respectively, during the geologic age of about 30 Ma of the samples. We also showed that the U/Th-(4)He age of 36 Ma of vein-type gold from the Southern Alps agrees with its K-Ar formation age derived from associated muscovite and biotite. We now studied the question of the origin of the (4)He and (40)Ar excesses of placer gold. We conclude that gold contains two components of noble gases, a low-temperature component from fluid inclusions or phases which release noble gases at less than 800 C and a high-temperature component released when gold melts (1064 C). In some samples extremely high U and K concentrations or an unreasonably high formation age would be required to explain the observed (4)He abundances. Thus, trapped (4)He and (40)Ar must be present in gold.
Gold ion implantation was carried out with the energy of 1.1 MeV into (100) oriented MgO single crystal. Implanted doses are 1, 3, 6, 10 x 10(exp 16) ions/sq cm. The gold irradiation results in the formation of gold ion implanted layer with a thickness of 0.2 microns and defect formation. In order to form gold colloids from the as-implanted samples, we annealed the gold implanted MgO samples in three kinds of atmospheres: (1)Ar only, (2)H2 and Ar, and (3)O2 and Ar. The annealing over 1200 C enhanced the gold colloid formation which shows surface plasmon resonance band of gold. The surface plasmon bands of samples annealed in three kinds of atmospheres were found to be at 535 nm (Ar only), 524 nm(H2+Ar), and 560 nm (02+Ar), The band positions of surface plasmon can be reversibly changed by an additional annealing.
Two gold-base active metal brazes (gold-ABA and gold-ABA-V) were evaluated for oxidation resistance to 850 C, and used to join yttria-stabilized zirconia (YSZ) to a corrosion-resistant ferritic stainless steel for possible use in solid oxide fuel cells. Thermogravimetric analysis and optical microscopy and scanning electron microscopy coupled with energy-dispersive spectroscopy were used to evaluate the braze oxidation behavior, and microstructure and composition of the YSZ/braze/steel joints. Both gold-ABA and gold-ABA-V exhibited nearly linear oxidation kinetics at 850 C, with gold-ABA-V showing faster oxidation than gold-ABA. Both brazes produced metallurgically sound YSZ/steel joints due to chemical interactions of Ti and V with the YSZ and steel substrates.
The GSFC (Goddard Space Flight Center) GOLD Rules (Goddard Open Learning Design; GSFC-STD-1000) provide a reasonably comprehensive list of guidelines for the design and testing of spacecraft and instruments based on the long heritage of successful GSFC missions. In general, all GSFC missions are required to comply with the GOLD Rules across a number of subsystems or to seek waivers to particular GOLD rules where compliance is not practical, either due to the risk posture of a mission or the cost and/or schedule associated with compliance. In thermal subsystems, GOLD Rules are applied to design margins throughout the project life cycle and include temperature margins, heater power margins, and two-phase transport margins. However, no explicit guidance is provided for two thermal design aspects: heater control authority (for stability requirements) and cryogenic design margins (which are often not reasonable to express in terms of temperatures). This can lead to ambiguity and inconsistency among projects when demonstrating GOLD Rules compliance. Two current GSFC projects, TIRS-2 (Thermal InfraRed Sensor 2) and WFIRST (Wide Field InfraRed Survey Telescope), are both missions with cryogenic aspects and active thermal control for stability. This paper seeks to outline the characterization of cryogenic margins during the design process for TIRS-2 and WFIRST as well as the project derived guidelines for heater control authority margin. This effort serves as potential first steps for updating the GOLD Rules to address these two areas in guiding thermal designs at GSFC.
The ultraviolet-imaging spectrograph that comprises Global-scale Observations of the Limb and Disk (GOLD) mission in geostationary orbit at 47.5°W longitude has taken full disk images at high cadence throughout the deep solar minimum period of 2019–2020. Synoptic (i.e., concurrent and spatially unified and resolved) observations of thermospheric temperature and composition at ∼150 km altitude are made for the first time, allowing GOLD to disambiguate temporal and spatial variations. Here we analyze the daytime effective temperature and column integrated O and N2 density ratio (ΣO/N 2 ) data simultaneously observed by GOLD over 120°W–20°E longitude and 60°S–60°N latitude from 13 October 2019 to 12 October 2020. Daily zonal mean values are calculated for each latitude and compared with NRLMSIS 2.0 and simulations from the Whole Atmosphere Community Climate Model with thermosphere and ionosphere extension (WACCM-X). On average, the GOLD observations show higher temperatures than Mass Spectrometer Incoherent Scatter radar (MSIS) and WACCM-X by ∼20–60 K (5%–10%) and 80–120 K (12%–18%), respectively. The ΣO/N 2 ratios observed by GOLD are larger than the MSIS results by ∼0.4 (40%) but smaller than the WACCM-X simulations by ∼0.3 (30%). The observed and modeled results are correlated at most latitudes (r = 0.4–0.8), and GOLD, MSIS, and WACCM-X all display a similar seasonal variation and change with latitude. WACCM-X simulates a larger annual variation in ΣO/N 2 , suggesting that the thermospheric circulation is overestimated and atmospheric waves and turbulence transport are not properly represented in the model.
The ultraviolet-imaging spectrograph that comprises Global-scale Observations of the Limb and Disk (GOLD) mission in geostationary orbit at 47.5°W longitude has taken full disk images at high cadence throughout the deep solar minimum period of 2019–2020. Synoptic (i.e., concurrent and spatially unified and resolved) observations of thermospheric temperature and composition at ∼150 km altitude are made for the first time, allowing GOLD to disambiguate temporal and spatial variations. Here we analyze the daytime effective temperature and column integrated O and N 2 density ratio (ΣO/N 2 ) data simultaneously observed by GOLD over 120°W–20°E longitude and 60°S–60°N latitude from 13 October 2019 to 12 October 2020. Daily zonal mean values are calculated for each latitude and compared with NRLMSIS 2.0 and simulations from the Whole Atmosphere Community Climate Model with thermosphere and ionosphere extension (WACCM-X). On average, the GOLD observations show higher temperatures than Mass Spectrometer Incoherent Scatter radar (MSIS) and WACCM-X by ∼20–60 K (5%–10%) and 80–120 K (12%–18%), respectively. The ΣO/N2 ratios observed by GOLD are larger than the MSIS results by ∼0.4 (40%) but smaller than the WACCM-X simulations by ∼0.3 (30%). The observed and modeled results are correlated at most latitudes (r = 0.4–0.8), and GOLD, MSIS, and WACCM-X all display a similar seasonal variation and change with latitude. WACCM-X simulates a larger annual variation in ΣO/N 2 , suggesting that the thermospheric circulation is overestimated and atmospheric waves and turbulence transport are not properly represented in the model.
Measured reflection efficiencies are presented for flat samples of diamond-turned aluminum, nickel, and evaporated gold surfaces fabricated by techniques suited for EUV telescopes. The aluminum samples were 6.2-cm-diameter disks of 6061-T6, the electroless nickel samples were formed by plating beryllium disks with 7.5-microns of Kanigen. Gold samples were produced by coating the aluminum and nickel samples with 5 strips of evaporated gold. Reflection efficiencies are given for grazing angles in the 5-75 degree range. The results indicate that for wavelengths over about 100 A, the gold-coated nickel samples yield highest efficiencies. For shorter wavelengths, the nickel samples yield better efficiencies. 500 A is found to be the optimal gold thickness.
Because tricresyl-phosphate (TCP) is a common antiwear additive in lubricants, there is great interest in its interactions with metal substrates. The TCP was allowed to adsorb on polycrystalline iron and gold at room temperature. X-ray photoelectron spectroscopy (XPS) was used to analyze the adsorbed species. The substrate was then heated in steps to 330 C, and the changes in the adsorbate were analyzed after each step. On both substrates saturation adsorption occurred at about one monolayer, but the sticking coefficient was less on gold than on iron. Comparison of the XPS spectra of TCP on each substrate with the spectrum from condensed TCP indicated nondissociative adsorption on gold, possibly by dipole-induced dipole interaction. On iron, there was apparently additional interaction between the substrate and the tolyl groups on the TCP molecule. TCP began to desorb molecularly from gold as soon as the gold was heated above room temperature. The desorption was complete by 200 C. However, when the iron substrate was heated, TCP did not desorb but decomposed between 150 and 250 C.
To obtain information on the adhesion between metal films and polymeric solids, the adhesion force was measured by means of a tensile pull test. It was found that the adhesion strengths between polymeric solids and gold films evaporated on polymer substrates were (1.11 + or - 0.53) multiplied by 10(6) N/M(2) on PTFE, about 5.49 multiplied by 10(6) N/m(2) on UHMWPE, and 6.54x10(6) on 6/6 nylon. The adhesion strengths for nickel films evaporated on PTFE, UHMWPE, and 6/6 nylon were found to be a factor of 1.7 higher than those for the gold coated PTFE, UHMWPE, and 6/6 nylon. To confirm quantitatively the effect of electron irradiation on the adhesion strength between a PTFE solid and metal films, a tensile pull test was performed on the irradiated PTFE specimens, which were prepared by evaporating nickel or gold on PTFE surfaces irradiated by 2-keV electrons for various times. After irradiation, the adhesion strength increased to (4.92 + or - 0.92)x10(6) N/m(2) for nickel coated PTFE and (1.82 + or - 0.48)x10(6) N/m(2) for gold coated PTFE. The improvement in adhesion for nickel is higher than that for gold.
The principles governing the design of metal films are reviewed, with attention also given to the choice of metals. A description is then given of the characteristics of a bolometer with a gold absorbing film. It is demonstrated that gold is effective as an absorbing film for a millimeter bolometer operated at 1.5 K. At 1.5 K, gold is significantly better than bismuth since gold has a lower heat capacity for the absorbing film. At 0.3 K, gold and bismuth are both suitable. It is pointed out that at temperatures below 0.3 K, a superconducting absorbing film can have a heat capacity low enough not to dominate the heat capacity of the detector; for this reason, it may give better performance than a nonsuperconducting absorbing film.
Gold and gold-based alloys, commonly used as solar-cell contact materials, are known to react readily with gallium arsenide. Experiments designed to identify the mechanisms involved in these GaAs-metal interactions have yielded several interesting results. It is shown that the reaction of GaAs with gold takes place via a dissociative diffusion process. It is shown further that the GaAs-metal reaction rate is controlled to a very great extent by the condition of the free surface of the contact metal, an interesting example of which is the previously unexplained increase in the reaction rate that has been observed for samples annealed in a vacuum environment as compared to those annealed in a gaseous ambient. A number of other hard-to-explain observations, such as the low-temperature formation of voids in the gold lattice and crystallite growth on the gold surface, are also explained by invoking this mechanism.
YBa2Cu3O(7-x) crystals are grown in a gold crucible by a self-flux method. The flux moves along the gold surface due to surface wetting and leaves Y123 crystals behind. The obtained crystals are clean and have a size up to two millimeters and a Tc is greater than 90 K. In an effort to recycle the used crucibles, it is found that the used gold is contaminated by copper. A CuO thin film is easily formed on the surface of the crucible that is made of the used gold. This film provides good surface wetting and a buffer layer, which reduces the reaction between gold and the Y-Ba-Cu-oxide melt.