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At least 19 records

Model studies in catalysis with uhv-deposited metal particles and clusters

Small supported metal particles have become a popular area of intense research interest, and important contributions to the considered problems are being made from the fields of uhv technology, thin film physics surface science, and surface and thin film instrumentation. Attention is given to insulating supports, particulate metal deposits and their properties, metal/support interactions and gas exposures, and integrated experimental approaches. It is concluded that major contributions to the field of model catalysis should be forthcoming in the near future from uhv-based methods of research. Catalysis and catalysis-related problem areas expected to benefit from advanced model studies include catalyst preparation processing, sintering mechanisms for metals and alloys, separation of initial and final state effects for supported clusters, and the influence of particle and/or support morphologies.

Poppa, H.↗

Surface studies with (clean) supported metal particles and clusters

Small particles are ideal for combined studies with surface analytical and electron microscopy/diffraction methods. In this way crystallography, microstructure, morphology, physical stability, and electronic structure can be correlated directly with chemical reactivity. Various integrated experimental approaches for conducting model studies with UHV-evaporated particles have been successfully developed; they entail the use of TPD, AES, XPS, and work function measurements on one hand and standard TEM/TED, in-situ TEM/TED, and in-situ STED/TEM techniques on the other hand. The essential features of four particular experimental approaches are discussed and a selection of representative results is presented to illustrate the potential usefulness of such studies in the field of catalysis.

Poppa, H. R.↗

The changes in small metal cluster size with adsorption Be13Xn, X = H, O, S, Cl and F

The Be-Be and Be-adsorbate distances are optimized for small Be13Xn clusters,s assuming only two independent degrees of freedom. Results for chemisorption into the three-fold hollows are quite similar to those found for small metal clusters on supports. It is predicted that Cl and F will have the same effect on the metal-metal bond lengths, and so will O and S.

Bauschlicher, C. W., Jr.↗

Friction at small displacement.

Low contact resistance between metal surfaces is often observed in spite of interposed lubricant and/or oxide films. To study this effect an apparatus is used with which normal force and tangential microdisplacement are applied between a small lead rider and a gold flat with various surface film conditions. Under nonoxidized and nonlubricated conditions, and with either oxide or stearic acid lubricant film alone, friction is high and contact resistance is low. With oxide and lubricant together, friction is much lower and slide is smooth, but contact resistance remains low and Ohm's law is obeyed. The results are consistent with Greenwood's theory of contact resistance for a cluster of minute metallic contact spots within the load-supporting area. The contact resistance of such a cluster is indistinguishable, for practical purposes, from that given by complete metallic contact.

Campbell, W. E.↗

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

Klettlinger, Jennifer Lindsey Suder↗

Effect of particle size on the chemisorption and decomposition of carbon monoxide by palladium and nickel clusters

The chemisorption of gases on well-defined, supported metal particles is a model for basic processes in heterogeneous catalysis. In this study, the chemisorption and decomposition of carbon monoxide on palladium and nickel particles was examined as a function of particle size. Particulate films with average particle sizes ranging from 1 to 10 nm were grown by vapor deposition on UHV-cleaved mica. Successive CO adsorption-desorption cycles resulted in the accumulation of carbon on the particles, which suppressed CO adsorption. The rate of carbon accumulation was strongly dependent on particle size and was higher for Ni than for Pd over the same size range. Carbon was removed from both metals by oxygen treatments at elevated temperatures. However, a mixture of CO and O2 was effective for monitoring the removal of carbon from palladium.

Doering, D. L.↗

Evidence for a Significant Intermediate-Age Population in the M31 Halo from Main Sequence Photometry

We present a color-magnitude diagram (CMD) for a minor-axis field in the halo of the Andromeda galaxy (M3l), 51 arcmin (11 kpc) from the nucleus. These observations, taken with the Advanced Camera for Surveys (ACS) on the Hubble Space Telescope, are the deepest optical images yet obtained, attaining 50% completeness at m(sub v) = 30.7 mag. The CMD, constructed from approx. 3 x 10(exp 5) stars, reaches more than 1.5 mag fainter than the old main-sequence turnoff. Our analysis is based on direct comparisons to ACS observations of four globular clusters through the same filters, as well as chi square fitting to a finely-spaced grid of calibrated stellar-population models. We find that the M31 halo contains a major (approx. 30% by mass) intermediate-age (6-8 Gyr) metal-rich ([Fe/H] greater than -0.5) population, as well as a significant globular-cluster age (11-13.5 Gyr) metal-poor population. These findings support the idea that galaxy mergers played an important role in the formation of the M31 halo.

Brown, Thomas M.↗

Preparation and analysis of particulate metal deposits

Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.

Poppa, H.↗

On the nature of the globular cluster X-ray sources

It is suggested that the globular cluster X-ray sources can be interpreted in terms of mass shed by evolving postmain-sequence stars in the central regions of the globular cluster and accreting onto a massive (approximately 100-1000 solar masses) central black hole. Tentative indications that support this hypothesis include the high central escape velocities and the distribution of metallicities among the four globular clusters containing luminous X-ray sources. We argue that these X-ray sources cannot be explained as a consequence of the close capture of a nuclear burning star by a compact stellar remnant.

Silk, J.↗

The chronology of the formation of the Galaxy

Recent advances in our understanding of horizontal-branch (HB) stars and in precision CCD photometry make it possible to establish a chronology of the formation of the Galaxy from the fossil record. The Lee et al. HB evolutionary models and the inferred age-metallicity relation of the Galactic globular-cluster system are now strengthened by many pieces of supporting evidence. This provides valuable information regarding the formation chronology of the halo and disk. Moreover, there is strong evidence from RR Lyrae stars that the radial variation in HB morphology observed in the halo continues to the very center of the Galaxy, which suggests that the formation of the bulge and halo was an inside-out process. These two crucial pieces of information are combined to extend the Searle and Zinn picture of halo formation to include the formation of the bulge and disk. The emerging picture is consistent with the idea that galaxies formed as clusters and mergers of many small gas-rich subsystems, rather than by the rapid collapse of single large protogalactic clouds.

Lee, Young-Wook↗

Globular cluster systems as clues to galaxy evolution

We investigate the properties of systems of globular clusters in light of the hypothesis that galaxy mergers play a major role in galaxy evolution. In a previous paper, we presented a model in which the formation of globular clusters occurs during galaxy interactions and mergers. We discussed several predictions of the model, including the existence of young globular clusters in currently merging galaxies and the presence of two or more metallicity peaks in the globular clusters systems of normal elliptical galaxies. Here, we present recent observational evidence which supports both of these predictions and suggests that mergers may have a significant influence on the formation and evolution of galaxies and their globular clusters.

Zepf, Stephen E.↗

A determination of the thick disk chemical abundance distribution: Implications for galaxy evolution

We present a determination of the thick disk iron abundance distribution obtained from an in situ sample of F/G stars. These stars are faint, 15 less than or approximately = V less than or approximately = 18, selected on the basis of color, being a subset of the larger survey of Gilmore and Wyse designed to determine the properties of the stellar populations several kiloparsecs from the Sun. The fields studied in the present paper probe the iron abundance distribution of the stellar populations of the galaxy at 500-3000 pc above the plane, at the solar Galactocentric distance. The derived chemical abundance distributions are consistent with no metallicity gradients in the thick disk over this range of vertical distance, and with an iron abundance distribution for the thick disk that has a peak at -0.7 dex. The lack of a vertical gradient argues against slow, dissipational settling as a mechanism for the formation of the thick disk. The photometric and metallicity data support a turn-off of the thick disk that is comparable in age to the metal-rich globular clusters, or greater than or approximately = 12 Gyr, and are consistent with a spread to older ages.

Gilmore, Gerard↗

IUE observations of the clusters of the Magellanic Clouds

IUE observations of 17 clusters in the Large Magellanic Cloud are presented. The derived ultraviolet colors become progressively redder as the cluster's classification in the scheme of Searle, Wilkinson, and Bagnuolo increases. With the aid of theoretical models of the integrated light of coeval clusters of varying ages, it is shown that the SWB classification is one of increasing age accompanied by decreasing metallicity toward later SWB classes. The behavior of the UV absorption line features in the integrated light of the LMC clusters supports the contention.

Cohen, J. G.↗

The metal-rich globular cluster NGC 6553 - Clump morphology and age

Stellar evolutionary tracks for metal-rich HB stars have been used to construct synthetic population models for the peculiar HB clump in NGC 6553. Although the uncertainties are large, it is possible to derive an age for NGC 6553 in the range 8-13 Gyr, which supports the idea that the disk globular cluster system is younger than the oldest stars in the Galactic halo and bulge.

Demarque, P.↗

The metallicity of M4: Accurate spectroscopic fundamental parameters for four giants

High-quality spectra, covering the wavelength range 5480 to 7080 A, have been obtained for four giant stars in the intermediate-metallicity CN-bimodal globular cluster M4 (NGC 6121). We have employed a model atmosphere analysis that is entirely independent from cluster parameters, such as distance, age, and reddening, in order to derive accurate values for the stellar parameters effective temperature, surface gravity, and microturbulence, and for the abundance of iron relative to the Sun, (Fe/H), and of calcium, Ca/H, for each of the four stars. Detailed radiative transfer and statistical equilibrium calculations carried out for iron and calcium suggest that departures from local thermodynamic equilibrium are not significant for the purposes of our analysis. The spectroscopically derived effective temperatures for our program stars are hotter by about 200 K than existing photometric calibrations suggest. We conclude that this is due partly to the uncertain reddening of M4 and to the existing photometric temperature calibration for red giants being too cool by about 100 K. Comparison of our spectroscopic and existing photometric temperatures supports the prognosis of a significant east-west gradient in the reddening across M4. Our derived iron abundances are slightly higher than previous high-resolution studies suggested; the differences are most probably due to the different temperature scale and choice of microturbulent velocities adopted by earlier workers. The resulting value for the metallicity of M4 is (Fe/H )(sub M4) = -1.05 + or - 0.15. Based on this result, we suggest that metallicities derived in previous high-dispersion globular cluster abundance analyses could be too low by 0.2 to 0.3 dex. Our calcium abundances suggest an enhancement of calcium, an alpha element, over iron, relative to the Sun, in M4 of (Ca/H) = 0.23.

Drake, J. J.↗

Complete Tem-Tomography: 3D Structure of Gems Cluster

GEMS (glass with embedded metal and sulfide) grains in interplanetary dust particles (IDPs) are considered to be one of the ubiquitous and fundamental building blocks of solids in the Solar System. They have been considered to be interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk but the elemental and isotopic composition measurements suggest that most of them have been formed in the protoplanetary disk as condensates from high temperature gas. This formation model is also supported by the formation of GEMS-like grains with respect to the size, mineral assemblage, texture and infrared spectrum by condensation experiments from mean GEMS composition materials. Previous GEMS studies were performed only with 2D observation by transmission electron microscopy (TEM) or scanning TEM (STEM). However, the 3D shape and structure of GEMS grains and the spatial distribution of Fe/FeS's has critical information about their formation and origin. Recently, the 3D structure of GEMS grains in ultrathin sections of cluster IDPs was revealed by electron tomography using a TEM/STEM (JEM-2100F, JEOL). However, CT images of thin sections mounted on Cu grids acquired by conventional TEM-tomography are limited to low tilt angles (e. g., less than absolute value of 75 deg. In fact, previous 3D TEM observations of GEMS were affected by some artifacts related to the limited tilt range in the TEM used. Complete tomographic images should be acquired by rotating the sample tilt angle over a range of more than absolute value of 80 deg otherwise the CT images lose their correct structures. In order to constrain the origin and formation process of GEMS grains more clearly, we performed complete electron tomography for GEMS grains. Here we report the sample preparation method we have developed for this study, and the preliminary results.

Matsuno, J.↗

The age of the galactic disk

The galactic disk is a dissipative structure and must, therefore be younger than the halo if galaxy formation generally proceeds by collapse. Just how much younger the oldest stars in the galactic disk are than the oldest halo stars remains an open question. A fast collapse (on a time scale no longer than the rotation period of the extended protogalaxy) permits an age gap of the order of approximately 10 to the 9th power years. A slow collapse, governed by the cooling rate of the partially pressure supported falling gas that formed into what is now the thick stellar disk, permits a longer age gap, claimed by some to be as long as 6 Gyr. Early methods of age dating the oldest components of the disk contain implicit assumptions concerning the details of the age-metallicity relation for stars in the solar neighborhood. The discovery that this relation for open clusters outside the solar circle is different that in the solar neighborhood (Geisler 1987), complicates the earlier arguments. The oldest stars in the galactic disk are at least as old as NGC 188. The new data by Janes on NGC 6791, shown first at this conference, suggest a disk age of at least 12.5 Gyr, as do data near the main sequence termination point of metal rich, high proper motion stars of low orbital eccentricity. Hence, a case can still be made that the oldest part of the galactic thick disk is similar in age to the halo globular clusters, if their ages are the same as 47 Tuc.

Sandage, Allan↗

Design of Refractory Metal Heat Pipe Life Test Environment Chamber, Cooling System, and Radio Frequency Heating System

A series of 16 Mo-44.5%Re alloy/sodium heat pipes will be experimentally tested to examine heat pipe aging. To support this evaluation, an environmental test chamber and a number of auxiliary subsystems are required. These subsystems include radio frequency (RF) power supplies/inductive coils, recirculation water coolant loops, and chamber gas conditioning. The heat pipes will be grouped, based on like power and gas mixture requirements, into three clusters of five units each, configured in a pentagonal arrangement. The highest powered heat pipe will be tested separately. Test chamber atmospheric purity is targeted at <0.3 ppb oxygen at an approximate operating pressure of 76 torr (.1.5 psia), maintained by active purification (oxygen level is comparable to a 10(exp -6) torr environment). Treated water will be used in two independent cooling circuits to remove .85 kW. One circuit will service the RF hardware while the other will maintain the heat pipe calorimetry. Initial procedures for the startup and operation of support systems have been identified. Each of these subsystems is outfitted with a variety of instrumentation, integrated with distributed real-time controllers and computers. A local area network provides communication between all devices. This data and control network continuously monitors the health of the test hardware, providing warning indicators followed by automatic shutdown should potentially damaging conditions develop. During hardware construction, a number of checkout tests.many making use of stainless steel prototype heat pipes that are already fabricated.will be required to verify operation.

Martin, J. J.↗