Kinetics of the Birch reduction

1998 ◽  
Vol 102 (12) ◽  
pp. 1808-1814 ◽  
A. Greenfield ◽  
U. Schindewolf
J. F. DeNatale ◽  
D. G. Howitt

The electron irradiation of silicate glasses containing metal cations produces various types of phase separation and decomposition which includes oxygen bubble formation at intermediate temperatures figure I. The kinetics of bubble formation are too rapid to be accounted for by oxygen diffusion but the behavior is consistent with a cation diffusion mechanism if the amount of oxygen in the bubble is not significantly different from that in the same volume of silicate glass. The formation of oxygen bubbles is often accompanied by precipitation of crystalline phases and/or amorphous phase decomposition in the regions between the bubbles and the detection of differences in oxygen concentration between the bubble and matrix by electron energy loss spectroscopy cannot be discerned (figure 2) even when the bubble occupies the majority of the foil depth.The oxygen bubbles are stable, even in the thin foils, months after irradiation and if van der Waals behavior of the interior gas is assumed an oxygen pressure of about 4000 atmospheres must be sustained for a 100 bubble if the surface tension with the glass matrix is to balance against it at intermediate temperatures.

R. J. Lauf

Fuel particles for the High-Temperature Gas-Cooled Reactor (HTGR) contain a layer of pyrolytic silicon carbide to act as a miniature pressure vessel and primary fission product barrier. Optimization of the SiC with respect to fuel performance involves four areas of study: (a) characterization of as-deposited SiC coatings; (b) thermodynamics and kinetics of chemical reactions between SiC and fission products; (c) irradiation behavior of SiC in the absence of fission products; and (d) combined effects of irradiation and fission products. This paper reports the behavior of SiC deposited on inert microspheres and irradiated to fast neutron fluences typical of HTGR fuel at end-of-life.

Shiro Fujishiro ◽  
Harold L. Gegel

Ordered-alpha titanium alloys having a DO19 type structure have good potential for high temperature (600°C) applications, due to the thermal stability of the ordered phase and the inherent resistance to recrystallization of these alloys. Five different Ti-Al-Ga alloys consisting of equal atomic percents of aluminum and gallium solute additions up to the stoichiometric composition, Ti3(Al, Ga), were used to study the growth kinetics of the ordered phase and the nature of its interface.The alloys were homogenized in the beta region in a vacuum of about 5×10-7 torr, furnace cooled; reheated in air to 50°C below the alpha transus for hot working. The alloys were subsequently acid cleaned, annealed in vacuo, and cold rolled to about. 050 inch prior to additional homogenization

L. J. Chen ◽  
L. S. Hung ◽  
J. W. Mayer

When an energetic ion penetrates through an interface between a thin film (of species A) and a substrate (of species B), ion induced atomic mixing may result in an intermixed region (which contains A and B) near the interface. Most ion beam mixing experiments have been directed toward metal-silicon systems, silicide phases are generally obtained, and they are the same as those formed by thermal treatment.Recent emergence of silicide compound as contact material in silicon microelectronic devices is mainly due to the superiority of the silicide-silicon interface in terms of uniformity and thermal stability. It is of great interest to understand the kinetics of the interfacial reactions to provide insights into the nature of ion beam-solid interactions as well as to explore its practical applications in device technology.About 500 Å thick molybdenum was chemical vapor deposited in hydrogen ambient on (001) n-type silicon wafer with substrate temperature maintained at 650-700°C. Samples were supplied by D. M. Brown of General Electric Research & Development Laboratory, Schenectady, NY.

J. Drucker ◽  
R. Sharma ◽  
J. Kouvetakis ◽  
K.H.J. Weiss

Patterning of metals is a key element in the fabrication of integrated microelectronics. For circuit repair and engineering changes constructive lithography, writing techniques, based on electron, ion or photon beam-induced decomposition of precursor molecule and its deposition on top of a structure have gained wide acceptance Recently, scanning probe techniques have been used for line drawing and wire growth of W on a silicon substrate for quantum effect devices. The kinetics of electron beam induced W deposition from WF6 gas has been studied by adsorbing the gas on SiO2 surface and measuring the growth in a TEM for various exposure times. Our environmental cell allows us to control not only electron exposure time but also the gas pressure flow and the temperature. We have studied the growth kinetics of Au Chemical vapor deposition (CVD), in situ, at different temperatures with/without the electron beam on highly clean Si surfaces in an environmental cell fitted inside a TEM column.

Harry A. Atwater ◽  
C.M. Yang ◽  
K.V. Shcheglov

Studies of the initial stages of nucleation of silicon and germanium have yielded insights that point the way to achievement of engineering control over crystal size evolution at the nanometer scale. In addition to their importance in understanding fundamental issues in nucleation, these studies are relevant to efforts to (i) control the size distributions of silicon and germanium “quantum dots𠇍, which will in turn enable control of the optical properties of these materials, (ii) and control the kinetics of crystallization of amorphous silicon and germanium films on amorphous insulating substrates so as to, e.g., produce crystalline grains of essentially arbitrary size.Ge quantum dot nanocrystals with average sizes between 2 nm and 9 nm were formed by room temperature ion implantation into SiO2, followed by precipitation during thermal anneals at temperatures between 30°C and 1200°C[1]. Surprisingly, it was found that Ge nanocrystal nucleation occurs at room temperature as shown in Fig. 1, and that subsequent microstructural evolution occurred via coarsening of the initial distribution.

R-R. Lee

Partially-stabilized ZrO2 (PSZ) ceramics have considerable potential for advanced structural applications because of their high strength and toughness. These properties derive from small tetragonal ZrO2 (t-ZrO2) precipitates in a cubic (c) ZrO2 matrix, which transform martensitically to monoclinic (m) symmetry under applied stresses. The kinetics of the martensitic transformation is believed to be nucleation controlled and the nucleation is always stress induced. In situ observation of the martensitic transformation using transmission electron microscopy provides considerable information about the nucleation and growth aspects of the transformation.

N. V. Larcher ◽  
I. G. Solorzano

It is currently well established that, for an Al-Ag alloy quenched from the α phase and aged within the metastable solvus, the aging sequence is: supersaturated α → GP zones → γ’ → γ (Ag2Al). While GP zones and plate-shaped γ’ are metastable phases, continuously distributed in the matrix, formation of the equilibrium phase γ takes place at grain boundaries by discontinuous precipitation (DP). The crystal structure of both γ’ and γ is hep with the following orientation relationship with respect to the fee α matrix: {0001}γ′,γ // {111}α, <1120>γ′,γ, // <110>α.The mechanisms and kinetics of continuous matrix precipitation (CMP) in dilute Al-Ag alloys have been studied in considerable detail. The quantitative description of DP kinetics, however, has received less attention. The present contribution reports the microstructural evolution resulting from aging an Al-Ag alloy with Ag content higher than those previously reported in the literature, focusing the observations of γ' plate-shaped metastable precipitates.

Tim Oliver ◽  
Michelle Leonard ◽  
Juliet Lee ◽  
Akira Ishihara ◽  
Ken Jacobson

We are using video-enhanced light microscopy to investigate the pattern and magnitude of forces that fish keratocytes exert on flexible silicone rubber substrata. Our goal is a clearer understanding of the way molecular motors acting through the cytoskeleton co-ordinate their efforts into locomotion at cell velocities up to 1 μm/sec. Cell traction forces were previously observed as wrinkles(Fig.l) in strong silicone rubber films by Harris.(l) These forces are now measureable by two independant means.In the first of these assays, weakly crosslinked films are made, into which latex beads have been embedded.(Fig.2) These films report local cell-mediated traction forces as bead displacements in the plane of the film(Fig.3), which recover when the applied force is released. Calibrated flexible glass microneedles are then used to reproduce the translation of individual beads. We estimate the force required to distort these films to be 0.5 mdyne/μm of bead movement. Video-frame analysis of bead trajectories is providing data on the relative localisation, dissipation and kinetics of traction forces.

M. Park ◽  
S.J. Krause ◽  
S.R. Wilson

Cu alloying in Al interconnection lines on semiconductor chips improves their resistance to electromigration and hillock growth. Excess Cu in Al can result in the formation of Cu-rich Al2Cu (θ) precipitates. These precipitates can significantly increase corrosion susceptibility due to the galvanic action between the θ-phase and the adjacent Cu-depleted matrix. The size and distribution of the θ-phase are also closely related to the film susceptibility to electromigration voiding. Thus, an important issue is the precipitation phenomena which occur during thermal device processing steps. In bulk alloys, it was found that the θ precipitates can grow via the grain boundary “collector plate mechanism” at rates far greater than allowed by volume diffusion. In a thin film, however, one might expect that the growth rate of a θ precipitate might be altered by interfacial diffusion. In this work, we report on the growth (lengthening) kinetics of the θ-phase in Al-Cu thin films as examined by in-situ isothermal aging in transmission electron microscopy (TEM).

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