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At least 235 records · Page 13

Impurity color centers in quartz and trapped electron dating - Electron spin resonance, thermoluminescence studies.

Investigation of impurity-related electron-hole traps that are known to be sensitive to ionizing radiations. Electron spin resonance (ESR) equivalent natural doses were determined for the Al hole trap in virgin specimens; the doses agreed with estimates based on published data for the Ge electron trap. The 0.17 deg/sec 180 and 300 C thermoluminescence (TL) peaks in natural specimens were found to have activation energies approximately correct for the Ge trap. The 300 C peak was also found to be correlated with annealing of the Ge electron resonance in gamma-irradiated, step-annealed specimens. Although the 300 C peak occurs in virgin specimens, the corresponding natural Ge electron resonance was not observed.

Mcmorris, D. W.↗

Mechanism of the oxidation of titanium disilicide.

Study of the oxidation of TiSi2 at temperatures of 300 to 1300 C. Wafers prepared using the techniques of powder metallurgy had densities of 95 to 98% of the theoretical value. On oxidation at temperatures up to 600 C, the polished wafers formed a protective, titania-silica glass. The rate data indicate a complex surface and diffusion-limited mechanism. Above 600 deg C, the oxide consisted of an amorphous SiO2 film with crystalline islands of TiO2 (rutile). From 1000 to 1300 C, parabolic kinetics with an activation energy of 21.3 kcal/mole were observed. These data are consistent with a model in which the rate-determining step is the diffusion of oxygen through the silica film with the simultaneous diffusion of titanium from the substrate to the islands of rutile growing on top of the amorphous silica.

Schwettmann, F. N.↗

Annealing effects in plated-wire memory elements. I - Interdiffusion of copper and Permalloy.

Results of investigations using X-ray diffraction and electron-beam microprobe techniques have shown that copper and Permalloy platings interdiffuse at low temperatures when plated-wire memory elements are annealed for times as short as 50 hr. Measurable interdiffusion between Permalloy platings and gold substrates does not occur in similar conditions. Both magnetic and compositional changes during aging are found to occur by a thermally activated process with activation energies around 38 kcal/mol. It is shown, however, that copper-diffusion and magnetic-dispersion changes during aging are merely concurrent processes, neither being the other's cause.

Knudson, C. I.↗

High-pressure liquid-monopropellant strand combustion.

Examination of the influence of dissolved gases on the state of the liquid surface during high-pressure liquid-monopropellant combustion through the use of a strand burning experiment. Liquid surface temperatures were measured, using fine-wire thermocouples, during the strand combustion of ethyl nitrate, normal propyl nitrate, and propylene glycol dinitrate at pressures up to 81 atm. These measurements were compared with the predictions of a variable-property gas-phase analysis assuming an infinite activation energy for the decomposition reaction. The state of the liquid surface was estimated using a conventional low-pressure phase equilibrium model, as well as a high-pressure version that considered the presence of dissolved combustion-product gases in the liquid phase. The high-pressure model was found to give a superior prediction of measured liquid surface temperatures. Computed total pressures required for the surface to reach its critical mixing point during strand combustion were found to be in the range from 2.15 to 4.62 times the critical pressure of the pure propellant. Computed dissolved gas concentrations at the liquid surface were in the range from 35 to 50% near the critical combustion condition.

Faeth, G. M.↗

Diffusion in the system K2O-SrO-SiO2. II - Cation self-diffusion coefficients.

The self-diffusion coefficients were measured by introducing a slab of glass previously irradiated in a reactor between two slabs of unirradiated glass. By heating the specimens, etching them sequentially and determining the radioactivity, self-diffusion coefficients for K and Sr were measured. It is pointed out that the results obtained in the investigations appear to support the proposal that the network of the base glass predominantly controls the activation energy for the diffusion of ions.

Varshneya, A. K.↗

Short-time oxidation of zirconium.

Study of zirconium oxidation kinetics for maximum exposure times of 3 min and in the temperature range 440 to 850 C. 'Discontinuous' oxidation runs were employed whereby a specimen was inserted into the gas stream for a predetermined time, removed and weighed, and reinserted into the oxidation atmosphere. It is considered that the increase in the observed activation energy for the early stage parabolic oxidation is a manifestation of a change from an n-type oxide to a predominantly p-type oxide, in agreement with the authors' earlier conclusion (1971) based on pressure effects.

Srivastava, L. P.↗

Abnormal grain growth in TD-nickel.

Characteristics of the coarse grain transformation occurring in TD-nickel 1 in. bar under certain conditions of deformation and annealing were examined. The transformation exhibits Avrami-type kinetics, with an activation energy of 250 kcal per mole. Characteristics of untransformed regions are like those of the as-received state. The transformed grain size increases with increasing deformation and decreasing annealing temperature. The coarse grain transformation is significantly different from primary recrystallization in pure nickel. Its characteristics cannot be rationalized in terms of primary recrystallization concepts, but may be explained in terms of an abnormal grain growth description. The coarse grain transformation in TD-nickel is abnormal grain growth rather than primary recrystallization. The analysis suggests an explanation for the effect of thermomechanical history on the deformation and annealing behavior of TD-nickel.

Petrovic, J. J.↗

The creep properties of dispersion-strengthened silver-gallium oxide alloys.

Steady-state creep rates were measured for two preparations of a dispersion-strengthened alloy of silver with 1 mol % gallium oxide. One preparation, an internally-oxidized type, had a grain size 40 times that of the other preparation, which was a consolidated-powder type of alloy. The temperature and stress dependence of the steady-state creep rate differs widely for the two alloys and must be attributed to the difference in grain size. The activation energy for steady-state creep of the internally-oxidized coarse grained material is near that for self-diffusion of silver, which strongly indicates a creep process controlled by dislocation climb.

Lenel, F. V.↗

Gaseous hydrogen-induced cracking of Ti-5Al-2.5Sn.

Study of the kinetics of hydrogen-induced cracking in the Ti-5Al-2.5Sn titanium alloy, which has a structure of acicular alpha platelets in a beta matrix. The crack-growth rate at low stress-intensity levels was found to be exponentially dependent on stress intensity but essentially independent of temperature. The crack-growth rate at intermediate stress-intensity levels was found to be independent of stress intensity but dependent on temperature in such a way that crack-growth rate was controlled by a thermally activated mechanism having an activation energy of 5500 cal/mole and varied as the square root of the hydrogen pressure. The crack-growth rate at stress-intensity levels very near the fracture toughness is presumed to be independent of environment. The results are interpreted to suggest that crack growth at high stress intensities is controlled by normal, bulk failure mechanisms such as void coalescence and the like. At intermediate stress-intensity levels the transport of hydrogen to some interaction site along the alpha-beta boundary is the rate-controlling mechanism. The crack-growth behavior at low stress intensities suggests that the hydrogen interacts at this site to produce a strain-induced hydride which, in turn, induces crack growth by restricting plastic flow at the crack tip.

Williams, D. P.↗

Selection and preliminary evaluation of three structures as potential solid conductors of alkali ions: Two hollandites, a titanate, and a tungstate

Utilization of crystal-chemical criteria has suggested three structure types in which alkali ions may be mobile: (1)hollandites K(x)Mg(x/2)Ti(8-x/2)O16 and K(x)Al(x)Ti(8-x)O16 for 1.6 less than or equal to x less than or equal to 2.0 tungstate K2W4013; and (3) sodium hexatitante Na2Ti6O13. Each is a tunnel structure. An electrical screening procedure, previously tested on beta-alumina, has indicated high K(+) ion mobility in the hollandites and in the tungstate, but not in the hexatitanate. Specimens were polycrystalline disks near 90 percent of theoretical density. The ac conductivity calculated from dielectric and capacitance measurements has been attributed to ion mobility. This ac conductivity was up to 0.01/ohm-cm for hollandites and about 0.0001/ohm-cm for the tungstate, with approximate activation energies of 21 to 25 and 16 kJ/mole (5 to 6 and 4 kcal/mole), respectively. Electronic conduction and chemical reactivity have eliminated the tungstate from further consideration. The hollandites have been considered worthy of further development and evaluation.

Singer, J.↗

Rate of reaction between molecular hydrogen and molecular oxygen

The shock tube data of Jachimowski and Houghton were rigorously analyzed to obtain rate constants for the candidate initiation reactions H2 + O2 yields H + HO2, H2 + O2 yields H2O + O, and H2 + O2 yields OH + OH. Reaction (01) is probably not the initiation process because the activation energy obtained is less than the endothermicity and because the derived rates greatly exceed values inferred in the literature from the reverse of reaction (01). Reactions (02) and (03) remain as possibilities, with reaction (02) slightly favored on the basis of steric and statistical considerations. The solution of the differential equations is presented in detail to show how the kinetics of other ignition systems may be solved.

Brokaw, R. S.↗

Some current problems in oxidation kinetics

Experimental data in low temperature and high temperature oxidations are examined from the point of view of reported quantitative inconsistencies. Activation energies for tBuO2 metathesis reactions with alkanes appear to be 7 kcal/mole higher than for comparable reactions of HO2. Related isomerization reactions are examined in the light of these differences without reaching any simple conclusions. The Russell mechanism for a 6-membered, cyclic, transition state for termination of primary and secondary alkyl peroxy radicals is shown to be either inconsistent with thermochemical data, or else unique to solution reactions. Addition reactions of O3 with olefins and acetylenes are shown thermochemically to have the possibility of following concerted and biradical pathways, respectively. Recent data showing strong inhibition by PbO coated surfaces of both oxidation and pyrolysis of i-C4H10 are examined in terms of mechanism.

Benson, S. W.↗

Perturbation of the Maxwellian distribution in chemically reacting gas mixtures

Chemically reacting gas mixtures are considered for the case in which inelastic collisions occur significantly less frequently than elastic ones. The first approximation of the general solution of the Boltzmann equation is developed and is shown to contain an additional scaler term. The concentration, the mean mass velocity, and the temperature of the mixture are determined and the rate of reaction in the first approximation is formulated. Tables are presented which give reaction rate values obtained by both the first and second approximation for different activation energies. The tables show that the first approximation is sufficient for practical purposes for calculating the reaction rate.

Alekseyev, B. V.↗

O(minus 2) grain boundary diffusion and grain growth in pure dense MgO

Grain growth behavior in fully dense compacts of MgO of very high purity was studied, and the results compared with other similar behaving materials. The activation energy for the intrinsic self-diffusion of Mg(2minus) is discussed along with the grain boundary diffusion of O(2minus). Grain boundary diffusion of O(2minus) is proposed as the controlling mechanism for grain growth.

Kapadia, C. M.↗

Viscous flow behavior of lunar compositions 14259 and 14310.

The flow characteristics of lunar compositions 14310 and 14259 have been determined over a wide range of viscosity. The temperature ranges covered by the measurements are 1270 to 1440 C and 700 to 825 C for the 14310 composition and 1154 to 1431 C and 700 to 820 C for the 14259 composition. Reliable data could not be obtained over the intermediate ranges of temperature because of the occurrence of crystallization. The apparent activation energies for viscous flow in the high-temperature and low-temperature regions are respectively about 60 and 160 kcal/gm at for the 14310 composition and 60 and 170 kcal/gm at for the 14259 composition.

Cukierman, M.↗

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

Mccallister, R. H.↗

Hydrogen evolution in nickel-water heat pipes.

A study was made of the evolution of hydrogen gas in nickel-water heat pipes for the purpose of investigating methods of accelerated life testing. The data were analyzed in terms of a phenomenological corrosion model of heat pipe degradation which incorporates corrosion and oxidation theory and contains parameters which can be determined by experiment. The gas was evolved with a linear time dependence and an exponential temperature dependence with an activation energy of 1.03 x 10 to the minus 19th joules. A flow-rate dependence of the gas evolution was found in the form of a threshold. The results were used to predict usable lifetimes of heat pipes operated at normal operating conditions from results taken under accelerated operating conditions.

Anderson, W. T.↗

Estimation of rate constants of elementary processes - A review of the state of the art.

'Thermochemical kinetics,' the codification and extrapolation of empirical observations, as applied to certain elementary reactions of importance to combustion studies, is described. This approach allows the critical scrutiny of experimental data in areas where sufficient previous data exist, while, at the same time, illuminating those key areas where more experimentation is crucial. It is shown that combination of transition-state theory with an understanding of the molecular basis of entropy puts fairly rigid constraints on the values of the Arrhenius A-factor for most reactions. This, in turn, means that the activation energy is often the key datum that is missing, and that such data can be obtained with some degree of confidence, even from measurements of rate constants at only one temperature. In complex mechanisms, it is often possible to distinguish among alternate pathways and pinpoint key processes.

Golden, D. M.↗