Loss of precious metal from Pt-Rh alloy under refractory oxide environments

Loss of precious metals from a Pt-10 wt% Rh alloy was studied at 1300° C in refractory oxides and fused quartz environments. After 60 and 150 h annealings, samples exposed to gaseous environments showed significant weight loss. The surface was attacked and characterized by micron-sized pits, as well as river-like striations. The pits were found to be enriched with silicon and/or aluminium depending upon the heating environment. Laser Raman microprobe identified that the major compound formed in the pits is -cristobalite.Direct solid state contact of Pt-Rh with Al₂O₃ and SiO₂ showed interactions between materials. The interaction was more extensive between Pt-Rh with SiO₂ than with Al₂O₃. On the other hand, no evidence of interaction except pitting and striation was observed on Pt-Rh when exposed to a vapour environment.The presence of pits and striation patterns indicated that refractory oxides attacked Pt-Rh under atmospheric conditions, and gave rise to the weight loss. Calculation of weight loss by an oxidation mechanism shows one to two orders of magnitude lower value than the actual weight loss. A new loss mechanism is proposed and discussed in this article.     

Characterising the energy deposition events produced by trapped protons in low earth orbit

Men and equipment in space vehicles in low earth orbit are exposed to a wide variety of radiations, but the majority of the dose is due to trapped protons, which have energies of the order of 100 MeV and are low LET particles. These high energy particles produce nuclear fragmentation with high LET secondaries that may be responsible for a significant fraction of dose equivalent. In order to understand better the biological effectiveness of this radiation environment, a portable tissue equivalent proportional counter spectrometer has been developed that automatically records the distribution of energy in a small tissue-like site as a function of time. This instrument weighs about 700 g and will be flown on a number of future space shuttle flights.     

Specific heat at constant flux density for a low-κ type II superconductor

The specific heat at constant flux densityC _B was measured to study the thermodynamic properties of the mixed state of a type II superconductor at low reduced temperaturet=T/T _c . The sample was a Pb_0.96Tl_0.04 alloy having =0.97. The results are thatC _B increases nearly linearly withB throughout the mixed state, with a discontinuous jump down to the normal state value at the upper critical field. Att<0.21 a small, positive curvature ofC _B versusB is consistent with Eilenberger's calculations. However, this positive curvature is not consistent with fluxoid interaction models for low flux density. These measurements supplement previous measurements fort<0.5 using isothermal calorimetry on the same sample. Taken together, the two experiments indicate that, at a givenT, the incremental entropy per fluxoid is nearly constant for allB. This result forces some interesting empirical relationships among the parameters that characterize the mixed state.On sabbatical leave from South Dakota School of Mines and Technology, Rapid City, South Dakota.     

Hysteresis effects with ZrO2 oxygen sensors exposed to non-equilibrium oxygen-hydrocarbon mixtures

Hysteresis effects are reported for ZrO₂ oxygen sensors exposed to non-equilibrium oxygen/hydrocarbon gas mixtures. With oxygen/toluene at 800° C, voltage-composition curves differ following composition changes (a) from excess oxygen to excess toluene and (b) from excess toluene to excess oxygen. A catalysis model is developed to account for this behaviour: the Thiele modulus of the catalyst/electrode is presumed to differ under (a) net oxidizing and (b) net reducing conditions. Large scale voltage fluctuations, sometimes exceeding 400 mV, were observed in experiments with oxygen/isobutane mixtures at 600° C. This behaviour is analysed in terms of a kinetic model involving stochastic variations of relative mass transfer coefficients of oxygen and isobutane.     

Diffusion-controlled adsorption processes

Numerical solutions of differential equations for diffusion-controlled adsorption processes in spherical particles are presented for slow diffusion of gaseous molecules followed by rapid adsorption according to the Langmuir isotherm. As the parameter in the denominator of the Langmuir equation is increased the rate increases and the generalized rate curves shift progressively from that for the linear isotherm, the Langmuir parameter = 0, to the curve of the parabolic law. Adsorption and desorption cycles are considered and parameters are provided for relating any of these processes to the generalized curves. A simple linear equation was shown to approximate the rate curves with moderate accuracy.     

Decomposition of sec-butyl acetate on charcoal

The decomposition of sec-butyl acetate on de-ashed 20-to 30-mesh coconut-shell charcoal (1500 m²/g) was studied in a fixed bed reactor in the temperature range 300–375°C, and at partial pressures of 1 atm. and 0.29 atm. The ester decomposed principally to n-butene and acetic acid, and only small amounts of other products were found. The ratio of 1-butene to 2-butene was about 1:1, very close to that observed for thermal decomposition of the ester but far removed from the equilibrium butene ratio. The butene selectivity was independent of conversion. The rate of reaction followed the rate equation r = kA P_E/1 + AP_E This expression corresponds to surface reaction on one site being rate controlling. The activation energy of rate constant k was 32.7 kcal/mole, compared to 46.6 kcal/mole for the gas-phase reaction. The temperature dependence of adsorption constant A showed a heat adsorption of 12 kcal/mole. Gas chromatographic measurements confirmed this value and also showed that ester is the principal adsor-bate on the charcoal.     

Influence of molecular weight and molecular weight distribution on the tensile properties of amorphous polymers

Tensile property data for polystyrene samples of varying polydispersity are correlated with various parametric measures of molecular weight. Traditional measures of molecular weight, such as M?_n, M?_w, and M?_z, are shown to be unable to account for the variation of tensile properties with molecular weight. However, a new molecular weight parameter, termed the failure property parameter, is able to provide a single relationship between tensile strength and the parameter for both the broad and narrow distribution polymers. The form of this parameter is consistent with its having origins in the view that it is the entanglement network in an amorphous polymer that provides the observed strength properties. Specifically for polystyrene, the failure property parameter results indicate that material below 60,000 molecular weight does not contribute to polymer strength. Although the results of this investigation are specifically for polystyrene, the arguments used to develop the failure property parameter are not dependent on polymer chemical structure. Consequently, we believe that both the concepts and definition of this new parameter are applicable to all amorphous polymers.     

Undercooling,Freezing Point Depression,and Ice Nucleation of Soil Water

Certain aspects of the phenomena of undercooling and ice nucleation in soils are discussed with respect to recently established properties of phase boundary water in soils. Nucleation temperature as a function of water content is given for representative clays. In view of the fact that silicate surfaces seem always to be separated from ice by an interfacial layer of unfrozen, liquid like water a new concept of heterogeneous nucleation is outlined. It is proposed that ice nucleation occurs in the undercooled interfacial water layer at some distance removed from the particle surfaces. This concept, in effect, suggests that heterogeneous nucleation (nucleation of ice due to the influence of a substrate) in all its essential aspects may be only a special case of homogeneous nucleation (no substrate present) of water.