The removal of radioactive caesium contaminants from simple aqueous solutions

Cs ions can be removed from aqueous solutions by forming a precipitate of copper ferrocyanide which, having occluded the Cs ions, can in turn be floated by means of an anionic collector. Collection was achieved with either α-sulphopalmitic acid or sodium dodecyl sulphate depending on what interfering ions were initially present in the solution. Recoveries of 98–99% were obtained on batch scale experiments and 97.5–98.5% on continuous scale operation. The investigations of the flotation parameters of pH, gas-rate, concentrations of precipitating reagents and collector, as well as the interference effects of other ions are discussed. Using data obtained in batch scale tests, continuous scale experiments were designed and operated.     

A MECHANISTICALLY BASED MATHEMATICAL MODEL OF SULFUR DIOXIDE ABSORPTION INTO A CALCIUM HYDROXIDE SLURRY IN A SPRAY DRYER

A mathematical model has been developed to predict So₂ absorption and removal during the constant rate drying period of a spray dryer. The model, based on film theory, treats the atomized slurry droplets as spheres containing discrete sorbent particles of slaked lime with the fluid uniformly distributed around the individual particles. The model includes gas and liquid phase mass transfer coefficients as well as resistance to Ca(OH)₂ dissolution. A sensitivity analysis has been conducted and a comparison was made between pilot-scale experimental data and model-predicted values of S0₂ removal efficiency.     

Particle size analysis by automatic siever

Automation of the wet sieving process in an instrument for particle size analysis is described. A powder is consecutively subjected to three sieves of any selected meshes from 38 μm up and the resulting fractions are collected individually, including both the undersize and oversize, in a submerged filter. The initial filter weight and the weights of all collected fractions are determined separately and stored in the microcomputer memory. Upon completion of an analysis, the sieved fraction weights are recalled, the total sample weight is calculated, and results are presented as weight per cent. Completion of each sieving step is established by filter weight constancy according to prearranged programming. Upon completion of an analysis, the system backwashes the filter and re-establishes conditions for the next analysis. Tests for accuracy with a standard material and repeated testing for short and long-term reproducibility are included. Applicability to a variety of powders is demonstrated.     

EVAPORATION FROM POROUS MEDIA: A CAPILLARY MODEL OF A PENETRATING FRONT

A capillary tube model was solved to investigate the influence of mass transfer coefficient, temperature, and front depth on the evaporation rate during the penetrating-front period of water-filled porous media dried in hot air. The results show that increasing the flow rate of the drying air is not so efficient as increasing the sample temperature. Due to attenuating diffusion rate, the rate of liquid front migration decreases with time. The calculations explain the falling rate period behavior of sandstone heated at 121°C. Trends depicted by the model may be useful for the design of heating conditions for drying processes.     

Fiber Coating Concepts for Brittle-Matrix Composites

The current interest in tough, high-temperature materials has motivated fiber coating development for brittle-matrix composites with brittle reinforcements. Such coatings are needed for controlled interface debonding and frictional sliding. The system investigated in this study was sapphire fiber-reinforced alumina. This system is thermochemically stable for severe use conditions, exhibits little thermal expansion mismatch, and utilizes the excellent strength and creep resistance of sapphire reinforcements. Porous oxide and refractory metal coatings which satisfy requirements for toughness improvement in these composites were identified by employing a variety of newly developed mechanical testing techniques for determining the interfacial fracture energies and sliding resistances.     

Fischer–Tropsch synthesis: Deactivation of promoted and unpromoted cobalt–alumina catalysts

The loss in activity of Pt-promoted and unpromoted 25 wt% Co–Al₂O₃ catalysts has been compared under identical conditions except for adjustment of the space velocity to give the same initial CO-conversion. Both catalysts underwent a 200 h period of rapid, initial decline in CO conversion and then a slower, linear decline during the next 1000 h. Pt-promotion did not alter the cobalt dispersion (or average particle size) from that of the unpromoted catalyst but did increase the amount of cobalt that was reduced. When compared not by time-on-stream, but by the moles of Co converted per unit weight of catalyst, both the Pt-promoted and unpromoted catalysts decline in activity at the same rate.     

Platinum-group metal cyclodextrin complexes and their use as command-cure catalysts in silicones

The Command-Cure concept is defined for a curable formulation as one with long work-like at ambient temperature and rapid cure time at elevated temperature. This concept is explored for a curable silicone system, cured via hydrosilylation. CODMCl₂ complexes (COD=1.5-cyclo-octadiene:M=Pt. Pd) are reacted with beta-cyclodextrin (-CD) to make 11 inclusion compounds,M=Pd.2;M=Pt.4. Compounds2 and4 were analyzed by¹H NMR and X-ray powder diffraction. Their catalytic ability was evaluated in a model system as well as a polymeric system that gels upon cure. Surprisingly, the Pd analog2 was a good command-cure catalyst whereas the guest compound CODPdCl₂,1, was not active in the hydrosilylation reaction. The Pt analog,4, was an effective command-cure catalyst while the corresponding guest. CODPtCl₂,3, was too active at low temperature in the hydrosilylation reaction. Additional Pt compounds and one Rh inclusion compound were evaluated as command cure catalysts. These inclusion compounds were: 11 -CD:[CODRhCl]₂,5: 11 -CD:CpPtMe₃,6 (Cp=cyclopentadienyl): 12 -CD:MeCpPtMe₃,7; 12 -CO:CODPtMe₂,8. The effectiveness of4 8 was evaluated in a number of silicone systems.     

Aging behavior of a hot‐cured epoxy system

The thermal and hydro‐thermal aging of a hot‐cured epoxy system (diglycidylether of bisphenol A (DGEBA) + dicyandiamide (DDA)) in the glassy state is revisited using DSC and IR attenuated total reflection spectroscopy. Because of the diffusion of DDA from the solid particles into the liquid DGEBA matrix, curing produces a highly crosslinked amorphous matrix that contains low crosslinked amorphous regions. After full curing, the network possesses a relatively low molecular mobility and no residual reactive groups. Thermal and hydro‐thermal loading is performed at 60°C, well below the principal glass transition temperature (T_g1 = 171°C). Both aging regimes cause significant chemical and structural changes to the glassy epoxy. It undergoes a phase separation of relatively mobile segments inside the low mobile matrix, providing a second glass transition that shifts from T_g2 = 86–114°C within 108 days of aging. This phase separation is reversible on heating into the viscoelastic state. Hydro‐thermal aging leads to a reversible and a nonreversible plasticizing effect as well. On thermal aging, no chemical changes are observed but hydro‐thermal aging causes significant chemical modifications in the epoxy system. These modifications are identified as a partial degradation of crosslinks produced by the cyano groups of the DDA and correspond to the nonreversible plasticitation. These changes in the cured epoxy should exert an influence on the mechanical properties of an adhesive bond. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Ammonia Decomposition on Ir(100): From Ultrahigh Vacuum to Elevated Pressures

Ammonia decomposition on Ir(100) has been studied over the pressure range from ultrahigh vacuum to 1.5 Torr and at temperatures ranging from 200 to 800 K. The kinetics of the ammonia decomposition reaction was monitored by total pressure change. The apparent activation energy obtained in this study (84 kJ/mol) is in excellent agreement with our previous studies using supported Ir catalysts (Ir/Al₂O₃ 82 kJ/mol). Partial pressure dependence studies of the reaction rate yielded a positive order (0.9±0.1) with respect to ammonia and negative order (–0.7 ±0.1) with respect to hydrogen. Temperature-programmed desorption data from clean and hydrogen co-adsorbed Ir(100) surfaces indicate that ammonia undergoes facile decomposition on both these surfaces. Recombinative desorption of N₂ is the rate-determining step with a desorption activation energy of 63 kJ/mol. Co-adsorption data also indicate that the observed negative order with respect to hydrogen pressure is due to enhancement of the reverse reaction (NH _x + H NH _x+1, x=0–2) in the presence of excess H atoms on the surface.