Investigation of iron oxide reduction by TEM

An “environmental cell” located in a high voltage transmission electron microscope has been used to study the reduction of single crystal iron oxides by hydrogen and hydrogen-argon mixtures. The cell enables a direct observation of the solid during reaction, thus permitting the nucleation and growth of solid reaction products to be observed. Hematite was reduced at temperatures in the range 387 to 610°C with gas pressures up to 5.3 kP. Reduction with pure hydrogen was considerably faster than when argon was present. Lath magnetite which rapidly transforms to porous magnetite and thence (more slowly) to porous iron was observed. The reduction of magnetite and of wustite single crystals was observed in the temperature range 300 to 514°C using both hydrogen and hydrogen-argon mixtures at gas pressures up to 6.6 kP. Incubation periods were found for magnetite reduction; during these periods faceted pits formed in the oxide. Iron formed in the early stages was epitaxial with the host magnetite; at later stages the epitaxy was lost and fissures frequently formed in the metal. The morphology of the iron differed between the gas mixtures. Disproportionation accompanied the reduction of wustite, producing intermediate polycrystalline magnetite despite reducing conditions. The disproportionation appeared to be promoted by the reduction reaction. For both oxides, reduction in the hydrogen-argon mixture was slower than in pure hydrogen.     

Some nitrosoamino acids in bacon adipose tissue and their contribution to the total N-nitroso compound concentration

Zusammenfassung Der Gehalt an Nitrosoaminosäuren und ihr Anteil an den Gesamt-N-Nitrosoverbindungen im Fettgewebe von rohem Schinkenspeck wurde untersucht. In 80% der Proben wurde ein Gehalt an Nitrosoaminosäuren von bis zu 0,2 mg/kg festgestellt. Scheinbare Gesamt-N-Nitrosoverbindungen waren in allen Proben in einer Konzentration von 0,4 bis 3,7 mg (N-NO)/kg vorhanden. Die eigentlichen Nitrosoaminosäuren machen nur etwa 1% der scheinbaren Gesamt-N-Nitrosoverbindungen aus. Die Mehrzahl der scheinbaren Gesamt-N-Nitrosoverbindungen im Fettgewebe findet sich im nichtlöslichen Bindegewebe, wobei der verbleibende Rest chloroformlöslich ist.Summary The levels of nitrosoamino acids and apparent total N-nitroso compounds in the adipose tissue of raw bacon have been examined. Nitrosoamino acids were detected in 80% of the samples in levels of up to 0.2 mg/kg. Apparent total N-nitroso compounds were present in all samples in concentrations of between 0.4 and 3.7 mg (N-NO)/kg. Nitrosoamino acids accounted for approximately only 1 % of the apparent total N-nitroso compounds. The majority of the apparent total N-nitroso compounds in the adipose tissue were associated with the insoluble connective tissue fraction, with the remainder present as chloroform soluble species.

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Einige Nitrosoaminosäuren im fettgewebe von Schinkenspeck und ihr anteil an der Konzentration der Gesamt-N-Nitrosoverbindungen

     

Synthesis and activation of Pt nanoparticles with controlled size for fuel cell electrocatalysts

Well-dispersed Pt nanoparticles with controlled size and narrow size distribution were prepared by polyalcohol reduction of platinum acetylacetonate, using oleylamine as a capping agent. The particle size was varied from 3.5 nm to 11.5 nm by decreasing the amount of oleylamine added in the synthesis. Size selection of the as-prepared particles by solvent fractionation yielded nearly monodispersed Pt particles. The as-prepared particles were loaded on a carbon support by physical deposition, but showed no electrocatalytic activity due to the oleylamine bound to the particle surface. The particles were activated for electrocatalysis after heating the particles in air at 185 °C for 5 h, conditions that gave no particle-sintering and no oxidation. Cyclic voltammetry showed that the particles after the heat treatment in air were electrocatalytically active for methanol oxidation. The smaller 3.5 nm and 4.0 nm Pt particles had a higher intrinsic activity for methanol oxidation, but a lower tolerance to CO poisoning, compared with 6.0 nm, 9.5 nm and 11.5 nm particles. CO-stripping results suggest that CO is more easily oxidized on larger Pt particles.     

Butyltin Species and Inorganic Tin in Water and Sediment of the Detroit and St. Clair Rivers

Water and sediment samples from 29 locations in the Detroit and St. Clair rivers were analyzed for the highly toxic tri-n-butyltin (Bu₃Sn⁺) species and for the less toxic di-n-butyltin (Bu₂Sn²⁺) and n-butyltin (BuSn³⁺) species and inorganic tin. In general, locations sampled in the St. Clair River were less contaminated with butyltin species than those in the Detroit River. Inorganic tin and BuSn³⁺ were detected in over 90% of all subsurface water samples, while Bu₂Sn²⁺ and Bu₃Sn⁺ were detected in 45 and 28% of the same samples, respectively. The highest concentration ofBu₃Sn⁺ in subsurface water, 5.9 × 10^?10 mol Sn/L, was at the mouth of the Ecorse River, a tributary of the Detroit River. The three butyltin species and inorganic tin were also detected in 23–46% of all sediment samples. The highest concentrations of Bu₃Sn⁺ in sediment were found close to the mouths of the River Rouge, another tributary of the Detroit River, and the Ecorse River, and were 6.2 × I0^–7 and 1.7 × I0^–7 mol Sn/kg dry weight, respectively, for the top 2 cm of sediment.     

An investigation of the synthesis and thermal stability of poly(dl-lactide)

Summary The synthesis and thermal degradability of poly (DL-lactide) were investigated. Key factors affecting the polymer molecular weight were found to be monomer recrystallization, initiator concentration and the vacuum level during drying/sealing of the polymerization reaction ampoule. It was found that poly (DL-lactide) is thermally unstable above its melting temperature. Monomer recrystallization, polymer precipitation and a low initiator content of the polymer significantly inhibited the rate and extent of thermal degradation.     

Formation of Ketoacids in Ozonated Drinking Water

Three ketoacids; glyoxylic acid, pyruvic acid and ketomalonic acid, were identified in ozonated drinking waters and fulvic acid solutions using gas chromatography-mass spectrometry. It was found that the concentrations of ketoacids were much higher than those of aldehydes in ozonated waters. The significance of ketoacids in finished drinking waters is discussed.     

NONDESTRUCTIVE EXAMINATION OF EPOXY ADHESIVE-BONDED STRUCTURES EXPOSED TO A HUMID ENVIRONMENT: A COMPARISONOF LOW- AND HIGH-FREQUENCY DIELECTRIC MEASUREMENTS

Broadband dielectric measurements (10 -2 to 3 GHz) are reported on the effects of exposure of thick film adhesive-bonded structures to moisture. Measurement of the dielectric properties over a broad frequency range allows identification of water both in voids and as a molecular dispersion in the matrix. Changes in the low frequency region of the dielectric spectrum can be attributed to a combination of processes associated with plasticisation of the adhesive, interfacial polarisation effects, and hydration of the surface oxide layer. The data obtained are complemented by mechanical testing and failure analysis of the bond structure measured as a function of the time of exposure. This study indicates that for thick film adhesives the ageing characteristics are apparently independent of the surface treatment. In one of the joints studied an additional feature is identified which appears to correlate with the premature aging of the joint structure.