Role of metal ion impurities in generation of oxygen gas within anodic alumina

The generation of oxygen gas within an amorphous anodic alumina film is reported. The film was formed by anodizing aluminum, which was first electropolished and then chemically polished in CrO₃-H₃PO₄ solution, in sodium tungstate electrolyte. The procedure results in incorporation of mobile Cr³⁺ species, from the chemical polishing film, and mobile W⁶⁺ species, from the electrolyte, into the amorphous structure. The tungsten species are present in the outer 27% of the film thickness, while Cr⁶⁺ species occupy a thin layer within the tungsten-containing region. Above the Cr³⁺ containing layer, a band develops that contains oxygen bubbles of a few nanometres size. The oxygen is generated by oxidation of O²⁻ ions of the alumina. A mechanism of oxygen generation within the alumina is proposed based on the electronic band structure of the oxide, modified by the Cr³⁺ and W⁶⁺ species, and on the ionic transport processes during oxide growth.     

Terminal composition control of a binary distillation column

Terminal composition control of a pilot scale binary distillation column operated under the control of an IBM 1800 digital computer has been studied for disturbances in feed flow rate. Conventional two point control, whereby the overhead composition is controlled by reflux flow rate and bottom composition by means of steam rate, was demonstrated to be unsatisfactory. Two alternate control systems, namely a noninteracting control system and a ratio control system were evaluated. The noninteracting control system was constructed from a transfer function representation of the distillation column dynamics, determined from a series of on-line pulse tests. The results show that a very significant improvement in the control of both compositions is achieved by using noninteracting control or the ratio control scheme suggested by Rijnsdorp compared to the behavior that results using conventional two point feedback control. However, the control performance obtained using noninteracting control was only marginally better than that using the ratio control scheme.     

Hedgerow species and environmental conditions effects on soil total C and N and C and N mineralization patterns of soils amended with their prunings

An important criterium in selecting species for alley cropping is themineralization pattern of their prunings. This study determined effects of 5years of hedgerow pruning applications on soil organic C and total N at threelocations in Haiti and mineralization patterns from soil amended with theprunings during an incubation using micro-lysimeters. Soils (0–5cm) under 5 hedgerows were collected at each site and analyzed fororganic C and total N. In the laboratory, ground leaves and stems (<1cm diameter) of the hedgerow species were mixed with soil at ratesof 3 and 1.5 Mg ha^–1, respectively, andaerobically incubated in the dark at 25 °C. A non-amended soilwas used as control. Soils were leached to determine mineral N at 1, 3, 7, 14,28, 42, 84 and 120 days of incubation. Evolved CO₂ was measuredfollowing each leaching procedure. At the calcareous site, application ofprunings from Leucaena leucocephala (Lam.) De Wit andDelonix regia (Boj. ex Hook. Raf.) resulted in 23 and 13%higher soil N than the control, respectively, after 5 years. There were nodifferences in total N at the other sites but soil N was highest underLeucaena hybrid and Acaciaangustissima (Mill.) Kuntze, respectively at the basaltic and highelevation sites. Soils under D. regia (calcareous) andA. angustissima and Leucaena hybrid(high elevation) had higher organic C than the respective controls. Carbon andNmineralization and C turnover were highest when soils were amended with leavesof Leucaena diversifolia (Schlecht.) Benth (calcareous andbasaltic soils) and A. angustissima (high elevation) andlowest in non-amended control soils. Stem-amended soils showed differences in Cmineralization for calcareous and high elevation soils whereas N mineralizationwas similar among treatments within sites. Carbon and N mineralization (highelevation soil) correlated positively with N concentrations of leaf prunings.Amendments with leaf prunings increased soil C and N mineralization andturnoverrates, suggesting greater nutrient availability for the crop during a shortperiod than in non-amended control soils.     

Intercorrelations among plasma high density lipoprotein,obesity and triglycerides in a normal population

The interrelationships among fatness measures, plasma triglycerides and high density lipoproteins (HDL) were examined in 131 normal adult subjects: 38 men aged 27–46, 40 men aged 47–66, 29 women aged 27–46 and 24 women aged 47–66. None of the women were taking estrogens or oral contraceptive medication. The HDL concentration was subdivided into HDL_2b, HDL_2a and HDL₃ by a computerized fitting of the total schlieren pattern to reference schlieren patterns. Anthropometric measures employed included skinfolds at 3 sites, 2 weight/height indices and 2 girth measurements. A high correlation was found among the various fatness measures. These measures were negatively correlated with total HDL, reflecting the negative correlation between fatness measures and HDL₂ (as the sum of HDL_2a and_2b). Fatness measures showed no relationship to HDL₃. There was also an inverse correlation between triglyceride concentration and HDL₂. No particular fatness measure was better than any other for demonstrating the inverse correlation with HDL but multiple correlations using all of the measures of obesity improved the correlations. Partial correlations controlling for fatness did not reduce any of the significant correlations between triglycerides and HDL₂ to insignificance. The weak correlation between fatness and triglycerides was reduced to insignificance when controlled for HDL₂. Presented (in part) at the Annual Meeting of the Oil Chemists' Society in St. Louis, MO, May 1978.     

Behavior of the western pine beetle during host colonization

After living ponderosa pines were baited with either female-infested bolts or synthetic pheromones,Dendroctonus brevicomis were caught on sticky screens throughout trapping periods of 15–46 days; however, large numbers of beetles were trapped during only a small portion (5–10 days) of these trapping periods. The most attractive portions of trees attacked contained 3–6 beetles dm², in galleries ca. 2 cm long. Catch increased following addition of males to female-infested bolts, supporting the hypothesis that male-produced frontalin is an attractive pheromone of the western pine beetle. Catch at bolts removed from trees under attack was strongly dependent upon levels of boring activity. We found no evidence of interruption of the response to attractants during host colonization.Coleoptera: Scolytidae. Trade names and commercial enterprises or products are mentioned solely for information and do not constitute endorsement by the U.S. Department of Agriculture or University of California.     

Chemical Defense in the Plant Bug Lopidea robiniae (Uhler)

Secretions from the metathoracic glands (MTG) of the black locust bug, Lopidea robiniae (Uhler) (Heteroptera: Miridae) contained six major compounds, including (E)-2-hexenal, (E)-2-hexen-1-ol, (E)-2-octenal, (E)-2-octen-1-ol (E)-2-heptenal, and (Z)-3-octen-1-ol. Males and females did not differ significantly in the relative compositions of identified compounds. In feeding trials, six bird species [robin (Turdus migratorious), blue jay (Cyanocitta cristata), brown thrasher (Toxostoma rufum), killdeer (Charadrius vociferus), starling (Sturnus vulgaris), and house wren (Troglodytes aedon)] demonstrated feeding aversions towards L. robiniae, implying that black locust bugs are chemically defended. Bugs discharged the liquid contents of their MTG when attacked, thereby producing a strong and distinct odor. Some birds immediately ejected bugs out of their mouth after biting them, suggesting that the MTG secretion was a deterrent.     

Production of Industrially Useful and Renewable p-Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

We report the dehydration and isomerization of renewable perillyl alcohol to industrially useful p-cymene in 91% yield utilizing 2.0 mol% para-toluenesulfonic acid (pTsOH) catalyst at 110 °C as a 3.0 M solution in toluene. Lower reaction temperatures, catalyst loadings, and/or starting concentrations resulted in lower yields of p-cymene as well as longer reaction times. Conversion of perillyl alcohol to p-cymene yielded atom and carbon economies of 88.1% and 100% as well as an E-factor of 2.7, thereby indicating that the process was both green and sustainable. A lower yield of 86% was observed when the reaction was performed neat, but a lower E-factor of 0.4 indicated that neat conditions were more desirable from an environmental perspective. Application of the optimized parameters to 3.0 M solutions of dl-limonene led predominantly to oligomerization (92%) as opposed to dehydroisomerization (5%), which was attributed to the strong Brønsted acidity of pTsOH. In addition, camphene (44%), terpinene isomers (15%), and limonene (14%) were obtained when dehydroisomerization was attempted on 3.0 M solutions of α- and β-pinene, which was once again attributed to the acidity of the catalyst. Oligomerization was strongly favored when dehydroisomerization of dl-limonene, α- and β-pinene was attempted neat. In summary, synthesis of renewable p-cymene was readily achieved from perillyl alcohol with catalytic pTsOH but competing side reactions suppressed yield when dehydroisomerization of dl-limonene, α- and β-pinene was attempted due to the strong Brønsted acidity of the catalyst.     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.     

The early stages of development of α-Al2O3 scales on Fe-Cr-Al and Fe-Cr-Al-Y Alloys at high temperature

The development ofthe oxides on Fe-14%Cr-4%Al, Fe-27%Cr-4%Al, and similar alloys containing 0.008% Y, 0.023% Y, and 0.8% Y has been investigated during the early stages of oxidation in 1 atm oxygen at 1000 and 1200°C. In all cases, a steady-state -Al₂O₃layer is established rapidly, after some initial formation of transient oxides rich in iron and chromium. For the yttrium-free alloys the steady-state situation is achieved more rapidly for the higher chromium-containing alloy and at the higher temperature. The amount of transient oxide formed is also determined by the specimen surface topography since the development of the -Al₂O₃ layer is less rapid at the base of alloy asperities than at a flat alloy-oxide interface. Following establishment of the complete -Al₂O₃layer, the oxide develops a convoluted oxide morphology at temperature, due to high compressive growth stresses in the oxide. These arise following reaction between oxygen ions diffusing inward down the oxide grain boundaries and aluminum ions diffusing outward through the bulk oxide. This results in lateral growth of the oxide and plastic deformation and movement of the alloy in a direction parallel to the alloy-oxide interface. The addition of yttrium to the alloys promotes the selective oxidation of aluminum. Also, the yttrium is incorporated into the growing oxide where it changes the mechanism of growth, reducing the production of the high compressive growth stresses and thus the development of the convoluted oxide morphology.