Experimental determination of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript>-KNO<Subscript>3</Subscript> binary phase diagram

The solid-state phase transitions in ammonium nitrate (AN)-potassium nitrate (KN) system, and the equilibrium AN-KN phase diagram have been determined by using differential scanning calorimetry and high-temperature in situ x-ray diffractometry. Sample preparation was performed in a special “dry room” with very low humidity. A single phase region (AN III) with no phase transitions to 373 K was observed in the composition range 5 to 20% KN; this is critical for use in air bag gas generators. The high-temperature KN phase (KN I) has a wide range of stability from 20 to 100 wt.% KN. There are one eutectic, two eutectoid, three peritectoid, and one congruent transformations in this phase diagram. Two new nonstoichiometric phases were found at lower temperatures in the mid-composition range between the AN and KN terminal solid solutions. Details of the phase equilibria are presented.     

Synthesis method comparison of compositionally complex rare earth-based Ruddlesden–Popper n = 1 T′-type cuprates

The multicomponent approach has been successfully expanded to the Ruddlesden–Popper structure with the synthesis of two different high-entropy cuprate compositions: (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ and (La_0.2Pr_0.2Nd_0.2Sm_0.2Eu_0.2)₂CuO₄. The effect of synthesis method is explored using both solid-state reaction and polymeric steric entrapment (PSE) methods. It is found that PSE leads to more randomly distributed cation species, providing an advantageous method of synthesis for the growing field of high entropy oxides. In situ high-temperature x-ray diffraction tracks the amorphous to crystalline phase transformation in (La_0.2Nd_0.2Gd_0.2Tb_0.2Dy_0.2)₂CuO₄ powder, synthesized using the PSE method. Using the High-Temperature XRD data, a method for gaining information on the kinetic behavior is also applied. Magnetometry of both compositions indicates ferrimagnetic behavior at low temperatures.     

Fiber optic sensing technology for detecting gas hydrate formation and decomposition

A fiber optic-based distributed sensing system (DSS) has been integrated with a large volume (72 l) pressure vessel providing high spatial resolution, time-resolved, 3D measurement of hybrid temperature-strain (TS) values within experimental sediment-gas hydrate systems. Areas of gas hydrate formation (exothermic) and decomposition (endothermic) can be characterized through this proxy by time series analysis of discrete data points collected along the length of optical fibers placed within a sediment system. Data are visualized as an animation of TS values along the length of each fiber over time. Experiments conducted in the Seafloor Process Simulator at Oak Ridge National Laboratory clearly indicate hydrate formation and dissociation events at expected pressure-temperature conditions given the thermodynamics of the CH(4)-H(2)O system. The high spatial resolution achieved with fiber optic technology makes the DSS a useful tool for visualizing time-resolved formation and dissociation of gas hydrates in large-scale sediment experiments.     

Dimensional changes and creep of silica core ceramics used in investment casting of superalloys

Dimensional changes and creep deformation of a silica/zircon (74%/24%, respectively) and a high silica (93% silica and 3% zircon) ceramic were characterized and compared. All specimens were tested with a thermal profile that consisted of a 300°C/h heating rate to 1475 or 1525°C, followed by a one-hour isothermal hold (where each specimen was compressively crept under a static stress of 2.07, 4.14, or 6.21 MPa). The specimens were cooled at a rate of 900°C/h under stress. Dimensional changes were interpreted from apparent thermal expansion behavior during heating as well as before-and-after dimensional measurements. The silica/zircon ceramic generally exhibited less total contraction than the high silica ceramic for a specific test condition even though it crept faster at all stresses and temperatures during the one-hour isothermal/isostress segment. This indicates that the total contraction for both was dominated by reinitiated sintering and subsequent cristobalite formation that occurred during the heating segment. Minimum creep rate during the one-hour isothermal/isostress segment was examined as a function of stress and temperature for both ceramics using a power-law creep model. Creep-rate stress exponents (n) and activation energies (Q) were equivalent (within 95% confidence) for both ceramics showing that their different contents of zircon (3 vs. 24%) did not affect them. Lastly, n 1.3–1.4 and Q 170 kJ/mol indicate that diffusion-assisted crystallization of cristobalite, combined with power-law sintering owing to the high concentration of porosity (28–30%) was likely the rate-limiting mechanism in the creep deformation for both ceramics.     

Variability in captan residues in apples from a Canadian orchard

Apple trees in an orchard in Quebec, Canada were treated, following label directions, with the fungicide captan (1,2,3,6-tetrahydro-N-(trichloromethylthio)phthalimide) during the 2003 agricultural season. A total of 142 apples from three rows of trees were selected for determination of captan by GC/MS. Individual apples were found to contain captan levels ranging from 16.9 to 6350 ng g^-1. Only two individual apple samples exceeded the Canadian maximum residue limit (5000 ng g^-1) for captan in apples. Six composite samples, comprising half portions of eight individual apples, were analysed from each of the three experimental rows. Composite samples ranged in concentration from 166 to 2620 ng g^-1. The greatest uncertainty associated with the measured concentrations was due to variability among apples rather than the measurement of residue levels.     

Canadian Total Diet Study in 1998: pesticide levels in foods from Whitehorse, Yukon, Canada, and corresponding dietary intake estimates.

The Canadian Total Diet Study is a national survey to determine the level of chemical contaminants in the Canadian food supply. Food samples were collected from Whitehorse, Yukon, supermarkets as part of the study in 1998. Whitehorse was chosen as a sampling centre, despite its small population (n = 19,000), to determine if residue levels were different in foods available in northern communities relative to levels observed in previous studies in the more populated south. Foods were prepared as for consumption before pesticide residue analysis. Residue levels observed in most foods were similar to levels observed in samples from previous surveys from southern Canadian cities. Malathion and DDE (1,1-dichloro-2,2-bis(p-chlorophenyl)ethylene), a transformation product of DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl(ethane), were the two most frequently detected compounds (26.4 and 25.8%, respectively). The majority of pesticides, however, had a detection frequency of < 5%. In general, pesticides in food composites were well below maximum residue limits established in the Canadian Food and Drug Regulations. Chlorpropham and captan had the highest dietary intakes (2.16 and 1.94 micrograms (kg body weight-day)-1, respectively), based on the results from Whitehorse. No dietary intakes above the acceptable daily intakes, however, were observed for any of the 39 pesticides investigated in any age-sex category, where an acceptable daily intake has been proposed.     

Magnetic properties of biosynthesized magnetite nanoparticles

Magnetic nanoparticles, which are unique because of both structural and functional elements, have various novel applications. The popularity and practicality of nanoparticle materials create a need for a synthesis method that produces quality particles in sizable quantities. This paper describes such a method, one that uses bacterial synthesis to create nanoparticles of magnetite. The thermophilic bacterial strain Thermoanaerobacter ethanolicus TOR-39 was incubated under anaerobic conditions at 65/spl deg/C for two weeks in aqueous solution containing Fe ions from a magnetite precursor (akaganeite). Magnetite particles formed outside of bacterial cells. We verified particle size and morphology by using dynamic light scattering, X-ray diffraction, and transmission electron microscopy. Average crystallite size was 45 nm. We characterized the magnetic properties by using a superconducting quantum interference device magnetometer; a saturation magnetization of 77 emu/g was observed at 5 K. These results are comparable to those for chemically synthesized magnetite nanoparticles.     

Phase Equilibria in the Systems CaO–CuO and CaO-Bi2O3

New data are presented on the phase equilibria of the binary systems CaO-CuO and CaO-Bi₂O₃. Corrected compositions are reported for Ca.Bi₆O₁₃ and Ca₂Bi₂O₅ and a new metastable high-temperature phase is reported for a composition near Ca₆Bi₇O_16.5. The composition and decomposition temperatures for Ca_1–x.CuO₂ are given for both air and 1 atm of oxygen at 755 ± 5° and 835 ± 5°C, respectively.     

Phase Equilibria and Crystal Chemistry in the Quaternary System Ba-Sr-Y-Cu-O in Air

Studies in the Sr-Y-Cu-O and Ba-Sr-Y-Cu-O systems have revealed that Sr will substitute for Ba in (Ba,Sr)₂YCu₃O_{6+ x} up to about 60%. There are no ternary compounds in the Sr-Y-Cu-O system equivalent to the three ternary phases in the Ba system. A new binary phase, "Sr₁₄Cu₂₄O₄₁"(CuO ∼ 63.158 mol%), was found which forms a solid solution with Y₂O₃ to a Sr:Y ratio of approximately 2:1. This phase can also incorporate considerable amounts of Ba and Ca and many other large ions.