Behavior of Volatile Elements in the Graphite Furnace in the Presence of Silver as Matrix Modifier

The effect of silver, as an aqueous solution of AgNO₃, on the pretreatment and atomization behaviour of As, Cd, Bi, Hg, Pb, Sb, Se, Sn and Tl during electrothermal atomic absorption spectrometry has been investigated. The presence of silver in the graphite furnace leads to thermal stabilisation of all investigated volatile elements to allow higher pyrolysis temperatures. The maximum, loss‐free, pretreatment temperatures (°C) in the presence of 100 µg Ag by atomization from the wall or from a platform are respectively: As (1500°C, –); Cd (800°C, 800°C); Bi (700°C, 700°C); Hg (250°C, –); Pb (600°C, 900°C); Sb (1200°C, 1200°C); Se (1400°C, 1400°C); Sn (1100°C, 1100°C) and Tl (1000°C, 1100°C). Also, silver facilitates a relatively low atomization temperature (°C) from the wall for Cd (1300°C), Bi (1700°C), Pb (1400°C), Se (1900°C) and Tl (1400°C). In addition, silver enhances the measurement sensitivity by a factor of 1.2–1.8.     

Composition of oxide compounds supported on metal meshes when synthesizing catalysts for the oxidation of hydrocarbons

Samples of a woven mesh of metal wire (fechral) with supported aluminum hydroxide compounds are studied. Aluminum hydroxide is formed in its bayerite modification. Aluminum oxides are produced during calcination: η-Al₂O₃ at 600°C, and θ-Al₂O₃ at 900°C. Subsequent modification with silicon, cerium, lanthanum, tungsten, and calcination at the same temperature results in the formation of their oxides. Interaction between alumina and tungsten at 600°C, and alumina and lanthanum at 900°C, are observed.     

Hematite reaction with tar to produce carbon/iron composites for the reduction of Cr(VI) contaminant

In this work, highly reactive carbon–iron composites were prepared using a waste, i.e. tar, as carbon precursor and a simple iron oxide, i.e. hematite. Tar was impregnated on Fe₂O₃ with different tar/hematite weight ratios of 1:1; 2:1 and 4:1, and thermally treated under N₂ atmosphere (400°C, 600°C and 800°C). Mössbauer, XRD and magnetization measurements suggested that treatment at 400°C and 600°C produces Fe₃O₄ but treatment at 800°C produced mainly Fe°. Raman and TG analyses of the different composites suggested the formation of carbon contents of 18, 24 and 32 wt.% as amorphous and graphitic highly dispersed on the Fe surface. The composites obtained at 800°C showed high efficiency to reduce Cr(VI) as CrO $_{4}^{2-}$ in aqueous medium with much better results compared to finely ground commercial Fe°.     

35Cl NQR study of the low temperature transition in ferroelectric (CH3NH3)HgCl3

In addition to the paraelectric-ferroelectric phase transition at T_c = + 62°C there is another low T phase transition in the −152 to −165°C range associated with a sudden change in the NQR spectra.The three ³⁵Cl NQR lines observed in the P3₂ ferroelectric phase of (CH₃NH₃)HgCl₃ below T_c = 62°C suddenly disappear on cooling below −152°C. No lines could be observed between 152 and −165°C. Below this temperature five ³⁵Cl NQR lines appear and remain down to liquid nitrogen temperature.     

Effect of sintering temperature on the elemental diffusion and electrical conductivity of SrTiO<Subscript>3</Subscript>/YSZ composite ceramic

The 50 vol% SrTiO₃/yttria-stabilized zirconia (YSZ) composite ceramic was prepared through powder sintering route in 1400～1500 °C. Only the cubic YSZ and SrTiO₃ phases are detected in all the sintered ceramics, and the typical XRD peak positions of both phases have varied dramatically. The grain sizes and relative densities of all specimens increase evidently with the sintering temperature. The width of the SrTiO₃/YSZ interfacial region increases from 100.4 to 468.8 nm as the sintering temperature rises from 1400 to 1500 °C. The total electrical conductivities of the sample sintered at 1500 °C are remarkably higher than those at 1400 and 1450 °C, while the ion transference numbers drop from 0.837 to 0.731 with sintering temperature from 1400 to 1500 °C. The variations in the electrical properties above can be interpreted based on the effects of sintering temperature on the elemental diffusions during the sintering process.     

Investigation of the phase transitions of ferroelectric KIO3 and KNbO3 crystals by optical diffraction

Optical diffraction is reviewed as a technique for investigation of the phase transitions in crystals with a multidomain structure. It has been used to study the phase transitions in KIO₃ and KNbO₃ single crystals. Strong optical diffraction bands resulted from electric domains in KNbO₃ crystals and their change with temperature were observed when a laser beam passed through the crystals. The diffraction patterns observed changed abruptly at 427°C, 223°C, and -50°C respectively, at which KNbO₃ crystals undergo structural phase transitions. It is considered that the change of the diffraction patterns with temperature is due to change of the electric domains in the crystals.     

Air temperature stabilization in the thermally isolated optical laboratory

For the studies and calibration of optoelectronic components of the high-precision laser based metrology systems the large volume (50 m³) thermoisolated lab based on seismic isolated concrete block is created. The inside lab volume temperature stabilization for the daily observation at 16.5°C is ±0.05°C with ±0.015°C temperature difference between maximal space separated points. This work was initiated by the needs of high-precision alignment of accelerator components of the CLIC, ILC-type colliders.     

Effect of preliminary low-temperature annealing on the kinetics of nucleation

The changes observed in the kinetics of CuCl nucleation in glass due to preliminary low-temperature annealing have been investigated using optical spectroscopy. The influence of the number of nuclei formed at a temperature of 500°C on the growth rate of the CuCl phase at 650°C has been examined. The amount of the CuCl phase in the sample is determined from the optical absorption coefficient in the range of band-to-band transitions in the CuCl nanocrystals. The average radius of CuCl particles is calculated from the position of the maximum of the exciton band. It has been demonstrated that the preliminary formation of CuCl nuclei at 500°C for 3 h makes it possible to increase the growth rate of the CuCl phase by a factor of 6. In the sample with preliminarily formed nuclei, there occur two opposite processes: thermal decomposition of part of the small nuclei, which have become subcritical at 650°C; and the growth of larger nuclei, which have become supercritical at 650°C due to the diffusive inflow of the components of the new phase. When the equilibrium concentration is reached, the new phase contains particles with a smaller radius but at a higher concentration as compared to those in the case of the conventional nucleation at 650°C.     

Nano-SiC implantation into the structure of carbon/graphite materials made by pyrolysis (carbonization) of the precursor system coal tar pitch/poly(dimethylsiloxane)

Conversion of the air-cured poly(dimethylsiloxane) {–O–Si(CH₃)₂–}_n to SiC during co-pyrolysis with a coal tar pitch is studied with reference to the related SiO₂/pitch system. Each binary mixture is first homogenized at 160 °C followed by carbonization at 500 °C under argon to afford initial carbonizates. In both cases, one part of the initial carbonizate is further pyrolyzed at 1300 °C and another part at 1650 °C under an argon flow resulting in composite products. All products are studied with FT-IR, XRD, and XPS spectroscopic methods supplemented with SEM and ‘wet’ Si-analyses, when applicable. Carbothermally assisted conversion of both silicon precursors to nanocrystalline SiC embedded in the evolving C-matrix, i.e. nano-SiC/C composites, is evident only after the 1650 °C carbonization stage.     

Investigation of domain behaviour in 0.7Pb(Mg1/3Nb2/3) O3-0.3PbTiO3 single crystals at different temperatures in the transmission electron microscope

Using transmission electron microscopy, in-situ changes in ferroelastic domains in 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ single crystals were observed at 60 to -163°C. At -163°C, the microscopic tweed morphology of the ferroelastic domains rotated by 90°, and certain orientation changes in the mesoscopic sawtooth domains took place. At this temperature, the ferroelastic domains became coarsened and certain S-shaped mesoscopic domains were reshaped. The disappearance and/or changes in the orientations of both the sawtooth and the ferroelastic domains were reversible upon return to room temperature. On heating to 60°C, both the mesoscopic sawtooth and the microscopic tweed domains were stable below 53°C. Above 53°C, the mesoscopic walls disappeared and the contrast of the tweed domains became blurred. Upon return to room temperature from 60°C, the mesoscopic domain patterns could not be retrieved, indicating that the transformation was irreversible. The morphology of the tweeds at this temperature indicated a structural transition from a two-variant domain state to a multivariant state, eliminating mesoscopic boundaries.     

Differential thermal analysis at high pressures—VII: Phase behaviour of solid methanol up to 3kbar

The phase behaviour of solid methanol was investigated from -196°C to the melting temperature and up to 3 kbar, using a low-temperature high-pressure dta apparatus. The melting temperature rises from -98°C at 1 atm to -64°C at 2775 bar. Solid methanol exhibits a transition at atmospheric pressure at approximately -115°C; the transition has a strong tendency to superheat and to occur at -110°C. The transition temperature rises from approximately -115°C at 1 atm to -81°C at 2725 bar. Small impurities of water induce a “second transition” at -117.3°C that must be attributed to the water-methanol eutectic. Volume changes accompanying the phase transition have been calculated using the Clausius Clapeyron equation.     

A study of the electrical conductivity and transition points of potassium carbonate

The electrical conductivity of K₂CO₃ was measured between 230°C and 840°C in both air and carbon dioxide. The conductivity depends upon the atmosphere because of the decomposition of Na₂CO₃ at the surface of the sample. There exists only one polymorphic transformation at 430°C, which is probably a second-order one. From conductivity measurements carried out on samples doped with CaCO₃, one can derive the migration energy of cation vacancies and the energy of formation of defects.     

Crystal recovery from Al‐implantation induced damaging in 3C‐SiC films

Damaging in Al‐implanted 3C‐SiC and subsequent crystal recovery due to thermal treatments up to 1350 °C are evaluated by X‐ray diffraction and micro‐Raman spectroscopy. Reciprocal space mapping of (004) 3C‐SiC planes shows a low‐intensity implantation‐induced secondary peak at higher interplanar spacing in the as‐implanted 3C‐SiC sample, with a generated misfit between the implanted and the epitaxial region of about 0.6%. Increasing the annealing temperature from 950 °C to 1350 °C, the secondary peak is gradually re‐absorbed within the epitaxial 3C‐SiC reciprocal lattice point. Finally, the disappearance of the secondary peak after a 1350 °C thermal treatment is observed. Thus, implantation‐induced average strain, resulting in a severe 3C‐SiC deforma‐ tion, has been totally relieved at the highest annealing temperature. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Influence of Nitrogen Supply and Temperature on Stable Carbon Isotope Ratios in Plants of Different Photosynthetic Pathways (C3, C4, CAM)

Abstract

One representative species of each of the three photosynthetic pathways (C₃, C₄, CAM) were cultivated in growth chambers with high and low nitrogen nutrition level respectively once at 20°C day/13°C night temperature, once at 30°C day/13°C night. Leaf conductances and δ¹³C values of the leaves of each plant were determined. At 20°C day temperature the C₃ species showed higher leaf conductance with low nitrogen nutrition level than with high nitrogen level, which is also reflected in a more negative δ¹³C value, whereas both C₄ and CAM plants did not respond in this manner to nitrogen supply. An increase of day temperature to 30°C diminished the significant response of the C₃ plant, while the response of C₄ and CAM representatives to nitrogen nutrition did not change markedly.     

Effect of temperature on the synthesis of silver nanoparticles with polyethylene glycol: new insights into the reduction mechanism

Polyethylene glycol (PEG) molecules act as a reducing and stabilizing agent in the formation of silver nanoparticles. PEG undergoes thermal oxidative degradation at temperatures over 70 °C in the presence of oxygen. Here, we studied how the temperature and an oxidizing atmosphere could affect the synthesis of silver nanoparticles with PEG. We tested different AgNO₃ concentrations for nanoparticles syntheses using PEG of low molecular weight, at 60 and 100 °C. At the higher temperature, the reducing action of PEG increased and the effect of PEG/Ag⁺ ratio on nanoparticles aggregation changed. These results suggest that different synthesis mechanisms operate at 60 and 100 °C. Thus, at 60 °C the reduction of silver ions can occur through the oxidation of the hydroxyl groups of PEG, as has been previously reported. We propose that the thermal oxidative degradation of PEG at 100 °C increases the number of both, functional groups and molecules that can reduce silver ions and stabilize silver nanoparticles. This degradation process could explain the enhancement of PEG reducing action observed by other authors when they increase the reaction temperature or use a PEG of higher molecular weight     

Magnetic properties of the nanocrystalline DyMnO3

We report on the X-ray and neutron diffraction and magnetic measurements of the nanosamples of DyMnO₃ annealed at temperatures of 800 °C, 850 °C and 900 °C. The diffraction data indicate that all the samples crystallize in an orthorhombic crystal structure (space group Pnma). The crystal structure parameters change slightly with preparation. All the samples are antiferromagnets at low temperatures. The Mn magnetic moments order near 40 K, while those of Dy below 8.4 K. The macroscopic magnetic and neutron diffraction data indicate a small difference of properties between the DyMnO₃ samples synthesized at different temperatures. The observed broadening of magnetic peaks connected with the Dy sublattice suggests a cluster-like character of magnetic ordering.     

Electrode activation of anode-supported SOFCs with LSM- or LSCF-type cathodes

Electrode activation of SOFCs refers to one or more processes, which generally occurs during a first period of usually not longer than 100 h of applying a constant electrical load, and is associated with a decrease of the area specific resistance. To study this effect in relation to different starting-up and test conditions in more detail, the electrochemical performance between 650 and 900 °C of two types of anode-supported single cells, one with an La_0.65Sr_0.3MnO₃ (LSM) and the other with an La_0.58Sr_0.40Co_0.2Fe_0.8O_3−δ (LSCF) cathode, was evaluated.Both types of cells, when heated to and reduced at 800 °C, showed a decrease of the area specific resistance during the first 70 h at 800 °C of exposure under constant electrical load. The initial area specific resistance of cells heated to and reduced at 900 °C was comparable with that of the cells reduced at 800 °C and exposed for 70 h at 800 °C under constant electrical load. In other words, electrode activation is much faster at 900 °C than at 800 °C.     

Graphite–boron composite heater in a Kawai-type apparatus: the inhibitory effect of boron oxide and countermeasures

We have investigated the performance of a graphite–boron composite (GBC) with 3?wt % boron as a precursor for a boron-doped diamond heater in a Kawai-type apparatus at 15?GPa. We first tested a machinable cylinder of GBC sintered at 1000°C in Ar/H₂ gas (99:1 molar ratio). Boron oxide (B₂O₃) formed during sintering frequently hindered the GBC heater from stable operation at temperatures higher than 1400°C by producing melt throughout the heater together with oxide and/or silicates. We then rinsed the GBC heater in hydrochloric acid to remove B₂O₃. After rinsing, we succeeded in stably generating temperatures higher than 2000°C. We also improved a molding process of different-sized GBC tubes for convenient use and tested the molded GBC heater. It was free from the B₂O₃ problem. The electromotive force of the W/Re thermocouple was successfully monitored up to 2400°C.     

A Spin Label Study of the Effects of Hydrostatic Pressure and Temperature on Cellular Lipids

Rabbit alveolar macrophages were labeled with fatty acid-derived spin labels and the effects of both hydrostatic pressure and temperature upon the fluidity of cell lipids were observed. The alveolar macrophage membrane is significantly more fluid than the erythrocyte membrane, with a value of 2T of 52.1 ± 0.7 gauss as compared to a literature value of 56.2 ± 0.8 gauss for erythrocyte ghosts. Arrhenius plots of the effects of temperature upon membrane lipids exhibit a constant slope as the temperature is reduced until a temperature of 2–3°C is obtained, at which point an abrupt change of slope is encountered indicating a lipid phase transition. When the temperature is held constant and hydrostatic pressure is applied in increasing increments, membrane lipids again exhibit a gradual, consistent decrease in fluidity. Moderate pressures in the range of atmospheric to 4000 psi were employed; and for the cells studied, an increase in pressure of 1000 psi appears roughly equivalent to a temperature reduction of 1°C. When hydrostatic pressure is applied in combination with reduced temperature, the temperature at which the lipid phase transition takes place is shifted from 2–3°C to approximately 10°C.