Chemical, physical and electrical properties of aged dodecylbenzene: thermal ageing of mixed isomers in air

A commercial dodecylbenzene (DDB) cable oil was aged at temperatures between 90 and 135 degrees C in air and was analyzed using various analytical techniques including optical and infra-red spectroscopy and dielectric analysis. On ageing, the oil darkened, significant oxidation features were found by infra-red spectroscopy and the acid number, water content and dielectric loss all increased. Ageing in the presence of paper or aluminum did not affect the ageing process, whereas ageing was significantly modified by the presence of copper. An absorption at 680 nm ("red absorbers") was detected by ultra-violet/visible spectroscopy followed by the production of an opaque precipitate. A reaction between copper and the acid generated on ageing is thought to produce copper carboxylates, and X-ray fluorescence confirmed that copper was indeed present in both the aged oil and the precipitate. Significantly, once red absorbers were detected, the dielectric loss increased to catastrophically high values and, therefore, the appearance of these compounds may serve as a useful diagnostic indicator. The development of acidity on ageing appears to be key in initiating the destructive copper conversion reaction and hence the control of oil acidity may be key to prolonging the life of DDB cable oils.

Chemical, physical and electrical properties of aged dodecylbenzene 3: thermal ageing of mixed isomers in nitrogen and under sealed conditions

Commercial dodecylbenzene cable fluid was aged at temperatures of 105 and 135 degrees C in dry oxygen-free nitrogen. In addition, selected samples were aged at 135 degrees C under sealed conditions where air was excluded from the headspace above the oil. A variety of analytical techniques, such as ultra-violet visible and infra-red spectroscopy, acid number and water content measurements, were then used to characterize the aged oils. In addition, their electrical properties were assessed by dielectric spectroscopy. Compared with ageing in air, the ageing rate was reduced significantly and, as expected, no major oxidation peaks were detected in the infrared spectrometer. Significantly, very little absorbance at 680 nm ("red absorbers") was detected in samples aged with copper and, consequentially, no large increases in dielectric loss were recorded within the ageing times considered here. This study compliments previous investigations on cable fluid and 1-phenyldodecane aged in air and show that the same ageing indicators are valid in oils aged under conditions which more closely resemble those found in high voltage plant.

Chemical, physical and electrical properties of aged dodecylbenzene 2: thermal ageing of single isomers in air

The linear isomer of dodecylbenzene (DDB), 1-phenyldodecane, was aged at temperatures of 105 and 135 degrees C in air and the resultant products were analyzed using a range of analytical techniques. On ageing, the 1-phenyldodecane darkened, the acid number, dielectric loss and water content increased and significant oxidation peaks were detected in the infrared spectrum. When aged in the presence of copper, a characteristic peak at 680 nm was also detected by UV/visible spectroscopy but, compared with previous studies of a cable-grade DDB, the strength of this peak was much increased and no appreciable precipitate formation occurred. At the same time, very high values of dielectric loss were recorded. On ageing in the absence of copper, an unusually strong infrared carbonyl band was seen, which correlates well with the detection of dodecanophenone by gas chromatography / mass spectrometry and nuclear magnetic resonance spectroscopy. It was therefore concluded that the ageing process proceeds via the initial production of aromatic ketones, which may then be further oxidized to carboxylic acids. In the presence of copper, these oxidation products are present in lower quantities, most of these oxidation products being combined with the copper present in the oil to give copper carboxylates. The behavior is described in terms of a complex autoxidation mechanism, in which copper acts as both an oxidizing and a reducing agent, depending on its oxidation state and, in particular, promotes elimination via the oxidation of intermediate alkyl radical species to carbocations.

Cloud optical and microphysical properties derived from ground-based and satellite sensors over a site in the Yangtze Delta region

Comprehensive surface-based retrievals of cloud optical and microphysical properties were made at Taihu, a highly polluted site in the central Yangtze Delta region, during a research campaign from May 2008 to December 2009. Cloud optical depth (COD), effective radius (Re), and liquid water path (LWP) were retrieved from measurements made with a suite of ground-based and spaceborne instruments, including an Analytical Spectral Devices spectroradiometer, a multi␣lter rotating shadowband radiometer, a multichannel microwave radiometer profiler, and the Moderate Resolution Imaging Spectroradiometer (MODIS) on Terra and Aqua satellites. Retrievals from zenith radiance measurements capture better the temporal variation of cloud properties than do retrievals from hemispherical fluxes. Annual mean LWP, COD, and Re are 115.8 ± 90.8 g/m2, 28.5 ± 19.2, and 6.9 ± 4.2 microns. Over 90% of LWP values are less than 250 g/m2. Most of the COD values (>90%) fall between 5 and 60, and ~80% of Re values are less than 10 microns. Maximum (minimum) values of LWP and Re occur in summer (winter); COD is highest in winter and spring. Raining and nonraining clouds have signi␣cant differences in LWP, COD, and Re. Rainfall frequency is best correlated with LWP, followed by COD and Re. Cloud properties retrieved from multiple ground-based instruments are also compared with those from satellite retrievals. On average, relative to surface retrievals, mean differences of satellite retrievals in cloud LWP, COD, and Re were -33.6 g/m2 (-26.4%), -5.8 (-31.4%), and 2.9 ␣m (29.3%) for 11 MODIS-Terra overpasses and -43.3 g/m2 (-22.3%), -3.0 (-10.0%), and -1.3 ␣m (-12.0%) for 8 MODIS-Aqua overpasses, respectively. These discrepancies indicate that MODIS cloud products still suffer from large uncertainties in this region.

Rheological and electrical properties of NaY zeolite electrorheological fluid

The relations between the rheological and electrical properties of NaY zeolite electrorheological fluid and its solid phase are studied. It is found that then exist complex relations between its electrical and theological properties. The temperature spectra of dielectric properties of the fluid under high AC electric field are strongly field strength dependent. The relation between the DC conductivity of the fluid and the exciting electric field is experimentally presented as log sigma =A+BE1/2, when A is a strong function, but B, a very weak function of temperature. The shear stress of the fluid under a fixed electric field and temperature decreases with shear rate. A relaxation time for the adsorbed charges is estimated to be about 0.3 to 6.6 s in the temperature range from 280 to 380 K. The relaxation time qualitatively corresponds to the shear rate at which the shear stress begins to drop. The time dependent leaking current of the ER fluids under DC electric field is also measured. The conductivity increase is mainly caused by the structure evolution of particles. The experimental results can he explained with the calculations of Davis (J. Appl. Phys. 81(1997) pp.1985-1991) and Martin (J. Chem. Phys. 110(1999) pp.4854-4866). It is predicted that the NaY zeolite ER fluid strength would get degraded slowly.

Optical and semi-conductor properties of Lead Telluride coatings

The optical and semiconductor properties of lead telluride coatings are dependant on various factors contributing to its performance. In this paper, we will present the temperature dependant effects of single layer lead telluride coatings on the dispersion and absorption characteristics, absorption edge, and carrier concentration from 15 K to 436 K using both experimental and theoretical analysis.

Structure and electrical transport properties of the ordered skutterudites MGe1.5S1.5 (M = Co, Rh, Ir)

High-resolution powder neutron diffraction data collected for the skutterudites MGe1.5S1.5 (M=Co, Rh, Ir) reveal that these materials adopt an ordered skutterudite structure (space group R3¯), in which the anions are ordered in layers perpendicular to the [111] direction. In this ordered structure, the anions form two-crystallographically distinct four-membered rings, with stoichiometry Ge2S2, in which the Ge and S atoms are trans to each other. The transport properties of these materials, which are p-type semiconductors, are discussed in the light of the structural results. The effect of iron substitution in CoGe1.5S1.5 has been investigated. While doping of CoGe1.5S1.5 has a marked effect on both the electrical resistivity and the Seebeck coefficient, these ternary skutterudites exhibit significantly higher electrical resistivities than their binary counterparts.

Independent evaluation of the ability of spaceborne radar and lidar to retrieve the microphysical and radiative properties of ice clouds

The combination of radar and lidar in space offers the unique potential to retrieve vertical profiles of ice water content and particle size globally, and two algorithms developed recently claim to have overcome the principal difficulty with this approach-that of correcting the lidar signal for extinction. In this paper "blind tests" of these algorithms are carried out, using realistic 94-GHz radar and 355-nm lidar backscatter profiles simulated from aircraft-measured size spectra, and including the effects of molecular scattering, multiple scattering, and instrument noise. Radiation calculations are performed on the true and retrieved microphysical profiles to estimate the accuracy with which radiative flux profiles could be inferred remotely. It is found that the visible extinction profile can be retrieved independent of assumptions on the nature of the size distribution, the habit of the particles, the mean extinction-to-backscatter ratio, or errors in instrument calibration. Local errors in retrieved extinction can occur in proportion to local fluctuations in the extinction-to-backscatter ratio, but down to 400 m above the height of the lowest lidar return, optical depth is typically retrieved to better than 0.2. Retrieval uncertainties are greater at the far end of the profile, and errors in total optical depth can exceed 1, which changes the shortwave radiative effect of the cloud by around 20%. Longwave fluxes are much less sensitive to errors in total optical depth, and may generally be calculated to better than 2 W m(-2) throughout the profile. It is important for retrieval algorithms to account for the effects of lidar multiple scattering, because if this is neglected, then optical depth is underestimated by approximately 35%, resulting in cloud radiative effects being underestimated by around 30% in the shortwave and 15% in the longwave. Unlike the extinction coefficient, the inferred ice water content and particle size can vary by 30%, depending on the assumed mass-size relationship (a problem common to all remote retrieval algorithms). However, radiative fluxes are almost completely determined by the extinction profile, and if this is correct, then errors in these other parameters have only a small effect in the shortwave (around 6%, compared to that of clear sky) and a negligible effect in the longwave.

On the electrical properties of insulation oils

Insulating oils are a major component of high voltage plant, including transformers, switchgear and cables. Consequentially, in terms of plant failure, changes in the electrical characteristics of the oil during ageing are of crucial importance. To address this issue, commercial insulating oil was subjected to controlled ageing under laboratory conditions. The electrical properties of the aged oils were then characterized using dielectric spectroscopy. The data suggest that a degree of electrical conductivity occurs in the aged oils, which reduces the insulating properties of the oil as ageing proceeds. The role of atmosphere and additives on the electrical properties of the oils were also explored. Results are compared with model samples, which contain known amounts of materials that may occur as by-products of the ageing process.

Electronic transitions and bonding properties in a series of five-coordinate “16-electron” complexes [Mn(CO)3(L2)]− (L2=chelating redox-active π-donor ligand)

In this article we present for the first time accurate density functional theory (DFT) and time-dependent (TD) DFT data for a series of electronically unsaturated five-coordinate complexes [Mn(CO)(3)(L-2)](-), where L-2 stands for a chelating strong pi-donor ligand represented by catecholate, dithiolate, amidothiolate, reduced alpha-diimine (1,4-dialkyl-1,4-diazabutadiene (R-DAB), 2,2'-bipyridine) and reduced 2,2'-biphosphinine types. The single-crystal X-ray structure of the unusual compound [Na(BPY)][Mn(CO)(3)(BPY)]center dot Et2O and the electronic absorption spectrum of the anion [Mn(CO)(3)(BPY)](-) are new in the literature. The nature of the bidentate ligand determines the bonding in the complexes, which varies between two limiting forms: from completely pi-delocalized diamagnetic {(CO)(3)Mn-L-2}(-) for L-2 = alpha-diimine or biphosphinine, to largely valence-trapped {(CO)(3)Mn-1-L-2(2-)}(-) for L-2(2-) = catecholate, where the formal oxidation states of Mn and L-2 can be assigned. The variable degree of the pi-delocalization in the Mn(L-2) chelate ring is indicated by experimental resonance Raman spectra of [Mn(CO)(3)(L-2)](-) (L-2=3,5-di-tBu-catecholate and iPr-DAB), where accurate assignments of the diagnostically important Raman bands have been aided by vibrational analysis. The L-2 = catecholate type of complexes is known to react with Lewis bases (CO substitution, formation of six-coordinate adducts) while the strongly pi-delocalized complexes are inert. The five-coordinate complexes adopt usually a distorted square pyramidal geometry in the solid state, even though transitions to a trigonal bipyramid are also not rare. The experimental structural data and the corresponding DFT-computed values of bond lengths and angles are in a very good agreement. TD-DFT calculations of electronic absorption spectra of the studied Mn complexes and the strongly pi-delocalized reference compound [Fe(CO)(3)(Me-DAB)] have reproduced qualitatively well the experimental spectra. Analyses of the computed electronic transitions in the visible spectroscopic region show that the lowest-energy absorption band always contains a dominant (in some cases almost exclusive) contribution from a pi(HOMO) -> pi*(LUMO) transition within the MnL2 metallacycle. The character of this optical excitation depends strongly on the composition of the frontier orbitals, varying from a partial L-2 -> Mn charge transfer (LMCT) through a fully delocalized pi(MnL2) -> pi*(MnL2) situation to a mixed (CO)Mn -> L-2 charge transfer (LLCT/MLCT). The latter character is most apparent in the case of the reference complex [Fe(CO)(3)(Me-DAB)]. The higher-lying, usually strongly mixed electronic transitions in the visible absorption region originate in the three lower-lying occupied orbitals, HOMO - 1 to HOMO - 3, with significant metal-d contributions. Assignment of these optical excitations to electronic transitions of a specific type is difficult. A partial LLCT/MLCT character is encountered most frequently. The electronic absorption spectra become more complex when the chelating ligand L-2, such as 2,2'-bipyridine, features two or more closely spaced low-lying empty pi* orbitals.

Structural, magnetic, and electronic properties of VxCr2−xS3(0

A new family of vanadium-substituted chromium sulfides (VxCr2-xS3, 0 < x < 2) has been prepared and characterized by powder X-ray and neutron diffraction, SQUID magnetometry, electrical resistivity, and Seebeck coefficient measurements. Vanadium substitution leads to a single-phase region with a rhombohedral Cr2S3 structure over the composition range 0.0 < x e 0.75, while at higher vanadium contents (1.6 e x < 2.0) a second single-phase region, in which materials adopt a cation-deficient Cr3S4 structure, is observed. Materials with the Cr2S3 structure all exhibit semiconducting behavior. However, both transport and magnetic properties indicate an increasing degree of electron delocalization with increasing vanadium content in this compositional region. Materials that adopt a Cr3S4-type structure exhibit metallic behavior. Magnetic susceptibility data reveal that all materials undergo a magnetic ordering transition at temperatures in the range 90–118 K. Low-temperature magnetization data suggest that this involves a transition to a ferrimagnetic state.

Synthesis, structural characterisation and thermoelectric properties of Bi1−xPbxOCuSe

The effect of Pb2+ doping on the structure and thermoelectric properties of BiOCuSe (also known as BiCuSeO or BiCuOSe) is described. With increasing Pb2+ content, the expansion of the unit cell results in a weakening of the bonding between the [Bi2(1-x) Pb2xO2]2(1-x)+ and the [Cu2Se2]2(1-x)- layers. The electrical resistivity and Seebeck coefficient decrease in a systematic way with growing Pb2+ levels. The thermal conductivity rises due to the increase of the electronic contribution with doping. The power factor of materials with a 4-5% Pb2+ content takes values of ca. 8 W cm-1 K-2 over a wide temperature range. ZT at 673 K is enhanced by ca. 50% when compared to values found for other dopants, such as Sr2+ or Mg2+.