The dielectric response of doped semiconducting glasses

Measurements are reported of the dielectric properties of two semiconducting glasses of composition SiO₂ · Na₂O with admixtures of Sb_{2O 5} and SnO₂, covering a wide range of temperatures and a range of six decades of frequency 10^–2 to 10⁴ Hz. Both glasses show a gradual evolution of growing low frequency dispersion (LFD) with increasing temperature, with both the real and imaginary components of the complex susceptibility following a power law of the type ^n–1, with n 1 at the lowest frequencies. There are also clear indications of reversible phase transitions taking place which manifest themselves by changes in the spectral shape of the dielectric response.     

Characterization and Reconstitution of Human Lipoyl Synthase (LIAS) Supports ISCA2 and ISCU as Primary Cluster Donors and an Ordered Mechanism of Cluster Assembly

Lipoyl synthase (LIAS) is an iron–sulfur cluster protein and a member of the radical S-adenosylmethionine (SAM) superfamily that catalyzes the final step of lipoic acid biosynthesis. The enzyme contains two [4Fe–4S] centers (reducing and auxiliary clusters) that promote radical formation and sulfur transfer, respectively. Most information concerning LIAS and its mechanism has been determined from prokaryotic enzymes. Herein, we detail the expression, isolation, and characterization of human LIAS, its reactivity, and evaluation of natural iron–sulfur (Fe–S) cluster reconstitution mechanisms. Cluster donation by a number of possible cluster donor proteins and heterodimeric complexes has been evaluated. [2Fe–2S]-cluster-bound forms of human ISCU and ISCA2 were found capable of reconstituting human LIAS, such that complete product turnover was enabled for LIAS, as monitored via a liquid chromatography–mass spectrometry (LC–MS) assay. Electron paramagnetic resonance (EPR) studies of native LIAS and substituted derivatives that lacked the ability to bind one or the other of LIAS’s two [4Fe–4S] clusters revealed a likely order of cluster addition, with the auxiliary cluster preceding the reducing [4Fe–4S] center. These results detail the trafficking of Fe–S clusters in human cells and highlight differences with respect to bacterial LIAS analogs. Likely in vivo Fe–S cluster donors to LIAS are identified, with possible connections to human disease states, and a mechanistic ordering of [4Fe–4S] cluster reconstitution is evident.     

Some aspects of the analysis of coal by X-ray fluorescence spectroscopy

Bituminous coal samples from 84 distinct sources were analysed by conventional British Standards (BS) methods for phosphorus, sulphur, chlorine, ash and the ash-forming elements (calcium, silicon, aluminium, iron, sodium, magnesium, potassium, titanium and manganese). In most cases four determinations were made per element per source. Samples were crushed to ?212 μm (72 BS mesh) and pressed into aluminium cups at 20 t in^?2 (309 MPa) without binder or backing. Two pellets from each sample were analysed by wave-length dispersive X-ray fluorescence techniques, using a spectrometer equipped with a rhodium rube; the X-ray count took 60 s. The X-ray results were calibrated against the conventional results using multiple regression. The accuracy obtained was comparable with routine ‘wet chemical’ techniques. The X-ray technique is suitable for the routine determination of large numbers of samples.     

High solids content emulsions. III. Synthesis of concentrated latices by classic emulsion polymerization

Two different methods of producing bi‐ and trimodal latices of a mixture of methyl methacrylate, butyl acrylate, and small amounts of acrylic acid were tested. It is shown that a combination of concentrating blends of seed particles by semibatch reaction, followed by a nucleation of small particles plus a second semibatch phase allowed us to obtain stable latices with solids contents over 65% and viscosities of below 2500 mPa s^?1 with little coagulum formation. The key parameter in determining latex stability, coagulum formation, and viscosity appears to be the the particle size distribution, and especially its modification attributed to secondary nucleation. Because it is not possible to eliminate water‐soluble monomers from the polymerization recipe, secondary (homogeneous) nucleation must be minimized by careful addition of the free‐radical initiator and choice of monomer feed flow rates. The nucleation of the third population in the trimodal latices is best accomplished with a mixed surfactant system because renucleation by anionic surfactant alone leads to detrimental changes in the particle size distribution (PSD) resulting from excessive flocculation of particles. In addition, it was found that the viscosity of the final products was not sensitive to small changes in the ionic strength of the latex, although neutralization to a pH of 6 effectively doubles the final latex viscosity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1916–1934, 2002; DOI 10.1002/app.10513     

High resolution STEM/EDX spectral imaging to resolve metal distributions within ∼100 nm combustion generated ash particles

Ultrafine ash particles play an important role in establishing a sticky inner deposit layer on heat transfer surface for power plants, but it is still unclear whether a thin surface alkali coating on these ultrafine particles might control this deposition behavior. In this research, we used a high resolution FE-TEM/STEM equipped with twin SDD EDX detectors for high X-ray detection efficiency, to determine the presence and absence of surface enrichment of alkali metals on ultrafine solid fuel ash samples that had low bulk alkali compositions but high deposition rates. Results from two types of combustion generated nano-sized ash particles are presented. One was from the oxy-combustion of pulverized bituminous coal, the other from oxy-combustion of pulverized rice husks, both being burned in a 100?kW rated down-flow laboratory combustor. Elemental mapping results from STEM/EDX uncovered some surface enrichment of alkali metals in ultrafine ash particles, where it existed, as it did for combustion of rice husks. However, it was not able to discern similar alkali metal surface enrichment for the bituminous coal ultrafines that had resulted in even higher deposition rates. Since deposition rates from both of these cases lie on the same correlation with PM₁, one can conclude that although surface enrichment of alkali metals is present for some ～100?nm particles, it is not a prerequisite to achieve high inner surface deposition rates. This is in contrast to prevailing theories that point to alkali metals as “bad actors” as far as the sticky inner deposition rate is concerned.

Copyright © 2019 American Association for Aerosol Research     

Evidence for the Participation of Singlet Oxygen in the Vat–dye Photosensitized Degradation of Cellulose

A study has been made of the vat–dye photosensitized degradation of cellulose. Whilst the part played by the dyes in direct hydrogen abstraction from a cellulose substrate cannot be overlooked, it is apparent that the role played by singlet oxygen is important. The ability of a dye to produce singlet oxygen has been studied by measuring the amount of tetraphenylcyclopentadienone the dye can photo–oxidize. It would appear that the singlet oxygen is initially formed in its high energy g state by energy transfer from the triplet state of the dye to ground state molecular oxygen. Luminescence spectroscopy has been employed in order to gain information about the excited state energies of the dye molecules, and an electron spin resonance study of the dyes in rigid media has been carried out in order to obtain information about the triplet state.     

Maternal diet and brain fatty acids in young rats

In order to determine to what extent maternal diet influenced the brain lipids of young rats, female rats were maintained on diets differing in fatty acid composition. Fatty acid determinations on the total brain lipids of the young from these dams indicated that the maternal dietary lipids influence the polyunsaturated fatty acid composition of these animals. A maternal diet with a high linoleic-linolenic acid ratio (corn oil) resulted in lower levels of 22∶6ω3 and higher levels of 22∶5ω6 than one with a low linoleic-linolenic acid ratio (grain). Transfer of young rats at birth to a foster mother, which was fed a diet differing from that of the natural dam, resulted in brain polyunsaturated fatty acid patterns at weaning similar to those of the natural young, and suckling, of the foster mother, thus indicating that the maternal diet in the immediate postnatal period can modify the brain lipids of young rats prior to weaning. The brain lipids of young rats from dams which were fed corn oil exhibited a marked tendency to incorporate 22∶6ω3 in the immediate postnatal period in spite of a relatively high linoleic-linolenic acid ratio in the milk.     

Property-composition relationships for diesel and kerosene fuels

A range of 18 diesel fuels and 21 kerosene fuels from mainly Australian petroleum and synthetic fuel sources, including coal, shale and peat, was investigated. Compositional details were defined as the weight per cent abundances of n-alkanes, branched plus cyclic saturates, single-ring aromatics, doublering aromatics and polynuclear aromatics, using both h.p.l.c. and ¹³C n.m.r. techniques. Relationships between fuel composition and a range of fuel properties were sought. Simple linear relationships between property values and compositional data were used. Explicit correlative expressions were derived using multiple linear regression analysis, with the coefficient of multiple determination, R², indicating the quality of the fit between observed and calculated property values. In most cases good correlations were achieved. For diesels the properties investigated, with R² values in parentheses, were: inverse specific gravity (0.99); ¹³C n.m.r. aromaticity (0.99); ¹H n.m.r. aromaticity (0.88); cetane index (0.97); aniline point (0.96); diesel index (0.98); and FIA-measured aromatics content (0.77). For kerosenes the properties, with R² values in parentheses, were: ¹³C n.m.r. aromaticity (0.98); ¹H n.m.r. aromaticity (0.97); smoke point (0.88); and FIA-measured aromatics content (0.94). The results are shown to be of value in assessing the potential and limitations of hydrotreating as a process for upgrading synfuels.     

Stress Analysis of Elastic-Plastic Contact Damage in Ceramic Coatings on Metal Substrates

An elastic-plastic analysis of damage in ceramic coatings on metal substrates from contacts with spherical indenters is made using finite element modeling. Computations are carried out specifically for plasma-sprayed alumina:titania on a soft steel. The algorithm assumes an elastic sphere with frictionless contact on a flat elastic-plastic layered specimen, and incrementally evaluates the expanding contact field as a function of applied load. Two key aspects of the contact field are examined: (i) the indentation stress-strain curve; (ii) the damage zone geometry. Composite coating/substrate indentation stress-strain curves are computed for two coating thicknesses, using input material parameters from iterative fits to data from control tests on free-standing coating and substrate materials. Contours of principal shear stresses, most notably those contours corresponding to yield zone boundaries in both the softer substrate and the harder coating, are mapped out in the fully plastic region. Corresponding distributions of tensile stresses are also mapped out, and are shown to correlate with the locations of transverse fractures in the coating. General implications concerning material and geometrical design of ceramic-based layer structures are discussed.     

In Situ Processing of Silicon Carbide Layer Structures

A novel route to low-cost processing of silicon carbide (SiC) layer structures is desribed. The processing involves pressureless liquid-phase cosintering of compacted power layers of SiC, containing alumina (Al₂O₃) and yttria (Y₂O₃ sintering additives to yield and yttrium aluminum garnet (YAG) second phase. By adjusting the β:α SiC phase ratios in the individual starting powders, alternate layers with distinctively different microstructures are produced: (i) "homogeneous" microstructures, with fine equiaxed SiC grains, designed for high strength; and (ii) "heterogeneous: microstructures with coarse and elongate SiC grains, designed for high toughness. By virtue of the common SiC and YAG phases, the interlayer interfaces are chemically compatible and strongly bonded. Exploratory Hertzian indetation tests across a bilayer interface confirm the capacity of the tough heterogeneous layer to inhibit potentially dangerous cracks propagating through the homogeneous layer. The potential for application of this novel processing approach to other layer architectures and other ceramic systems is considered.