Evaluation of the quantitative reliability of the 13C CP/MAS technique for the analysis of coals and related materials

The percentages of aromatic carbon in three representative solid coal samples and one pitch sample have been determined by three different n.m.r. techniques. The first two involve the use of cross-polarization/magic-angle spinning (CP/MAS) and in one case, the magnetization curves were fitted to a theoretical expression and the fit parameters used to calculate the percentage of aromatic carbon. In the second case, the percentage of aromatic carbons was obtained from a choice of contact time in the cross-polarization pulse sequence which gave maximum signal intensity. The third technique used MAS together with a simple 90° carbon pulse sequence with a 5 × T₁, (for the carbon-13 nuclei) recycle time and was assumed to give the absolute quantitative values. It was found that the results obtained using cross-polarization techniques could be substantially different from those obtained using 90° pulses and that caution must be exercised in the application of these techniques to the quantitative analysis of solid carbonaceous fuels.     

Mössbauer studies of iron-bearing minerals in coal and coal ash

⁵⁷Fe Mössbauer spectroscopy has been used to characterize the iron-bearing minerals present in some British Columbia coals. The minerals observed in a range of samples include pyrite/marcasite, siderite, jarosite, rozenite or melanterite, and Fe²⁺ -bearing clay minerals such as illite. The presence of jarosite is confirmed through the magnetic hyperfine interaction observed at 4.2 K. The absence of magnetic ordering at 4.2 K for the ferrous sulphate component indicates the presence of rozenite, FeS0₄ · 4H₂0, or melanterite, FeS0₄ · 7H₂0, rather than szomolnokite, FeS0₄ · H₂0 or FeS0₄. The effects of ashing on two of the coals is also studied.     

Quantitative X-ray powder diffraction analysis of clay minerals in Australian coals using Rietveld methods

The mineralogy of clay-rich mineral matter isolated from a range of Australian bituminous coals has been evaluated in quantitative terms from X-ray powder diffraction (XRD) patterns using a Rietveld-based data processing technique. The chemical composition of coal ash derived from this mineral matter has been calculated and compared to the directly determined composition of the ash prepared from the same coal samples. Although there are some minor differences due in part to uncertainty regarding the actual composition of several minerals, the compositions indicated by the two methods show a relatively high correlation, suggesting that the Rietveld technique provides mineralogical analyses that are consistent with independently determined chemical data. Comparison of the normalised clay mineral percentages from the Rietveld analysis to quantitative interpretations based on a peak intensities in glycolated and heat-treated oriented aggregates of the respective clay fractions also shows a high correlation, confirming mutual consistency of the two different mineralogical analysis methods. Such quantitative mineralogical data are significant to a range of coal exploration, mining and utilization activities, including seam correlation, material handling and ash and slag formation in combustion processes.     

Determination of glass content and estimation of glass composition in fly ash using quantitative X-ray diffractometry

The proportion of amorphous or glassy material in a series of fly ashes has been evaluated by X-ray powder diffraction (XRD) using the Rietveld-based SIROQUANT software package. Several different sample preparation and processing methods were investigated, including XRD analysis of samples spiked with known masses of synthetic corundum and zinc oxide as well as techniques based on analysing the raw or unspiked fly ash directly using the SIROQUANT process. In the latter case, two different poorly crystallised silicate mineral patterns, metakaolin and tridymite, were used in the SIROQUANT processing of the raw ash XRD data to represent the amorphous constituents. The results of the different methods based on XRD of spiked samples were found to be mutually consistent, and also consistent with other published data for an international reference fly ash sample. SIROQUANT analysis of the unspiked fly ashes gave similar results, although different poorly crystallised silicate reference patterns seem to be more suited for ashes from Australian and North American sources.The mineralogy of the ashes, including the proportions of quartz, iron oxide and glassy constituents, appears to be related to the nature of the mineral matter in the relevant feed coals. Calculations based on subtracting the inferred chemistry of the crystalline minerals in the fly ashes from the total fly ash chemistry were also used to estimate the overall chemical composition of the glass fraction in each ash. The results indicate that ashes derived from lower-rank coals in the samples studied have different glass compositions to those derived from higher-rank (bituminous) materials. These different glass compositions appear to be related to several other ash properties, including particle density and particle surface area. Evaluation of glass content and composition may be significant in different aspects of ash utilisation, and also in evaluating interactions with water at ash disposal sites.     

The effects of Cl-induced alloying in Pt–Sn/Al2O3 catalysts on butane/H2 reactions

The effects of oxidation/reduction regeneration treatments, with and without 1,2-dichloropropane present as a chlorinating agent, on the structure of Pt(3%)–Sn(4.5%)/Al₂O₃ catalysts have been correlated with selectivities for butane/H₂ reactions. Particles of Pt⁰ fin Cl-free catalysts were partly covered by Sn⁰, but retained exposed ensembles of Pt atoms which were active for isomerisation, hydrogenolysis and dehydrogenation reactions, the latter becoming dominant at high reaction temperatures. Coking reduced Pt ensemble size and, hence, also favoured high selectivities for dehydrogenation as hydrogenolysis and isomerisation sites became poisoned. In contrast, the addition of 1,2-dichloropropane in an oxychlorination step before reduction promoted 1:1 Pt⁰–Sn⁰ alloy formation after reduction, the proportion of the total Pt in alloy being enhanced by increasing 1,2-dichloropropane concentration and oxychlorination temperature. The alloy surfaces were inactive for isomerisation and hydrogenolysis reactions, giving dehydrogenation as the sole catalytic reaction.     

Clustering semantically heterogeneous distributed aggregate databases

Databases developed independently in a common open distributed environment may be heterogeneous with respect to both data schema and the embedded semantics. Managing schema and semantic heterogeneities brings considerable challenges to learning from distributed data and to support applications involving cooperation between different organisations. In this paper, we are concerned mainly with heterogeneous databases that hold aggregates on a set of attributes, which are often the result of materialised views of native large-scale distributed databases. A model-based clustering algorithm is proposed to construct a mixture model where each component corresponds to a cluster which is used to capture the contextual heterogeneity among databases from different populations. Schema heterogeneity, which can be recast as incomplete information, is handled within the clustering process using Expectation-Maximisation estimation and integration is carried out within a clustering iteration. Our proposed algorithm resolves the schema heterogeneity as part of the clustering process, thus avoiding transformation of the data into a unified schema. Results of algorithm evaluation on classification, scalability and reliability, using both real and synthetic data, demonstrate that our algorithm can achieve good performance by incorporating all of the information from available heterogeneous data. Our clustering approach has great potential for scalable knowledge discovery from semantically heterogeneous databases and for applications in an open distributed environment, such as the Semantic Web.     

HDPE/LLDPE reactor blends with bimodal microstructures—Part II: rheological properties

Reactor blends of polyethylene/poly(ethylene-co-1-octene) resins with bimodal molecular weight and bimodal short chain branching distributions were synthesized in a two-step polymerization process. The compositions of these blends range from low molecular weight (LMW) homopolymer to high molecular weight (HMW) copolymer and vice versa HMW homopolymer to LMW copolymer. The shear flow characteristics of these polymers in the typical processing range mostly depend on the molecular weight and MWD of the polymer and are independent of the short chain branch content. From oscillatory shear measurements, it was observed that the viscosity of HMW polymers was reduced with the addition of LMW material. For the polymers produced with this two-step polymerization process, the LMW homopolymer and HMW copolymer blends and HMW homopolymer and LMW copolymer blends were melt miscible, despite the large viscosity differences of the pure components.     

Test-data generation for control coverage by proof

Many tools can check if a test set provides control coverage; they are, however, of little or no help when coverage is not achieved and the test set needs to be completed. In this paper, we describe how a formal characterisation of a coverage criterion can be used to generate test data; we present a procedure based on traditional programming techniques like normalisation, and weakest precondition calculation. It is a basis for automation using an algebraic theorem prover. In the worst situation, if automation fails to produce a specific test, we are left with a specification of the compliant test sets. Many approaches to model-based testing rely on formal models of a system under test. Our work, on the other hand, is not concerned with the use of abstract models for testing, but with coverage based on the text of programs.     

Occurrence of wax esters in the tissues of the organge roughy (Hoplostethus atlanticus)

The skin, skeleton and a fat-filled swim bladder of the orange roughy (Hoplostethus atlanticus) each contained greater than 20% lipid by wet weight which was almost entirely wax esters. These had carbon numbers of 34–40 consistent with the major fatty acid being 18∶1 and the major fatty alcohols being 16∶0, 18∶1, 20∶1 and 22∶1. In contrast, the liver and the roe contained appreciable quantities of glycerolipids with 18∶1 and 22∶6 as the major fatty acids.     

Responses of the Aphids Phorodon humuli and Rhopalosiphum padi to Sex Pheromone Stereochemistry in the Field

Gynoparous female and male damson-hop aphids, Phorodon humuli (Schrank), were caught in the field by water traps that were releasing the sex pheromone of this species, (1RS,4aR,7S,7aS)-nepetalactol. No behavioral activity was elicited by (4aS,7S,7aR)-nepetalactone, the major sex pheromone component of other aphid species such as Megoura viciae Buckton, even though olfactory cells were found in the secondary rhinaria on the third antennal segment of P. humuli that responded strongly to this compound. Gynoparous female P. humuli in the field responded less strongly to (1R,4aS,7S,7aR)-nepetalactol, the sex pheromone of the bird cherry-oat aphid, Rhopalosiphum padi (L.), than they did to the (4aR,7S,7aS)-nepetalactols, but males responded only to the latter. The (4aR,7S,7aS)-nepetalactone showed no electrophysiological activity so was not used in field trials. Releasing either the (4aS,7S,7aR)-nepetalactone or the (1R,4aS,7S,7aR)-nepetalactol with the (4aR,7S,7aS)-nepetalactols did not inhibit the response of P. humuli gynoparous females and males to the latter. Males of R. padi responded as strongly to the (4aR,7S,7aS)-nepetalactols as they did to (1R,4aS,7S,7aR)-nepetalactol. Males of P. humuli and R. padi responded positively to an increased concentration of the (4aR,7S,7aS)-nepetalactols released from two vials compared with that from a single vial, as did P. humuli (in one of two experiments) and R. padi to the (1RS,4aR,7S,7aS)- and (1R,4aS,7S,7aR)-nepetalactols when released together.