High temperature phase chemistry of system Eu-Pd-O

An isothermal section of the phase diagram for the system Eu - Pd - O at 1223 K has been established by equilibration of samples representing 20 different compositions, and phase identification after quenching by optical and scanning electron microscopy, X-ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides, Eu4PdO7, Eu2PdO4, and Eu2Pd2O5, were identified. Liquid alloys and the intermetallic compounds EuPd2 and EuPd3 were found to be in equilibrium with EuO. The compound EuPd3 was also found to coexist separately with Eu3O4 and Eu2O3. The oxide phase in equilibrium with EuPd5 and Pd rich solid solution was Eu2O3. Based on the phase relations, four solid state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 925 to 1350 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to crosscheck the data. An advanced version of the solid state cell incorporating a buffer electrode with yttria stabilised zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high temperature thermodynamic measurements. Equations for the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides Eu2O3 with C type structure and PdO have been established. Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Eu - Pd - O have been developed.

MOCVD of aluminium oxide films using aluminiurn beta-diketonates as precursors

Deposition of Al2O3 coatings by CVD is of importance because they are often used as abrading material in cemented carbide cutting tools. The conventionally used CVD process for Al2O3 involves the corrosive reactant AlCl3. In this paper, we report on the thermal characterisation of the metalorganic precursors namely aluminium tristetramethyl-heptanedionate [Al(thd)(3)] and aluminium tris-acetylacetonate [Al(acac)(3)] and their application to the CVD of Al2O3 films. Crystalline Al2O3 films were deposited by MOCVD at low temperatures by the pyrolysis of Al(thd)(3) and Al(acac)(3). The films were deposited on a TiN-coated tungsten carbide (TiN/WC) and Si(100) substrates in the temperature range 500-1100degreesC. The as-deposited films were characterised by x-ray diffraction, optical microscopy, scanning and transmission electron microscopy, Auger electron spectroscopy. The observed crystallinity of films grown at low temperatures, their microstructure, and composition may be interpreted in terms of a growth process that involves the melting of the metalorganic precursor on the hot growth surface.

Transmission of elastic waves through a frictional boundary

Incident energy gets transmitted, reflected and absorbed across an interface in jointed rock mass leading to energy dissipation and alteration of waves. Wave velocities get attenuated during their propagation across joints and this behavior is studied using bender/extender element tests. The velocity attenuation and modulus reduction observed in experimental tests are modeled with three dimensional distinct element code and results are validated. Normal propagation of an incident shear wave through a jointed rock mass cause slip of the rock blocks if shear stress of wave exceeds the shear strength of the joint. As the properties of joint determine the transmission of energy across an interface, a parametric study is then conducted with the validated numerical model by varying the parameters that may determine the energy transmission across a joint using modified Miller's method. Results of the parametric study are analyzed and presented in the paper. (C) 2014 Elsevier Ltd. All rights reserved.

Reprodução eleitoral, especialização ou cartelização legislativa? A Comissão de Minas e Energia da Câmara dos Deputados em pauta

Avalia a dinâmica da Comissão de Minas e Energia da Câmara dos Deputados, entre 2003 e 2006, sob o enfoque das Teorias do Legislativo e do Agenda Setting, tendo-se verificado dominância das perspectivas distributivista e partidária sobre a informacional, visto que os trabalhos no âmbito do órgão nortearam-se por preferências do Poder Executivo e que a motivação de seus membros centrou-se na reeleição.

Nature of the radical intermediates in a substituted cyclopropylcarbiny-allylcarbinyl system

We have sought to determine the nature of the free-radical precursors to ring-opened hydrocarbon 5 and ring-closed hydrocarbon 6. Reasonable alternative formulations involve the postulation of hydrogen abstraction (a) by a pair of rapidly equilibrating classical radicals (the ring-opened allylcarbinyl-type radical 3 and the ring-closed cyclopropylcarbinyl-type 4), or (b) by a nonclassical radical such as homoallylic radical 7.

[Figure not reproduced.]

Entry to the radical system is gained via degassed thermal decomposition of peresters having the ring-opened and the ring-closed structures. The ratio of 6:5 is essentially independent of the hydrogen donor concentration for decomposition of the former at 125° in the presence of triethyltin hydrdride. A deuterium labeling study showed that the α and β methylene groups in 3 (or the equivalent) are rapidly interchanged under these conditions.

Existence of two (or more) product-forming intermediates is indicated (a) by dependence of the ratio 6:5 on the tin hydride concentration for decomposition of the ring-closed perester at 10 and 35°, and (b) by formation of cage products having largely or wholly the structure (ring-opened or ring-closed) of the starting perester.

Relative rates of hydrogen abstraction by 3 could be inferred by comparison of ratios of rate constants for hydrogen abstraction and ortho-ring cyclization:

[Figure not reproduced.]

At 100° values of k_a/k_r are 0.14 for hydrogen abstraction from 1,4-cyclohexadiene and 7 for abstraction from triethyltin hydride. The ratio 6:5 at the same temperature is ~0.0035 for hydrogen abstraction from 1,4-cyclohexadiene, ~0.078 for abstraction from the tin hydride, and ≥ 5 for abstraction from cyclohexadienyl radicals. These data indicate that abstraction of hydrogen from triethyltin hydride is more rapid than from 1,4-cyclohexadiene by a factor of ~1000 for 4, but only ~50 for 3.

Measurements of product ratios at several temperatures allowed the construction of an approximate energy-level scheme. A major inference is that isomerization of 3 to 4 is exothermic by 8 ± 3 kcal/mole, in good agreement with expectations based on bond dissociation energies. Absolute rate-constant estimates are also given.

The results are nicely compatible with a classical-radical mechanism, but attempted interpretation in terms of a nonclassical radical precursor of product ratios formed even from equilibrated radical intermediates leads, it is argued, to serious difficulties.

The roles played by hydrogen abstraction from 1,4,-cyclohexadiene and from the derived cyclohexadienyl radicals were probed by fitting observed ratios of 6:5 and 5:10 in the sense of least-squares to expressions derived for a complex mechanistic scheme. Some 30 to 40 measurements on each product ratio, obtained under a variety of experimental conditions, could be fit with an average deviation of ~6%. Significant systematic deviations were found, but these could largely be redressed by assuming (a) that the rate constant for reaction of 4 with cyclohexadienyl radical is inversely proportional to the viscosity of the medium (i.e., is diffusion-controlled), and (b) that k_a/k_r for hydrogen abstraction from 1,4-cyclohexadiene depends slightly on the composition of the medium. An average deviation of 4.4% was thereby attained.

Degassed thermal decomposition of the ring-opened perester in the presence of the triethyltin hydride occurs primarily by attack on perester of triethyltin radicals, presumably at the –O-O- bond, even at 0.01 M tin hydride at 100 and 125°. Tin ester and tin ether are apparently formed in closely similar amounts under these conditions, but the tin ester predominates at room temperature in the companion air-induced decomposition, indicating that attack on perester to give the tin ether requires an activation energy approximately 5 kcal/mole in excess of that for the formation of tin ester.

Carbon-13 magnetic resonance spectroscopy

High-resolution, natural-abundance ¹³C spectra have been obtained from a wide variety of organic compounds; ¹³C chemical shifts and coupling constants have been correlated with other molecular properties.

Geminal and vicinal, carbon-proton couplings in benzene and the five- and six-membered aromatic heterocycles have been related to the corresponding proton-proton couplings in substituted ethylenes. The carbon-proton coupling constants in benzene are J_CCH = + 1.0, J_CCCH = +7.4 and J_CCCH = -1.1 Hz. Extended Hückel wavefunctions are uniformly poor in explaining the long-range, carbon-proton couplings in aromatic systems.

Couplings between carbon and elements other than hydrogen have been observed in proton decoupled ¹³C spectra. All of the carbons in fluorobenzene and 1-fluoronaphthalene, but only six of the carbons in 2-fluoronaphthalene are coupled to the fluorine. One-bond, carbon-phosphorus coupling in trialkylphosphines is negative, while one-bond, carbon-phosphorus coupling in tetra-alkylphosphonium ions is positive. Atoms which do not use hybrid orbitals to form bonds to carbon (F, P(III), Se, Te) may have negative, one-bond coupling constants because of the failure of the average energy approximation. One-bond couplings between carbon and carbon, silicon, tin, lead and mercury appear to be explainable in terms of an effective nuclear charge and the s-bond order of the metal. Couplings between carbon and nitrogen and phosphorus (IV) have significant negative contributions to the Fermi contact coupling expression, though, within one series, correlations with s-bond order may be valid. Carbon-carbon coupling in cyclopropane derivatives (10-15 Hz) is consistent with a high degree of p character in the interior orbitals. Some two- and three-bond carbon-carbon coupling constants have also been observed.

Substituent effects of hydroxyl groups on the ¹³C chemical shifts of continuous-chain alkanes depend both on steric and electronic factors. The hydroxyl substituent effects in the long-chain, primary alcohols are α = -48.3, β = -10.2, and γ = +6.0 ppm. The upfield γ effect is attributed to steric crowding in the gauche conformations. Additivity of the hydroxyl and carbonyl and alkyl substituent effects in alkyl-substituted cyclohexanols and cyclohexanones has been demonstrated.

Dependência e mineração no quadrilátero ferrífero-aquífero: o discurso do desenvolvimento minerador e o Projeto Apolo

Pretendemos com esse trabalho analisar as relações entre as Mineradoras e a sociedade civil local das regiões mineradoras, por meio principalmente da Teoria da Dependência. Tentamos refletir sobre os efeitos da atividade minério-exportadora nas populações locais e as maneiras de manutenção dessa ordem social. O estudo pode ser dividido em dois que se interrelacionam: 1) no primeiro, empreendemos uma discussão sobre o subdesenvolvimento, a dependência e a mineração num país semiperiférico como o Brasil; 2) no segundo, analisamos, especificamente, a conjuntura da instalação da Mina Apolo da Vale. Esta parte da pesquisa está baseada no trabalho de campo e na análise das entrevistas com os envolvidos no debate sobre a Mina Apolo e o Parque Nacional do Gandarela. Ao buscarmos nas relações de classe da região as razões para a manutenção da atividade mineira-exportadora, intentamos discutir o tipo de desenvolvimento que a mineração engendra. Partimos da hipótese de que são inúmeros os danos causados pela mineração à sociedade civil local, principalmente a longo e médio prazo. A população local e as classes populares não mobilizam um discurso contra-hegemônico, ou mesmo questionador, de ampla aceitação na sociedade civil local porque o discurso do desenvolvimento minerador e a dependência econômica da região frente à mineração desmobilizam os movimentos críticos e contrários às mineradoras. Esta dependência econômica é traduzida em dependência sócio-política.

Remote sensing of the oceans from space with special reference to marine resources

A number of ocean science fields have profitted, either directly or indirectly from satellite remote sensing, including physical, biological and geological oceanography. User oriented applications include fishing, shipping, offshore drilling and mining, coastal engineering and coastal hydrology. Following a brief account of the technology involved, areas in oceanography benefitting from satellite information are detailed. Examples are given of satellite data applications to marine resources.

Mechanical characterisation of hydrogel materials

Interest in hydrogel materials is growing rapidly, due to the potential for hydrogel use in tissue engineering and drug delivery applications, and as coatings on medical devices. However, a key limitation with the use of hydrogel materials in many applications is their relatively poor mechanical properties compared with those of (less biocompatible) solid polymers. In this review, basic chemistry, microstructure and processing routes for common natural and synthetic hydrogel materials are explored first. Underlying structure-properties relationships for hydrogels are considered. A series of mechanical testing modalities suitable for hydrogel characterisation are next considered, including emerging test modalities, such as nanoindentation and atomic force microscopy (AFM) indentation. As the data analysis depends in part on the material's constitutive behaviour, a series of increasingly complex constitutive models will be examined, including elastic, viscoelastic and theories that explicitly treat the multiphasic poroelastic nature of hydrogel materials. Results from the existing literature on agar and polyacrylamide mechanical properties are compiled and compared, highlighting the challenges and uncertainties inherent in the process of gel mechanical characterisation. © 2014 Institute of Materials, Minerals and Mining and ASM International.

黄土高原沟壑区王东沟流域土地利用/覆被变化过程初探

黄土高原沟壑区王东沟流域从1986年至2006年的土地利用/覆被发生了较大变化,土地利用动态指数分别为:耕地3.21%,园地-36.11%,林地-4.05%,牧草地4.24%,居民点及独立工矿用地-0.62%,交通运输用地-12.27%,未利用地1.85%;变化趋势是:耕地逐年向园地流转,园地变化烈度较大,其他各类用地变化不太显著。引起这一变化的主要因素是自然、社会、经济、技术以及政策因素。结合这一变化,针对黄土高原沟壑区的实际情况,在黄土高原沟壑区土地利用经营与管理方面,应重视土地产出效益与粮食安全的关系,在保障区域粮食安全的基础上实现效益最大化。

黄土高原(陕西部分)雨水资源化潜力初步分析

根据黄土高原（ 陕西部分） 的１４５ 个雨量观测站的３０ａ 逐月降水资料，分析了陕西雨水资源的时空分布特征，并在次基础上，分别对西北地区的作物地土壤拦蓄潜力，陕北、渭北、关中３ 地区居民工矿与交通用地的雨水汇流潜力进行了测算。初步结果为：两北地区作物地年总无效蒸发耗水达３３ ×１０８ ｍ３ ，若采取集流保墒措施，年可减少蒸发损失６－４ ×１０８ ｍ３ ；３ 地区居民工矿与交通用地年可汇流６－２７ ×１０８ ｍ ３ ，若一半用于粮食生产，并采取节水灌溉，初步推算黄土高原地区可增产粮食约２８－８ ×１０８ ｋｇ。

Performance improvement by charge trapping of doping fluorescent dyes in organic memory devices

We studied the memory effect in the devices consisting of dye-doped N, N'-di(naphthalene-1-yl)-N, N'-diphenyl-benzidine sandwiched between indium-tin oxide and Ag electrodes. It was found that the on/off current ratio was greatly improved by the doped fluorescent dyes compared with nondoping devices. A mechanism of charge trapping was demonstrated to explain the improvement of the memory effect. For the off state, the conduction process is dominated by the trapping current, which is a characteristic of the space-charge limited current, whereas the on state is dominated by the detrapping current, and interpreted by Poole-Frenkel emission.

松辽盆地古龙地区葡萄花油层组沉积成岩相研究

The sediment and diagenesis process of reservoir are the key controlling factors for the formation and distribution of hydrocarbon reservoir. For quite a long time, most of the research on sediment-diagenesis facise is mainly focusing on qualitative analysis. With the further development on exploration of oil field, the qualitative analysis alone can’t meet the requirements of complicated requirements of oil and gas exploreation, so the quantitative analysis of sediment-diagenesis facise and related facies modling have become more and more important. On the basis of the research result from stratum and sediment on GuLong Area Putaohua Oil Layer Group, from the basic principles of sedimentology, and with the support from the research result from field core and mining research results, the thesis mainly makes the research on the sediment types, the space framework of sands and the evolution rules of diagenesis while mainly sticking to the research on sediment systement analysis and diagenetic deformation, and make further quantitative classification on sediment-diageneses facies qualitatively, discussed the new way to divide the sediment-diagenesis facies, and offer new basis for reservoir exploration by the research. Through using statistics theory including factor analysis, cluster analysis and discriminant analysis, the thesis devided sediment-diagenesis facies quantitatively. This research method is innovative on studying sediment-diagenesis facies. Firstly, the factor analysis could study the main mechanism of those correlative variables in geologic body, and then could draw a conclusion on the control factors of fluid and capability of reservoir in the layer of studying area. Secondly, with the selected main parameter for the cluster analysis, the classification of diagenesis is mainly based on the data analysis, thus the subjective judgement from the investigator could be eliminated, besides the results could be more quantitative, which is helpful to the correlative statistical analysis, so one could get further study on the quantitative relations of each sediment-diagenesis facies type. Finally, with the reliablities of discriminant analysis cluster results, and the adoption of discriminant probability to formulate the chart, the thesis could reflect chorisogram of sediment-diagenesis facies for planar analysis, which leads to a more dependable analytic results.According to the research, with the multi-statistics analysis methods combinations, we could get quantitative analysis on sediment-diagenesis facies of reservoir, and the final result could be more reliable and also have better operability.