Band theoretical studies of the electronic structure of oxides

The O^2? ion is a useful concept in ionic solids. Its electron density and large polarizability is well described by the Watson sphere model. The large variation in the electronic structure of oxides is illustrated by discussing the ionic MgO, the partly ‘covalent’ Cu₂O, and TiO and NbO which have defects with respect to the ideal NaCl structure. The variation in physical properties is shown for the oxides in the rutile structure ranging from the insulating TiO₂, the metallic RuO₂ to the ferromagnetic CrO₂. Electron densities, total energies and densities of states are used to study these materials.     

Molecular models of alginic acid: Interactions with calcium ions and calcite surfaces

Cation binding by polysaccharides is observed in many environments and is important for predictive environmental modeling, and numerous industrial and food technology applications. The complexities of these cation-organic interactions are well suited for predictive molecular modeling and the analysis of conformation and configuration of polysaccharides and their influence on cation binding. In this study, alginic acid was chosen as a model polymer system and representative disaccharide and polysaccharide subunits were developed. Molecular dynamics simulation of the torsion angles of the ether linkage between various monomeric subunits identified local and global energy minima for selected disaccharides. The simulations indicate stable disaccharide configurations and a common global energy minimum for all disaccharide models at Φ = 274 ± 7°, Ψ = 227 ± 5°, where Φ and Ψ are the torsion angles about the ether linkage. The ability of disaccharide subunits to bind calcium ions and to associate with the surface of calcite was also investigated. Molecular models of disaccharide interactions with calcite provide binding energy differences for conformations that are related to the proximity and residence densities of the electron-donating moieties with calcium ions on the calcite surface, which are controlled, in part, by the torsion of the ether linkage between monosaccharide units. Dynamically optimized configurations for polymer alginate models with calcium ions were also derived.     

Theoretical studies of the electronic structure of copper in tetrahedral and triangular coordination with sulfur

Molecular orbital calculations are presented for the copper-sulfur polyhedral clusters CuS ₄ ^7? , CuS ₄ ^6? , CuS ₃ ^5? and CuS ₃ ^4? , which occur in many minerals. Calculated and experimental optical and X-ray energies are found to be in good agreement. The crystal field orbitals of Cu⁺ in tetrahedrally coordinated sulfides are found to be less tightly bound than the S3p nonbonding orbitals by about 2–3 eV whereas the e and t ₂ crystal field orbitals are split by about 1 eV. The crystal field splitting of Cu²⁺ in tetrahedral coordination is about 0.7–0.8 eV while the separation of the S3p nonbonding orbitals and the partially filled t ₂ crystal field orbital is about 2 eV. In triangular coordination both the Cu⁺ and Cu²⁺ crystal field orbitals are more stable than in tetrahedral coordination, more widely split and more strongly mixed with the S3p orbitals. CuS is shown to be unstable as the mixed oxidation state compound Cu^2+III (Cu^+IV)₂S^2?(S ₂ ^2? ); rather each Cu is predicted to have a fractional oxidation state and partially-empty crystal field orbitals.     

B NMR investigation of boron interaction with mineral surfaces: Results for boehmite, silica gel and illite

Boron is an important micronutrient for plants but is toxic at high pore solution concentrations. Its mobility and migration in many geochemical environments is often controlled by reactions with mineral surfaces, and thus its speciation on mineral surfaces has been extensively investigated. Most previous studies have used IR spectroscopy to characterize the surface B-environments. We present here the first ¹¹B MAS NMR study of surface sorbed boron on minerals. The results demonstrate the capability of this method to effectively probe the local structure of the sorption sites at total B-concentrations in the samples as small as 0.03 wt% and to provide insight into the mechanisms of sorption. Signal is readily resolved for both trigonal (B(3)) and tetrahedral (B(4)) boron exchanged onto boehmite, silica gel and illite, and the resonances are readily assigned on the basis of chemical shift and quadrupole coupling constant. Boron surface densities on illite are approximately order of magnitude greater than on silica gel or boehmite. For boehmite, both B(3) and B(4) occur dominantly as inner-sphere complexes formed by ligand exchange reaction with surface aluminol sites. The B(3)/[B(3) + B(4)] ratio of approximately 0.87 does not vary significantly with pH from 3 to 11, with solution B-concentration, or with washing. The occurrence of B(3) and B(4) as inner-sphere complexes is in agreement with previous suggestions from IR studies of B-sorption on iron hydroxide, allophone, kaolinite, and hydrous ferric oxide. For silica gel, B(3) and B(4) occur principally as outer-sphere complexes or as residual precipitate from un-removed solution. The B(3)/B(4) ratio decreases with increasing pH paralleling the speciation in solution, but the relative abundance of B(4) is greater than in solution. A small fraction of the B(4) occurs as inner-sphere complexes with B(4)-O-Si linkages formed by ligand exchange reaction with silanol sites. For illite, surface boron occurs as outer-sphere B(3) and B(4), as for silica gel, and as inner-sphere B(3) and B(4), as for boehmite. Outer-sphere B(3) and B(4) are dominant at pH 3 and 5, whereas inner-sphere B(3) and B(4) are dominant at pH 9 and 11. The inner-sphere complexes probably form dominantly by ligand exchange reactions involving sites on the broken edges of illite layers.     

Particulate matter source apportionment in Cairo: recent measurements and comparison with previous studies

This paper presents results of an atmospheric particulate matter (PM) monitoring and source apportionment study conducted during summer and fall 2010 in Cairo. These results are compared to those of similar studies in 1999 and 2002. Concentrations of PM_2.5 and PM₁₀ mass and their chemical constituents were determined and chemical mass balance modeling was conducted to estimate the source contributions to ambient PM. Emphasis was placed on characterizing the long-term trends in atmospheric lead (Pb) concentrations and their sources in Cairo. PM_2.5 and PM₁₀ concentrations were highest during fall 1999 at four of the five study sites. This was also the case for open (vegetative/trash) burning contributions, which showed a smaller increase during fall 2010. Burning of agricultural waste after the fall harvest continues to be a major source of PM in Cairo. Both PM_2.5 and PM₁₀ mass decreased dramatically at Shobra, an industrial site, from 1999 to 2010. A reduction of lead smelting has resulted in a decrease of ambient Pb concentrations of up to two orders of magnitude from 1999 to 2010 at Shobra, El-Zamalek, and El-Qualaly. From 1999 to 2010, the mobile source contribution has been relatively stable at most of the study sites. Future efforts to reduce ambient PM should focus on controlling emissions from motor vehicles and open burning and implementing mitigation strategies for reducing resuspended road and construction dust.     

The effects of Mg and H on apatite nucleation at silica surfaces

Apatite (Ca₁₀[PO₄]₆[OH]₂) precipitation from aqueous solutions involves multiple steps, such as nucleation of a precursor calcium phosphate phase, cluster aggregation, crystal growth, and transformation to apatite, which are affected by the presence of other ions in solution. I report the mechanisms by which two ions common in natural solutions, Mg²⁺ and H⁺, affect heterogeneous calcium phosphate nucleation on the amorphous silica surface.     

Association of dissolved aluminum with silica: Connecting molecular structure to surface reactivity using NMR

We studied uptake mechanisms for dissolved Al on amorphous silica by combining bulk-solution chemistry experiments with solid-state Nuclear Magnetic Resonance techniques (²⁷Al magic-angle spinning (MAS) NMR, ²⁷Al{¹H} cross-polarization (CP) MAS NMR and ²⁹Si{¹H} CP-MAS NMR). We find that reaction of Al (1 mM) with amorphous silica consists of at least three reaction pathways; (1) adsorption of Al to surface silanol sites, (2) surface-enhanced precipitation of an aluminum hydroxide, and (3) bulk precipitation of an aluminosilicate phase. From the NMR speciation and water chemistry data, we calculate that 0.20 (±0.04) tetrahedral Al atoms nm⁻² sorb to the silica surface. Once the surface has sorbed roughly half of the total dissolved Al (∼8% site coverage), aluminum hydroxides and aluminosilicates precipitate from solution. These precipitation reactions are dependent upon solution pH and total dissolved silica concentration. We find that the Si:Al stoichiometry of the aluminosilicate precipitate is roughly 1:1 and suggest a chemical formula of NaAlSiO₄ in which Na⁺ acts as the charge compensating cation. For the adsorption of Al, we propose a surface-controlled reaction mechanism where Al sorbs as an inner-sphere coordination complex at the silica surface. Analogous to the hydrolysis of , we suggest that rapid deprotonation by surface hydroxyls followed by dehydration of ligated waters results in four-coordinate (>SiOH)₂Al(OH)₂ sites at the surface of amorphous silica.     

Incorporation of silica into the goethite structure: a microscopic and spectroscopic study

Quartz and iron (hydr)oxide are reactive surface phases that are often associated with one another in soils and sediments. Despite the several studies on the coating of quartz with iron oxides, the reactivity of dissolved species (Si) leached from quartz with iron (hydr)oxides has received limited attention. In this study, goethite synthesized on quartz substrates were characterized using field emission scanning electron microscopy, X-ray diffraction (XRD), transmission electron microscopy, and Fourier-transform infrared (FT-IR) spectroscopy. The SEM characterization revealed that bundles of thin parallel aligned goethite rods were formed at pH?>?10, while large pseudohexagonal crystals of twinned goethite needles were synthesized at pH?≤?10 after dehydration and hydration in the alkaline media. TEM analysis showed expanded and distorted lattice spacing of the crystal structure of iron (hydr)oxide due to silica incorporation. The characterization showed that silica increased the crystallite size of the goethite and transformed its acicular texture to a larger, twinned needle structure. FT-IR and XRD analyses revealed band shifts in crystal bonds as well as new bond formations, which indicate the presence of changes in the chemical environment of Fe–O and Si–O bonds. Thus, the presence of sorbed silicates modifies the crystal and lattice structure of goethite.     

双排桩支护结构的计算方法研究及工程应用

总结了目前基于弹性土抗力法的双排桩支护结构常用计算模型,分别编制了平面杆系有限差分法计算程序,介绍了双排桩支护结构在某实际工程中的应用,比较了这些模型之间计算结果的差异。通过与实测数据的对比,提出了较为合理的模型,并对双排桩支护结构的诸多影响因素进行了计算分析,所得结论对双排桩支护结构的优化设计具有参考价值。     

Structure and properties of loaded silica contacts during pressure solution: impedance spectroscopy measurements under hydrothermal conditions

In order to investigate directly the structure and properties of grain boundaries in silicate materials undergoing pressure solution, in situ measurements of these properties are required. We report electrical impedance spectroscopy measurements, performed, under hydrothermal conditions, on individual glass–glass and glass-quartz contacts undergoing pressure solution. Resulting estimates of the average grain boundary diffusivity product ( Z = Dd_\textav C^* Z = D\delta_{\text{av}} C^{*} ) for silica transport and of the average grain boundary fluid film thickness ( d_\textav \delta_{\text{av}} ) fall in the ranges 6.3 ± 1.4 × 10⁻¹⁸ m³ s⁻¹ and 350 ± 210 nm, respectively. However, the average values for Z and d_\textav \delta_{\text{av}} obtained were likely influenced by cracking and irregular dissolution of the dissolving contact surfaces, rather than representing uniformly wetted grain boundary properties. Post-mortem SEM observations indicate that the contact surfaces were internally rough. Taken together, our data support the notion that during pressure solution of quartz, grain boundary diffusion is rapid, and interface processes (dissolution and precipitation) are more likely to be rate-limiting than diffusion.     

Diagenesis of plant biopolymers: Decay and macromolecular preservation of Metasequoia

Analysis of modern Metasequoia leaves revealed the presence of the structural polyester cutin, guaiacyl lignin units and polysaccharides. Analysis of environmentally decayed Metasequoia leaves revealed that guaiacyl lignin units and cellulose were degraded more than vinyl phenol (the last being the primary pyrolysis product of cutin and plant cuticles) suggesting that cutin is more stable than lignin and cellulose during degradation, contrary to some previous studies. This observation is supported by electron microscopy showing changes in the cellular structure and cuticle of modern, decayed and fossil Metasequoia leaves. Metasequoia fossils from the Eocene of Republic (Washington State) showed a significant aliphatic component, but biopolymeric lignin and polysaccharides were not detected. Fossils from the Eocene of Axel Heiberg revealed the presence of lignin and an aliphatic polymer up to C₂₉ with cellulose, and fossils from the Miocene Clarkia deposit (Idaho) revealed lignin and an aliphatic polymer up to C₂₇ without any polysaccharides. Modern Metasequoia needles heated experimentally in confined conditions generated a macromolecular composition with an aliphatic polymer up to C₃₂ and additional phenolic compounds similar to those present in the fossils. Experimental heating of cutin is known to generate an aliphatic polymer with carbon chain length units <C₂₀. Thus, the n-alkyl component with chain length units >C₂₀ in the heated Metasequoia needles is a product of incorporation of longer chain plant waxes, indicated by the odd/even predominance of the >C₂₇ n-alkanes. The resistant nature of cutin compared to lignin and polysaccharides explains the presence of an n-alkyl component (<C₂₀) in fossil leaves even when polysaccharides are absent and lignin has decayed; cutin and its diagenetically altered products contribute significantly to the presence of aliphatic components in terrestrially derived sedimentary organic matter.     

祁连山七一冰川雷达测厚及冰储量估算北大核心CSCD

冰厚分布和冰储量是冰川水资源、冰川变化和冰川动力学模拟研究的基础数据。本文基于七一冰川冰厚度雷达测量结果,结合GPS位置数据、遥感数据和冰川地形数据,运用协同克里金空间插值算法,绘制了冰厚分布图和冰床地形图,并运用厚度积分法估算了冰川冰储量。2015年七一冰川的面积为2.517km^(2),平均冰厚和冰储量分别为44.9m和0.1129km^(3),实测最大冰厚为115m。海拔4 480~4 600m和海拔4 640~4 800m是七一冰川两个冰厚值较大的区域,平均冰厚分别为88m和97m。     

组合式棚洞结构优化及其计算方法

棚洞是山区公路常见的崩塌落石灾害防治结构。本文通过增设夹心层和增设薄壁管二次消能装置对组合式棚洞结构进行了优化。通过对夹层结构等效并采用薄板理论,建立了棚洞优化结构的内力计算式。利用圆柱壳冲击动力学分析二次消能特性,将组合式棚洞优化结构在落石冲击作用下的动力响应分为四个阶段,建立了三个临界冲击速度的计算式。实例分析表明,棚洞优化结构横梁和纵梁的上、下侧最大弯矩比优化前分别降低了19.7%, 23.7%和10.2%。第一、第二、第三界限冲击速度分别为6.24 m/s、13.50 m/s、15.20 m/s。研究成果对组合式棚洞优化结构的构件预制有指导意义。     

<Superscript>57</Superscript>Fe Mössbauer measurements and electronic structure calculations on natural lawsonites

Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by ⁵⁷Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. ⁵⁷Fe Mössbauer spectra are consistent with the assumption that high-spin Fe³⁺ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with ⁵⁷Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe²⁺. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe³⁺ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe³⁺ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe²⁺. However, it cannot be excluded that Fe²⁺ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H₂O molecule.     

Numerical studies of hyperplasticity with single,multiple and a continuous field of yield surfaces

The development of a new constitutive model would normally require a new procedure to be established for derivation of the incremental response. However, for models generated within the framework of hyperplasticity (using single, multiple or continuous yield surfaces), this derivation can be carried out using standard procedures. In this paper we present first the unified incremental response for a model using a single internal variable for general loading conditions. Next, we develop and explore three different numerical techniques for implementation of this procedure. One of the approaches, which seems superior, is extended to the multi‐surface hyperplastic formulation. Finally, to allow integration of continuous hyperplastic models within the same multi‐surface hyperplastic setting, the issue of discretization of the continuous field of yield surfaces is addressed. Copyright © 2003 John Wiley & Sons, Ltd.     

Electron spectroscopic studies of perfect and defect metal oxide surfaces

A number of surface sensitive electron spectroscopic techniques have been used during the last few years to study the geometric and electronic structure of well characterized surfaces of metal oxide single crystals. For rocksalt monoxides, the (100) surface has been found to be very nearly a truncation of the bulk lattice; only qualitativelow energy electron diffraction (LEED) measurements have been performed on other oxide crystal structures. The electronic structure of nearly perfect oxide surfaces is generally very similar to that of the bulk, although excitonic surface states have been found on some rocksalt oxides. However, the presence of O-vacancy point defects on transition metal oxide surfaces changes their electronic structure drastically, increasing the d-orbital population of the cations adjacent to the defect. These surface defects are generally the active sites for chemisorption, with nearly perfect surfaces being relatively inert with respect to most of the molecules that have been studied.     

Computer simulation of the structure and stability of forsterite surfaces

The aim of this paper is to demonstrate that atomistic simulations can be used to evaluate the structure of mineral surfaces and to provide reliable data for forsterite surfaces up to a plane index of 2 using the code METADISE. The methods used to calculate the surface structure and energy which have more commonly been used to study ceramics are briefly explained as is a comparison with experimental data, most notable the crystal morphology. The predicted morphologies show that all the methods (Donnay-Harker, Attachment energies and equilibrium) show most of the surfaces that are expressed in observed crystals. The equilibrium morphology calculated from the relaxed surface energies is the only method which expresses the {201} surfaces and the {101} surfaces, which appear only upon relaxation. The more stable surfaces are shown to be those which have the highest surface density and more closely resemble close packed structures with highly coordinated surface ions and silicon as far from the surface as possible. The most stable surfaces the {100} which has alternating layers of MgO and SiO₂ terminating with an MgO layer. The structure is similar to the MgO {100} surfaces and has a similar energy (1.28?Jm^?2 compared to 1.20). The second most stable are the {201} which have a stepped surface topology, but is also compact with a relaxed surface energy of 1.56?Jm^?2. The results indicate that atomistic simulation is well suited to the prediction of surface structure and morphology although care must be taken in choosing potentials which model the structure and elastic properties accurately.     

采场内结构体解算及其稳定性计算

采场内结构体的存在对矿块安全回采影响较大,开展其解算方法与稳定性计算方法研究具有重要意义。应用一般块体理论,以采场四周的开拓巷道结构面调查数据为基础,运用GeneralBlock程序初步解算出采场内结构体,分析结构体的真实性,制定真实性分级表。结合3DMine软件,用定义包裹长方体的方法准确刻划结构体的位置,建立简单材料力学模型,计算出固定结构体的最小固定面面积。对于解算出的结构体,在块体可移动性定理和稳定性原理的基础上,运用材料力学、集合等方法,分析矿块回采过程中结构体可移动性,计算结构体稳定性系数。研究成果成功解算出采场内结构体并进行了稳定性分析,对于裂隙岩体加固与采矿工艺优化具有较好的指导意义。