Theoretical modelling of cis -vacant and trans -vacant configurations in the octahedral sheet of illites and smectites

 The cis-vacant configurations of smectites and illites have been studied theoretically by using transferable empirical interatomic potentials. A wide range of compositions of octahedral and tetrahedral cation and interlayer charge has been considered. All results have been compared with the trans-vacant configurations in each sample. The calculated values reproduce the differences in the lattice parameters between the cis- and trans-vacant configurations of experimental studies. Taking into account the cis-/trans-vacant proportion, the calculated structures agree with experiment for the main structural features of the crystal lattice. The effect of the cation substitution in the octahedral and tetrahedral sheets on the cell parameters has been also studied, finding good linear relationships. The calculated cation substitution effects are consistent with experimental results. Although the energy difference between the cis- and trans-vacant configurations is small, the cis-vacant is more stable when the composition of clays is more smectitic, like the experimental behaviour. Similar trends of the cation substitution effect on the cis-/trans-vacant proportion to the experimental results are found. The structure of the hydroxy groups has also been analysed. The OH bond length, the orientation of the O–H bond with respect to the (001) plane and the non-bonding H...O distances have been studied. Received: 4 September 2000 / Accepted: 29 January 2001     

Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M₁₂(Sb,As)₄S₁₃. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S1₂S2 triangle is about 0.56 and 0.65 Å for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 Å. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 Å and the interatomic distances by 0.01 Å on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 Å for tetrahedrite and by more than 0.15 Å for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.     

酸前法合成羧甲基淀粉的研究

本文采用酸前法合成工艺,探讨了木薯淀粉羧甲基化反应的一般规律;考察了反就绎产物取代度和粘度的影响,通过正交试验,找到了最佳工艺条件,并对产物的性能与羟甲基纤维素进行了对比测试。     

Simulated slope development sequences in a three-dimensional context

Downvalley sequences of slope profiles have been inferred to represent temporal sequences. Results from a simulation model are presented which demonstrate that for a slope system in dynamic equilibrium, the downvalley variation in form is best explained as a response to downvalley variation in basal conditions, and hence that in such an equilibrium system the direct substitution of time for space is not valid.     

Aluminum substitution mechanisms in perovskite-type MgSiO<Subscript>3</Subscript>: an investigation by Rietveld analysis

Al-containing MgSiO₃ perovskites of four different compositions were synthesized at 27 GPa and 1,873 K using a Kawai-type high-pressure apparatus: stoichiometric compositions of Mg_0.975Si_0.975Al_0.05O₃ and Mg_0.95Si_0.95Al_0.10O₃ considering only coupled substitution Mg²⁺ + Si⁴⁺ = 2Al³⁺, and nonstoichiometric compositions of Mg_0.99Si_0.96Al_0.05O_2.985 and Mg_0.97Si_0.93Al_0.10O_2.98 taking account of not only the coupled substitution but also oxygen vacancy substitution 2Si⁴⁺ = 2Al³⁺ + V_O¨. Using the X-ray diffraction profiles, Rietveld analyses were performed, and the results were compared between the stoichiometric and nonstoichiometric perovskites. Lattice parameter–composition relations, in space group Pbnm, were obtained as follows. The a parameters of both of the stoichiometric and nonstoichiometric perovskites are almost constant in the X _Al range of 0–0.05, where X _Al is Al number on the basis of total cation of two (X _Al = 2Al/(Mg + Si + Al)), and decrease with further increasing X _Al. The b and c parameters of the stoichiometric perovskites increase linearly with increasing Al content. The change in the b parameter of the nonstoichiometric perovskites with Al content is the same as that of the stoichiometric perovskites within the uncertainties. The c parameter of the nonstoichiometric perovskites is slightly smaller than that of the stoichiometric perovskites at X _Al of 0.10, though they are the same as each other at X _Al of 0.05. The Si(Al)–O1 distance, Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O distance of the nonstoichiometric perovskites keep almost constant up to X _Al of 0.05, and then the Si(Al)–O1 increases and both of the Si(Al)–O1–Si(Al) angle and minimum Mg(Al)–O decrease with further Al substitution. These results suggest that the oxygen vacancy substitution may be superior to the coupled substitution up to X _Al of about 0.05 and that more Al could be substituted only by the coupled substitution at 27 GPa. The Si(Al)–O1 distance and one of two independent Si(Al)–O2 distances in Si(Al)O₆ octahedra in the nonstoichiometric perovskites are always shorter than those in the stoichiometric perovskite at the same Al content. These results imply that oxygen defects may exist in the nonstoichiometric perovskites and distribute randomly.     

Phase relations and equation-of-state of aluminous Mg-silicate perovskite and implications for Earth's lower mantle

We have investigated the effect of Al³⁺ on the room-temperature compressibility of perovskite for stoichiometric compositions along the MgSiO₃-AlO_1.5 join with up to 25 mol% AlO_1.5. Aluminous Mg-perovskite was synthesized from glass starting materials, and was observed to remain a stable phase in the range of ∼30-100 GPa at temperatures of ∼2000 to 2600 K. Lattice parameters for orthorhombic (Pbnm) perovskite were determined using in situ X-ray diffraction at SPring8, Japan. Addition of Al³⁺ into the perovskite structure increases orthorhombic distortion and unit cell volume at ambient conditions (V₀). Compression causes anisotropic decreases in axial length, with the a axis more compressive than the b and c axes by about 25% and 3%, respectively. The magnitude of orthorhombic distortion increases with pressure, but aluminous perovskite remains stable to pressures of at least 100 GPa. Our results show that substitution of Al³⁺ causes a mild increase in compressibility, with the bulk modulus (K₀) decreasing at a rate of −67±35 GPa/X_Al. This decrease in K₀ is consistent with recent theoretical calculations if essentially all Al³⁺ substitutes equally into the six- and eight-fold sites by charge-coupled substitution with Mg²⁺ and Si⁴⁺. In contrast, the large increase in compressibility reported in some studies with addition of even minor amounts of Al is consistent with substitution of Al³⁺ into six-fold sites via an oxygen-vacancy forming substitution reaction. Schematic phase relations within the ternary MgSiO₃-AlO_1.5-SiO₂ indicate that a stability field of ternary defect Mg-perovskite should be stable at uppermost lower mantle conditions. Extension of phase relations into the quaternary MgSiO₃-AlO_1.5-FeO_1.5-SiO₂ based on recent experimental results indicates the existence of a complex polyhedral volume of Mg-perovskite solid solutions comprised of a mixture of charge-coupled and oxygen-vacancy Al³⁺ and Fe³⁺ substitutions. Primitive mantle with about 5 mol% AlO_1.5 and an Fe³⁺/(Fe³⁺+Fe²⁺) ratio of ∼0.5 is expected to be comprised of ferropericlase coexisiting with Mg-perovskite that has a considerable component of Al³⁺ and Fe³⁺ defect substitutions at conditions of the uppermost lower mantle. Increased pressure may favor charge-coupled substitution reactions over vacancy forming reactions, such that a region could exist in the lower mantle with a gradient in substitution mechanisms. In this case, we expect the physical and transport properties of Mg-perovskite to change with depth, with a softer, probably more hydrated, defect dominated Mg-perovskite at the top of the lower mantle, grading into a stiffer, dehydrated, charge-coupled substitution dominated Mg-perovskite at greater depth.     

提高金刚石钻头工作能力的试验研究

根据实验研究结果建议从金刚石镀膜、胎体添加稀土元素两个方面来提高金刚石的热稳定性、胎体对胎体的包镶能力及其使用性能.这两个措施为实现以铁代替胎体材料中的钴创造了有利条件.      

城市化进程中工业用地置换的生态环境影响探讨

城市工业用地置换是城市化发展的必然要求,本文对城市开发过程中工业用地置换产生的生态环境影响进行了理论探讨,并以上海某工业区的工业用地置换过程为例进行了实证分析,认为原生产遗留的土壤污染以及置换过程的搬迁、施工对区域的生态环境产生影响,应通过实施环境影响评价及建立全过程的生态环境管理体系予以控制。     

北极航道的贸易替代效应与贸易互补效应分析

随着北极冰雪加速消融,北极航道在国际贸易运输中的关注度日益提升。文章采用理论模型进行分析,认为北极航道通过贸易替代效应与贸易互补效应对世界贸易格局产生影响。研究发现北极航道开通将：提升航道沿线各国间的贸易潜力,改变沿线国与非沿线国间部分贸易活动的流向;催生北极航道沿线国之间部分贸易活动的产生,改变北极航道沿线国之间部分贸易活动的流量。     

类质同象置换对磁铁矿表面反应性的制约机制

铁(氢)氧化物矿物对环境物质的地球化学行为有着重要的制约作用。相比于其他铁氧化物,磁铁矿具有一些独特的结构特征与表面性质,而赋予其良好的氧化还原活性。天然磁铁矿结构中广泛存在类质同象置换,探讨类质同象置换对磁铁矿表面反应的制约机制,有助于深刻理解磁铁矿族矿物在环境自净化过程中的作用机制。本文介绍了典型置换离子在磁铁矿结构中的赋存状态,及其对磁铁矿物化性质影响,重点阐述类质同象置换对磁铁矿表面反应性(如吸附、氧化、还原等性能)的制约机制,最后针对已有的相关研究现状以及面临的挑战,为未来的研究方向提出了一些设想和建议。