Thermal expansion of gehlenite, Ca2Al[AlSiO7], and the related aluminates LnCaAl[Al2O7] with Ln=Tb, Sm

The thermal expansion of gehlenite, Ca₂Al[AlSiO₇], (up to T=830 K), TbCaAl[Al₂O₇] (up to T=1,100 K) and SmCaAl[Al₂O₇] (up to T=1,024 K) has been determined. All compounds are of the melilite structure type with space group Thermal expansion data was obtained from in situ X-ray powder diffraction experiments in-house and at HASYLAB at the Deutsches Elektronen Synchrotron (DESY) in Hamburg (Germany). The thermal expansion coefficients for gehlenite were found to be: α₁=7.2(4)×10⁻⁶ K⁻¹+3.6(7)×10⁻⁹ΔT K⁻² and α₃=15.0(1)×10⁻⁶ K⁻¹. For TbCaAl[Al₂O₇] the respective values are: α₁=7.0(2)×10⁻⁶ K⁻¹+2.0(2)×10⁻⁹ΔT K⁻² and α₃=8.5(2)×10⁻⁶ K⁻¹+2.0(3)×10⁻⁹ΔT K⁻², and the thermal expansion coefficients for SmCaAl[Al₂O₇] are: α₁=6.9(2)× 10⁻⁶ K⁻¹+1.7(2)×10⁻⁹ΔT K⁻² and α₃=9.344(5)×10⁻⁶ K⁻¹. The expansion-mechanisms of the three compounds are explained in terms of structural trends obtained from Rietveld refinements of the crystal structures of the compounds against the powder diffraction patterns. No structural phase transitions have been observed. While gehlenite behaves like a ’proper’ layer structure, the aluminates show increased framework structure behaviour. This is most probably explained by stronger coulombic interactions between the tetrahedral conformation and the layer-bridging cations due to the coupled substitution (Ca²⁺+Si⁴⁺)-(Ln ³⁺+Al³⁺) in the melilite-type structure. Electronic Supplementary Material Supplementary material is available for this article at     

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The Role of Fluvial and Glacial Erosion in Landscape Evolution: The Ben Ohau Range,New Zealand

A morphometric comparison of valleys has been made for the Ben Ohau Range in the central Southern Alps of New Zealand. The range is undergoing rapid tectonic transport and uplift. The humid north of the range is a glacial trough-and-arête landscape, with a temperate glacial climate. The dry south has rounded divides and plateau remnants dissected by fluvial valleys. Assuming that space–time substitution allows today's spatial valley-form transition to represent evolutionary stages in valley development, the tectonic history allows time constraints to be placed on the rate of transition to an alpine glacial landscape. Morphometric change has been quantified using hypsometric curves, and distance–elevation plots of cirque and valley-floor altitudes. Ancestral fluvial valleys have less concave long profiles but are stepped at altitude owing to the presence of high-level cirques and remnant plateau surfaces, and possess a low proportion of land area at low elevation. Increasing glacial influence is manifest as smoother, more deeply concave long profiles and U-shaped cross-profiles associated with a higher proportion of the land area at lower elevation. The full morphological transition has involved up to 2.4 km of vertical denudation over the 4 Ma lifetime of the mountain range, of which 80 per cent would have occurred by preglacial fluvial erosion. Combining the trajectory of tectonic transport with reconstructed glaciation limits and climatic history, it is indicated that about 200 ka of temperate glacial erosion produces recognizable trough-and areête topography. Mean and modal relief increase where glacial activity is confined to cirques, but decrease when trough incision by ice becomes established as a dominant process in the landscape. © 1997 by John Wiley & Sons, Ltd.     

Effect of pore geometry on Gassmann fluid substitution

Although there is no assumption of pore geometry in derivation of Gassmann's equation, the pore geometry is in close relation with hygroscopic water content and pore fluid communication between the micropores and the macropores. The hygroscopic water content in common reservoir rocks is small, and its effect on elastic properties is ignored in the Gassmann theory. However, the volume of hygroscopic water can be significant in shaly rocks or rocks made of fine particles; therefore, its effect on the elastic properties may be important. If the pore fluids in microspores cannot reach pressure equilibrium with the macropore system, assumption of the Gassmann theory is violated. Therefore, due to pore structure complexity, there may be a significant part of the pore fluids that do not satisfy the assumption of the Gassmann theory. We recommend that this part of pore fluids be accounted for within the solid rock frame and effective porosity be used in Gassmann's equation for fluid substitution. Integrated study of ultrasonic laboratory measurement data, petrographic data, mercury injection capillary pressure data, and nuclear magnetic resonance T₂ data confirms rationality of using effective porosity for Gassmann fluid substitution. The effective porosity for Gassmann's equation should be frequency dependent. Knowing the pore geometry, if an empirical correlation between frequency and the threshold pore‐throat radius or nuclear magnetic resonance T₂ could be set up, Gassmann's equation can be applicable to data measured at different frequencies. Without information of the pore geometry, the irreducible water saturation can be used to estimate the effective porosity.     

Structure refinement of astrophyllite

The crystal structure of astrophyllite K₂Na(Fe, Mn, Mg,□)₇[Ti₂(Si₄O₁₂)₂|O₃](OH, F)₄ has been refined. The dimensions of the triclinic unit cell are: a = 0.5359(2) nm,b = 1.1614(4) nm, c = 1.1861(4) nm, α= 113.16(2)°, β= 103.04(2)°,γ= 94.56(2)°,V = 0.6495(5) nm³, Z= 1, space group P1, R=0.057 for 5308 reflections |F_o|>3σ|F_o|. According to structural and compositional differences the monoclinic astrophyllite K₂NaNa(Fe, Mn)₄Mg₂Ti2[Si₄O₁₂]₂(OH)₄(OH, F)₂ and astrophyllite should be considered as two different mineral species. Astrophyllite, monoclinic astrophyllite, bafertisite and lamprophyllite contain heteropolyhedral sheets which topologically are related with Si, O sheets of mica where one or several SiO₄ tetrahedra are replaced by TiO _n polyhedra. Therefore this heterophyllotitanosilicate series represents a kind of functional substitution in inorganic crystals.     

不同取代位置羧甲基壳聚糖的核磁共振波谱和电位滴定分析

本文制备了O-羧甲基壳聚糖、N-羧甲基壳聚糖和N,O-羧甲基壳聚糖,并采用核磁共振波谱以及电位滴定方法对不同取代位置羧甲基壳聚糖取代度进行了分析。结果表明,核磁共振碳谱及DEPT谱可以确定羧甲基壳聚糖中羧甲基的取代位置,电位滴定法可以确定O-位羧甲基、N-位羧甲基以及总羧甲基的取代度,是一种简单易行的方法。     

Modeling of dioctahedral 2:1 phyllosilicates by means of transferable empirical potentials

 Dioctahedral 2:1 phyllosilicates with different interlayer charge have been studied theoretically by using transferable empirical interatomic potentials. The crystal structures of pyrophyllite, muscovite, margarite, beidellite, montmorillonite, and different smectites and illites have been simulated. The interatomic potentials were able to reproduce the experimental structure of phyllosilicates with high, medium and low interlayer charge. The calculated structures are in agreement 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 structural features has been also studied. Good linear relationships have been found, and the calculated effects are consistent with experimental results. Some unknown structural features of the crystal structures of clays are predicted in this work. Received: 8 March 2000 / Accepted: 19 September 2000     

常用海图投影平面上大椭圆航线的表象与曲率分析

利用空间矢量方法推导出了椭球面上只与起止点地理坐标有关的大椭圆航线方程,代入4种常用海图投影的正解公式,得到不同投影平面上的大椭圆参数方程;利用上述参数方程进而推导出了不同投影面上大椭圆航线的曲率与曲率半径公式。选取伦敦到纽约的大椭圆航线为例,通过绘制不同投影面上的大椭圆航线并分析其曲率、曲率半径变化曲线可知,大椭圆航线在日晷投影上的表象为曲率处处为0的直线,而在其他投影面上的表象为曲率较小但不断变化的曲线。利用推导的曲率半径公式可以计算各类大椭圆航线上任意位置的“代曲直距”,方便在不同比例尺的海图上对大椭圆航线进行量测和绘制,提高作图效率。     

土地利用空间格局的置换变化与代换变化分析

为揭示土地利用空间格局的动态变化,本文基于土地利用转移矩阵,从类型间的空间转移过程出发,构建了置换变化与代换变化的计算模型,并对其2种变化进行了分析。置换变化是2种类型之间以相同面积发生空间位置的置换过程,且各种类型的数量结构保持不变;代换变化则是所研究类型的数量结构保持不变,而与之转换的其他类型数量上的增加或减少;从而将单一类型的总变化进一步细分为置换变化、代换变化与净变化。以晋江流域1985年与2006年2期土地利用格局的变化为例进行分析,结果显示：在1985-2006年间,晋江流域的土地利用空间格局发生了显著变化;园地、建设用地、未利用地呈现扩张态势,草地与旱地呈现萎缩变化,水域变化不大;这6种地类的交换变化面积相对较少,以置换变化为主。水田与林地则主要表现为空间位置的交换变化,其中,水田呈现出与林地、旱地2种类型之间的置换变化,而林地则主要是园地-林地与林地-草地这2对类型间的代换变化。结果表明,通过置换变化与代换变化的分析,更细化了各种类型之间的动态变化过程。