缺陷化学在新材料研究中的作用

简述了缺陷的类型及其在新材料制备中的作用,通过实例分析固溶体和非化学计量化合物缺陷对材料物理化学性能的影响,阐明缺陷化学是一种研究新型功能材料的有力手段,根据新材料的发展趋势分析了缺陷化学可能取得的重大突破及新的研究热点。     

古玉器的化学风化机理初探之二——块状模拟实验

在前文粉末态模拟实验基础上,初步模拟古玉埋藏的酸性以及碱性环境,通过对不同材质玉料的块状形态在酸、碱缓冲溶液中的浸泡实验,并与粉末态玉料的浸泡结果进行对比分析,以深化对古玉器风化机理的认识。     

Evidence for kinks in structural and thermodynamic properties across the forsterite–fayalite binary from thin-film IR absorption spectra

Infrared absorbance spectra over ∼100 to 1,800 cm⁻¹ were collected from optically thin films of 21 samples with compositions spanning the forsterite–fayalite binary. Polarization information from previous specular reflectance data on end-members was used in tracing the peaks across the entire binary. Peak positions (ν_i) were constrained by Lorentzian decompositions. Fitting also constrained widths for singlet peaks but for doublets and triplets, variation in ν_i with composition among the constituent polarizations alters widths from intrinsic. Because film thicknesses of 0.6–1.4 μm were estimated, our band strengths are approximate; however, relative intensities should be correct. Only for a few peaks does ν_i vary smoothly across the entire binary; instead, distinct linear trends exist for Fe- and Mg-rich olivines. Discontinuities and kinks in ν_i(X) occur at X = Mg/(Fe + Mg) = 0.7 and are accompanied by a change in intensity patterns. This interesting behavior was not revealed in previous spectra of powder dispersions. The contrasting character of IR vibrations for Fe- and Mg-rich olivines is inferred to arise from structural variations because (1) frequency is related to bond length, (2) other factors affecting frequency (cation mass and probably bonding type) vary linearly across the binary, and (3) available data on unit cell parameters are consistent with distinct trends for forsterites and fayalites. Vibrational components of heat capacity (C _V) and enthalpy (H) calculated from ν_i, were found to be slightly more negative than linear interpolations between values for forsterite and fayalite. Our computations give smaller negative excesses from ideality in H than do previous calorimetric measurements, but are equal within experimental uncertainties.     

Effects of orientation on the diffusive properties of fluid-filled grain boundaries during pressure solution

An unresolved issue in the study of pressure solution in rock materials is the dependence of grain boundary structure and diffusive properties on the mutual orientation of neighbouring grain lattices. We report electrical measurements yielding the diffusivity of differently oriented halite–glass and halite–halite contacts loaded in the presence of brine. The halite–glass contact experiments show pressure solution of the halite and an effect of halite lattice orientation on grain boundary transport. Post-mortem observations show an orientation-dependent grain boundary texture controlled by the periodic bond chains in the halite structure. It is inferred that this texture determines the internal grain boundary structure and properties during pressure solution. In the halite–halite experiments neck-growth occurred, its rate depending on twist-misorientation. The results imply that deformation by pressure solution may lead to lattice-preferred orientation development, and that polymineralic rocks may deform faster at lower stresses than monomineralic rocks.     

Thermodynamics of mixing in diopside–jadeite,CaMgSi<Subscript>2</Subscript>O<Subscript>6</Subscript>–NaAlSi<Subscript>2</Subscript>O<Subscript>6</Subscript>, solid solution from static lattice energy calculations

Static lattice energy calculations (SLEC), based on empirical interatomic potentials, have been performed for a set of 800 different structures in a 2 × 2 × 4 supercell of C2/c diopside with compositions between diopside and jadeite, and with different states of order of the exchangeable Na/Ca and Mg/Al cations. Excess static energies of these structures have been cluster expanded in a basis set of 37 pair-interaction parameters. These parameters have been used to constrain Monte Carlo simulations of temperature-dependent properties in the range of 273–2,023 K and to calculate a temperature–composition phase diagram. The simulations predict the order–disorder transition in omphacite at 1,150 ± 20°C in good agreement with the experimental data of Carpenter (Mineral Petrol 78:433–440, 1981). The stronger ordering of Mg/Al within the M1 site than of Ca/Na in the M2 site is attributed to the shorter M1–M1 nearest-neighbor distance, and, consequently, the stronger ordering force. The comparison of the simulated relationship between the order parameters corresponding to M1 and M2 sites with the X-ray refinement data on natural omphacites (Boffa Ballaran et al. in Am Mineral 83:419–433, 1998) suggests that the cation ordering becomes kinetically ineffective at about 600°C.     

大别造山带毛屋超镁铁岩的铂族元素研究

采用镍锍火试金法结合ICP-MS分析了毛屋斜方辉石岩和石榴二辉岩样品中的Ir、Ru、Rh、Pt和Pd的含量,结果显示其铂族元素(PGE)的含量随岩石类型无规律性的变化,原始地幔标准化后的铂族元素分布模式呈负斜率,Pd、Ir发生了分异。毛屋超镁铁岩铂族元素特征的形成受岩石中铂族元素的存在相制约,PPGE富集在富Cu硫化物,而IPGE以类似残留相、不熔的单硫化物固熔体形式存在,其中地壳混染也起了一定的作用;同时,成岩过程中流体的存在造成了Pt和Pd的活化。因此,单硫化物固熔体和流体的共同作用形成了毛屋超镁铁岩类似残留地幔岩的铂族元素分布特征。     

GEO导航卫星定轨观测模型

根据GEO导航卫星的轨道特性,给出了严密的伪距观测和载波相位观测数学模型;讨论了其轨道和星钟差的解算条件,以及多星组差定轨的可行性。结果表明:在利用伪距时,如果测站钟差已知,需要4个以上站的数据才能进行定轨和星钟解算;如果站钟、星钟钟差已知,需要3个以上站的数据才能确定轨道。在利用站间组差伪距时,须有4个以上测站的钟差信息才能进行轨道和星钟解算;利用GEO卫星与MEO(IGSO)卫星组差定轨时,需要GEO卫星钟差已知且有3组星间组差数据。利用GEO卫星载波相位观测资料,不能单独解算轨道。     

大地主题解算方法综述

大地主题解算是大地测量中的重要问题,由于椭球的复杂性,随之产生的解算方法也是多种多样。本文分析了大地主题解算的一般方法及其公式的适用范围,指出了它们的特点和不足,讨论了现今常用解算方法存在的问题和进一步的研究方向。     

Computing periodic orbits of the three-body problem: Effective convergence of Newton’s method on the surface of section

We consider Newton’s method for computing periodic orbits of dynamical systems as fixed points on a surface of section and seek to clarify and evaluate the method’s uncertainty of convergence. Several fixed points of various multiplicities, both stable and unstable are computed in a new version of Hill’s problem. Newton’s method is applied with starting points chosen randomly inside the maximum possible—for any method—circle of convergence. The employment of random starting points is continued until one of them leads to convergence, and the process is repeated a thousand times for each fixed point. The results show that on average convergence occurs with very few starting points and non-converging iterations being wasted.     

The GPS-gravimetry boundary value problem

Boundary value problem (BVP) plays a funda-mental role in physical geodesy that aims at determin-ing the earth’s shape and its external gravity field. TheMolodensky BVP and the Stokes BVP are typical inphysical geodesy, and the gravity anomaly is a kind ofbasic data. With the wide use of GPS, measurementaccuracy of the earth’s surface can reach one centime-ter, while that of the gravity measurement can reachμgals. Hence, it is necessary to establish a new kind ofBVP which can satisfy…