Structural changes and valence states in the MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript>–FeCr<Subscript>2</Subscript>O<Subscript>4</Subscript> solid solution series

The influence on the structure of Fe²⁺ Mg substitution was studied in synthetic single crystals belonging to the MgCr₂O₄–FeCr₂O₄ series produced by flux growth at 900–1200 °C in controlled atmosphere. Samples were analyzed by single-crystal X-ray diffraction, electron microprobe analyses, optical absorption-, infrared- and Mössbauer spectroscopy. The Mössbauer data show that iron occurs almost exclusively as ^IVFe²⁺. Only minor Fe³⁺ (<0.005 apfu) was observed in samples with very low total Fe. Optical absorption spectra show that chromium with few exceptions is present as a trivalent cation at the octahedral site. Additional absorption bands attributable to Cr²⁺ and Cr³⁺ at the tetrahedral site are evident in spectra of end-member magnesiochromite and solid-solution crystals with low ferrous contents. Structural parameters a₀, u and T–O increase with chromite content, while the M–O bond distance remains nearly constant, with an average value equal to 1.995(1) Å corresponding to the Cr³⁺ octahedral bond distance. The ideal trend between cell parameter, T–O bond length and Fe²⁺ content (apfu) is described by the following linear relations: a₀=8.3325(5) + 0.0443(8)Fe²⁺ (Å) and T–O=1.9645(6) + 0.033(1)Fe²⁺ (Å) Consequently, Fe²⁺ and Mg tetrahedral bond lengths are equal to 1.998(1) Å and 1.965(1) Å, respectively.     

P–V Equations of State and the relative stabilities of serpentine varieties

Serpentines are hydrous phyllosilicates which form by hydration of Mg–Fe minerals. The reasons for the occurrence of the structural varieties lizardite and chrysotile, with respect to the variety antigorite, stable at high pressure, are not yet fully elucidated, and their relative stability fields are not quantitatively defined. In order to increase the database of thermodynamic properties of serpentines, the P–V Equations of State (EoS) of lizardite and chrysotile were determined at ambient temperature up to 10 GPa, by in situ synchrotron X-ray diffraction in a diamond-anvil cell. Neither amorphization nor hysteresis was observed during compression and decompression, and no phase transition was resolved in lizardite. In chrysotile, a reversible change in compression mechanism, possibly due to an unresolved phase transition, occurs above 5 GPa. Both varieties exhibit strong anisotropic compression, with the c axis three times more compressible than the others. Fits to ambient temperature Birch–Murnaghan EoS gave for lizardite V ₀=180.92(3) Å³, K ₀ = 71.0(19) GPa and K′ ₀=3.2(6), and for chrysotile up to 5 GPa, V ₀ = 730.57(31) Å³ and K ₀ = 62.8(24) GPa (K′ ₀ fixed to 4). Compared to the structural variety antigorite is stable at high pressure (HP) (Hilairet et al. 2006), the c axis is more compressible in these varieties, whereas the a and b axes are less compressible. These differences are attributed to the less anisotropic distribution of stiff covalent bonds in the corrugated structure of antigorite. The three varieties have almost identical bulk compressibility curves. Thus the compressibility has negligible influence on the relative stability fields of the serpentine varieties. They are dominated by first-order thermodynamic properties, which stabilizes antigorite at high temperature with respect to lizardite, and by out-of-equilibrium phenomena for metastable chrysotile (Evans 2004).     

Induced modifications of kaolinite under ionizing radiation: an infrared spectroscopic study

Radiation effects on kaolinite were investigated using He⁺ ions of 1.5 MeV at radiation doses up to 4.3 × 10⁸ Gy, which are comparable to the doses expected for clay barriers in high-level nuclear waste repositories. The concentration of paramagnetic radiation-induced defects in kaolinite reaches 2 × 10¹⁶ spins/mg (400 at. ppm), as determined by electron paramagnetic resonance spectroscopy. The broadening of X-ray diffraction patterns and transmission infrared (IR) absorption bands is mostly related to the structural strain induced by radiation-induced point defects. The broadening of IR absorption spectra is analyzed using an autocorrelation approach and is related to a change in the distribution of vibrational frequencies due to crystal heterogeneities. We theoretically analyze how the effective dielectric properties of kaolinite samples depend on macroscopic parameters and how irradiation can modify some of them. Irradiation leads to an increase in the electronic polarizability of kaolinite particles, related to the accumulation of radiation-induced electronic point defects.     

Tracing sediment transport history using mineralogical fingerprinting in a river basin with dams utilizing sediment sluicing

Sediment causes a serious problem in relation to dam function. A cooperative sediment sluicing operation has been under way since 2017 to prevent sediment from accumulating in dams in the Mimi River,Miyazaki, Japan. To achieve a smooth and stable operation, it is very important to determine the sediment source and a sediment transport system to maintain the dam’s function. In the current study, the source and transport of sediment from the Mimi River basin have been analyzed with X-ray diffracti...     

淡水珍珠中文石球粒的发现与成珠机制探讨

长期以来,珍珠的成因理论很少涉及在超显微镜结构研究基础上的具体的珍珠形成机制。珍珠与贝壳珍珠层具有较多的相似性,但也存在很多不同。本文在对AFM下首次观察到的淡水珍珠表面纳米级的六方最紧密堆积文石球粒的研究基础上,结合XRD分析对珍珠内部矿物成分差异的研究,试图在贝壳珍珠层成因理论的基础上探讨淡水珍珠的成珠机制。本文将珍珠的形成过程初步归纳为碳酸钙凝胶的形成,碳酸钙球粒的形成,矿物相的转变和后继生长四个阶段。     

铁含量对滑石脱水动力学的影响及其地质意义

在常压下研究了2种不同铁含量滑石的原位X射线衍射高温脱水反应。选取粒径2~5μm的2种不同铁含量的滑石样品,在常压、空气氛围下进行了同步辐射原位X射线衍射脱水实验。实验结果表明,铁含量高的滑石脱水温度明显偏低,2个滑石样品在常压下发生明显脱水反应的温度相差达127℃以上。滑石在常压下的脱水动力机制为随机成核和生长机制,符合Avrami方程。将实验数据拟合Avrami方程得出:n=1.669。由实验结果可以推测,不同铁含量的滑石脱水深度可能有几十到上百千米的差别,研究铁含量与滑石脱水动力的相关性对于了解俯冲带浅-中源地震的成因机制具有重要意义。     

陆相页岩非晶态二氧化硅定量分析新方法探索

通过扫描电镜观察和全岩矿物X衍射实验图谱分析发现,鄂尔多斯盆地延长组页岩中含有一定量的非晶态二氧化 硅。现有的三种计算非晶态二氧化硅含量的方法都有一定的缺陷：化学溶解方法分析周期长、且对其他矿物有一定程度的 溶解;X衍射定量分析法需要计算非晶态二氧化硅衍射图谱上圆丘散射曲线的积分强度,人为误差较高;增量法标样难以 配制,而且误差较高。在总结前人研究的基础上,提出了X衍射与微区矿物定量分析相结合的方法来解决计算多相体系中 非晶态二氧化硅含量这一问题。该方法避开了前人所提出方法的缺点,分别计算得到了结晶态石英含量与二氧化硅含量, 从而间接计算出非晶态二氧化硅含量,然而超高的实验成本也成为该方法在现阶段难以普及的主要原因。     

陕西洛南绿松石的结构构造特征研究

采用偏光显微镜观察、扫描电镜、X射线粉晶衍射分析,对产于绿松石遗址陕西洛南的绿松石进行了详细的结构构造研究。结果表明,陕西洛南绿松石的结构多呈隐晶质结构,部分可见环带状结构、结核状结构;可见块状构造、致密块状构造,部分见葡萄状构造;扫描电镜下观察陕西洛南绿松石多呈鳞片状结构、不规则团块状分布,可见板状绿松石微晶不规则分布,部分见孔隙分布;绿松石微晶越接近它形,孔隙越少,排列越均匀,则结构越紧密,呈现致密块状构造;反之则呈葡萄状构造;XRD实验结果表明,样品中均含有绿松石和石英,部分样品中含有少量的伊利石和高岭石。     

长江三峡库区不同坡段坡地土壤风化特征

通过野外采样和实验室XRD分析,建立了基于XRD分析图谱的风化指标,研究了三峡库区不同坡段坡地的风化程度.三峡库区草堂河流域不同坡段坡地风化特征有一定的共性,如土壤中的主要特征矿物种类相同,主要有高岭石、云母和蛭石;所有样品中高岭石峰值均不高,甚至个别样品图谱上几乎没有高岭石峰的出现;3种主要的特征粘土矿物中以蛭石峰值最高;表层和底层的粘土矿物总量差异也不大.但是不同坡段土壤的风化程度仍存在一定差异.从顶部的分水岭山脊段到山坡上部直形坡崩塌段、山坡下部直形坡搬运段以及最下部的山坡坡麓洪冲积堆积段这4个坡段,4项风化指标均呈增加的趋势,说明从坡上到坡下土壤的风化程度逐渐加大.     

以煤矸石为原料水热法制备4A沸石的动力学研究

以依兰矿区煤矸石为原料研究了4A型沸石的合成方法及其合成动力学模型.推导出含有速率常数的分段式动力学方程;实验分析了最佳反应条件下,不同反应时间内产品的结晶度,通过待定系数法确定出各方程速率常数,整合动力学方程,最终得到利用煤矸石制备4(A)沸石的动力学模型.采用模型方程对实验晶化曲线进行拟合,得到如下结论:4(A)沸石结晶反应发生在凝胶后期;在晶化后期,凝胶的溶解速率决定了晶体生长速率和在有限晶化时间内产品的结晶度.