Red clays from Central and Eastern Crete: geochemical and mineralogical properties in view of provenance studies on ancient ceramics

The existing geochemical diversity of clay deposits consists the underlying assumption for the determination of provenance of archaeological ceramics on the basis of their chemical composition. This assumption was tested on Quarternary red clayey alluviums from Central and Eastern Crete (Greece), an area rich in archaeological pottery and very popular for ceramics provenance studies. This type of clay has been used for pottery production on the island since the antiquity and it is still in use by traditional workshops. Altogether, 17 samples of clayey raw materials were collected from 7 different locations in Central and Eastern Crete, and characterised by chemistry, mineralogy and petrography. The study was focussed on the internal variability within deposits and the diversity among different deposits.It was possible to distinguish all seven deposits from each other on the basis of their chemical composition, taking into account the available mineralogical and petrographical information, although some deposits presented compositional relations. Compared to Neogene clay deposits in the same area, the variability among the examined red clayey deposits was clearly higher and exceeded by far the intra-deposit variability.     

循环荷载作用下饱和黏性土的弹塑性双面模型

基于作者新近提出的一种混合塑性硬化准则和临界状态土力学理论建立了一个三维形式表述的适于饱和黏性土的弹塑性双面模型,此硬化准则是著名的M asing方法在三维应力空间中的推广。该模型的二维形式已采用饱和黏性土样室内动态三轴不排水剪切试验的结果进行了验证并已在另文发表。本文所建的三维弹塑性动本构模型与一个半经验的孔隙水压力增长模式相结合,通过有限元程序ABAQUS*对一个循环荷载作用下的条形基础下部地基土层内的位移、应力分布和超孔隙水压力随时间的变化进行了分析,计算结果表明模型预测的地基土的力学响应是符合实际的。     

Preparation and characterisation of vanadium catalysts supported over alumina-pillared clays

Supported vanadium-containing catalysts were prepared by impregnation of Al-pillared clays with NaVO₃ precursor aqueous solutions. A montmorillonite and a saponite, both natural as well as previously pillared with Al₁₃-Keggin polycations, were used as supports, being impregnated with solutions of the precursor by means of the incipient wetness technique. The layered structure of the supports is maintained after impregnation, and even after calcination of the impregnated solids at 500 °C, although with a significant worsening of the textural properties of the solids, in particular, a loss of specific surface area. Three crystalline vanadium-containing phases were identified in the impregnated solids, namely, NaV₃O₈, AlVO₄ and V₂O₅ (shcherbinaite). The reduction of these phases to V³⁺ species was observed as wide processes in the 450–750 °C range, all of them centred at ca. 600 °C.     

Effect of the nature and structure of pillared clays in the catalytic behaviour of supported manganese oxide

In the present work, the complete oxidation of acetone has been studied over a series of supported manganese oxide catalysts on the unpillared and the Al- and Zr-pillared forms of two natural clays, a montmorillonite and a saponite. A significant influence of the clay supports characteristics on the catalytic performance has been found. The following order of improving catalytic performance is established with respect to the pillars composition: Al-pillared clays < unpillared clays < Zr-pillared clays.     

From clay- to organoclay-film modified electrodes: tuning charge selectivity in ion exchange voltammetry

The surface of two natural smectite-type clay samples was chemically modified by covalent grafting of amine groups, by reaction with γ-aminopropyltriethoxysilane, which were easily protonated in HCl medium. Multisweep cyclic voltammograms of clay-film modified glassy carbon electrodes made of either the raw clays or the propylammonium-functionalized samples exposed to Ru(NH₃)₆³⁺ or Fe(CN)₆³⁻ electroactive probes were obtained. The results indicated a permselective behavior of these clay and organoclay-films based on either favorable or unfavorable electrostatic interactions. The cation-exchanging raw clay film modified electrodes exhibited accumulation properties for Ru(NH₃)₆³⁺ species while rejecting Fe(CN)₆³⁻, whereas the anion-exchanging organoclay coatings acted as a barrier against Ru(NH₃)₆³⁺ while increasing dramatically the concentration of Fe(CN)₆³⁻ species at the electrode surface. Strong binding of the probe to the organoclays resulted in a potential shift of ca. 0.1 V of the voltammetric signals characteristic of the Fe(CN)₆^3−/4− couple in the anodic direction. Their good preconcentration efficiency at low analyte concentration highlighted their interest for electroanalytical applications.     

Molecular design and characterization of catalysts for NO x selective reduction by hydrocarbons in the oxygen excess based upon ultramicroporous zirconia pillared clays

Approaches to design of zirconia pillared clays via control of the properties of pillaring species in solutions were elaborated. Structural features of pillars and Pt + Cu active components fixed at these nanoparticles were shown to determine catalytic properties of pillared clays in NO_x selective reduction by hydrocarbons in the oxygen excess.     

掺灰膨胀土的膨胀特性试验研究

通过生石灰对膨胀土的改性作用,在相同初始含水率的条件下,比较改性前后膨胀力、膨胀率的变化趋势,寻求最佳掺灰率;分析了膨胀力与初始含水率,膨胀率与初始含水率以及终止吸水量与初始含水率等关系.     

Kaolinitic calcined clays: Factors affecting its performance as pozzolans

Five natural kaolinitic clays from different regions of Argentine, with different kaolinite content, different impurities and different degree of crystallinity were calcined in a fixed-bed electrical furnace at 700 °C. Clays were characterized by X-ray diffraction (XRD) and Fourier transformed infra-red spectrometry (FTIR) that provides an index about the order/disorder of the structure. After heat treatment, the structural changes were characterized by XRD and FTIR, and pore size distribution and specific surface were determined. Their pozzolanic activity was evaluated with the Frattini test, electrical conductivity in saturated Ca(OH)₂ solution and compressive strength on mortars at 7, 28 and 90 days. Among tested clays, four of them can be classified as pozzolan by the Frattini test. The pozzolanic activity of the natural clays showed good correlation with the content of kaolinite, the inversed of structure order determined by FTIR, and the specific surface of calcined clays. This study confirms that natural clays other than pure kaolinite can be interesting pozzolanic materials when thermally activated.     

The meaning of surface area and porosity measurements of clays and pillared clays

Pillared clays (PC) generally present textural complexity, geometrical constraints and possible chemical heterogeneity by pillaring. As far as surface area and porosity measurements by physical adsorption of nitrogen are concerned, this overall complexity introduces interpretation difficulties. We consider two aspects of this problem in pillared clays.The textural complexity stems from the distribution of charge density, from the deformation of the host layers and from their entanglement. The microtexture is controlled by the wet preparation chemistry, to a large extent by the drying method as examplified by the titanium pillared montmorillonites.The geometrical constraints arise from the fact that the interlamellar space of the PC is (so far) microporous or just mesoporous. The small distance between the layers, of the order of one or a few molecular diameters, is therefore expected to perturb the arrangement of the pore filling molecules. The molecular confinement is a major source of underestimation of the total pore volume in the interlamellar space. It makes the surface area determination difficult and of little physical significance. Probably microporosity values are more valuable criterion of pillaring as shown in the titanium pillared samples.In addition to these two aspects, one has also to consider a possible chemical heterogeneity arising from the simultaneous presence of pillars, exchangeable ions and precipitated species. This can lead to a complex behaviour of surface area and microporosity as examplified by the mixed aluminium-iron pillared laponites.