SANS investigation on evolution of pore morphology for varying sintering time in porous ceria

Precipitates of ceria were synthesized by homogeneous precipitation method using cerium nitrate and hexamethylenetetramine at 80°C. The precipitates were ground to fine particles of average size ∼0.7 μm. Circular disks with 10 mm diameter, 2 and 3 mm thickness were prepared from the green compacts by sintering at 1300° C for three different sintering times. Evolution of the pore structures in these specimens with sintering time was investigated by small-angle neutron scattering (SANS). The results show that the peak of the pore size distribution shifts towards the larger size with increasing sintering time although the extent of porosity decreases. This indicates that finer pores are eliminated from the system at a faster rate than the coarser ones as sintering proceeds and some of the finer pores coalesce to form bigger ones.     

On Determining the Percolation Reynolds Number and the Characteristic Linear Dimension for Ideal and Fictitious Porous Media

Various versions of representations of the percolation Reynolds number for porous media with isotropic and anisotropic flow properties are considered. The formulas are derived and the variants are analyzed with reference to model porous media with a periodic microstructure formed by systems of capillaries and packings consisting of spheres of constant diameter (ideal and fictitious porous media, respectively). A generalization of the Kozeny formula is given for determining the capillary diameter in an ideal porous medium equivalent to a fictitious medium with respect to permeability and porosity and it is shown that the capillary diameter is nonuniquely determined. Relations for recalculating values of the Reynolds number determined by means of formulas proposed earlier are given and it is shown that taking the microstructure of porous media into account, as proposed in [1, 2], makes it possible to explain the large scatter of the numerical values of the Reynolds number in processing the experimental data.     

一种岩石损伤本构模型在地下强爆炸中的应用

为了描述地下爆炸波的传播,建立了一种考虑塑性硬化、剪胀和损伤软化效应的岩石本构模型,并应用于地下强爆炸自由场的数值计算,获得的速度和位移波形以及峰值速度衰减曲线等与国外地下试验测量数据和同类计算相比十分接近,从而验证了本构模型的有效性。     

后处理工艺制备多级孔Ti-BEA沸石及其环氧化催化性能

基于脱铝多级孔BEA沸石与二氯二茂钛的固相反应,开展了钛掺杂量可调的多级孔Ti-beta后处理工艺制备研究.对制备的多级孔Ti-beta样品的理化性质进行了表征,包括X射线衍射、氮气吸附脱附测试、扫描电镜、透射电镜、紫外可见吸收光谱和紫外拉曼光谱等.结果表明,多级孔BEA沸石具有较好的化学稳定性,脱铝-钛化的后处理过程未对样品多级孔结构产生明显影响. 以环己烯和十二烯的烯烃环氧化为探针反应表征了合成多级孔Ti-beta与纯相微孔Ti-beta沸石的催化性能.结果表明,在小分子环己烯的环氧化反应中,多级孔Ti-beta沸石的催化活性(转化率59.4%)与微孔Ti-beta相当(转化率57.9%);但是在较大分子十二烯的催化反应中,多级孔结构Ti-beta材料的催化性能(转化率11.1%)明显优于纯相微孔材料(转化率6.8%),且产物中环氧化物选择性更高(分别为60.3%和37.8%).     

The Critical Effect of Niobium Doping on the Formation of Mesostructured TiO2: Single‐Crystalline Ordered Mesoporous Nb‐TiO2 and Plate‐like Nb‐TiO2 with Ordered Mesoscale Dimples

Highly ordered mesoporous niobium‐doped TiO₂ with a single‐crystalline framework was prepared by using silica colloidal crystals with ca. 30 nm in diameter as templates. The preparation of colloidal crystals composed of uniform silica nanoparticles is a key to obtain highly ordered mesoporous Nb‐doped TiO₂. The XPS measurements of Nb‐doped TiO₂ showed the presence of Nb⁵⁺ and correspondingly Ti³⁺. With the increase in the amount of doped Nb, the crystalline phase of the product was converted from rutile into anatase, and the lattice spacings of both rutile and anatase phases increased. Surprisingly, the increase in the amount of Nb led to the formation of plate‐like TiO₂ with dimpled surfaces on one side, which was directly replicated from the surfaces of the colloidal silica crystals.     

Kinetically Controlled Layer-by-Layer Stacking of Metal Oxide 2D Nanosheets

An efficient chemical way to finely control the layer-by-layer stacking of inorganic nanosheets (NS) is developed by tuning the type and composition of intercalant ion, and the reaction temperature for restacking process. The finely controlled stacking of NS relies on a kinetic control of the self-assembly of NS in the presence of coordinating organic cations. A critical role of organic cations in this assembly highlights the importance of the appropriate activation energy. Of prime importance is that a fine-control of the interstratification of 2D NS is highly effective not only in tailoring its pore structure but also in enhancing its electrode activity. The present study clearly demonstrates that the kinetically controlled restacking of NS provides a facile and powerful method to tailor their stacking number and functionality.     

Numerical Solution and Sensitivity Analysis of Pore Liquid Pressure and Cake Porosity to Model Parameters

Filter cake formation is important in groundwater and oil wells where drilling contains suspended mud particles. The accumulation of these mud particles on the borehole wall creates a pressure drop in the well. Furthermore, the migration of colloidal particles into adjacent porous rock could damage the formation and cause productivity decline. In this study, numerical solutions for pore liquid pressure variation across the cake with variable total stress and associated porosity variation are obtained. Mass equations for captured and suspended particles are averaged along the mud cake thickness, taking into account conditions on the cake surface and at the filter septum. The variability of total stress in soil consolidations problem is considered to determine the pore liquid pressure along the mud cake thickness. Then, the relation between porosity and pressure is studied to determine the mud cake porosity. Experimental data obtained by various researchers is used to compare and test the validity of numerical solutions to develop guidelines for model applications. Results show that the pore liquid pressure increases with the decrease of membrane impedance value (i.e. less pervious membrane). Also, the pressure profile has a cubic function of dimensionless cake thickness. The conclusions from the sensitivity analysis conducted in this study agree with earlier conclusions.     

Mean field calculation of effective permeability based on fractal pore space

Effective permeability for porous rocks is calculated using mean field theory. We make two simplifying assumptions about the internal conductances in a network representation of the porous rock: (i) Pore space is characterized by a uniform fractal scaling; (ii) the internal conductances depend only on the characteristic pore sizes. Within these approximations, it is possible to derive a simple probability density for the internal conductances which is used for calculating effective permeability. Good agreement between calculations and experimental data of permeability vs. porosity is achieved.     

Non-gaussian diffusion modeling in composite porous media by homogenization: Tail effect

In the paper anomalous diffusion appearing in a porous medium composed of two porous components of considerably different diffusion characteristics is examined. The differences in diffusivities are supposed to result either from two medium types being present or from variations in pore size (double porosity media). The long-tail effect is predicted using the homogenization approach based on the application of multiple scale asymptotic developments. It is shown that, if the ratio of effective diffusion coefficients of two porous media is of the order of magnitude smaller or equal O( ²), where is a homogenization parameter, then the macroscopic behaviour of the composite may be affected by the presence of tail-effect. The results of the theoretical analysis were applied to a problem of diffusion in a bilaminate composite. Analytical calculations were performed to show the presence of the long-tail effect in two particular cases.Notations c _i the concentration of chemical species in water within the medium i - D _i the effective diffusion coefficient for the medium i - D _ij ^eff the macroscopic (or effective) diffusion tensor in the composite - ERV the elementary representative volume - h the thickness of the period - l a chracteristic length of the ERV or the periodic cell - L a characteristic macroscopic length - n the volumetric fraction of the material 2 - 1–n the volumetric fraction of the material 1 - N the unit vector normal to - t the time variable - x the macroscopic (or slow) space variable - y the microscopic (or fast) space variable - c _1c ,C _2c ,D _1c ,D _2c the characteristic quantities - T,T _1L ,T _2L ,T _1l ,T _2l the characteristic times - c ₁ ^* ,c ₂ ^* ,D ₁ ^* ,D ₂ ^* ,t ^* the non-dimensional variables - the homogenization parameter - ₁ the domain occupied by the material 1 - ₂ the domain occupied by the material 2 - the interface between the domains 1 and 2 - the total volume of the periodic cell - /x_i the gradient operator - the gradient operator