多孔介质分形结构热方程的多重双尺度概率模型与数值模拟

多孔介质分形结构既含有大量微米量级甚至纳米量级的微孔隙,也含有大量厘米甚至米量级的宏观孔洞。如果又假设复相材料和孔隙的就位性及形状大小服从某一概率分布。此时无论是理论分析或是数值计算均非常困难。本文对此问题,初步建立多重双尺度概率模型,井给出数值实验结果。     

频率搅拌嵌套混响室场分布的统计特性

为明确频率搅拌方式下嵌套混响室内的场分布,在混响室电磁统计特性的基础上,对嵌套小室内外的场分布进行了理论研究,重点对小混响室开窗大小对场分布的影响进行了分析。当窗口为电大尺寸时,小混响室内外均服从瑞利分布;为电小尺寸时,参考车-车链路通信的统计特性,小混响室内部应满足双瑞利分布。在某大型混响室内,借助矢量网络分析仪,通过测试收、发天线间的散射参数S21,实现了样本数据的快速采集,并将样本数据与理论分布模型进行了拟合优度检验(KS检验),检验结果证明了假设分布的正确性。     

多孔性固体与气体传递反应过程特性研究

本文建立了多孔性固体与气体反应的流态化实验装置,进行烟气脱硫反应实验,以此分析反应过程中固体颗粒的孔隙结构变化,确定转化率等重要数据。实验表明,固体孔隙特性对反应过程起关键性作用。相同条件下,初始孔隙率越大,可使相同反应时间内达到的转化率越高,即初始孔隙率决定最终转化率,但是孔隙分布方式则影响反应过程特性,即具有相同初始孔隙率不同孔隙结构分布的固体反应物达到最终转化率的过程不同。     

泡沫镍孔隙尺度光谱辐射特性的实验与数值研究

实验测量了不同厚度的泡沫镍在0.4~2.2μm波长的法向-半球反射率/透射率,采用蒙特卡罗法对泡沫镍的计算机断层扫描结构进行孔隙尺度辐射传输建模,对比研究了泡沫镍辐射特性随入射光谱和样品厚度的变化,计算得到了泡沫镍辐射特性的孔隙尺度分布特征。结果表明:所建立的泡沫镍孔隙尺度辐射传输模型在计算其光谱辐射特性方面具有正确性。波长增长,吸收率逐渐降低,反射率逐渐升高;样品厚度增加,吸收率逐渐升高并趋于稳定,透射率逐渐降低至0。孔隙尺度辐射特性分布强烈依赖于局部纹理结构,波长1.5μm时,泡沫孔隙中的平均吸收率是肋筋上的1.5倍,而肋筋上的平均反射率则达到孔隙中平均反射率的3.7倍。     

离子浓度及表面结构对岩石孔隙内水流动特性的影响

酸性环境引发的岩石孔隙表面溶解增加了孔隙内水溶液的盐离子浓度,破坏了孔隙的表面结构.本文采用分子动力学模拟的方法研究了纳米级岩石孔隙内水溶液的流动特性,分析了盐离子浓度和孔隙表面结构对水流速度分布的影响及原因.研究结果表明:纳米级岩石孔隙内的水溶液流动符合泊肃叶流动特性,流速呈"抛物线"分布;随盐离子浓度增加,水溶液内部氢键网络变得更为致密,水黏度随其呈线性增长;水溶液中离子浓度越大,孔隙表面对水流动的阻力越大,最大流速越小,速度分布的"抛物线"曲率半径越大;岩石孔隙表面结构的破坏改变了流动表面的粗糙程度,增加了孔隙表面对H2O分子的吸引力.随表面结构破坏程度的增大,水溶液在近壁区域的密度增大,流速降低;当表面破坏程度达到50%时,水溶液在近壁区域出现了明显的负边界滑移现象.     

单一微孔隙中油水相对渗透率特性研究

孔隙渗流是多孔介质渗流的微观基础。本文对孔隙中的两相流应用分相模型,结合达西渗流定律,提出了适用于油水两相的相对渗透率模型,得到相对渗透率与孔隙度无关、相对渗透率只是微孔隙中相态分布的几何尺度以及流体饱和度的函数等结论。设计了微流动实验装置,以去离子水和白油的乳化液为两相流体,在不同含油率下研究了微孔隙中油水两相的渗流特性,并与相应条件下的模型计算结果进行对比。结果表明,对于低渗透尺度等级的微孔隙,实验与计算结果吻合较好,对于高渗透尺度等级的微孔隙,实验与计算结果存在偏差。在某些条件下,油与水的相对渗透率之和存在大于1的情形。     

无限流体中孔隙介质圆柱周向导波的传播特性

为研究无限大流体约束的孔隙圆柱中周向导波的传播规律,分析孔隙参数对导波传播特性的影响,建立了无限流体中孔隙介质圆柱的理论模型,利用孔隙介质弹性波动理论,建立了周向导波频散方程,通过数值模拟计算得到无限流体中孔隙介质圆柱的频散曲线,探讨了圆柱半径和孔隙参数对导波传播特性的影响,并对导波的衰减特性进行了分析;通过数值计算,得到了周向导波的时域波形,讨论了孔隙参数对波形的影响.结果表明,孔隙介质圆柱半径的改变影响圆柱尺度,孔隙度的改变影响孔隙介质中体声波的波速,都对周向导波频散曲线产生一定的影响,所得到的频散曲线特征及衰减曲线与时域波形吻合.研究结果对开展无限流体中孔隙介质圆柱的超声无损评价提供了一定的理论参考.     

木材微结构对其传热特性影响的实验研究

对落叶松和红松的试样进行了剖面结构的扫描电镜观察,图片显示在木材内部有非常明显而规则的多孔结构。通过实验测量了不同含水率的木材试样在20-200℃范围内的导热系数,并根据其多孔结构的特点对木材的传热特性进行了理论分析。结果表明,木材微结构的不同对其传热特性有显著影响,木材多孔部分在整个传热过程中起重要作用。木材的传热特性随着其多孔部分的孔隙分布和孔隙大小的不同而变化,在相同含水率的情况下,孔隙率高而孔隙小的木材传热能力较弱。     

扫描探针针尖与试样间的静电力分析与建模

针对主体为圆锥、尖端为球冠的扫描探针针尖物理模型,提出了针尖与试样之间等效电场分布假设,基于该假设导出了二者之间静电力的解析模型,分析了针尖结构参数与静电力间的关系.模拟计算结果和数值计算结果一致,并与相关的实验结果吻合,证实了电场分布假设的合理性.     

曲面光源蒙特卡罗建模方法

光源建模方法是光学仿真算法的核心之一,决定了仿真结果的精度。然而对任意面型的光源建模难度高,建模方法很少被公开讨论。本研究系统地介绍曲面光源建模方法。基于均匀性假设,对曲面光源的空间特性、方向特性进行统计学描述,给出采样光线参数应满足的概率密度函数和采样方法。对两个曲面光源实例进行建模,当采样光线数量在107量级时,建模结果在指定接收器上形成的辐照度分布与理论值间最大相对偏差在1%之内,建模精度很高。同时,分析了两种采样方法对曲面光源建模精度和速度的影响,可为曲面光源建模过程提供一定指导。     

Preparation of Ni-doped carbon nanospheres with different surface chemistry and controlled pore structure

In classic carbon supports is very difficult to control pore size, pore size distribution, and surface chemical properties at the same time. In this work microporous carbons derived from furfuryl alcohol are used as support to prepare Ni-doped carbon materials. The N₂ flow rate used during the carbonisation process of the precursor influences on the size of the nanospheres obtained but not in their textural properties. Microporous carbon nanospheres have been synthesised with a narrow pore size distribution centred in 5.5 Å. The surface chemistry of these materials can be easily modified by different treatments without detriment of the pore structure of the doped carbon nanospheres.     

Xenon porometry: a novel method for the derivation of pore size distributions

Xenon porometry is a novel method used for characterizing porous materials by the (129)Xe nuclear magnetic resonance of xenon gas. With the method, the diffusion of gas is slowed down by immersing the material in a medium, which can be in liquid or solid state during measurements. Because of slow diffusion, the signal of a xenon atom is characteristic of the properties of only one pore, and the composite signal of all atoms represents the distribution of properties. The method is especially applicable for determining pore size distribution because the chemical shifts of two different xenon signals (one from liquid and the other from gas pockets in solid) are dependent on pore size. Therefore, the shapes of these signals represent pore size distribution function. In addition, the porosity of the material can be determined by comparing the intensities of two signals. This article focuses on describing xenon signals observed from gas pockets in a solid medium, which has turned out to be most convenient for pore size determination.     

Adsorption characterization of surfactant-templated ordered mesoporous silicas synthesized with and without hydrothermal treatment

This work reports a systematic study of ordered mesoporous silicas (OMSs) synthesized with and without hydrothermal treatment at 373 K for a series of surfactants of different alkyl chain length (from C10 to C18). For these samples nitrogen adsorption and small angle X-ray scattering (SAXS) data were measured to characterize their adsorption and surface properties. Namely, nitrogen adsorption isotherms were used to evaluate their specific surface area, pore volume and pore size distribution, whereas SAXS data provided information about their structural ordering. It is shown that while the room temperature synthesis afforded OMS samples with cubic MCM-48 structure, an additional 5-day hydrothermal treatment of these samples at 373 K caused their transformation to MCM-41 (two-dimensional hexagonal structure) and improved their pore uniformity, which was manifested by reducing the width of pore size distribution.     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

Study to improve the quality of a Mexican straight run gasoil over NiMo/γ-Al2O3 catalysts

Four NiMo catalyst supported on Al₂O₃ with different textural properties have been studied in the hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and hydrodearomatization (HDA) of a Mexican straight run gasoil (SRGO). All reactions were carried out at three different temperatures 613, 633, and 653 K. Alumina supports were analysed by pyridine FTIR-TPD and nitrogen physisorption in order to determine their surface acidity and textural properties, respectively. TPR studies of the NiMo catalysts were analysed to correlate their hydrogenating properties. Metallic particles were characterized (after sulfidation) using transmission electron microscopy (TEM). Catalytic activities are discussed in relation to the physicochemical properties of NiMo catalysts. The importance of textural properties on coke deposition has been emphasized. The results of catalytic activity of these materials varied depending on dispersed MoS particles and pore distribution in final catalysts. The optimum pore diameter was found around 80 Å for HDS and HDN.     

Preparation and characterization of porous DVB copolymers and their applicability for adsorption (solid-phase extraction) of phenol compounds

Using DVB, three new porous copolymers in the form of microspheres were prepared, characterized and used as adsorbents for phenol and its chlorinated derivatives. As the monomers: 4,4′-bis(maleimidodiphenyl)methane (BM), 2,3-bis(2-hydroxy-3-methylacryloyloxy-propoxy)naphthalene (2,3-NAF) and 2,3-epoxypropyl methacrylate (GLY) were used. All the studied materials were synthesized under the same conditions by means of suspension copolymerization. The DVB copolymers were characterized by elemental analysis, FTIR spectroscopy, TG and DSC analyses and N₂ sorption. The off-line solid-phase extraction method (SPE) was used to estimate sorption properties of the copolymers. The results show that the newly obtained materials are mesoporous but their shape of pores and chemical structures are different. BM-DVB and GLY-DVB are characterized by slit-shaped pores and wide pore size distribution. 2,3-NAF-DVB also possesses slit pores but distribution of pore size is narrower. Of those studied BM-DVB is the most interesting material. It has good sorption properties and heat resistance.     

Water confined in mesoporous silica glasses: Influence of temperature on adsorption/desorption hysteresis loop and fluid structure

In natural as well as industrial processes, water is frequently confined in silica porous materials with pore sizes in the nanometer scale. Understanding the confinement effects on the fluid properties is a fundamental issue, helpful to optimize the industrial processes. The molecular simulation is a powerful tool to study complex polar fluid like water at the atomic scale. The water adsorption/desorption properties in a mesoporous silica glass are investigated by means of Grand Canonical Monte Carlo simulations (GCMC). The SPC and PN TrAZ potential are used to describe water-water and water-silica interactions. The numerical sample of mesoporous silica glass (pore size: 3.6nm) was obtained by off-lattice reconstruction, known to reproduce in a realistic way the geometrical complexity of high specific surface Vycor (pore size distribution, pore interconnections, etc). The intermolecular potential is shown to reproduce the experimental data at 300K (adsorption isotherm and isosteric heat of adsorption). The water structure is analyzed and confinement effects are emphasized. The temperature influence is studied: the hysteresis loop is shown to shrink with an increase in temperature.     

溶剂对块体La基气凝胶性能的影响

采用溶胶-凝胶工艺,以氯化镧(LaCl3·7H2O)为前驱体,以甲醇和乙醇为溶剂,聚丙烯酸为分散剂,环氧丙烷为凝胶促进剂,分别合成两种性能不同的稀土La基气凝胶。采用扫描电子显微镜、傅里叶红外光谱仪、比表面积与孔径分析仪、力学性能测试仪对不同溶剂制备的两种稀土La基气凝胶的微观结构、成分、比表面积、孔径分布和力学性能进行了研究表征。结果表明,以甲醇和乙醇为溶剂制备的稀土La基气凝胶都具有纳米多孔材料的典型特征,由大量nm量级的球形和长条形颗粒胶连而成,孔洞结构丰富。以乙醇为溶剂制备的稀土La基气凝胶的网络骨架更纤细,孔洞更大,比表面积达到220m2·g-1,密度约为160mg·cm-3,但力学性能较差。而以甲醇为溶剂制备的稀土La基气凝胶的网络骨架更强壮,孔洞更小,比表面积达到95m2·g-1,密度约为350mg·cm-3,力学性能较好。样品性能上的差异可能是由甲醇的极性比乙醇的极性强引起的。