新型复合干燥剂吸附分形特性

基于复合干燥剂表面的氮气平衡吸附实验数据,利用分形等温吸附理论模型,对氮气平衡吸附量进行非线性拟 合,确定了表面分形维数,并对表面几何形态进行定最描述,得到了分形等温吸附式;对比测试和拟合结果,发现分形维 数随氯化钙含量增加几呈波动变化,分析得到的单分子层饱和吸附量与实验数据基本一致。     

二氧化硅多孔介质气凝胶和干凝胶的分形结构研究

二氧化硅多孔介质气凝胶和干凝胶的结构用小角Ｘ射线散射进行了研究．实验表明，用一步法制备的各种气凝胶全部具有分形结构．而干凝胶和用两步法制备的气凝胶没有分形结构．实验还证明干凝胶由尺度较大的球形颗粒组成     

Mesoporous Silica Materials Synthesized via Sol-Gel Methods Modified with Ionic Liquid and Surfactant Molecules

采用离子液体1-甲基-3-丁基咪唑四氟硼酸盐改性的溶胶-凝胶法以及表面活性剂十六烷基三甲基溴化铵进一步改性的溶胶-凝胶法制备介孔二氧化硅. 通过X射线衍射、氮气吸附脱附和扫描电子显微镜对所制备的样品进行表征. 结果表明,与仅用离子液体为模板制备的介孔二氧化硅相比,采用表面活性剂和离子液体的混合物为模板制备的介孔二氧化硅具有较小的孔径和较规则的孔结构. 说明利用该方法制备介孔二氧化硅,表面活性剂的加入会在一定程度上影响所制介孔二氧化硅的微结构.     

小角X射线散射方法测定二氧化硅干凝胶的平均孔径

提出了当多孔体系的小角X射线散射不遵守Porod定理的情况下,应用Debye法(相关函数法) 和Guinier法(逐级切线法和多级斜线法)计算它们的平均孔径的方法.对不同制备条件下部分 二氧化硅干凝胶的测试,取得了比较一致的结果,并与氮气吸附法测定结果进行了对比. 关键词： 小角X射线散射 二氧化硅干凝胶 平均孔径     

处理污泥焦颗粒内部孔结构在燃烧过程中变化

在管式炉反应器中进行了1种污泥定温燃烧试验,进行了5个不同燃烬率样品的液氮静态容量法等温物理吸附试验.发现不同燃烬率的污泥样品孔分布特性相似,其孔系统可能主要是由一端封闭的不透气的孔构成;随着燃烬率的增加,比表面积、平均孔径和孔体积等参数变化不同;样品颗粒内孔表面分形维数随燃烬率的增长呈先降低再升高的趋势.     

快速吸附与脱附的声表面波H2S传感器

本文主要研究了基于SnO₂/CuO薄膜的声表面波（SAW）传感器（室温下,工作频率约为147.8 MHz）检测H₂S气体的特性。以36°YXLiTaO₃为基片制作声表面波器件,通过采用射频磁控溅射法在其表面淀积SnO₂/CuO的复合薄膜制作出H₂S气体传感器。由场发射电子扫描电镜观察薄膜,薄膜连续均匀且表面分布大量微气孔,因而具有良好的吸附性。然后本文在85℃～205℃范围内对传感器的吸附和脱附速率、灵敏度及选择性等进行了实验研究。实验结果表明,所制备的传感器在较低温度下同时具备快速吸附和脱附特性,工作在190℃时气体吸附和脱附速率最快,检测20ppm H₂S的响应和恢复时间分别为30s、15s;工作在160℃时,传感器检测20ppmH₂S的灵敏度最高,工作频率变化约230 kHz,且对于低浓度2 ppm H₂S,频率变化可达45 kHz。同时,传感器也表现出良好的重复性和选择性。     

水分子凝聚体系的介孔结构分形学

透射电镜研究表明，4,40-双硬脂酰胺基二苯醚在水中聚集、自组装成缠绕细纤维状聚集体，进而使整个体系形成三维网络结构．水分子被包囊在这个网络结构中，形成一种新型的凝聚体系(水分子凝胶)．水分子凝胶是一种典型的纳米介孔物质，其复杂的微孔结构可以用分形维数D来表征，通过气体吸附方法(孔度法和比表面积法)计算，求得水分子凝胶体系的微孔结构的分形维数为2.1?2.2．对于纤维状三维网络结构的分形表征，通过粘度法和Cayley分形树模型得出分形维数为1.98．由此推测其分形网络形成的过程是一个初始成核-生长-枝化的循环过程．     

有序介孔SiO2的制备及其在色谱填料方面的应用

利用水热合成方法,在低浓度盐酸下用三嵌段共聚物EO106PO70EO106（F127）作为模板剂,在100℃,130℃和150℃的条件下,制备了3种笼型介孔二氧化硅.通过粉末N2气吸附-脱附实验表征其孔径（PD）及比表面积（BET）、扫描电镜（SEM）观察其表面形貌、透射电子显微镜（TEM）分析其微观结构;通过表征结果分析,该材料具有笼型介孔结构.同时,将该介孔材料应用在色谱分离方面,对氯苯,苯乙烯,1,2-二苯乙烯,联苯4种物质混合物进行分离,与其他多种二氧化硅材料比较,150℃的条件下合成的KIT-5-150分离效果最好.     

球状胶束中表面活性剂脱附的离子调控机制

建立耦合伞状采样的粗粒度分子动力学方法,研究球状胶束中表面活性剂分子的脱附过程,揭示表面活性剂聚集数、盐种类及浓度对表面活性剂脱附过程的影响机制。发现球状胶束半径及偏心率均随聚集数增加而增大,盐浓度的影响主要取决于抗衡离子的半径和吸附特性,半径更大、吸附更强的水杨酸根离子对胶束结构的影响更为显著;基于伞状采样方法获得了表面活性剂脱附自由能、脱附时间等关键参数,发现球状胶束中表面活性剂脱附自由能和脱附时间均随聚集数和盐浓度呈非单调变化,揭示其主要机制为离子吸附引起的静电屏蔽作用;发现自由能在表面活性剂脱附过程中起主导作用,结合胶束热力学理论发展了临界胶束浓度预测方法,获得了临界胶束浓度下胶束尺寸的分布范围。     

纳米流体对流换热机理分析

考虑在纳米流体中纳米颗粒做布朗运动引起的对流换热, 基于纳米颗粒在纳米流体中遵循分形分布, 本文得到纳米流体对流换热的机理模型. 本解析模型没有增加新的经验常数, 从该模型发现纳米流体池沸腾热流密度是温度、纳米颗粒的平均直径、 纳米颗粒的浓度、纳米颗粒的分形维数、沸腾表面活化穴的分形维数、基本液体的物理特性的函数. 对不同的纳米颗粒浓度和不同的纳米颗粒平均直径与不同的实验数据进行了比较, 模型预测的结果与实验结果相吻合. 所得的解析模型可以更深刻地揭示纳米流体对流换热的物理机理.     

Scale-dependent nature of the surface fractal dimension for bi- and multi-disperse porous solids by mercury porosimetry

The surface fractal dimension was calculated by using a mathematical model and mercury intrusion data for a variety of bi- and multi-disperse porous solids including silica gels, alumina pellets, and building stones. The mathematical model was obtained by modifying the well-established scaling relation published previously [Ind. Eng. Chem. Res., 34 (1995) 1383-1386]. It was also verified by comparing with the theoretical surface fractal dimensions for regular fractal structures (Skerpinski tetrahedron and Menger sponge) and the calculated surface fractal dimensions for silica gel and alumina particles via the linear fitting method established previously. The calculation results for various bi- and multi-disperse porous solids have demonstrated that the scale-dependent nature of the surface fractal dimension is ubiquitous. The difference in the surface fractal dimension between pore size intervals usually exists. The estimation of the surface fractal dimension on an average stand may lead to erroneous results.     

随机多孔介质的蒙特卡罗重构与渗流特性模拟

根据多孔介质微观结构的分形尺度标度特征,采用蒙特卡罗方法分别重构随机多孔介质的微观颗粒和孔隙结构,并基于分形毛管束模型研究多尺度多孔介质的气体渗流特性,建立多孔介质微观结构和宏观渗流特性的定量关系。结果表明：分形蒙特卡罗重构的多孔介质微细结构接近真实介质结构,气体渗流特性的计算结果与格子玻尔兹曼模拟数据较为吻合; 多孔介质气体渗透率随着克努森数的增加而增大,孔隙分形维数对于气体渗流的微尺度效应具有显著影响,而迂曲度分形维数对于表观渗透率和固有渗透率的比值影响可以忽略。提出的分形蒙特卡罗方法具有收敛速度快且计算误差与维数无关的优点,有利于深入理解多尺度多孔介质的渗流机理。     

Dielectric constant of porous ultra low-k dielectrics by fractal-Monte Carlo simulations

The effective dielectric constant of porous ultra low-k dielectrics is simulated by applying the fractal geometry and Monte Carlo technique in this work. Based on the fractal character of pore size distribution in porous media, the probability models for pore diameter and for effective dielectric constant are derived. The proposed model for the effective dielectric constant is expressed as a function of the dielectric coefficient of base medium and the volume fractions of pores and base medium, fractal dimension for pores, the pore size, as well as random number. The Monte Carlo simulations combined with the fractal geometry are performed. The predictions by the present simulations are shown in good accord with the available experimental data. The proposed technique may have the potential in analyzing other properties such as electrical conductivity and thermal conductivity in porous ultra low-k dielectrics.     

Design of organic supercapacitors with high performances using pore size controlled active materials

In this study, we thoroughly investigate the required properties of active materials for organic supercapacitors with high performances. In this regard, we synthesize carbon xerogels with different physical properties, including specific surface area and pore size. The carbon xerogels are prepared via the sol-gel reaction of resorcinol and formaldehyde under different gelation temperature conditions. Through Fourier-transform infrared, nitrogen adsorption–desorption, and scanning electron microscopy analysis, we can confirm that carbon xerogels with different physical properties can be successfully synthesized. We apply the prepared carbon xerogels to organic supercapacitor electrodes. As a result of electrochemical experiments, carbon xerogels with high surface area exhibit high electrochemical performances at low-rate charge?discharge processes. However, as the charge–discharge rate increases, carbon xerogels with low surface area and high conductivity exhibit higher performances. Therefore, the surface area of active materials is a key factor for supercapacitors with high performances at low-rate charge–discharge processes. However, the effects of conductivity can be more crucial as compared with those of surface area as the charge–discharge rates increase. In addition, we suggest that the physical properties of active materials should be differently optimized as the charge–discharge rate is employed.     

A 3D non-local density functional theory for any pore geometry

A general framework of classical non-local density functional theory (NLDFT) is presented, in order to consider the adsorption of spherical molecules in porous materials of any geometry. Fluid-fluid interactions and fluid-solid interactions can be repulsive or attractive. Some techniques that have been developed for the computation of weighted densities of hard-spheres are extended to attractive ones, in order to deal with an arbitrary pore geometry. This way, the computation method introduced in this work is validated by a comparison with analytical results for simple cases, and is directly applied to more complex systems. Density distributions depending on multi-dimensional effects are presented, and some radial distribution functions are recovered from NLDFT computations. Finally, the case of attractive continuous curved walls is detailed, which represents a large variety of real systems (e.g. micro and mesoporous silica, zeolites, carbonaceous nanoporous materials, etc.). With the new way of computation proposed, a general solution is presented, valid for any shape of continuous pore surface, by considering mathematical properties of discrete geometry due to the discretisation of the computational space with FFT computations.     

Fractal Analysis of Surface Roughness of Particles in Porous Media

A fractal dimension for roughness height （RH） is introduced to characterize the degree of roughness or disorder of particle surface characters which significantly influence physical-chimerical processes in porous media. An analytical expression for the fractal dimension of RH on statistically self-similar fractal surfaces is derived and is expressed as a function of roughness parameters. The specific surface area （SSA） of porous materials with spherical particles is also derived, and the proposed fractal model for the SSA of particles with rough surfaces is expressed as a function of fractal dimension for RH and fractal dimension for particle size distribution, relative roughness of particle surface, and ratio of the minimum to the maximum particle diameters of spherical particles.     

超声波作用下污泥水分扩散过程的数值模拟

建立了超声波作用下污泥内部水分扩散模型,利用分形理论对超声波(20 kHz)作用下污泥内部孔隙结构进行描述,探讨了超声波声能密度对污泥孔隙表面分形维数df及孔隙通道曲折度分形维数dw的影响,在此基础上建立了超声波作用下多孔介质中液体有效扩散系数的分形模型,对不同声能密度超声波辐照下污泥水分扩散过程进行了数值模拟.研究发...     

Studies of the collision frequency of ideal gas particles with the surfaces of the objects created using the ballistic deposition technique

This paper is a continuation of our studies of the collision frequency of ideal gas particles with the rough/fractal surfaces. Here, we applied a more realistic surface growth model, i.e. ballistic deposition for creation of fractal objects. We found that the collision frequency with irregular surfaces is the linear function of pressure and this frequency per unit pressure is quite a complicated function of the surface fractal dimension as well as the diameter of colliding particle. The collision frequency with rough surfaces cannot be exactly described by the analytical formula called the Langmuir-Hertz equation. However, we have stated that the deviations of the true collision frequency from the Langmuir-Hertz prediction are not huge and in typical catalytic studies the error introduced by replacing the true frequency by the Langmuir-Hertz prediction can be safely neglected. We have also studied the probability of finding on the surface an atom which has been hit a certain number of times by a gas particle. This probability reveals an interesting behaviour for small gas particles, i.e. it perfectly correlates with the number of directions from which the surface atom is accessible from the gas phase. We have also estimated the evolution of the adsorption energy distribution with the increasing fractal dimension of the surface in the ballistic deposition.     

Evaluation of adsorption energy distribution of microporous materials by a multivariant identification

The applicability of new BET-like adsorption models (uLBET and LBET formulas) for the examination of microporous materials of irregular structure is discussed. The models are intended to handle the main effects of random pore geometry on the adsorption isotherm shape. They are based on a generalized BET theory and employ simple (but realistic) adsorption energy-pore geometry relationships. To overcome numerical problems inherent in fitting any more advanced adsorption model, a multivariant identification procedure is proposed with a subset of parameters being fixed in each variant. The reliability assessment of the system parameters evaluation is stressed. The paper outlines formal and numerical bounds for adsorption measurements-based identifiability of irregular porous structures. The LBET-type formulas are recommended for the examination of such materials, as a relatively simple alternative versus DFT-based techniques. Numerous simulation results and exemplary examinations of an empirical isotherm are discussed.     

爆轰裂解法制备纳米石墨粉的吸附性能研究(英文)

在酸含量不同的原材料中,通过爆轰的方法制备纳米石墨粉,并利用BET方程以及BJ H方法对所得纳米石墨粉进行比表面积和孔径分布分析。分析结果表明,所得爆轰产物中有的比表面积大致为天然鳞片石墨的5.3~9.2倍,而且随酸含量的增大逐渐增大,产物的等温线中存在吸附滞后现象。其中,增大的比表面积主要由分布在3 nm至7 nm之间的孔引起的,而且在爆轰后,孔径4 nm左右的孔,其数量达到最大值。通过对纳米石墨粉的研究,分析了酸在爆轰过程中的积极作用,并为纳米石墨粉的进一步应用提供了结构信息。