Porous properties/pore structure

A microscopic description characterizes the structure of the pores. The objective of a pore-structure analysis is to provide a description that relates to the macroscopic or bulk flow properties. The major bulk properties that need to be correlated with pore description or characterization are the four basic parameters porosity, permeability, tortuosity and connectivity. In studying different samples of the same medium, it becomes apparent that the number of pore sizes, shapes, orientations and interconnections are enormous. Due to this complexity, pore-structure description is most often a statistical distribution of apparent pore sizes. This distribution is apparent because to convert measurements to pore sizes one must resort to models that provide average or model pore sizes. A common approach to defining a characteristic pore size distribution is to model the porous medium as a bundle of straight cylindrical or rectangular capillaries (refer to Figure 2). The diameters of the model capillaries are defined on the basis of a convenient distribution function. 

Coimectivity is a term that describes the arrangement and number of pore coimections. For monosize pores, coimectivity is the average number of pores per junction. The term represents a macroscopic measure of the number of pores at a junction. Connectivity correlates with permeability, but caimot be used alone to predict permeability except in certain limiting cases. Difficulties in conceptual simplifications result from replacing the real porous medium with macroscopic parameters that are averages and that relate to some idealized model of the medium. Tortuosity and connectivity are different features of the pore structure and are useful to interpret macroscopic flow properties, such as permeability, capillary pressure and dispersion. 

Other key features in the analysis of pore structure are the length scales associated with the various micro- (nano)-scale obstacles and pores, the possible larger-scale variations in structure, and the averaging domain over which information is needed [6,341,436], The hterature refers to analysis of homogeneous and heterogeneous porous media, where homogeneous refers to media with no variation in physical properties (e.g., porosity, diffu-... 

As surface area and pore structure are properties of key importance for any catalyst or support material, we will first describe how these properties can be measured. First, it is useful to draw a clear borderline between roughness and porosity. If most features on a surface are deeper than they are wide, then we call the surface porous (Fig. 5.16). Although it is convenient to think about pores in terms of hollow cylinders, one should realize that pores may have all kinds of shapes. The pore system of zeolites consists of microporous channels and cages, whereas the pores of a silica gel support are formed by the interstices between spheres. Alumina and carbon black, on the other hand, have platelet structures, resulting in slit-shaped pores. All support materials may contain micro, meso and macropores (see text box for definitions). 

Improved characterization of the morphological/microstructural properties of porous solids, and the associated transport properties of fluids imbibed into these materials, is crucial to the development of new porous materials, such as ceramics. Of particular interest is the fabrication of so-called functionalized ceramics, which contain a pore structure tailored to a specific biomedical or industrial application (e.g., molecular filters, catalysts, gas storage cells, drug delivery devices, tissue scaffolds) [1-3]. Functionalization of ceramics can involve the use of graded or layered pore microstructure, morphology or chemical composition. 

Materials with uniform pore structures offer a wide range of applications, including catalysis, adsorption, and separation. These materials have the benefit ofboth specific pore systems and intrinsic chemical properties [1-3]. The pores in the materials are able to host guest species and provide a pathway for molecule transportation. The skeletal pore walls provide an active and/or affinity surface to associate with guest molecules. According to the International Union of Pure and Applied Chemistry (IUPAC), porous materials can be classified into three main categories based on the diameters of their pores, that is, microporous, mesoporous, and macroporous... 

A.P. Karnaukhov, Adsorption. Texture of Dispersed and Porous Materials, Nauka, Novosibirsk, 1999 (in Russian) in Pore Structure and Properties of Materials (Proc. I Inter. Sump. RILEM/IUPAC), Part I, Academia, Prague, 1973, p. A-3. 

Because the monoliths allow total convection of the mobile phase through their pores, the overall mass transfer is dramatically accelerated compared to conventional porous structures. Based on the morphology and porous properties of the molded monoliths, which allow fast flow of substrate solutions, it can be safely anticipated that they would also provide outstanding supports for immobilization of biocatalysts, thus extending the original concept of monolithic materials to the area of catalysis. 

In most porous media the pore structure is so complicated (variations in pore size and shape) that one can only expect to determine average properties, like the average surface to volume ratio of the pores. In some cases, however, the pores have a well-defined shape but vary only in size. This is the case for emulsions if the concentration of one of the components is low. 

Surface area is by no means the only physical property which determines the extent of adsorption and catalytic reaction. Equally important is the catalyst pore structure which, although contributing to the total surface area, is more conveniently regarded as a separate factor. This is because the distribution of pore sizes in a given catalyst preparation may be such that some of the internal surface area is completely inaccessible to large reactant molecules and may also restrict the rate of conversion to products by impeding the diffusion of both reactants and products throughout the porous medium. 

Recently various kinds of porous materials have been developed and their properties and structures have been gathering great concerns in science. There are two types of pores of intraparticle pores and interparticle ones[l]. The intraparticle pores are in the primary particle itself, while the interparticle pores originate from the interparticle void spaces. Zeolites are the most representative porous solids whose pores come from the structurally intrinsic intraparticle pores. The pore geometry can be evaluated by their crystallographic data. The carbon nanotube of which pore wall is composed of graphitic sheets is also the... 

Natural porous media may be consolidated (solids with holes in them), or they may consist of unconsolidated, discrete particles. Passages through the beds may be characterized by the properties of porosity, permeability, tortuosity, and connectivity. The flow of underground water and the production of natural gas and crude oil, for example, are affected by these characteristics. The theory and properties of such structures is described, for instance, in the book of Dullien (Porous Media, Fluid Transport and Pore Structure, Academic, New York, 1979). A few examples of porosity and permeability are in Table 6.9. Permeability is the proportionality constant k in the flow equation u = (k/p) dP/dL. 

The transport properties across an MIP membrane are controlled by both a sieving effect due to the membrane pore structure and a selective absorption effect due to the imprinted cavities [199, 200]. Therefore, different selective transport mechanisms across MIP membranes could be distinguished according to the porous structure of the polymeric material. Meso- and microporous imprinted membranes facilitate template transport through the membrane, in that preferential absorption of the template promotes its diffusion, whereas macroporous membranes act rather as membrane absorbers, in which selective template binding causes a diffusion delay. As a consequence, the separation performance depends not only on the efficiency of molecular recognition but also on the membrane morphology, especially on the barrier pore size and the thickness of the membrane. 

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