Microporous matrices

In Sec. 3 our presentation is focused on the most important results obtained by different authors in the framework of the rephca Ornstein-Zernike (ROZ) integral equations and by simulations of simple fluids in microporous matrices. For illustrative purposes, we discuss some original results obtained recently in our laboratory. Those allow us to show the application of the ROZ equations to the structure and thermodynamics of fluids adsorbed in disordered porous media. In particular, we present a solution of the ROZ equations for a hard sphere mixture that is highly asymmetric by size, adsorbed in a matrix of hard spheres. This example is relevant in describing the structure of colloidal dispersions in a disordered microporous medium. On the other hand, we present some of the results for the adsorption of a hard sphere fluid in a disordered medium of spherical permeable membranes. The theory developed for the description of this model agrees well with computer simulation data. Finally, in this section we demonstrate the applications of the ROZ theory and present simulation data for adsorption of a hard sphere fluid in a matrix of short chain molecules. This example serves to show the relevance of the theory of Wertheim to chemical association for a set of problems focused on adsorption of fluids and mixtures in disordered microporous matrices prepared by polymerization of species. 

Haute, S. and Stimming, U. 2001. Proton conducting membranes based on electrolyte filled microporous matrices. Journal of Membrane Science 185 95-103. 

Proton-Conducting Membranes Based on Electrolyte-Filled Microporous Matrices/Composite Membranes... 

Enzymes immobilized microporous matrices, such as organic polymer beads, silica particles, and ceramic carriers, have been widely used for the production... 

Section two includes two chapters on bio-materials which deal with the preparation of new t)cpes of collagen nanostructured bio-materials in the form of spongeous, microporous matrices, nontoxic and biocompatible with osteoblast cells, and modification of magnetite particles with different functionalizations specific for desired applications such as biomedical and industrial applications. 

Extensive theoretical and experimental work has previously been reported for supported liquid membrane systems (SLMS) as effective mimics of active transport of ions (Cussler et al., 1989 Kalachev et al., 1992 Thoresen and Fisher, i995 Stockton and Fisher, 1998). This was successfully demonstrated using di-(2-ethyl hexyl)-phosphoric acid as the mobile carrier dissolved in n-dodecane, supported in various inert hydrophobic microporous matrices (e.g., polypropylene), with copper and nickel ions as the transported species. The results showed that a pH differential between the aqueous feed and strip streams, separated by the SLMS, mimics the PMF required for the emulated active transport process that occurred. The model for transport in an SLMS is represented by a five-step resistance-in-series approach, as follows (1) diffusion of the ion through a hydrodynamic boundary layer (2) desolvation of the ion, where it expels the water molecules in its coordination sphere and enters the organic phase via ion exchange with the mobile carrier at the feed/membrane interface (3) diffusion of the ion-carrier complex across the SLMS to the strip/membrane interface (4) solvation of the ion as it enters... 

In this zeolitic material a very low percentage of Ti(IV), dispersed in a pure siliceous microporous matrix (with the MFI framework, the same as that of the ZSM-5 zeolite), is able to oxidize in mild conditions many substrate with extremely high activity and selectivity (see Sect. 2). However, after more than three decades, a complete picture of reaction mechanisms is still missing. Major problems related to characterization are due to the extremely high dilution of Ti(IV) in the zeolitic matrix and the presence of high amounts of water in the reaction media. The first point requires characterization techniques very sensitive and selective towards Ti(IV). For instance, XRD measurements have been able to recognize the presence of Ti(IV) in the framework only indirectly, via the measured unit cell volume increase [21,22], but attempts to... 

The ESR data shows that both the number of centers and the local structure of active sites associated with Cu isolated ions are not changed noticeably at T < 500°C as a result of cobalt introduction. At the same time, catalytic testing shows a 3-fold rise in oxidative activity of bi-cationic sample (Fig. 1) demonstrating an increase either in the number of sites or in the intrinsic activity of catalytic centers. The effect can be explained only in assumption of the high dispersion of cobalt ions in microporous matrix it is difficult to imagine a considerable contribution from the big particles of cobalt oxide on the outer surface of zeolitic crystals. 

Four different three-dimensional numerical infiltration experiments were carried out in a simulated porous medium with a central parallel crack as shown in Fig. 4-2. The lattice size is 10 by 100 by 150 sites in the x, y and z directions, respectively. Solid sites are represented in red. A probabilistic algorithm generated at random the solid distribution of the microporous matrix. The mean microporosity and macroporosity are 0.52, and 0.192, respectively, of the total volume of the medium. A gravity force was simulated as described in Di Pietro et al. (1994), oriented parallel to the crack in the z-downward direction. Void sites (white color in Fig. 4-2) are initially f ss are expressed in arbitrary lat-... 

Even if we computed the microscopic velocity field in the x, y and z directions, we only considered the macroscopic averages in the y and z directions, as no heterogeneity is considered in the x-direction. The macroscopic fluxes were calculated by averaging the microscopic velocities over 50 time steps, over five sites in the z-direction, and over half-cross sections of the micropore matrix and of the crack, multiplied by the respective mean water contents. 

Phosphoric Acid Fuel Cells (PAFC) are operating in the range of 160-200 °C. The phosphoric acid electrolyte is soaked in a microporous matrix of corrosion resistant, non-conducting materials. At this high temperature, PAFC can tolerate a substantial... 

Ion-selective electrodes are widely used in pharmaceutical analysis. Numerous ion-selective electrodes based on poly(vinyl)chloride (PVC) have been constructed in order to determine various pharmacologically active substances in pharmaceutical preparations. The inherent advantages of ISE-s are simple design, construction and manipulation, reasonable selectivity, fast response time, low cost, adequate detection limit and adequate precision and accuracy. Therefore, the ISE potentiometric method is very attractive for pharmaceutical analysis. The first part of this chapter describes the properties and uses of PVC, as well as the general characteristics and preparation of the polymer membranes of ion-selective electrodes. The second part deals with the development of solid contact electrodes formed on non-crystal electrodes with a microporous matrix (e.g., vinyl polychloride dissolved in an appropriate modifier) selective for various nonsteroidal anti-inflammatory drugs (NSAlD-s) and their applications in pharmaceutical research. 

Development of ion-selective electrodes for pharmaceutical analysis is still an actual, progressing scientific direction. Currently, the most frequently developed types of electrodes are those with a microporous matrix (PVC) and mobile active centers. The goal is to reach the best parameters, in particular the selectivity and the longest lifetime. It would allow application of these devices in industrial practice. There are many options to choose from, both in terms of the electrode design and the modifications of the membrane. Solid-state electrodes are becoming more and more popular. In the future, there can be much development in the field of sensors for determination of drugs, based on conductive polymers, which are currently rare. 

The surface morphological changes of the GNP-PPy-Pt nanocomposite electrode were also investigated by SEM and energy dispersive X-ray spectroscopy (EDX) as shown in Figure 3.37. The SEM image of GNP-PPy-Pt electrode (Figure 3.37) reveals the incorporation of GNP onto the microporous matrix of PPy. This GNP-PPy nanocomposite increases the specific surface area available on the PPy-Pt electrode for the efficient functionalization of the enzymes. 

Adsorption of hard sphere fluid mixtures in disordered hard sphere matrices has not been studied profoundly and the accuracy of the ROZ-type theory in the description of the structure and thermodynamics of simple mixtures is difficult to discuss. Adsorption of mixtures consisting of argon with ethane and methane in a matrix mimicking silica xerogel has been simulated by Kaminsky and Monson [42,43] in the framework of the Lennard-Jones model. A comparison with experimentally measured properties has also been performed. However, we are not aware of similar studies for simpler hard sphere mixtures, but the work from our laboratory has focused on a two-dimensional partly quenched model of hard discs [44]. That makes it impossible to judge the accuracy of theoretical approaches even for simple binary mixtures in disordered microporous media. 

However, before proceeding with the description of simulation data, we would like to comment the theoretical background. Similarly to the previous example, in order to obtain the pair correlation function of matrix spheres we solve the common Ornstein-Zernike equation complemented by the PY closure. Next, we would like to consider the adsorption of a hard sphere fluid in a microporous environment provided by a disordered matrix of permeable species. The fluid to be adsorbed is considered at density pj = pj-Of. The equilibrium between an adsorbed fluid and its bulk counterpart (i.e., in the absence of the matrix) occurs at constant chemical potential. However, in the theoretical procedure we need to choose the value for the fluid density first, and calculate the chemical potential afterwards. The ROZ equations, (22) and (23), are applied to decribe the fluid-matrix and fluid-fluid correlations. These correlations are considered by using the PY closure, such that the ROZ equations take the Madden-Glandt form as in the previous example. The structural properties in terms of the pair correlation functions (the fluid-matrix function is of special interest for models with permeabihty) cannot represent the only issue to investigate. Moreover, to perform comparisons of the structure under different conditions we need to calculate the adsorption isotherms pf jSpf). The chemical potential of a... 

Base catalysis is another area which has received a recent stimulus from developments in materials science and microporous solids in particular. The Merk company, for example, has developed a basic catalyst by supporting clusters of cesium oxide in a zeolite matrix [13]. This catalyst system has been developed to manufacture 4-methylthiazole from acetone and methylamine. 

The first position can be safely excluded since a high temperature calcination, causing the removal of Fe atoms from the lattice, remarkably increases the a>site concentration [27]. Besides, a-sites can be prepared via the impregnation of a ready zeolite matrix [28], when the probability for Fe atoms to incorporate into the lattice is very low. a-Sites do not occupy also the 3rd type position deactivation of the outer zeolite surface by its covering with an inert Si02 layer affects neither catalytic activity no a-site concentration [29]. Thus, we may deduce that the active iron occupies the second type position in ZSM-S matrix and is either isolated Fe ions or small complexes inside the micropore zeolite space. 

Bone is a porous tissue composite material containing a fluid phase, a calcified bone mineral, hydroxyapatite (HA), and organic components (mainly, collagen type). The variety of cellular and noncellular components consist of approximately 69% organic and 22% inorganic material and 9% water. The principal constiments of bone tissue are calcium (Ca ), phosphate (PO ), and hydroxyl (OH ) ions and calcium carbonate. There are smaller quantities of sodium, magnesium, and fluoride. The major compound, HA, has the formula Caio(P04)g(OH)2 in its unit cell. The porosity of bone includes membrane-lined capillary blood vessels, which function to transport nutrients and ions in bone, canaliculi, and the lacunae occupied in vivo by bone cells (osteoblasts), and the micropores present in the matrix. 

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