Electrochemistry of capillary systems with narrow pores. IV. Dialysis potentials

The dialysis potentials of different collodion membranes with graded pore sizes and electrochemical activities have been measured in dilute aqueous KCl solutions as functions of concentration. It is possible to predict the value of the diffusion potential within a few millivolts on the basis of electrical conductivity data obtained with the same membranes. In general, the measured values are lower than those calculated. It is assumed that this difference is caused by the membranes having a distribution of pore sizes.     

Modelling of the pore structure variation with pH for pore-filled pH-sensitive poly(vinylidene fluoride)–poly(acrylic acid) membranes

Pore structure variation as a function of pH was investigated for the pore-filled pH-sensitive poly(acrylic acid)-poly(vinylidene fluoride) membranes. The pore radius reduced drastically as the poly(acrylic acid) gel incorporated inside the nascent substrate, which is from 113 nm of nascent substrate to as low as 7.0 nm of pore-filled membranes at pH acidic. For the membranes, the pore radii at pH neutral estimated by the extend Nernst–Planck equation (2.76–4.20 nm) and by the Spiegler–Kedem model with the steric-hindrance pore model (3.4–4.1 nm) are close to each other and comparable with that calculated from the poly(acrylic acid) gel correlation length (1.79–2.93 nm). The calculated pore density at pH neutral (49–258 × 10¹⁴ m⁻²) is much higher than that at pH acidic (2.8–39.8 × 10¹⁴ m⁻²). The results are interpreted in terms of the gel structure in the pore-filled membranes.     

Pore size distribution of ceramic UF membranes by liquid–liquid displacement porosimetry

Commercial ceramic tubular membranes made by Tami^® have been characterized by several techniques. Their pore size distributions (PSD) have been obtained by liquid–liquid displacement porosimetry (LLDP).

Computerized image analysis (CIA) of SEM pictures has been used to get information on the width of the active layer of the studied membranes. These values of thickness have helped to evaluate the porosity of the membranes and to get representative radii from measurements of the permeability to several gases and liquids. A fully automated porosimeter designed by us has been used in the determination of pore size distributions. Results show a good accuracy and reproducibility of LLDP measurements.

Binary and ternary liquid mixtures have been used to wet and penetrate into the membrane pores when performing LLDP leading to quite similar results when an effective surface tension is assigned for the ternary mixture. This procedure can be used to calibrate the technique to be extended to thick ultrafiltration and even to nanofiltration membranes.     

Conductimetric Assay of a Bacterial Lipase,Using Triacetin as a Substrate

Abstract

A conductimetric method has been applied to measure lipase activity. When using triacetin as a substrate, a linear relationship between initial rate and enzyme concentration is demonstrated up to 600 U in the cell (4 ml). Kinetic parameters of triacetin hydrolysis have been derived from conductimetric data, in the concentration range of solubility of the substrate. The limiting parameters (temperature, choice of buffer, substrate) are discussed in the last part.     

Surface treatment and porosity control of porous silica microspheres

Summary Porous silica microspheres (PSM) have been treated with ammonium bifluoride to adjust porosity, pore size, remove surface impurities, and minimize surface acidity. The porosities of four silicas having mean pore diameters ranging from 150 to 750 ? have been altered from initial values to the point at which the mechanical strength is insufficient to allow packed columns with acceptable performance. It is shown that a linear relationship exists between a change in porosity and the relative amount of ammonium bifluoride used to treat the silica. This reagent removes silica homogeneously from all pores in a given microsphere in a controllable and predictable manner. This treatment increases the peak capacity and improves chromatographic performance. The surfaces of treated silicas were probed with thiamine in the ion-exchange chromatographic mode. The slopes and intercepts of plots in which retention is plotted against the reciprocal of buffer concentration were both significantly reduced indicating that surface acidity is minimized by this treatment.     

Low thermalconductive,transparent and hydrophobic ambient pressure dried silica aerogels with various preparation conditions using sodium silicate solutions

The experimental results on the preparation of low thermal conductivity and transparent ambient pressure dried silica aerogels with the sodium silicate solution, TMCS silylating agent with methanol, isopropyl alcohol, hexane and xylene solvents, are reported. This study is focussed on the effect of preparation conditions such as varying the number of preparation steps, pH of the hydrosol and hydrogel ageing temperature, for the production of the low thermal conductive silica aerogels and the results are analysed. Density, thermal conductivity, % of optical transmission and contact angle of the aerogels were measured. The Fourier Transform Infrared Spectroscopy (FTIR) studies revealed the presence of Si–C and C–H along with the Si–O–Si and OH bonds and their intensities strongly depend on the processing steps, pH of the hydrosol and gel ageing temperature. The UV–Visible spectra indicated the % of optical transmission of the aerogels decreased with increasing the number of processing steps, increase in the pH of the hydrosol from 3 to 8 and decreased for ageing temperature up to 50 °C. Further increase in temperature >50 °C, the % of optical transmission of the aerogels increased. The TGA-DTA data showed the thermal stability of the aerogels with respect to hydrophobicity is 325 °C. Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM) analyses revealed the nanostructure of the aerogels. The porosity of the aerogels was studied using the pore size distribution. Silica aerogels with low density (0.051 g/cc), low thermal conductivity (0.049 W/m K), optical transmission (65%), high hydrophobicity (159°) and resistance to humid atmosphere >1 year was obtained in the present studies.     

An improved capillary model for describing the microstructure characteristics, fluid hydrodynamics and breakthrough performance of proteins in cryogel beds

A capillary-based model modified for characterization of monolithic cryogels is presented with key parameters like the pore size distribution, the tortuosity and the skeleton thickness employed for describing the porous structure characteristics of a cryogel matrix. Laminar flow, liquid dispersion and mass transfer in each capillary are considered and the model is solved numerically by the finite difference method. As examples, two poly(hydroxyethyl methacrylate) (pHEMA) based cryogel beds have been prepared by radical cryo-copolymerization of monomers and used to test the model. The axial dispersion behaviors, the pressure drop vs. flow rate performance as well as the non-adsorption breakthrough curves of different proteins, i.e., lysozyme, bovine serum albumin (BSA) and concanavalin A (Con A), at various flow velocities in the cryogel beds are measured experimentally. The lumped parameters in the model are determined by matching the model prediction with the experimental data. The results showed that for a given cryogel column, by using the model based on the physical properties of the cryogel (i.e., diameter, length, porosity, and permeability) together with the protein breakthrough curves one can obtain a reasonable estimate and detailed characterization of the porous structure properties of cryogel matrix, particularly regarding the number of capillaries, the capillary tortuousness, the pore size distribution and the skeleton thickness. The model is also effective with regards to predicting the flow performance and the non-adsorption breakthrough profiles of proteins at different flow velocities. It is thus expected to be applicable for characterizing the properties of cryogels and predicting the chromatographic performance under a given set of operating conditions.     

PAN基活性炭纤维的氮吸附研究

用相同原料不同活化方法制备聚丙烯腈基活性炭纤维,并对其进行了氮吸附研究.结 果表明,由不同活化方法所制备的活性炭纤维的孔结构存在较大差异,并对随着活化程度的 改变其孔结构的发展进行了研究.结果表明,通过简单的改变活化方法即可以制得不同孔隙占 主导地位的炭质吸附剂;也揭示出,不同的活化方法其活化机理有所差别.     

Peptide pore accessibility in reversed-phase chromatography

The effect of salt or peptide concentration on peptide porosity (i.e. the porosity accessible to a given peptide) is investigated on six different reversed-phase stationary phases. The peptide porosity is found to increase with the local concentration of negative charges following a saturation-type function within the same porosity boundaries for both cases. This can induce the formation of anti-Langmuirian peaks in non-adsorbing conditions since the local increase of the ionic strength due to the peptide concentration increases the porosity accessible to the peptide. This behavior can be well reproduced by the ideal model of chromatography assuming non-constant porosity. The acetonitrile adsorption isotherm was also measured on all the considered reversed-phase stationary phases. A comparison between the stationary phases shows a correlation between the amount of acetonitrile accumulated in the pores and the reduced pore accessibility for the peptide.     

Pore size distributions in microporous membranes. A critical analysis of the bubble point extended method

An extended bubble point method has been used to examine the porous morphology of several track-etched microporous polycarbonate membranes with nominal pore sizes ranging from 0.1 to 5.0 μm. The technique has been carefully analyzed and corrected to take into account the diverse non-ideal factors in flow along with the prevalence of Knudsen flow over the Hagen-Poiseuille one in the smaller pores.     

Dynamic polymer membranes displaying tunable transport properties on constitutional exchange

Functional dynamic polymers, “dynamers”, are used to design new membrane materials. Our efforts involve the synthesis and the fabrication of dynamic thin-layer supported solid membrane films. The transport performances of (permeability, selectivity and partition coefficients) are evaluated by using the solution-diffusion model. The membrane performances designed to transport ionic salts NaCl and KCl depend and are based on encoded molecular features of the monomeric subcomponents. Thanks to the possibility to combine the structural and functional features of different monomers, the heteropolymeric membrane materials can exhibit very different properties from their original homopolymeric components. In the examples developed here, this strategy revealed itself as a versatile way for the synthesis of new membranes presenting different permeabilities and preserving their selectivity (SK_+/Na₊∼1.4)$(S_{{\text{K}}^{+}/\text{N}{\text{a}}^{+}}\sim 1.4)$.     

Surface chemical and physical properties of TEOS-TBOT-PDMS hybrid materials

The application of nitrogen adsorption, mercury porosimetry and inverse gas chromatography (IGC) for the examination of surface physical and chemical properties of hybrid materials is discussed. Hybrid materials were prepared from tetraethoxysilane (TEOS), tetrabutyl orthotitanate (TBOT), and hydroxyl terminated polydimethyl siloxane (PDMS) for different TBOT concentrations. It was found that TBOT affects specific surface areas, pore volumes and pore sizes, but does not affect pore morphology. Surface chemical properties were analyzed by IGC. It was found that the dispersive surface energy was a function of the material pore size. Values between 36 and 42 mJ···m^-2 were obtained for the dispersive surface energy which are consistent with those of hybrid materials. On the other hand, the acid-base (k , k ) surface constants showed good correlation with the TBOT concentration. These materials can be considered as anphoteric ones, and it was found that k increases from 1.07 to 1.47, and k increases from 0.76 to 1.73 when the TBOT concentration increases from 0 to 7%. Such increase is assigned to the formation of Si–O–Ti bonds as it was deduced from an IR band appearing at 930 cm^-1 in the FT-IR spectra.     

The influence of particle shape and size on electric conductivity of metal-polymer composites

The effective electric conductivity of metal-polymer composite is investigated theoretically as a function of the electric conductivities of the constituents, of the particle shape and size and of the volume of loading. And, in order to consider the interaction between the metal particles, a self-consistent way is used to improve this function. Firstly, the percolation threshold decreases rapidly with increasing the metal particles axial ratio and decreasing the metal particle size. Secondly, the dependence of the metal particle shape and size on the effective electric conductivity of metal-polymer composite is investigated. Finally, the theoretical results on the effective electric conductivity of tin-polypropylene composite are in good agreement with the experimental data.     

几种植物基活性炭材料的孔结构与吸附性能比较——(I)孔结构表征

测定了3种植物基活性炭材料:椰壳活性炭 (CAC4)、剑麻茎基活性炭 (SSAC) 和剑麻基活性碳纤维 (SACF) 的氮吸附等温线,并用不同的理论方法对其孔结构进行了分析和表征。结果表明:CAC4为微孔型,孔径分布集中且大部分是0.7nm以下的极微孔;在相同条件下制备的SSAC和SACF孔分布较为相似,都呈多分散性,结构中除微孔外,还含有丰富的中孔,中孔率均超过50%以上。两者相比,SACF的中孔量和平均孔径更大。3个样品的形态特征和孔结构虽然不同,但其吸附过程都可以用微孔多段填充机理来解析。     

Effect of solution chemistry on the surface charge of polymeric reverse osmosis and nanofiltration membranes

A streaming potential analyzer has been used to investigate the effect of solution chemistry on the surface charge of four commercial reverse osmosis and nanofiltration membranes. Zeta potentials of these membranes were analyzed for aqueous solutions of various chemical compositions over a pH range of 2 to 9. In the presence of an indifferent electrolyte (NaCl), the isoelectric points of these membranes range from 3.0 to 5.2. The curves of zeta potential versus solution pH for all membranes display a shape characteristic of amphoteric surfaces with acidic and basic functional groups. Results with salts containing divalent ions (CaCl₂, Na₂SO₄, and MgSO₄) indicate that divalent cations more readily adsorb to the membrane surface than divalent anions, especially in the higher pH range. Three sources of humic acid, Suwannee River humic acid, peat humic acid, and Aldrich humic acid, were used to investigate the effect of dissolved natural organic matter on membrane surface charge. Other solution chemistries involved in this investigation include an anionic surfactant (sodium dodecyl sulfate) and a cationic surfactant (dodecyltrimethylammonium bromide). Results show that humic substances and surfactants readily adsorb to the membrane surface and markedly influence the membrane surface charge.     

Pore structural characteristics, size exclusion properties and column performance of two mesoporous amorphous silicas and their pseudomorphically transformed MCM-41 type derivatives

Highly ordered mesoporous silicas such as, mobile composition of matter, MCM-41, MCM-48, and the SBA-types of materials have helped to a large extent to understand the formation mechanisms of the pore structure of adsorbents and to improve the methods of pore structural characterization. It still remains an open question whether the high order, the regularity of the pore system, and the narrow pore size distribution of the materials will lead to a substantial benefit when these materials are employed in liquid phase separation processes. MCM-41 type 10 microm beads are synthesized following the route of pseudomorphic transformation of highly porous amorphous silicas. Highly porous silicas and the pseudomorphically transformed derivatives are characterized by nitrogen sorption at 77 K and by inverse size-exclusion chromatography (ISEC) employing polystyrene standards. Applying the network model developed by Grimes, we calculated the pore connectivity n(T) of the materials. The value of n(T) varies between the percolation threshold of the lattice and values of n(T) > 10, the latter being the limiting value above which the material can be considered to be almost infinitely connected such that the ISEC behavior of the material calculated with the pore network model is the same when calculated with a parallel pore model which assumes an infinite connectivity. One should expect that the pore connectivity is reflected in the column performance, when these native and unmodified materials are packed into columns and tested with low molecular weight analytes in the Normal Phase LC mode. As found in a previous study on monolithic silicas and highly porous silicas, the slope of the plate height (HETP) - linear velocity (u) curve decreased significantly with enhanced pore connectivity of the materials. First results on the pseudomorphically transformed MCM-41 type silicas and their highly porous amorphous precursors showed that (i) the transformation did not change the pore connectivity (within the limits detectable by ISEC) from the starting material to the final product and (ii) the slope of the HETP versus u curve for dibutylphtalate did not change significantly after the pseudomorphic transformation.