The kinetics of silylation of hydroxylated silica II CPG-10 porous glasses

 The kinetics of chemisorption of trimethylchlorosilane, trimethylbromosilane, and triethylchlorosilane on samples of porous silica, CPG-10 porous glasses, of varying pore diameter were investigated and found to follow a first-order kinetics law in which the reaction is retarded by one of its products. At constant temperature, the rate was found to increase with increasing diameter of the pores in the range used. Increasing the molecular cross-sectional area of the adsorptive, the silane molecule, in the range 0.35–0.465 nm² decreased the rate of reaction. Received: 3 November 1999/In revised form: 21 January 1999/Accepted: 27 January 1999     

The influence of long additional thermal treatment of controlled porous glasses on the structuralization of their silica network

The materials used as sorbents in gas and liquid chromatography include controlled porosity glasses (CPG). The heating of CPG in the temperature range 400–800 °C leads not only to dehydroxylation of their surface, but also to a diffusion of the boron atoms (and a smaller amount of sodium atoms) remaining in the silica network of the CPG towards the glass surface. Simultaneously, crystallization of the silica network of the CPG takes place.The present paper deals with the changes of the crystallographic structures in thermally treated glasses which differ in their mean pore diameters. The results show not only the existence of cristobalite in the siliceous lattice of the heated glasses, but also the presence of -quartz, the very symmetrical structure of SiO₂.

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Zusammenfassung Gläser kontrollierter Porosität (CPG) gehören zu den in der Gas- und Flüssigkeitschromatographie verwendeten Sorbenten. Erhitzen von CPG auf 400–800 °C führt nicht nur zur Dehydroxylierung ihrer Oberflächen, sondern auch zur Diffusion der im Siliciumdioxidgitter des CPG verbleibenden Boratome (und in geringerem Maße auch von Natriumatomen) zur Glasoberfläche. Gleichzeitig erfolgt die Kristallisation des Siliciumdioxidgitters der CPG. Im vorliegenden Artikel werden die Veränderungen der kristallographischen Strukturen in thermisch behandelten, sich im mittleren Porendurchmesser unterscheidenden Gläsern untersucht. Es wird gezeigt, daß im Siliciumdioxidgitter der hitzebehandelten Gläser nicht nur Cristobalit, sondern auch die hochsymmetrische SiO₂-Struktur des -Quarzes vorliegt.

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, , . 400–800 °C , ( ) . . , . , - .

     

Adsorption of CsOH on controlled porous glasses

Adsorption of CsOH has been studied for 18 samples of porous glasses prepared from different raw glass materials by means of different thermal and chemical treatment. For all the samples studied and for 3 samples of chromatographic silica gels the adsorption capacity in relation to CsOH is proportional to the BET surface area and equals 4 mol of cesium per 1 m² of BET surface.     

Photochemistry of ketones adsorbed on porous silica

The Phetochemical reactions of several families of ketones adsorbed on various forms of silica have been investigated. The influence of surface coverage, silica average pore diameter, temperature, applied magnetic fields, and additives on the product distributions have been determined. The results are consistent with a model in which the silica surface consists of two major regions, one consisting of stronger binding sites (active silanol groups) and the other consisting of weaker binding sites (free silanol groups). The relative proportions of these two types of sites are related to the pore size of the silica, smaller pores correlating with a larger fraction of the stronger binding sites and larger pores correlating with a smaller fraction of the stronger binding sites. At low coverage, the initial location of a ketone in one of the two binding sites is an important factor in determining the product distributions. Some preliminary results are reported on the time resolved spectroscopy of ketones adsorbed on silica investigated by diffuse reflectance absorption spectrescopy.     

The relationship between micro- and mesoporous substructures upon removal of colloidal silica from porous glasses subjected to alkaline treatment

The effect of alkaline treatment of two basal liquation sodium borosilicate porous glasses on their micro- and mesoporous substructures has been studied. The morphology of pores has been investigated and the structural characteristics of micro- and mesoporosity have been determined by the equilibrium and kinetic adsorption-desorption methods at low, moderate, and high relative pressures. It has been established that the alkaline treatment leads to a substantial increase in the volume of mesopores and a noticeable decrease in the volume of micropores, which correlates with a reduction in the specific surface area of the mesopores. After the alkaline treatment, the trimodal distribution and the average diameter (0.5–0.6 nm) of micropores remain unchanged and ultramicropores do not arise in the range of 0.27–0.37 nm. It has been concluded that micropores represent only the regions of interglobular contacts of secondary silica in liquation channels with sizes of 1–2 diameters of an adsorbate molecule. The alkaline treatment is accompanied by the structuring and dissolution of silica globules in liquation channels; as a result, wide-porous glass samples with monomodal interglobular pores are obtained, while new micropores are not formed via the etching of channel walls in the glass matrix. Correlation dependences between the coordination number, porosity, and diameters of pores and globules of colloidal silica have been proposed for a large set of standard globular packings. It has been shown that, as the boron content in a porous glass rises, secondary silica globules in liquation channels grow, while their packing becomes looser.     

Acidic and catalytic properties of boron-containing porous glasses

Heat treatment of porous glasses results in a migration of boron to the surface changing surface acidity. The surface acidity of thermally modified porous glasses was characterized by NH₃ desorption and the catalytic activity for conversion of alcohols was investigated.

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, . NH₃, .

     

Liquid chromatography of dextrans on porous silica beds

Kinetics, equilibrium isotherms and chromatography retention times for sorption of dextrans T-10, T-20, T-40, T-70, T-110, T-161, T-250 and T-500 on porous silica were measured at 25 degrees C. The Henry constant and retention factors for the dextrans were obtained. The values of the partition coefficient for the distribution of the dextrans between the bulk solution and the pore space were calculated within the framework of a pore volume filling model with consideration given to the ratio between the sizes of the macromolecular coils and the pore inlet. The measurements showed that this parameter depends on the structure of the sorbent and the molecular mass distribution of the dextran. The interaction of aqueous dextran solution with porous silica is characterized by the sieve effect. Large macromolecular coils of dextran T-161 cannot penetrate into the pore space of the silica sorbent with pore diameter 14 nm. The difference in Henry law constants calculated from adsorption and chromatographic data for dextrans T-70 and T-110 can be explained by the slow diffusion of dextran macromolecules into silica pores under chromatographic conditions.     

Adsorption of charged diblock copolymers on porous silica

Block copolymers of styrene and 2-vinylpyridine of different molecular weights were synthesized and chemically modified to poly(vinyl pyridine)/poly(styrene sulfonate) or polystyrene/poly(2-vinyl pyridinium) salts. Adsorption on “Spherosil” silica with a high specific surface area was performed from aqueous solutions of polyelectrolyte copolymers or from noncharged copolymer in an organic medium and subsequent sulfonation or quaternization in the adsorbed state. The adsorption mechanism was studied under various solvent conditions to give silica maximal ion-exchange properties. Modification of silica resulted in a highly stable coated material which combines the mechanical properties of the porous beads and the ion-exchange properties of the “supported” and “pellicular” ion-exchangers and should have potential use in chromatography.     

Diffusion into and adsorption of polyethylenimine on porous silica gel

The polyethyleneimine (PEI)–water–silica gel absorption system was used as a model system to investigate the relationship between diffusion into the porous structure, adsorption rate, and molecular weight of the polymer. Three silica gels, Porasil A, B, and and C having a range of characteristic porosity were used as adsorbents. Adsorption of PEI on Porasil C, which has the majority of its pores much larger than the dimensions of the adsorbate molecule, increased initially with increased molecular weight but became nearly constant at higher molecular weight. Little increase in adsorption occurred for this silica gel with increased ionic strength or with increased pH between 9.5 and 10.8. In contrast, adsorption increased sharply with increased ionic strength and for the same pH range on Porasil A. Molecular weight dependence was reversed. Adsorption decreased with increased molecular weight on Porasil A. In this case, the molecular size of PEI investigated was the same as the majority of pore apertures in the adsorbent. Solution environments (i.e., pH and ionic strength) that decrease the size of the PEI molecule and its affinity for the anionic silica gel surface, thus enabling it to more readily diffuse into the smaller porous regions of the adsorbent, are the apparent causes of the very large adsorption increase. Electrostatic repulsion between PEI molecules do not appear greatly to affect adsorption. Similar adsorption behavior has been reported in the literature for the PEI–cellulosic fiber adsorption system. Maximum adsorption on Porasil A occurred at pH 10.8, the same maximum generally reported for adsorption of PEI on cellulosic fibers. In this case, the silica gel (Porasil A) was found to have a pore size distribution and specific surface area of the same magnitude as cellulosic fibers prepared in the expanded state.     

Determination of silica in glasses,ceramics and refractories

A rapid method for the determination of silica in glasses, glass ceramics and refractories is described. The utilization of direct coulometric titration of the excess of 8-quinolinol employed to precipitate the silico-12-molybdate complex, enables duplicate determinations in the presence of diverse ions to be completed in about 3h. Studies of the optimum, conditions indicated that the acidity and choice of acid were critical. For greatest versatility a sulfuric acid medium was better than hydrochloric or perchloric acids. The addition of glycerol allowed analysis of titanium-containing refractories. The accuracy of the method for a wide variety of materials is similar to that of the conventional acid-dehydration method.     

Wettability of proteins adsorbed on silica glasses treated with fluorosurfactants

Generally, the apolar/polar surface is probed by water-wetting, which is measured using a method such as the sessile liquid drop method. However, when one tries to measure the wetting of a surface where biological macromolecules are adsorbed, there is the problem of a change in conformation due to drying the surface; hence, using this method in situ information cannot be obtained. We have developed a new method that can be used to measure the wettability of the adsorbed protein surface without drying. This method, the dropping time method, which is based on measuring the dropping time of a film of liquid along a protein-covered surface when this surface is instantaneously vertically removed from the protein solution. The adsorption behavior of four proteins (albumin, lysozyme, β-lactoglobulin, ovalbumin) on the surface of silica glass that has been treated with various fluorosurfactants is studied using this method. At a high concentration of protein, the surfaces of adsorbed proteins of any kind are fairly hydrophilic on glass treated with all fluorosurfactants. At a lower concentration of protein, the hydrophilicity of the protein layer depends on the kind of fluorosurfactant and also on the protein adsorption process. The apolar glass surface becomes more hydrophilic with increasing dipping time in the protein solution. On the other hand, the hydrophilic glass surface shows a complex change in the hydrophilicity with elapsed time after dipping it into a solution of albumin or lysozyme, i.e., the hydrophilicity decreases in the early stage of the adsorption and then increases with proceeding adsorption. Received: 19 March 1999 Accepted in revised form: 10 June 1999     

A model for polybutadiene coatings on porous silica

Summary Non-wetting viscous liquids such as oligobutadiene prefer active sites such as pores during the process of physisorption. Thus, polybutadiene (PBD) coatings on porous silica do not result in a homogeneous polymer film but in an inhomogeneous loading where the bulk polymer is mainly sited in the pores of the silica. An increasing polymer loading leads to increasingly filled pores instead of a thicker polymer film. We cannot exclude the possibility that most of the surface is covered at least with a thin polymer film since the chromatographic behaviour is relatively good for polypeptides, which are highly susceptible to the silanol groups of silica.     

Adsorption of potential-determining ions on porous glasses of different compositions

The adsorption characteristics are studied for nano- and ultraporous glasses (PGs) produced from sodium borosilicate glasses and a glass containing small amounts of fluoride ions and phosphorus oxide by acid (HCl) leaching and additional alkaline (KOH) and thermal treatment. The surface charges σ₀ of PGs are determined by continuous potentiometric titration in 10⁻³−1 M NaCl, KCl, and (C₂H₅)₄NCl solutions. Only negative surface charges of PGs are observed for all investigated systems. The |σ₀| value is predetermined by the following factors: the composition of PG, the pore radius in the nanometer region (r ≤ 13 nm), the specificity of counterions, the content of secondary silica in the pore space, and the temperature of the additional thermal treatment of the membranes. The introduction of fluoride ions and phosphorus oxide into sodium borosilicate glass, an increase in the pore sizes and the amount of the secondary silica in PGs, and a rise in the specificity of counterions enhance the |σ₀| values, which decrease with a rise in the temperature of the thermal treatment due to the surface dehydration and dehydroxylation. For ultraporous glasses (r > 13 nm), the surface charge is almost independent of the pore radius.     

Selectivity of alkali metal cations adsorption on controlled porous glasses

Alkali metal ions are adsorbed on controlled porous glasses from basic solutions. Narrow porous glasses show a relatively high selectivity with adsorption decreasing in the series Cs, K, Na, Li.     

Adsorption of cesium on,and desorption from,controlled porous glasses

Cesium contained in aqueous solutions of different composition was adsorbed in columns packed with controlled porous glasses (CPG) and then removed by means of 1M HCl. Recovery of cesium in the eluate was studied as a function of the solution composition and the kind of CPG.     

The kinetics of water desorption from porous glasses

The kinetics of water desorption from porous glasses silica gel and porous aluminosilicates were followed through the TG and DTG methods. In all cases only one thermodesorption peak appeared. The kinetic parameters were determined by standard nonisothermal methods. The activation energy is constant and independent of the coverage degree and pore diameter in the system porous glass-water. The functionE(θ) were determined for the silica gel and porous aluminosilicatesE=E ₀+a exp (-bθ). The parametersE ₀,a andb depend on the SiO₂/Al₂O₃ ratio and on the distribution of active centers on the surface.     

Microporous silica membranes deposited on porous supports by filtration

Water based particulate silica sols have been coated onto Anodisc® filters by filtration. The membranes prepared by this technique are more uniform than those formed by slip-casting. The average diameter of the silica particles used in these studies is 6 nm. Unsupported silica membranes formed from these sols have a microporous structure. The adhesion between silica and the alumina support is influenced by the sol pH. Coating thickness can be controlled by the concentration and volume of the sol filtered. Polyvinyl alcohol (PVA) was used to improve adhesion and to prevent cracking during drying. When the PVA/SiO₂ ratio by weight is less than 20%, the membranes retain their microporosity after firing. The membranes prepared by this filtration method have their pore size in Knudsen diffusion range.     

Solid dispersions of carvedilol with porous silica

Solid dispersion particles of carvedilol (CAR) were prepared with porous silica (Sylysia 350) by the solvent evaporation method in a vacuum evaporator to ensure an effective pore-filling procedure. Two sets were prepared, each with various amounts of CAR in solid dispersions, and with the pore-filling process differing each time. Set A was prepared by a one-step filling method and set B by a multiple-step pore-filling method of CAR into porous silica. The solid dispersions were then characterized using thermal analysis, X-ray diffraction, and nitrogen adsorption experiments. The results showed that the drug release can be significantly improved compared with the dissolution of the drug in its pure crystalline or amorphous state. Drug release from solid dispersion was faster when the drug content in the solid dispersion was low, which enabled the drug to be finely dispersed along the hydrophilic carrier's surface. The results also showed that a multiple-step pore-filling procedure is more effective for drug loading as indicated by the absence of a crystalline drug state, greatly reduced porosity, and improved wettability and physical stability of the amorphous CAR.