Coverage homogenity of chemically bonded C18 phases for HPLC. Investigation of the changes in the free surface energy of the packings

Summary Packings containing chemically bonded C₁₈ groups with different coverage density were prepared using monochlorooctadecylsilane. The method permitting the determination of the free surface energy on the basis of adsorption measurements of two different liquids, noctane and water, was utilized to evaluate the coverage homogeneity of the silica gel surface by the alkylsilyl ligands. It was found that the packing is characterized by a coverage greater than 3.8 mol/m², it is homogenous and the support surface is fully screened.     

Studies of surface properties of Na- and La-montmorillonites

This paper presents possible applications of thermal analysis, sorptometry and porosimetry to study physico-chemical properties of Na- and La-montmorillonite samples, especially for determination of total surface heterogeneity. The quasi-isothermal thermogravimetric (Q-TG) mass loss and its first derivative (Q-DTG) curves with respect to temperature and time obtained during programmed liquid thermodesorption under quasi-isothermal conditions have been used to study adsorbed layers and heterogeneous properties of the Na- and La-montmorillonites. Calculations of the desorption energy distribution functions by analytical procedure using mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption under quasi-isothermal conditions of polar and non-polar liquid vapours preadsorbed on a material surface are presented. Parameters relating to porosity of samples were determined by sorptometry, mercury porosimetry and atomic force microscopy (AFM). From nitrogen sorption isotherms from sorptometry and porosimetry methods, the fractal dimensions of montmorillonites have been calculated. Moreover, a new approach is proposed to calculate fractal dimensions of materials obtained from Q-TG curve; this is compared with values obtained by the above methods. The total heterogeneous properties (energy distribution function and pore-size distribution functions) of samples studied were estimated. The radius and pore volume of the tested samples calculated on the basis of thermogravimetry, sorptometry and porosimetry techniques were compared and good correlations obtained.     

Studies of physico-chemical properties of mixed adsorbent in the zeolite/SiO2 system

The paper presents physico-chemical properties of mixed adsorbents in the clinoptylolite (mordenite)/SiO₂ system containing 30, 50, 80 mass% zeolite. Adsorption capacity towards polar (water, butanol) and non-polar (n-octane) substances as well as total surface heterogeneity (energetic and geometrical) were determined. Desorption energy distribution functions as well as fractal dimensions were also determined and compared with the low-temperature nitrogen adsorption data. Irregular shapes of the curves q=f(E _d) as well as large values of volumetric fractal dimensions (D _f~2.6) revealed heterogeneous properties of the zeolite/SiO2 system surfaces. Addition of zeolite increases total heterogeneity of the material.     

Determination of total heterogeneity and fractal dimensions of high-temperature superconductors

Using thermo-analytical and sorptometric methods physicochemical properties and especially surface heterogeneity of HgBa₂Ca₂Cu₃O₈₊, (Hg-1223) was investigated. The desorption energy distribution was derived from mass loss Q-TG and differential mass loss Q-DTG curves of thermodesorption in quasi-isothermal conditions of pre-adsorbed n-octane and water vapour. It is shown that the superconducting Hg-1223 phase is highly sensitive to water vapours. The mechanism of water adsorption depends largely on the activation time. By water vapour saturation in a period of 90 min, physisorption takes place. Prolonged periods result in a chemical decomposition. From nitrogen ad- and desorption isotherms the fractal dimension of superconductors were calculated. A new approach is proposed to calculate fractal dimension from Q-TG curves.This revised version was published online in November 2005 with corrections to the Cover Date.     

Application of fractal geometry for studies of heterogeneity properties of nanomaterials

Calculations based on the fractal geometry in the estimation of surface heterogeneity are superior compared with conventional calculation methods (e.g. from the data of gas adsorption or X-ray radiation scattering) as they can be applied without limitation as far as the range of surface sizes of the studied structures is concerned. This paper presents structural characteristics of carbon and carbon- free nanomaterials based on the determined surface and volumetric fractal coefficients. Fractal coefficients were determined from the data obtained by means of two independent methods: sorptometry and atomic force microscopy (AFM). Correlation between porosity parameters and fractal coefficients is presented.     

Determination of liquid adsorption and desorption on and from solids by means of the derivatograph

This paper presents a method for calculation of the adsorption and immersion heats of water on a silica gel surface from the DTA curve obtained with a modified derivatograph. The adsorption and desorption heats have also been determined. The relationship between the adsorption heat and the amount of water adsorbed is presented.

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Zusammenfassung Eine Methode zur Berechnung der Adsorptions- und Immersionswärmen von Wasser an Silikagel aus den mit einem modifizierten Derivatographen gemessenen DTA-Kurven wird beschrieben. Adsorptions- und Desorptionswärmen wurden bestimmt. Die Beziehung zwischen der Adsorptionswärme und der Menge des adsorbierten Wassers wird angegeben.

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The Studies of the Heterogeneous Properties of Solid Surfaces by Means of the Derivatograph Q-1500 D

A simple method has been adopted to obtain an important information on the heterogeneous properties of materials studied, adsorbed liquid films and liquid-solid interactions. The method utilizes Q-TG mass loss and the first derivative Q-DTG mass loss curves with respect to temperature and time obtained during programmed liquid thermodesorption in quasi-isothermal conditions. The values of the adsorption capacity, total porosity of material, the value of active centers, desorption energy distribution and mesopore-size distribution functions obtained by this method are in good agreement with those estimated on the basis of independent methods. The theoretical and experimental results provided novel and unique data on the heterogeneity of solid surfaces, properties of liquid adsorbed films and thermal stability of the liquid/solid interfaces. This paper presents the more important results obtained so far in the studies the liquid/solid systems by means of the Paulik's classical and quasi-isothermal techniques. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies of modified carbon nanotubes by means of thermogravimetry Q-TG and sorptometry techniques

The paper presents the physicochemical (adsorption and porosity) properties of closed carbon nanotubes, opened through the action of an oxidizing acid and modified with metal ions of nickel, cobalt, and iron/cobalt. The carbon nanotubes were prepared via the oxidation process by means of 65 % nitric acid and/or nickel and cobalt nitrates dissolved with 65 % nitric acid. Using special thermogravimetry Q-TG and sorptometry methods physicochemical properties of pure and modified nanotube surfaces were investigated. A numerical and analytical procedure for the evaluation of heterogeneous properties (adsorption capacity, statistical number of adsorbed liquid layers, desorption energy distribution functions) on the basis of liquid thermodesorption Q-TG from the sample surfaces under the quasi-equilibrium conditions are presented. The calculations of the specific surface areas, pore size and volume, and fractal dimensions of carbon nanotubes were made from sorptometry data.     

Surface properties of silica gel samples modified by selected proteins

The adsorption of a polar (water) and a non-polar (n-octane) liquid on silica gels, modified by adsorption of proteins, has been studied by thermal analysis. Silica gels with physically adsorbed BSA and ovalbumin layers were used. Thermodesorption energies were determined from Q-TG and Q-DTG curves recorded under quasi-equilibrium conditions. Significant differences in liquid desorption were observed from the surfaces due to heterogeneous changes (energetic and geometrical) as a result of modification. These results are compared with those obtained for the samples heated at 160°C for 1 h.     

Studies of heterogeneity properties of selected high-temperature superconductor surfaces

Nitrogen adsorption measured at 77 K was used to characterize the surface heterogeneity of high-temperature superconductor surfaces. Properties relating to adsorption and porosity of the solids (adsorption capacity, specific surface area, radii and volume of the pores, pore-size distribution function) were determined from nitrogen adsorption–desorption isotherms and atomic force microscopy (AFM) for a series of oxide superconductors. It is shown that the adsorption isotherms of all samples are S-shaped and belong to type II according to the IUPAC classification. On the basis of the nitrogen adsorption isotherms and AFM data, fractal dimensions were determined and correlations found with adsorption and porosity parameters.