Modeling of interaction properties of surfaces of phyllosilicates: A theoretical forecast of adsorption isotherms of noble gases at the talc surface

The electrostatic potential and the intensity of the electric field above the isolated layer of the phyllosilicate mineral talc (layer group symmetry C2/m) were computed using the semiempirical INDO /2 method. The electrostatic potential V_c and the intensity of electric field (OVERBAR)E_c, above the surface of semi-infinite crystal were obtained as the sum of the contributions of the infinite number of individual layers. The interaction energy U_int between a noble gas atom and the talc crystal was computed as (a) a pure Lennard-Jones energy U_LJ and (b) the sum of U_LJ and interaction energy with induced dipole moment: U_ind = α|(OVERBAR)E|², where α is the dipole polarizability of the noble gas atom. The one-particle configurational integral was calculated within the classical mechanics limit. Both the free and adsorbed gas phases were assumed to be ideal. The obtained results demonstrate that in the case of uncharged and nonpolar adsorbate and an uncharged surface the electrostatic part of the interaction energy should be included in the total interaction energy. © 1996 John Wiley & Sons, Inc.     

Surface characterization of polyimide films

 Various kinds of poly(amide acid)s were prepared by the reaction of four kinds of acid dianhydride and three kinds of diamine in N,N-dimethylacetamide (DMAc). Polyimide films were prepared by casting the poly(amide acid) solution on soda glass substrates, followed by thermal imidization at various temperatures. Contact angles of polyimide films for the sides in contact both with air and with glass substrate (air side and glass side, respectively) were measured to evaluate the dispersive component (γ^D _S) and the nondispersive component (γ^P _S) of surface free energy (γ_S) of polyimide films. It was shown that, for the air side, γ^P _S value decreased greatly and γ^D _S values increased slightly with the development of imidization. Values of γ^P _S for the glass side were much higher than those for the air side. Poly(amide acid) solution was also cast on quartz glass and silicone rubber, and was thermally imidized. The γ^P _S for the quartz glass side was almost the same as that for the soda glass side. But the γ^P _S for the silicone rubber side was as low as the γ^P _S for the air side. Attenuated total reflection infrared spectroscopy of polyimide films showed that the degree of imidization for the glass side surface was not as high as that for the air side surface, and that the amount of polar groups for the glass side surface was higher than that for the air side surface. Among the various kinds of polyimides, there is a slight but clear difference in the values of γ_S and its components, which can be rationalized from the difference in the chemical structure. It was also found that thermal degradation and oxidation can be easily detected from the change of surface free energy and its components for the polyimide films after being treated at high temperatures in both air and vacuo. Received: 22 January 1998 Accepted: 10 March 1998     

Physicochemical Properties and Surface Tension Prediction of Mixed Surfactant Systems: Triton X‐100 with Dodecylpyridinium Bromide and Triton X‐100 with Sodium Dodecylsulfonate

Dependences of the surface tension of aqueous solutions of ionic (dodecylpyridinium bromide, sodium dodecylsulfonate) and nonionic (Triton X‐100) surfactants and their mixtures on total surfactant concentration and solution composition were studied, and the surface tension of the mixed systems were predicted using different Miller's model. It was found that how to select the model for calculation of ω is corresponding to the degree of the deviation from the ideality during the adsorption of mixed surfactants. The compositions of micelles and adsorption layers at air‐solution interface as well as parameters (β^m, β^ads) of headgroup‐headgroup interaction between the molecules of ionic and nonionic surfactants were calculated based on Rubingh model. The parameters (B₁) of chain‐chain interaction between the molecules of ionic and nonionic surfactants were calculated based on Maeda model. The free energy of micellization calculated from the phase separation model (ΔG ₂ ^m ), and by Maeda's method (ΔG ₁ ^m ) agree reasonably well at high content of nonionic surfactant. The excess free energy ΔG _ads ^E and ΔG _m ^E (except α=0.4) for TX‐100/SDSn system are more negative than that TX‐100/DDPB system. These can be probably explained with the EO groups of TX‐100 surfactant carrying partial positive charge.     

Characterization of wood fibers modified by phenol-formaldehyde

Wood-fiber phenol-formaldehyde-resin (PFR) modified surfaces, obtained from the adsorption of a PFR/water solution, are investigated as a function of the nature and the amount of PFR adsorbed. Surface are measurements are performed by using krypton adsorption at 77 K. Chemical modification is monitored by the electron spectroscopy for chemical analysis (ESCA) technique and the surface energy by the inverse phase gas chromatography (IPGC) method at infinite dilution. The London dispersive componentγ _S ^L of the surface energy shows a relationship to the concentration of carbon and oxgen at the fiber surface.γ _S ^L increases from 27.5 mN·m⁻¹ for the untreated fiber to 42.5 mN·m⁻¹ for the fibers treated with 20% high molecular-weight-grade phenol-formaldehyde. The surface atomic ratio O/C determined using the ESCA technique exhibits a decrease from 44% for untreated to 31% for treated samples. Surface area also decreases from 2.09 m²/g to 1.50 m²/g. The PFR adsorbed by wood fibers is observed as the dispersive component of surface energy starts to increase, as the surface oxygen concentration decreases, and on the surface area of the wood fiber.     

Gas‐phase dissociation of ionic liquid aggregates studied by electrospray ionisation mass spectrometry and energy‐variable collision induced dissociation

Positive singly charged ionic liquid aggregates [(C_nmim)_m+1(BF₄)_m]⁺ (mim = 3‐methylimidazolium; n = 2, 4, 8 and 10) and [(C₄mim)_m+1(A)_m]⁺ (A = Cl⁻, BF₄⁻, PF₆⁻, CF₃SO₃⁻ and (CF₃SO₂)₂N⁻) were investigated by electrospray ionisation mass spectrometry and energy‐variable collision induced dissociation. The electrospray ionisation mass spectra (ESI‐MS) showed the formation of an aggregate with extra stability for m = 4 for all the ionic liquids with the exception of [C₄mim][CF₃SO₃]. ESI‐MS‐MS and breakdown curves of aggregate ions showed that their dissociation occurred by loss of neutral species ([C_nmim][A])_a with a ≥ 1. Variable‐energy collision induced dissociation of each aggregate from m = 1 to m = 8 for all the ionic liquids studied enabled the determination of E_{cm, 1/2} values, whose variation with m showed that the monomers were always kinetically much more stable than the larger aggregates, independently of the nature of cation and anion. The centre‐of‐mass energy values correlate well with literature data on ionic volumes and interaction and hydrogen bond energies. Copyright © 2008 John Wiley & Sons, Ltd.     

Organic electroluminescent devices using organosilicon polymers containing phenylene or diethynylanthracene units

Double‐layer electroluminescent (EL) devices composed of an alternating polymer with mono‐, di‐, or tri‐silanylene and phenylene units, [(Si R) _m (C₆H₄)] _n (R = alkyl, m = 1–3) as a hole‐transporting layer, and tris(8‐quinolinolato)­aluminium(III) complex (Alq) as an electron‐transporting–emitting layer were fabricated. The longer silanylene chain lengths in the polymer, on going from m = 1 to m = 2 and 3, result in better electrical properties for the EL devices, implying that the σ–π conjugation in the polymers plays an important role in the hole‐transporting properties, including the hole‐injection efficiency from an anode. This is in marked contrast to the improved hole‐transporting properties that occur in response to reducing the silanylene chain length of silanylene‐diethynylanthracene polymers previously reported. The UV absorption maxima of silanylene‐phenylene polymers shift to longer wavelengths with increasing m, and their oxidation peak potentials in cyclic voltammograms shift to lower potential with increasing m, in accordance with the improved electrical properties of the device that are observed with the polymers containing the longer silanylene chain. A triple‐layer EL device with a hole‐transporting layer of monosilanylene‐diethynylanthracene polymer, an electron‐transporting–emitting layer of Alq, and an electron‐blocking layer of N,N′‐diphenyl‐N,N′‐bis(3‐methylphenyl)‐1,1′‐biphenyl‐4,4′‐diamine (TPD) exhibited a maximum efficiency of 1.0 lm W⁻¹ and a maximum luminance of 14750 cd m⁻², both of which are much higher than the values obtained from a conventional EL device with TPD/Alq. Copyright © 1999 John Wiley & Sons, Ltd.     

Characterisation of the surface of a cellulosic multi-purpose office paper by inverse gas chromatography

The surface of multi-purpose cellulosic office paper has been analysed by inverse gas chromatography (IGC). The parameters determined were the dispersive component of the surface free energy, the enthalpy of adsorption and the entropy of adsorption of polar and apolar probes, the Lewis acidity constant, K _a, and the Lewis basicity constant, K _b. It can be concluded that the dispersive component of the surface free energy, _s ^d decreases with temperature, in the range 50–90°C. The temperature coefficient of _s ^d, d_s ^d/dT, is –0.35 mJm ^–2K^–1. The values of K _a and K _b were determined to be 0.11±0.011 and 0.94±0.211, respectively. The predominant surface basicity agrees with expectation, bearing in mind the presence of calcium carbonate, and of a styrene-acrylic copolymer, in the surface sizing formulation. It is thought that during the drying stages following the surface sizing treatment, the starch used as the binder migrates to the interior of the surface sizing layer and then to the paper bulk itself. This migration contributes to a decrease in the hydrophilicity of the surface, and also results in the surface showing only slight Lewis.     

Novel drug‐based Fe(III) heterochelates: synthetic,spectroscopic, thermal and in‐vitro antibacterial significance

A series of novel heterochelates of the type [Fe(Aⁿ)(L)(H₂O)₂]^?mH₂O [where H₂Aⁿ = 4,4′‐(arylmethylene)bis(3‐methyl‐1‐phenyl‐4,5‐dihydro‐1H‐pyrazol‐5‐ol); aryl = 4‐nitrophenyl, m = 1 (H₂A¹); 4‐chlorophenyl, m = 2 (H₂A²); phenyl, m = 2 (H₂A³); 4‐hydroxyphenyl, m = 2 (H₂A⁴); 4‐methoxyphenyl, m = 2 (H₂A⁵); 4‐hydroxy‐3‐methoxyphenyl, m = 1.5 (H₂A⁶); 2‐nitrophenyl, m = 1.5 (H₂A⁷); 3‐nitrophenyl, m = 0.5 (H₂A⁸); p‐tolyl, m = 1 (H₂A⁹) and HL = 1‐cyclopropyl‐6‐fluoro‐4‐oxo‐7‐(piperazin‐1‐yl)‐1,4‐dihydroquinoline‐3‐carboxylic acid] were investigated. They were characterized by elemental analysis (FT‐IR, ¹H‐ & ¹³C‐NMR, and electronic) spectra, magnetic measurements and thermal studies. The FAB‐mass spectrum of [Fe(A³)(L)(H₂O)₂]^?2H₂O was determined. Magnetic moment and reflectance spectral studies revealed that an octahedral geometry could be assigned to all the prepared heterochelates. Ligands (H₂Aⁿ) and their heterochelates were screened for their in‐vitro antibacterial activity against Bacillus subtilis, Staphylococcus aureus, Escherichia coli and Serratia marcescens bacterial strains. The kinetic parameters such as order of reaction (n), the energy of activation (E_a), the pre‐exponential factor (A), the activation entropy (ΔS^#), the activation enthalpy (ΔH^#) and the free energy of activation (ΔG^#) are reported. Copyright © 2009 John Wiley & Sons, Ltd.     

Carpetlike dense‐layer formation in a polyelectrolyte brush at the air/water interface

A carpetlike dense‐layer formation between a hydrophobic layer and a polyelectrolyte brush layer has been found in the monolayers of an ionic amphiphilic diblock copolymer, poly(1,1‐diethylsilacyclobutane)_m‐block‐poly(methacrylic acid)_n, on a water surface by an X‐ray reflectivity technique. By detailed analysis, we have found that the hydrophilic layer under the water is not a simple layer but is divided into two layers, that is, a carpetlike dense methacrylic acid (MAA) layer near the hydrophobic layer and a polyelectrolyte brush layer. We have also confirmed that a well‐established polyelectrolyte brush is formed only for the m:n = 43:81 polymer monolayer: For m:n = 40:10 and m:n = 45:60 polymer monolayers, only a dense MAA layer is formed. This dense‐layer formation should be the origin of the interesting hydrophobic‐layer thickness variation previously reported; The hydrophobic‐layer thickness takes a minimum as a function of the hydrophilic chain length at any surface pressure studied. An overview of the data for three samples with different chain lengths (m:n = 40:10, 45:60, or 43:81) has shown that the thickness of this dense layer is 10–20 Å and is independent of the surface pressure and polymerization degree of poly(methacrylic acid) (PMAA) in the range studied. This dense‐layer formation is explained by the reasonable speculation that contact with PMAA is thermodynamically more stable than direct contact with water for the diethylsilacyclobutane (Et₂SB) layer on water. In this sense, the dense layer acts like a carpet for the hydrophobic Et₂SB layer, and a 10–20‐Å thickness could be a critical value for the carpet. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1921–1928, 2003     

Wettability of commercial starches and galactomannans

This paper describes the wettability of basic commercial polysaccharides: starches (potato PS, wheat WS, corn CS, tapioca TS, kuzu KS) and galactomannans (fenugreek gum FG, guar gum GG, tara gum TG, locust bean gum LBG). The study was conducted using the Washburn capillary rise method and thermal drying. This allowed one to determine the material constant C, contact angle θ, surface free energy of solid SFE, and initial moisture content M. The measured values of contact angle θ and surface free energy SFE indicated that potato starch (70.9°, 41.1?mN?·?m^?1) and wheat starch (88.4°, 30.2?mN?·?m^?1) were characterized by the highest and lowest wettability among the examined starches, respectively. In turn, the galactomannans were poorly wettable substances. Their contact angles θ were approximately equal to 90°, showing a slight increase with increasing substitution degree. The observed decrease in surface free energy SFE from 30 to 29.6?mN?·?m^?1 indicated a very minor hydrophobization of their surfaces. Material constant C was practically independent of temperature, and an increase in initial moisture content M in the examined starches and galactomannans proceeded according to the following schemes: CS?相似文献   

The elastic free energy and the elastic equation of state: Elongation and swelling of polydimethylsiloxane networks

The elastic free energy for a tetrafunctional network is here expressed as where λ₁, etc., are the principal extension ratios relative to the state of reference (wherein 〈r²〉 = 〈r²〉₀), and C₁, C₂, and m are arbitrary parameters. The free energy of a swollen system is taken to be the sum G = G_mix + G_el of G_el and the free energy of mixing \documentclass{article}\pagestyle{empty}\begin{document}$ G_{{\rm mix}} = RT\left[ {n_1 \ln v_1 + n_2 \ln v_2 + \bar \chi n_1 v_2 } \right] $\end{document}. Stress-strain relations and the chemical potential μ₁ are derived from G as functions of the elasticity parameters C₁, C₂, and m, and of the thermodynamic interaction parameter χ or of \documentclass{article}\pagestyle{empty}\begin{document}$\chi = \bar \chi + n_1 v_2^{ - 1} \partial \bar \chi /\partial n_1 $\end{document}. The dilation of the semi-open system subject to deformation when exposed to diluent at fixed activity is derived as the sum of the dilation at fixed composition and the dilation due to absorption of diluent. Experiments are reported on the dependence of the equilibrium retractive force on elongation for cross-linked polydimethylsiloxanes (PDMS) exposed to benzene or hexamethyldisiloxane vapor at regulated activities. Volume fractions of samples covered the range v₂ = 1.00 to v₂ ≈ 0.30. With the choice of m = ½ the elastic behavior of a given polymer is well represented by one combination of values for C₁ and C₂ at all dilutions by either diluent. The dependence of the Mooney-Rivlin (C₂) term on volume is thus established, at least for PDMS, and the scope of the semi-empirical free energy expression and its consequents is greatly enlarged. Values of χ deduced from the equilibrium swelling of the unstrained networks exposed to benzene at various activities are in excellent agreement with those obtained previously from vapor pressures and osmotic pressures on linear PDMS. The results of Allen, Kirkham, Padget, and Price on the elastic behavior of natural rubber are discussed, with particular reference to the coefficients of dilation with elongation which they determined at fixed composition. The present results lend strong support to the principle of additivity of the free energies attributable to the network and to the bulk liquid system, respectively. This principle is fundamental to the analysis of rubber elasticity.     

Utilization of waste tire rubber in hybrid plywood composite panel

The aim of this work was to use waste tire rubber (WTR) in the middle layer of hybrid plywood materials. The effects of four variable parameters, namely, WTR contents (430 and 720 g), resin contents (120 and 160 g/m²), hot pressing (single‐stage and two‐stage), and arrangements of veneer layers on the mechanical, physical, and acoustical properties, were studied. Beech (Fagus orientalis) and alder (Alnus glutinosa) veneers having 1.8‐mm thickness were used in the production of hybrid plywood panels. Rubber layers of 3‐ and 5‐mm thickness were used in the middle layer of plywood samples. To produce plywood panels, single‐stage and two‐stage hot‐pressing processes were used. Bonding of wood layers was performed using 120 and 160 g/m² urea‐formaldehyde resins, and to form the rubber layers and bond them to wood layers, methylene diisocyanate resin (150 g/m²) was used. Overall trend showed that with the increase in rubber content, the physical properties (water absorption, thickness swelling, and sound absorption) of the manufactured panels were improved, while the mechanical properties (modulus of rapture, modulus of elasticity, and impact strength) of the panels were reduced. Both physical and mechanical performances of plywood panels were improved with increase in resin content. An increase in the WTR content in plywood improved the composite's acoustical property. The production process of the wood/rubber plywood did not significantly affect their properties. The order of improvement in the physical properties of the panels is rubber content > resin content > arrangement of layers > pressing process. Copyright © 2015 John Wiley & Sons, Ltd.     

Low-Frequency Sub-Terahertz Absorption in HgII−XCN−FeII (X=S,Se) Coordination Polymers

Self-assembly Fe^II complexes of phenazine (Phen), quinoxaline (Qxn), and 4,4′-trimethylenedipyridine (Tmp) with tetrahedral building blocks of [Hg^II(XCN)₄]²⁻ (X=S or Se) formed six new high-dimensional frameworks with the general formula of [Fe(L)_m][Hg(XCN)₄]⋅solvents (L=Phen, m/X=2/S, 1 ; L=Qxn, m/X=2/S, 2 ; L=Qxn, m/X=1/S, 3 ; L=Qxn, m/X=1/Se, 3-Se ; L=Tmp, m/X=1/S, 4 ; and L=Tmp, m/X=1/Se, 4-Se ). 1 , 3 , and 3-Se show an intense sub-terahertz (sub-THz) absorbance of around 0.60 THz due to vibrations of the solvent molecules coordinated to the Fe^II ions and crystallization organic molecules. In addition, crystals of 1 , 4 , and 4-Se display low-frequency Raman scattering with exceptionally low values of 0.44, 0.51, and 0.53 THz, respectively. These results indicate that heavy metal Fe^II−Hg^II systems are promising platforms to construct sub-THz absorbers.     

A Single Drop Fabrication of the Cholesterol Biosensor Based on Synthesized NiFe2O4NPs Dispersed on PDDA‐CNTs

A cholesterol biosensor based on cholesterol oxidase‐poly(diallyldimethylammonium chloride)‐carbon nanotubes‐nickel ferrite nanoparticles (ChOx‐PDDA‐CNTs‐NiFe₂O₄NPs) solution is easily fabricated by using a single dropping step on a glassy carbon electrode (GCE) surface. This technique is an alternative way to reduce complexity, cost and time to produce the biosensor. The uniformly dispersed materials on the electrode surface enhance the catalytic reaction of cholesterol oxidase and electron transfer from the oxidation of hydrogen peroxide in the system. The nickel ferrite nanoparticles were synthesized by co‐precipitation and calcination at various temperatures. These nanoparticles were then characterized using field emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV) and X‐ray diffraction (XRD). The synthesized material calcined at 700 °C was well defined and presented the octahedral metal stretching with cubic NiFe₂O₄NPs phase. In cyclic voltammetric study, the ChOx‐PDDA‐CNTs‐NiFe₂O₄NPs/GCE showed 0.43 s⁻¹ charge transfer rate constant (K _s), 7.79×10⁻⁶ cm² s⁻¹ diffusion coefficient value (D ), 0.13 mm² electroactive surface area (A _e) and 3.58×10⁻⁸ mol cm⁻² surface concentration ( ). This modified electrode exhibits stability in term of percent relative standard deviation (%RSD=0.62 %, n=10), reproducibility (%RSD=0.81, n=10), high sensitivity (25.76 nA per mg L⁻¹ cm⁻²), linearity from 1 to 5,000 mg L⁻¹ (R²=0.998) with a low detection limit (0.50 mg L⁻¹). Its Michaelis‐Menten constant (K _m) was 0.14 mM with 0.92 μA maximum current (I _max) and demonstrated good selectivity without the effects of electroactive species such as ascorbic acid, glucose and uric acid. The cholesterol biosensor was successfully applied to determine cholesterol levels in human blood samples, showing promise due to its simplicity and availability.     

Purification, characterization, and structural investigation of a new moderately thermophilic and partially calcium-independent extracellular α-amylase from Bacillus sp. TM1

A new α-amylase was extracted from a recently found strain of Bacillus sp. and purified by ion-exchange chromatography. Sodium dodecyl sulfate polyacrylamide gel electrophoresis showed a single band for the purified enzyme with an apparent molecular weight of 59 kDa. The optimum temperature and pH range of the enzyme were 40–60°C and 4.5–7.5, respectively, and its activation energy was 1.974 kcal/mol. The K _m value for the enzyme activity on solubie starch was 4 mg/mL, and the T _m values obtained from the circular dichroism (CD) results of thermal unfolding were 78.7 and 80.2°C in the absence and presence of the calcium, respectively. The enzyme was almost completely inhibited by the addition of Fe³⁺, Mn²⁺, and Zn²⁺ and was activated by EDTA, Cr³⁺, and Al³⁺. Moreover, it was partially inhibited by Ca²⁺, Ba²⁺, Ni²⁺, and Co²⁺. Proteolytic digestion of the enzyme using trypsin combined with results from T _m using CD and irreversible thermoinactivation suggests that this enzyme can be considered a moderate thermophile with both mild flexibility and rigidity.     

Electron donor–acceptor properties of thin polymer films on silicon. II. Tetrafluoroethylene polymerized by RF glow discharge techniques

Metal–insulator–semiconductor (MIS) techniques were used to show that 86–210 nm thick plasma-polymerized tetrafluoroethylene films on silicon stored only negative charge (electron acceptors). This property persisted at a reduced level when a 7 nm thick inner layer of hydrolyzed γ-aminopropyltriethoxysilane was combined with an outer layer of plasma-polymerized tetrafluoroethylene. The dispersion force contribution to the surface energy, γ^d_s, for the fluorocarbon films was found to be 6 mJ/m² (erg/cm²) which is comparable with the lowest values found in the literature. X-ray photoelectron spectroscopy (XPS) revealed a substantial content of ? CF₃ groups in the fluorocarbon films. This finding coupled with the reported effects of noncrystallinity, crosslinking, and branching on the surface energies of fluorocarbon systems were used to explain the low surface energy and electrophilicity of the plasma-deposited poly(tetrafluoroethylene)s.     

Surface segregation measurements of In and S impurities from a dilute Cu(In,S) ternary alloy

The surface segregation of In and S from a dilute Cu(In,S) ternary alloy were measured using Auger electron spectroscopy coupled with a linear programmed heater. The alloy was linearly heated and cooled at constant rates. Segregation data of a linear heat run showed surface segregation of In that reached a maximum surface coverage of 25% followed by S, which reached a coverage of 30%. It was found that after In had reached a maximum surface coverage, it started to desegregate as soon as the S enriched the surface until In was completely replaced by S. The segregation parameters, namely, the pre‐exponential factor (D₀), activation energy (Q), segregation energy (ΔG?) and interaction energy (Ω) were extracted from the measured segregation data for both In and S segregation in Cu by simulating the measured segregation data with a theoretical segregation model (modified Darken model). The segregation parameters obtained for In segregation in Cu are D₀ = 1.8 ± 0.5 × 10^?5 m² s^?1, Q = 184.3 ± 1.0 kJ.mol^?1, ΔG? = ?61.4 ± 1.4 kJ.mol^‐1, Ω_Cu?In = 3.0 ± 0.4 kJ.mol^?1; for S segregation in Cu the parameters are D₀ = 8.9 ± 0.5 × 10^?3 m² s^?1, Q = 212.8 ± 3.0 kJ.mol^?1, ΔG? = ?120.0 ± 3.5 kJ.mol^?1, Ω_Cu?S = 23.0 ± 2.0 kJ mol^?1 and the In and S interaction parameter is Ω_In?S = ?4.0 ± 0.5 kJ.mol^?1. The initial parameters used for the Darken calculations were extracted from fits performed with the Fick's and Guttmann model. Copyright © 2013 John Wiley & Sons, Ltd.     

Dielectric isotherms of water sorption on pyrogenic silica and titania surfaces

Water sorption on the surfaces of pyrogenic SiO₂ (S=290 m²/g) and TiO₂ (S=50 m²/g) has been studied. The dielectric isotherm curves show that on the surface of TiO₂ (anatase) a continuous water layer is formed at =1.9 but none is formed on the silica surface. Sorption occurs only as definite clusters.     

Boron-doped TiO2: Characteristics and photoactivity under visible light

Boron-doped TiO₂ was prepared by the sol-gel method and by grinding TiO₂ powder with a boron compounds (boric acid and boric acid triethyl ester followed by calcinations at temperature range 200 to 600°C. Three types of pristine TiO₂: ST-01 (Ishihara Sangyo Ltd., Japan; 300 m²/g), P25 (Degussa, Germany, 50 m²/g), A11 (Police S.A., Poland 12 m²/g) were used in grinding procedure. The photocatalytic activity of obtained powders in visible light was estimated by measuring the decomposition rate of phenol (0.21 mmol/dm³) in an aqueous solution. The photocatalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron emission spectroscopy (XPS), UV-VIS absorption and BET surface area measurements. The best photoactivity under visible light was observed for B-TiO₂ modified with 2 wt% of boron prepared by grinding ST-01 with dopant followed by calcinations at 400°C. This photocatalyst contains 16.9 at.% of carbon and 6.6 at.% of boron in surface layer and its surface area is 192 m²/g.     

Synthesis of polysiloxane xerogels with fluorine-containing groups in the surface layer and their sorption properties

Hydrolysis and polycondensation reactions of tetraethoxysilane (TEOS) with 3,3,3-trifluoropropyl-trimethoxysilane (TFMS) or 1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFES) were used to synthesize xerogels functionalized with fluorine-containing groups. According to transmission electron microscopy, the skeletons of synthesized polysiloxane xerogels have globular structures and consist of agglomerates of particles with fluorinated groups on their surfaces. FTIR spectroscopy showed that primary xerogel particles possess spatial polysiloxane networks, with fluorinated groups along with silanol groups and water in the surface layer. According to thermal analyses, the water content was 3–8 wt.%, and it decreased with increasing length of the fluorinated chain. Thermal destruction of the surface layer starts above 300 °C. The sorbents that were obtained were predominantly mesoporous materials with well-developed porous structures (S_BET = 400–960 m² g⁻¹, V_s = 0.66–0.93 cm³ g⁻¹). The influence of the TEOS/functional silane ratio and the natures of the functional groups on the structural and adsorptive properties were shown. The samples synthesized are organophilic. The affinity for n-hexane increases with increasing length of the fluorine-containing chain (PFES) and the content of fluorinated groups in the surface layer. The hybrid organic–inorganic materials that were obtained can be used for adsorption of hydrocarbons, including oil, from water.