Desorption of benzoic and stearic acid adsorbed upon montmorillonites: a thermogravimetric study

The desorption of benzoic acid and stearic acid from sodium and calcium montmorillonites has been studied using thermogravimetric and differential thermogravimetric analysis. Desorption of benzoic acid from sodium montmorillonites occurs at 140 °C and from calcium montmorillonites at 179 °C. This increase in temperature is attributed to the benzoic acid bonding to the calcium in the interlayer. A lowering of the dehydroxylation temperature of montmorillonites is observed with acid adsorption. Stearic acid desorbs at 218 °C as observed by the DTG curves. The desorption pattern differs between the sodium montmorillonites and the calcium montmorillonites.     

Influence of the intercalated cations on the surface energy of montmorillonites: consequences for the morphology and gas barrier properties of polyethylene/montmorillonites nanocomposites

Organically modified montmorillonites obtained by cation exchange from the same natural layered silicate were studied. The surface properties of the pristine and a series of organically modified clays were determined by inverse gas chromatography and the water adsorption mechanisms were studied by a gravimetric technique coupled with a microcalorimeter. A significant increase of the specific surface area, a decrease of the water adsorption, and a decrease of the dispersive component of the surface energy were observed when the sodium cations of the natural montmorillonite were exchanged for a quaternary ammonium. Slighter differences in surface properties were observed, on the other hand, between the different types of organically modified montmorillonites. Indeed, similar dispersive components of the surface energy were determined on the organoclays. Nevertheless, the specific surface area increased in the range 48-80 m(2)/g with increasing d-spacing values and the presence of specific groups attached to the quaternary ammonium, such as phenyl rings or hydroxyl groups, led to some specific behaviors, i.e., a more pronounced base character and a higher water adsorption at high activity, respectively. Differences in interlayer cation chain organization, denoted as crystallinity, were also observed as a function of the nature of the chains borne by the quaternary ammonium. In a later step, polyethylene-based nanocomposites were prepared with those organically modified montmorillonites. The clay dispersion and the barrier properties of the nanocomposites were discussed as a function of the montmorillonite characteristics and of the matrix/montmorillonite interactions expected from surface energy characterization.     

Atomic force microscopic study of variations in the surface morphology of porous silica upon thermal treatment

A combination of atomic force microscopy and adsorption methods is used to investigate variations caused by thermal treatment at 200?C1100°C in the structure of ShSKG silica gel and its surface morphology. It is shown that silica gel is characterized by two hierarchic levels of structural organization. The structural characteristics of silica gel begin to vary at a temperature above 800°C. The analytical potential of atomic force microscopy is illustrated as applied to studying the initial stages of physicochemical transformations of the surface of the coarse-pore silica carrier.     

Properties of polyamide 6 and thermoplastic polyurethane blends containing modified montmorillonites

In this paper are reported some experimental data related to the influence of preparation regimes and characteristics of exfoliated graphite based sorbents produced by thermal expansion of H₂SO₄-graphite intercalation compounds (H₂SO₄-GICs) on their sorption properties. Investigations involving X-ray diffraction analyses, surface area, bulk density and oil sorption capacity measurements, have been performed. Sorption capacity was discussed as a function of bulk density, total pore volume and surface area. Some empirical correlation between studied characteristics of exfoliated graphite have been found. The differences among the obtained samples, as a consequence of synthesis conditions, were also put in evidence by thermal analysis (TG, DTG and DTA) performed after their exposure to oil sorption.It was found that thermal analysis method could provide information about the exfoliated graphite pore system related to the sorbed oil oxidation rate. The capacity for oil uptake was also discussed in the case of graphite oxide soot.     

Preparation and characterization of UV-cured acrylic nanocomposites based on modified organophilic montmorillonites

UV-cured nanocomposites have been prepared through the photopolymerization of the acrylic resin BEMA (Bisphenol A ethoxylate dimethacrylate) added with organophifilic montmorillonites. Two types of commercially available nanoclays namely Cloisite 30B and Cloisite Na⁺ were further modified with organic compatibilizers (dodecylsuccinic anhydride, octadecylamine, octadecanoic alcohol and octadecanoic acid) in order to increase their basal spacing and improve the dispersion in the acrylic matrix. The modification with the organic compatibilizers determined an increase of the interlayer distance, as revealed by XRD (X-Ray Diffraction) analysis. The different types of the modified nanoclays were then dispersed in BEMA monomer at 5% m/m concentration and UV-cured in order to prepare the nanocomposites. XRD measurements performed on the nanocomposites showed a slight increase of the interlayer distance indicating the formation of intercalated structures. The photopolymerization reaction was monitored through real-time FT-IR (Fourier Transform Infrared Spectroscopy) in order to check any influence of the nanofillers on the cure kinetics. The nanocomposites were investigated by DSC (Differential Scanning Calorimetry) and TG (Thermogravimetric) analyses and compared to the neat UV-cured resin. The presence of the nanofillers did not influence the glass transition temperature (T_g) of the acrylic resin; in addition an increase of the thermal stability in air of the nanocomposites was evidenced through TG analysis.     

Characteristics and surface morphology change of modified PtRh 10 gauze of HCN synthesis

The modification of PtRh10 gauze catalysts by coating their surfaces with a thin film of PtRh/Al₂O₃ is reported. The investigation of the activity, selectivity and morphological change of the surface of the catalyst for standard gauzes and those covered with a thin film, applied in the HCN synthesis is deseribed.

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PtRh 10 PtRh–Al₂O₃. , HCN.

     

Evolution of phase morphology of high impact polypropylene particles upon thermal treatment

Solvent fractionation and differential scanning calorimetry (DSC) results show that high impact polypropylene (hiPP) produced by a multistage polymerization process consists of PP homopolymer, amorphous ethylene-propylene random copolymer (EPR), and semicrystalline ethylene-propylene copolymer. For the original hiPP particles obtained right after polymerization, direct transmission electron microscopy (TEM) observation reveals a fairly homogeneous morphology of the ethylene-propylene copolymer (EP) phase regions inside, while the polyethylene-rich interfacial layer observed between the EP region and the iPP matrix supports that EP copolymers form on the subglobule surface of the original iPP particles. Compared with that in original hiPP particles, the dispersed EP domains in pellets have much smaller average size and relatively uniform size distribution, indicating homogenization of the EP domains in the hiPP by melt-compounding. Upon heat-treatment, phase reorganization occurs in hiPP, and the dispersed EP domains can form a multiple-layered core-shell structure, comprising a polyethylene-rich core, an EPR intermediate layer and an outer shell formed by EP block copolymer, which accounts to some extent for the good toughness-rigidity balance of the material. The results indicate that to establish the optimum phase structure and desired properties for hiPP, both the architecture of original hiPP particles and subsequent melt-processing conditions should be carefully modulated.     

Adsorption of nicotinic acid on the surface of nanosized hydroxyapatite and structurally modified hydroxyapatite

In the present paper, hydroxyapatite and structurally modified hydroxyapatite were investigated to establish the best material for nicotinic acid adsorption. Structurally modified hydroxyapatite wa prepared by adding sodium silicate in the reaction medium. The influence of silica concentration, presence of small amounts of metal ions, temperature and initial concentrations of nicotinic acid solutions on the adsorption capacity, were studied. Results indicated that structurally modified hydroxyapatite doped with copper adsorbed the highest amount of nicotinic acid. For this material the adsorption capacity was 0.232 mg nicotinic acid / g material, at an initial concentration of 10⁻⁴ M nicotinic acid. For all types of materials, best results were obtained at 15°C. The amount of nicotinic acid adsorbed increases with the decrease in temperature and with the increase in the initial concentration of nicotinic acid. Adsorption kinetics data were modeled using pseudo-first and pseudo-second order models while the interference due to diffusion was analyzed with intraparticle diffusion model. The results indicate that pseudo-second order model best describes the adsorption kinetics data, indicating the formation of chemical bonding.     

Effect of thermochemical treatment on the surface morphology and hydrophobicity of heterogeneous ion-exchange membranes

A comparative analysis is performed on the effect thermochemical treatment in aqueous, alkali, and acid media has on the surface morphology and hydrophobicity of swelling heterogeneous ion-exchanged membranes. A correlation between changes in surface morphology and hydrophobicity is established. It is shown that under prolonged (50 h) membrane thermal treatment above room temperature, hydrophobicity is reduced due to substantial enlargement of cavities and cracks resulting from the partial destruction of inert binder (polyethylene) and reinforcing poly-?-caproamide fabric (capron).     

Immobilization of porphyrins on the surface of polypropylene films modified with acrylic acid

Russian Journal of General Chemistry - The process of immobilization of the aminoporphyrins: 5-(p-aminophenyl)-10,15,20-triphenylporphyrin (I), 5,10,15,20-tetra(p-aminophenyl)porphyrin (II),...     

Effects of hypochlorite treatment on the surface morphology and mechanical properties of polyethersulfone ultrafiltration membranes

Polyethersulfone membranes are widely used for ultrafiltration and microfiltration especially in the dairy industry, but they are believed to degrade when exposed to the sodium hypochlorite solution that is used to sanitize the processing equipment. Such membranes were exposed to sodium hypochlorite for up to 25,000 ppm-day at 55 °C, and pH 9 and 12. Mechanical properties as measured by dynamic mechanical analysis and tensile strength did not change greatly, but surface properties measured by FTIR-ATR, field emission scanning electron microscopy and associated energy dispersive X-ray spectroscopy detected significant changes in the surface. Surface pitting was observed and was found to be most severe at pH 9. It was thought that pitting was the likely cause of degradation in performance of the membranes and that pits could act as stress raisers leading to cracking.     

Influence of the physicochemical treatment procedure on the morphology and properties of the polyvinyl chloride film surface

Atomic-force microscopy was applied to examination of the topography of the surface of polyvinyl chloride films treated by corona discharge and nitrogen-oxygen plasma at atmospheric pressure. The structure of the modified surface was examined, as well as the influence of the surface activation method on the possibility of its subsequent chemicophysical functionalization.     

Mass-spectrometric study of thermodesorption from the surface of rutile successively modified with butylamine and acetic acid

Using the method of mass-spectroscopic thermal analysis, it has been shown that when the surface of rutile is modified with n-butylamine and acetic acid, it is possible for the two substances to interact in the surface layer, with the result that the order in which the amine and the acid are adsorbed affects the structure of the resulting adsorbed layers. The chemisorbed layer on the surface of a sample of TiO₂-AA-BA consists of molecules of both modifiers and the product of their surface reaction. Acetic acid adsorbed on TiO₂-BA displaces the coordinatively bound amine molecules from the surfaces, leading to the formation of butylacetamide and the chemisorption of the acid molecules on unoccupied areas of the TiO₂ surface.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 305–310, February, 1991.     

Spectral properties of rhodamine 3B adsorbed on the surface of montmorillonites with variable layer charge

Montmorillonite was thermally treated at several temperatures to reduce the charge density of its layer surface. Absorption and fluorescence (steady-state and time-resolved) spectroscopies are now applied to study the adsorption of rhodamine 3B (R3B) laser dye in reduced charge montmorillonites (RCMs) in aqueous suspensions. The decrease in the charge density increases the intermolecular distance between adsorbed R3B molecules, reducing the tendency of the dye to self-associate. H-type and J-type aggregates of R3B in RCMs are spectroscopically characterized, the fluorescent J-aggregates being more extensively formed by decreasing the charge density. Both the reduction in the dye aggregation and the formation of J-type aggregates enhance the fluorescence efficiency of R3B dye adsorbed in montmorillonite particles. Absorption with linearly polarized light reveals that the H-aggregates are more disposed toward the perpendicular of the clay surface than the monomer and J-aggregates species.     

ESR probe study of acid sites on the silica surface modified by organotin compounds

Bronsted acid sites formed due to the interaction of coordinately unsaturated tin atoms with water on the silica surface modified by organotin compounds were found and studied using an ESR spin probe technique. The half-life period of a probe at room temperature can serve as an additional characteristic of the acidity of the surface.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 144–146, January, 2005.     

Crystallization behavior and morphology of poly(butylene succinate) modified with rosin maleopimaric acid anhydride

The melting behavior, crystallization behavior, and morphology of PBSR, which is Poly(butylene succinate) modified with rosin maleopimaric acid anhydride (RMA), were investigated with differential scanning calorimetry (DSC) and polarized optical microscope (POM). The multiple endotherms were ascribed to the recrystallization during DSC measurement and the equilibrium melting temperature determined by the Peak L, which was associated with the fusion of the crystals grown by normal primary crystallization, was 125.9 °C. After the kinetic parameters for isothermal crystallization of PBSR were determined by Avrami equation, to make a detailed regime transition analysis, the well‐established Lauritzen–Hoffman equation was employed. The results indicated that there were two regimes, regime II and regime III, in the range of higher and lower crystallization temperature, respectively. The regime transition temperature is about 81 °C. At last, the spherulitic morphologies of PBSR after being crystallized isothermally at different temperature were observed with the help of POM. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2694–2704, 2005     

Adsorption and preconcentration of 2,4-dichlorophenoxyacetic acid on a chemically modified silica gel surface

The herbicide 2,4-dichlorophenoxyacetic acid (2,4-D), chemically anchored to a silica gel surface, was used to adsorb and preconcentrate the same herbicide from aqueous solutions at room temperature. From a series of adsorption isotherms adjusted to a modified Langmuir equation, the maximum number of moles adsorbed was calculated as 4.67 x 10(-5) mol g(-1), with the highest retention capacity at pH 5. This modified silica gel was used in a column for preconcentrating trace levels of 2,4-D. The preconcentrated herbicide can be directly eluted with methanol with a recovery efficiency higher than 97%. The concentration factor was 8.33.     

Preparation and characterization of zwitterionic surfactant-modified montmorillonites

A series of zwitterionic surfactant-modified montmorillonites (ZSMMs) were synthesized using montmorillonite and three zwitterionic surfactants with different alkyl chain lengths at different concentrations [0.2-4.0 cation exchange capacity (CEC)]. These ZSMMs were characterized by X-ray diffraction (XRD), thermo-gravimetric analysis and differential thermo-gravimetric (TG/DTG) analyses. The zwitterionic surfactant could be intercalated into the interlayer spaces of montmorillonites and causing interlayer space-swelling. From XRD measurements, the amount of the surfactants loaded and the basal spacing increased with surfactant concentration and alkyl chain length. One endothermic DTG peak occurred at ~390 °C, which was assigned to the decomposition of the zwitterionic surfactant on the organo-montmorillonites from 0.2 to 0.6 CEC. When the surfactant loading was increased, a new endothermic peak appeared at ~340 °C. From the microstructures of these ZSMMs, the mechanism of zwitterionic surfactant adsorption was proposed. At relatively low loadings of the zwitterionic surfactant, most of surfactants enter the spacing by an ion-exchange mechanism and are adsorbed onto the interlayer cation sites. When the concentration of the zwitterionic surfactant exceeds the CEC of montmorillonite, the surfactant molecules then adhere to the surface-adsorbed surfactant. Some surfactants enter the interlayers, whereas the others are attached to the clay surface. When the concentration of surfactant increases further beyond 2.0 CEC, the surfactants may occupy the inter-particle space within the house-of-cards aggregate structure.