Preparation of porous clay minerals with organic-inorganic hybrid pillars using solvent-extraction route

A microporous clay mineral with organic-inorganic hybrid pillars was synthesized using a hydrochloric acid (HCl)/ethanol extraction method after intercalation of tetraethoxysilane (TEOS) or TEOS/methyltriethoxysilane (MTS) into the cetyltrimetylammonium ion (CTA)-exchanged vermiculite. The products retained their layered structure, due to the formation of stable pillars by the polymerization of hydrolyzed TEOS and MTS during the HCl/ethanol treatment. The BET surface areas, which increased to above 500 m2g(-1) with an increase in the HCl concentration up to 0.4 moldm(-3), are nearly equal to that of the calcined product obtained by the conventional method. However, the pore sizes of HCl/ethanol-treated materials were narrower than those of the calcined product, owing to the formation of the polysiloxane networks in the gallery. A water adsorption study showed that the product treated with a TEOS/MTS mixture had a hydrophobic surface as a result of the successful incorporation of methyl groups at the surface of the pillars. This novel method is advantageous for the synthesis of organophilic pillared clays with different kinds of organic materials in the interlayers.     

Polarographic reduction behaviour of clay minerals

Suspensions of the clay minerals bentonite, kaolinite illite and chlorite have been examined polarographically and reduction waves found. The differences in their behaviour, with and without the addition of surface active reagents, are reported.     

Thermal investigation of acid-activated clay minerals

Samples of the clay mineral from the Çanakkale reserve in Turkey were activated with sulphuric acid under three different sets of conditions. DTA and TG curves of both natural and activated samples were then obtained and compared with one other.     

Ultrathin films of semiconducting polymers on water

Ultrathin films of polythiophene derivatives spread on water were studied by means of synchrotron radiation, using grazing incidence diffraction and (specular) reflectometry to obtain the molecular orientation in the films. The semicrystalline films were anisotropic, showing a strong tendency of orienting the crystalline alpha-axis perpendicularly to the water subphase. The crystalline domains extend essentially through the entire sample thickness, found to be 10-15 nm. A large expansion of the unit cell alpha-parameter was seen upon doping the films in situ. The reflectometry data were well-fitted by a model with a sinusoidal density variation being damped toward the water subphase. This indicates that the crystalline order was most developed at the polymer-air interface and deteriorated down toward the water, possibly due to the hydrophobicity of the alkyl side chains.     

Release of cationic drugs from loaded clay minerals

The adsorption of promethazine chloride [10-(2-dimethylammonium propyl) fenothiazine chloride] and buformin hydrochloride (1-butylbiguanidine chloride) on montmorillonite was studied in previous work. The present article focuses on the desorption of these molecules from their organocomplexes in a medium of artificial intestinal juice (pH 7.0 ± 0.1) at the temperature of the human body (37 ± 0.5 °C). The desorption was investigated by kinetic studies, basal spacing measurements and Fourier transform IR studies. Important quantitative differences were observed: buformin, which adsorbed in a monolayer coverage, exhibited a very high desorption rate, whereas promethazine formed a pseudotrilayer arrangement and showed a lower dissolution rate. Received: 20 January 2001 Accepted: 8 March 2001     

Radiolysis of carboxylic acids adsorbed in clay minerals

This research is aimed at studing the effect of ionizing radiation in an heterogeneous system formed by a carboxylic acid adsorbed in a clay mineral. The study is focussed to discriminate if the presence of a solid surface alters the formation and distribution of radiolytic products in relation to the radiolysis of the carboxylic acid without the surface (clay). The results showed that the radiolysis of the system clay-acid goes along a defined path rather than showing various pathways of decomposition as in the case of simple aqueous solutions. The main pathway was the decarboxylation of the target compound rather than condensation/dimerization reactions.     

Ultrathin layer chromatography on nanostructured thin films

Ultrathin layer chromatography (UTLC) is a relatively new variant of thin layer chromatography, with a 10mum thick monolithic silica sorbent layer that gives faster separations with lower limits of detection and reduced analyte and solvent volumes. We have produced UTLC plates with controllable nanostructure and thickness, and show that the layer separation characteristics depends on the film nanostructure. We also show that layers made with in-plane anisotropic nanostructures will exhibit a decoupling effect, where the analyte spots do not develop in the same direction as the solvent front movement. The added layer morphology and material selection adds a degree of freedom to UTLC, and may have applications in multi-dimensional TLC.     

Luminescence properties of rhodamine 6G intercalated in surfactant/clay hybrid thin solid films

To develop the solid-state laser oscillator based on laser dye compounds, the incorporation of rhodamine 6G (R6G, a laser dye) in cetyltrimethylammonium (CTA+) cationic surfactant/montmorillonite clay hybrid (HpC) thin solid films was investigated. The R6G/HpC samples were prepared by immersing the HpC films into a R6G aqueous solution with various concentration. X-ray diffraction patterns of the films of HpC, measured before and after the intercalation of R6G, proved the coexistence of both the dye and surfactant in clay interlayer spaces. All prepared thin films exhibited luminescence. It indicates that CTA+ molecules play a role as a partial suppressor of the aggregation of R6G molecules which prevents fluorescence. Moreover, the luminescence property of the present thin films was observed to be dependent on the co-intercalated degree of R6G molecules, indicating that the R6G intercalating in HpC interlayer space molecules exist as two or more luminescence species in the clay interlayer space.     

Structural characteristics and moisture sorption behavior of nylon‐6/clay hybrid films

The structure of nylon‐6 hybrids with synthetic or natural clays was investigated for melt‐pressed films with Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry in comparison with the nylon‐6 homopolymer. In contrast to the development of familiar α‐form crystals in plain nylon‐6 film, the hybrid films produced γ‐form crystals when nylon‐6 was conjugated with synthetic mica, whereas the hybridization with natural montmorillonite gave rise to both α‐ and γ‐crystalline modifications. The degree of crystallinity of the nylon‐6 hybrid with synthetic mica was the highest of the three series. Moisture sorption isotherms obtained for these nylon‐6‐based films were all typically sigmoid‐shaped, although the prevalence of a higher crystallinity in the hybrid samples lowered the degree of moisture regain. The sorption behavior was analyzed well in terms of the parameters of a Brunauer–Emmett–Teller multiplayer adsorption model and a Flory–Huggins treatment. It was also observed that the cluster formation of the water adsorbed into the nylon‐6 matrix tended to be restricted by the hybridization with clay. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 479–487, 2002; DOI 10.1002/polb.10106     

Neodymium sorption by clay minerals and zeoliferous rocks

The sorption of neodymium from its aqueous solutions (concentration range approx. 10–450 mg l^–1) by montmorillonite, kaolinite and a clinoptilolite-containing rock has been investigated, using¹⁴⁷Nd as radioactive tracer and -ray spectrometry. The neodymium uptake by montmorillonite was found to be much higher than of the other two materials in the whole investigated concentration range. However, in the case of montmorillonite and zeoliferous rock, the uptake ability is lower than that allowed by the measured CEC values and can be described by Langmuir-type equations. In the case of kaolinite, the observed higher than CEC-allowed uptake values could be attributed to sorption by mechanisms other than ion-exchange. The corresponding data obey a Freundlich-type sorption equation. Among the three geological materials investigated, montmorillonite exhibits the highest perspectives of application for the treatment and disposal of neodymium and trivalent actinides in nuclear industry.     

Infrared study of influence of temperature on clay minerals

The effect of temperature on the infrared absorption bands of different clay minerals has been investigated with a view to identify the thermal transformation occurring between 30 and 1000°C.     

The titration of clay minerals II. Structure-based model and implications for clay reactivity

The potentiometric titration and CEC data presented in part I are modeled in this paper, part II. Two models are compared: the two pK, three complexation sites plus exchange sites nonelectrostatic model developed by Baeyens and Bradbury and a model based on the MUSIC approach developed by Hiemstra and Van Riemsdijk. Both morphological and structural information is used to develop this new model. Morphological information is taken from the literature, while structural information is taken from the literature and constrained by supporting FTIR experiments. The Baeyens and Bradbury model is found to reproduce the general tendency of the titration curve, whereas the model based on the Hiemstra and Van Riemsdijk MUSIC approach provides a better fit to the experimental data. The former uses only 3 edge reaction sites, whereas the latter uses at least 27 edge reaction sites. Five main reactive sites are sufficient to fit the MUSIC model curve, but the model allows us to derive the properties of 22 other reactive sites. Logically, the greater the number of sites, the better the fit. Nevertheless, fewer adjustable parameters are necessary for the Hiemstra and Van Riemsdijk MUSIC model than for the Baeyens and Bradbury model, thanks to structural and morphological constraints. The precision of the potentiometric titration curve is insufficient to verify that the properties of the 27 sites given by the MUSIC model are effective. Thus, we coupled some properties of clay minerals, such as dissolution, to the modeled acid-base properties of these sites to assess our model. We then questioned the ability of simplified models such as the Baeyens and Bradbury model to predict the interactions between clay minerals and solutions in natural environments. In addition, we derived the cation exchange selectivity coefficients for CaCl+ ionic pairs and H+ from our CEC data and gave an estimate for the CaOH+ selectivity coefficient.     

Sorption and immobilization of cellulase on silicate clay minerals

The interaction of organic molecules with mineral surfaces is a subject of interest in a variety of disciplines. Enzymes are able to be sorbed and immobilized by clay minerals and humic colloids in soil environment. The present study was done to elucidate some aspects of sorption and immobilization of cellulase on soil components by analysis of the sorption, and immobilization of cellulase on Avicel, a soil sample, illite, kaolinite, montmorillonite, and palygorskite. Palygorskite displayed the highest sorption capacity. Sorbents coated with hydroxyaluminum displayed significantly higher capacity than uncoated sorbents. The positive effects of Al(OH)(x) coating on sorption capacities of the different sorbents were not equal. The effect decreased in the order soil > palygorskite > kaolinite > Avicel > montmorillonite > illite. The amount of sorbed cellulase desorbed from external surfaces of soil was quite low (about 16%), especially in coated samples (about 6%). X-ray diffraction analysis of K-montmorillonite and Ca-montmorillonite showed that Al(OH)(x) was intercalated between the montmorillonite layers. Immobilization of cellulase on the sorbents did not result in expansion of their crystal structures. Therefore, it may be concluded that the amount of cellulase immobilized on internal surfaces of the sorbents was negligible.     

Removal of diphenhydramine from water by swelling clay minerals

Frequent detection of pharmaceuticals in surface water and wastewater attracted renewed attention on studying interactions between pharmaceuticals and sludge or biosolids generated from wastewater treatment. Less attention was focused on studying interactions between pharmaceuticals and clay minerals, important soil and sediment components. This research targeted on investigating interactions between diphenhydramine (DPH), an important antihistamine drug, and a montmorillonite, a swelling clay, in aqueous solution. Stoichiometric desorption of exchangeable cations accompanying DPH adsorption confirmed that cation exchange was the most important mechanism of DPH uptake by the swelling clay. When the solution pH was below the pK(a) of DPH, its adsorption on the swelling clay was less affected by pH. Increasing solution pH above the pK(a) value resulted in a decrease in DPH adsorption by the clay. An increase in d(001) spacing at a high DPH loading level suggested interlayer adsorption, thus, intercalation of DPH. The results from this study showed that swelling clays are a good environmental sink for weak acidic drugs like DPH. In addition, the large cation exchange capacity and surface area make the clay a good candidate to remove cationic pharmaceuticals from the effluent of wastewater treatment facilities.     

Ultrathin functional films of titanium(IV) oxide

Chemistry and physics of thin semiconducting layers of various types are subjects of intense research. Especially when nanotechnology methods such as self-assembly are involved, amazing structural and/or functional properties may appear. Also modern physical methods using variously organized plasma arrangements are able to produce uniform structures with distinctive functionality. In this review, based virtually on our own work, discussions on the preparation, structure, morphology, and function of titanium(IV) oxide nanoscopic thin films are presented. It was shown that structurally and functionally similar titanium(IV) oxide films can be prepared via completely different preparation techniques. Function tests were arranged as “primary”, covering the assessment of the light induced charge separation efficiency, and “secondary”, based on photocatalytic surface oxidations.     

Ultrathin transparent conductive films of polymer-modified multiwalled carbon nanotubes

Deposition of multiwalled carbon nanotubes modified by poly(2-vinylpyridine) (CNT-g-P2VP) from aqueous dispersions at low pH is an effective method to prepare homogeneous ultrathin films with a tunable CNTs density. A percolation threshold of 0.25 mug/cm2 and a critical exponent alpha = 1.24 have been found from dc conductivity measurements. The sheet resistance value agrees with the percolation theory for 2D films. According to AFM and electrical measurements, even when only 5% of the surface is covered by CNT-g-P2VPs, the sheet resistance is of the order of 1 MOmega/sq, which indicates that conductivity is imparted by a network of an ultralow density. When the film transmittance decreases down to approximately 70% at 550 nm, the occupied surface area is approximately 15% and sheet resistance falls down to approximately 90 kOmega/sq. These data show that undesired in-plane clustering does not occur upon the dispersion casting of the films and that high-quality networks of CNT-g-P2VPs are built up. The electrosteric stabilization of the CNT-g-P2VP dispersions in water at low pH is at the origin of this desired behavior. Although the multiwalled CNT films prepared in this work are less conductive and less transparent than the SWNTs films, they could find applications, e.g., in touch screens, reflective displays, EMI shielding, and static charge dissipation.     

Structure and mechanical properties in drawn poly(l‐lactide)/clay hybrid films

Films composed of poly(l ‐lactide) (PLLA)/organophilic montmorillonite hybrids (PLACHs) have been prepared via a melt‐compounding process, which is followed by uniaxial drawing at 90°C in air. In addition, an enhancement of the mechanical properties of these drawn PLACH films, which is expected to differ depending on the drawn ratios, is also estimated by dynamic viscoelastic measurements. Three different organoclay concentrations in the hybrid of 3, 5, and 9 wt% were investigated. The structural parameters for the PLLA crystallites in the drawn films, such as the c‐axis orientation function (f_PLLA) and crystallite size, were measured by X‐ray diffraction, and their drawn ratio (λ) and clay concentration dependence were examined from a textural viewpoint. Another orientation function (f_clay) of the organoclay particles was obtained by transmission electron microscopy (TEM). The values of f_PLLA and crystallinity for PLLA sharply increased with λ for λ < 3, although f_clay was unchanged during the initial stage of elongation. In the high‐λ region (>5), the organoclay particles in the PLACHs started orienting themselves parallel to the draw direction. Copyright © 2008 John Wiley & Sons, Ltd.     

Polarographic reduction of methylene blue in presence of clay minerals

Clay-Methylene Blue suspensions have been examined polarographically. The degree of binding of the dye on the clay particles has been calculated. The possibility of using the data in estimating the clay content of a sample and identifying the mineral is suggested.