Thermo-XRD-analysis of Co-, Ni- and Cu-montmorillonite treated with anionic alizarinate

Co- and Ni-montmorillonites adsorb in aqueous suspensions up to 13 mmol alizarinate per 100 g clay, onto the broken-bonds whereas Cu-clay adsorbs up to 25 mmol dye per 100 g clay into the interlayer space. Unloaded Co-, Ni- and Cu-clays and samples loaded with increasing amounts of alizarinate, were gradually heated in air to 360°C and analyzed by X-ray diffraction. All diffractograms were curve-fitted. Fitted diffractograms of non-heated samples, showed two peak components labeled C and D, at<span lang=EN-US style='font-size:10.0pt;font-family:Symbol;mso-bidi-font-family: Symbol;mso-ansi-language:EN-US'>?1.22 and<span lang=EN-US style='font-size:10.0pt;font-family:Symbol;mso-bidi-font-family: Symbol;mso-ansi-language:EN-US'>?1.32 nm, characterizing tactoids with mono- and non-complete bilayers of water, respectively. After heating at 120°C component D decreased or disappeared and two new components A and B appeared at<span lang=EN-US style='font-size:10.0pt;font-family:Symbol;mso-bidi-font-family:Symbol; mso-ansi-language:EN-US'>?0.99 and<span lang=EN-US style='font-size:10.0pt;font-family:Symbol;mso-bidi-font-family: Symbol;mso-ansi-language:EN-US'>?1.08 nm, representing collapsed tactoids and tactoids with interlamellar oxy-cations, respectively. At 250°C, C and D decreased or disappeared but A and B appeared in all fitted diffractograms. Co- and Ni-clay after heating at 360°C did not show C and D. Components A and B proved that these clays collapsed indicating that initially there was no alizarinate in the interlayers. At 360°C, C and D persisted in the fitted-diffractograms of Cu-clay, representing tactoids with interlamellar charcoal formed from the partial oxidation of adsorbed dye initially located in the interlayers.     

Thermo-XRD analysis of the adsorption of Congo-red by montmorillonite saturated with different cations

The adsorption of the organic anionic dye Congo red (CR) by montmorillonite saturated with Na⁺, Cs⁺, Mg²⁺, Cu²⁺, Al³⁺ and Fe³⁺ was investigated by XRD of unwashed and washed samples after equilibration at 40% humidity and after heating at 360 and at 420°C. The clay was treated with different amounts of CR, most of which was adsorbed. Clay samples, untreated with CR, after heating showed collapsed interlayer space. Unwashed and washed samples, which contained CR, before heating were characterized by three peaks or shoulders, labeled A (at 0.96-0.99 nm, collapsed interlayers), B (at 1.24-1.36 nm) and C (at 2.10-2.50 nm). Peak B represents adsorbed monolayers of water and dye anions inside the interlayer spaces. Peak C represents interlayer spaces with different orientations of the adsorbed water and organic matter. Diffractograms of samples with small amounts of dye were similar to those without dye showing peak B whereas diffractograms of most samples with high amounts of dye showed an additional peak C. Heated unwashed and washed samples were also characterized by three peaks or shoulders, labeled A' (at 0.96 nm), B' (at 1.10-1.33 nm) and C' (at 1.61-2.10 nm), representing collapsed interlayers, and interlayers with charcoal composed of monolayers or multilayers of carbon. When the samples were heated from 360 to 420°C some of the charcoal monolayers underwent rearrangement to multilayers. In the case of Cu the charcoal decomposed and oxidized. The present results show that most of the adsorbed dye was located inside the interlayer space.This revised version was published online in November 2005 with corrections to the Cover Date.     

Mechanochemical Adsorption of Phenol by Tot Swelling Clay Minerals

The mechanochemical adsorption of phenol by laponite, saponite, montmorillonite, beidellite and vermiculite was studied by IR and X-ray spectroscopy. Mixtures containing phenol and clay in the ratio of 6:10 were manually ground by a mortar and pestle for 1,3,5 and 10 min and the ground mixtures were investigated. Depending on the basicity of the clay mineral and the time of grinding, two different associations between interlay er cations, water and phenol were identified. In these associations phenol can act either as a proton acceptor or donor (Configurations I and II, respectively). The phenol is more acidic than water and in most cases phenol acts as a proton donor. With montmorillonite and beidellite phenol acts as a proton acceptor. In this association the aromatic ring forms π bonds with atoms of the oxygen planes of the tetrahedral sheets which donate electrons to the anti-bonding π orbitals of the phenol.     

The effect of mechanochemical treatments of sepiolite with CsCl on the calcination products

Calcination of sepiolite and of two sepiolite/CsCl mixtures, unground and air-ground was investigated by thermo-XRD-analysis. At 200 °C sepiolite, neat, mixed or air-ground with CsCl lost interparticle and zeolitic water. The framework of sepiolite persisted during the dehydration but became defected, mainly in the air-ground mixture, less in the unground mixture and little in the neat clay. At 500 °C, with the loss of bound water, the neat clay was folded and transformed into sepiolite anhydride. In sepiolite/CsCl mixtures the dehydrated variety persisted but the degree of crystal-imperfection increased in the air-ground mixture more than in the unground mixture. At 700 °C the neat clay remained crystallized, but the CsCl mixtures became amorphous. Some crystalline dehydrated sepiolite or sepiolite anhydride persisted in the unground and air-ground CsCl mixtures, respectively. At 850 °C, the neat clay crystallized into protoenstatite with some enstatite and clinoenstatite. The amorphous fraction of sepiolite in the unground sepiolite/CsCl mixtures crystallized into pollucite and forsterite and the crystalline fraction was transformed into enstatite, protoenstatite, and clinoenstatite. In the air-ground mixture, the amorphous phase was transformed into pollucite with some forsterite and the crystalline fraction into enstatite.     

Secondary adsorption of nitrobenzene and m-nitrophenol by hexadecyltrimethylammonium-montmorillonite thermo-XRD-analysis

In the present research we studied the effect of the solvent used, whether it was polar water or a non-polar organic solvent (n-hexane or n-hexadecane), on the basal-spacing and bulk structure of the sorbate-sorbent complexes obtained by the secondary adsorption of nitrobenzene and m-nitrophenol by two types of organo-montmorillonites. X-ray measured basal spacings before and after thermal treatments up to 360°C. The organo-clays were synthesized, with 41 and 90% replacement of the exchangeable Na⁺ by hexadecyltrimethylammonium (HDTMA), with mono-and bilayers of HDTMA cations in the interlayer space, labelled OC-41 and OC-90, respectively. After heating at 360°C both organo-clays showed spacing at 1.25–1.28 nm, due to the presence of interlayer-charcoal, indicating that in the preheated organo-clays the HDTMA was located in the interlayer. The thermo-XRD-analysis of Na-clay complexes showed that from organic solvents both sorbates were adsorbed on the external surface but from water they were intercalated. m-Nitrophenol complexes of both organo-clays obtained in aqueous suspensions contain water molecules. Spacings of nitrobenzene complexes of OC-41 and OC-90 and those of nitrophenol complexes of OC-41 showed that the adsorbed molecules were imbedded in cavities in the HDTMA layers. Adsorption of m-nitrophenol by OC-90 from water and n-hexane resulted in an increase of basal spacing (0.21 and 0.29 nm, respectively) suggesting the existence of a layer of nitrophenol molecules sandwiched between two parallel HDTMA layers.     

Thermal Intercalation of Alkali Halides into Kaolinite

Solid state intercalation of alkali halides into kaolinite takes place by heating pressed disks of dimethylsulfoxide (DMSO)-kaolinite complex ground in different alkali halides. This reaction involves diffusion of the DMSO outside the interlayer space and the alkali halide into the interlayer space. IR and Raman spectroscopy reveal two types of intercalation complexes: (i) almost non-hydrous, obtained during thermal treatment of the DMSO complex; and (ii) hydrated, obtained by regrinding the disk in air. The strength of the hydrogen bonds between intercalated water or halide anions and the inner surface hydroxyls decreases in the order Cl⁻>Br⁻>I⁻. Chlorides penetrate the ditrigonal holes and form hydrogen bonds with the inner OH groups. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermo-infrared-spectroscopy analysis of dimethylsulfoxide-kaolinite intercalation complexes

Dimethylsulfoxide (DMSO) kaolinite complexes of low-and high-defect kaolinites were studied by thermo-IR-spectroscopy analysis. Samples were gradually heated up to 170°C, three hours at each temperature. After cooling to room temperature, they were pressed into KBr disks and their spectra were recorded. From the spectra two types of complexes were identified. In the spectrum of type I complex two bands were attributed to asymmetric and symmetric H-O-H stretching vibrations of intercalated water, bridging between DMSO and the clay-O-planes. As a result of H-bonds between intercalated water molecules and the O-planes, Si-O vibrations of the clay framework were perturbed, in the low-defect kaolinite more than in the high-defect. Type II complex was obtained by the thermal escape of the intercalated water. Consequently, the H-O-H bands were absent from the spectrum of type II complex and the Si-O bands were not perturbed. Type I complex was present up to 120°C whereas type II between 130 and 150°C. The presence of intercalated DMSO was proved from the appearance of methyl bands. These bands decreased with temperature due to the thermal evolution of DMSO but disappeared only in spectra of samples heated at 160°C. Intercalated DMSO was H-bonded to the inner-surface hydroxyls and vibrations associated with this group were perturbed. Due to the thermal evolution of DMSO the intensities of the perturbed bands decreased with the temperature. They disappeared at 160°C together with the methyl bands.     

Thermal analysis of tetraethylammonium and benzyltrimethylammonium montmorillonites

Na-montmorillonite was loaded with tetraethylammonium cations (TEA) or with benzyltrimethylammonium cations (BTMA) by replacing 77 and 81% of the exchangeable Na with TEA or BTMA, labeled TEA-MONT and BTMA-MONT, respectively. TEA- and BTMA-MONT were heated in air up to 900?°C. Thermally treated organoclays are used in our laboratory as sorbents of organic compounds from water. The two organoclays were studied by TG and DTG in air and under nitrogen. Carbon content in each of the heated sample was determined. They were diffracted by X-ray, and fitting calculations of d(001) peaks were performed on each diffractogram. TG and thermo-C analysis showed that at 150 and 250?°C both organoclays lost water but not intercalated ammonium cations. DTG peak of the first oxidation step of the organic cation with the formation of low-temperature stable charcoal (LTSC) appeared at 364 and 313?°C for TEA- and BTMA-MONT, respectively. The charcoal was gradually oxidized by air with further rise in temperature. DTG peak of the second oxidation step with the formation of high-temperature stable charcoal (HTSC) appeared at 397 and 380?°C for TEA- and BTMA-MONT, respectively. DTG peak of the final oxidation step of the organic matter appeared at 694 and 705?°C for TEA- and BTMA-MONT, respectively, after the dehydroxylation of the clay. Thermo-XRD analysis detected TEA-MONT tactoids with spacing 1.40 and 1.46?nm up to 300?°C. At 300 and 360?°C, LTSC-MONT tactoids were detected with spacing of 1.29?nm. At higher temperatures, HTSC-MONT-?? and -?? tactoids were detected with spacings of 1.28 and 1.13?nm, respectively. BTMA-MONT tactoids with spacings 1.46 and 1.53?nm were detected up to 250?°C. At 300 and 360?°C, LTSC-MONT tactoids were detected with a spacing of 1.38?nm. At higher temperatures, HTSC-MONT-?? and -?? tactoids were detected with spacings of 1.28 and 1.17?nm, respectively. At 650?°C, both clays were collapsed. HTSC-??-MONT differs from HTSC-??-MONT by having carbon atoms keying into the ditrigonal holes of the clay-O-planes. At 900?°C, the clay fraction is amorphous. Trace amounts of spinel and cristobalite are obtained from thermal recrystallization of amorphous meta-MONT.     

Synthesis and thermo-XRD-analysis of the organo-clay color pigment

An intense blue organo-clay color pigment was obtained by adding naphthyl-1-ammonium chloride to a Na-montmorillonite aqueous suspension followed by treatment with sodium nitrite. This treatment resulted in the synthesis of the azo dye 4-(1-naphthylazo)-1-naphthylamine adsorbed onto the clay. The pigment was subjected to thermo-XRD-analysis and the diffractograms were curve-fitted. Heating naphthylammonium-montmorillonite at 360°C resulted in the evolution of the amine at temperatures lower than those required for the formation of charcoal and consequently the clay collapsed. On the other hand, heating the pigment at 360°C resulted in the conversion of the adsorbed azo dye into charcoal. The clay did not collapse, thus proving that the azo dye was located inside the interlayer space. Before the thermal treatment a short basal spacing in the pigment compared with that in the ammonium clay (1.28 and 1.35 nm, respectively) indicated stronger surface π interactions between the clayey O-plane and the azo dye than between this plane and naphthylammonium cation. The amount of dye after one aging-day of the synthesis-suspension increased with [NaNO₂]/[C₁₀H₇NH₃] ratio but did not increase with naphthylammonium when the [NaNO₂]/[C₁₀H₇NH₃] ratio remained 1. After 7 and 56 aging days it decreased, indicating that some of the dye decomposed during aging.