Partially exchanged organophilic bentonites

Using a sodium bentonite (VCNa) as substrate differently exchanged organophilic clays were obtained by reaction with hexadecyltrimethylammonium (HDTMA) chloride, at increasing reacting ratios (R) from 20 to 120 meq/100 g of clay (VC20–VC120). The sodium bentonite was previously synthesized from a Verde Claro policationic bentonite (VC) from Bravo, Paraiba State, Brazil. From the thermogravimetric (TG) and derivative thermogravimetric (DTG) analyses of these clays on calcined mass basis and from TG and DTG curves data of VCNa clay, a method was developed to estimate the mass fraction of the exchanged cation present in each organophilic clay (M _org), as a function of R. When all sodium cations of VCNa are exchanged by HDTMA, the obtained organophilic clay presents a maximum value for M _org. From this value and TG and DTG curves data of VC and VCNa clays, the cation exchange capacity of the original VC bentonite can be estimated.     

Alternative Synthetic Routes to Epoxy Polymer – Clay Nanocomposites using Organic or Mixed-Ion Clays Modified by Protonated Di/Triamines (Jeffamines)

The use of homoionic organic clays and mixed-ion organic/inorganic clays modified by di- or triamines (Jeffamines), which are being used as epoxy resin curing agents, in the synthesis of polymer nanocomposites has been studied in this work. Our aim is to enhance polymer crosslinking and interfacial adhesion in the nanocomposite structure by utilizing the functionality of the di/triamines on the surface of clay nanolayers and by reducing the organic modifier via formation of homostructured mixed-ion organic/inorganic clays. The results show that the use of homoionic organic clays exchanged with relatively short chain di- or triamines and mixed-ion organic/inorganic clays partially exchanged (ca. 35%) with long chain diamines resulted in intercalated structures with enhanced thermo-mechanical properties (Young's Modulus, Storage Modulus). On the other hand, homoionic organic clays exchanged with long chain diamines and triamines resulted in exfoliated nanocomposites but with compromised mechanical properties due to the plasticizing effect of the long chain amine modifiers.     

Monitoring and Statistical Analysis of Formation of Organochlorine and Organobromine Compounds in Drinking Water of Different Water Intakes

The main drawback of drinking water chlorination involves the formation of quite hazardous disinfection by-products (DBPs), represented mainly by halogenated species. Based on the authors’ monitoring data since 2002, the prevalence of chlorine over bromine in the composition of volatile DBPs was shown for the drinking water in Ufa (Russia). However, the situation was completely reversed in the case of semi-volatile DBPs. The principal goal of the present study involved rationalization of the results of the long-term monitoring. Gas chromatography–mass spectrometry (GC-MS) was used for the qualitative and quantitative analysis of volatile DBPs. Identification of semi-volatile compounds was carried out with GC-MS, while gas chromatography with an atomic emission detector (GC-AED) was used for their quantification. A significant contribution of oxygen to the composition of semi-volatile compounds proves the decisive role of the dissolved organic matter oxidative destructive processes. Statistical analysis revealed notable linear correlations for trihalomethane and haloacetic acid formation vs. chlorine dose. On the contrary, halogenated semi-volatile products do not demonstrate any correlations with the water quality parameters or chlorine dose. Principal component analysis (PCA) placed them into separate groups. The results allow for proposing that formation of the organohalogenated species involved the fast penetration of bromine into the humic matter molecules and, further, their oxidative destruction by active chlorine.     

Chemoselective anti-Markovnikov hydroamination of α,β-ethylenic compounds with amines using montmorillonite clay

The catalytic activity of montmorillonite clays as a catalyst for the hydroamination of α,β-ethylenic compounds with amines was tested. Aniline and substituted anilines reacted with α,β-ethylenic compounds in the presence of catalytic amount of commercially available clay to afford exclusively anti-Markovnikov adduct in excellent yields. Aniline reacted with ethyl acrylate to yield only anti-Markovnikov adduct N-[2-(ethoxycarbonyl)ethyl]aniline (mono-addition product). No Markovnikov adduct (N-[1-(ethoxycarbonyl)ethyl]aniline and double addition product N,N-bis[2-(ethoxycarbonyl)ethyl]aniline were formed under selected reaction conditions. For a better exploitation of the catalytic activity in terms of increased activity and improved selectivity for the mono-addition product, the reaction parameters were optimized in terms of temperature, solvent, reactant mole ratio. Under optimized reaction conditions, montmorillonite clay K-10 showed a superior catalytic performance in the hydroamination of ethyl acrylate with aniline with a conversion of aniline to mono-addition product (almost 100% chemoselectivity) with a high rate constant 0.3414 min⁻¹ compared to the reported protocols. The dependence of conversion of aniline over different types of montmorillonite clays (K-10, K-20, K-30, Al-Pillared clay and untreated clay) has also been discussed. The activities of clay for the hydroamination of different aromatic and aliphatic amines have also been investigated. Under harsh reaction conditions (increased temperature and long reaction time) small amounts of di-addition products were observed. The kinetics data has been interpreted using the initial rate approach model.     

Use of a polyhedral oligomeric silsesquioxane (POSS)-imidazolium cation as an organic modifier for montmorillonite

Recent studies on organically modified clays (OMCs) have reported enhanced thermal stabilities when using imidazolium-based surfactants over the typical ammonium-based surfactants. Other studies have shown that polyhedral oligomeric silsesquioxanes (POSS) also improve the thermal properties of composites containing these macromers. In an attempt to utilize the beneficial properties of both imidazolium surfactants and POSS macromers, a dual nanocomposite approach to prepare OMCs was used. In this study, the preparation of a new POSS-imidazolium surfactant and its use as an organic modifier for montmorillonite are reported. The purity, solubility, and thermal characteristics of the POSS-imidazolium chloride were evaluated. In addition, several OMCs were prepared by exchanging the Na+ with POSS imidazolium cations equivalent to 100%, 95%, 40%, 20%, and 5% of the cation exchange capacity of the clay. The subsequent OMCs were characterized using thermal analysis techniques (DSC, SDT, and TGA) as well as 29Si NMR to determine the POSS content in the clay interlayer both before and after thermal oxidation degradation. Results indicate the following: (1) the solvent choice changes the efficiency of the ion-exchange reaction of the clay; (2) self-assembled crystalline POSS domains are present in the clay interlayer; (3) the d-spacing of the exchanged clay is large (3.6 nm), accommodating a bilayer structure of the POSS-imidazolium; and (4) the prepared POSS-imidazolium exchanged clays exhibit higher thermal stabilities than any previously prepared imidazolium or ammonium exchanged montmorillonite.     

Catalytic charring-volatilization competition in organoclay nanocomposites

The thermal behaviour of organoclays, and especially their organic treatment, is an important issue in polymer nanocomposite preparation and their fire retardant properties. The thermal behaviour of the organomodifier is strongly affected by the different composition parameters of the clays. Thus the thermal degradation, in inert and in oxidative atmosphere, of natural montmorillonite and synthetic fluorohectorite both exchanged with polar and non-polar organomodifiers was studied using a combined thermogravimetry/Fourier transform infrared and a flash pyrolysis GC-MS system. Decomposition and charring mechanisms of the organic molecules in the clays are proposed for each kind of clay and a relationship between the composition of the clays and the kinetics of the decomposition reactions is found. Furthermore, it is shown that the charring-volatilization competition on heating organoclays in the presence of oxygen depends on the structure of the clay, the confined or unconfined position of the organic molecules and their polarity.     

Proportion of bromo-DBPs in total DBPs during reclaimed-water chlorination and its related influencing factors

During the chlorine disinfection of reclaimed-water, the proportion of bromo-disinfection by-products (bromo-DBPs) in total DBPs is affected by chlorine dosage, reaction time, pH, ammonia nitrogen (NH3-N) and preozonation. Results show that bromo-trihalomethanes (bromo-THMs) form more easily than bromo-haloacetic acids (bromo-HAAs) and bromine incorporation in DBPs decreases with the increase of chlorine dosage. Within 5 h, bromine incorporation in THMs (n(Br)) increases but bromine incorpo-ration in HAAs (n′(Br)) decreases with the extension of reaction time; however, n(Br) decreases and n′(Br) keeps relatively constant at a longer reaction time. Furthermore, bromine incorporation in DBPs is low under acidic and alkaline conditions. The increase of NH3-N concentration inhibits the formation of chloro-DBPs, resulting in the increase of n(Br) and n′(Br) to some extent. Preozonation enhances the formation of HOBr and the increase of bromine incorporation in DBPs; however, ozone of a high con-centration oxidizes HOBr to its salt form, leading to the decrease of bromine incorporation in DBPs.     

Correlation Analysis of the Carboxyl and Carbonyl Groups of Natural Organic Matter and the Formation Potential of Trihalomethanes and Chloral Hydrate

Natural organic matter (NOM) has always been considered the main precursor of disinfection by-products (DBPs) during the chlorine disinfection of drinking water. This research focuses on investigating the correlation between the functional group (carboxyl and carbonyl groups) content of NOM and the formation of trichloromethane (TCM) and chloral hydrate (CH). The quantitative determination of carboxyl groups, carbonyl groups, TCM, and CH were conducted during the drinking water treatment processes with different coagulant dosages and with/without pre-oxidation by KMnO₄ or NaClO. The most appropriate coagulant for the removal of conventional components was polyaluminum chloride (PAC), and the dosage was 110 mg/L. Up to 43.7% and 14.5% of the carboxyl and carbonyl groups, respectively, were removed through the coagulation and sedimentation processes, which can be enhanced by increasing PAC dosage. The filtration process further increased the removal rates of these two functional groups to 59.8% and 33.5%, respectively. The formation potential of the TCM and CH decreased as the PAC dosage increased. Pre-oxidation by KMnO₄ (0.8–1.0 mg/L) effectively controlled the formation of DBPs while increasing the carboxyl and carbonyl group content. Pre-oxidation by NaClO decreased the formation of TCM rather than CH, and a suitable amount (0.5–1.0 mg/L) decreased the carboxyl and carbonyl groups. It was found that there was a good linear correlation between carboxyl groups and TCM and CH. The linear fit R² values of the carboxyl groups to TCM and CH were 0.6644 and 0.7957, respectively. The linear fit R² values of the carbonyl groups to TCM and CH were 0.5373 and 0.7595, respectively.     

XRD study of the dehydration and rehydration behaviour of Al-pillared smectites differing in source of charge

The swelling properties of Al-pillared clays, obtained from five different smectites, were studied using X-ray diffraction. These clays, the dioctahedral beidellite and montmorillonite and the trioctahedral saponite, hectorite and laponite differ in source of isomorphic substitution and represent a series of decreasing basicity along the siloxane plane. An Al oxyhydroxy cation was inserted between the layers to form the respective pillared clays and these clays were heated incrementally to 600°C. The XRD peaks at each stage of heating were recorded as well as the same samples subsequently wetted. Basal spacings of each clay at each stage of dehydration d rehydration indicated that the swelling of tetrahedrally substituted saponite and beidellite was indeed restricted, compared with the other three clays. This was attributed to greater basicity of the oxygen plane of beidellite and saponite due to tetrahedral substitution of Si by Al, resulting in an increase in the strength of hydrogen bonds between either water or the interlayer polyhydroxy cation and the clay.The data from the XRD analyses helped in addition, to clarify the thermal transformations of the Keggin ion itself. According to the changes in thed-spacings of the pillared clays it was concluded that the Keggin ion lost its structural water at 200°C and dehydroxylated in a range beginning at 350°C. Between 500 to 600°C this polymer cation, which is thought to form the Al₂O₃ oxide, did not rehydrate.Dedicated to Prof. Menachem Steinberg on the occasion of his 65th birthdayThe authors wish to thank Laporte Industries, Inc., U.K. for the laponite sample.     

Nanocomposite of montmorillonite with telechelic sulfonated poly(butylene terephthalate): Effect of ionic groups on clay dispersion, mechanical and thermal properties

Telechelic ionomeric poly(butylene terephthalate) nanocomposites with organically modified clays have been prepared by the melt intercalation technique both in Brabender mixer and in twin screw-extruder. The presence of ionic groups tethered at the end of the polymer chains permits electrostatic interaction between the polymer and the surface of an organically modified clays providing a thermodynamic driving force for the dispersion of the clay platelets in the polymer matrix. The improved dispersion has been verified by TEM and XRD analyses. Nanocomposites with telechelic polymers present therefore consistently higher thermo-mechanical properties and improved thermal and hydrolytic stability respect to nanocomposites with standard PBT. Nanocomposite obtained using PBT with 3% telechelic ionic groups and with 5% of clay present a heat deflection temperature that is 48 °C higher compared to that of the commercial material. The presence of the clay also slightly increases the thermal and hydrolytic stability respect to standard PBT.     

Interaction of smectites with organic photochromic compounds

Reversible light induced colour changes have been observed in a variety of organic and inorganic systems: the phenomenon is termed photochromism. Suitable materials have potential uses ranging from data storage to labelling. The fulgide α-2,5-dimethyl-3-furylethylidene (isopropylidene) succinic anhydride shows photochromic behaviour which is modified considerably when the fulgide is supported on a smectite clay. We have shown that Smectites cause a bathochromic shift in the fight absorption of the fulgide and the photochrome of 20 and 80 nm, respectively, relative to the values in hydrocarbon solution. Moreover, the clays catalyse several reactions on different timescales.

1. Z →E isomerization of the fulgide. This process is an acid catalysed interlayer reaction strongly sensitive to the presence of polar molecules even at low concentrations. The most effective catalysts were clays exchanged with trivalent interlayer cations, equilibrated at low relative humidity before use. In toluene, reflux reactions were complete in ≈ I hour. The procedure can be used in a preparative sense.
2. The ring closure reaction to give the photochrome (i.e.E →P). This is a surface (and interlayer) catalysed thermal reaction, taking of the order of a day in toluene reflux. The reaction does not depend to any great extent on the type of smectite used, nor, within reason, on any pretreatment of the clay.
3. The decomposition of the fulgide and photochrome. These reactions were found to be acid catalysed and gave at least four products. The reactions occur in the interlayer region of the clay, but at a rate slower than those listed above, taking months to reach levels at which products could be detected.

Although the shifts in light absorption noted above are of potential interest in a range of applications, the chemical activity of the clay, and the resistance of the coloured form to bleaching when supported on the clay, make such usage unlikely.     

Novel architectures in porous materials based on clays

Modification of layered clays in view to develop porous materials, mainly for catalytic applications, has been afforded in the past via intercalation reaction of aluminum and other polyoxycations or through generation of mesoporous silica between the layers of the silicate. In this paper it is introduced examples of an alternative route for the preparation of porous nanoarchitectures based on the sol–gel method that profits from the swelling ability of organoclays in organic solvents to incorporate silicon and/or other metal (e.g., Ti, Al,…) alkoxides in the interlayer region of the silicates where they are hydrolyzed in a controlled manner. Their further polycondensation originates the formation of an oxide matrix and after a thermal treatment is possible the consolidation of oxide nanoparticles between delaminated smectites and vermiculites. It is also showed how this colloidal route can be applied to the generation of oxide nanoparticles bonded to the external surface of fibrous clays, such as sepiolite. Finally, it is also summarized with various examples the potential interest of the resulting porous clay nanoarchitecture materials in applications as acid catalysts, photocatalysts or nanofillers in polymer–clay nanocomposites.     

Nanocomposite Polymer Electrolytes of Sodium Alginate and Montmorillonite Clay

Nanocomposite polymer electrolytes (NPEs) were synthesized using sodium alginate (Alg) and either sodium (SCa-3-Na⁺)- or lithium (SCa-3-Li⁺)-modified montmorillonite clays. The samples were characterized by structural, optical, and electrical properties. SCa-3-Na⁺ and SCa-3-Li⁺ clays’ X-ray structural analyses revealed peaks at 2θ = 7.2° and 6.7° that corresponded to the interlamellar distances of 12.3 and 12.8 Å, respectively. Alg-based NPEs X-ray diffractograms showed exfoliated structures for samples with low clay percentages. The increase of clay content promoted the formation of intercalated structures. Electrochemical Impedance Spectroscopy revealed that Alg-based NPEs with 5 wt% of SCa-3-Na⁺ clay presented the highest conductivity of 1.96 × 10⁻² S/cm², and Alg with 10 wt% of SCa-3-Li⁺ showed conductivity of 1.30 × 10⁻² S/cm², both measured at 70 °C. From UV-Vis spectroscopy, it was possible to infer that increasing concentration of clay promoted a decrease of the samples’ transmittance and, consequently, an increase of their reflectance.     

Silicon‐methoxide‐modified clays and their polystyrene nanocomposites

Silicon‐methoxide‐containing modified clays were obtained through cationic exchange between the sodium clay and the ammonium cation of [3‐(trimethoxysilyl)propyl]octadecyldimethylammonium chloride (Si18). The nanocomposites were prepared through bulk polymerization of styrene in which the Si18 clay was dispersed. The silicon‐methoxide offers the possibility of reaction between the methoxide and a clay hydroxyl group to link together the cation and the clay. The nanocomposites were characterized by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy. Their thermal stability and flame retardancy were measured by thermogravimetric analysis (TGA) and cone calorimetry. Linkage between the silicon and the clay apparently occurs in the clay but is not likely to occur in the nanocomposite, perhaps because of the presence of the polystyrene spreading the distance between the reactive sites, which makes reaction more difficult. The results from TGA and cone calorimetry were similar to those obtained with other nanocomposites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1498–1503, 2002     

Examination of the cleavage and formation of the disulfide bond in poly[dithio-2,5-(1,3,4-thiadiazole)] by redox reaction

Reduction and oxidation peak potentials of poly[dithio-2,5-(1,3,4-thiadiazole)] were observed in hot γ-butyrolactam (90°C) at −0.1 and 0.1 V vs. Ag respectively. To clarify the redox reaction of the polymer (oligomer), bis(2-methyl-1,3,4-thiadiazoyl)-5,5′-disulfane was synthesized as a model compound and its redox reaction examined by experiment and molecular orbital calculation. Reduction and oxidation peak potentials of this model were observed at −0.65 and 0.2 V respectively, potentials corresponding to the cleavage and formation reactions of the disulfide bond. The bond cleavage reaction was also suggested by molecular orbital calculations. From a comparison of the shape and response of the cyclic voltammogram between the monomeric and polymeric disulfides, it became clear that reduction and oxidation of the polymer meant the cleavage and formation reactions of the disulfide bond respectively, and that the redox reaction is quasi-reversible.     

Ester interchange reactions catalyzed by tin compounds in reactive processing: NMR contribution via reactions with model compounds

Interchange reactions involving esters were used in reactive processing with a view to obtaining polymer blends with stabilized morphology. Dibutyltinoxide (DBTO) appeared to be an excellent catalyst for these reactions. In fact, it was shown that the true catalytic entity is a dimeric alkoxy, acyloxy distannoxane entity formed in situ, during processing, by the reaction of the DBTO with the polymer ester groups. This compound was first obtained with model esters and characterized by multinuclear NMR analysis (¹H, ¹³C, ¹¹⁹Sn). The catalytic efficiency of the in situ polymeric distannoxane was compared with other added parent distannoxanes. Later on – still with model compounds – ligand exchanges at the tin sites were investigated and it was shown that these exchanges are not essential to the catalyst activity, but when they take place it increases the catalytic efficiency. Then, this type of catalysis was successfully used for interchange reactions in reactive extrusion of different polymer blends, some applications are briefly presented. To cite this article: M.-F. Llauro and A. Michel, C. R. Chimie 9 (2006).     

Evaluation of chlorinated by-products in drinking waters of Central Friuli (Italy)

Drinkable water supplied by aqueducts undergoes preliminar potabilization which, in Italy, is mainly accomplished by chlorine addition. The bactericidal action involved in this process is always accompanied by chlorination and oxidation of organic species (mainly humic and fulvic acids) naturally present in treated waters, so that many disinfection by-products (DBPs) are formed, such as trihalomethanes (THMs) and halo-acetic acids (HAA), which can represent a chemical risk for public health. The aim of this study was the monitoring of DBPs in drinking water disinfected by chlorination, supplied by four different aqueducts of Central Friuli (Italy). DBP evaluations were performed in water samples consisting of both input and output of disinfection plants. The results of analytical determinations were worked out to provide the THM and HAA parameters for disinfected waters, while in feeding waters the following different conventional parameters were adopted: (i) trihalomethanes formation potential (THMFP), (ii) halo-acetic acids formation potential (HAAFP) and (iii) UV absorbance at 254 nm (UV254). The quite moderate content of chlorinated products found in all samples considered highlighted the excellent quality of potabilized waters available in Central Friuli. Moreover, our results confirmed that the majority of DBPs formed when chlorine is used for water disinfection consists of THMs, while chlorites and chlorates prevailed when potabilization is accomplished by using chlorine dioxide. Finally, simple UV254 monitoring turned out to be a profitable approach for the determination of chlorinated by-products only when THMs prevail among DBPs.     

Clay minerals as photochemical reaction fields

This article surveys the intercalation characteristics of a number of clay minerals which can be utilized as host materials for photofunctional organic–inorganic hybrid systems as well as photochemical anisotropic reaction fields. The introduction of this review describes the chemical compositions and the structural features of various kinds of artificial as well as naturally produced clays. The chemical structures of these clays are often considered to be complicated due to their unfamiliar names which are sometimes taken from the areas where they originate although, structurally, only slight differences actually exist. The second chapter summarizes the adsorption and aggregation properties of typical organic dyes in clays. The aggregation behavior is sensitive to the kind and amount of metallic ions present in the lattice of the clays, the amount of adsorbed water as well as the structure of the organic guests to be intercalated. All of these factors are discussed in relation to the adsorption and aggregation behavior. In the third chapter, the photochemical reactions of excited metal complexes adsorbed in clays are discussed. Electron transfers for [Ru(bpy)₃]²⁺ in clays are described, showing that the clay layers provide reaction fields which stabilize the resulting charge separated species. This article aims to provide important insights into the fundamental mechanisms and properties of anisotropic reaction fields for the applications in design of promising, new photochemical and photobiological systems and processes.     

Analysis of Thermally Stimulated Depolarization Currents (TSDC) Measured on Exchanged Clays

This work shows that hydration of clays can be studied by means of a new interpretation of thermally stimulated depolarization currents technique. These measurements have been performed on four exchanged natural clays: Na-montmorillonite, Ca-montmorillonite, kaolinite, and illite. The results are analyzed using both the recently developed analysis of relaxation times distribution and the electronegativity equalization method. They provide evidence of the surface heterogeneity of clays. It is established that sites, identical from a crystallographic point of view, are different when the energy of the phenomenon is considered. The main interest of this work is to give for the first time a value of the hydration energy of cation onto clay surfaces. Copyright 2000 Academic Press.     

Mid-infrared and infrared emission spectroscopy of Cu-exchanged montmorillonite

Middle Infrared Spectroscopy (Mid-IR) and Infrared Emission Spectroscopy (IES) were employed to characterise Cu-exchanged montmorillonites, which were derived from two different types of montmorillonite clays, Ca-exchanged montmorillonite (Cheto clay) and Na-exchanged montmorillonite (Miles clay). Copper was exchanged under both acidic and basic conditions at different Cu/clay ratios. All Cu-exchanged montmorillonites experienced a shift in most of non-lattice bands, with hydroxyl bands playing a major role in the characterisation of the clays. Furthermore, a relationship between the ratio of bands at 3630 and 3500 cm(-1) and the Cu concentration of the starting solutions was indicated and used to compare the degree of cation exchange between two preparation methods. Two dehydration stages were observed in the IES experiments. Additional bands were observed in all Cu-exchanged montmorillonites prepared with the 'basic conditions method,' and these bands were assigned to ammonia molecules trapped within the clay structure or absorbed on the surface of the clay.