Catalytic activity of acid-treated montmorillonite in polar and non-polar reaction media

The catalytic activity of acid-treated montmorillonite clay towards Brønsted acid catalysed reactions is shown to be highly dependent on the degree of acid treatment received by the clay. Using two contrasting model reactions, one involving highly polar reactants and the other a non-polar reactant, the optimum treatment conditions for an acid-treated clay catalyst are also shown to depend upon the type of reaction being catalysed. In addition, the role of exchangeable Al³⁺ ions in generating catalytically active acid sites in the two reactions is investigated.     

CHEMICAL CHANGES IN CLAY AND CLAY-LIME MIXTURES ON FIRING1

The results of the experiments indicate that lime added to a clay, of the type studied here, combined chemically with certain of the various constituents of the clay when the mixture was fired at 1000°C. There is also an indication of reactions between iron oxide and silica. The exact nature and extent of these several possible reactions cannot be determined from the data of this limited experimental work. It would be of great value for work of this kind if more information was available relative to the chemical action of various reagents upon the several constituents of clay. Obviously it would be necessary to use pure substances representing these constituents rather than any mixture of them. Work was undertaken to obtain indication of the chemical changes which occur on firing a low lime clay and the same clay with calcium-carbonate additions.     

Thermoplastic polyurethane nanocomposites of reactive silicate clays: effects of soft segments on properties

This paper addresses the effects of soft-segment on clay particle exfoliation and resultant mechanical and thermal properties of nanocomposites of reactive layered silicate clay and thermoplastic polyurethanes (TPU). The composites were synthesized via a two-step bulk polymerization scheme from polyether- and polyesterpolyols of molecular weight 2000, diphenylmethanediisocyanate, butanediol, and up to 5 wt% reactive layered silicate clay. It was found that the extent of tethering reactions between polymer chains carrying residual -NCO groups and reactive clay particles was significant, although did not depend on the nature of polyol used. Nanocomposites were obtained only in the case of polyesterpolyol, which can be attributed to both clay-polymer reactions and higher viscosity in the clay-polymer mixing step. These nanocomposites showed 125% increase in tensile stress, 100% increase in elongation, and 78% increase in tensile modulus along with 130% increase in tear strength and a 60% reduction in volume loss in abrasion test. It was observed that hydrogen bonding did not influence the properties and the extent of hydrogen bonding was not affected by the clay particles.     

The influence of phosphate on the properties of clay bricks

The fabrication, properties and composition of heated phosphate-bonded clay bricks are reported. The strength of phosphate-bonded clay bodies is shown to be related to the equilibrium pH of the clay mix. The highest strengths were obtained for mixes with equilibrium pH 7 fired at 500°C which gave a modulus of rupture 60% higher than the unmodified clay heated under similar conditions but at 800°C firing temperature. The phosphate-bonded products were also of low porosity and improved dimensional stability. An insight into the probable mechanism of strength development of the heated product has been obtained from XRD, SEM and DSC studies. The results show that the properties of the phosphate-bonded clay bodies are critically affected by new mineral phases resulting from the reactions of phosphates with clay which subsequently undergo physico-chemical changes above 550°C.     

Opposing effects of nanoclay on viscoelastic response of reactive phenoxy/poly (trimethylene terephthalate) blends: Clay‐induced transreactions versus percolated network formation

The role of nanofillers in reactive blends, which are compatibilized via interchange/exchange reactions, in particular transesterification reactions, is still a challenge. In this study, effects of clay on viscoelastic response of reactive melt intercalated phenoxy/poly (trimethylene terephthalate) blends are investigated. Using rheological plots, it was found that at low clay contents, clay‐induced transreactions could cause an unexpectedly enhanced viscous response. But higher clay contents lead to an enhancement in elastic behavior by inducing the formation of a percolated network. The observed opposing effects of clay particles on viscoelastic response were further examined by stress relaxation analysis, which verified the enhanced viscous response at low clay contents. The effect of interaction between the silicate layers and the blend matrix is also probed by using two different organo‐modifiers. Viscoelastic behavior of samples was also studied by dynamic mechanical analysis, and the results corroborated our findings from rheological measurements. Based on loss modulus data, the improved dynamic homogeneity of nanocomposites is attributed to the enhanced transreactions and stronger hydrogen bonds between the blend components. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Synthesis of thermoplastic polyurethane nanocomposites of reactive nanoclay by bulk polymerization methods

This paper reports synthesis and characterization of thermoplastic polyurethane nanocomposites of reactive silicate clays. Pre-polymer (method I) and chain-extended polymer molecules (method II) with residual -NCO groups participated in tethering reactions with clay during clay-polymer mixing. It was found that both clay-polymer reactions and shear stress of mixing are responsible for clay exfoliation. In method I, more clay-tethered polymer chains were produced, but clay particles did not exfoliate due to low shear stress of mixing. Method II provided an order of magnitude higher shear stress of mixing and yielded exfoliated nanocomposites. Control experiments with high shear stress of mixing and no clay-polymer reactions resulted in only intercalated composites. It was found that clay particles deterred hydrogen bonding among hard segments. The exfoliated nanocomposites exhibited optical clarity and more than 100% increase in tensile strength and tensile modulus over pristine polyurethanes.     

Formation and characterization of polyurethane—vermiculite clay nanocomposite foams

Nanocomposites of rigid polyurethane foam with unmodified vermiculite clay are synthesized. The clay is dispersed either in polyol or isocyanate before blending. The viscosity of the polyol is found to increase slightly on the addition of clay up to 5 pphp (parts per hundred parts of polyol by weight). The gel time and rise time are significantly reduced by the addition of clay, indicating that the clay acts as a heterogeneous catalyst for the foaming and polymerization reactions. X‐ray diffraction and transmission electron microscopy of the polyurethane composite foams indicate that the clay is partially exfoliated in the polymer matrix. The clay is found to induce gas bubble nucleation resulting in smaller cells with a narrower size distribution in the cured foam. The closed cell content of the clay nanocomposite foams increases slightly with clay concentration. The mechanical properties are found to be the best at 2.3 wt% of clay when the clay is dispersed in the isocyanate; the compressive strength and modulus normalized to a density of 40 kg/m³ are 40% and 34% higher than the foam without clay, respectively. The thermal conductivity is found to be 10% lower than the foam without clay. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of the layer charge of clay minerals on optical properties of organic dyes. A review

Interactions between clay minerals and cationic organic dyes cause significant changes in the optical, spectral and chemical properties of the chromophores. These changes are due to the formation of supramolecular assemblies of dye cations, called molecular aggregates. Numerous experiments indicate that dye molecular aggregation is sensitively controlled by the layer charge of a clay mineral. Interpretations are based on a detailed analysis of papers investigating reactions of dyes with clay minerals but also considering the reactions with other inorganic solid materials and templates. Older papers dealing with the subject and alternative interpretations of the phenomenon are analysed and critically reviewed. Significance for clay science, material sciences, nanotechnology and potential industrial applications are discussed.     

Kinetics of potassium exchange in heterogeneous systems

A plant's nutritional requirement for potassium (K) is usually satisfied by release of K⁺ from the phases of soil K. The rates of the reactions between the forms of K in a heterogeneous system are primarily dependent upon the types and amounts of clay minerals present. An overview of the kinetics of K exchange in clay and soil systems will be presented. Discussion will include: rates of K exchange on kaolins, smectites, vermiculites, and soils; models and methods to describe these reactions; and, the rate determining steps involved. A knowledge of the reaction kinetics between the phases of K is paramount in modeling the fate of applied K in soils.     

The thermal degradation of polystyrene nanocomposite

Nanocomposite formation brings about an enhancement of many properties for a polymer, including enhanced fire retardancy. This study was carried out to determine if the presence of clay causes changes in the degradation pathway of polystyrene. In the case of virgin PS, the degradation pathway is chain scission followed by β-scission (depolymerization), producing styrene monomer, dimer and trimer, through an intra-chain reaction. As the clay loading is increased, the evolved products produced through inter-chain reactions become significant. Due to the barrier effect of the clay layers, the radicals have more opportunity to undergo radical transfer, producing tertiary radicals, and then radical recombination reactions, producing head-to-head structures, and hydrogen abstraction from the condensed phase also occurs. In the presence of clay, the color of solid residues darkens as the clay content increases. It is thought that this color change is caused by the formation of conjugated double bonds in the presence of clay.     

Estolide production with modified clay catalysts and process conditions

The 20% yields of estolides prepared from oleic acid and meadowfoam oil fatty acids are improved when the montmorillonite clay catalysts are modified to increase their activity. Changes we explored included acidifying the clay, treating to increase the surface area of clay to introduce new active sites, and decreasing the ionic character of the clay surface to enhance adsorption of the fatty acids. We also evaluated the use of higher levels of clay in the reactions. Clays treated with Fe³⁺ salts increase the estolide yield from 21 to 27%, a 28% increase. Clay catalysts were also treated with surface-active reagents. The most active were cationic surfactants, and montmorillonite clays treated with cetyltrimethylammonium chloride increased the estolide yield to 30%. Estolide yields could not be improved beyond 30% by increasing the amount of clay. However, nitrogen sparging increases the efficiency of stirring and increased the estolide yield to 35% estolide.     

Al-pillared clay supported CuPd catalysts for nitrate reduction

PdCu catalysts on clay and Al-pillared clay supports were prepared by wet impregnation procedure and characterized by powder x-ray diffraction (PXRD), Scanning Electron Microscope Dispersive x-ray analysis (SEM-EDAX) and Transmission Electron Microscopy (TEM). The incorporation of [Al₁₃O₄(OH)₂₄(H₂O) ₁₂]⁷⁺ clusters in the clay interlayers and subsequent formation of Al-pillared clays was confirmed from PXRD patterns. The EDAX analysis indicated good homogeneous mix of metallic components, in the form of monometallic or inhomogeneous bimetallic particles, on the clay and pillared clay surfaces. TEM pictures showed striking particle size differences upon Al₂O₃-pillaring. The metallic particles were much smaller in size on Al-pillared clay than those formed on parent clay. The clay supported PdCu catalysts were tested for nitrate ion reduction in aqueous phase under hydrogen atmosphere. Preliminary results show that the catalysts with Pd and Cu components together exhibit superior performance in activity and selectivity to nitrogen compared to their monometallic particles supported on both clay samples. This study indicates the possibility of using PdCu catalysts supported on pillared clays as environmental friendly and efficient catalysts for nitrate reduction reactions.     

Analysis of the cure of epoxy based layered silicate nanocomposites: Reaction kinetics and nanostructure development

The cure reaction kinetics of epoxy resin, with organically modified montmorillonite loadings of up to 20 wt % and with stoichiometric conditions, has been studied by differential scanning calorimetry with a view to understanding further the fabrication of epoxy‐based polymer layered silicate nanocomposites. The kinetic analysis of isothermal and nonisothermal cure shows that the autocatalytic model is the more appropriate to describe the kinetics of these reactions, and it is observed that a dominant effect of the montmorillonite is to catalyze the curing reaction. However, it was not possible to model the reactions over the whole range of degrees of conversion, in particular for nonisothermal cure. This attributed to the complexity of the reactions, and especially to the occurrence of etherification by cationic homopolymerization catalyzed by the onium ion of the organically modified montmorillonite. The homopolymerization reaction results in an excess of diamine in the system, and hence in practice the reaction is off stoichiometric, which leads to a reduction in both the heat of cure and the glass transition temperature as the montmorillonite content increases. Small angle X‐ray scattering of the cured nanocomposites shows that an exfoliated nanostructure is obtained in nonisothermal cure at slow heating rates, whereas for nonisothermal cure at faster heating rates, as well as for isothermal cure at 70°C and 100°C, a certain amount of exfoliation is accompanied by the growth of d‐spacings of 1.4 nm and 1.8 nm for dynamic and isothermal cure, respectively, smaller than the d‐spacings of the modified clay before intercalation of the resin. A similar nanostructure, consisting of extensive exfoliation accompanied by a strong scattering at distances less than the d‐spacing of the modified clay, is also found for resin/clay mixtures, before the addition of any crosslinking agent, which have been preconditioned by storage for long times at room temperature. The development of these nanostructures is attributed to the presence of clay agglomerations in the original resin/clay mixtures and highlights the importance of the quality of the dispersion of the clay in the resin in respect of achieving a homogeneous exfoliated nanostructure in the cured nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and anti‐clay‐swelling ability of new water‐soluble cellulose derivatives containing quaternary ammonium groups

New water‐soluble cellulose derivatives containing quaternary ammonium groups were prepared by the heterogeneous reactions of hydroxyethyl cellulose with a quaternary chlorohydrin and characterized by reaction parameters and infrared analyses. The dependence of the heterogeneous reaction on the different affecting factors was studied. The cellulose derivatives obtained were investigated for their property as the water‐soluble polymer for inhibiting the swelling of water‐sensitive clay in oilfields. Based on the kinetic curves for clay hydration swelling, a mathematical model that relates linear clay expansion as a function of hydration rate and hydration equilibrium constant was developed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1416–1422, 2001     

An optimum organic treatment of nanoclay for PMR-15 nanocomposites

The present study examined ion exchange of layered silicate clay by ammonium ions and investigated thermal dissociation of ammonium ions and the presence of nadic endgroups in ammonium ions on the potential of clay exfoliation in nanocomposites of PMR-15 (an oligomer with molecular weight 1500). A novel method of organoclay exfoliation was used. It involved organoclay intercalation by lower molecular weight PMR-5 oligomer, dispersion of PMR-5/clay mixture in higher molecular weight PMR-15 resin, and curing of the resultant mixtures at approximately 315 °C. The PMR-5 resin residing inside the clay galleries underwent crosslinking during curing and produced higher elastic forces to facilitate clay platelets exfoliation against a slower rising viscous force in the matrix PMR-15 resin. It was found that the ammonium ions with nadic endgroups participated in intra-gallery PMR-5 resin crosslinking reactions and promoted better exfoliation compared to non-reactive ammonium ions. Improvements in thermal and mechanical properties were also observed.     

Linear viscoelasticity and structure of polypropylene-montmorillonite nanocomposites

Polypropylene (PP)/clay composites were prepared by melt mixing in a thermoplastic mixer using a polypropylene grafted with maleic anhydride (PPg) as the compatibilizer. Concentrations of an organophilic montmorillonite (MMT) between 2 and 15 wt% and concentration ratios of PPg/clay between 1:3 and 3:1 were employed to investigate the relationship between the structural characteristics of the hybrids and their rheological properties. The structure was analyzed with electron microscopy, X-ray diffraction and melt rheology. Thermogravimetric analysis and infrared spectroscopy were also used. The clay interlayer spacing increases after mixing with PP while the addition of PPg only facilitates the partial exfoliation of the clay platelets without changing that spacing. When clay loadings of 8 wt% or larger were used, an important fraction of the original clay particles was found to remain unmodified. The dynamic moduli show little effect of the presence of the inorganic material when no compatibilizer is added or the amount of PPg or clay is too small. As the extent of exfoliation increases, the linear viscoelastic behavior of the composites gradually changes with time while in the molten state, mainly at low frequencies. Evidence of solid-like behavior appears as the concentration of clay increases, for a given PPg/clay or PP/PPg concentration, or as the PPg concentration increases (for a given clay concentration). The concentrations of PPg and clay that induce percolation were observed to have an inverse relation. Evidence of regions with large concentration of MMT was obtained in the annealed samples of composites with solid-like rheological behavior. Additionally, infrared spectra of these materials suggest the simultaneous occurrence of chemical reactions between the PPg and the surfactant or products derived from its thermal decomposition during the annealing process.     

Intercalation strategies in clay/polymer hybrids

Layered silicate clays are natural crystallites and are well recognized for their structures and industrial applications, but there are very few reports on their structural confinement properties and on the mechanisms that underlie their polymer interactions. In this review, we summarize the recent progress on clay modification via conventional ion exchange reactions, sol–gel linking, atom transfer radical polymerization, and polymer intercalation. The organic interaction of ionic clays involves different noncovalent bonding forces, such as amido acid five-membered ring chelation, carboxylic acid chelation, intermolecular hydrogen bonding, and double-layer hydrophobic alignment in a layered clay confinement. Controlling the organic species, their amounts and their self-assembled conformation in a clay confinement could lead to the tailoring of the silicate platelet interlayer distance and of their organophilic properties.     

Resistance to fire of intumescent silicone based coating: The role of organoclay

The fire performance of a curable-silicone based coatings containing expandable graphite (EG) and an organoclay is evaluated in hydrocarbon fire scenario (standard UL1709) using a lab-scale furnace test. It is shown that the use of organoclay allows achieving better performance. The influence of the clay as additional filler is investigated on the fire performance and on the mechanical properties of the char. It is shown that the clay increases significantly the mechanical properties of the char and hence, the fire performance of the silicone based coating. In a next part, the silicone/clay material was characterized by electron microscopy, wide-angle X-ray scattering and solid state ²⁹Si nuclear magnetic resonance (NMR). It evidences the nanodispersion of the clay into the silicone matrix and two main interactions: (i) intercalation of some silicate layers and (ii) chemical reactions between the hydroxyl groups of the clay and the silicone matrix. Finally, X-ray fluorescence of the residue after fire testing shows the organoclay is present uniformly throughout the thickness of the char, due to the previous interaction, and hence increasing the cohesion of the char.     

An in situ intercalative polymerization method for preparing UV curable clay–polymer nanocomposites

A novel in situ intercalative polymerization technique was used to disperse clay mineral in a precursor resin for use in UV curing by performing an in situ ion exchange reaction during polyesterification. Unmodified montmorillonite (MMT) was added to a reaction mixture composed of monomers and methyl, tallow, bis‐2‐hydroxyethyl ammonium (MTEtOH) during the synthesis of unsaturated polyesters to create resins containing highly dispersed, organically modified MMT. UV‐curable clay–polymer nanocomposite (CPN) films were then prepared utilizing donor–acceptor chemistry through reactions of the unsaturated polyester resin with triethylene glycol divinyl ether. Functional group conversion improved up to 15% by the incorporation of clay mineral into the polymer matrix through the in situ polymerization method. The CPNs also had improved barrier, mechanical, and thermal properties over a control film containing no clay mineral. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42601.     

Impact of iron-reducing bacteria on the properties of argillites in the context of radioactive waste geological disposal

The presence of indigenous microorganisms in deep clayey geological formations raises the issue, regarding radioactive waste geological disposal, of the influence of bacterial activity on the confinement properties of materials, including the clayey host rock. Iron-reducing bacteria (IRB) activity is assessed in batch experiments in the presence of argillite samples from an in situ experimental laboratory at Tournemire (Aveyron, France). The results show the availability of structural Fe(III) from the clay minerals for biochemical reactions (bioreduction). In laboratory conditions, a significant impact of IRB on the alteration of clay minerals, mainly the illite–smectite mixed layer (I–Sm), is indeed observed. Such reactions may locally modify the physicochemical conditions and the stability of clay minerals (essentially smectites) prevailing in such deep facilities. More generally, bacterial activity could play an important role on clay mineral alteration and in situ experiments need to be performed in order to quantify the reaction rates and show the representative of these phenomena in the framework of the safety assessment of waste disposal.