Oxidation of anilinium ions intercalated in montmorillonite clay by electrochemical route

Resonance Raman, FTIR, X-ray diffraction, UV-vis-NIR, electron paramagnetic resonance, X-ray absorption at Si K-edge and electron microscopy were employed for characterizing the products formed through electrochemical oxidation of intercalated anilinium ions inside the cationic montmorillonite (MMT) clay. The layer silicate structure was not affected by the anilinium oxidation between the layers. The intercalated products present only an electronic absorption band at 400 nm, very low conductivity (ca. 10(-7) S cm(-1)) and their Raman spectrum displays bands, with high relative intensities, assigned to the benzidine dication, indicating that this product was formed in high amount. Nevertheless, bands that can be correlated to phenazine-like segments and 1,4-phenylenediamine repeat units (PANI like segments) are also observed. The very low EPR signal indicates that diamagnetic species are predominant. All results are compared to those obtained by anilinium-MMT chemically oxidized by persulfate and the differences are pointed out. (C) 2008 Elsevier B.V. All rights reserved.

Spectroscopic study of the polymerization of intercalated anilinium ions in different montmorillonite clays

The polymerization of the intercalated aniline ions was studied in three different clays, Swy2-montmorillonite (MMT), synthetic mica-montmorillonite (Synl) and pillarized Swy2-montmorillonite (PILC). PANI is formed between the MMT and Syn1 clay layers, being confirmed by the shift of d(001) peak in the X-ray pattern. X-ray Absorption near to Si K edge (Si K XANES) data show that the structures of clays are preserved after the polymerization process and in addition to the SEM images show that morphologies of the clays are maintained after polymerization, indicating no polymerization in their external surface. UV-vis-NIR and resonance Raman data display that the PANI formed in Syn1 galleries has higher amount of phenazinic rings than observed for PANI intercalated in montmorillonite (MMT) clay. No polymer formation was detected in the PILC. N K XANES and EPR spectroscopies show the presence of azo and radical nitrogen in intercalated PAN! chains. Hence, the results are rationalized considering the structural differences between the clays for understanding the role of the anilinium polymerization within the clays galleries. (C) 2011 Elsevier B.V. All rights reserved.

Laponite RD/polystyrenesulfonate nanocomposites obtained by photopolymerization

The present paper describes the synthesis and characterization by dynamic light scattering, X-ray diffraction, scanning electron microscopy and atomic force microscopy of Laponite RD/Sodium polystyrenesulfonate nanocomposites obtained by radical photopolymerization initiated by the cationic dye safranine. The presence of the clay mineral does not affect the hydrotropic aggregation of the monomers, but allows a better deaggregation of the initiator molecules, decreasing the quenching of the excited states that leads to the radicals that initiate polymerization. Increasing the amount of clay mineral loading in the polymerization mixture promotes higher monomer conversion and faster polymerization. The size of the nanocomposite particles, measured by light scattering decreases from 400 to 80 nm for clay mineral loadings of 1.0 wt.%. The X-ray diffraction patterns indicate that the clay mineral does not present a regular crystalline structure in the nanocomposite. Atomic force microscopy studies show films of sodium polystyrenesulfonate polymer with embedded Laponite platelets in its structure, forming 1-8 nm height and 25-100 nm diameter aggregates. (C) 2011 Elsevier B.V. All rights reserved.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

Thermal behaviour of intercalated 8-hydroxyquinoline (oxine) in montmorillonite clay

The composite montmorillonite-8-hydroxyquinoline (Swy-1-8-HQ) was prepared by two different processes and studied by using thermogravimetric analysis (TG/DTG and DSC), as well as helpful techniques as fluorescence in the UV-visible region and X-ray diffraction. The composites developed fluorescent appearance, however with quantum poor efficiency and they exhibited distinct TG and DSC thermal behavior. The fluorescence data of spectra associated to the TG/DT curves allowed to suggest that the 8-HQ was present in the composites in two different circumstances: 1 - intercalated in the interlayer spaces (Swy-1-8-HQ2), rigidly associated to the Substrate feasible as a monolayer with the aromatic rings parallel to the silica layer; and/or, 2 - adsorbed on the Surface (Swy-1-8-HQ1), either as a bilayer formation or tilting of the molecules to the silicate layer sheet. All results confirmed above are in agreement with X-ray diffraction patterns, once the interlayer space increases when 8-HQ is incorporated. The experimental results confirm the formation of the composites in agreement with the method used in the preparation.

New strategies in the preparation of exfoliated thermoplastic starch-montmorillonite nanocomposites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

A simple procedure for the preparation of laponite and thermoplastic starch nanocomposites: Structural, mechanical, and thermal characterizations

The aim of this article is to propose advances for the preparation of hybrid nanocomposites prepared by the combination of intercalation from solution and melt-processing methods. This research investigates the effect of the laponite RDS content on the thermal, structural, and mechanical properties of thermoplastic starch (TPS). X-ray diffraction was performed to investigate the dispersion of the laponite RDS layers into the TPS matrix. The results show good nanodispersion, intercalation, and exfoliation of the clay platelets, indicating that these composites are true nanocomposites. The presence of laponite RDS also improves the thermal stability and mechanical properties of the TPSmatrix due to its reinforcement effect which was optimized by the high degree of exfoliation of the clay. Thus, these results indicate that the exfoliated TPS-laponite nanocomposites have great potential for industrial applications and, more specifically, in the packaging field. © The Author(s) 2011 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.

Synthesis, structure, and thermal stability of poly(methyl methacrylate)-co- poly(3-tri(methoxysilyil)propyl methacrylate)/ montmorillonite nanocomposites

The structure and the thermodegradation behavior of both poly(methyl methacrylate)-co-poly(3-tri(methoxysilyil)propyl methacrylate) polymer modified with silyl groups and of intercalated poly(methyl methacrylate)-co-poly(3- tri(methoxysilyil)propyl methacrylate)/Cloisite 15A™ nanocomposite have been in situ probed. The structural feature were comparatively studied by Fourier transform infrared spectroscopy (FTIR), 13C and 29Si nuclear magnetic resonance (NMR), and small angle X-ray scattering (SAXS) measurements. The intercalation of polymer in the interlayer galleries was evidenced by the increment of the basal distance from 31 to 45 Å. The variation of this interlayer distance as function of temperature was followed by in situ SAXS. Pristine polymer decomposition pathway depends on the atmosphere, presenting two steps under air and three under N2. The nanocomposites are more stable than polymer, and this thermal improvement is proportional to the clay loading. The experimental results indicate that clay nanoparticles play several different roles in polymer stabilization, among them, diffusion barrier, charring, and suppression of degradation steps by chemical reactions between polymer and clay. Charring is atmosphere dependent, occurring more pronounced under air. © 2012 Society of Plastics Engineers.

PLA and Organoclays Nanocomposites: Degradation Process and Evaluation of ecotoxicity Using Allium cepa as Test Organism

In this study, nanocomposites of PLA and organoclays Cloisite 20A and Cloisite 30B were prepared by the melt intercalation method and the obtained samples were characterized by transmission electron microscopy (TEM). Since composting is an important proposal to the final disposal of biopolymers, the influence of clays on the hydrolytic degradation process of PLA was evaluated by visual analysis and monitoring of molecular weight after periods of 15 and 30 days of degradation in compost. After degradation of the materials in composting environment, the evaluation of cytotoxic, genotoxic and mutagenic effects of compost aqueous extract was carried out using a bioassay with Allium cepa as test organism. The TEM micrographs permitted the observation of different levels of dispersion, including exfoliated regions. In the evaluation of hydrolytic degradation it was noted that the presence of organoclays can decrease the rate of degradation possibly due to the barrier effect of clay layers and/or the higher degree of crystallinity in the nanocomposite samples. Nevertheless, even in the case of nanocomposites, the molecular weight reduction was significant, indicating that the composting process is favorable to the chain scission of PLA in studied materials. In the analysis performed by the bioassay using A. cepa as test organism, it was found that after degradation of the PLA and its nanocomposites the aqueous extract of compost samples induced a decreasing in the mitotic index and an increasing in the induction of chromosomal abnormalities. These results were statistically significant in relation to the negative control (distilled water). By comparing the results obtained for the nanocomposites in relative to pure polymer, there were no statistically significant differences. The types of the observed chromosomal aberrations indicated a possible genotoxic effect of the materials, which may be related to an aneugenic action of PLA degradation products. © 2013 Springer Science+Business Media New York.

Enhanced bulk and superficial hydrophobicities of starch-based bionanocomposites by addition of clay

In this work, thermoplastic starch (TPS)-clay bionanocomposites were obtained by an innovative methodology using a combination of methodologies commonly used in the composites and nanocomposites preparations. The main objectives or novelties were to confirm efficiency of the processing methodology by field emission gun scanning electron microscopy and investigate the effect of clay content on the spectroscopic, bulk and surface hydrophilic/hydrophobic properties of these bionanocomposites. Raman and FTIR spectroscopies confirmed the changes in the spectroscopic properties of the TPS bionanocomposites with the addition of the clay materials. Water absorption and contact angle measurements were also used to analyze the effect of the clay content on the hydrophilic properties of the TPS bionanocomposites. The results also showed that the addition of the cloisite-Na+ clay increased the bulk and surface hydrophobicities of the TPS matrix, which may increase its industrial application, particularly in manufacturing of food containers. © 2013 Elsevier B.V.

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg 2+, Pb 2+, Cd 2+, Cu 2+, and Zn 2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO 3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 μg L -1. The precision of determination was satisfactory for the respective concentration level. 2005 © The Japan Society for Analytical Chemistry.

Preparation and characterization of poly(vinyl butyral)-polyaniline-montmorillonite nanocomposites

Poly(vinyl butyral)-polyaniline-sodium montmorillonite nanocomposites were prepared via polymerization of aniline between clay mineral platelets at two different pH levels (2.0 and 5.0), followed by dispersion of the polyaniline-sodium montmorillonite nanocomposite in a poly(vinyl butyral) solution. A comparison was made of the effect of the pH levels and the polyaniline-sodium montmorillonite nanocomposite precursor on the final structures of the poly(vinyl butyral) nanocomposites and their electrical conductivities. X-ray diffraction patterns revealed the formation of nanocomposites at both pH levels. UV-Vis spectra indicated that the polyaniline formed at both pH levels was conductive, with the UV-Vis spectra presenting a band at 420 nm corresponding to the polaronic form and the beginning of a new band at 600 nm indicating the presence of polaronic segments. FTIR spectra revealed the peaks of the groups present in polyaniline and poly(vinyl butyral) nanocomposites. The electrical conductivities of the polyaniline and poly(vinyl butyral) nanocomposites prepared at pH 2.0 were lower than those of the same nanocomposites prepared at pH 5.0, probably due to the lower formation of polyaniline chains in a more acidic dispersion and to the final configuration of polyaniline in the nanocomposites.

Molecular dynamics of poly(Ethylene Glycol) intercalated in clay, studied using 13C solid-state NMR

In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na+ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.

Efficient fabrication of polymer nanocomposites with effective exfoliation and dispersion by solid-state/melt extrusion

In this communication, solid-state/melt extrusion (SSME) is introduced as a novel technique that combines solid-state shear pulverization (SSSP) and conventional twin screw extrusion (TSE) in a single extrusion system. The morphology and property enhancements in a model linear low-density polyethylene/organically modified clay nanocomposite sample fabricated via SSME were compared to those fabricated via SSSP and TSE. The results show that SSME is capable of exfoliating and dispersing the nanofillers similarly to SSSP, while achieving a desirable output rate and producing extrudate similar in form to that from TSE.

Biogeochemical processes in a clay formation in situ experiment: Part F - Reactive transport modelling

Reactive transport modelling was used to simulate solute transport, thermodynamic reactions, ion exchange and biodegradation in the Porewater Chemistry (PC) experiment at the Mont Terri Rock Laboratory. Simulations show that the most important chemical processes controlling the fluid composition within the borehole and the surrounding formation during the experiment are ion exchange, biodegradation and dissolution/precipitation reactions involving pyrite and carbonate minerals. In contrast, thermodynamic mineral dissolution/precipitation reactions involving alumo-silicate minerals have little impact on the fluid composition on the time-scale of the experiment. With the accurate description of the initial chemical condition in the formation in combination with kinetic formulations describing the different stages of bacterial activities, it has been possible to reproduce the evolution of important system parameters, such as the pH, redox potential, total organic C. dissolved inorganic C and SO(4) concentration. Leaching of glycerol from the pH-electrode may be the primary source of organic material that initiated bacterial growth, which caused the chemical perturbation in the borehole. Results from these simulations are consistent with data from the over-coring and demonstrate that the Opalinus Clay has a high buffering capacity in terms of chemical perturbations caused by bacterial activity. This buffering capacity can be attributed to the carbonate system as well as to the reactivity of clay surfaces.