Qualitative assessment of nanofiller dispersion in poly(ε-caprolactone) nanocomposites by mechanical testing, dynamic rheometry and advanced thermal analysis

A comprehensive overview of available methods for assessing nanofiller dispersion is presented for a wide range of layered silicate-based poly(ε-caprolactone) (PCL) nanocomposites. Focusing on their respective strengths and weaknesses, rheological, mechanical and thermal characterization approaches are evaluated in direct relation to morphological information. Pronounced changes in the rheological and mechanical properties of the materials are only observed for nanocomposites displaying the highest nanofiller dispersion levels, as confirmed by an innovative and highly reliable thermal analysis approach based on quasi-isothermal crystallization. As such, the data obtained from the different methods also allow a detailed investigation of the crucial factors affecting nanofiller dispersion, evidencing the importance of specific matrix/filler interactions and the need for proper melt processing conditions when targeting significant property enhancements. Finally, the wide potential of the developed methodologies for the characterization of polymeric nanocomposites in general is illustrated by an extension to carbon nanotube-based PCL composites, unambiguously demonstrating their complementarity and broad applicability.     

Effects of hydration and hydrophilicity on Na‐Clay‐supported aqueous‐phase catalysis for atom transfer radical polymerization

Hydrated sodium montmorillonite (Na‐clay) has been used as a catalyst support for the heterogeneous atom transfer radical polymerization of benzyl methacrylate in the presence of various concentrations of water, reducing agent, and CuBr₂ in anisole at ambient temperature. The polymerization was promoted via reduction of Cu^II to Cu^I through the addition of sodium ascorbate (NaAsc) as a reducing agent in aqueous solution. The polymerizaton proceeded in a controlled manner and produced poly(benzyl methacylate) with moderately narrow molecular weight distribution (MWD) when performed under optimum conditions of hydration (10 wt % ≤ H₂O/Na‐clay ≤ 21 wt %) and reducing agent (0.15 ≤ [NaAsc]/[I] ≤ 0.23). The polymerization was uncontrolled if hydration and NaAsc exceed above their optimum range of concentrations. Apparent rate of the polymerization (k_app) increased in the presence of decane–anisole (1/3, v/v) mixture solvent. Selective adsorption of decane at the interfaces of the hydrated clay was attributed for the rate enhancement due to increased polymer and hydrophobic interface interaction. The polymerization progressed in a controlled manner as confirmed by the first‐order time‐conversion plot, linear increase in molecular weights, and moderately narrow MWDs over conversion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Investigating the effect of nanolayered silicates on blend segmental dynamics and minor component relaxation behavior in poly(ethylene oxide)/poly(methyl methacrylate) miscible blends

Polymer–silicate nanocomposites based on poly (ethylene oxide), PEO, poly(methyl methacrylate), PMMA, and sodium montmorillonite clay were fabricated and characterized to investigate the effect of nanolayered silicates on segmental dynamics of PEO/PMMA blends. X‐ray results indicate the formation of an exfoliated morphology in the nanocomposites. At low silicate contents, an enhancement in segmental dynamics of blend nanocomposites and also PEO, minor component in blend, is observed at temperature region below blend glass transition. This result can be attributed to the improvement of the confinement effect of rigid PMMA matrix on the PEO chains by introducing a low amount of layered silicates. On the other hand, at high silicate contents, an enhancement in segmental dynamics of blend nanocomposites and PEO is observed at temperature region above blend glass transition. This behavior could be interpreted based on the reduction of monomeric friction between two polymer components, which can facilitate segmental motions of blend components in nanocomposite systems. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Synthesis of attapulgite-MnO2 nanocomposite from manganese complex by ultrasound for hydrogen storage

The research included the synthesis of a new complex of manganese with 3,4,5-tri-methoxybenzoic acid in the presence of triethylamine as a base to which gives the complex with formula [Mn (TMB)₂].2H₂O. This complex was characterized by FTIR, CHN, magnetic susceptibility and thermal analysis. Furthermore, this complex was used as a novel precursor of manganese in preparing the attapulgite-MnO₂ nanocomposite by one-pot addition method using ultrasound. The resulting nanocomposite was characterized by X-ray diffraction and TEM and the results prove that this composite was found as nanochannel of the diameter 45 nm decorated with 26–41 nm of MnO₂ nanoparticles. The attapulgite-MnO₂ nanocomposite was used in the application of hydrogen storage, and the results proved that attapulgite-MnO₂ nanocomposite has the ability to store 3.55 wt% of hydrogen under a pressure of 90 bar and a temperature of 77 K. Furthermore, the measurement demonstrated that increasing the pressure increased the stored hydrogen, implying that the stored gas will be liberated by altering the pressure, implying that the storage will be of the physical kind.     

One-pot multi-component synthesis of N,N′-alkylidene bisamides and imidazoles using heteropoly-11-tungsto-1-vanadophosphoric acid supported on natural clay as catalyst: A green approach

One-pot multi-component synthesis of N,N′-alkylidene bisamides, 2,4,5-trisubstituted imidazoles and 1,2,4,5-tetrasubstituted imidazoles in the presence of catalytic material heteropoly-11-tungsto-1-vanadophosphoric acid (HPV) supported on activated natural clay for about 20% (HPVAC-20) under solvent-free reaction condition have been achieved. Green heterogeneous reaction condition, simple workup procedure, short reaction time, high yield of products, and reusability of the catalyst are the advantages of this protocol.     

Comparative study of natural rubber/clay nanocomposites prepared from fresh or concentrated latex

Rubbers are usually compounded with different chemicals and fillers in order to modify their properties to suit the end applications. Natural rubber (NR) contains different natural occurring materials and this brings about subtle complexities in controlling compound and vulcanizate properties. Thus, the aim of this paper is to illustrate that the properties of compounds and vulcanizates of NR/clay prepared from fresh field latex and from concentrated latex are different. Different amounts of pristine clay were added to the two latices and their viscosity determined. The latex mixtures were next coagulated to form solid filled rubbers and their properties examined. Vulcanizates of these solid rubbers were then prepared and their properties, also, were determined. The cause of an observed variation is attributed to soluble proteins in the fresh field latex. Structural models to explain this are proposed.     

Improving the water resistance of epoxy–anhydride matrices by the incorporation of bentonite

Epoxy–anhydride‐based polymers are commonly used as a matrix in pipeline systems exposed to water during their in‐service life. Water absorption at moderate temperatures and/or at long exposure times could lead to irreversible hydrolysis reaction decreasing considerably the polymer overall performance. A strategy to enhance the barrier properties of epoxy resins is to add nanofillers to traditional matrices. In this work, we added bentonite and chemically modified bentonite to this purpose. Water absorption of the resulting materials at three different temperatures (22°C, 80°C, and 93°C) was studied, and simultaneously, the evolution during the immersion tests of glass transition temperature and flexural modulus was recorded. Long‐term gravimetric results showed that composites with chemically modified bentonite produce a delay on the hydrolysis of epoxy–anhydride matrix, which is a relevant result, because of the tough application and uses of the system, from the technological point of view. Copyright © 2016 John Wiley & Sons, Ltd.     

Delamination of sodium montmorillonite in PA6 in the presence of melamine polyphosphate

This study describes the influence of melamine polyphosphate (MPP) flame retardant addition on layered structure of virgin sodium montmorillonite (MMT) in PA6/MMT system obtained in extrusion process. It was found that the extrusion of the PA6/MMT binary system in co‐rotating twin screw extruder gives intercalated clay nanocomposites, while during extrusion of ternary PA6/MMT/MPP composite, full exfoliation of clay was obtained in the system. Structure of the composites was proved utilizing wide angle X‐ray scattering and transmission electron microscopy techniques. Exfoliation of MMT in ternary PA6/MMT/MPP system was also confirmed by rheological studies (viscosity and creep measurements) which were carried out using rotational rheometer. Young's modulus of PA6/MMT/MPP was found to be ~25% greater comparing to PA6/MPP of the same filling level. Cone calorimetry experiments proved decrease of heat release rate peak of PA6/MMT/MPP by ~55% comparing to PA6/MPP with the same total filling level. Copyright © 2017 John Wiley & Sons, Ltd.     

Influence of Interfacial Tension on Seeded Calcium Carbonate Scale Precipitation: Effect of Adsorbed Asphaltenes

Clay particles with adsorbed asphaltenes, which are commonly found in produced water, have been used as seed particles during precipitation of calcium carbonate in order to determine whether such particles may influence the kinetics of precipitation. The results show that the presence of the adsorbed asphaltenes accelerates the precipitation, and there is also a significant difference between different types of adsorbed asphaltenes. The adsorption of asphaltenes at the seed surface leads to a significant increase in the interfacial tension between the seed surface and the aqueous solution, and calcium carbonate therefore precipitates at the seed surface in order to reduce this high interfacial tension.     

Green synthesis of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives catalyzed by heteropoly acid supported montmorillonite K-10 clay

Herein, synthesis of a series of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives directly by one-pot multi-component reaction of 1,3-dicarbonyl compounds (1,3-indanedione/1,3-cyclohexanedione), 2-aminoantharacene/2-naphthylamine and various substituted aldehydes under solvent-free conditions using heteropoly-11-molybdo-1-vanadophosphoric acid supported on montmorillonite K-10 clay catalyst (10% PVMoK-10) is reported. The successful formation of naphtho[2,3-f]quinolin-13-one and naphtho[2,3-a]acridin-1(2H)-one derivatives was confirmed by various spectroscopic techniques. This study offers a green approach for the synthesis of novel quinolinone derivatives.