Preparation, characterisation, and dielectric properties of polypyrrole-clay composites

In this study, polypyrrole-clay (PPy-clay) composites were prepared by the in situ chemical oxidative polymerisation of pyrrole in the presence of clay. The chemical structures of the composites were characterised by FTIR and XRD analysis. The thermal properties of these novel composites were analysed by TGA and DSC measurements. Glass-transition temperatures and char yields increased with the increase in clay content in the nanocomposites. The interactions between PPy and clay were mainly between polypyrrole and the layers of clay. It was observed that, as the amount of clay in the composites increased, the dielectric permittivity decreased while the dielectric conductivity of the composite materials increased.     

Bionanocomposites poly(ϵ-caprolactone)/organomodified Moroccan beidellite clay prepared by in situ ring opening polymerization: Characterizations and properties

In this study, a series of poly(?-caprolactone) (PCL)/clay bionanocomposites were prepared via in situ ring opening polymerization (ROP) of ?-caprolactone catalyzed by titanium butoxide. The natural Moroccan clay beidellite (BDT), used as nanocharge, was organomodified with cetyltrimethylammonium bromide, CTA, to obtain the organically modified 3CTA-BDT (3 = CTA/BDT equivalent feed ratio). Characteristics of the final nanocomposites are investigated by FTIR, SEC, XRD, SEM, TGA, DSC, optical tensiometry, thermal conductivity and water vapor sorption analysis. The intercalated/exfoliated morphologies, revealed by XRD and SEM analyses, confirm uniform dispersion of the nanoclay within the PCL matrix. Thermal stability of all the nanocomposites is improved by the addition of 3CTA-BDT clay compared to pure PCL polymer. The DSC data show that the addition of 3CTA-BDT particles promotes an increase in the disorder of the crystalline phase, which reduces the crystallinity degree. The hydrophobicity of Polymer/clay compatibility was analyzed by studying surface polarity degree of samples by contact angle measurements. Thermal conductivity and water vapor sorption was also discussed. The permeability (P), the sorption coefficient (S) and the diffusion coefficient (D), showed a significant decrease with increasing 3CTA-BDT loading.     

Melt blending of ethylene‐vinyl alcohol copolymer/clay nanocomposites: Effect of the clay type and processing conditions

Ethylene‐vinyl alcohol copolymer (EVOH)/clay nanocomposites were prepared via dynamic melt blending. The effect of the processing parameters on blends containing two clay types in different amounts was examined. The blends were characterized with a Brabender plastograph and capillary rheometer, differential scanning calorimetry, dynamic mechanical thermal analysis (DMTA), X‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). XRD showed advanced EVOH intercalation within the galleries, whereas TEM images indicated exfoliation, thereby complementing the XRD data. A dilution process with EVOH and clay treatment in an ultrasonic bath before melt blending did not add to the intercalation level. Different trends were observed for the EVOHs containing two different clay treatments, one claimed to be treated for EVOH and the other for amine‐cured epoxy. They reflected the differences in the amounts of the strongly interacting polymer for the two nanocomposites. Thermal analysis showed that the melting temperature, crystallization temperature, and heat of fusion of the EVOH matrix sharply decreased with both increasing clay content and processing times. Significantly higher viscosity levels were obtained for the blends in comparison with those of the neat polymer. The DMTA spectra showed higher glass‐transition temperatures for the nanocomposites in comparison with those of the neat EVOH. However, at high clay loadings, the glass‐transition temperature remained constant, presumably because of an adverse plasticizing effect of the low moleculared mass onium ions treating the clays. The storage modulus improved when clay treated for EVOH was used, and it deteriorated when amine‐cured epoxy clay was incorporated, except for the sonicated clay. TGA results showed significant improvements in the blends' thermal stability in comparison with that of the neat EVOH, which, according to TEM, was greater for the intercalated structures rather than for exfoliated ones. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1741–1753, 2002     

Polyethylene-Montmorillonite Nanocomposites: Preparation,Characterization and Properties

Polyethylene(PE)/clay nanocomposites have been successfully prepared by in situ polymerization with an intercalation catalyst titanium-montmorillonite (Ti-MMT) and analyzed by X-ray diffraction analysis (XRD), Fourier transform infrared analysis (FT-IR), Transmission electron microscopy (TEM), differentail scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and tensile testing. XRD and TEM indicate that the clay is exfoliated into nanometer size and disorderedly dispersed in the PE matrix, and the PE crystallinity of PE/clay nanocomposite declines to 15∼30%. Compared with pure PE, PE/clay nanocomposites behave higher thermal, physical and mechanical properties; the layer structure of the clay decreases the polymerization activity and produce polymer with a high molecular weight. For PE/clay nanocomposites, the highest tensile strength of 33.4 MPa and Young's modulus of 477.4 MPa has been achieved when clay content is 7.7 wt %. The maximum thermal decomposition temperature is up to 110 °C higher, but the thermal decomposition temperature of the PE/clay nanocomposites decreases with the increases of the clay contents in the PE matrix.     

In situ synthesis of A3‐type star polymer/clay nanocomposites by atom transfer radical polymerization

A series of A₃‐type star poly(methylmethacrylate)/clay nanocomposites is prepared by in situ atom transfer radical polymerization (ATRP) initiated from organomodified montmorillonite containing quaternary trifunctional ATRP initiator. The first order kinetic plot shows a linear behavior, indicating the controlled character of the polymerization. The resulting nanocomposites are characterized by spectroscopic (XRD), thermal (DSC and TGA), and microscopic (TEM) analyses. The exfoliated nanocomposite has been obtained when polymerization was conducted with 1% of organic clay loading. Thermal analyses show that all nanocomposites have higher glass transition values and thermal stabilities compared to neat polymer. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 5257–5262     

Influence of four different types of organophilic clay on the morphology and thermal properties of polystyrene/clay nanocomposites prepared by using the γ-ray irradiation technique

Polystyrene (PS)/clay nanocomposites were successfully prepared by the γ-ray irradiation technique. Four different types of organophilic clays were used: three of the four contained a reactive group, while the other did not. Exfoliated PS/clay nanocomposites can be obtained by using reactive organophilic clay and intercalated PS/nanocomposites can be formed by using non-reactive ones, which was confirmed by X-ray diffraction (XRD) and by transmission electron microscopy (TEM). In the formation of exfoliated PS/nanocomposites, the effect of the double bond of the clay-intercalated agents is much more important than the alkyl chain length. The enhanced thermal properties of PS/nanocomposites were characterized by thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). In particular, the enhancement of the thermal properties of PS/nanocomposites made using the reactive organophilic clay was much higher than that of the thermal properties of PS/nanocomposites incorporating non-reactive clay.     

Inclusion of aramid chains into the layered silicates through solution intercalation route

Aramid–organoclay nanocomposites were fabricated through solution intercalation technique. Montmorillonite was modified with p-amino benzoic acid in order to have compatibility with the matrix. The effect of clay dispersion and the interaction between clay and polyamide chains on the properties of nanocomposites were investigated using X-ray diffraction (XRD), transmission electron microscopy (TEM), tensile testing of thin films, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and water uptake measurements. Excessive clay dispersion was achieved even on the addition of high proportions of clay. The structural investigations confirmed the formation of delaminated nanostructures at low clay contents and disordered intercalated morphology at higher clay loadings. The tensile behavior and thermal stability significantly amplified while permeability reduced with increasing dispersibility of organoclay in the polyamide matrix.     

Polymerization of β‐cyclodextrin in the presence of bentonite clay to produce polymer nanocomposites for removal of heavy metals from drinking water

New hybrid organic–inorganic nanocomposites consist of β‐cyclodextrin (β‐CD)/epichlorohydrin (ECH), and bentonite clay were prepared by direct intercalation through one step emulsion polymerization. The structure and thermal stability of prepared nanocomposites were investigated by Fourier‐transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), field emission‐scanning electron microscopy (FE‐SEM), energy dispersive X‐ray analysis (EDAX), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), differential of differential scanning calorimetry (DDSC), thermogravimetric analysis (TGA) and differential thermogravimetric (DTG) analyses. The observed results show that the β‐CD polymer/clay nanocomposites (β‐CD–ECH polymer/clay) with higher thermal stability than β‐CD–ECH polymer were successfully prepared. The removal of heavy metals such as Cu(II), Zn(II) and Co(II) ions from drinking water was studied using a batch method at ambient temperature. The removal percentage and distribution coefficients (Kd) were determined for the adsorption system. It was found that the β‐CD–ECH polymer/clay nanocomposites showed higher removal capacity for Co²⁺, Cu²⁺ and Zn²⁺ ions in comparison with β‐CD–ECH polymer. The selectivity order could be given as Zn²⁺ > Cu²⁺ > Co²⁺. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation and characterization of poly(butylene terephthalate) nanocomposites from thermally stable organic-modified montmorillonite

In this paper, cetyl pyridium chloride (CPC) was employed to modify the montmorillonite. TGA analysis shows that the organic modified clay has higher thermal stability than hexadecyl trimethyl ammonium chloride modified montmorillonite and is suitable to be used for preparing poly(butylene terephthalate) (PBT)/clay nanocomposites at the high temperature. And then PBT/clay nanocomposites were prepared by direct melt intercalation. The results of XRD, TEM and HREM experiments show the formation of exfoliated-intercalated structure. The thermal stability of the nanocomposites does not evidently decrease, but the char residue at 600 °C remarkably increase compared with pure PBT. DSC results indicate that clay improves the melting temperature, the crystallization rate and crystallinity of the PBT molecules in the nanocomposites.     

Thermal behaviour of compatibilised polypropylene nanocomposite: Effect of processing conditions

The thermal properties and fire behaviour of polypropylene (PP) nanocomposites were investigated using differential scanning calorimetry, dynamic-mechanical analysis, thermogravimetric analysis and glow wire test. In order to study the morphological structure of the materials obtained, TEM and XRD analyses were also carried out. The nanocomposites were prepared using the melt intercalation technique in a co-rotating intermeshing twin screw extruder. Particular attention was given to studying the influence of different processing conditions (barrel temperature profile and screw rate) and compositions of PP-nanoclay blends (clay content, use of compatibiliser) on the thermal properties of the nanocomposites.The results show that all the properties analysed were strongly influenced by the nanocomposite composition; instead, the processing conditions greatly affect only the dynamic-mechanical properties. DSC curves show that the crystallinity is deeply influenced by the presence of the clay in the matrix, owing to the fact that the filler acts as nucleating agent. DMA curves show that materials processed at low temperature profile and high shear stress, i.e. when a good clay dispersion is achieved, are characterised by an enhanced modulus, thus indicating that the incorporation of clay into the PP matrix remarkably enhances its stiffness and has good reinforcing effects. TGA traces in oxidizing atmosphere show a drastic shift of the weight loss curve towards higher temperature and no variation of the onset temperature (i.e. the temperature at which degradation begins). The TGA analyses in inert atmosphere show instead marked increase of this parameter (about 200 °C) and no shift of weight loss curves. Glow wire results highlight that polymer nanocomposites are characterised by enhanced fire behaviour.     

Thermal and electrical behaviors of acid functionalized MWCNT/ABC-type triblock copolymer grafted-MWCNT nanocomposites

In this work, ABC-type triblock copolymer grafted onto the surface of the MWCNT/acid functionalized MWCNT (MWCNT-COOH) composites were prepared and the properties of nanocomposites were characterized extensively using differential scanning calorimetry (DSC), scanning electronic microscopy (SEM), thermogravimetric analysis (TGA), ac electrical conductivity and dielectrical measurements.

DSC study showed that the glass transition temperatures of the nanocomposites are a some higher than that of the matrix polymer. The increase in oxidized MWCNT in the nanocomposite improved the thermal stability of the composite, according to initial decomposition temperatures. The ac electrical conductivity has increased moderately with increasing frequency, but has increased slowly with increase in the oxidized MWCNT content in the nanocomposites. The electrical conductivity increases slowly with increasing temperature to about the glass transition temperature, then it increases faster. The dielectric constants for the matrix polymer and all the composites decreases slightly with increasing frequency from 0.1 kHz to 2.0 kHz. The dielectric constant increases slightly with increasing temperature up to about the glass transition temperature region and then the increase in temperature is accelerated the increase in the dielectric constant.     

Synthesis of a novel benzoxazine monomer‐intercalated montmorillonite and the curing kinetics of polybenzoxazine/clay hybrid nanocomposites

Polybenzoxazine (PBZ), which has a structure similar to that of phenolic resin, is formed through the thermal self‐curing of benzoxazine, that is through a heterocyclic ring opening reaction that requires no catalyst and releases no condensation byproducts. We have used the solvent blending method to prepare PBZ/clay nanocomposites possessing various clay contents. We synthesized a monofunctional benzoxazine monomer (MBM) and then treated the clay with this intercalation agent. The results of X‐ray diffraction (XRD) analysis indicated that MBM intercalated into the galleries of the clay; the nanocomposite possessed an exfoliated structure at 3% clay content. To better understand the curing kinetics of the PBZ/clay nanocomposites, we performed dynamic and isothermal differential scanning calorimetry (DSC) measurements. We describe the thermodynamics of the curing process, using all three of the Kissinger, Ozawa, and Kamal models. The Kissinger and Ozawa methods gave fairly close results for the calculated activation energies, which decreased upon increasing the clay content. The Kamal method, based on an autocatalytic model, suggested a total reaction order of between 2.4 and 2.8. The glass transition temperature (T_g) decreased upon increasing the clay content. Thermogravimetric analysis (TGA) indicated that the nanocomposites have higher decomposition temperatures than does the pristine PBZ; this finding suggests an enhancement in their thermal stability. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 347–358, 2006     

Preparation and characterization of poly(propylene carbonate)/montmorillonite nanocomposites by solution intercalation

Poly(propylene carbonate) (PPC) is a new biodegradable aliphatic polycarbonate. However, the poor thermal stability and low glass transition temperatures (T_g) have limited its applications. To improve the thermal properties of PPC, organophilic montmorillonite (OMMT) was mixed with PPC by a solution intercalation method to produce nanocomposites. An intercalated-and-flocculated structure of PPC/OMMT nanocomposites was confirmed by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal and mechanical properties of PPC/OMMT nanocomposites were investigated by thermal gravimetric analysis (TGA), differential scanning calorimetric (DSC), and electronic tensile tester. Due to the nanometer-sized dispersion of layered silicate in polymer matrix, PPC/OMMT nanocomposites exhibit improved thermal and mechanical properties than pure PPC. When the OMMT content is 4 wt%, the PPC/OMMT nanocomposite shows the best thermal and mechanical properties. These results indicate that nanocomposition is an efficient and convenient method to improve the properties of PPC.     

Morphology and thermal properties of polyhedral oligomeric silsesquioxane/polybutadiene nanocomposites prepared by anionic polymerization

The morphology and thermal properties of Allylisobutyl Polyhedral Oligomeric Silsesquioxane (POSS)/Polybutadiene (PB) nanocomposites prepared through anionic polymerization technique were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The results of XRD, SEM and TEM showed that the aggregation of POSS in PB matrix occurred obviously, forming crystalline domains and the size of POSS particles increased with increasing POSS content. The DSC and TGA results indicated that the glass transition temperature (T _g) of the nanocomposites was significantly increased and the maximum degradation temperature (T _dmax) of nanocomposites was slightly increased compared with pure PB, implying an increase in thermal stability.     

Synthesis and Characterization of Conductive Polypyrrole/Montmorillonite Nanocomposites via One-pot Emulsion Polymerization

A series of electrically conductive polypyrrole/clay nanocomposites were synthesized in this work by using one-pot emulsion oxidative polymerization of pyrrole in the presence of unmodified clay and using DBSNa as the surfactant. The effect of surfactant on the morphological and electrical properties of PPy also were investigated and discussed in some extent. Electrical conductivity of the samples was measured by using samples in which the conductive materials was sandwiched between two Ni electrodes at room temperature. PPy/MMT nanocomposites were characterized by using XRD, TEM, TGA and DSC means of investigation. Intercalated structures were determined for the nanocomposites as confirmed by XRD and TEM studies. Electrical conductivity of the nanocomposites was measured to be dependent to the clay content, and the methods of preparation. Measurement also showed that polymerization of pyrrole monomers pre-intercalated between the clay gallery spaces of the clay led to higher conductivity for the nanocomposite in the same level of clay content. Thermal property measurements showed a lower thermal decomposition rate for the PPy/MMT nanocomposites with respect to the PPy.     

ABS/clay nanocomposites obtained by a solution technique: Influence of clay organic modifiers

Acrylonitrile-butadiene-styrene (ABS) polymer/clay nanocomposites were produced using an intercalation-adsorption technique from polymer in solution: polymer/clay suspensions were subjected to ultrasonic processing to increase the effectiveness of mixing. Several kinds of organically modified layered silicates (OMLS) were used to understand the influence of the surfactant nature on the intercalation-exfoliation mechanism. We show that only imidazolium-treated montmorillonite (DMHDIM-MMT) is stable at the processing temperature of 200 °C, used for hot-pressing, whereas alkyl-ammonium modified clays show significant degradation.The morphology of ABS based polymer nanocomposites prepared in this work was characterized by means of wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Dynamic-mechanical analysis (DMA) was used to determine the storage modulus and damping coefficient as a function of temperature, and to investigate the correlations between mechanical properties and morphology of the nanocomposites. The thermal stability was assessed by means of thermogravimetric analysis (TGA). DMA and TGA show that the nanocomposites based on imidazolium-modified clay out-perform the nanocomposites based on quaternary-ammonium-modified clays in terms of mechanical properties and thermal stability.     

Influence of SEBS-g-MA on morphology, mechanical, and thermal properties of PA6/PP/organoclay nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organically modified clay (organoclay) toughened with maleated styrene-ethylene-butylene-styrene (SEBS-g-MA) were prepared by melt compounding using co-rotating twin-screw extruder followed by injection molding. X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize the structure of the nanocomposites. The mechanical properties of the nanocomposites were determined by tensile, flexural, and notched Izod impact tests. The single edge notch three point bending test was used to evaluate the fracture toughness of SEBS-g-MA toughened PA6/PP nanocomposites. Thermal properties were studied by using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). XRD and TEM results indicated the formation of the exfoliated structure for the PA6/PP/organoclay nanocomposites with and without SEBS-g-MA. With the exception of stiffness and strength, the addition of SEBS-g-MA into the PA6/PP/organoclay nanocomposites increased ductility, impact strength and fracture toughness. The elongation at break and fracture toughness of PA6/PP blends and nanocomposites were increased with increasing the testing speed, whereas tensile strength was decreased. The increase in ductility and fracture toughness at high testing speed could be attributed to the thermal blunting mechanism in front of crack tip. DSC results revealed that the presence of SEBS-g-MA had negligible effect on the melting and crystallization behavior of the PA6/PP/organoclay nanocomposites. TGA results showed that the incorporation of SEBS-g-MA increased the thermal stability of the nanocomposite.     

Polymer-clay nanocomposites: chemical grafting of polystyrene onto Cloisite 20A

An account of the experiments on preparing polystyrene(PS) nanocomposites through grafting the polymer onto organophilic montmorillonite is reported.Cloisite 20A was reacted with vinyltrichlorosilane to replace the edge hydroxyl groups of the clay with a vinyl moiety.Because the reaction may liberate HC1,it was performed in the presence of sodium hydrogencarbonate to prevent the exchange of quaternary alkylammonium cations with H~+ ions.Only the silanol groups on the edge of the clay react with vinyltrichlorosilane.The radical polymerization of the product with styrene as a vinyl monomer leads to chemical grafting of PS onto the montmorillonite surface.The homopolymer formed during polymerization was separated from the grafted organoclay by Soxhlet extraction.Chemical grafting of the polymer onto Cloisite 20A was confirmed by infrared spectroscopy.The prepared nanocomposite materials and the grafted nano-particles were studied by XRD.Exfoliated nanocomposites may be obtained for 0.5 wt%-l wt%clay content.The nanocomposites were studied by thermogravimertic analysis(TGA) dynamic thermal analysis(DTA) and dynamic mechanical analysis (DMTA).     

Thermal stability, crystallization, structure and morphology of syndiotactic 1,2-polybutadiene/organoclay nanocomposite

Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches. The nanocomposites exhibit smaller Avrami exponent and larger crystallization rate constant, with respect to pristine sPB. Primary crystallization under isothermal conditions displays both athermal nucleation and three-dimensional spherulite growth and under nonisothermal processes the mechanism of primary crystallization becomes very complex. Secondary crystallization shows a lower-dimensional crystal growth geometry for both isothermal and nonisothermal conditions. The activation energy of crystallization of sPB and sPB/organoclay nanocomposites under isothermal and nonisothermal conditions were also calculated based on different approaches.     

Preparation of polylactic acid/epoxidized palm oil/fatty nitrogen compounds modified clay nanocomposites by melt blending

In this study, new biopolymer nanocomposites have been prepared. Fatty nitrogen compounds (FNCs); fatty amide (FA), fatty hydroxamic acid (FHA), and carbonyl difatty amide (CDFA), which were synthesized from palm oil, have been used as one of organic compounds to modify natural clay (sodium montmorillonite). The clay modification was carried out by stirring the clay particles in an aqueous solution of FA, FHA, and CDFA by which the clay layer distance increases from 1.23 to 2.71, 2.91 and 3.23 nm, respectively. The modified clay was then used in the preparation of the polylactic acid/epoxidized palm oil (PLA/EPO) blend nanocomposites. The interaction of the modifier in the clay layer was characterized by X-ray diffraction (XRD), and Fourier transform infrared (FTIR). Elemental analysis was used to estimate the presence of FNCs in the clay. The nanocomposites were synthesized by melt blending of the modified clay and PLA/EPO blend at the weight ratio of 80/20. The nanocomposites were then characterized using XRD, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and tensile properties measurements. The XRD and TEM results confirmed the production of nanocomposites. PLA/EPO modified clay nanocomposites show higher thermal stability and significant improvement of mechanical properties in comparison with those of the PLA/EPO blend.