Modification of montmorillonite by novel geminal benzimidazolium surfactant and its use for the preparation of polymer organoclay nanocomposites

A new benzimidazolium derivative, the benzimidazolium-N,N′-hexadecane-2-hydroxy-ethyl bromide (Bz) featuring two geminal hexadecyl hydrophobic buttress has been synthesized and used for the functionalization of sodium montmorillonite (MMT-Na) via cationic exchange process. The resulting benzimidazolium-modified MMT (MMT-Bz) exhibits a large d-spacing of 3 nm between silicate layers and shows a high thermal stability compared to the commonly used clay modified alkyl ammonium salts (cloisite 20A and cloisite 20B). MMT-Bz was incorporated in high density polyethylene (HDPE) matrix via melt mixing method to produce HDPE/MMT-Bz nanocomposites. The microstructure and the morphology of these nanocomposites were studied by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The dispersion state of the organoclay within HDPE was monitored by UV–Vis spectroscopy and melt rheology. A more homogeneous dispersion or a greater content of the MMT-Bz in the matrix produced stronger solid-like and non-terminal behavior in the nanocomposites. Tensile properties and thermal stability were evaluated and discussed on the basis of the amount of clay incorporated within the nanocomposites. The intercalated structure in the nanocomposites, resulting from both the better dispersion/distribution of clay nano-platelets and their strong interaction with the polymer chains, provides the driving force to significantly enhance the HDPE properties.     

Preparation and properties of nitrile rubber/montmorillonite nanocomposites via latex blending

The nitrile rubber (NBR)/unmodified montmorillonite (Na-MMT) clay nanocomposites were prepared by latex blending method followed by melt mixing of compounding ingredients by using two-roll mill. The X-ray diffraction (XRD) studies showed an increase in the basal spacing and broadening of peak corresponding to crystal structure of Na-MMT indicating the formation of intercalated/exfoliated clay layers in the NBR matrix. Increase in clay content of nanocomposite increased the XRD peak height due to the formation of many of clay tactoids at higher loading. The transmission electron microscopy (TEM) strengthened the XRD finding by showing the presence of intercalated/exfoliated morphology of clay platelets having good dispersion. The modulus and tensile properties of the nanocomposites were improved with addition of Na-MMT which is proportional to clay concentration. The retention of tensile properties of aged nanocomposites, with all clay concentration, was superior to either pure NBR and carbon black filled NBR composite. The dynamic mechanical analysis showed proportional increase in storage modulus analogous to Na-MMT loading at all the temperature ranges due to the confinement of polymer chains between the clay layers. Nanocomposites with different proportions of clay showed a decrease in tan δ_max peak height with a shift towards higher temperature indicating the reduction in the segmental mobility of polymer chain. A linear model was proposed to correlate the influence of Na-MMT content on storage modulus of nanocomposites. Differential scanning calorimetry indicated a linear increase in glass transition of nanocomposites which is proportional to clay loading. Thermogravimetric analysis revealed a small improvement in the thermal stability of nitrile rubber/clay nanocomposites.     

Dispersion of nanoplatelets of graphite on PMMA matrix by in situ polymerisation technique

Poly(methyl methacrylate)/expanded graphite (PMMA/EG) composites were prepared by the incorporation of EG in various proportions (1%, 2%, 3%, 4% and 5%) with PMMA by in situ polymerisation technique. The polymer composites were characterised by ultraviolet–visible (UV–vis) and Fourier transform infra-red spectroscopies. The structural property of PMMA/EG nanocomposites was studied by X-ray diffraction. The scanning electron microscopy and transmission electron microscopy of synthesised composites were taken in order to study their morphological properties. The conductivity of composites was measured as function of EG concentration. It was found that conductivity of composites gradually increased with the increase in EG loading. Oxygen permeability of PMMA/EG nanocomposites was calculated and it was found that the property was reduced substantially with rise of EG proportion. The thermal stability of PMMA/EG nanocomposites was improved by dispersion of EG with PMMA matrix.     

Manufacturing polymer/clay nanocomposites through elongational flow technique

A novel processing technique that employs continuous elongational flow to fabricate polymer/clay nanocomposites has been developed and evaluated in this work. A self-made vane mixer has been used to supply the continuous elongational flow, while high-density polyethylene (HDPE) and organic montmorillonite (O-MMT) were used as the polymer matrix and clay, respectively. The morphology of resultant nanocomposites has been carefully revealed and studied by examining wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Intercalation effect and dispersion of O-MMT layers have been investigated by the morphology study. The results indicate that the elongational flow has a great potential in melt intercalation of O-MMT, and can lead to an orderly O-MMT layers’ distribution. Thermal properties of as-mixed nanocomposites that prepared under elongational flow have been determined by the differential scanning calorimetry (DSC), which demonstrates that the introduction of O-MMT nano-sheets is bad for the crystal of HDPE matrix. The universal tensile test shows how O-MMT layers affect the mechanical properties of nanocomposites, including the tensile strength and elongation at break. The strain–stress relationship reveals that with continually adding O-MMT layers, the tensile strength increases at first, and then decreases. While the elongation at break shows the same trend.     

Effect of nanoclays on physico-mechanical properties and adhesion of polyester-based polyurethane nanocomposites: structure–property correlations

Polyester–polyurethane nanocomposites based on unmodified and modified montmorillonite clays were compared in terms of their morphology, mechanical, thermal, and adhesive properties. Excellent dispersion of the modified nanoclay in polymer with 3 wt% loading was confirmed from X-ray diffraction, and low-, and high-magnification transmission electron micrographs. The properties of the clay-reinforced polyurethane nanocomposites were a function of nature and the content of clay in the matrix. The nanocomposite containing 3 wt% modified clay exhibits excellent improvement in tensile strength (by ~100%), thermal stability (20 °C higher), storage modulus at 25 °C (by ~135%), and adhesive properties (by ~300%) over the pristine polyurethane.     

Thermal and thermomechanical properties of poly(butylene succinate) nanocomposites

This article describes the thermal and thermomechanical properties of poly(butylene succinate) (PBS) and its nanocomposites. PBS nanocomposites with three different weight ratios of organically modified synthetic fluorine mica (OMSFM) have been prepared by melt-mixing in a batch mixer at 140 degrees C. The structure and morphology of the nanocomposites were characterized by X-ray diffraction (XRD) analyses and transmission electron microscopy (TEM) observations that reveal the homogeneous dispersion of the intercalated silicate layers into the PBS matrix. The thermal properties of pure PBS and the nanocomposite samples were studied by both conventional and temperature modulated differential scanning calorimetry (DSC) analyses, which show multiple melting behavior of the PBS matrix. The investigation of the thermomechanical properties was performed by dynamic mechanical analysis. Results reveal significant improvement in the storage modulus of neat PBS upon addition of OMSFM. The tensile modulus of neat PBS is also increased substantially with the addition of OMSFM, however, the strength at yield and elongation at break of neat PBS systematically decreases with the loading of OMSFM. The thermal stability of the nanocomposites compared to that of the pure polymer sample was examined under both pyrolytic and thermo-oxidative environments. It is shown that the thermal stability of PBS is increased moderately in the presence of 3 wt% of OMSFM, but there is no significant effect on further silicate loading in the oxidative environment. In the nitrogen environment, however, the thermal stability systematically decreases with increasing clay loading.     

Thermal properties of PMMA/montmorillonite clay nanocomposites

Polymer/Clay offer tremendous improvement in wide range of physical and engineering properties for polymers with low filler loading. In nanotechnology polymer/clay nanocomposites use smectitetype clays that have layered structures. In this work, Poly (methyl methacrylate) (PMMA) was synthesized by free radical addition polymerization in the presence of high power ultrasound. The Poly (methyl methacrylate) (PMMA)-Montmorillonite (MMT) clay nanocomposites were synthesized by two different techniques viz., ultrasonic mixing and magnetic stirring. An analysis of the XRD data confirms that the composites are in the nanometer scale. The FTIR spectra show that there is strong interaction between the clay and the polymer that enhances the thermal stability. The thermal stability of the experimental nanocomposite prepared by the two processes is compared. Further analysis of XRD data shows that intercalation as well as exfoliation has taken place in both the types of nanocomposites preparation. An analysis of the TG, DTG curves reveal that the thermal stability is found to increase by nearly 30% for ultrasonic mixing than that of magnetic stirring.     

Influence of clay incorporation on the physical properties of polyethylene/Brazilian clay nanocomposites

High density polyethylene/Brazilian clay nanocomposites were prepared by the melt intercalation technique. A montmorillonite sample from Boa Vista/PB, Northeast of Brazil, was organically modified with esthearildimethylammonium chloride (Praepagen WB) quaternary ammonium salt. The unmodified and modified clays with the quaternary ammonium salt were introduced in 1, 2, 3 and 5 wt% in a PE polymer matrix. The dispersion analysis and the interlayer distance of the clay particles were obtained by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The mechanical properties of tensile and the flammability of the nanocomposites were studied. In general, the mechanical properties of the systems presented superior values compared to the matrix. The systems showed a reduction on the burning rate, indicating that the flammability resistance of nanocomposites was improved.     

Carbon black–clay hybrid nanocomposites based upon EPDM elastomer

The present study explored the effect of nanoclay on the properties of the ethylene–propylene–diene rubber (EPDM)/carbon black (CB) composites. The nanocomposites were prepared with 40 wt% loading of fillers, where the nanoclay percentage was kept constant at 3 wt%. As the modified nanoclay contains the polar groups and the EPDM matrix is nonpolar, a polar rubber oil extended carboxylated styrene butadiene rubber (XSBR), was used during the preparation of nanocomposites to improve the compatibility. Primarily the nanoclay was dispersed in XSBR by solution mixing followed by ultrasonication. After that EPDM-based, CB–clay hybrid nanocomposites, were prepared in a laboratory scale two roll mill. The dispersion of the different nanoclay in the EPDM matrix was observed by wide-angle X-ray diffraction (WAXD) and high resolution transmission electron microscopy. It was found that the mechanical properties of the hybrid nanocomposites were highly influenced by the dispersion and exfoliation of the nanoclays in the EPDM matrix. Thermo gravimetric analysis, scanning electron microscopy and dynamic mechanical thermal analysis was carried out for each nanocomposite. Among all the nanocomposites studied, the thermal and mechanical properties of Cloisite 30B filled EPDM/CB nanocomposite were found to be highest.     

Enhanced dielectric properties and energy storage density of surface engineered BCZT/PVDF-HFP nanodielectrics

Polymer nanocomposites have proved to be promising energy storage devices for modern power electronic systems. In this work we have studied the dielectric properties and dielectric energy storage densities of 0–3 type BCZT/PVDF-HFP polymer nanocomposites with different filler volume concentrations. BCZT nanopowder was synthesized by solgel method through citrate precursor method. The structural and morphological features of the BCZT nanopowder were examined by X-ray diffraction and transmission electron microscopy. For better polymer ceramic interface coupling, BCZT was surface functionalized with extended aromatic ligand, naphthyl phosphate (NPh). The surface functionalization was validated and quantified by thermogravimetric analysis and X-ray photoelectron spectroscopy. The dielectric constant of surface passivated BCZT nanoparticles was estimated to be ~?155 using slurry technique, while the dielectric permittivity of pristine BCZT nanopowder could not be assessed due to high innate surface conductivity. BCZT/PVDF-HFP polymer nanocomposite thin films were fabricated using solution casting technique. The dispersion quality of the ceramic fillers in the polymer matrix was examined by scanning electron microscopy. Due to better polymer ceramic interface, At 5 vol% filler concentration, NPh modified nanoBCZT/PVDF-HFP films showed enhanced dielectric breakdown strength and energy storage density than untreated nanoBCZT/PVDF-HFP and even pure polymer films. Maximum energy storage density of 8.5 J cm^?3 was obtained at an optimum filler concentration of 10 vol% for surface functionalized BCZT/PVDF-HFP composite films of 10 μm thickness.     

Effect of processing parameters and clay volume fraction on the mechanical properties of epoxy-clay nanocomposites

The influence of processing parameters and particle volume fraction was experimentally studied for epoxy clay nanocomposites. Nanocomposites were prepared using onium ion surface modified montmorillonite (MMT) layered clay and epoxy resin (DEGBF). Two different techniques were used for dispersing the clay particles in the epoxy matrix, viz. high-speed shear dispersion and ultrasonic disruption. The volume fraction of clay particles was systematically varied from 0.5 to 6%, and mechanical properties, viz. flexural modulus and fracture toughness, were studied as a function of clay volume fraction and the processing technique. The flexural modulus was observed to increase monotonously with increase in volume fraction of clay particles, while, the fracture toughness showed an initial increase on addition of clay particles, but a subsequent decrease at higher clay volume fractions. In general, nanocomposites processed by shear mixing exhibited better mechanical properties as compared to those processed by ultrasonication. Investigation by X-ray diffraction (XRD) revealed exfoliated clay structure in most of the nanocomposites that were fabricated. Morphologies of the fracture surfaces of nanocomposites were studied using a scanning electron microscopy (SEM). Presence of river markings at low clay volume fractions provided evidence of extrinsic toughening taking place in an otherwise brittle epoxy.     

Effect of Amino alcohol functionalized polyethylene as compatibilizer for LDPE/EVA/clay/flame-retardant nanocomposites

The synergistic effect of organo-modified montmorillonite (Nanomer I28E and Cloisite 20A) and metal hydroxides (magnesium hydroxide MH and alumina trihydrate ATH) as flame retardants in LDPE/EVA nanocomposites compatibilized with amino alcohol grafted polyethylene (PEgDMAE) was studied. Morphological characterization of nanocomposites was carried out by means of X-ray diffraction (XRD) and scanning transmission electron microscopy (STEM). Flame-retardant properties of nanocomposites were evaluated by the UL-94 horizontal burning and cone calorimeter tests and limiting oxygen index (LOI). Thermal degradation behavior was analyzed with a Fourier transform infrared coupled with the thermogravimetric analyzer (TG-FTIR). The XRD analysis showed a displacement of the d₀₀₁ plane characteristic peak of clay to lower angles, which indicates an intercalated–exfoliated morphology. From STEM images it was observed a good dispersion of flame retardants (MH and ATH) throughout the polymer matrix which was reflected in flame-retardant properties. TG-FTIR showed a better thermal stability of nanocomposites and the gases evolved during combustion showed an important reduction. Based on thermal stability and thermal degradation results, the flame-retardant mechanism of LDPE/PEgDMAE/EVA/Clay/MH nanocomposites was proposed.     

Characterization of poly(ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate-<Emphasis Type="Italic">co</Emphasis>-carbon monoxide)/layered silicate clay hybrids obtained by melt mixing

In recent times, polymer-layered silicate nanocomposites have drawn a great deal of attention because they often exhibit tremendous improvements in material properties compared with virgin polymers or conventional micro- or macro-composites. In the present study, nanocomposites were developed from organically modified clay and poly(ethylene-co-vinyl acetate-co-carbon monoxide) by melt mixing. FTIR spectroscopy reveals that the interaction between the organoclay and EVACO is thermodynamically favored. High resolution wide angle X-ray diffraction and transmission electron microscopy were used to study the morphology of the nanocomposites. Elemental mapping by scanning electron microscopy indicates good dispersion and distribution of the nanoclay in EVACO matrix. The mechanical properties of the nanocomposites are optimum at a clay loading of 3%.     

Morphological and thermomechanical characterization of thermoplastic starch/montmorillonite nanocomposites

A combination of starch and clay for the preparation of nanocomposite materials is proposed. In this work, starch was plasticized by pequi (Caryocar brasiliense) oil, and thermoplastic starch (TPS)/montmorillonite (MMT) nanocomposites were analyzed by X-ray diffraction (XRD), thermogravimetry (TG), thermomechanical analyses (TMA) and scanning electron microscopy (SEM). Exfoliated and intercalated nanocomposites were found to be dependent on MMT content. Exfoliation is the predominant mechanism of clay dispersion for low filler loading. Increase of the clay loading (>5 wt.%) causes intercalation. The introduction of low content (?5 wt.%) of MMT improves the thermal stability and the stiffness of the materials. There is a limit content of clay that can be added to improve the thermal and thermomechanical properties of the composites. Beyond that value the composite presents properties below the original polymer.     

Morphology,rheology and mechanical properties of polypropylene/ethylene–octene copolymer/clay nanocomposites: Effects of the compatibilizer

The objective of this study was to investigate the effects of two compatibilizers, namely maleated polypropylene (PP-g-MA) and maleic anhydride grafted poly (ethylene-co-octene) (EOC-g-MA), on the morphology and thus properties of ternary nanocomposites of polypropylene (PP)/ethylene–octene copolymer (EOC)/clay nanocomposite. In this regard the nanocomposites and their neat polymer blend counterparts were processed twice using a twin screw extruder. X-ray diffraction, transmission electron microscopy, Energy dispersive X-ray spectroscopy, and scanning electron microscopy were utilized to characterize nanostructure and microstructure besides mechanical and rheological behaviors of the nanocomposites. Clay with intercalated structure was observed in EOC phase of the PP/EOC/clay nanocomposite. Better dispersion state of the intercalated clay in EOC phase was observed by adding EOC-g-MA as a compatibilizer. On the other hand, adding PP-g-MA resulted in migration of the intercalated clay from the EOC to the PP and to the interface regions. It was also demonstrated that the elastomer particles became smaller in size where clay was present. The finest and the most uniform morphology was found in the PP/EOC/clay nanocomposite. In addition, the rheological results illustrated a higher complex viscosity and storage modulus for PP/EOC/PP-g-MA/clay nanocomposite in which clay particles were present in the matrix. Mechanical assessments showed improvements in the toughness of the nanocomposites with respect to their neat blends, without significant change in stiffness and tensile strength values. These results highlight a toughening role of clay in the polymer blend nanocomposites studied.     

Effect of organoclay addition on the two-body abrasive wear characteristics of polyamide 6 nanocomposites

Polymer clay nanocomposites (PCN) exhibit improved mechanical properties due to nanolevel dispersion of clay in the polymer matrix. They also exhibit good tribological performance under dry sliding conditions. Abrasive wear behaviour of these materials would be different from dry sliding behaviour as the mechanisms of the both are entirely different. Hence the abrasive wear behaviour of these materials needs to be investigated. The abrasive wear characteristics of polyamide 6 nanocomposites, with 1, 3 and 5% (wt.) clay prepared by melt intercalation technique, under two-body abrasive wear conditions have been reported. Abrasive wear tests were conducted using a pin-on-disc tribometer containing an abrasive counterface. All the polyamide nanocomposites investigated exhibited a low abrasive wear resistance compared with pristine Nylon. The wear performance of the nanocomposites was correlated with the mechanical properties. Dominant ploughing and cutting wear were observed in polymer clay nanocomposites. The amount of clay present alters the wear mechanism.     

The location and extent of exfoliation of clay on the fracture mechanisms in nylon 66-based ternary nanocomposites

The primary focus of this work is to elucidate the location and extent of exfoliation of clay on fracture (under both static and dynamic loading conditions) of melt-compounded nylon 66/clay/SEBS-g-MA ternary nanocomposites fabricated by different blending sequences. Distinct microstructures are obtained depending on the blending protocol employed. The state of exfoliation and dispersion of clay in nylon 66 matrix and SEBS-g-MA phase are quantified and the presence of clay in rubber is shown to have a negative effect on the toughness of the nanocomposites. The level of toughness enhancement of ternary nanocomposites depends on the blending protocol and the capability of different fillers to activate the plastic deformation mechanisms in the matrix. These mechanisms include: cavitation of SEBS-g-MA phase, stretching of voided matrix material, interfacial debonding of SEBS-g-MA particles, debonding of intercalated clay embedded inside the SEBS-g-MA phase, and delamination of intercalated clay platelets. Based on these results, new insights and approaches for the processing of better toughened polymer ternary nanocomposites are discussed.     

Effects of modified Clay on the morphology and thermal stability of PMMA/clay nanocomposites

The potential to improve the mechanical, thermal, and optical properties of poly(methyl methacrylate) (PMMA)/clay nanocomposites prepared with clay containing an organic modifier was investigated. Pristine sodium montmorillonite clay was modified using cocoamphodipropionate, which absorbs UVB in the 280–320 nm range, via ion exchange to enhance the compatibility between the clay platelets and the methyl methacrylate polymer matrix. PMMA/clay nanocomposites were synthesized via in situ free-radical polymerization. Three types of clay with various cation-exchange capacities (CEC) were used as inorganic layered materials in these organic–inorganic hybrid nanocomposites: CL42, CL120, and CL88 with CEC values of 116, 168, and 200 meq/100 g of clay, respectively. We characterized the effects of the organoclay dispersion on UV resistance, effectiveness as an O₂ gas barrier, thermal stability, and mechanical properties of PMMA/clay nanocomposites. Gas permeability analysis demonstrated the excellent gas barrier properties of the nanocomposites, consistent with the intercalated or exfoliated morphologies observed. The optical properties were assessed using UV–Visible spectroscopy, which revealed that these materials have good optical clarity, UV resistance, and scratch resistance. The effect of the dispersion capability of organoclay on the thermal properties of PMMA/clay nanocomposites was investigated by thermogravimetric analysis and differential scanning calorimetry; these analyses revealed excellent thermal stability of some of the modified clay nanocomposites.     

Dielectric properties of montmorillonite clay filled poly(vinyl alcohol)/poly(ethylene oxide) blend nanocomposites

Organic–inorganic nanocomposites of poly(vinyl alcohol) (PVA)–poly(ethylene oxide) (PEO) blend filled with montmorillonite (MMT) nanoclay up to 10 wt.% concentration were synthesized by aqueous solution-cast technique. The complex dielectric function, electrical conductivity, electric modulus and impedance spectra of the nanocomposites were measured in the frequency range 20 Hz–1 MHz at ambient temperature. A direct correlation was observed between the real part of dielectric function and the mean relaxation time of the polymer chain segmental dynamics, with the exfoliated and intercalated MMT clay structures, and the extent of miscibility between PVA and PEO due to hydrogen bonded bridging through exfoliated MMT clay nanosheets. The large increase of dielectric relaxation time revealed that the dispersed exfoliated nanoscale MMT clay in the polymers blend matrix produces a large hindrance to the polymer chain dynamics. Results confirm that the real part of dielectric function of the nanocomposites can be tailored by varying amount of MMT clay filler for their use as nanodielectric materials in the microelectronic technology.     

Evaluation of the influence of nanoparticles' shapes on the formation of poly(lactic acid) nanocomposites obtained employing the solution method

PLA nanocomposites were prepared by adding organically modified montmorillonite clay (Viscogel B8) and a homoionic clay (NT25), as well as unmodified silica (A200) and modified organic silica (R972). All nanocomposites were obtained by the solution intercalation method using chloroform as a solvent. The materials obtained were essentially characterized by X-ray diffraction and low-field nuclear magnetic resonance relaxometry, through the measurement of proton spin-lattice relaxation time (LF-NMR). Both clays and silicas used to obtain the polymeric nanocomposites showed good dispersion in the polymeric matrix. The relaxation times were distinct for each type of nanoparticle used. The nanocomposite formed with homoionic clay, NT25, presented an increase in the relaxation data, indicating formation of intercalated nanocomposites, contrary to the action of the organoclay Viscogel B8, which preferentially formed an exfoliated nanocomposite. When unmodified and organo-modified silica were added to PLA, an increase in the relaxation time of the polymer matrix was observed. According to the relaxation data, the organosilica R972 dispersed better in the polymeric matrix and consequently interacted better than the A200.