Effect of montmorillonite filler on structural and electrical properties of polymer nanocomposite electrolytes

Polymer–clay nanocomposites consisting of polymer (polyethylene oxide) and NaI as salt with different concentration of organically modified Na⁺-montmorillonite (DMMT) have been fabricated and characterized. X-ray diffraction analysis shows that the polymer–salt complexes have been intercalated into the nanometric silicate layers of DMMT. Fourier transform infrared analysis shows that the polymer structure in the clay interlayer is similar to that of the polymer–salt complexes, and there is a strong interaction between the polymer–salt complexes and clay layers. A study of surface morphology using scanning electron microscopy reveals that microstructure of composites is affected by clay addition. Complex impedance analysis was used to calculate the bulk resistance of the composites. An enhancement in the conductivity of about one order of magnitude has been observed on 5% clay addition compared to that of the polymer–salt complexes, and it decreases monotonically for higher clay concentration. The effect of clay concentration on the structural and physical properties of polymer nanocomposites is well correlated.     

Improved Biodegradation and Thermal Properties of Poly(lactic acid)/Layered Silicate Nanocomposites

Poly(lactic acid) (PLA)/layered silicate nanocomposites have successfully been prepared using the solution route. Two types of organically modified nanoclays, namely, MEE and MAE have been used. The nanostructure, as observed from wide angle X-ray diffraction, indicates an intercalated hybrid for both PLA–MEE and PLA–MAE, and depends on the type of organic modifier used. Intercalation is higher in PLA–MEE as compared to PLA–MAE system. Crystallite dimensions of nanoclays and nanocomposites have been calculated from the Scherrer equation. Crystallite size of nanocomposites is higher than that of pure nanoclay, which in turn affects the properties of the nanocomposites. Wide angle X-ray diffraction patterns also suggest that PLA and its nanocomposites are predominantly amorphous before annealing but, after annealing, PLA and its nanocomposites are fairly crystalline. The crystallinity of the nanocomposites has decreased in comparison to neat polymer suggesting some sort of interaction between organically modified nanoclay and polymer. The nanohybrids show significant improvement in the thermal properties of the matrix as compared to pristine polymer. The nature of interaction between nanoparticles and polymer is higher in PLA–MEE against PLA–MAE, as evident from the lower value of the heat of fusion in the case of PLA–MEE. The nanoparticles act as nucleating agent, and thereby, control the spherulite dimension of the matrix. The comparison of biodegradation of PLA and its nanocomposites has been studied in several media. Biodegradability of PLA has significantly been enhanced in the presence of nanoclays which has been explained on the basis of amorphous content in the polymer matrix. Finally, the regulated biodegradation has been discussed.     

Synthesis and characterization of PMMA/silylated MMTs

Commercially available Sodium clay (Dellite HPS) and organo-clay (Dellite 72T) are modified via a silylation reaction. These silylated clays are characterized by IR, XRD, thermogravimetric analyses, and their equilibrium contact angles are measured. They are used to prepare nanocomposites at different loading percentage (1, 3, 5% wt) by in situ intercalative polymerization of Methyl methacrylate and morphology and thermal properties of nanocomposites are examined. SEM images of nanocomposites fractured surface show the absence of clays aggregates, confirming a good dispersion and distribution of montmorillonites in the polymer matrix. The effects of modified clays on the thermal properties of nanocomposites are analyzed by differential scanning calorimetry and thermogravimetric analyses showing an increase of glass and decomposition temperatures of all nanocomposites respect to homopolymer ones. The best results are obtained in the presence of silylated montmorillonites, clearly the organosilane improves the compatibility between polymer matrix and clay and as effect the properties of nanocomposites.     

Effect of interfacial interaction on the structure and rheological properties of polyamide-6/clay nanocomposites

A series of polyamide-6 (PA6)/layered silicate (clay) nanocomposites were prepared via direct melt compounding using a conventional single screw extruder, and then the effect of interfacial interaction on the characteristic internal structure and rheological properties of PA6/clay nanocomposites was investigated. XRD diffractograms indicated a large extent of exfoliation of the layered silicate entering into a strong interaction with PA6. The formation of such morphology was further supported by TEM images. In addition, various rheological properties were interpreted in conjunction with morphological characteristics depending on interfacial interaction between PA6 and the layered silicate.     

Clay dispersion and physical properties of melt-blended PP/organoclay nanocomposites: effect of interfacial interaction

Melt blending of maleic anhydride-grafted polypropylene (PPgMA) and organically modified clay nanocomposites was first carried out in a plasticorder. The structure was investigated with x-ray diffraction (XRD) and transmission electron microscopy (TEM). The interfacial interaction between PB3150 compatibilizer and I30 clay surface was altered with the addition of different loadings of PB3150. It was found at the PB3150 compatiblizer gave rise to a high degree of clay dispersion beyond the PB3150/I30 weight ratio of 3. We then also modified polypropylene/organoclay nanocomposites with different loadings of PB3150 on a twin-screw extruder. When the PB3150 loading exceeded 15 wt%, extensive exfoliation of clay was observed. The relative complex viscosity curves also revealed a systematic trend with the extent of exfoliation and showed promise for quantifying the hybrid structure of the nanocomposites. Mechanical properties and thermal stability were determined by tensile and impact tests and thermogravimeric analysis (TGA), respectively. Although high loading of PB3150 leads to better clay dispersion in the polypropylene nanocomposites, it causes deterioration in both mechanical and thermal properties of the hybrid systems.     

Morphology and thermal properties of clay/PMMA nanocomposites obtained by miniemulsion polymerization

Miniemulsion polymerization was used as the synthetic method to produce clay/poly(methyl methacrylate) nanocomposites. Two kinds of interfacial interactions clay–polymer particle were observed by electron microscopy, one where the polymer particles are adhered on the surface of the larger fragments of clay, and another where nanometric fragments of clay are encapsulated by polymer particles. Variations in the glass transition temperature (T_g) and thermomechanical properties of the matrix, as function of clay content, were observed. In particular, at the highest clay loading (1.0 wt%) depression of T_g and thermomechanical properties were observed. The increased clay–polymer matrix interfacial area appears to be the conditioning factor that determines such behavior.     

Thermal Degradation Behavior,Permeation Properties and Impact Response of Polyethylene/Organo-montmorillonite/(Ethylene Methacrylic Acid) Ternary Nanocomposites

Through this work we explored the effect of melt compounding a commercial grade of HDPE with organoclays of different precedence using EMAA as compatibilizing agent on the thermal behavior, barrier properties and biaxial impact response of composites. Morphology was examined by XRD and TEM. Crystalline structure was examined by DSC. Thermal behavior was evaluated by TGA. Barrier properties to low-molecular-weight penetrants were experimentally determined employing a gravimetric technique. Mechanical properties under impact conditions were evaluated by instrumented puncture tests. Intercalated nanocomposites were obtained. Throughout the thermal degradation of the nanocomposites in oxidant atmosphere a charring process of the PE, which is normally a non-char-forming polymer, was observed. The addition of OMMT improves barrier properties due to its contribution to tortuosity path and to the reduction of molecular mobility. Impact properties were only slightly reduced by nanocomposite formation. Results demonstrate that EMAA did not improve exfoliation, but it enhanced polymer–organoclay interactions giving rise to better thermal and permeation properties, without detriment of impact response.     

Clay‐induced Preferred Orientation in Polyethylene/Compatibilized Clay Nanocomposites

Nanocomposites of the organically modified clay Cloisite^® 15A (CL15A) dispersed in HDPE‐g‐MA were prepared by melt‐compounding. Microcomposites of the same clay with HDPE were also obtained with similar procedures. The spherulitic morphology of the polymer matrix was evidenced by optical microscopy in thin films, whereas the structure of the up to 2‐mm–thick, compression‐molded samples was investigated by WAXD and SAXS. Preferred orientation of both the clay and the HDPE crystallites were evidenced in the microcomposites and, to a greater extent, in nanocomposites, whereas in HDPE and HDPE‐g‐MA control specimens hardly any anisotropy was detected. The degree of orientation of PE crystals increases with CL15A concentration, but also with clay exfoliation, with lower cooling rates and decreasing sample thickness. The orientation of the clay platelets parallel to the compression‐molded surface appears to be determined by the platelets anisotropy and by shear in the mixing and the compression‐molding procedures. In turn, it determines the preferred uniaxial orientation of HDPE crystals, which have their crystallographic a axis orthogonal, while b and c are coplanar, to the sample surface, as already reported in the literature for melt‐crystallized HDPE films with thickness below 0.3 μm. It is proposed that the HDPE orientation results from confined crystallization between parallel clay platelets which are on average less than 0.1 μm apart. Simple models, qualitatively accounting for the observed orientation of HDPE, are discussed. Organized architectures resulting from confined crystallization of the polymer matrix in nanocomposites with appropriate anisotropic fillers may be a general feature, important in determining key properties of these systems.     

Micro-molding with ultrasonic vibration energy: New method to disperse nanoclays in polymer matrices

Ultrasound technology was proved as an efficient processing technique to obtain micro-molded specimens of polylactide (PLA) and polybutylene succinate (PBS), which were selected as examples of biodegradable polyesters widely employed in commodity and specialty applications. Operational parameters such as amplitude, molding force and processing time were successfully optimized to prepare samples with a decrease in the number average molecular weight lower than 6%.Ultrasonic waves also seemed an ideal energy source to provide effective disaggregation of clay silicate layers, and therefore exfoliated nanocomposites. X-ray diffraction patterns of nanocomposites prepared by direct micro-molding of PLA or PBS powder mixtures with natural montmorillonite or different organo-modified clays showed the disappearance of the 0 0 1 silicate reflection for specimens having up to 6 wt.% clay content. All electron micrographs revealed relatively homogeneous dispersion and sheet nanostructures oriented in the direction of the melt flow.Incorporation of clay particles during processing had practically no influence on PLA characteristics but enhanced PBS degradation when an organo-modifier was employed. This was in agreement with thermal stability data deduced from thermogravimetric analysis. Cold crystallization experiments directly performed on micro-molded PLA specimens pointed to a complex influence of clay particles reflected by the increase or decrease of the overall non-isothermal crystallization rate when compared to the neat polymer. In all cases, the addition of clay led to a clear decrease in the Avrami exponent.     

Thermal,Mechanical, and Rheological Characterization of Polylactic Acid/Halloysite Nanotube Nanocomposites

Halloysite nanotube (HNT) clay and biodegradable polylactic acid (PLA) nanocomposites were fabricated by a melt-blending method with five different clay levels (1, 3, 5, 7, and 9 wt%). The effect of HNT loading on the thermal and mechanical properties of the PLA/HNT nanocomposites was examined by thermogravimetric analysis and universal tensile testing, respectively. Morphological characteristics were investigated by transmission electron microscopy. The composites' melt rheological characteristic analyses were conducted using a rotational rheometer in both steady-shear and oscillatory dynamic testing modes. The data were found to be well-analyzed using the Carreau model, Cox–Merz rule, modified Cole–Cole plot, and van Gurp–Palmen plot.     

Rheology,Crystallization, Mechanical and Barrier Properties of Polyamide 6/66 Nanocomposites with Exfoliated Organoclays

Nylon copolymer/clay (NC) nanocomposites were prepared using PA6/66 as a matrix and organoclay as a nanofiller through a two-step melt-compounding method. It was shown that the organoclay flakes were well exfoliated and dispersed in the PA6/66 matrix. With increasing content of organoclay, the apparent shear viscosity and the entrance pressure drop of the NC nanocomposites decreased whereas the corresponding shear activation energy increased, suggesting that the NC nanocomposites were suitable to be used in shear-flow rather than extension-flow related processes. Investigations of the crystallization behaviors of the NC nanocomposites indicated that the organoclay addition was capable of facilitating the γ-form crystal formation, which is suggested to be due to the restriction effect of the organoclay on the PA6/66 chain motion during the crystallization. Compared to the neat PA6/66, the tensile strength and elongation at break of the NC nanocomposites were both enhanced at an appropriate content of the organoclay. In addition, the NC nanocomposites exhibited enhanced barrier properties due to the high specific surface area and the homogeneous dispersion of the organoclay.     

Effect of sodium alginate modification of graphene (by ‘anion-π’ type of interaction) on the mechanical and thermal properties of polyvinyl alcohol (PVA) nanocomposites

Layered aligned dispersion of graphene in graphene/polyvinyl alcohol (PVA) nanocomposites is prepared in the form of films through simple solution processing route. The results indicate that there exist an interfacial interaction between PVA and graphene because of hydrogen bonding. This is responsible for the change in structure of PVA (such as decrease in the level of crystallization) and exhibiting ductile PVA nanocomposite film with improved tensile modulus, tensile strength, and thermal stability. Moreover, to improve the mechanical properties of PVA nanocomposites, graphene is successfully modified using a non-covalent modifier, sodium alginate (SA) and there exist an ‘anion-π’ type of interaction in between SA and graphene. The modification results in finer dispersion of the graphene in PVA/SA-m-graphene nanocomposites. In addition, there exist a hydrogen bonding in between PVA and SA. This has resulted in the remarkable improvement in mechanical properties of PVA/SA-m-graphene nanocomposites as compared to pure PVA and PVA/graphene nanocomposites. The increase in mechanical properties of PVA/SA-m-graphene nanocomposites is achieved through better load transfer from graphene to polymer matrix, despite decrease in crystallinity of PVA. Improvement in tensile modulus and tensile strength is highest at 0.5 wt.% of SA-modified graphene in PVA/SA-m-graphene nanocomposites because of finer dispersion of graphene and is 62 and 40% higher than that of pure PVA. Addition of SA-modified graphene also improves the thermal stability of PVA/SA-m-graphene nanocomposites remarkably as compared to unmodified graphene PVA nanocomposites.     

Investigating the effect of interphase and surrounding resin on carbon nanotube free vibration behavior

The free vibration analysis of a carbon nanotube (CNT) embedded in a volume element is performed using 3D finite element (FE) and analytical models. Three approaches consist of molecular and continuum mechanics FE methods and continuum analytical method are employed to simulate the CNT, interphase region and surrounding matrix. The bonding between CNT and polymer is treated as non-perfect bonding using van der Waals and triple phase material interaction in first and second approaches. In analytical approach a perfect bonding is assumed between nanotube and matrix. First, natural frequencies of CNT under different boundary conditions and aspect ratios are obtained by three approaches and the results are compared with published data. The results show the frequency response variations of CNT in GHz to THz range. Subsequently, vibration behaviors of CNT/polymer are evaluated and the results revealed the importance of interphase region role in the performance of nanocomposites. The results also showed the convergence of the natural frequencies for 1–2.5% of CNT volume in high aspect ratios using three methods, so that the interphase effects is negligible. In addition, it is observed that the molecular method due to interphase role has proper performance in vibration behavior investigation of volume elements.     

A Kinetic Study of the Thermal Degradation of Nylon-6/Attapulgite Nanocomposites

The thermal degradation behavior of nylon-6 (PA6) and PA6/attapulgite (ATP) nanocomposites was investigated by thermogravimetric analysis under non-isothermal conditions at various heating rates in nitrogen. It is suggested that during thermal degradation, ATP, as a protective barrier, can slow down degradation of polymer, but the catalytic effects of structural water and hydroxyl groups may accelerate the degradation of PA6. The combination of these two effects determined the final thermal stability of nanocomposites. The apparent activation energies of the samples were evaluated by the Kissinger and Flynn–Wall–Ozawa methods. The results showed that the presence of ATP adversely affected the thermal stability of PA6. The degradation activation energies of PA6/ATP nanocomposites decreased monotonically with increase in ATP content; thus, it is suggested that the ATP has a disadvantageous effect on the thermal stability of PA6.     

Polymer–Clay Nanocomposites Based on Blends of Various Types of Polyethylenes and PE-g-MA: Morphology,Thermal Properties,Microhardness, and Transparency

Polymer–clay nanocomposites have been prepared by melt blending of commercial organoclay Cloisite 15A with blends of polyethylenes (PE) and maleic-anhydride-grafted PE (PE/PE-g-MA) with wide range of composition. Three types of PE/PE-g-MA blends with different molecular structure, namely blends of high-density PE (HD) with HD-g-MA (HDMA), blends of low-density PE (LD) with LD-g-MA (LDMA), and blends of linear low-density PE (LL) with LL-g-MA (LLMA) were used. The influence of the molecular structure of the PE matrixes and the compatibility between the blend components on the morphology of the nanocomposites was studied. The thermal properties, microhardness, and transparency of the nanocomposites were investigated. The influence of the degree of exfoliation/intercalation on the materials characteristics is discussed.     

Effects of Modifier Concentration on Structure and Viscoelastic Properties of Copolyester/Clay Nanocomposites

Abstract

Poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate)(PETG)/clay nanocomposites were prepared via melt intercalation technique. The effects of concentration of the organic modifier in the clay on the properties of the nanocomposites were studied. Three clays modified using the same alkyl ammonium modifier, but differing in modifier concentration, are used for this purpose. The nanocomposites are characterized using wide‐angle x‐ray diffraction for their structure. Dynamic mechanical analysis of these nanocomposites is also studied to investigate their viscoelastic behaviors. The x‐ray diffraction study shows an increase in the interlayer spacing of organically modified clays as compared to that of Na⁺ clay. The extent of increase in the interlayer spacing is dependent on the concentration of organic modifier used to modify the montmorillonite. The presence of well‐defined diffraction peaks and the observed increase in the interlayer spacing in the nanocomposites imply the formation of an intercalated hybrid. Dynamic mechanical properties show an increase in the storage modulus of the nanocomposite over the entire temperature range studied, as compared to the pristine polymer. Investigation of the rubbery plateau modulus confirms the reinforcing effect of organically modified clay. The observed enhancement in the modulus was greater for the clay with the lowest content of the organic modifier. These results indicate that in nanocomposites, apart from the compatibility of the organic modifier with the polymer, its concentration in the interlayer also plays a critical role in the structure development and thus in the enhancement of the properties. The nanocomposites showed reduced damping, which was governed by the modifier concentration in the clay.     

Prediction of complex dielectric constants of polymer-clay nanocomposites

In this Letter, simple theoretical models are presented to predict the influence of aspect ratio, orientation, distribution, and interphase of layered silicates on the dielectric properties of polymer-clay nanocomposites. The predictions are in good agreement with experimental data. The results show that the morphology of the clay fillers and the thickness and dielectric properties of the interphases play an important role in determining the dielectric properties of polymer-clay nanocomposites.     

Effect of Rubber Content of ABS on the Mechanical Properties of ABS/Clay Nanocomposites

One approach to improve the impact strength of acrylonitrile–butadiene–styrene (ABS)/clay nanocomposites is to increase rubber content. To investigate the effect of the rubber content of ABS on the mechanical properties of the ABS/clay nanocomposites, other parameters were fixed and ABS/clay nanocomposites containing various rubber contents were prepared in this study. Also the effect of the UV stabilizer on the mechanical properties of ABS/clay nanocomposite was studied. For addition of 3 wt% clay, ABS nanocomposite with 35 wt% content of rubber displayed the highest reinforcement ratio for tensile properties and impact strength.     

Structure and Properties of Polypropylene/Polyolefin Elastomer/Organic Montmorillonite Nanocomposites

The crystallinity, mechanical properties, and thermal stability of polypropylene (PP)/organic montmorillonite (OMMT) and PP/polyolefin elastomer (POE)/OMMT composites, with polypropylene-g-maleic anhydride/styrene (PPMS) as a compatibilizer for both, were compared. The results showed that the strong interaction between the clay platelets and compatibilizer, which were generated by the maleic anhydride (MAH), improved the compatibility of the polymer matrices with the OMMT. A unique lamellar, flocculated structure of OMMT was formed after introduction of the POE. The highly dispersed clay layers could act as nucleating agents, resulting in smaller spherulites and higher crystallization temperatures. Compared with pure PP, the PP/OMMT nanocomposite showed enhanced mechanical properties and thermal stability; however, the PP/POE/OMMT had the best impact toughness.     

Organo clay mineral-melted polyolefin nanocomposites Effect of surfactant/CEC ratio

Clay mineral-polymer nanocomposites are prepared by dispersing solid organo clay minerals in two different melted polyolefin matrices, namely polyethylene (PE) and ethylene vinyl acetate (EVA). The organo clay minerals are prepared by adding different amounts of surfactant corresponding to the CEC of the pristine clay mineral. The characteristics of the organo clay minerals are obtained by XRD, IR spectroscopy, TGA, and swelling volume measurements. The amount of added surfactant has a direct effect on the interlayer separation and organophilicity-hydrophilicity balance of the clay mineral, evidencing a particular behavior transition about OMt1.2 The intercalation of PE is found to be dependent on the interlayer distance of the organo clay minerals while EVA intercalates in the organo clay minerals whatever the amount of surfactant (> 0.5CEC), leading to the same interlayer spacing (4 nm). The polymer intercalation is more homogeneous in clay minerals having high surfactant loading corresponding to 1.5 and 2 CEC. Cone calorimeter results of the studied nanocomposites show a PHRR reduction of 32% for PE-OMt1.5 and of 47% for EVA-OMt1. For both polymers, the best compromise between mechanical and thermal properties, is obtained for organoclay filler obtained with an amount of added surfactant in a range 1-1.5 CEC.