Polypropylene/clay nanocomposites prepared with masterbatches of polypropylene ionomer and organoclay

Polypropylene (PP) ionomers were obtained by the neutralization of maleic anhydride groups in a maleated PP of which maleic anhydride content was 1 wt%; these were studied as vehicle resins for the masterbatches of an organoclay for PP nanocomposites. PP/clay nanocomposites were prepared by melt mixing of PP with the masterbatches employing a twin screw extruder. Intercalation and/or exfoliation of the organoclay in the PP nanocomposites were observed. It was found that the PP nanocomposite prepared with the masterbatch of an organoclay and the PP ionomer obtained by 75% neutralization of maleic anhydride groups in the maleated PP showed the largest improvement in dispersion of organoclay. Very large increase of Young's modulus was observed in the nanocomposites with the PP ionomer obtained by 75% neutralization of maleic anhydride groups in the maleated PP. The improvements in the dispersion and mechanical properties were attributed to strong interactions between ionic groups of the PP ionomer and ionic surfactants of the organoclay.     

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.     

Preparation and Properties of Epoxy‐Clay Nanocomposites

Epoxy‐clay nanocomposites were synthesized to examine the effects of adding different contents of nanoclays on the physical, mechanical, and thermal properties of the epoxy resin system used in composite pipes manufacturing. Diglycidyl ether of bisphenol‐A (epoxy) with a cycloaliphatic amine heat curing hardner was reinforced by 1–7 wt.% of an organically modified type of montmorillonite. SEM results showed the change in failure of epoxy from brittle to tough mode by addition of nanoclays. X‐ray results indicated some degree of exfoliation by 1 wt.% clay and a decrease in d‐spacing in higher clay loadings after that. The heat‐distortion temperature of epoxy-clay nanocomposites increased from 125.5 to 138.7°C with 3 wt.% organoclay loading. Tensile and flexural modulus increased with increasing clay loading in this type of nanocomposite, but addition of organically modified clay decreased the tensile and flexural strengths and tensile elongation at break. Addition of 7 wt.% nanoclay improved the impact strength by 25.6%.     

Influence of Compatibilizer-Type and Processing Approach on the Dispersion of OMMT in High-Density Polyethylene Matrix

High-density polyethylene/organoclay nanocomposites were prepared via melt intercalation in an internal mixer using both a direct mixing and master batching method. Two types of maleic anhydride grafted polyethylene, high-density polyethylene grafted maleic anhydride, and linear low-density polyethylene grafted maleic anhydride, (HDPE-g-MA, LLDPE-g-MA) were used as compatibilizers to enhance the dispersibility of nanoclay in HDPE. Dispersion of organoclay in the nanocomposites was characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), and rheological mechanical spectroscopy (RMS). Effects of clay content and degree of clay dispersion on the rheological and tensile properties were also investigated. Furthermore, the effect of order of mixing on the dispersion and distribution of the clay layers was studied. The obtained results showed that organoclay in the nanocomposites were dispersed homogeneously and exfoliated better when HDPE-g-MA and the direct mixing route were used. Although in the master batching method clay intercalated better, clay layers chiefly remain in compatibilizer rich areas. On the other hand, direct mixing was observed to lead to clay particles being dispersed in the HDPE matrix or at the interface of the matrix and compatibilizer and, consequently, better improvement in the tensile modulus was achieved. It was determined that the compatibilizer with the higher miscibility with the matrix was the key factor for achieving better exfoliation of clay sheets.     

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.     

Melt intercalation and exfoliation of maleated polypropylene modified polypropylene nanocomposites

Melt blending of maleic anhydride-grafted polypropylene (PPgMA) and organically modified clay nanocomposites were first prepared in a plasticorder. PPgMAs, including PB3150, PB3200, PB3000, and E43, with a wide range of MA content and molecular weight were used. The structure was investigated with X-Ray diffraction (XRD) and transmission electron microscopy (TEM). PPgMA compatiblizers gave rise to similar degree of dispersion beyond the weight ratio of 3 to 1 with the exception of E43, which had the highest MA content and the lowest molecular weight. It was found that thermal instability and high melt index were responsible for ineffective modification by E43. Furthermore, PPgMA with lower molecular weight and higher melt index had to be compounded at lower mixing temperature in order to achieve a reasonable level of torque for clay dispersion. We then modified polypropylene/organoclay nanocomposites with different levels of PPgMA compatibilizers on a twin-screw extruder. The PP/E43/clay system, as shown through XRD patterns and TEM observation, yielded the poorest clay dispersion among the compatibilizers under investigation. 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 dynamical mechanical analysis (DMA) and thermogravimeric analysis (TGA), respectively. Though PPgMA with lower molecular weight would lead to better clay dispersion in the polypropylene nanocomposites, it caused deterioration in both mechanical and thermal properties of the hybrid systems.     

Synthesis of poly(butylene succinate) nanocomposites via in-situ interlayer polymerization: thermo-mechanical properties and morphology of the hybrid fibers

A series of poly(butylene succinate) (PBS) nanocomposites with the organoclay C₁₂PPh-Mica were synthesized by using the in-situ interlayer polycondensation of 1,4-butanediol with succinic acid. The PBS nanocomposites were melt-spun to produce monofilaments with various organoclay contents and draw ratios (DRs). The thermo-mechanical properties and morphologies of the PBS nanocomposites were determined using differential scanning calorimetry, thermogravimetric analysis, wide angle X-ray diffraction, transmission electron microscopy, and a universal tensile machine. Some of the clay particles were found to be well dispersed in the PBS matrix, with some agglomerated at a size level greater than approximately 20 nm. The thermal degradation properties of undrawn PBS hybrid fibers were found to improve with increasing clay content. The ultimate tensile strengths and initial moduli of the hybrid fibers increased with increasing clay content at DR = 1. However, the ultimate strengths were found to decrease markedly with increases in DR from 1 to 6. In contrast to the trend for the tensile strengths, the initial moduli of the hybrid fibers increased only slightly with increases in DR up to 6.     

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.     

Water Expandable Polystyrene-Organoclay Nanocomposites: Role of Clay and Its Dispersion State

A published process for preparing expandable polystyrene containing water as a blowing agent was applied to synthesize water expandable polystyrene-organoclay nanocomposites (WEPS-OCN). Organoclay was uniformly dispersed in styrene monomer. During suspension polymerization, water was trapped in the polystyrene (PS) matrix through the use of starch, ending up with spherical PS-organoclay beads. By selecting organoclays with various surfactants and modifier concentrations, different distribution states of nanoclay in the PS matrix, from cluster (poor dispersion) to either intercalated (limited dispersion) or exfoliated (full dispersion) were obtained. The incorporation of organoclay led to higher water content in the expandable beads. However, as expected, the flammability of the expanded product was increased with organoclay content. Furthermore, the results showed that the average unexpanded bead size, density of preexpanded beads, foam cell morphology, and flammability were directly influenced by the dispersion status of the organoclay. The best results were obtained when full dispersion (exfoliation) of nanoclay in PS matrix occurred.     

Influence of Surfactant Functional Groups on Morphology and Rheology of Polypropylene/Organoclay Nanocomposites

Three surfactants, with the same long alkyl tail but varying in functional groups, were selected to modify two pristine clays with different cation exchange capacities (CEC). Each of the modified clays was melt-mixed with polypropylene (PP) to prepare nanocomposites. The microstructure of the resultant nanocomposites was investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and rheological techniques. The results showed that the surfactant structure had remarkable effects on the morphology and shear rheology of the nanocomposites based on the high-CEC organoclay: use of benzyl functional groups led to the highest extent of intercalation and highest enhancement of shear properties, while use of 2-hydroxyethyl groups had the opposite effect. Nanocomposites based on low-CEC organoclay all exhibited poor dispersion and their shear behavior was changed only slightly in comparison to the polymer matrix. In the case of extensional rheology, strain hardening was observed only in the two nanocomposites containing surfactants with 2-hydroxyethyl groups, regardless of the dispersion state of the nanoparticles.     

Effect of clay silylation on curing and mechanical and thermal properties of unsaturated polyester/montmorillonite nanocomposites

This work focuses on the chemical modification of montmorillonite (MMT) (Cloisite® Na) with compatible silanes, vinyltriethoxysilane (CVTES) and γ-methacryloxypropyltrimethoxysilane (CMPS) in order to prevent agglomeration and to improve montmorillonite interaction with an unsaturated polyester resin matrix seeking to achieve a multifunctional composite. Clays were dispersed in the resin by mechanical stirring and sonication and the nanocomposites were prepared by resin transfer into a mold. The mechanical, morphological, thermal and flammability properties of the obtained composites were compared with those prepared using commercial Cloisite® 30B (C30B) and Cloisite® 15A (C15A) clays. Advantages of using silane-modified clays (CVTES and CMPS) as compared with organic-modified clays (C30B and C15A) can be summarized as similar flexural strength and linear burning rate but higher storage modulus and improved adhesion to the polyester resin with consequent higher thermal deflection temperature and reinforcement effectiveness at higher temperatures. However, organic modified clays showed better dispersion (tendency to exfoliate) and consequently delayed thermal volatilization due to the clay barrier effect.     

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.     

A Kinetic Study on the Thermal Degradation of Polypropylene/Attapulgite Nanocomposites

In this work, a polypropylene (PP)/attapulgite nanocomposite was prepared via melt blending using a novel organically modified attapulgite (OATP). The thermal stability of PP/clay nanocomposites compared to pure PP was examined in nitrogen using a kinetic analysis. The kinetic parameters, including reaction order and activation energy (A and E _a) of the degradation process were determined by applying the Flynn‐Wall‐Ozawa method using derivative thermogravimetric (DTG) curves. At the same time, the effect of organic attapulgite on thermal decomposition of polypropylene matrix was analyzed. As a result, PP/OATP nanocomposites have slightly higher degradation temperature than that of the pure PP. The values of the reaction order of PP and PP/OATP nanocomposites are close to 1 in the nonisothermal degradation process. The activation energies of PP/OATP nanocomposites also increase slightly compared to the pure PP, thus it is suggested that the org‐attapulgite has little effect on the thermal stability of the pure PP.     

Preparation and Rheological Characteristics of Ethylene‐Vinyl Acetate Copolymer/Organoclay Nanocomposites

Ethylene‐vinyl acetate copolymer (EVA) with 40 wt.% vinyl acetate content (EVA40)/organoclay nanocomposites were prepared using a melt intercalation method with several different clay concentrations (2.5, 5.0, 7.5, and 10.0 wt.%). X‐ray diffraction confirmed the formation of exfoliated nanocomposite in all cases with disappearance of the characteristic peak corresponding to the d‐spacing of the pristine organoclay. Transmission electron microscopy studies also showed an exfoliated morphology of the nanocomposites. Morphology and thermal properties of the nanocomposites were further examined by means of scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA), respectively. Rheological properties of the EVA40/organoclay nanocomposites were investigated using a rotational rheometer with parallel‐plate geometry in both steady shear and dynamic modes, demonstrating remarkable differences with the clay contents in comparison to that of pure EVA40 copolymer.     

Effect of Compatibilizer Content on the Shear and Extensional Rheology of Polypropylene/Clay Nanocomposites

The shear and extensional rheology of polypropylene (PP)/organoclay nanocomposites in the presence of various maleic anhydride grafted polypropylene (PP-g-MA) compatibilizer concentrations were investigated. The PP nanocomposites were prepared via direct melt intercalation in an internal mixer. The structures of the nanocomposites were characterized by X-ray diffraction (XRD) and scanning electron microscopy. It was found that both the compatibilized and uncompatibilized nanocomposites could form an intercalated structure. However, the organoclay particles can disperse well only in the compatibilized systems. The linear viscoelastic properties, including the storage modulus G′ and complex viscosity η* were very sensitive to the microstructure of the nanocomposites. The extensional viscosities of PP nanocomposites were enhanced under a low deformation rate with increasing compatibilizer content and displayed a lack of superposition for different strain rates. It was proposed that the lack of superposition might originate from the formation of a three-dimensional organoclay network, which decreased in its complexity and strength as the deformation rate increased.     

PVDF-Based Nanocomposite Solid Polymer Electrolytes; the Effect of Affinity Between PVDF and Filler on Ionic Conductivity

Nanocomposite solid polymer electrolytes (NSPEs) based on poly(vinylidene fluoride) (PVDF) were prepared by dispersing two kinds of organoclay (Cloisite^® 30B, Cloisite^® 15A) consisting of silicate layers in the polymer matrix. The effect of affinity between PVDF and organoclay as the filler on ionic conductivity was investigated in relation to its content, dispersed condition of organoclay, and structural changes of nanocomposites. The characterizations of PVDF-based nanocomposites with various organoclay contents were carried out by XRD, TEM, DSC, and DMA. In order to confirm the ion conduction properties of NSPEs with LiCF₃SO₃ at room temperature, ac impedance analyzer and FT-IR spectrometer were used. As a result, a higher ionic conductivity appeared in the case of NSPE with C15A than that with C30B and the maximum conductivity was 1.04 × 10^–3 S/cm for the NSPE containing 5 wt% of C15A and 40 wt% of LiCF₃SO₃.     

Effect of Mixing Sequence on Phase Morphology and Mechanical Properties in Polyamide 6/Butadiene (Core) Styrene Acrylonitrile-G-Maleic Anhydride (Shell) Latex/Organoclay Ternary Nanocomposites

Ternary nanocomposites based on polyamide-6, maleated butadiene (core) -acrylonitrile-styrene (shell) rubber particles (PB-g-SAM), and modified montmorillonite (organoclay) were prepared by a twin-screw extruder. The glassy shell of the core-shell particles can act as a barrier which can resist the entrance of clay into the rubber phase. The influence of mixing sequence on the phase morphology and mechanical properties were studied. The microstructure of the ternary nanocomposites was characterized by X-ray diffraction, transmission electron microscopy, and scanning electron microscopy. It was found that the clay in the polyamide nanocomposites was partially exfoliated, exhibiting a mixture of exfoliated structures. The organoclay plates affected the interfacial adhesion between the polyamide-6 and the core-shell particles. The location of the organoclay plates in the blends with different mixing sequences produced differences of the mechanical properties. The results of mechanical testing revealed that the optimum mixing sequence to achieve balanced mechanical properties was mixing the polyamide-6 and organoclay first followed by mixing with the core-shell particles.     

Thermal Properties and Fire Resistance of Jute-Reinforced Composites

The thermal behaviour, fire resistance and mechanical properties of jute-reinforced composites with vinylester and resol matrix were studied. Organically modified clay was added to the polymeric matrix in order to enhance the properties of the composites. An inhomogeneous distribution of the nanoreinforcement in the polymer was observed by X-ray diffraction. Thermogravimetric analyses revealed that the addition of clay to the resol resin by sonication enhanced the thermal resistance of the jute-reinforced composite at temperatures higher than 300°C. The fire resistance of the composites was evaluated by means of a cone calorimeter. A diminution in the peak of the heat release rate was observed when clay was added to the polymeric matrix. On the other hand, neither the time to ignition nor the total heat evolved was significantly reduced by the clay addition. Additionally, an increment in the flexural modulus as well as in the flexural strength of the resol composites was observed when the clay was added to the matrix. The fiber–matrix interface of the composites was studied by scanning electron microscopy. It was observed that as the clay dispersion degree was increased the interface quality was diminished in the resol composites.     

Parametric Studies on the Grafting of Poly(Methyl Methacrylate) onto Organophilic Montmorillonite Using Silylated Clay Platelets

Poly(methyl methacrylate) (PMMA)/organophilic montmorillonite (Cloisite 30B) nanocomposites were synthesized by the chemical grafting of PMMA onto Cloisite 30B via solution polymerization of methyl methacrylate (MMA) with vinyl-modified organoclay. The effects of different parameters such as clay weight percent (CWP), solvent per monomer volume ratio, and dispersion time on the properties of the PMMA grafted Cloisite 30B were investigated using the Taguchi experimental design method. This method gives a much-reduced variance for the experiments with optimum setting of control parameters and provides a set of minimum experiments compared to the conventional methods. Qualitative evidence for the chemical grafting of the PMMA onto Cloisite 30B was confirmed by Fourier transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) was used to investigate interlayer changes of the clay in the grafted nanoplatelets. The exfoliated/intercalated morphology of the nanocomposites was confirmed by XRD. Furthermore, thermal properties were measured by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA). Statistical analysis of results revealed that clay weight percent and solvent per monomer ratio had significant effects on the properties of final products. The percent of grafted PMMA and storage modulus of PMMA/30B nanocomposites decreased with increasing clay content due to better dispersion of the clay at lower loadings. On the other hand, because of a tendency to formation of homopolymer and oligomers at higher solvent loadings; the percent of grafted PMMA, storage modulus and glass transition temperature of PMMA/30B nanocomposites decreased with an increase in solvent per monomer volume ratio. However, the obtained PMMA/30B nanocomposites at the optimum conditions, was exhibited a higher glass transition temperature, higher storage modulus and better thermal stability than the pure PMMA.     

Enhancements in crystallinity,thermal stability,tensile modulus and strength of sisal fibres and their PP composites induced by the synergistic effects of alkali and high intensity ultrasound (HIU) treatments

In this investigation, sisal fibres were treated with the combination of alkali and high intensity ultrasound (HIU) and their effects on the morphology, thermal properties of fibres and mechanical properties of their reinforced PP composites were studied. FTIR and FE-SEM results confirmed the removal of amorphous materials such as hemicellulose, lignin and other waxy materials after the combined treatments of alkali and ultrasound. X-ray diffraction analysis revealed an increase in the crystallinity of sisal fibres with an increase in the concentration of alkali. Thermogravimetric results revealed that the thermal stability of sisal fibres obtained with the combination of both alkali and ultrasound treatment was increased by 38.5 °C as compared to the untreated fibres. Morphology of sisal fibre reinforced composites showed good interfacial interaction between fibres and matrix after the combined treatment. Tensile properties were increased for the combined treated sisal fibres reinforced PP composites as compared to the untreated and pure PP. Tensile modulus and strength increased by more than 50% and 10% respectively as compared to the untreated sisal fibre reinforced composite. It has been found that the combined treatment of alkali and ultrasound is effective and useful to remove the amorphous materials and hence to improve the mechanical and thermal properties.