Preparation and characterisation of polyamide–polyimide organoclay nanocomposites

BACKGROUND: Ternary nanocomposites containing an organomodified layered silicate polyimide additive within a polyamide matrix have been investigated to gain greater insight into structure–property relationships and potential high‐temperature automotive applications. RESULTS: Polyamide nanocomposite blends, containing 3 wt% of organoclay, were prepared and compared with organoclay‐reinforced polyamide and neat polyamide. Nanoclay addition significantly increased heat distortion temperature, as well as both the tensile and flexural moduli and strength. The addition of polyimide demonstrated further increases in heat distortion temperature, glass transition temperature and the flexural and tensile moduli by about 17, 21 and 40%, respectively. The tensile and flexural strengths were either unaffected or decreased modestly, although the strain‐to‐failure decreased substantially. Morphological studies using transmission electron microscopy (TEM) and X‐ray diffraction showed that the nanoclay was dispersed within the ternary blends forming highly intercalated nanocomposites, regardless of the presence and level of polyimide. However, TEM revealed clay agglomeration at the polyamide–polyimide interface which degraded the mechanical properties. CONCLUSIONS: A range of improvements in mechanical properties have been achieved through the addition of a polyimide additive to a polyamide nanocomposite. The decrease in ductility, arising from the poor polyamide–polyimide interface and nanoclay clustering, clearly requires improving for this deficiency to be overcome. Copyright © 2008 Society of Chemical Industry     

Preparation and characterization of poly(hydroxybutyrate‐co‐hydroxyvalerate)–organoclay nanocomposites

This study describes the microstructure and thermal and mechanical properties of poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHB/HV)–organoclay nanocomposites prepared by melt intercalation using Cloisite 30B, a monotallow bis‐hydroxyethyl ammonium‐modified montmorillonite clay. X‐ray diffractometry and transmission electron microscopy analyses clearly confirm that an intercalated microstructure is formed and finely distributed in the PHB/HV copolymer matrix because PHB/HV has a strong hydrogen bond interaction with the hydroxyl group in the organic modifier of Cloisite 30B. The nanodispersed organoclay also acts a nucleating agent, increasing the temperature and rate of crystallization of PHB/HV; therefore, the thermal stability and tensile properties of the organoclay‐based nanocomposites are enhanced. These results confirm that the organoclay nanocomposite greatly improves the material properties of PHB/HV. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 525–529, 2003     

Synthesis and characterization of tanninsulfonic acid doped polyaniline–metal oxide nanocomposites

Composites of conducting polymers and metal oxides have a potential role in electronic devices because of their enhanced physical and electronic properties. An in situ synthesis of metal oxide nanocomposites of polyaniline (PANI) and tanninsulfonic acid doped PANI was carried out at ?10°C with two different ratios of aniline to sodium persulfate (oxidant) and the simultaneous incorporation of TiO₂, Al₂O₃, and ZnO nanopowders. The products were characterized by X‐ray diffraction (XRD), thermal analysis, spectroscopy, and electrical conductivity measurements. XRD and thermogravimetric analysis confirmed the presence of the metal oxide in the final product, whereas the spectroscopic characterization revealed interactions among the tannin, metal oxides, and PANI. The electrical properties were determined by four‐point‐probe bulk conductivity measurements. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and properties of BCDA‐based polyimide–clay nanocomposites

Bicyclo[2.2.2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride (BCDA)‐based polyimide–clay nanocomposites were prepared from their precursor, namely polyamic acid, by a solution‐casting method. The organoclay was prepared by treating sodium montmorillonite (Kunipia F) clay with dodecyltrimethylammonium bromide at 80 °C. Polyamic acid solutions containing various weight percentages of organoclay were prepared from 4,4′‐(4,4′‐isopropylidenediphenyl‐1,1′‐diyldioxy)‐dianiline and BCDA in N‐methyl‐2‐pyrrolidone containing dispersed particles of organoclay at 20 °C. These solutions were cast on a glass plate using a Doctor's blade and then heated subsequently to obtain nanocomposite films. The nanocomposites were characterized using Fourier transform infrared spectroscopy, differential scanning calorimetry, thermal mechanical analysis, dynamic mechanical analysis, polarizing microscopy, scanning electron microscopy, transmission electron microscopy, wide‐angle X‐ray diffraction (WAXD) and thermogravimetric analysis. The glass transition temperature of the nanocomposites was found to be higher than that of pristine polymer. The coefficient of thermal expansion of the nanocomposites decreased with increasing organoclay content. WAXD studies indicated that the extent of silicate layer separation in the nanocomposite films depended upon the organoclay content. Tensile strength and modulus of the nanocomposite containing 1% organoclay were significantly higher when compared to pristine polymer and other nanocomposites. The thermal stability of the nanocomposites was found to be higher than that of pristine polymer in air and nitrogen atmosphere. Copyright © 2007 Society of Chemical Industry     

Dynamic rheological study of paraffin wax and its organoclay nanocomposites

Dynamic rheological data for paraffin wax and its organoclay nanocomposites are reported. Dynamic mechanical analysis of paraffin wax for temperatures ranging from ?40 to 55°C showed a decrease of several orders of magnitude in the dynamic moduli and a significant shift toward viscous behavior, which resulted from the occurrence of two solid–solid phase transitions. In both the crystalline and mesophase regions, the dispersion of organoclay platelets in paraffin wax via ultrasonication increased the storage modulus, whereas the effect on the loss modulus was temperature‐dependent. The melt rheology data of the wax–clay nanocomposites at 70°C showed that the complex viscosities increased monotonically with clay addition and demonstrated shear‐thinning behavior for frequencies between 0.1 and 100 rad/s. The complex viscosity versus angular frequency data were well fit by a power‐law function for which the shear‐thinning exponent provides a gauge for the extent of clay exfoliation. The nanocomposites exhibited low‐frequency solid behavior, which indicated good exfoliation of the organoclay in the wax matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Morphology and mechanical properties of heterophasic PP–EP/EVA/organoclay nanocomposites

The effect of vinyl acetat (VA) on the morphological, thermal stability, and mechanical properties of heterophasic polypropylene–(ethylene‐propylene) copolymer (PP–EP)/poly(ethylene vinyl acetate) (EVA)/organoclay nanocomposites was studied. Tailored organoclay C20A was selected to enhance the exfoliation of the clay platelets. Depending on the VA content, there were two morphological organoclay populations in the systems. Both populations were directly observed by scanning transmission electron microscopy and measured by wide‐angle X‐ray diffraction and small‐angle X‐ray scattering. The content of VA in EVA originated spherical and elongated morphologies in the resultant nanocomposites. High‐VA content led to a better intercalation of the organoclay platelets. Measurement of thermal properties suggested that higher VA decreases thermal stability in samples both with and without organoclay, although nanocomposites had higher thermal stability than samples without clay. The storage modulus increased both with nanoclay and VA content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Batch and continuous processing of polymer layered organoclay nanocomposites

The generation of nanocomposites upon intercalation and exfoliation of clay tactoids using melt compounding is a difficult process. In this study various polymeric binders were melt compounded with organophilic clay particles using myriad methods, including sonication, batch mixing, and twin screw extrusion. The characterization of the compounded samples employing X‐ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that there is little intercalation and exfoliation when nonpolar poly(dimethyl siloxane) (PDMS) and poly(propylene) (PP) binders were used, resulting in no significant changes in the dynamic properties of the suspensions upon small‐amplitude oscillatory shearing. On the other hand, when polar polymeric binders, i.e., silanol terminated poly(dimethyl siloxane) and maleic anhydride modified PP were used for compounding with organoclays, TEM and XRD revealed intercalation with some partial exfoliation, resulting in increases in the dynamic properties, along with sensitivity to the thermomechanical history during processing. These results reinforce earlier findings, which suggest that the interfacial properties between the organoclays and the polymeric binders need to be tailored properly to enable the generation of nanocomposites of organoclays using melt compounding technologies. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1391–1398, 2007     

Synthesis and characterization of conducting polyaniline‐activated carbon nanocomposites

Conducting polyaniline (PAni)/activated carbon (AC) nanocomposites were synthesized by the in situ chemical polymerization method. The resultant shell–core PAni–AC nanocomposites were characterized by elemental analysis, Fourier transform infrared, scanning electron microscopy, thermal gravimetric analysis, X‐ray diffraction, and transmission electron microscopy. We did not observe any significant chemical interaction between the PAni and AC, only core–shell coupling between the AC and the tightly coated polymer chain was revealed. Measurement of the physical properties showed that the incorporation of conducting PAni on to AC particles during chemical synthesis increased electrical conductivity and thermal stability by several orders of magnitude to that of the pristine PAni powders. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1973–1977, 2007     

Synthesis and characterization of poly(urethane‐benzoxazine)/clay hybrid nanocomposites

Poly(urethane‐benzoxazine)/clay hybrid nanocomposites (PU/Pa–OMMTs) were prepared from an in situ copolymerization of a polyurethane (PU) prepolymer and a monofunctional benzoxazine monomer, 3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Pa), in the presence of an organophilic montmorillonite (OMMT), by solvent method using DMAc. OMMT was made from cation‐exchange of Na‐montmorillonite (MMT) with dodecyl ammonium chloride. The formation of the exfoliated nanocomposite structures of PU/Pa‐OMMT was confirmed by XRD from the disappearance of the peak due to the basal diffraction of the layer‐structured clay found in both MMT and OMMT. DSC showed that, in the presence of OMMT, the curing temperature of PU/Pa lowered by ca. 60°C for the onset and ca. 20°C for the maximum. After curing at 190°C for 1 h, the exothermic peak on DSC disappeared. All the obtained films of PU/Pa–OMMT were deep yellow and transparent. As the content of OMMT increased, both the tensile modulus and strength of PU/Pa–OMMT films increased, while the elongation decreased. The characteristics of the PU/Pa–OMMT films changed from plastics to elastomers depending on OMMT content and PU/Pa ratio. PU/Pa–OMMT films also exhibited excellent resistance to the solvents such as tetrahydrofuran, N,N‐dimethylformamide and N‐methyl‐2‐pyrrolidinone. The thermal stability of PU/Pa were enhanced remarkably even with small amount of OMMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4075–4083, 2003     

Synthesis and characterization of in situ sodium‐activated and organomodified bentonite clay/styrene–butadiene rubber nanocomposites by a latex blending technique

In this article, we describe a method used to prepare an in situ sodium‐activated, organomodified bentonite clay/styrene–butadiene rubber nanocomposite master batch via a latex blending technique. The clay master batch was used for compound formulation. Octadecyl amine was used as an organic intercalate. The clay was purchased from local suppliers and was very cheap. Sodium chloride was used for in situ activation of the clay. The wide‐angle X‐ray diffraction data indicated that the in situ sodium activation helped to increase the intergallery distance from 1.28 to 1.88 nm. A transmission electron micrograph indicated intercalation and partial exfoliation. The thermal properties were relatively better in the case of the sodium‐activated, organomodified bentonite‐clay‐containing compound. A substantial improvement in physical properties such as the modulus, tensile strength, tear strength, and elongation at break was observed in the case of the in situ sodium‐activated compound. A cation‐exchange capacity equivalent (of the clay) of 1.5 times the octadecyl amine was the optimum dose for the modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Properties of high‐impact polystyrene/organoclay nanocomposites synthesized via in situ polymerization

High‐impact polystyrene (HIPS)/organically modified montmorillonite (organoclay) nanocomposites were synthesized via in situ polymerization. The effects of the organoclay on the morphology and material properties of HIPS/organoclay nanocomposites were investigated. X‐ray diffraction and transmission electron microscopy experiments revealed that intercalation of polymer chains into silicate layers was achieved, and the addition of nanoclay led to an increase in the size of the rubber domain in the composites. In comparison with neat HIPS, the HIPS/organoclay nanocomposites exhibited improved thermal stability as well as an increase in both the complex viscosity and storage modulus. The presence of intercalated organoclay drastically enhanced the gas‐barrier properties because of the increase in the tortuosity of the diffusive path for a penetrating gas molecule. Some mechanical properties, including the tensile modulus, were superior to those of conventional HIPS. Finally, the preparation of the nanocomposites with a minimal loss of impact properties was proposed through changes in the synthetic procedure. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of organic modification on mechanical properties of melt processed intercalated poly(methyl methacrylate)–organoclay nanocomposites

The influence of organic modifiers on intercalation extent, structure, thermal and mechanical properties of poly(methyl methacrylate) (PMMA)–clay nanocomposites were studied. Two different organic modifiers with varying hydrophobicity (single tallow versus ditallow) were investigated. The nanocomposites were prepared from melt processing method and characterized using wide angle X‐ray diffraction, transmission electron microscopy, thermogravimetric analysis, differential scanning calorimetry (DSC), and tensile tests. Mechanical properties such as tensile modulus (E), break stress (σ_brk), and % break strain (ε_brk) were determined for nanocomposites at various clay loadings. Extent of PMMA intercalation is sufficient and in the range 9–15 Å depending on organoclay and filler loading. Overall thermal stability of nanocomposites increases by 16–30°C. The enhancement in T_g of nanocomposite is merely by 2–4°C. With increase in clay loading, tensile modulus increases linearly while % break strain decreases. Break stress is found to increase till 4 wt % and further decreases at higher clay loadings. The overall improvement in thermal and mechanical properties was higher for the organoclay containing organic modifier with lower hydrophobicity and single tallow amine chemical structure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of organoclay nanocomposites based on natural rubber

Rubber compounds based on natural rubber (NR) reinforced with octadecylamine‐modified bentonite have been prepared via a vulcanization process and characterized by several techniques. The silicate nanolayers are exfoliated and uniformly dispersed in the polymer chains. Monsanto measurements have shown that the organoclay accelerates the vulcanization reaction and, furthermore, gives rise to a marked increase of the torque, indicating that the elastomer becomes more crosslinked in the presence of the organoclay. These results were corrobated by swelling measurements since a noticeable increase in the curing degree was observed when the organoclay was added to the rubber recipe. Moreover, thermodynamic parameters have shown an increase in the structural order of the nanocomposite. In addition, thermal analysis supports the assumption that the degree of curing of the elastomer increases when the organoclay is added to the elastomer. An appreciable increase of the involved heat during the curing reaction has been observed. Moreover, the T_g of the NR increases in the presence of the organoclay due to the confinement of the elastomer segment into the organoclay nanolayers, which restricts the mobility of the chains. Copyright © 2003 Society of Chemical Industry     

Diffusion behavior of water and sulfuric acid in epoxy/organoclay nanocomposites

The research on polymer‐layered silicate nanocomposites is currently an expanding field of study because they often exhibit a wide range of improved properties over their unmodified starting polymers. Epoxy/organoclay nanocomposites have been prepared by intercalating epoxy into the organoclay montmorillonite. The intercalation and/or exfoliation of the clay within the nanocomposite were monitored using X‐ray diffraction and transmission electron microscopy. Diffusion was studied through epoxy samples containing up to 10 phr of organically treated montmorillonite following the gravity method. The water and sulfuric acid diffusion within the epoxy‐based nanocomposites were evaluated in terms of diffusivity, weight change and penetration depth of the sulfuric acid element S as function of immersion time and immersion temperature. An investigation of the resistance of epoxy nanocomposite to a corrosive environment by immersion into sulfuric acid at elevated temperature was performed. The effect of the degree of exfoliation of the clay on moisture barrier effect and corrosion resistance is specifically studied. The data has been compared to those obtained from the neat epoxy resin to evaluate the diffusion properties of the nanocomposites. It was found that the diffusion of water and that of acid do not obey Fick's law, and that the higher the organoclay content the higher weight change was obtained. The presence of the organoclay enhanced the diffusivity and delayed the penetration of the sulfuric acid. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(ethylene terephthalate) nanocomposites with organoclay

Poly(ethylene terephthalate) (PET)/montmorillonite (MMT) nanocomposites were prepared by solution intercalation method. The clay was organo‐modified with the intercalation agent cetylpyridinium chloride (CPC). Wide‐angle X‐ray diffraction (XRD) showed that the layers of MMT were intercalated by CPC. Four nanocomposites with organoclay contents of 1, 5, 10, and 15 wt % were prepared by solution blending. XRD showed that the interlayer spacing of organoclay in the nanocomposites depends on the amount of organoclay present. According to the results of differential scanning calorimetry (DSC) analysis, clay behaves as a nucleating agent and enhances the crystallization rate of PET. The maximum enhancement of crystallization rate for the nanocomposites was observed in those containing about 10 wt % organoclay within the studied range of 1–15 wt %. From thermogravimetric analysis (TGA), we found that the thermal stability of the nanocomposites was enhanced by the addition of 1–15 wt % organoclay. These nanocomposites showed high levels of dispersion without agglomeration of particles at low organoclay content (5 wt %). An agglomerated structure did form in the PET matrix at 15 wt % organoclay. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 140–145, 2004     

Rubber toughening of polyamide 6/organoclay nanocomposites obtained by melt blending

Rubber toughening of polyamide 6 (PA6)/layered‐silicate nanocomposites was investigated. Different systems were prepared via melt blending according to different formulations. Wide‐angle X‐ray diffraction and transmission electron microscopy analyses showed that the nanocomposites had an appreciable degree of exfoliation. A linear elastic fracture mechanics approach was applied to characterize the material fracture behavior in dry conditions, whereas, because of the considerable ductility exhibited by the samples in the wet state, an elastic–plastic approach based on the essential work of fracture methodology was employed. In the absence of rubber, the presence of silicate layers makes the material fracture resistance decrease relative to neat polymer, depending on the degree of humidity. The results showed that the toughening action of rubber strongly depends on the degree of humidity of the material, at least for the rubber contents considered in this study (lower than 10 wt %). In particular, in slightly wet conditions, it was found that the addition of small amounts of rubber increased the fracture resistance of PA6/layered‐silicate nanocomposites without appreciably impairing the material stiffness. Thus, the results indicated that, for the given humidity conditions, a good balance between stiffness and toughness was obtainable by employing a suitable ratio of rubber to layered‐silicate content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3406–3416, 2006     

Preparation and properties of nanocomposites based on different polarities of nitrile–butadiene rubber with clay

Nanocomposites were prepared with different grades of nitrile–butadiene rubber (NBR) [with nitrile (CN) contents of 26, 35, and 42%] with organoclay (OC) by a melt‐compounding process. The rubber/clay nanocomposites were examined by transmission electron microscopy (TEM) and X‐ray diffraction (XRD). An increase in the polarity of NBR affected the XRD results significantly. The dispersion level of the nanofiller in the nanocomposites was determined by a function of the polarity of the rubber, the structure of the clay, and their mutual interaction. The intercalated structure and unintercalated structure coexisted in the lower polar of NBR. In addition, a relatively uniformly dispersed state corresponded to a more intercalated structure, which existed in the higher polar of NBR matrix. Furthermore, high‐pressure vulcanization changed the extent of intercalation. The mechanical properties and gas barrier properties were studied for all of the compositions. As a result, an improvement in the mechanical properties was observed along with the higher polarity of NBR. This improvement was attributed to a strong interaction of hydrogen bonding between the CN of NBR and the OH of the clay. Changes in the gas barrier properties, together with changes in the polarity of the rubbers, were explained with the help of the XRD and TEM results. The higher the CN content of the rubber was, the more easily the OC approached to the nanoscale, and the higher the gas barrier properties were. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Morphology and thermomechanical properties of recycled PET–organoclay nanocomposites

Recycled PET/organoclay nanocomposites were prepared by melt intercalation process with several amounts (1, 3, and 5 wt %) of clay modified with quaternary ammonium salt (DELLITE 67G) dispersed in a recycled poly(ethylene terephthalate) (rPET) matrix. The resultant mechanical properties (modulus and yield strength) of the nanocomposites were found to be different from those of rPET. Wide angle X‐ray scattering (WAXS) and Transmission Electron Microscopy (TEM) measurements have shown that although complete exfoliation was not achieved, delaminated clay platelets could be observed. Thermal analysis did not show significant changes in the thermal properties from those of recycled PET. Mechanical testing showed that nanocomposite properties were superior to the recycled PET in terms of strength and elasticity modulus. This improvement was attributed to nanoscale effects and strong interaction between the rPET matrix and the clay interface, as revealed by WAXS and TEM. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1839–1844, 2007     

Morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite nanocomposites

The morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite (MMT) nanocomposites were investigated with wide‐angle X‐ray scattering (WAXS), transmission electron microscopy (TEM), tensile testing, and dynamic mechanical thermal analysis. An ultrasonicator was used to apply external shearing forces to disperse the silicate clay layers in the epoxy matrix. The first step of the nanocomposite preparation consisted of swelling MMT in a curing agent, that is, an aliphatic diamine based on a polyoxypropylene backbone with a low viscosity for better diffusion into the intragalleries. Then, the epoxy prepolymer was added to the mixture. Better dispersion and intercalation of the nanoclay in the matrix were expected. The organic modification of MMT with octadecylammonium ions led to an increase in the initial d‐spacing (the [d₀₀₁] peak) from 14.4 to 28.5 Å, as determined by WAXS; this indicated the occurrence of an intercalation. The addition of 5 phr MMTC18 (MMT after the modification) to the epoxy matrix resulted in a finer dispersion, as evidenced by the disappearance of the diffraction peak in the WAXS pattern and TEM images. The mechanical and viscoelastic properties were improved for both MMT and MMTC18 nanocomposites, but they were more pronounced for the modified ones. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 103: 3547–3552, 2007     

NR/SBR/organoclay nanocomposites: Effects of molecular interactions upon the clay microstructure and mechano‐dynamic properties

Nanocomposites based on (70/30) blends of natural rubber (NR), styrene‐butadiene rubber (SBR), and organoclay (OC) have been prepared successfully via melt‐mixing process. Effects of the extent of polymers/clay interactions upon the developed microstructure, fatigue life, and dynamic energy loss by the nanocomposites have been investigated. Maleated EPDM (EPDM‐g‐MAH) and epoxidized NR (ENR50) were employed as compatibilizer. Nanocomposites were characterized by means of X‐ray diffractometer (XRD), transmission electron microscope (TEM), scanning electron microscope, atomic force microscopy, root mean square, and dynamic mechanical thermal analysis. EPDM‐g‐MAH showed more potential in enhancing dispersion of the clay nanolayers and their interaction with rubber phases. More potential for separating and dispersing the clay nanoplatelets with better interface enhancement was exhibited by EPDM‐g‐MAH as compatibilizer. This was consistent with higher resistance towards large strain cyclic deformations along with more heat build‐up characteristics showed by EPDM‐g‐MAH based nanocomposites especially at compatibilizer/organoclay ratio of 3. Pronounced non‐terminal behavior within low frequency region was also observed for melt storage modulus of this nanocomposite, indicating higher extent of intercalation/exfoliation microstructure with reinforced interfaces than the nanocomposite generated by ENR50. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012