Preparation and properties of polyhedral oligosilsequioxane tethered aromatic polyamide nanocomposites through Michael addition between maleimide‐containing polyamides and an amino‐functionalized polyhedral oligosilsequioxane

Polyhedral oligosilsequioxane (POSS) tethered aromatic polyamide nanocomposites with various POSS fractions were prepared through Michael addition between maleimide‐containing polyamides and amino‐functionalized POSS. The chemical structures of the polyamide–POSS nanocomposites were characterized with Fourier transform infrared and ¹H NMR. The polyamide–POSS nanocomposites exhibited good homogeneity in scanning electron microscopy and transmission electron microscopy observations. POSS modification increased the storage modulus and Young's modulus of the polyamides, slightly decreased their glass‐transition temperatures from 312 to 305 °C, and significantly lowered their dielectric constants from 4.45 to 3.35. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4632–4643, 2006     

Real Time Monitoring of Morphologic and Mechanical Properties of Polymer Nanocomposites During Extrusion by near Infrared and Ultrasonic Spectroscopy

Extrusion is one of the most applied technologies for the processing of polymer nanocomposites for applications in automotive, electrical and packaging industrial sectors. These nanostructured materials have advantages in comparison to traditional polymer materials, so that properties like tensile strength and modulus, barrier and surface properties, electrical properties and flame retardancy will be improved. There is a need to control amount and dispersion of the nanofillers in the polymer matrix during melt processing and to control the influence of the processing conditions on the nanocomposite formation. For an adequate real time characterization it is necessary to measure directly in the extruder. Spectroscopic methods and Ultrasonic measurements are outstanding methods for this kind of in-line monitoring. This paper deals with the real time determination of the dispersion and the impact strength of polymer nanocomposites in the melt during extrusion by Ultrasonic measurements and NIR spectroscopy. These in-line measurements were correlated with off-line rheological measurements, transmission electron microscopy and mechanical test measurements by multivariate data analysis. The polymers used are polypropylene and polyamide 6. As nanofillers we used different modified layered silicates. We determined the degree of exfoliation as an indicator for the dispersion of the nanofiller in the polymer matrix for different layered silicates and at different process conditions.     

Morphology and mechanical properties of a novel amorphous polyamide/nanoclay nanocomposite

A novel amorphous polyamide/montmorillonite nanocomposite based on poly(hexamethylene isophthalamide) was successfully prepared by melt intercalation. Wide angle X-ray diffraction and transmission electron microscopy showed that organoclay containing quaternary amine surfactants with phenyl and hydroxyl groups was delaminated in the polymer matrix resulting in well-exfoliated morphologies even at high montmorillonite content. Differential scanning calorimetry results indicated that clay platelets did not induce the formation of a crystalline phase in this amorphous polymer. Tensile tests demonstrated that the addition of nanoclay caused a dramatic increase in Young's modulus (almost twofold) and yield strength of the nanocomposites compared with the homopolymer. The nanocomposites exhibited ductile behavior up to 5 wt % of nanoclay. The improvement in Young's modulus is comparable with semicrystalline aliphatic nylon 6 nanocomposites. Both the main chain amide groups and the amorphous nature of the polyamide are responsible for enhancing the dispersion of the nanofillers, thereby, leading to improved properties of the nanocomposites. The structure-property relationship for these nanocomposites was also explored. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2605–2617, 2008     

Elastomer Nanocomposite; Properties

Polymer nanocomposites represent a class of materials that have assumed great importance in recent years and are the focus of extensive research. Unlike plastomer nanocomposites, the elastomer nanocomposites are in the stage of infancy in respect to their applications.

In general, in polymer composites, the matrix and the filler are bonded to each other by weak intermolecular forces and covalent bonding are rarely involved. If the filler could be dispersed in the polymer matrix at the nanometre level and is able to interact with the matrix by chemical bonding, nanocomposites with significant properties improvement are obtained. These improvements can include mechanical properties (module, strength, etc.), thermal resistance, decrease in gas permeability (barrier), flammability, etc.

This paper is a review of the property improvements of different elastomers using nanofillers like silicates, carbon black, metallic powders, cellulose crystals, mixture of nanofillers, etc, with the intention of obtaining elastomer nanocomposites.     

Processing and Final Properties Improvement of Polyolefin-Sepiolite and Carbon Nanofibre Nanocomposites

Summary: In this work polypropylene (PP) nanocomposites with different nanofillers (sepiolites and carbon nanofibres) have been produced, processed by injection moulding and fibre spinning and analyzed in terms of mechanical properties improvements. Different concentrations of both fillers were used in nanocomposites preparation. The influence of nanofiller type and amount on mechanical properties were analyzed and discussed for each process studied. This study was completed with a basic morphological characterization in order analyze the nanofiller dispersion, distribution and orientation in the nanocomposites. The results achieved show that it is possible to obtain a good dispersion and distribution of the each kind of nanofillers with conventional processing methodologies when the nanofiller concentration is small. Moreover the nanocomposites obtained had better properties than the starting polymers, showing that sepiolite and carbon nanofiller are able to provide an important contribution to the improvement of mechanical properties of the materials analyzed, enlarging the final application possibilities of PP based products.     

Melt‐compounded nanocomposites of titanium dioxide atomic‐layer‐deposition‐coated polyamide and polystyrene powders

Polyamide and polystyrene particles were coated with titanium dioxide films by atomic layer deposition (ALD) and then melt‐compounded to form polymer nanocomposites. The rheological properties of the ALD‐created nanocomposite materials were characterized with a melt flow indexer, a melt flow spiral mould, and a rotational rheometer. The results suggest that the melt flow properties of polyamide nanocomposites were markedly better than those of pure polyamide and polystyrene nanocomposites. Such behavior was shown to originate in an uncontrollable decrease in the polyamide molecular weight, likely affected by a high thin‐film impurity content, as shown in gel permeation chromatography (GPC) and scanning electron microscope (SEM) equipped with an energy‐dispersive spectrometer. Transmission electron microscope image showed that a thin film grew on both studied polymer particles, and that subsequent melt‐compounding was successful, producing well dispersed ribbon‐like titanium dioxide with the titanium dioxide filler content ranging from 0.06 to 1.12 wt%. Even though we used nanofillers with a high aspect ratio, they had only a minor effect on the tensile and flexural properties of the polystyrene nanocomposites. The mechanical behavior of polyamide nanocomposites was more complex because of the molecular weight degradation. Our approach here to form polymeric nanocomposites is one way to tailor ceramic nanofillers and form homogenous polymer nanocomposites with minimal work‐related risks in handling powder form nanofillers. However, further research is needed to gauge the commercial potential of ALD‐created nanocomposite materials. Copyright © 2011 John Wiley & Sons, Ltd.     

Cysteine cyclic pyrrole-imidazole polyamide for sequence-specific recognition in the DNA minor groove

Pyrrole-imidazole (PI) polyamides are small DNA-binding molecules that can recognize predetermined DNA sequences with high affinity and specificity. Hairpin PI polyamides have been studied intensively; however, cyclic PI polyamides have received less attention, mainly because of difficulties with their synthesis. Here, we describe a novel cyclization method for producing PI polyamides using cysteine and a chloroacetyl residue. The cyclization reaction is complete within 1 h and has a high conversion efficiency. The method can be used to produce long cyclic PI polyamides that can recognize 7 bp DNA sequences. A cyclic PI polyamide containing two β-alanine molecules had higher affinity and specificity than the corresponding hairpin PI polyamide, demonstrating that the cyclic PI polyamides can be used as a new type of DNA-binding molecule.     

C−N Coupling Reactions on Graphene with Aromatic Macromolecules and the Spatial Conformation of Grafted Macromolecules

The fabrication of advanced graphene-based nanocomposites with high-performance polymers requires covalent modification of graphene with aromatic macromolecules. Herein, C−N coupling reactions between fluorinated graphene (FG) and aromatic polyamides containing the benzimidazole moiety are successfully achieved. The optimized conditions are presented based on the nucleophilic behavior of the C−N coupling reaction on graphene. Different from the C−N coupling reaction between two small aromatic molecules, the conformation of grafted aromatic polyamide after reaction changes from torsional to paralleled alignment on graphene with the molecular length increment. Non-covalent interactions between graphene and aromatic polyamides result in this conformational change owing to the extended π systems of graphene and aromatic polyamides, and the synergistic effect of covalent and non-covalent interactions is put forward. As a consequence, graphene dispersibility is greatly enhanced in the solution of aromatic polyamide.     

Molecular composites prepared by in situ direct synthesis of wholly aromatic rigid‐rod polyamides via the phosphorylation reaction in a dissolved nylon‐6 matrix

Wholly aromatic rigid‐rod polyamides such as poly(p‐phenyleneterephthalamide) (PPD‐T) were synthesized in situ in a solution of nylon‐6 via the phosphorylation polycondensation method to form nanocomposites or so‐called “molecular composites.” The incorporation of PPD‐T into a nylon‐6 matrix was achieved by this approach in a more compatibilized form than that obtained by the conventional coagulation method that entails precipitation of a blend of PPD‐T and nylon‐6 in a solvent, for example, concentrated sulfuric acid. Gelation occurred during the synthesis, presumably because of the formation of interpenetrating networks accompanied by some block‐copolymer formation. The transparency and tensile properties of the resultant composite films from the rigid‐rod aromatic polyamide/nylon‐6 combination were improved over those of nylon‐6 film alone. Rainbow‐colored intense birefringence was observed for the composite films under crossed polarizers. These properties are discussed in context with the in situ synthesized rigid‐rod polyamides uniformly incorporated in nylon‐6. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1014–1026, 2003     

Fabrication of Bioactive Polyoxymethylene Nanocomposites for Bone Tissue Replacement

Summary: Stearic acid modified nano hydroxyapatite (n-SHA) filled polyoxymethylene (POM) nanocomposites were prepared by melt mixing method for bone tissue replacement and regeneration applications. Contact angle measurements of POM nanocomposites were carried out to understand the effect of n-SHA addition on the hydrophobicity of nanocomposites. The mechanical properties like tensile strength, Young's modulus and elongation at break were found to be increased significantly by the incorporation of n-SHA into the POM matrix. The bone-bonding ability of the nanocomposites was evaluated by examining the apatite formation on their surface after soaking in simulated body fluid (SBF) and apatite formation was studied by atomic force microscopy (AFM). The protein adhesion studies revealed the enhanced biocompatibility of the nanocomposites due to the presence of n-SHA nanofillers on the surface and it provides favorable binding sites for protein adsorption. The significant improvement in the biocompatibility as well as mechanical, thermal and hydrophobic properties of the POM nanocomposites makes it a potential future material for bone implantation.     

Nanofillers based upon organophilic layered silicates

A wide variety of polymer nanocomposites exhibiting novel property combinations were obtained via in‐situ formation of silicate nanofillers during polymerization and processing. Key intermediates were tailor‐made silicates which were renderer organophilic by means of cation exchange and exfoliated upon applying shear forces. As a function of organophilic modification, interfacial coupling, and processing conditions it was possible to control nanostructure formation and to improve thermal and mechanical properties such as toughness/stiffness balance, heat distortion temperature, and flame retardency. Basic structure/property correlations were established for nanocomposites based upon in‐situ nanofillers and polymers such as polystyrene, polyamide 12, polypropylene, polymethylmethacrylate, polyurethan, and epoxy resins.     

Processing and Characterization of Polypropylene Filled with Multiwalled Carbon Nanotube and Clay Hybrid Nanocomposites

Nanocomposites reinforced with hybrid fillers of carbon nanotubes (CNTs) and clays were developed, aiming at enhancing the dispersion of nanofillers with balanced mechanical properties while lowering the cost of the final product. Polypropylene-based nanocomposites were prepared by the master batch dilution technique with varying combinations of CNTs and clays as fillers by using commercially available highly concentrated master batches of polypropylene/organoclays and polypropylene/multiwalled carbon nanotubes using high-shear twin-screw extrusion. Their mechanical and morphological properties were then evaluated. It was shown that the addition of hybrid filler to polypropylene enhanced the ductility and flexural properties of nanocomposites, confirming the synergistic effect of nanofillers as a multifunctional fillers. The novelty of this work lies in the synergy arising from the combination of two nanofillers with unique dimensions and aspect ratios as well as different dispersion characteristics, which have not been specifically considered previously.     

Introduction of Multiple Hydrogen Bonding for Enhanced Mechanical Performance of Polymer-Carbon Nanotube Composites

Due to their outstanding mechanical properties and high aspect ratios, carbon nanotubes (CNTs) are envisioned as attractive nanofillers in polymer composites. However, due to strong van der Waals interactions, deleterious aggregation of CNTs is typically observed in polymer nanocomposites. Moreover, due to low stress transfer between the matrix polymer and the nanotube filler, only limited reinforcement is obtained. We report here a novel functionalization strategy to obtain CNTs with pendant self-complementary hydrogen bonding groups in order to address these limitations. Multi-walled CNTs were functionalized with ureidopyrimidinone (UPy) groups, which display multiple hydrogen bonding. The functionalized CNTs were blended with acrylic copolymers containing pendant UPy moieties and significant enhancement in tensile performance of the nanocomposites was observed.     

Polyolefin,olefin copolymers and polyolefin polyblend nanocomposites

This paper reviews recent studies done in academia or industrial laboratories on polymer nanocomposites based on various type of polyolefins like homopolymers, copolymers and polyblends reinforced with various mineral (montmorillonite, bentonite, closite, laponite, layered double hydroxide, etc.) carbon based (graphite, carbon nanotubes, carbon nanofibers, exfoliated graphite, graphene, carbon black, etc.) nanofillers. The review covers their preparation, their mechanical, thermal, flammability, gas barrier capability, electrical, dielectrical, antibacterial characteristics and their potential applications like low weight structural materials, part of optical devices, thermal interface materials, electric and electromagnetic components, absorption, antibacterial materials, etc.     

Obtaining nanocomposites of polyamide 6 and cellulose whiskers via extrusion and injection molding

Nanocomposites of polyamides with cellulose whiskers are difficult to obtain by conventional processing of extrusion and injection molding because of the low thermal stability of the cellulosic nanostructures and the relatively high processing temperature of polyamides, which is higher than the temperature of thermal degradation of cellulose whiskers. Thus, in this study cellulose whiskers were coated with polyamide 6 (PA6) in order to increase their thermal stability and prevent the formation of agglomerates. This coating on cellulose whiskers allows their application to obtain nanocomposites with polyamides, whose processing temperatures are relatively high, around 250 °C. Cellulose whiskers (CWs) were obtained from cotton fibers by acid hydrolysis. The freeze-dried CWs were coated with PA6 by dispersing them in formic acid; PA6 was solubilized in this suspension. The cellulose-coated whiskers (CCWs) were characterized by X-ray diffraction, differential scanning calorimetry (DSC), thermogravimetry (TG), scanning electron microscopy (SEM-FEG) and infrared spectroscopy. SEM-FEG and TG results showed that the PA6 coating on CWs prevented high agglomeration of dried CWs and promoted an increase in their thermal stability from 180 to 280 °C, allowing the use of CCWs to obtain nanocomposites with PA6 using conventional processing routes, such as extrusion and injection molding, at appropriate processing temperatures. In this way, 1 wt% CCWs was used to prepare nanocomposites with PA6. The PA6 + 1CW nanocomposites were compared to neat PA6 without CWs. The samples were characterized by tensile tests and DSC, and the results showed that the PA6 coating on CWs was effective in raising the thermal stability of CWs, improving the dispersion of CWs in the matrix of PA6, resulting in a 45 % increase in the elastic modulus of the nanocomposite with only 1 wt% of coated cellulose whiskers in comparison to neat PA6.     

Impact of coated calcium carbonate nanofillers and annealing treatments on the microstructure and gas barrier properties of poly(lactide) based nanocomposite films

Amorphous poly(lactide) (PLA) and nanocomposite films were prepared from melt‐blending with precipitated calcium carbonate nanofillers (PCC). Nanocomposites based on uncoated PCC (PCC‐UT), stearic acid coated PCC (PCC‐S), and poly(ε‐caprolactone) coated PCC (PCC‐P) were investigated for an inorganic content fixed to 8 wt %. Using coated nanofillers allowed preserving both PLA average molar mass and thermal stability while enhancing the nanofiller dispersion state. Poly(ε‐caprolactone) was identified as the best coating for optimized morphology and thermal properties. Maxwell law accurately described the increase in oxygen barrier properties observed for the nanocomposites based on PCC‐S. A modified Maxwell law was proposed to take account of the additional increase in barrier properties evidenced for the PLA/PCC‐P nanocomposites and assigned to the particularly strong compatibility between PCL and PLA. Different annealing conditions were investigated to respectively study the impact of physical ageing and PLA crystallization on gas permeability. Different extents of physical ageing did not significantly modify the oxygen transport properties. However, a high permeability decrease was observed for the semicrystalline nanocomposites with respect to the amorphous reference PLA film. Finally, the gain in barrier properties was shown to result from both contribution of the nanofillers and the crystalline phase. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 649–658     

Homoionic inorganic montmorillonites as fillers for polyamide 6 nanocomposites

The homoionic montmorillonites Ca-MMT, Mg-MMT, Ba-MMT and Ca-MMT intercalated with ε-caprolactam - Ca-MMT·CL were prepared from commercial Na-MMT and characterized by WAXS and TGA. They were used as fillers for nanocomposites of polyamide 6 synthesized either by anionic polymerization of ε-caprolactam (monomer casting) or by melt blending. WAXS analysis showed that the intercalation of MMT by the polyamide was complete for all nanocomposites, with only a very small fraction of exfoliated platelets being detected by TEM. The decrease in the number of layers in the MMT tactoids suggests that tactoid splitting was lower for the blended nanocomposites than for the polymerized ones. Both the rate of polymerization and the polyamide yield in the nanocomposites were comparable to those of an unfilled system. The MMT fillers, the density of which was more than twice that of the ε-caprolactam in which they were suspended, sedimented during the first stage of polymerization. TGA was used to determine the degree of sedimentation at various levels of the resulting mold. In line with the coordination of polyamide chains to the surface cations of MMT particles, the sedimentation level increased in the following sequence: Mg-MMT < Ba-MMT < Ca-MMT·CL << Na-MMT. Ca-MMT was found to be the only non-sedimenting filler suitable for use in the synthesis of polyamide nanocomposites by either monomer casting or the use of reactive injection molding (RIM) technologies.     

Characterization of HDPE /Polyamide 6/ Nanocomposites Using Scanning-and Transmission Electron Microscopy

Summary: Preparation and morphology of high density polyethylene (HDPE)/ polyamide 6 (PA 6)/modified clay nanocomposites were studied. The ability of PA 6 in dispersing clays was used to prepare modified delaminated clays, which were then mixed with HDPE. Mixing was performed using melt processing in a torque rheometer equipped with roller rotors. After etching the materials with boiling toluene and formic acid at room temperature, the morphology was examined by SEM analyses, showing that the PA 6 formed the continuous phase and HDPE the dispersed phase. X-ray diffraction patterns show that the (001) peak of the clay is dramatically decreased and shifted to lower angles, indicating that intercalated/exfoliated nanocomposites are obtained. TEM analyses confirmed the typical structure of exfoliated nanocomposites. A scheme for the mechanism of exfoliation and/or intercalation of these HDPE /PA 6/ /organoclay nanocomposites is proposed.     

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe‐Layered Double Hydroxide‐Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes (CNTs) and flame retardancy of layered double hydroxide (LDH) in epoxy resin (EP), organic nickel‐iron layered double hydroxide (ONiFe‐LDH‐CNTs) hybrids were assembled through co‐precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe‐LDH‐CNTs nanocomposites containing 4 wt% of ONiFe‐LDH‐CNTs with different ratios of ONiFe‐LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy (TEM). The results revealed a coexistence of exfoliated and intercalated ONiFe‐LDH‐ CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe‐LDH‐CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe‐LDH and synergistic effect between ONiFe‐LDH and CNTs.     

LDPE/Mg-Al layered double hydroxide nanocomposite: Thermal and flammability properties

Layered double hydroxides (LDHs) are new nanofillers which exhibit improved thermal and flammability properties in various kinds of polymer matrices. These materials have certain advantages over conventional metal hydroxides and also layered silicates so far as the flame retardancy is concerned. In this article, flammability and thermal properties of the nanocomposite based on low density polyethylene (LDPE) and Mg-Al based layered double hydroxide (Mg-Al LDH) are reported in detail. The nanocomposites containing different LDH concentrations were prepared by melt-compounding using a tightly intermeshing co-rotating twin-screw extruder. The morphological analysis reveals an exfoliated/intercalated type LDH particle morphology in these nanocomposites. The thermogravimetric analysis (TGA) shows that even a small amount of LDH improves the thermal stability and onset decomposition temperature in comparison with the unfilled LDPE. The heat release rate (HRR) and its maximum (PHRR) during cone-calorimeter investigation are found to be reduced significantly with increasing LDH concentration. The nanocomposites not only exhibit reduced total heat released (measure of propensity to produce long duration fire), but also lower tendency to fast fire growth (measured by the ratio of PHRR and time of ignition). The limited oxygen index (LOI) and the dripping behavior are also improved with increasing LDH concentration.