Layered Silicate Clay Research Articles

Polyamide‐6/natural clay mineral nanocomposites prepared by solid‐state shear milling using pan‐mill equipment

AbstractThe polyamide‐6 (PA6)/natural clay mineral nanocomposites were successfully prepared by solid‐state shear milling method without any treatment of clay mineral and additives. PA6/clay mixture was pan‐milled to produce PA6/clay compounding powder, using pan‐mill equipment. The obtained powder as master batch was diluted with neat PA6 to prepare composites by a twin‐screw extruder. The clay silicate layers were found to be partially exfoliated and dispersed homogeneously at nanometer level in PA6 matrix. The rheological measurements and mechanical properties of nanocomposites were characterized. The shear viscosities of nanocomposites were higher than that of pure PA6, and tensile strength and tensile modulus increased, but Izod impact strength decreased, with increasing concentration of clay. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 249–255, 2006

Nanoclay‐induced morphology development in chaotic mixing of immiscible polymers

AbstractThis study investigated the role of layered silicate clay on morphology development in chaotic mixing of two immiscible polymers, polypropylene (PP) and polyamide 6 (PA6). The study showed that clay particles helped to produce droplets of much smaller size and with narrower size distribution due to their direct influence on the breakup of PP domains. In the experiments, a small quantity of organically modified layered silicate clay was initially mixed in PP and the mixture was blended with PA6 in a chaotic mixer. All morphological forms, such as lamellas, fibrils, and droplets were seen as in the case with no clay. The clay particles reduced interfacial tension between PP and PA6 phases. As a consequence, the PP domains sustained lamellar and fibrillar forms, and thin fibrils were formed. These thin fibrils in turn broke rapidly into smaller droplets. It was also found that a large fraction of clay particles migrated into PA6 phase and contained intercalated PA6 chains in their galleries. These results indicate that clay particles did not participate in compatibilization in this system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3638–3651, 2005

One-pack cross-linkable waterborne methyl ethyl ketoxime-blocked polyurethane/clay nanocomposite dispersions

One-pack cross-linkable nanocomposites of waterborne methyl ethyl ketoxime (MEKO)-blocked aromatic polyurethane dispersion (BPUD) reinforced with organoclay (quaternary ammonium salt of Cloisite 25A) were synthesized by the acetone process using 4,4′-methylenedi-p-phenyl diisocyanate (MDI), poly(tetramethylene) glycol (PTMG), dimethylol propionic acid (DMPA), and methyl ethyl ketoxime (MEKO). Particle size, viscosity, and storage stability of these nanocomposites were investigated. TEM and XRD studies confirmed that the silicate layers of organophilic clay were exfoliated and intercalated at a nanometer-scale in the BPUD matrix.

Improvements on the synthesis and properties of fluorinated polyimide–clay nanocomposites by using double-swelling agents

Polyimide (6FBpA–6FDA)–montmorillonite nanocomposites (PiCN) were synthesized from modified montmorillonite (MMT) and poly(amic acid), using single- and double-swelling agents. The silicate layers of clay in the matrix of 6FBpA–6FDA were intercalated and became more exfoliated when double (DAETPB–ODA) swelling agents were used to modify the montmorillonite. Structures of exfoliation were confirmed by wide-angle X-ray diffraction (WAXRD) and transmission electron microscopy (TEM). The improved exfoliation of nanocomposites by the double-swelling agents resulted in enhanced thermal and mechanical properties. In particular, the maximum increase in Td, Tg, and storage modulus of these nanocomposites was found to be those with addition of 5.0wt% DAETPB–ODA modified-MMT. The moisture absorption of these nanocomposites was also reduced by the addition of double-swelling agent-modified MMT. The dielectric properties of PiCN in the form of film with MMT loading from 1.0 to 5.0wt% were measured under frequencies of 100Hz–1MHz at 35–150°C. Reduced dielectric constants were observed for these fluorinated polyimide–clay nanocomposites.

Thermoplastic polyurethane nanocomposites of reactive silicate clays: effects of soft segments on properties

This paper addresses the effects of soft-segment on clay particle exfoliation and resultant mechanical and thermal properties of nanocomposites of reactive layered silicate clay and thermoplastic polyurethanes (TPU). The composites were synthesized via a two-step bulk polymerization scheme from polyether- and polyesterpolyols of molecular weight 2000, diphenylmethanediisocyanate, butanediol, and up to 5 wt% reactive layered silicate clay. It was found that the extent of tethering reactions between polymer chains carrying residual –NCO groups and reactive clay particles was significant, although did not depend on the nature of polyol used. Nanocomposites were obtained only in the case of polyesterpolyol, which can be attributed to both clay–polymer reactions and higher viscosity in the clay–polymer mixing step. These nanocomposites showed 125% increase in tensile stress, 100% increase in elongation, and 78% increase in tensile modulus along with 130% increase in tear strength and a 60% reduction in volume loss in abrasion test. It was observed that hydrogen bonding did not influence the properties and the extent of hydrogen bonding was not affected by the clay particles.

Properties of bulk-polymerized thermoplastic polyurethane nanocomposites

The thermal, rheological, and mechanical properties of bulk-polymerized thermoplastic polyurethane nanocomposites of reactive and non-reactive layered silicate clay were characterized as a function of the state of dispersion of particles. True exfoliated nanocomposites were produced by mixing reactive clay particles with polymer chains carrying residual isocyanate groups. On the other hand, non-reactive clay particles yielded only intercalated composites. Most significant improvement in mechanical properties were obtained when clay particles were fully exfoliated, e.g. 110% increase in tensile modulus, 170% increase in tensile strength, 110% increase in tear strength, 120% increase in fracture toughness, and 40% increase in abrasion resistance over pristine polyurethane with 5 wt% clay. In addition, the terminal dynamic rheological data showed strong dependence on the clay content, indicating substantial hindrance to chain relaxation by tethering clay particles. The peak location and the area under the peak of hydrogen-bonded carbonyl showed two distinct zones of temperature dependence, which indicate additional hydrogen bonding between polymer chains and organic modifier of reactive clays.

High-strength and low-stiffness composites of nanoclay-filled thermoplastic polyurethanes

In this study, bulk polymerized clay-tethered thermoplastic polyurethane (TPU) composites were synthesized that offered much improved tensile strength with negligible changes in tensile modulus. These composites contained intercalated, tethered layered silicate particles and were synthesized by mixing low molecular weight prepolymer chains containing unreacted –NCO groups with reactive layered silicate clay followed by catalyzed chain extension reaction with butanediol. The molar ratio of –NCO and –OH functional groups in the composite was varied between 1.0 and 1.2. It was found that an appreciable amount of –NCO groups was consumed in reaction with moisture present in the clay and some in quaternary ammonium ion-catalyzed dimerization and trimerization. Composites with –NCO to –OH molar ratio 1.1 provided the best improvement in mechanical properties—the composite with 5 wt% clay provided a 60% increase in tensile strength and 50% increase in strain at break, while the tensile modulus increased only by 15% over TPU. POLYM. ENG. SCI., 45:1532–1539, 2005. © 2005 Society of Plastics Engineers

Influence of fillers on free volume and gas barrier properties in styrene-butadiene rubber studied by positrons

The measurements of free-volume hole property by positron annihilation lifetime spectroscopy (PALS) have been carried out for polymer–clay nanocomposite materials that consist of styrene–butadiene rubber (SBR) and layered silicate clay of rectorite and conventional composite materials N326 (carbon black) /SBR. The PALS and differential scanning calorimeter (DSC) results show layered rectorite has a stronger effect on restraining polymer chain mobility which results in the decrease of fraction free volume and gas permeation than carbon black. The dispersion of nanoscale rectorite clay in SBR largely enhances gas barrier property in contrast to results obtained in N326/SBR system. Experimental results reveal that gas permeability in rectorite/SBR nanocomposite is mainly influenced by fractional free volume and tortuous diffusional path effects attributed to the clay plateletlike morphology.

Novel biobased nanocomposites from functionalized vegetable oil and organically-modified layered silicate clay

The new biobased nanocomposites are processed from anhydride-cured epoxidized linseed oil (ELO)/ or octyl epoxide linseedate (OEL)/diglycidyl ether of bisphenol F (DGEBF) epoxy matrix and organomontmorillonite clay. The selection of anhydride curing agent and biobased epoxy resulted in an excellent combination to provide an epoxy matrix having high elastic modulus, high glass transition temperature, and high heat distortion temperature (HDT), with higher amounts of functionalized vegetable oil (FVO), compared with amine-cured biobased epoxy. The sonication technique was utilized to process the organically-modified clay nanoplatelets in the glassy biobased epoxy network resulting in nanocomposites where the clay nanoplatelets are almost completely exfoliated and homogeneously dispersed in the epoxy network. The processed exfoliated clay nanocomposites showed higher storage modulus compared with the neat epoxy containing the same amount of FVO. Therefore, the lost storage modulus with larger amount of FVO can be regained with exfoliated clay nanoreinforcement.

Adverse effects of thermal dissociation of alkyl ammonium ions on nanoclay exfoliation in epoxy–clay systems

It has been shown recently that storage modulus of intra-gallery epoxy plays a crucial role in producing exfoliated clay structures in epoxy-nanoclay systems. In this study, the possibility of thermal dissociation of alkyl ammonium ions used as cation exchange agents of layered silicate clays and its effects on plasticization of epoxy networks and the growth of storage modulus of intra-gallery epoxy were investigated. It was found that at cure temperatures higher than the dissociation temperature, primary amines were generated from the thermal dissociation of alkyl ammonium ions and the excess chloride salt, which reacted readily with the epoxy molecules and formed linear chains. In addition, such reactions resulted in an excess of diamine curing agents, which in turn caused additional plasticization of epoxy networks and lowered the values of intra-gallery storage modulus. In such cases, only intercalated epoxy composites were produced.

Preparation and properties of ethylene propylene rubber (EPR)–clay nanocomposites based on maleic anhydride‐modified EPR and organophilic clay

AbstractEthylene propylene rubber–clay nanocomposites (EPR–CNs) were prepared by melt‐compounding maleic anhydride modified EPR (EPR‐MA) with organophilic clay, and their properties were examined. Silicate layers of organophilic clay were found to exfoliate and homogeneously disperse into the nanometer level in the nanocomposites by transmission electron microscopy observation. EPR–CNs exhibited higher tensile moduli compared to EPR‐MA and composites containing conventional fillers such as carbon black, talc. The storage moduli of EPR–CNs were also higher than those of EPR‐MA and the conventional composites. Creep resistances of EPR–CNs were much improved compared for EPR‐MA. Degree of swelling in hexadecane was remarkably restricted. Improvement of these properties is caused because dispersed silicate layers have much large interface with the EPR matrix and are thought to strongly restrain the EPR polymer chains. Nanocomposite technology using small amount of silicate layers is useful to improve properties of thermoplastic elastomer. Various kinds of thermoplastic elastomers are expected to be produced by loading of silicate layers with or without conventional fillers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 758–764, 2004

Novel Mechanism for Layered Silicate Clay Intercalation by Poly(propylene oxide)‐Segmented Carboxylic Acid

AbstractSummary: Poly(propylene oxide)‐amidoacids were used to intercalate montmorillonite clay to afford organoclays with an X‐ray basal spacing as wide as 81 Å. Differing from the ionic exchange between quaternary ammonium salts and the metal ions in clays, the intercalation mechanism involves a beta‐amidoacid chelation with sodium ions in the silicate interlayer confinement. With the end groups tethered on the silicate surface, the hydrophobic poly(propylene oxide)‐backbones self‐aggregate and consequently widen the interlayer space between neighboring silicate plates.Postulated structure of the chelation of sodium ions by the poly(propylene oxide)‐amido acid.magnified imagePostulated structure of the chelation of sodium ions by the poly(propylene oxide)‐amido acid.

Arranged Microdomain Structure Induced by Clay Silicate Layers in Block Copolymer-Clay Nanocomposites

We propose a novel scheme for controlling the nanostructures of organic polymer materials by using nanoparticles as templates and we also demonstrate a spontaneous formation of arranged microdomain structures in block copolymers controlled by clay silicate layers dispersed at the nanometer level. Block copolymer-layered silicate nanocomposites were prepared by melt compounding of hydrogenated styrene-butadiene-styrene triblock copolymer with organophilic layered silicates intercalated with stearylammonium. Their morphologies were observed by transmission electron microscopy. The triblock copolymer microdomain structures were found to be arranged along the dispersed silicate layers. Such structures did not exist in the original block copolymer. TEM images suggest that the formation of the arranged microdomain structures are induced and controlled by the interaction of the silicate layers, which act as templates. It is thought that these controlled nanostructures were formed through the selective absorption of the polystyrene segments on dispersed silicate surfaces followed by segregation of each segment.

Preparation and electrorheological characterization of suspensions of poly(urethane acrylate)/clay nanocomposite particles

AbstractMicron‐sized poly(urethane acrylate) (PUA)/clay nanocomposite particles were synthesized by suspension polymerization. UA containing a poly(ethylene oxide) group in the main chain was first inserted into the silicate layers of montmorillonite clay through mixing the UA with the clay. Then, ethylene glycol dimethacrylate and an oil‐soluble initiator were added into this UA/clay mixture, followed by the emulsification of the monomer mixture in an aqueous solution of polymeric stabilizer. Suspension polymerization was carried out at 60°C for 12 h to obtain the PUA/clay composite particles. The incorporation of clay into the polymer phase was verified by FTIR spectroscopy, and the intercalation structure of the clay composite was confirmed by X‐ray diffraction analysis. Other characterizations including thermal analysis, morphological observation, and dielectric analysis were also performed. After suspensions of bare PUA and PUA/clay nanocomposite particles in silicone oil were prepared, their electrorheological properties were measured under various electric fields and compared. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 458–464, 2003

Structure and properties of nitrile rubber (NBR)–clay nanocomposites by co‐coagulating NBR latex and clay aqueous suspension

AbstractNitrile rubber (NBR)–clay nanocomposites were prepared by co‐coagulating the NBR latex and clay aqueous suspension. Transmission electron microscopy showed that the silicate layers of clay were dispersed in the NBR matrix at the nano level and had a planar orientation. X‐ray diffraction indicated that there were some nonexfoliated silicate layers in the NBR–clay nanocomposites. Stress–strain curves showed that the silicate layers generated evident reinforcement, modulus, and tensile strength of the NBR–clay nanocomposites, which were significantly improved with an increase in the amount of clay, and strain‐at‐break was higher than that of the gum NBR vulcanizate when the amount of clay was more than 5 phr. The NBR–clay nanocomposites exhibited an excellent gas barrier property; the reduction in gas permeability in the NBR–clay nanocomposites can be described by Nielsen's model. Compared with gum NBR vulcanizate, the oxygen index of the NBR–clay nanocomposites increased slightly. The feasibility of controlling rubber flammability via the nanocomposite approach needs to be evaluated further. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3855–3858, 2003

Nylon 6/Na–montmorillonite nanocomposites prepared by compounding Nylon 6 with Na–montmorillonite slurry

We report a novel compounding process using Na–montmorillonite water slurry for preparing novel nylon 6/Na–montmorillonite nanocomposites. In this compounding process, the Na–montmorillonite slurry was blended with melting nylon 6 using an extruder, followed by removing the water. The Na–montmorillonite silicate layers were found to be exfoliated and dispersed homogeneously at nanometer level in the nanocomposites with an electron transmission microscope. The exfoliated Na–montmorillonite silicate layers were fixed in the nylon 6 matrix almost as they were in water. The nylon 6/Na–montmorillonite nanocomposites, loaded with only 1.6 wt% clay silicate layers, exhibited high strength, high modulus, high heat distortion temperature and low gas permeability compared to neat nylon 6. The properties of the nylon 6/Na–montmorillonite nanocomposites were nearly equal to those of conventional nylon 6/clay nanocomposites prepared by dry-compounding nylon 6 and organophilic clay ion-exchanged with alkylammonium ions.

Flammability and phase-transition studies of nylon 6/montmorillonite nanocomposites

Nylon 6 (PA6)/clay hybrids have been prepared using a direct melt intercalation technique by two processes. One is PA6 melt-mixing with modified clay, the other is PA6 melt-mixing with natural (Na+ base) clay using an ammonium salt bearing long alkyl chains as a polymer/clay reactive compatibilizer. Their structure and flammability properties are characterized by X-ray diffraction, transmission electron microscopy and cone calorimeter experiments. The results of the cone calorimeter experiments show that hybrids made by these two processes have a lower heat release rate peak and higher thermal stability than that of original PA6. Meanwhile, X-ray diffraction was used to investigate PA6/clay hybrids with various cooling histories from the melt, including medium-rate cooling (air cooling) and rapid cooling (water-quenched). In contrast to pure PA6 dominated by the α phase, the addition of clay silicate layers by these two methods favors the formation of the γ crystalline phase in PA6/clay hybrids. Flammability and phase-transition studies confirm that silicate layers added by these two methods have a similar nanoeffect and nanodispersion in the PA6 matrix.

Effects of organoclay Soxhlet extraction on mechanical properties, flammability properties and organoclay dispersion of polypropylene nanocomposites

The organic treatment on a layered silicate used in nanocomposite synthesis is the interface between the hydrophilic layered silicate (clay) and hydrophobic polymer in the case of polypropylene. However, the typical synthesis of an organoclay can result in excess organic treatment which can hinder mechanical and flammability benefits. This excess organic treatment may result in plasticization of the polymer matrix, possibly removing some of the mechanical and flammability property benefits provided by the nanocomposite. In this paper, the effects of using Soxhlet Extraction on the Organoclays after synthesis was investigated. Soxhlet extraction times on organoclays were found to have an effect on the mechanical and flammability properties of the resulting polypropylene nanocomposite. The removal of excess organic treatment by Soxhlet extraction resulted in improvements in flex modulus, improved clay dispersion, delayed time to ignition, and lowered heat release rate during burning.

ミクロ不均質構造への最新アプローチ 共重合ポリマーにおけるクレイシリケート層の分散に関する考察

Polymer-clay nanocomposites have been actively researched in these decades. We studied exfoliation of clay silicate layers in copolymers. Four types of organophilic clay, as bellow, were prepared and examined; (1) organophilic clay ion-exchanged with alkyl ammonium ions consisted of different alkyl chain lengths, (2) partially ion-exchanged with alkyl ammonium ions, (3) ion-exchanged with organophilic reagents containing two ammonium ions, (4) ionexchanged with alkyl ammonium ions containing hydroxide groups(-OH). The dispersibility of the silicate layers in polymers is dependent on polarity matching between the polymers and the organophilic clay.

Toughness of nanoscale and multiscale polyamide‐6,6 composites

AbstractFracture initiation and fracture propagation toughening (R‐curve behavior) of polyamide 6,6 (PA‐66) polymers with different types of layered silicate clay having nanoscale (fully dispersed) or multiscale (mixed nanoscale/microscale) structure were studied. These results were compared to fracture data for conventional kaolin clay particulate reinforcements and a PA‐66 polyblend containing rubber and rigid poly(styrene‐co‐acrylonitrile) particulates. The stiffness increase due to the intercalated clay was the same as would be predicted by classical models for conventional elongated reinforcements at the same volume fraction level. The special benefit of the nanoscale reinforcement derived from their high surface area of contact with the matrix. Toughness in layered silicate clay composites was enhanced by better dispersion of the clay, by exfoliation of the clay layers, and by a stronger clay/matrix interface. A multiscale microstructure was found to be the more desirable microstructure, combining toughness from the nanodispersed clay with resistance curve behavior from the micrometer‐sized particulates. Fracture toughness was proportional to the crack‐tip plastic zone size at fracture, indicating that the clay reinforcements, by influencing shear deformation in the crack tip region, played an important role in promoting toughness. There was indirect evidence for the formation of a zone of damage within the crack‐tip plastic zone that could explain why toughness was not optimal.