Intumescent flame retardant–montmorillonite synergism in polypropylene‐layered silicate nanocomposites

Polypropylene/clay nanocomposites have been prepared starting from pristine mont morillonite (MMT) and reactive compatibilizer hexadecyltrimethylammonium bromide (C16). The nanocomposite structure is evidenced by the X‐ray diffraction and high resolution electronic microscopy. Intumescent flame retardant has been added to polypropylene/clay hybrids. Their flammability behaviours have been evaluated using cone calorimetry. Synergy was observed between the nanocomposites and intumescent flame retardant. Copyright © 2003 Society of Chemical Industry     

Synthesis of resol–layered silicate nanocomposites by reaction exfoliation with acid‐modified montmorillonite

Resol–layered silicate nanocomposites were prepared by the intercalative polymerization of phenol and formaldehyde in the presence of acid‐modified montmorillonite (HMMT). The nanocomposites were studied by means of X‐ray diffraction, scanning electron microscopy, transmission electron microscopy, dynamic mechanical analysis (DMA), and rheological measurements. The exfoliation of HMMT was promoted by the intragallery reactions catalyzed by protons in the galleries of the clay, whereas the extragallery polymerization catalyzed by ammonia went on simultaneously. The nanocomposites showed higher glass‐transition temperatures in the DMA diagram compared with the resol counterparts. The impact strength was improved significantly by the incorporation of the clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 791–797, 2004     

Reduced shrinkage polyester–montmorillonite nanocomposite

A new approach is described for utilizing the swelling characteristics of montmorillonite (MMT) to compensate for polymerization‐induced shrinkage in unsaturated polyester. The naturally sorbed sodium cation, at the lamellar interface of the mineral, was exchanged with the onium salt of 12‐aminolauric acid to produce organophilic MMT, which was compatible with the host resin. The latter, boosted by a small amount of dimethylformamide, swelled into a polymerizing polyester resin, thus reducing polymerization shrinkage. The incorporation of 5% 12‐aminolauric MMT caused the shrinkage of the neat isophthalic polyester resin to be reduced from 8.7 to 2.6%. Wide‐angle X‐ray diffraction and high resolution scanning electron microscopy analyses showed that the shrinkage reduction was associated with increased interparticle spacing and uniform dispersion of the MMT domains on the nanoscale. Mechanical measurements indicated that the flexural strength of the new compound was comparable to that of the neat resin; however, a remarkable 100% increase in toughness was observed in association with a minor decrease in the modulus of elasticity. This increased toughness may be attributed to macromolecular changes associated with the monofunctional acid moiety of the 12‐aminolauric acid. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 767–773, 2005     

Electrokinetic properties of polypropylene‐layered silicate nanocomposite fibers

Nanocomposite fibers based on polypropylene (PP) polymer were prepared with different content of nanofiller. Filaments were spun from an isotactic iPP homopolymer. Montmorillonite modified by N,N‐dimethyl‐N,N dioctadecylammonium cations was used for preparation of PP nanocomposite fibers. A PP grafted with acrylic acid was added as a coupling agent. Nanocomposite fibers were characterized, i.e., the surface morphology of PP nanocomposite fibers was observed and surface properties were defined by electrokinetic properties determination by zeta potential measurements. For particle distribution observation the plasma etching was involved as a method for sample preparation. The addition of nanoparticles has an impact on ZP value of nanofilled fibers, however, isoelectric point IEP is not significantly influenced by different concentrations of nanofiller. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel preparation of poly(propylene)–layered silicate nanocomposites

We used a novel approach to prepare poly(propylene)–clay nanocomposite starting from pristine montmorillonite and reactive compatibilizer hexadecyl trimethyl ammonium bromide. The nanocomposite structure was revealed by X‐ray diffraction and high‐resolution electronic microscopy. The thermal properties of the nanocomposite were investigated by thermogravimetric analysis. An increase of thermal stability was observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2586–2588, 2003     

Nanostructure and viscoelasticity of layered silicate nanocomposite–electrolyte supports

There is the need for novel polyelectrolytes with enhanced thermal and mechanical properties. In this report, we have reinforced a polyelectrolyte based on poly(dimethylaminoethylmethacrylate) (PDMAEM) using nanoclay montmorillonite (MMT), and have studied the thermal and viscoelastic properties. The protonated polymer (PDMAEMH) was solution mixed with functionalized MMT. Recognizing that the sort of surfactant may have a profound influence on the physical properties of the polymer matrix, neat MMT, and MMT treated with different surfactants (sulfobetaine and ammonia) were used, and the concentration of the nanofiller was varied from 1 to 5%w/w. Strikingly, while PDMAEM exhibited a glass transition temperature T_g of 32°C, the protonated PDMAEMH showed T_g = 155°C. Master curves obtained by applying the time‐temperature superposition principle showed that PDMAEM behaved predominantly elastic (G″ < G′) suggesting an entangled polymer melt. However, PDMAEMH exhibited much longer relaxation times, a shift of ca. seven decades in frequency, suggesting that ionic interactions significantly hampered the molecular dynamics. X‐ray scattering demonstrated that lower concentration and sulfobetaine surfactant favored exfoliation whereas ammonia and untreated MMT favored intercalation of the nanoplates. Furthermore, an enhancement in dynamic storage shear modulus was observed for the nanocomposites exhibiting intercalated morphologies relative to those displaying an exfoliated morphology. It is then suggested that the molecular dynamics is further slowed down due to confinement of the macromolecules between the nanoplates. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of poly(acrylonitrile–butadiene–styrene)/montmorillonite nanocomposites and degradation studies during extrusion reprocessing

In this study, the preparation of organically modified montmorillonite/poly(acrylonitrile–butadiene–styrene) (ABS) nanocomposites was studied by melt blending in a twin‐screw extruder. The composite material was subjected to a series of five extrusion cycles, and the effect of reprocessing on the material's structural properties was investigated. More specifically, chemical changes were studied with attenuated total reflectance/Fourier transform infrared analysis, the thermal response was recorded by differential scanning calorimetry experiments, and the thermal stability was detected with thermogravimetric analysis. Also, the rheological properties of these blends were investigated via melt flow index tests as a measure of their processability during melt mixing and molding processes. Furthermore, the mechanical strength of the obtained mixtures was explored, and the observed interactions were interpreted in terms of the influence of each component on the functional properties of the final mixture. This attempt enriched our knowledge about the recycling of ABS, with the additional aspect of the use of collected data from more complex systems, that is, composite materials, where the montmorillonite nanoparticles play a role in the interactions initiated by repeated processing. The experimental results of this study show that the reprocessing of ABS/montmorillonite induced oxidation products, but the rheological, mechanical, and thermal properties and the thermal and color stabilities of the composites remained almost stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of compatibilizer on the layered silicate/ethylene vinyl acetate nanocomposite

Dispersion behavior of monmorillonite (MMT) is investigated in ethylene vinyl acetate (EVA)/MMT nanocomposite with various vinyl acetate content. Maleic anhydride (MAH) grafted polyethylenes with various MAH contents are used as a compatibilizer to enhance the dispersion of MMT. DMA and XRD studies indicate that an intercalated/exfoliated structure is obtained and vinyl acetate content and the concentration of PEMA play a critical role in EVA/MMT nanocomposite. Higher vinyl acetate content and concentration of grafted maleic anhydride result in better dispersion of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1057–1061, 2004     

Organo‐soluble polyimde (ODA–BSAA)/montmorillonite nanocomposite materials prepared by solution dispersion technique

A series of polymer–clay nanocomposite materials, consisting of organo‐soluble polyimide (ODA‐BSAA) matrix and dispersed nanolayers of inorganic montmorillonite clay, were successfully prepared by solution dispersion technique and subsequently characterized by FTIR, powder X‐ray diffraction patterns, transmission electron microscopy, and atomic force microscopy. Effects of the materials composition on the corrosion protection performance, gas barrier, and optical properties, in the form of both coating and film, were also studied by electrochemical corrosion measurements (e.g., corrosion potential, polarization resistance, corrosion current, impedance spectroscopy), gas permeability analysis, and UV–visible transmission spectroscopy, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1082–1090, 2005     

Preparation and properties of (BATB–ODPA) polyimide–clay nanocomposite materials

A series of polymer–clay nanocomposite (PCN) materials consisting of 1,4‐bis(4‐aminophenoxy)‐2‐tert‐butylbenzene–4,4′‐oxydiphthalic anhydride (BATB–ODPA) polyimide (PI) and layered montmorillonite (MMT) clay were successfully prepared by an in situ polymerization reaction through thermal imidization up to 300°C. The synthesized PCN materials were subsequently characterized by Fourier‐Transform infrared (FTIR) spectroscopy, wide‐angle powder X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of material composition on thermal stability, mechanical strength, molecular permeability and optical clarity of bulk PI and PCN materials in the form of membranes were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), molecular permeability analysis (GPA) and ultraviolet‐visible (UV/VIS) transmission spectra, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1072–1079, 2004     

Characteristics of nitrile–butadiene rubber layered silicate nanocomposites with silane coupling agent

Nanocomposites of organophilic montmorillonite (C18‐MMT), nitrile–butadiene rubber (NBR), and a coupling agent were produced during a melt compounding process at room temperature. During the process, it was clearly observed that organo‐MMT particles were exfoliated into nanoscale layers of approximately 1–30 nm thickness, in addition to their original 40 μm thickness. These MMT layers were uniformly dispersed in the NBR matrix. The effects of a coupling agent such as 3‐(mercaptopropyl)trimethoxy silane in C18‐MMT/NBR nanocomposites were studied. The C18‐MMT/NBR nanocomposites in the presence of the coupling agent were identified and characterized by X‐ray diffraction, transmission electron microscopy, a universal testing machine, thermogravimetric analysis, and IR spectroscopy. It was observed that an additional silane coupling agent, 3‐(mercaptopropyl)trimethoxy silane, enhanced the chemical interaction and was accompanied by the formation of Si? O? Si coupling bonds between C18‐MMT and the coupling agent and Si? C coupling bonds between NBR and the coupling agent. This work resulted in improved properties of organo‐MMT/NBR nanocomposites because of the nanoscale effects and strong interaction of the coupling bonds between NBR and organo‐MMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2633–2640, 2003     

Mechanical and rheological properties of the maleated polypropylene–layered silicate nanocomposites with different morphology

Three types of maleated polypropylene–layered silicate nanocomposites with different dispersion states of layered silicate (deintercalated, intercalated, and exfoliated states) are prepared from two kinds of polypropylenes with different molecular weights, organically modified layered silicate and pristine montmorillonite to investigate the effect of the final morphology of the nanocomposite on the rheological and mechanical properties. Maleated polypropylene with high molecular weight intercalates slowly and the other with low molecular weight exfoliates fast into the organophilic layered silicates. Rheological properties such as oscillatory storage modulus, nonterminal behavior, and relative viscosity has close relationship with the dispersion state of layered silicates. The exfoliated nanocomposite shows the largest increase and the deintercalated nanocomposite shows almost no change in relative shear and complex viscosities with the clay content. The exfoliated nanocomposite shows the largest drop in complex viscosity due to shear alignment of clay layers in the shear flow. In addition, the final dispersion state of layered silicates intimately relates to the mechanical property. The dynamic storage moduli of nanocomposites show the same behavior as the relative shear and complex viscosities. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1526–1535, 2003     

Evaluation of degradation on Nylon-6 and Nylon-6/montmorillonite nanocomposite by color measurement

An evaluation of degraded level is an important subject for industrial products. Ordinarily, many kinds of polymer material changes its color through the degrading process by altering its chemical structure, and IR and UV are applicable to ensure the production of the functional groups. However, these methods are hardly applicable to measurements of product on site without the sample collection. A spectrophotometer is sufficiently lightweight, compact, and capable of measurements on site without the sample collection. With these backgrounds, the correlation of the color with the tensile strength and the molecular weight was studied by using the spectrophotometer. Through the thermal aging test at various temperatures, specimens became yellowish and the increase rate of color change was different between neat Nylon-6 and Nylon-6 nanocomposite. Such changes were closely related to the tensile strength and the molecular weight. As a method to evaluate the polymer degradation, the correlation of the difference of yellowness index (ΔYI) with the tensile strength and the molecular weight was sufficiently high and the ΔYI indicated a difference between neat Nylon-6 and Nylon-6 nanocomposite. From these results, it is found that the color measurement with the spectrophotometer is a practical method for evaluation of polymer degradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Mechanical and gas permeation properties of compatibilized polypropylene–layered silicate nanocomposites

Nanocomposites of polypropylene with montmorillonite modified with dimethyldioctadecylammonium ions were prepared and the effect of compatibilizers on the mechanical and permeation properties was investigated. Compatibilizers were selected on the basis of their chemical nature, molecular weight, amount of grafting and location of the polar groups. Addition of small amount of compatibilizers led to improvements in the basal spacings of clay platelets indicating enhanced exfoliation. The modulus of the composites increased as compared with the values without compatibilizer. The oxygen permeation through the composite films either increased or remained unaffected due to possible interfacial free volume enhancement owing to the incompatibility of the surface modification and the compatibilizer. Increasing the amount of compatibilizer also increased correspondingly the extent of exfoliation. The modulus reached a plateau value after which the increasing compatibilizer led to its decrease. The gas permeation through the composite films remained unchanged with increase in the amount of compatibilizer owing to a possible balance between the decrease in permeation due to path tortuity and exfoliation and increase in permeation due to interfacial incompatibility. The improving exfoliation improved the yield and break stress indicating that the absence of tactoids can hinder the premature failure owing to better stress transfer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fiber spinning from poly(propylene)–organoclay nanocomposite

SOMASIF ME C16, a filler that enables generation of anisotropic nanoparticles by in situ exfoliation of organic layered silicates, was melt compounded with poly(propylene) (PP) in the presence of maleic anhydride‐grafted PP. Fibers were prepared from this composite by a spinning procedure. The prepared anisotropic fibers were partially oriented by using different drawing ratios. The morphological study showed that the drawing ratio of the fibers particularly influences the level of exfoliation of the SOMASIF ME C16 where the nanoparticles are formed. The layered sheets of the SOMASIF particles are oriented in the direction of the fiber axis. The tensile strength of the filled fibers increases with the increase of drawing ratio much more than that of unfilled PP fibers. This result is accounted for by the formation of exfoliated structures from the nanoparticles of SOMASIF ME C16 by fiber drawing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 604–611, 2003     

Properties of poly(vinyl alcohol)—Bentonite clay nanocomposite films in relation to polymer–clay interactions

This study describes an effective way for the preparation of well‐dispersed, high‐loaded PVA/bentonite nanocomposites with improved properties, based on nanoscale interactions. To this end, a series of Poly(vinyl alcohol)—bentonite clay nanocomposites have been prepared via solvent casting technique and their properties were thoroughly investigated by atomic force microscopy, transmission electron microscopy, X‐Ray diffraction, oxygen and water permeability, water sorption along with mechanical and thermal studies. Microscopic and XRD techniques revealed highly organized regions. Clay content up to 10% led to nanocomposites with high degree of exfoliation. In addition samples with increased filler content (20%) demonstrated also, apart from the delaminated, well‐organized intercalated regions. The nanocomposites exhibited increased mechanical, thermal and gas barrier properties, though they retained their optical clarity. Thus, the Young's modulus of the sample containing 20% clay was increased by 193 times, while the oxygen permeability was decreased about seven times, in regard to the corresponding values of the neat polymer. The obtained results were explored on the basis of nanoscale phenomena and it was concluded that the organized structures and intercalated regions observed on highly loaded samples are attributed to the competitive effect between weaker polymer–polymer interactions in relation to stronger polymer–clay ones. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Poly(m‐xylene adipamide)–kaolinite and poly(m‐xylene adipamide)–montmorillonite nanocomposites

Two clay compounds, montmorillonite (Cloisite 30B) and kaolinite, were dispersed in a poly(m‐xylene adipamide) resin at loading levels of 2 wt % clay. The samples were melt‐compounded and extruded. The extruded samples were injection‐molded into preforms and then blow‐molded into multilayer bottles. Rheology, calorimetry, electron microscopy, and gas‐transport measurements were performed. Both clays were nucleating agents, giving crystallite sizes that did not cause haze. Kaolinite was more difficult to exfoliate than montmorillonite, and under similar processing conditions, kaolinite resulted in a higher degree of crystallinity. Both nanocomposites exhibited improved gas‐barrier properties over the neat resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1377–1381, 2007     

Influence of montmorillonite layered silicate on plasticized poly(l-lactide) blown films

Plasticized poly(l-lactide) (PLA) montmorillonite layered silicate (MLS) nanocomposites were compounded and blown-film processed using a co-rotating twin screw extruder. PLA was mixed with 10 wt% acetyltriethyl citrate ester plasticizer and 5 wt% of an organically modified montmorillonite at various screw speeds. Wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM) determined that the compounded pellets and the blown film PLA/MLS nanocomposites were intercalated. The effect of processing screw speeds on the barrier, thermal, mechanical, and biodegradation properties of the nanocomposites were analyzed and compared to the neat polymer. Nanocomposite films show a 48% improvement in oxygen barrier and a 50% improvement in water vapor barrier in comparison to the neat PLA. The thermogravimetric analysis (TGA) showed an overall 9 °C increase in the decomposition temperature for all of the nanocomposites. Differential scanning calorimetry (DSC) has determined that the glass transition, cold crystallization and melting point temperatures were not significantly influenced by the presence of MLS. Mechanical properties of the nanocomposites showed that the Young's modulus increased by 20% and the ultimate elongation of the nanocomposites were not sacrificed in comparison to the neat samples. Biodegradation rates in soil were slightly greater for the PLA/MLS nanocomposite than the pure PLA. However, none of the PLA pure and nanocomposites achieved significant biodegradation levels after 180 days.     

Water uptake behavior of layered silicate/starch–polycaprolactone blend nanocomposites

The water uptake behavior of biodegradable layered silicate/starch–polycaprolactone blend nanocomposites was evaluated. Three different commercial layered silicates (Cloisite Na⁺, Cloisite 30B and Cloisite 10A) were used as reinforcement nanofillers. Tests were carried out in two different environments: 60 and 90% relative humidity using glycerol solutions. The clay/starch–polycaprolactone blend nanocomposites were obtained by melt intercalation and characterized by gravimetric measurements and tensile tests. The intercalated structure (determined by wide‐angle X‐ray diffraction) showed a decrease in water absorption as a function of clay content probably due to the decrease of the mean free path of water molecules. The diffusion coefficient decreased with clay incorporation but a further increase in the clay content did not show an important effect on this parameter. Elongation at break increased with exposure showing matrix plasticization. Mechanical properties of the nanocomposites deteriorated after exposure whereas they remained almost constant in the case of the neat matrix. Copyright © 2007 Society of Chemical Industry     

Adhesion and permeability of polyimide–clay nanocomposite films for protective coatings

A polyimide (PI)–clay nanocomposite was prepared from a solution of poly(amic acid), a precursor of 2,2‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and p‐phenylenediamine, and dodecylamine–montmorillonite. Fourier transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, and atomic absorption spectroscopy were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the modified clay into the PI matrix. Both PI and PI–clay films were subsequently prepared by solution casting. The gas permeability, resistivity, and adhesion properties were determined. In the case of gas permeability, only a 3 wt % addition of clay reduced oxygen permeability to less than half that of unfilled PI. Furthermore, this hybrid showed an improvement in electrical resistivity because of the prevention of electrical tree growth by clay particles. More importantly, adhesion between the films and silicon increased with increasing clay content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2875–2881, 2003