Effect of reactive diluents on properties of unsaturated polyester/montmorillonite nanocomposites

Unsaturated polyester (UP)/montmorillonite (MMT) nanocomposite was prepared by using hydroxypropylacrylate (HPA) as a reactive diluent instead of conventional styrene monomer and the effect of polarity of reactive diluent on properties of nanocomposite was investigated. X‐ray and mechanical test data indicated that mixing for an extended period of time is essential to enhance the physical properties of nanocomposites in the UP/Cloisite 6A system. This was attributed to the high polarity of HPA that may disturb the preintercalation of UP resin into the galleries of MMT. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 238–242, 2004     

Preparation of nanocomposite by adding of Tunisian nanoclay in unsaturated polyester matrix: mechanical and thermal study

Unsaturated Polyester (UP) resin is widely used for many applications such as reinforced plastic (FRP) and polymer composites. However, these materials suffer from their low mechanical and thermal properties. For enhancing their performance, researchers have used Tunisian montmorillonite (MMT) for manufacturing of unsaturated polyester-montmorillonite (UP-MMT) nanocomposite synthesized by dispersing the UP resin into the silicate layers of MMT. The MMT has been modified ammonium quaternary as organic cation (OMMT). Test results, supported by mechanical testing, X-ray diffraction, thermal analysis (DSC and TGA) and transmission electron microscopy, indicated that the mechanical properties and the thermal stability of unsaturated polyester with OMMT nanocomposite (UP/OMMT) are better than those of pure UP. The degradation temperature increased by 78 °C with the addition of organic modification, and SEM micrographs show good dispersion of modified montmorillonite in the polymer matrix. Tensile strength is increased by 81 % for the UP/OMMT nanocomposite.     

Effect of fiber‐forming conditions and type of MMT modifier on the structure and properties of multifunctional polyimideamides nanocomposite fibers

The effect of fiber‐spinning conditions on the structure, sorption, and strength properties of polyimideamides (PIA) nanocomposite fibers has been examined. Montmorillonite (MMT) modified with octadecylamine was used as a nanoadditive. The properties of fibers containing differently modified MMT were compared. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2940–2944, 2007     

Preparation and properties of polyethylene–clay nanocomposites by an in situ graft method

The polyethylene–clay nanocomposites were prepared by the in situ graft copolymerization of styrene containing twin‐benzyldimethyldioctadecylammonium bromine modified montmorillonite (TBDO‐MMT) in polyethylene with dicumyl peroxide (DCP) as an initiator in molten state. XRD and TEM analysis indicated that intercalated polyethylene/MMT nanocomposites are obtained. The mechanics performance, crystal behavior, thermal properties, and the effect of MMT contents on PE/MMT nanocomposite were also studied. As comparison, polyethylene/montmorillonite composites prepared by a simply melt compounding without styrene were studied as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4921–4927, 2006     

Ethylene propylene diene terpolymer/ethylene vinyl acetate/layered silicate ternary nanocomposite by solution method

A new ternary nanocomposite has been developed using ethylene propylene diene terpolymer (EPDM), ethylene vinyl acetate (EVA‐45) copolymer, and organically modified layered silicate (16 Me‐MMT) from sodium montmorillonite (Na⁺‐MMT). Wide angle X‐ray diffraction and transmission electron microscopic analysis confirmed the intercalation of the polymer chains in between the organosilicate layers and the nanoscale distribution of 16 Me‐MMT in polymer matrix, respectively. The measurement of mechanical properties for 2–8 wt% of 16 Me‐MMT loadings showed a significant increase in tensile strength, elongation at break, and modulus at different elongations. Such an improvement in mechanical properties has been correlated based on the fracture behavior of nanocomposite by SEM analysis. Thermal stability of EPDM/EVA/layered silicate ternary nanocomposites also showed substantial improvements compared with the neat EPDM/EVA blend, confirming thereby the formation of a high performance nanocomposite. POLYM. ENG. SCI., 46:437–843, 2006. © 2006 Society of Plastics Engineers     

Application of response surface methodology for modeling of reactive dye removal from solution using starch‐montmorillonite/polyaniline nanocomposite

In this study, starch‐montmorillonite/polyaniline (St‐MMT/PANI) nanocomposite was synthesized by chemical oxidative polymerization of aniline in the presence of St‐MMT nanocomposite dispersion. The prepared ternary nanocomposite was characterized using FTIR, XRD, and SEM techniques. Adsorption properties of the nanocomposite were investigated for removal of reactive blue (RB 194) as a model reactive dye from aqueous solution. Response surface methodology was employed for the modeling of adsorption capacity of the nanocomposite. A second‐order empirical relationship between adsorption capacity and independent variables (initial dye concentration, amount of the nanocomposite, and pH of the solution) was obtained. Pareto analysis for identification of the factors effect on the system revealed that initial dye concentration was the most effective parameter. The adsorption capacity value of reactive dye on St‐MMT/PANI nanocomposite was 91.74 mg g^?1. Further investigations indicated that the adsorption experimental data were well fitted to the Langmuir isotherm and pseudo‐second‐order kinetic model. POLYM. ENG. SCI., 54:1595–1607, 2014. © 2013 Society of Plastics Engineers     

Structural effects of type of intercalant in poly (4‐vinylpyridine) nanocomposites: compatible homopolymer or block copolymer

4‐vinylpyridine monomer was mixed with organophilic montmorillonite (MMT) clay and polymerized in the presence of free‐radical initiator. MMT clay was rendered organophilic by means of ion‐exchanging sodium cations for low‐molecular‐weight quaternized poly(4‐vinylpyridine) (P4VP) homopolymer and diblock copolymers of styrene and quaternized 4‐vinylpyridine (SVP) with different sequence lengths. The swelling behaviour of the MMT clay was studied by X‐ray diffraction (XRD). After the cation exchange, the resulting organophilic clays showed an expansion of interlayer distance indicating the nanoscale ordering of intercalant polymer and MMT layers. The nanocomposite materials, when moulded, exhibited improved thermal stability and dynamic mechanical properties compared with neat P4VP. The composite, having longer ionic segments in its organophilic MMT, showed exfoliated nanocomposite structure as well as higher stiffness and damping properties at higher temperatures even for MMT loading as low as 2 wt%. Copyright © 2006 Society of Chemical Industry     

Analysis of the effect of the amount and type of montmorillonite on the supermolecular structure,porosity, and properties of polyimidoamide fibres

The effect of the amount and type of montmorillonite (MMT) on the supermolecular structure, porosity, and properties of polyimidoamide (PIA) fibres has been investigated. An increase in the quantity of nanoadditive incorporated into the fiber‐forming polymer from 1 to 5% results in a decrease in the strength properties of fibers. The level of the sorption parameters of PIA nanocomposite fibers depends not only on the nanoadditive content, but also on the type of modifier used to change the MMT properties from hydrophilic to organophilic. It has been found that the exfoliation of MMT depends on the chemical structure of its modifier. The exfoliation takes place when MMT is modified with aminododecane acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Nanocomposites based on montmorillonite and unsaturated polyester

The concept of nanoscale reinforcement provides opportunity for synthesis of new polymer materials with unique properties. Montmorilonite (MMT) was derived from bentonite, purified, activated by sodium ions and mixed with reacting unsaturated polyester (UP). X-ray and transmission electron microscopy data were in support of the formation of a partially delaminated nanocomposite material. At an MMT content of only 1.5 vol%, the fracture energy, G_Q, of the nanocomposite was doubled, 138 J/m² as compared with 70 J/m² for the pure UP.     

Property enhancement in unsaturated polyester nanocomposites by using a reactive intercalant for clay modification

Polymeric nanocomposites were synthesized from unsaturated polyester (UPE) matrix and montmorillonite (MMT) clay using an in situ free radical polymerization reaction. Organophilic MMT was obtained using a quaternary salt of coco amine as intercalant having a styryl group making it a reactive intercalant. The resultant nanocomposites were characterized via X‐ray diffraction and transmission electron microscopy. The effect of increased nanofiller loading on the thermal and mechanical properties of the nanocomposites was investigated. All the nanocomposites were found to have improved thermal and mechanical properties as compared with neat UPE matrix, resulting from the contribution of nanolayer connected intercalant‐to‐crosslinker which allows a crosslinking reaction. It was found that the partially exfoliated nanocomposite structure with an exfoliation dominant morphology was achieved when the MMT loading was 1 wt %. This nanocomposite exhibited the highest thermal stability, the best dynamic mechanical performance and the highest crosslinking density, most probably due to more homogeneous dispersion and optimum amount of styrene monomer molecules inside and outside the MMT layers at 1 wt % loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical properties and water vapor permeability of starch/montmorillonite nanocomposites

Results of an investigation into an unmodified‐montmorillonite (MMT)‐filled nanocomposite based on plasticized starch are reported. Data on the influence of MMT content on the tensile mechanical properties of the material are presented. Particular attention is given to the water vapor permeability of the nanocomposite. It is found that the resistance to water permeation of plasticized starch can be improved considerably by introducing a rather small amount of the filler into it. Data on the influence of MMT content on the coefficients of moisture diffusion, solubility, and permeability are reported. Also, a simple method for determining the effect of irregularly oriented platelike filler particles on the permeability of the composite material is suggested. The calculation results are compared with experimental data. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

A study of the effect of surfactants on the properties of polystyrene‐montmorillonite nanocomposites

Polystyrene‐Organo Montmorillonite (PS‐MMT) nanocomposites were prepared by suspension free radical polymerization of styrene in the dispersed organophilic montmorillonite. The results of X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) indicated that exfoliated nanocomposites were achieved. The effect of organic modifiers (surfactants) on the properties of the synthesized nanocomposites was studied. It is found that polystyrene‐MMT nanocomposite with 5.0 wt% of organo‐MMT gave the greatest improvement in thermal stability, and polystyrene‐MMT nanocomposites with 7.5 wt% of organo‐MMT showed the greatest improvement in mechanical properties, compared with that of pure polystyrene (PS) in our experimental conditions. The alkyl chain length of surfactant used in fabricating organo‐MMT affects the synthesized PS nanocomposites: the longer the alkyl chain length that the surfactant possesses, the higher the glass transition temperature of the PS nanocomposite, However, the organoclay in the nanocomposites seems to play a dual role: (a) as nanofiller leading to the increase of storage modulus and (b) as plasticizer leading to the decrease of storage modulus. This results in a lower storage modulus of PS‐TMOMMT and PS‐TMTMMT nanocomposites than that of PS‐TMDMMT and PS‐TMCMMT nanocomposites. Further study is needed to confirm the above hypothesis.     

Synthesis and properties of polyimide (containing naphthalene) nanocomposites with organo‐modified montmorillonites

2,7‐Bis(4‐aminophenoxy) naphthalene (BAPN), a naphthalene‐containing diamine, was synthesized and polymerized with a 3,3′,4,4′‐benzophenone tetracarboxylic dianhydride (BTDA) to obtain a polyimide (PI) via thermal imidization. To enhance the thermal and mechanical properties of the polymer, PI–Montmorillonite (MMT) nanocomposites were prepared from a DMAc solution of poly(amic acid) and a DMAc dispersion of MMT, which were organo‐modified with various amounts of n‐dodecylamine (DOA) or cetylpyridium chloride (CPC). FTIR, XRD, and TEM (transmission electron microscopy) were used to verify the incorporation of the modifying agents into the clay structure and the intercalation of the organoclay into the PI matrix. Results demonstrated that the introduction of a small amount of MMT (up to 5%) led to the improvement in thermal stability and mechanical properties of PI. The decomposition temperature of 5% weight loss (T_d,5%) in N₂ was increased by 46 and 36°C in comparison with pristine PI for the organoclay content of 5% with DOA and CPC, respectively. The nanocomposites were simultaneously strengthened and toughened. The dielectric constant, CTE, and water absorption were decreased. However, at higher organoclay contents (5–10%), these properties were reduced because the organoclay was poorly dispersed and resulted in aggregate formation. The effects of different organo‐modifiers on the properties of PI–MMT nanocomposite were also studied; the results showed that DOA was comparable with CPC. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Properties of na‐montmorillonite and cellulose nanocrystal reinforced poly(butyl acrylate‐co‐methyl methacrylate) nanocomposites

Poly(butyl acrylate‐co‐methyl methacrylate) (BA‐co‐MMA) nanocomposite latexes were synthesized in the presence of sodium montmorillonite (Na‐MMT) and cellulose nanocrystal (CNC) as fillers. Nanocomposite preparation with 3 wt% Na‐MMT based upon the total monomer amount was conducted by semi‐batch emulsion polymerization. Furthermore, direct blending of neat copolymer latex with Na‐MMT was performed for comparison. CNC/BA‐co‐MMA nanocomposites were obtained via blending process with varying CNC content (1, 2, and 3 wt %). Good dispersion of both Na‐MMT and CNC within the copolymer matrix was achieved as demonstrated by X‐ray diffraction and transmission electron microscope. Particle size of the nanocomposite latexes was around 120 nm. Thermal, mechanical, and barrier properties of the copolymer showed great improvement with the addition of both Na‐MMT and CNC. CNC nanocomposites displayed enhanced properties with increasing CNC level. Tensile strength of copolymer latex with 3 wt% CNC reached 262.5% of the pristine latex, while tensile strength of Na‐MMT nanocomposite at the same content was 187.5% of the pristine latex. POLYM. ENG. SCI., 55:2922–2928, 2015. © 2015 Society of Plastics Engineers     

Synthesis of unsaturated polyester‐clay nanocomposites using reactive organoclays

Two polymerizable cationic surfactants, vinylbenzyl n‐alkyldimethyl (n = 12 or 18) ammonium chlorides, were used for functionalization of montmorillonite (MMT) and preparation of unsaturated polyester (UP)‐clay nanocomposites. Polymerizable organophilic clays were prepared by exchanging the sodium ions of MMT with vinylbenzyldodecyldimethyl ammonium chloride (VDAC) or vinylbenzyloctadecyldimethyl ammonium chloride (VOAC) in an aqueous medium. The dispersion of organoclays in UP led to gel formation. UP/VDAC‐MMT resulted in intercalated nanocomposites while UP/VOAC‐MMT formed partially exfoliated nanocomposites. The nanocomposites exhibited higher dynamic modulus than pristine UP.     

A New Type of Dispersant [Sodium Salt of Styrene–Methacrylic Acid Copolymer (SSMA)/Montmorillonite (MMT) Nanocomposite] for Pesticide Water Dispersible Granules

A new type of dispersant [sodium salt of styrene–methacrylic acid copolymer (SSMA)/montmorillonite (MMT) nanocomposite] with different content of the MMT was synthesized through in situ solution free radical copolymerization. X‐ray diffraction measurements and electron microscopy observations prove that SSMA molecules can enter the interlayer space of MMT and form an intercalated structure. There are both fully intercalated and partly intercalated structures in the nanocomposites, which are related to the loading content of MMT. Transmission and scanning electron microscopy images indicate that the exfoliation degree of MMT in the nanocomposites decrease with increasing MMT content. Infrared spectroscopy (FTIR) analysis shows that there are hydrogen‐bonding interactions between carboxyl groups of SSMA and hydroxyl groups of MMT. Atrazine water dispersible granules were prepared by using SSMA/MMT nanocomposite as dispersant and their suspensibility in aqueous solution was determined to evaluate the dispersion properties of the nanocomposite. The results show that the addition of MMT can not only increase the steric effect of the SSMA to improve its dispersion properties, but also reduce the production cost of SSMA. The optimum loading content of MMT is 10 wt%.     

Preparation and properties of PET/PA6 copolymer/montmorillonite hybrid nanocomposite

From in situ polycondensation, a poly(ethylene terephthalate)/Polyamide 6 copolymer/montmorillonite nanocomposite was prepared, after the treatment of montmorillonite (MMT) with a water soluble polymer. The resulting nanocomposites were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), nuclear magnetic resonance (NMR), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM). The results of DSC, ¹H NMR, and DMA proved that the nanocomposite synthesized was PET/PA6 copolymer/MMT nanocomposite, not the PET/PA6 blend/MMT nanocomposite. The results of XRD and TEM proved that the dispersion of MMT was improved observably after the introduction of PA6 molecular chain into PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2512–2517, 2006     

High‐temperature‐resistant polyimide/montmorillonite nanocomposite foams by solid blending

A series of high‐temperature‐resistant polyimide/montmorillonite (PI/MMT) nanocomposite foams were prepared by solid blending method. The dispersion of MMT and effects of MMT content on the properties of the PI/MMT nanocomposite foams were investigated. Results indicated that MMT could be exfoliated effectively and dispersed uniformly in the PI matrix by the solid blending method. The introduction of MMT could considerably increase the reduced compressive strength, thermal resistance, and decrease the dielectric constant of the PI/MMT nanocomposite foams. The reduced compressive strength of nanocomposite foams showed a maximum value at the MMT content of 5 wt%, which was 197% higher than that of pure PI foams. It was worth noting that a significant increase in glass‐transition temperature (T _g) could be achieved with the increase of MMT content, and the maximum T _g was as high as 436°C at the MMT content of 7 wt%. This study may provide a useful method to prepare PI/MMT nanocomposite foams with improved properties for targeted high‐temperature applications. POLYM. ENG. SCI., 2011. ©2011 Society of Plastics Engineers     

Strength properties of polyimideamide nanocomposite fibers in terms of their porous and supermolecular structure

The strength properties of fibers made from polyimideamide (PIA) nanocomposite were investigated and the effect of the presence of MMT in the fiber‐forming polymer on the porous structure and supermolecular structure of fibers was analyzed. It was found that lower strength properties (tenacity, elongation at break) of PIA nanocomposite fibers, as compared with those ones of fibers without montmorillonite (MMT), are connected with a lower deformability of the polymer during drawing stage and the collapse of MMT galleries, confirmed by WAXS investigations. This results in the formation of agglomerates that are weakly connected with the fiber‐forming polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 339–344, 2007     

Effects of silane grafting on the morphology and thermal stability of poly(ethylene terephthalate)/clay nanocomposites

An alkylammonium intercalated montmorillonite (A‐MMT) was modified by edge grafting with 3‐glycidoxypropyltrimethoxysilane. In comparison with poly(ethylene terephthalate) (PET)/A‐MMT, the resultant grafted clay, S‐A‐MMT, exhibited improved miscibility with PET matrix and revealed better dispersion state in the melting compounded PET/S‐A‐MMT nanocomposites. As a result, the PET/S‐A‐MMT nanocomposite had slower degradation rate owing to the enhanced clay barrier effect. Meanwhile, the nanocomposite exhibited lower degradation onset temperature under nitrogen because of the clay catalysis effect, which can be explained by the decreasing degradation reaction energy calculated from Coats–Redfern method of degradation kinetics. In the other hand, nanocomposite with better clay dispersion state exhibited increasing thermal oxidative stability due to clay barrier effect of hindering oxygen to diffuse in, which accorded with the continuous and compact char surface formed during polymer degradation. The clay catalysis and barrier effect of silicate layers were presented directly in isothermal oxidative TGA experiment. Furthermore, the mechanical and crystallization properties of PET/clay nanocomposites were investigated as well. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers