Preparation and properties of thermoplastic starch/montmorillonite nanocomposites using N,N‐bis(2‐hydroxyethyl)formamide as a new additive

N,N‐Bis(2‐hydroxyethyl)formamide (BHF) was synthesized efficiently and used as a new additive to prepare thermoplastic starch/montmorillonite (TPS/MMT) nanocomposites. Here, BHF acted as both plasticizer for TPS and swelling agent for MMT. The hydrogen bond interaction among BHF, starch, and MMT was proven by Fourier transform infrared (FTIR) spectroscopy. By scanning electron microscope (SEM), starch granules were completely disrupted. Atomic force microscopy demonstrated that partially exfoliated TPS/MMT nanocomposites were formed. The crystallinity of corn starch, MMT, BHF‐plasticized TPS (BTPS), and TPS/MMT nanocomposites was characterized by X‐ray diffraction (XRD), XRD demonstrated that partially intercalated TPS/MMT nanocomposites were formed. The water resistance of TPS/MMT nanocomposites increased compared with that of pure BTPS. Mechanical properties of BTPS and TPS/MMT nanocomposites were examined. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Development of high‐performance epoxy/clay nanocomposites by incorporating novel phosphonium modified montmorillonite

Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (T_g) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the T_g and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation of exfoliated high‐impact polystyrene/MMT nanocomposites via in situ polymerization under controlling viscosity of the reaction medium

Exfoliated high‐impact polystyrene (HIPS)/montmorillonite (MMT) nanocomposites were prepared via in situ polymerization of styrene in the presence of polybutadiene, using an intercalated cationic radical initiator‐MMT hybrid (organoclay). In the solution polymerization in toluene, the silicate layers of the clay were well exfoliated, due to the low extra‐gallery viscosity that can facilitate the diffusion of styrene monomers into the clay layers during the polymerization. The exfoliated HIPS/MMT nanocomposites were also successfully prepared by controlling the viscosity of the reaction medium with prolong swelling of the organoclay in styrene, prior to bulk polymerization. The HIPS/MMT nanocomposites, obtained from bulk polymerization, exhibited a significant improvement in thermal stability, compared to those obtained from solution polymerization as well as the pure polymer counterparts. POLYM. COMPOS., 2008. © 2007 Society of Plastics Engineers     

Mechanical and physical properties of polymer‐based nanocomposites containing different types of clay

Epoxy‐clay nanocomposites based on diglycidyl ether of bisphenol A (DGEBA) epoxy reinforced with 2 wt% of four different types of clay were prepared by high shear mixing (HSM) technique. The resultant nanocomposites were investigated to determine the effects of clay addition and clay types on their mechanical, thermal, and physical properties. The XRD and TEM analyses revealed that good dispersions of nanoclay within the epoxy matrix have been achieved especially for the samples prepared with I.30E clay where a combination of disordered intercalated and exfoliated morphology was observed. The structure of samples synthesized with other types of clay was dominated by intercalated morphologies. The tensile results illustrated that the nanocomposite containing I.30E clay has the best mechanical properties as compared to other nanocomposites. This is mainly due to better dispersion of I.30E nanoclay in the epoxy matrix for this nanocomposite. The increase or decrease in the glass transition temperatures of nanocomposites were found to be dependent on the type of clay used. The effect of clay addition on the barrier properties was examined using water exposure test which demonstrated that the addition of 2% of I.30E and C10A clays resulted in 60% reduction in diffusivity. Noticeable reduction in maximum water uptake was also observed for all nanocomposites. The improvement in these physical properties was attributed to the tortuosity effect, where water molecules have to move around clay layers during diffusion in nanocomposites. POLYM. COMPOS., 36:1998–2007, 2015. © 2014 Society of Plastics Engineer     

Preparation and characterization of polystyrene–clay nanocomposites by free‐radical polymerization

The polymerizable cationic surfactant, vinylbenzyldimethylethanolammouium chloride (VBDEAC), was synthesized to functionalize montmorillonite (MMT) clay and used to prepare exfoliated polystyrene–clay nanocomposites. The organophilic MMT was prepared by Na⁺ exchanged montmorillonite and ammonium cations of the VBDEAC in an aqueous medium. Polystyrene–clay nanocomposites were prepared by free‐radical polymerization of the styrene containing intercalated organophilic MMT. Dispersion of the intercalated montmorillonite in the polystyrene matrix determined by X‐ray diffraction reveals that the basal spacing is higher than 17.6 nm. These nanocomposites were characterized by differential scanning calorimetry (DSC), transmission electron micrograph (TEM), thermal gravimetric analysis (TGA), and mechanical properties. The exfoliated nanocomposites have higher thermal stability and better mechanical properties than the pure polystyrene. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1370–1377, 2002     

Preparation of polypropylene–clay nanocomposites by the co‐intercalation of modified polypropylene and short‐chain amide molecules

The effect of short‐chain amide (AM) molecules on the intercalation of montmorillonite clay has been investigated by the melt blending of polypropylene (PP) with clay in the presence of AM molecules such as 13‐cis‐docosenamide (erucamide). Polypropylene–clay nanocomposites (PPCNs) were prepared by the co‐intercalation of maleic anhydride grafted polypropylene (PP–MA) and an AM compound. The resulting nanocomposite structures were characterized with X‐ray diffraction (XRD) and transmission electron microscopy, whereas the thermal characterization of the PPCNs was conducted by thermogravimetric analysis. XRD results showed that the AM molecules intercalated into clay galleries and increased the interlayer spacing, a result confirmed by surface energy (contact angle) and melt flow index measurements. This additive allowed the formation of an intercalated nanocomposite structure, but an exfoliated PPCN structure was also formed with the use of AM with a PP–MA‐based compatibilizer. A new preparation method for PPCNs was, therefore, developed by the co‐intercalation of AM and PP–MA; this resulted in a significantly improved degree of intercalation and dispersion. The enhanced thermal stability of PPCN, relative to pure PP, further demonstrated the improved clay dispersion in the nanocomposite structures prepared by this method. A possible mechanism for the co‐intercalation of AM and PP–MA into the clay galleries is proposed, based on hydrogen bonding between these additives and the silicate layers. Consideration is also given to possible chemical reactions and physical interactions in this rather complex system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and evaluation of high‐performance ethylene–propylene–diene terpolymer/organoclay nanoscale composites

The main objective of this study was to synthesize and characterize the properties of ethylene–propylene–diene terpolymer (EPDM)/clay nanocomposites. Pristine clay, sodium montmorillonite (Na⁺–MMT), was intercalated with hexadecyl ammonium ion to form modified organoclay (16Me–MMT) and the effect of intercalation toward the change in interlayer spacing of the silicate layers was studied by X‐ray diffraction, which showed that the increase in interlayer spacing in Na⁺–MMT by 0.61 nm is attributed to the intercalation of hexadecyl ammonium ion within the clay layers. In the case of EPDM/16Me–MMT nanocomposites, the basal reflection peak was shifted toward a higher angle. However, gallery height remained more or less the same for different EPDM nanocomposites with organoclay content up to 8 wt %. The nanostructure of EPDM/clay composites was characterized by transmission electron microscopy, which established the coexistence of intercalated and exfoliated clay layers with an average layer thickness in the nanometer range within the EPDM matrix. The significant improvement in thermal stability and mechanical properties reflects the high‐performance nanocomposite formation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2429–2436, 2004     

New aramid‐based nanocomposites: Synthesis and characterization

New type of nanocomposites containing various proportions of montmorillonite in aromatic polyamide was prepared via solution intercalation method. Aramid chains were synthesized by reacting 4,4′‐oxydianiline with isophthaloyl chloride in N,N′‐dimethyl acetamide. Dodecylamine was used as swelling agent to change the hydrophilic nature of montmorillonite into organophilic. Appropriate amounts of organoclay were mixed in the polymer solution using high‐speed mixer for complete dispersion of the clay. Thin films cast from these materials after evaporating the solvent were characterized by XRD, TEM, mechanical, thermal, and water absorption measurements. The structure and morphology of the nanocomposites determined by XRD and TEM revealed the formation of exfoliated and intercalated clay platelets in the aramid matrix. Mechanical data indicated improvement in the tensile strength and modulus of the nanocomposites with clay loading up to 6 wt%. The glass transition temperature increased up to 12 wt% clay content and thermal stability amplified with increasing clay loading. The water absorption reduced gradually as a function of organoclay and approached to zero with 20 wt% organoclay in the aramid. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Role of the cation‐exchange capacity in the formation of polystyrene–clay nanocomposites by in situ intercalative polymerization

An effect of the cation‐exchange capacity (CEC) on the formation of polystyrene–clay nanocomposites is reported. Two types of 2:1 layered silicates with different CECs, Wyoming (97 mequiv/100 g of clay) and bentonite H (BNH; 131 mequiv/100 g of clay) were investigated. The organoclay was prepared through the mixing of purified clay and octadecyldimethylammonium chloride (ODA) in an aqueous solution. The packing of the intercalated ODA surfactant depended on the CEC and the degree of solvent extraction. Two possible phases of the interlayer packing, solidlike and liquidlike, were detected for the extracted BNH because of the charge heterogeneity of the clay. The liquidlike phase showed a good affinity toward the styrene monomer, which promoted the formation of exfoliated nanocomposites. On the other hand, the solidlike phase showed a restricted dispersion in the styrene monomer. The organoclay interlayer showed limited expansion by the styrene monomer. This led to the formation of intercalated nanocomposites. An increase in the organoclay loading hindered the formation of the exfoliated nanocomposites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 785–789, 2005     

Preparation,crystallization, and properties of biodegradable poly(butylene adipate‐co‐terephthalate)/organomodified montmorillonite nanocomposites

Intercalated and exfoliated nanocomposites of biodegradable poly(butylene adipate‐co‐terephthalate) (PBAT) and Cloisite 30B (C30B) were fabricated by a solution‐casting method to study the effects of the clay loading on the crystallization behavior, thermal stability, and dynamic mechanical properties of PBAT in PBAT/C30B nanocomposites. X‐ray diffraction and transmission electron microscopy results indicated the formation of exfoliated nanocomposites at low clay loadings (<5 wt %) and a mixture of exfoliated and intercalated nanocomposites with a clay content of 8 wt % throughout the PBAT matrix. Nonisothermal melt crystallization studies indicated that C30B enhanced the crystallization of PBAT, apparently because of a heterogeneous nucleation effect. Moreover, an attempt was made to quantitatively study the influence of the presence of C30B and its contents on the nucleation activity of PBAT in the PBAT/C30B nanocomposites. The thermal stability of PBAT decreased slightly in the nanocomposites. However, the storage modulus of PBAT apparently increased with the C30B loading increasing in the PBAT/C30B nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Clay intercalation and influence on flammability and crystallization behaviors of POE‐based nanocomposites

Ethylene‐octene copolymer (POE)‐based nanocomposites were prepared from POE or maleic anhydride grafted POE with organo‐modified montmorillonite (OMT) using melt blending technique. Their morphology, flammability, and crystallization behavior were investigated by X‐ray diffraction (XRD), transmission electron microscopy (TEM), cone calorimeter, and differential scanning calorimetry (DSC). XRD and TEM studies confirmed the intercalation of clay layers within the POE matrix whereas the exfoliation throughout the maleated POE matrix. Cone calorimetry results exhibited that the reduction in heat release rate of exfoliated maleated‐POE/OMT nanocomposite was greater than that of intercalated POE/OMT nanocomposite. The DSC results suggested that the nonisothermal kinetics crystallization of the exfoliated nanocomposite corresponded to tridimensional growth with heterogeneous nucleation. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

The structure‐property relationship of novolac cured epoxy resin/clay nanocomposites

Intercalated or exfoliated novolac cured epoxy resin nanocomposites were prepared with two different kinds of layered silicates – montmorillonite (PK‐802) and nontronite (PK‐805). The bifunctional modifiers (PI/BEN or MI/BEN) are used to modify the clays for improvement of the properties of polymer where benzalkonium chloride (BEN) acts as a compatibilizing agent and 2‐phenylimidazole (PI) or 2‐methylimidazole (MI) as the accelerators. Both the compatibilizer and accelerator are simultaneously intercalated into the gallery space of pure clays to form the modified clay. The novolac cured epoxy nanocomposites are prepared with these modified clays by crosslinking polymerization reaction. The properties of novolac cured epoxy/clay nanocomposites were characterized by wide‐angle X‐ray diffraction (WAXD), thermo‐gravimetric analysis (TGA), dynamic mechanical analysis (DMA), and transmission electron microscopy (TEM) methods. According to the measurement, these novolac cured epoxy‐clay nanocomposites have been shown the significant improvement in the thermal, mechanical, and barrier properties that may be applied to make printed circuit board. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Effect of organic modifiers and silicate type on filler dispersion,thermal, and mechanical properties of ABS‐clay nanocomposites

Acrylonitrile–butadiene–styrene (ABS)–clay composite and intercalated nanocomposites were prepared by melt processing, using Na‐montmorillonite (MMT), several chemically different organically modified MMT (OMMT) and Na‐laponite clays. The polymer–clay hybrids were characterized by WAXD, TEM, DSC, TGA, tensile, and impact tests. Intercalated nanocomposites are formed with organoclays, a composite is obtained with unmodified MMT, and the nanocomposite based on synthetic laponite is almost exfoliated. An unintercalated nanocomposite is formed by one of the organically modified clays, with similar overall stack dispersion as compared to the intercalated nanocomposites. T_g of ABS is unaffected by incorporation of the silicate filler in its matrix upto 4 wt % loading for different aspect ratios and organic modifications. A significant improvement in the onset of thermal decomposition (40–44°C at 4 wt % organoclay) is seen. The Young's modulus shows improvement, the elongation‐at‐break shows reduction, and the tensile strength shows improvement. Notched and unnotched impact strength of the intercalated MMT nanocomposites is lower as compared to that of ABS matrix. However, laponite and overexchanged organomontmorillonite clay lead to improvement in ductility. For the MMT clays, the Young's modulus (E) correlates with the intercalation change in organoclay interlayer separation (Δd₀₀₁) as influenced by the chemistry of the modifier. Although ABS‐laponite composites are exfoliated, the intercalated OMMT‐based nanocomposites show greater improvement in modulus. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

In‐situ synthesis of poly(ethylene terephthalate)/clay nanocomposites using TiO2/SiO2 sol‐intercalated montmorillonite as polycondensation catalyst

A novel organic montmorillonite, which could act as both polycondensation catalyst of poly(ethylene terephthalate) (PET) and filler of PET/clay nanocomposites, was prepared. Original montmorillonite was first treated with different amounts of poly(vinylpyrrolidone) (PVP), and then intercalated by TiO₂/SiO₂ sol to gain polycondensation catalytic activity. The acquired clay possessed excellent thermal stability and would not degrade during the polycondensation step. PET/clay nanocomposites were prepared via in‐situ polymerization using the organo‐clay as polycondensation catalysts. The morphologies of the nanocomposites were characterized by X‐ray diffraction and transmission electron microscope. The results indicated that the amount of PVP and TiO₂/SiO₂ sol strongly affected the dispersion state of the clay, and finally, partially exfoliated PET/clay nanocomposites were obtained. The nanocomposites had better properties than pure PET due to the incorporation of the delaminated clay layers. POLYM. ENG. SCI., 2009. © 2009 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.     

Preparation and characterization of light‐cured methacrylate/montmorillonite nanocomposites

Polymer/clay nanocomposites were prepared from dimethacrylate monomers, commonly used in dental restorative resins, and an organically modified silicate (montmorillonite). The photopolymerization process was hardly affected by the presence of the silicate filler, and thus 2 mm thick samples containing 3 wt% clay were extensively cured. Transmission electron microscopy revealed that the montmorillonite platelets were either intercalated or exfoliated. Nevertheless, for all formulations, intermediate‐sized aggregates of about 1 µm were present and their fraction increased as the amount of filler increased. The presence of the clay was found to have no major effect on the flexural modulus and compressive yield strength of the nanocomposites. Moreover, the water uptake of nanocomposites containing 3 wt% clay was about 10–15% higher than that of unfilled monomers. Modification of the clay surface with alternative organic cations is certainly necessary in order to achieve an optimal dispersion of the clay in the polymer matrix. Copyright © 2010 Society of Chemical Industry     

基于体积拉伸流场的TPS/OMMT纳米复合材料制备及性能研究

通过基于体积拉伸流场作用为主的双轴偏心转子挤出机制备了热塑性淀粉(TPS)和TPS/有机蒙脱土(OMMT)纳米复合材料,并研究了TPS/OMMT纳米复合材料的微观结构、力学性能、热稳定性及耐水性能.结果 表明,在甘油和拉伸流场的协同作用下,OMMT片层间距增加,并均匀分散在塑化良好的TPS基体中.低含量时,OMMT在T...     

Deformation and fracture behavior of polyamide nanocomposites: The effect of clay dispersion

This study describes the effect of the clay content and its dispersion on deformation and fracture behavior of polyamide nanocomposites. Two nanocomposite systems, intercalated and exfoliated nanocomposites containing layered silicate, were compared. They were prepared by melt‐compounding of polyamide with sodium montmorillonite or organophilized montmorillonite. It has been shown that while the exfoliated structure imparts to the nanocomposite higher stiffness and strength, the toughness is inferior to the intercalated nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of vinylsilane crosslinked high‐density polyethylene composites filled with nanoclays

High‐density polyethylene (HDPE) treated with various vinyltriethoxysilane (VTES) contents and filled with different Cloisite 15A contents were investigated. VTES was used to improve the HDPE‐clay interaction. The morphology and extent of crosslinking, as well as the thermal, mechanical, and thermomechanical properties were studied. X‐ray diffraction (XRD) results of the treated HDPE/clay nanocomposites showed an increase in interlayer spacing, which indicates that the polymer chains were intercalated between the clay layers. Transmission electron microscopy micrographs showed some evidence of exfoliated clay layers, indicating that the system exhibited a mixed morphology. The clay containing samples had a better thermal stability than HDPE, but the thermal stability did not differ much with increasing clay loading. VTES observably decreased the melting enthalpy of HDPE, while the presence of clay had little influence on this value. This is somewhat contrary to the gel content results, which showed a decrease in the extent of crosslinking in the presence of clay and with increasing clay content. VTES treatment and the presence of clay observably changed the dynamic mechanical and tensile behavior of the HDPE. POLYM. COMPOS., 34:1720–1727, 2013. © 2013 Society of Plastics Engineers