Effect of the grafted silane on the dispersion and orientation of clay in polyethylene nanocomposites

The CTAB ammonium intercalated montmorillonite clay, CMT, was modified by an alkylsilane, Dodecyltrimethoxylsilane, to improve the miscibility of organoclays with PE matrix, involving the grafting reaction between the silane and silanol groups on the edge of clay. The silane modified clays (DMT) exhibited improved thermal stability due to the replacement of the physically adsorbed ammonium by the covalently bonded silane. The clays were melt compounded with polyethylene. Compared with the composite of PE/CMT, the clay dispersion state was improved, and a unique orientation of the clay layered was observed in PE/DMT nanocomposites, which was confirmed by XRD and TEM studies. The dispersion state, orientation degree of clay and, as a result, the mechanical and thermal properties of the nanocomposites were enhanced with the increasing amount of the grafted silane, indicating that the edge grafting of silane played a crucial role in controlling the structure and properties of nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Effect of both silane‐grafted and ion‐exchanged organophilic clay in structural,thermal, and mechanical properties of unsaturated polyester nanocomposites

Unsaturated polyester (UPE) resin including styrene monomer was mixed with organophilic montmorillonite (MMT) clay and its crosslinking polymerization reaction was done in the presence of free‐radical initiator. MMT clay was modified with cetyl trimethly ammonium bromide and trimethoxy vinyl silane. The nanocomposites were characterized by X‐ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), thermogravimetric and dynamic mechanical analyses (TGA and DMA). The exfoliated nanocomposite structure was obtained when the MMT clay was modified in the presence of both modifiers, whereas individual modifications all resulted in intercalated structures. The exfoliated UPE nanocomposite exhibited better thermal and dynamic mechanical properties when compared with pure UPE and other composites, even with 3 wt% clay loading. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Preparation and investigation of the physical and chemical properties of clay-based polyacrylamide/Cr (III) hydrogels as a water shut-off agent in oil reservoirs

The effects of clay (montmorillonite and kaolinite) in the hydrogels were investigated on various properties such as syneresis and strength of thermal and salinity situations in one of the southern Iranian oil reservoirs. The X-ray diffraction (XRD) patterns exhibited a significant increase in interplanar spacing between the montmorillonite clay layers, varying from the initial value of 12.43 °A to 19.45 °A, which evidences the intercalation formation. It was revealed that even increasing of the interlayer spacing due to kaolinite modification had no effect on the clay compositions. Formation water was used to study the strength of the hydrogel in the presence of ions. The results indicated that 15 wt% increase of kaolinite clay (modified and non-modified) leads to 20% decrease of the hydrogels’ syneresis. The diffusion of polymer chains between the clay layers increased the elastic modulus (G′) of the prepared hydrogels with modified kaolinite and montmorillonite, where the maximum value of G’ was observed in 3 wt% of montmorillonite. Finally, the thermogravimetric analysis (TGA) indicated an increase in the thermal stability of the mentioned hydrogels.     

Modifying montmorillonite clay via silane grafting and interfacial polycondensation for melt compounding of nylon‐66 nanocomposite

A trifunctional organo alkoxysilane (3‐aminopropyl)triethoxysilane (γ‐APS) has been used as reagent for the chemical modification of montmorillonite clay. Silane grafting was taken place in dry and hydrolyzing conditions. Silane grafted and pristine clay took part in interfacial polycondensation process to deposit a layer of nylon‐66 onto the clay lamellae and therefore, enhance their affinity with nylon‐66 matrix. Evidence of presence of grafted silane molecules and deposition of nylon‐66 on clay particles were provided by Fourier transform‐infrared, thermogravimetric analysis (TGA), and X‐ray diffraction (XRD). Such modified clays and pristine clays were melt compounded with nylon‐66. The structures of the resulting nylon composites were characterized using XRD and transmission electron microscopy and the results showed presence of both intercalation and exfoliation. TGA thermograms of nanocomposites indicated improved thermal stability upon the incorporation of silane grafted montmorillonite. Furthermore, differential scanning calorimetry scans showed that silane modified clays promoted crystallization in nanocomposites. Increase of storage modulus and depression of tan δ peak in nanocomposites in dynamical mechanical thermal analysis were observed. The rheological properties of nylon‐66 and nanocomposites were also evaluated and differences in values of complex viscosity of samples were noticed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A conducting nanocomposite via intercalative polymerisation of 2-methylaniline with aniline in montmorillonite cation-exchanged

Polymer/montmorillonite nanocomposites were prepared. Intercalation of 2-methylaniline with aniline monomers into montmorillonite modified by cation was followed by subsequent oxidative polymerization of the monomers in the interlayer spacing. The clay was prepared by cation exchange process between sodium cation in (M-Na) and copper cation (M-Cu). We prepared a series of polymer/clay nanocomposite materials that consisted of an emeraldine base of poly(2-MA), poly(2-MA-co-ANI) and PANI by layered copper montmorillonite. All organic monomers used were first intercalated into the interlayer regions of clay hosts followed by a one-step in situ oxidative polymerization. The unique properties of the as-synthesized nanocomposites materials are investigated by electronic conductivity measurements, X-ray diffraction, FTIR spectroscopy, UV-vis spectroscopy, thermogravimetric analysis and SEM, were also studied by cyclic voltammetry which indicates the electroactive effect of nanocomposite gradually increased with aniline in the polymer chain.     

Use of a new natural clay to produce poly(methyl methacrylate)‐based nanocomposites

Nanocomposites of poly(methyl methacrylate) (PMMA) filled with 3 wt% of modified natural Algerian clay (AC; montmorillonite type) were prepared by either in situ polymerization of methyl methacrylate initiated by 2,2′‐azobisisobutyronitrile or a melt‐mixing process with preformed PMMA via twin‐screw extrusion. The organo‐modification of the AC montmorillonite was achieved by ion exchange of Na⁺ with octadecyldimethylhydroxyethylammonium bromide. Up to now, this AC montmorillonite has found applications only in the petroleum industry as a rheological additive for drilling muds and in water purification processes; its use as reinforcement in polymer matrices has not been reported yet. The modified clay was characterized using X‐ray diffraction (XRD), which showed an important shift of the interlayer spacing after organo‐modification. The degree of dispersion of the clay in the polymer matrix and the resulting morphology of nanocomposites were evaluated using XRD and transmission electron microscopy. The resulting intercalated PMMA nanocomposites were analysed using thermogravimetric analysis and differential scanning calorimetry. The glass transition temperature of the nanocomposites was not significantly influenced by the presence of the modified clay while the thermal stability was considerably improved compared to unfilled PMMA. This Algerian natural montmorillonite can serve as reinforcing nanofiller for polymer matrices and is of real interest for the fabrication of nanocomposite materials with improved properties. Copyright © 2009 Society of Chemical Industry     

Improvement of corrosion protection offered to galvanized steel by incorporation of lanthanide modified nanoclays in silane layer

Silane sol–gel based films are very promising alternatives to the traditional chromate pre-treatments. However, the protection offered by the silane films strongly decreases when the coating is damaged. Some previous studies showed that the barrier properties of the silane layer can be improved by incorporation of clay nanoparticles. Moreover, inhibitive metallic cations can be incorporated in the nanoclays by ion exchange, providing a way to prepare cheap corrosion inhibitors nanoreservoirs offering self-healing properties. Rare earth (RE) metal salts have been shown to be effective corrosion inhibitors on a wide range of metals, including hot dip galvanized (HDG) steel. For this study, montmorillonite clay is modified to obtain a Ce(III) montmorillonite clay (Ce-MMT). The amount of incorporated Ce(III) is characterized by means of XRF measurements. X-ray diffraction showed that the Ce(III) is located in the interlayer space.     

Aliphatic polyamidoamine hyperbranched polymers/layered silicate nanocomposites

Polyamidoamine hyperbranched polymer (Hyp)/clay nanocomposites were synthesized by using both of montmorillonite and laponite clays. Poly amidoamine hyperbranched polymer (Hyp) was prepared by one‐pot polymerization via couple monomer methodology. Afterward, the amino ends of Hyp were modified with methyl methacrylate (MMA), styrene (St) and butyl methacrylate (n‐BuMA) polymers which were previously prepared via ATRP (atom transfer radical polymerization) to form the corresponding new hyperbranched polymers Hyp₁, Hyp₂ and Hyp₃. Those formed polymers were inserted into the modified clay, such as montmorillonite and laponite to form their nanocomposites. The formed polymer/clay nanocomposites were characterized via XRD, TEM, and thermal analyses. The formed hyperbranched polymers generally showed intercalation behavior more than the exfoliation one mostly because of the bulkiness of the hyperbranched skeleton. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

表面活性剂和硅烷偶联剂有机复合改性蒙脱土的制备及性能表征

为增加蒙脱土与有机物的相容性,采用十六烷基三甲基溴化铵(CTAB)与硅烷偶联剂(KH-560)对蒙脱土进行了有机复合改性。X-射线衍射和红外光谱的结果表明,CTAB已插入蒙脱土片层,平均层间距离从1.54 nm增大到3.98 nm和2.08 nm,而KH-560未插入蒙脱土片层,只是覆盖在蒙脱土表面,未改变蒙脱土的插层结构;分散性实验表明,表面活性剂和硅烷偶联剂有机复合改性的蒙脱土在苯乙烯、液体石蜡中的分散性好于其他改性蒙脱土;有机复合改性不仅增大了蒙脱土层间距,且改善了蒙脱土与聚氯乙烯的界面效果,提高了蒙脱土在聚氯乙烯基体中的分散均匀性,从而使聚氯乙烯/蒙脱土复合材料玻璃化转变温度的提高和力学性能的改善更明显。     

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     

Influence of clay exfoliation on the physical properties of montmorillonite/polyethylene composites

Melt compounding was used to prepare conventional composites of montmorillonite clay and polyethylene (PE) as well as nanocomposites of exfoliated montmorillonite platelets dispersed in a maleated polyethylene (PE-g-MAn) matrix. The extent of clay platelet exfoliation in the PE-g-MAn nanocomposites was confirmed by X-ray diffraction and resulted in a significant reduction of the degree of crystallinity and increased polymer crystallization rates. Studies of non-isothermal crystallization kinetics suggested that the exfoliated clay promotes heterogeneous nucleation and two-dimensional crystallite growth.PE/clay composites behaved in a similar manner as conventional macrocomposites, exhibiting modest increases in their rheological properties and Young's modulus. Conversely, the nanoscale dimensions of the dispersed clay platelets in the nanocomposites led to significantly increased viscous and elastic properties and improved stiffness. This was attributed to the high surface area between the polymer matrix and the exfoliated clay, which resulted in enhanced phase adhesion.     

Studies on properties of softwood (Ficus hispida)/PMMA nanocomposites reinforced with polymerizable surfactant-modified nanoclay

Soft wood (Ficus hispida) was chemically modified by impregnation of methyl methacrylate monomer, glycidyl methacrylate (GMA), a cross-linking agent, and montmorillonite (MMT) using catalyst heat treatment. MMT was modified by using a polymerizable surfactant 2-acryloloxy ethyl trimethyl ammonium chloride (ATAC) and a mixture of surfactants ATAC and cetyl trimethyl ammonium bromide (CTAB) in a molar ratio of (1:1). A comparative study on different properties of the prepared wood polymer nanocomposite (WPNC) based on impregnation of intercalating mixture containing MMA/GMA/clay modified by both the surfactants (ATAC and CTAB) and MMA/GMA/clay modified by only surfactant ATAC were done. FTIR, XRD, and TGA studies were employed for the characterization of clay and WPNC. WPNC prepared by using combined surfactant-modified clay along with MMA/GMA exhibited improved dimensional stability, chemical resistance, thermal stability, mechanical properties, and lower water uptake than that of WPNC prepared by using single surfactant-modified clay and MMA/GMA system.     

Morphology and mechanical properties of UV-curable castor oil-based waterborne polyurethane/organic montmorillonite nanocomposites

Water resistance is a unique advantage of castor oil-based polyurethane, permitting the application of coatings in humid environments. However, its low thermal decomposition temperature remains a limitation. Here, to demonstrate a simple method to improve the thermal stability of cured films, we prepared an organic montmorillonite dispersion utilising 3-(methacryloyloxy)propyltrimethoxysilane and protonated 3-aminopropyltriethoxysilane for modifying the clay. The method was put into practice by directly mixing the dispersion with a UV-curable castor oil-based waterborne polyurethane dispersion. The inclusion of organic molecule chains from the silane coupling agents noticeably improves the compatibility of polyurethane with organic montmorillonite, which imparts the composite latex with better thermal stability and mechanical properties when the organic montmorillonite additive is 5.0?wt-%.     

Melt‐intercalation nanocomposites with fluorinated polymers and a correlation for nanocomposite formation

Various fluorinated polymers were investigated to produce polymer nanocomposites with special clays. Natural and organically treated montmorillonite clays were melt‐compounded with the polymers. Characterization by wide‐angle X‐ray scattering and transmission electron microscopy showed the separation of montmorillonite layers and the formation of polymer nanocomposites. Organically treated montmorillonite clay dispersed in poly(vinylidene fluoride) and various vinylidene fluoride copolymers and formed nanocomposites. Natural and organophilic clays were not well dispersed in other fluorinated copolymers and polyethylene. A correlation was developed for the formation of polymer–clay nanocomposite structures in chlorinated and fluorinated polymers in terms of the dielectric constant. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1061–1071, 2004     

Bio‐based polymer nanocomposites based on layered silicates having a reactive and renewable intercalant

Soybean oil‐based polymer nanocomposites were synthesized from acrylated epoxidized soybean oil (AESO) combined with styrene monomer and montmorillonite (MMT) clay by using in situ free radical polymerization reaction. Special attention was paid to the modification of MMT clay, which was carried out by methacryl‐functionalized and quaternized derivative of methyl oleate intercalant. It was synthesized from olive oil triglyceride, as a renewable intercalant. The resultant nanocomposites were characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The effect of increased nanofiller loading in thermal and mechanical properties of the nanocomposites was investigated by thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The nanocomposites exhibited improved thermal and dynamic mechanical properties compared with neat acrylated epoxidized soybean oil based polymer matrix. The desired exfoliated nanocomposite structure was achieved when the OrgMMT loading was 1 and 2 wt % whereas partially exfoliated nanocomposite was obtained in 3 wt % loading. It was found that about 400 and 500% increments in storage modulus at glass transition and rubbery regions, respectively were achieved at 2 wt % clay loading compared to neat polymer matrix while the lowest thermal degradation rate was gained by introducing 3 wt % clay loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2031–2041, 2013     

Computer simulation of polypropylene/organoclay nanocomposites: characterization of atomic scale structure and prediction of binding energy

Molecular simulation techniques are used to explore and characterize the atomic scale structure, and to predict binding energies and basal spacing of polymer/clay nanocomposites based on polypropylene (PP) and maleated polypropylene (PPMA), montmorillonite (MMT), and different alkylammonium ions (quats) as surfactants. Our evidences suggest that shorter hydrocarbonic chains are more effective in producing favorable binding energies with respect to longer ones, and the substitutions of hydrogen atoms with polar groups on the quaternary ammonium salt (quat) generally results in greater interaction between quat and both polymer and clay. Under the hypothesis, that montmorillonite platelets are uniformly dispersed in a polymer matrix, the modified polypropylene yields higher interfacial strength with clay than neat polypropylene. The use of neat PP and quats with higher molecular volume offer the higher values of the basal spacing and thus, in principle, they should be more effective in the exfoliation process.     

图像分析技术在聚合物/粘土纳米复合材料微观结构形态研究中的应用

基于MATLAB图形及影像处理技术，开发了适用于处理聚合物／粘土纳米复合材料（PCN）微观结构形态的应用程序。应用程序包含边界探测和颗粒尺寸分析两个子程序，具有探测孤立颗粒边界和计算颗粒尺寸功能。应用该程度分析了聚丙烯／蒙脱土（PP／MMT）纳米复合材料初级结构的TEM照片，得到蒙脱土片层在PP基体中的微观结构形态和尺寸分布。结果表明：该图像分析技术能够快速有效地确定PCN的TEM照片中粘土片层的形状和尺寸。此外，该图像分析技术还可以用于共混物形态的研究。     

Effect of the silane modification of an organoclay on the properties of polypropylene/clay composites

A commercial clay, Cloisite®20A (C20A) was modified with three different silane compounds, propyltrimethoxy silane, octyltrimethoxy silane, and octadecyltrimethoxy silane, to control the hydrophobicity of C20A. The amount of the silane compounds grafted to C20A was quantified from the weight loss by using TGA, and the hydrophobicity was evaluated by the amount of water absorption. The variation of the interlayer distance was traced by XRD and TEM observation. SEM/EDS was employed to visualize the morphology of the fractured surface and the degree of dispersion of the clay layers in the PP/clay composites. Measurements of the tensile properties of the PP/clay composites indicated that the composite made from PP and the C20A modified with octadecyltrimethoxy silane exhibited the most excellent tensile properties. This was ascribed to the fact that the C20A modified with octadecyltrimethoxy silane possessed the most favorable interfacial interaction with PP and thus the degree of dispersion of the clay layers was the best in the PP matrix. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and chemical treatments of montmorillonite clay

Montmorillonite clay from a natural deposit was processed to remove impurities and later submitted for thermal and chemical treatments. The sample was first subjected to a thermal treatment at 400 °C, for 1 h, to remove organic components. The chemical treatment was conducted first by using an acid attack with nitric acid and sulfuric acid, then, adding sodium acetate in ethylene glycol clay dispersion, and finally the clay was dispersed in xylene with subsequent addition of silane, N-(b-aminoethyl)-g-aminopropyiltrimethylsilane. The combined thermal and chemical treatment was found to have a significant effect on the final chemical composition of the nanoclay. X-ray diffraction patterns suggested that the combined thermal and chemical treatment resulted in increased interplanar distances, thus favoring exfoliation of the clay lamellae, which was also confirmed by SEM images. Fourier transform infrared (FTIR) spectroscopy analysis suggested that the combined thermal and chemical treatment resulted in removal of water from the montmorillonite, without any modification or destruction of the clay structure. Thus, the combination of thermal and chemical treatments proposed in this work may be a promising approach to process montmorillonite intended for the production of advanced materials.     

Organoclays assisted vat and disperse dyeing of poly(ethylene terephthalate) nanocomposite fabrics via melt spinning

Polyethylene terephthalate nanocomposites containing six modified montmorillonite nanoclays were prepared by a melt compounding technique. The effect of intercalated compounds of montmorillonite on textile mechanical properties of resultant polyethylene terephthalate nanocomposite fabrics was investigated. Winding was not possible, when the polymers were first compounded with the desired amount of montmorillonite and then spun, as filament breakage occurred. Spinable polymer were only obtained by mixing polyethylene terephthalate master batches with 4 wt% montmorillonite, which contained tallow intercalating compound with pure untreated polyethylene terephthalate to a montmorillonite content of 0.5 wt%, thus decreasing the concentration of thermally degraded polymer chains. After spinning the fibres were drawn and knitted into fabric samples for further testing. The prepared polyethylene terephthalate nanocomposite fabrics using montmorillonite exhibited higher colour strength using vat and disperse dyes compared with those of the reference fabrics made from fibres spun without montmorillonite clay content and regular fabrics. The carbocyclic‐based vat dyes have higher colour strength values on polyethylene terephthalate nanocomposite fabrics if compared with heterocyclic‐based vat dyes. The colour fastness ratings for both vat and disperse dyeings secured very good to excellent washing and perspiration fastness on polyethylene terephthalate nanocomposite fabrics. All dyed fabrics showed excellent light fastness using vat and disperse dyes. The preparation of polyethylene terephthalate nanocomposite fabrics with improved textile mechanical and vat dyeing properties needs further investigations.