Effect of organophilic montmorillonite on polyurethane/montmorillonite nanocomposites

Different kinds of organophilic montmorillonite cotreated by cetyltrimethyl ammonium bromide (CTAB) and aminoundecanoic acid (AUA) were synthesized and applied to prepare polyurethane/montmorillonite nanocomposites via solution intercalation. The results of wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy showed that, for the montmorillonite modified with CTAB and CTAB/AUA (molar ratio of 1/2), an ordered intercalated nanostructure was derived, while for the montmorillonite treated with AUA, a disordered nanostructure was derived. The tensile properties of the polyurethane (PU) nanocomposites showed higher enhancement relative to PU matrix. TG showed that there is some enhancement in degradation behavior between the nanocomposites and PU matrix. DMTA results showed that nanocomposites from some organophilic montmorillonites showed a much higher storage modulus below and above glass transition temperature, while the nanocomposites from montmorillonite treated by AUA show an even lower storage modulus. The loss curves showed that the main glass transition temperature of PU was improved to some extent for the nanocomposites. The water absorption of PU and nanocomposites was also studied and the difference in reduction was thoroughly analyzed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2536–2542, 2004     

New toughened polypropylene/organophilic montmorillonite nanocomposites

A new toughened polypropylene (PP)/organophilic montmorillonite (OMMT) nanocomposite was obtained by melt intercalation extrusion in a twin‐screw extruder without any compatibilizer. The nanocomposites were characterized by transmission electron microscopy (TEM) observation, melt flow rate (MFR) testing, mechanical properties measurement, melting and crystallization behaviors, and thermal stability determination. TEM images revealed the existence of intercalated OMMT layers dispersed throughout the PP matrix. A clear reduction in MFR was observed as the OMMT content increased. The yield strength, elongation at yield, and initial modulus of the PP/OMMT nanocomposites increased slightly as the result of the reinforcement of the OMMT nanofiller. The ultimate value of notched impact strength of the nanocomposites was over twofold that of neat PP after incorporation with 4 wt % OMMT; meanwhile, the heat deflection temperature values showed that the thermal stability increased a little. This is a new approach for preparation for the production of a toughened PP material with a high thermal stability and rigidity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

剥离型酚醛树脂/蒙脱土纳米复合材料研究

用十六烷基三甲基溴化铵(CTAB)对蒙脱土进行了有机化处理,使蒙脱土由亲水性变成亲油性。采用XRD、FTIR及TEM研究了有机蒙脱土及其在酚醛树脂中的剥离行为,制备了酚醛树脂/蒙脱土纳米复合材料并测试了其层间剪切性能和烧蚀性能。实验结果表明,经CTAB处理的蒙脱土与酚醛树脂具有良好的相容性,且CTAB的含量较多时所制得的有机蒙脱土的结构较好,根据Bragg方程计算,CTAB用量超过蒙脱土量50%时,蒙脱土的片层间距由原来的1.48 nm增加到2.33 nm;有机蒙脱土用量小于5%时生成完全剥离型酚醛树脂/蒙脱土纳米复合材料;与碳布增强酚醛树脂复合材料相比,碳布增强酚醛树脂/蒙脱土纳米复合材料的力学性能和烧蚀性能均有一定的提高和改善,层间剪切强度随蒙脱土含量的增多而增大,蒙脱土用量为15%时,层间剪切强度提高了27.1%,线烧蚀率在用量为3%时降低了48.5%,质量烧蚀率变化不明显。     

Novel polyether polyurethane/clay nanocomposites synthesized with organicly modified montmorillonite as chain extenders

A kind of novel polyether polyurethane (PU)/clay nanocomposite was synthesized using poly(tetramethylene glycol), 4,4′‐diphenylmethane diisocyanate (MDI), 1,6‐hexamethylenediamine, and modified Na⁺‐montmorillonite (MMT). Here, organicly modified MMT (O‐MMT) was formed by applying 1,6‐hexamethylenediamine as a swelling agent to treat the Na⁺‐MMT. The X‐ray analysis showed that exfoliation occurred for the higher O‐MMT content (40 wt %) in the polymer matrix. The mechanical analysis indicated that, when the O‐MMT was used as a chain extender to replace a part of the 1,2‐diaminopropane to form PU/clay nanocomposites, the strength and strain at break of the polymer was enhanced when increasing the content of O‐MMT in the matrix. When the O‐MMT content reached about 5%, the tensile strength and elongation at break were over 2 times that of the pure PU. The thermal stability and the glass transition of the O‐MMT/PU nanocomposites also increased with increasing O‐MMT content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 6–13, 2006     

不饱和聚酯/粘土纳米复合材料的制备与性能

为了改善不饱和聚酯树脂的力学性能,将有机改性的蒙脱土与苯乙烯均匀混合后再掺合到不饱和聚酯(UP)中,制备了不同粘土含量的不饱和聚酯树脂/粘土(UPR/Clay)纳米复合材料。差热分析发现随着粘土含量的增加,玻璃化温度有所增加。X射线衍射数据表明,纳米复合材料中粘土原有的峰基本消失,表明粘土结构层间距增大,结合透射电镜(TEM),确定此纳米复合材料为插层和剥离结构。冲击试验发现随着粘土加入冲击强度有一最大值。     

Epoxy‐clay nanocomposites: Influence of the clay surface modification on structure

In this article, the effect of four different clay surface modifiers on the structure of epoxy‐clay nanocomposites was studied. Various organoclays were prepared via cation exchange reaction between inorganic cations naturally occuring in the clay gallery and different alkylammonium ions. Epoxy‐clay nanocomposites were prepared by in situ intercalative polymerization using a hardener of polyoxypropylenediamine type. It was found that various clay surface modifiers exhibit different catalytic effect on curing of epoxy inside the clay gallery as observed by measuring of the gel time with dynamic mechanical analysis. This was confirmed by monitoring the change in the d‐spacing by wide angle X‐ray scattering performed in situ during curing. Morphology of the cured systems was probed by transmission electron microscopy (TEM) and wide angle X‐ray scattering (WAXS). The degree of dispersion observed by TEM and WAXS corresponds with achieved mechanical properties of cured composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of polypropylene filled with organo‐montmorillonite nanocomposites

Organo‐Montmorillonite (Org‐MMT)/maleic anhydride grafted polypropylene (PP‐g‐MAH)/polypropylene nanocomposites have been prepared by melt blending with twin‐screw extruder. The mechanical properties of the nanocomposites and the dispersion of Org‐MMT intercalated by the macromolecular chain were investigated by transmission electron microscopy and mechanical tests. The crystal properties of the nanocomposites have been tested by a differential scanning calorimeter. The thermal properties of the nanocomposites were investigated by thermo gravimetric analysis. The results show that not only the impact property but also the tensile property and the bending modulus of the system have been increased evidently by the added Org‐MMT. The Org‐MMT has been dispersed in the matrix in the nanometer scale. With the addition of the Org‐MMT, the melting point and the crystalling point of the nanocomposites increased; the total velocity of crystallization of the nanocomposites also increased. Thermal stability of the nanocomposites is increased by the filled Org‐MMT. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2875–2880, 2006     

Preparation and physical properties of wood/polypropylene/clay nanocomposites

Wood plastic composites (WPCs) are attracting a lot of interests because they are economic, environmentally friendly, and show fairly good performance. To improve the performance of a wood/polypropylene (PP) composite, an organoclay was incorporated as a nanosize filler in this work. WPCs were prepared by melt blending followed by compression molding, and their performance was investigated by universal testing machine, izod impact tester, dynamic mechanical analyzer, thermal mechanical analyzer, differential scanning calorimetry, and TGA. Maleic anhydride polypropylene copolymer (MAPP) was used to increase compatibility between the PP matrix and wood particles and also improve the dispersion and exfoliation of the organoclay in the PP matrix. XRD analysis showed that the matrix of the WPCs with organoclay had intercalated structure. The SEM images of the WPCs with MAPP showed improved interfacial adhesion between the matrix and wood particles. The degree of water absorption increased with immersion time, but it could be restrained by incorporating MAPP. The performance of the WPCs was improved by the incorporation of the organoclay. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of epoxy resin on morphology and physical properties of PVC/organophilic montmorillonite nanocomposites

Poly(vinyl chloride)/organophilic montmorillonite (PVC/OMMT) nanocomposites were prepared by means of melt blending. A liquid epoxy resin was used to aid PVC chains in intercalating into silicate layers. The effects of the preparation methods and epoxy resin contents on the melt intercalation of PVC were investigated. The morphology development, mechanical properties and optical properties of the PVC/OMMT composites were tested as functions of epoxy resin content and OMMT content. Wide‐angle X‐ray diffraction, transmission electron microscopy and scanning electron microscopy were used to characterize the morphology of the resulting composites. After being pretreated by the epoxy resin, the OMMT layers were largely intercalated into the PVC matrix, and even exfoliated at high epoxy resin content. The addition of epoxy resin led to a decrease in optical clarity of the composites but improved the processing stability, as indicated by yellowness index and haze measurement. However, the optical clarity of the composites containing 4 phr of epoxy resin (PVC/E‐OMMT) was improved by increasing the OMMT content, as shown by light transmission. Both the tensile strength and notched Izod impact strength of the PVC/E‐OMMT composites reached their maximum values when the OMMT content was 0.5 phr and the epoxy resin content was 2 phr. With further increase of the OMMT content and the epoxy resin content, the tensile strength decreased but was still higher than that of original PVC. The method of addition of epoxy resin had little effect on the physical properties but mainly influenced the morphology of PVC/OMMT nanocomposites. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2184–2191, 2003     

Polyamide 6/clay nanocomposites using a cointercalation organophilic clay via melt compounding

Polyamide 6/clay nanocomposites (PA6CN) were prepared via the melt compounding method by using a new kind of organophilic clay, which was obtained through cointercalation of epoxy resin and quaternary ammonium into Na‐montmorillonite. The dispersion effect of this kind of organophilic clay in the matrix was studied by means of X‐ray diffraction (XRD) and transmission electron microscopy (TEM); the silicate layers were dispersed homogeneously and nearly exfoliated in the matrix. This was probably the result of the strong interaction between epoxy groups and amide end groups of PA6. The mechanical properties and heat distortion temperature (HDT) of PA6CN increased dramatically. The notched Izod impact strength of PA6CN was 80% higher than that of PA6 when the clay loading was 5 wt %. Even at 10 wt % clay content, the impact strength was still higher than that of PA6. The finely dispersed silicate layers and the strong interaction between silicate layers and matrix decreased the water absorption. At 10 wt % clay content, PA6CN only absorbs half the amount of water compared with PA6. The dynamic mechanical properties of PA6CN were also studied. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 953–958, 2003     

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     

Silicate layer exfoliation in polyolefin/clay nanocomposites based on maleic anhydride modified polyolefins and organophilic clay

Silicate layer exfoliation processes in maleic anhydride (MA) modified polyolefins were studied by using X‐ray diffraction measurements, scanning electron microscopy, and transmission electron microscopy observations. Modified polyolefins grafted with 0.09–4.5 wt % MA groups intercalate into the organophilic clay galleries modified with stearyl ammonium ions. Molten MA‐modified polypropylene continuously intercalates into the galleries and the silicate layers exfoliate spontaneously without shear. However, the silicate layers maintain arranging parallel together, although the interlayer spacing expands over 10 nm. By adding shear, the silicate layers homogeneously disperse into MA‐modified polypropylene matrix. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 464–470, 2004     

Preparation and properties of polyethylene/montmorillonite nanocomposites formed via ethylene copolymerization

BACKGROUND: In situ formation of polyethylene/clay nanocomposites is one of the prevalent preparation methods that include also solution blending and melt blending with regard to process simplification, economy in cost, environment protection and marked improvement in the mechanical properties of the polymeric matrix. In the work reported here, the preparation of linear low‐density polyethylene (LLDPE) and fabrication of polymer/clay nanocomposites were combined into a facile route by immobilizing pre‐catalysts for ethylene oligomerization on montmorillonite (MMT). RESULTS: [(2‐ArN?C(Me))₂C₅H₃N]FeCl₂ (Ar = 2,4‐Me₂(C₆H₃)) was supported on MMT treated using three different methods. The MMT‐supported iron complex together with metallocene compound rac‐Et(Ind)₂ZrCl₂ catalyzed ethylene to LLDPE/MMT nanocomposites upon activation with methylaluminoxane. The oligomer that was formed between layers of MMT promoted further exfoliation of MMT layers. The LLDPE/MMT nanocomposites were highly stable upon heating. Detailed scanning electron microscopy analysis revealed that the marked improvement in impact strength of the LLDPE/MMT nanocomposites originated from the dispersed MMT layers which underwent cavitation upon impact and caused plastic deformation to absorb most of the impact energy. In general, the mechanical properties of the LLDPE/MMT nanocomposites were improved as a result of the uniform dispersion of MMT layers in the LLDPE matrix. CONCLUSION: The use of the MMT‐supported iron‐based diimine complex together with metallocene led to ethylene copolymerization between layers of MMT to form LLDPE/MMT nanocomposites. The introduction of exfoliated MMT layers greatly improved the thermal stability and mechanical properties of LLDPE. Copyright © 2009 Society of Chemical Industry     

Orientation of montmorillonite clay in dicyclopentadiene/organically modified clay dispersions and nanocomposites

Highly delaminated dispersions of the organically modified clay I‐28 (Nanocor, Inc.) in liquid dicyclopentadiene (DCPD) were prepared. In situ ring‐opening metathesis polymerization of I‐28/DCPD nanodispersions generated I‐28/poly(DCPD) nanocomposites. When clay/DCPD dispersions were cured under shear, alignment of clay platelets, tactoids, and small particles was captured. This orientation was confirmed by X‐ray diffraction and transmission electron microscopy. The Herman's orientation parameters were calculated for the oriented nanocomposites. Viscosities of these liquid nanodispersions exhibited thixotropic flow behavior, prior to curing. The time‐dependent viscosity effects became more pronounced with an increase in delamination. Initial viscosities increased with progressive clay platelet generation during delamination and nanodispersion within the liquid monomer. Viscosity can be used to follow clay exfoliation/delamination. Etching the surface of a 2 wt % I‐28 clay/poly(DCPD) nanocomposite with oxygen plasma eroded the matrix, exposing clay tactoids protruding from the surface. These surfaces were examined by SEM and energy dispersive X‐ray spectroscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2743–2751, 2006     

The physical and mechanical properties of beta‐nucleated polypropylene/montmorillonite nanocomposites

Polypropylene (PP) and polypropylene/polypropylene‐g‐maleic anhydride/ organomontmorillonite (PP/PP‐g‐MA/OMMT) nanocomposites were modified with 0.05 to 0.3% (w/w) of the aryl amide β‐nucleator to promote the formation of hexagonal crystal modification (β‐phase) during melt crystallization. The nonisothermal crystallization behavior of PP, PP/PP‐g‐MA/OMMT and β‐nucleated PP/PP‐g‐MA/OMMT nanocomposites were studied by means of differential scanning calorimetry. Structure‐property relationships of the PP nanocomposites prepared by melt compounding were mainly focused on the effect and quantity of the aryl amide nucleator. The morphological observations, obtained from scanning electron microscopy, transmission electron microscopy and X‐ray diffraction analyses are presented in conjunction with the thermal, rheological, and mechanical properties of these nanocomposites. Chemical interactions in the nanocomposites were observed by FT‐IR. It was found that the β‐crystal modification affected the thermal and mechanical properties of PP and PP/PP‐g‐MA/OMMT nanocomposites, while the PP/PP‐g‐MA/OMMT nanocomposites of the study gained both a higher impact strength (50%) and flexural modulus (30%) compared to that of the neat PP. β‐nucleation of the PP/PP‐g‐MA/OMMT nanocomposites provided a slight reduction in density and some 207% improvement in the very low tensile elongation at break at 92% beta nucleation. The crystallization peak temperature (T_cp) of the PP/PP‐g‐MA/OMMT nanocomposite was slightly higher (116°C) than the neat PP (113°C), whereas the β‐nucleation increased the crystallization temperature of the PP/PP‐g‐MA/OMMT/aryl amide to 128°C, which is of great advantage in a commercial‐scale mold processing of the nanocomposites with the resulting lower cycle times. The beta nucleation of PP nanocomposites can thus be optimized to obtain a better balance between thermal and mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Structure and properties of nanocomposites based on poly(butylene succinate) and organically modified montmorillonite

Poly(butylene succinate) and organically modified montmorillonite nanocomposites with there different compositions were prepared via melt blending in a twin‐screw extruder. The structure of the nanocomposites was studied with X‐ray diffraction and transmission electron microscopy, which revealed the formation of intercalated nanocomposites, regardless of the silicate loading. Dynamic mechanical analysis revealed a substantial increase in the storage modulus of the nanocomposites over the entire temperature range investigated. The tensile property measurements showed a relative increase in the stiffness with a simultaneous decrease in the yield strength in comparison with that of neat poly(butylene succinate). The oxygen gas barrier property of neat poly(butylene succinate) improved after nanocomposite preparation with organically modified montmorillonite. The effect of the layered‐silicate loading on the melt‐state linear viscoelastic behavior of the intercalated nanocomposites was also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 777–785, 2006     

Solid‐state mechanical properties of polypropylene/nylon 6/clay nanocomposites

The mechanical and thermomechanical properties as well as microstructures of polypropylene/nylon 6/clay nanocomposites prepared by varying the loading of PP‐MA compatibilizer and organoclay (OMMT) were investigated. The compatibilizer PP‐MA was used to improve the adhesion between the phases of polymers and the dispersion of OMMT in polymer matrix. Improvement of interfacial adhesion between the PP and PA6 phases occurred after the addition of PP‐MA as confirmed by SEM micrographs. Moreover, as shown by the DSC thermograms and XRD results, the degree of crystallinity of PA6 decreased in the presence of PP‐MA. The presence of OMMT increased the tensile modulus as a function of OMMT loading due to the good dispersion of OMMT in the matrix. The insertion of polymer chains between clay platelets was verified by both XRD and TEM techniques. The viscosity of the nanocomposites decreased as PP‐MA loading increased due to the change in sizes of PA6 dispersed phase, and the viscosity increased as OMMT loading increased due to the interaction between the clay platelets and polymer chains. The clay platelets were located at the interface between PP and PA6 as confirmed by both SEM and TEM. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite nanocomposites

The morphology and mechanical and viscoelastic properties of rubbery epoxy/organoclay montmorillonite (MMT) nanocomposites were investigated with wide‐angle X‐ray scattering (WAXS), transmission electron microscopy (TEM), tensile testing, and dynamic mechanical thermal analysis. An ultrasonicator was used to apply external shearing forces to disperse the silicate clay layers in the epoxy matrix. The first step of the nanocomposite preparation consisted of swelling MMT in a curing agent, that is, an aliphatic diamine based on a polyoxypropylene backbone with a low viscosity for better diffusion into the intragalleries. Then, the epoxy prepolymer was added to the mixture. Better dispersion and intercalation of the nanoclay in the matrix were expected. The organic modification of MMT with octadecylammonium ions led to an increase in the initial d‐spacing (the [d₀₀₁] peak) from 14.4 to 28.5 Å, as determined by WAXS; this indicated the occurrence of an intercalation. The addition of 5 phr MMTC18 (MMT after the modification) to the epoxy matrix resulted in a finer dispersion, as evidenced by the disappearance of the diffraction peak in the WAXS pattern and TEM images. The mechanical and viscoelastic properties were improved for both MMT and MMTC18 nanocomposites, but they were more pronounced for the modified ones. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 103: 3547–3552, 2007     

Effect of the organoclay preparation on the extent of intercalation/exfoliation and barrier properties of polyethylene/PA6/montmorillonite nanocomposites

Nanocomposites of HDPE matrix and 3 wt % organoclay/PA6 discontinuous phase were prepared in a mixer chamber. These nanocomposites of organoclay, PA6, and HDPE were characterized by X‐ray diffraction, scanning electron and transmission electron microscopy (SEM and TEM). Barrier properties were determined by cyclohexane pervaporation and solubility. The results show that the degree of exfoliation and/or intercalation and the barrier properties depend on a combination of the proper chemical treatment and optimized processing in these polyethylene‐organoclays nanocomposites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

环氧树脂/蒙脱土纳米复合材料的制备和性能

利用插层法制备了环氧树脂/蒙脱土纳米复合材料。X射线衍射分析表明,改性使蒙脱土层间距变大,制备出的环氧树脂/蒙脱土纳米复合材料剥离结构较好。性能测试表明,复合材料的力学性能和热性能均比纯环氧树脂有所提高:拉伸强度提高了70.8%,无缺口冲击强度提高了64.5%,热变形温度提高了17.7℃。