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     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Nanostructure of EVA/organoclay nanocomposites: Effects of kinds of organoclays and grafting of maleic anhydride onto EVA

Nanostructure of poly(ethylene‐co‐vinyl acetate)/organically modified montmorillonite (MMT; EVA/organoclay) nanocomposites prepared by melt intercalation process was investigated using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). Three kinds of organoclays were used to see their influences on the nanostructure of the EVA hybrids. The effects of the polar interactions between the polymer and the silicate layers of organoclays were also investigated by grafting maleic anhydride onto EVA. It was found that the strong polar interactions between the polymer and the silicate layers of organoclays are critical to the formation of polymer‐layered silicate nanocomposites. The results also showed that increasing the mixing temperature was unfavorable to improve the dispersion of organoclays in the EVA matrix. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1901–1909, 2003     

Effect of clay modification on the morphological,mechanical, and thermal properties of polyamide 6/polypropylene/montmorillonite nanocomposites

Polyamide 6/polypropylene (PA6/PP = 70/30 parts) blends containing 4 phr (parts per hundred resin) of organophilic montmorillonite (OMMT) were prepared by melt compounding. The sodium montmorillonite (Na‐MMT) was modified using three different types of alkyl ammonium salts, namely dodecylamine, 12‐aminolauric acid, and stearylamine. The effect of clay modification on the morphological and mechanical properties of PA6/PP nanocomposites was investigated using x‐ray diffraction (XRD), transmission electron microscopy (TEM), tensile, flexural, and impact tests. The thermal properties of PA6/PP nanocomposites were characterized using thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and heat distortion temperature (HDT). XRD and TEM results indicated the formation of exfoliated structure for the PA6/PP nanocomposites prepared using stearylamine modified montmorillonite. On the other hand, a mixture of intercalated and exfoliated structures was found for the PA6/PP nanocomposites prepared using 12‐aminolauric acid and dodecylamine modified montmorillonite. Incorporation of OMMT increased the stiffness but decreased the ductility and toughness of PA6/PP blend. The PA6/PP nanocomposite containing stearylamine modified montmorillonite showed the highest tensile, flexural, and thermal properties among all nanocomposites. This could be attributed to better exfoliated structure in the PA6/PP nanocomposite containing stearylamine modified montmorillonite. The storage modulus and HDT of PA6/PP blend were increased significantly with the incorporation of both Na‐MMT and OMMT. The highest value in both storage modulus and HDT was found in the PA6/PP nanocomposite containing stearylamine modified montmorillonite due to its better exfoliated structure. POLYM. COMPOS., 31:1156–1167, 2010. © 2009 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     

Ternary polymer blends of polyamide 6, polypropylene,and acrylonitrile‐butadiene‐styrene: Influence of multiwalled carbon nanotubes on phase morphology,electrical conductivity,and crystallization

Ternary polymer blends of 80/10/10 (wt/wt/wt) polyamide6 (PA6)/polypropylene (PP)/acrylonitrile‐butadiene‐styrene (ABS), PP/PA6/ABS, and ABS/PP/PA6 were prepared in the presence of multiwalled carbon nanotubes (MWCNTs) by melt‐mixing technique to investigate the influence of MWCNTs on the phase morphology, electrical conductivity, and the crystallization behavior of the PP and PA6 phases in the respective blends. Morphological analysis showed the “core–shell”‐type morphology in 80/10/10 PA6/PP/ABS and 80/10/10 PP/PA6/ABS blends, which was found to be unaltered in the presence of MWCNTs. However, MWCNTs exhibited “compatibilization‐like” action, which was manifested in a reduction of average droplet size of the dispersed phase/s. In contrast, a separately dispersed morphology has been found in the case of 80/10/10 ABS/PP/PA6 blends in which both the phases (PP and PA6) were dispersed separately in the ABS matrix. The electrical percolation threshold for 80/10/10 PA6/PP/ABS and 80/10/10 PP/PA6/ABS ternary polymer blends was found between 3–4 and 2–3 wt% of MWCNTs, respectively, whereas 80/10/10 ABS/PP/PA6 blends showed electrically insulating behavior even at 5 wt% of MWCNTs. Nonisothermal crystallization studies could detect the presence of MWCNTs in the PA6 and the PP phases. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Dynamic mechanical,thermal, and morphological properties of silane‐treated montmorillonite reinforced polycarbonate nanocomposites

Three different loading of 3‐aminopropyltriethoxysilane (APS) was used to modify the Na‐montmorillonite via cation exchange technique. The Na‐MMT and silane‐treated montmorillonite (STMMT) were melt‐compounded with polycarbonate (PC) by using Haake Minilab machine. The PC nanocomposite samples were prepared by using Haake Minijet injection molding technique. The intercalation and exfoliation of the PC/MMT nanocomposites were characterized by using X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The thermal properties of the PC nanocomposites were investigated by using dynamic mechanical analyzer and thermogravimetry analyzer. XRD and TEM results revealed partial intercalation and exfoliation of STMMT in PC matrix. Increase of APS concentration significantly enhanced the storage modulus (E′) and improved the thermal stability of PC nanocomposites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

ABS/蒙脱土纳米复合材料的制备、结构及性能

将SAN／蒙脱土纳米复合材料与ABS高胶粉熔融共混得到ABS／蒙脱土纳米复合材料。对纳米复合材料的机械性能进行了表征．结果发现蒙脱土的加入一定程度上提高了ABS的杨氏模量和弯曲模量，但冲击强度有明显的降低。采用XRD、TEM和SEM对纳米复合材料的结构进行表征，结果表明在共混过程中，蒙脱土片层的物理特性导致其基本分布在橡胶粒子的表面．甚至造成粒子的变形和破裂；ABS／蒙脱土纳米复合材料在冲击过程中，蒙脱土片层的分散状态导致橡胶粒子不能发生塑性变形，冲击断面呈多孔形态。     

聚丙烯/尼龙6/纳米蒙脱石复合材料的制备及热性能研究

采用熔融插层法成功制备了聚丙烯(PP)/尼龙6(PA6)/有机化蒙脱石(OMMT)纳米复合材料.用X射线衍射分析(XRD)和透射电镜(TEM)观察了OMMT层间距的变化和材料的结构;用示差扫描量热法(DSC)和热重分析(TG)研究了热性能,并考察了纳米复合材料的拉伸强度.研究结果表明,OMMT的层间距由2.200 nm扩大到2.800 nm,PP/PA6合金高分子链取代了有机化蒙脱石层间的十六烷基三甲基溴化铵而进入到蒙脱石的片层间,加入质量分数为4%的OMMT的复合材料不仅使材料的拉伸强度提高了约15%,还提高了材料的热稳定性,使剩炭率增加了8.1%.     

PLA/OMMT纳米插层复合材料的合成、表征及降解性研究

以乳酸单体和有机蒙脱土(OMMT)为原料,通过原位插层聚合法合成了聚乳酸(PLA)/OMMT纳米插层复合材料, 分别采用傅立叶变换红外光谱( FT-IR)、X 射线衍射（XRD）、透射电子显微镜（TEM）等对PLA/OMMT复合材料的结构、形貌进行了表征和分析,同时研究了材料的降解性能。FT-IR表明,OMMT在聚合过程中被剥离成很小的粒子并分散在PLA基体中形成PLA/OMMT复合材料。由XRD分析可知MMT的层间距为1.260 nm,OMMT层间距为1.993 nm,PLA/OMMT复合材料中OMMT层间距为2.287 nm,层间距明显增大,表明PLA分子链插入到OMMT片层间,实现了原位插层聚合。透射电镜（TEM）分析表明,制备的PLA/OMMT复合材料形成了插层型结构,与红外光谱与XRD表征结果吻合。降解试验表明,介质对材料降解作用的次序为：NaOH＞HCl＞去离子水。在磷酸盐缓冲溶液中,随着降解时间的延长,材料的特性黏度在降解过程中不断下降。PLA/OMMT复合材料的降解速度要快于PLA,表明由于OMMT纳米粒子的存在,会加速材料的降解。     

Application of styrene‐acrylonitrile random copolymer–polyarylate block copolymer as reactive compatibilizer for polyamide and acrylonitrile‐butadiene‐styrene blends

Styrene‐acrylonitrile random copolymer (SAN) and polyarylate (PAr) block copolymer were applied as a reactive compatibilizer for polyamide‐6 (PA‐6)/acrylonitrile‐butadiene‐styrene (ABS) copolymer blends. The SAN–PAr block copolymer was found to be effective for compatibilization of PA‐6/ABS blends. With the addition of 3.0–5.0 wt % SAN–PAr block copolymer, the ABS‐rich phase could be reduced to a smaller size than 1.0 μm in the 70/30 and 50/50 PA‐6/ABS blends, although it was several microns in the uncompatibilized blends. As a result, for the blends compatibilized with 3–5 wt % block copolymer the impact energy absorption reached the super toughness region in the 70/30 and 50/50 PA‐6/ABS compositions. The compatibilization mechanism of PA‐6/ABS by the SAN–PAr block copolymer was investigated by tetrahydrofuran extraction of the SAN–PAr block copolymer/PA‐6 blends and the model reactions between the block copolymer and low molecular weight compounds. The results of these experiments indicated that the SAN–PAr block copolymer reacted with the PA‐6 during the melt mixing process via an in situ transreaction between the ester units in the PAr chain and the terminal amine in the PA‐6. As a result, SAN–PAr/PA‐6 block copolymers were generated during the melt mixing process. The SAN–PAr block copolymer was supposed to compatibilize the PA‐6 and ABS blend by anchoring the PAr/PA‐6 and SAN chains to the PA‐6 and ABS phases, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2300–2313, 2002     

Morphological and Thermal Properties of ABS/Montmorillonite Nanocomposites Using ABS with Different AN Contents

Acrylonitrile‐butadiene‐styrene (ABS)/clay nanocomposites have been prepared using two types of ABS with different AN contents and a chemically modified clay, Cloisite 20A. The composites were prepared by melt mixing in a twin‐screw extruder. Their morphological properties were characterized by XRD and TEM. The thermal stability of the polymer nanocomposites was studied using TGA and flammability tests. The results were analyzed in terms of the effect of the clay content and the type of ABS used on the clay dispersion and the thermal stability of the nanocomposites. Experimental results confirmed that better dispersion and intercalation and/or exfoliation can be obtained when using an ABS with a higher AN content. The study using TGA and flammability tests showed that the nanodispersed layers of silicate enhanced the thermal stability of the ABS matrix, and that an ABS with higher AN content was more effective in providing fire retardancy. This suggests that when using higher AN contents, more polar groups are present within the polymer matrix, allowing a more homogeneous dispersion and intercalation of the chain polymers into the organomodified montmorillonite clay (MMT), and even some exfoliation of the nanoclay.

     

蒙脱土(MMT)/PA纳米复合材料的制备与性能研究

用熔融插层法制备 MMT/PA纳米复合材料 ,先合成有机改性蒙脱土 ,再将 PA6和 PA66分别与改性 MMT共混制成纳米复合材料。表征了其结构和力学性能 ,观察了 MMT/PA6和 MMT/PA66纳米复合材料的阻燃特性。发现纳米 MMT也能将 PA66的冲击强度提高近 50 % ,并能提高 PA6的 LOI,与其他阻燃剂起协同效应     

Preparation and properties of polypropylene/montmorillonite layered nanocomposites

Polypropylene (PP)/montmorillonite (MMT) nanocomposites have been prepared by melt intercalation using organomontmorillonite and conventional twin screw extrusion. The dispersibility of silicate layers of the montmorillonite in the composites was investigated by using X‐ray diffractometer and transmission electron microscopy (TEM). The silicate layers of montmorillonite are dispersed at the nanometer level in the PP matrix, as revealed by X‐ray and TEM results. The tensile strength of PP/MMT is not much improved compared with pure PP or conventional filled composites. However, the impact strength is greatly improved at lower content of MMT. © 2000 Society of Chemical Industry     

Effect of drawing on the molecular orientation,polymorphism, and properties of melt‐spun nanocomposite fibers based on nylon 6 with polyhedral oligomeric silsesquioxane,montmorillonite, and their combination

In this work, binary and ternary nanocomposite systems based on nylon 6 with montmorillonite (MMT), polyhedral oligomeric silsesquioxane (POSS), and their combination were prepared using a melt‐compounding process. In the transmission electron microscope (TEM) images, the MMT was found to be generally well dispersed in all materials resulting in its good chemical compatibility with nylon 6, affording intercalated disordered microstructures. On the other hand, the TEM images showed that POSS formed micron‐size crystalline agglomerates possibly resulting from a lack in chemical compatibility with nylon 6. These nanocomposite systems were melt‐spun into fibers, and the relevant structure–property relationships that occur during the cold drawing process was established by correlating the tensile properties to the changes in crystallinity, polymorphic crystal forms, and molecular orientation. The properties of the resulting fibers were found to be rather skewed and significantly affected by the polymer/nanoparticles interface. The agglomeration of POSS and POSS–MMT particles coupled with the weak nylon 6/POSS interface, reflected on the tensile properties of the nylon 6/POSS and nylon 6/MMT‐POSS fibers which underperformed. Some nanocomposite fiber systems offered significant improvements in modulus without excessively compromising the extensibility of the fibers. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Preparation and characterization of poly(butylene terephthalate) nanocomposites with various organoclays

Layered‐silicate‐based polymer–clay nanocomposite materials were prepared depending on the surface modification of montmorillonite (MMT). Nanocomposites consisting of poly(butylene terephthalate) (PBT) as a matrix and dispersed inorganic clay modified with cetyl pyridinium chloride (CPC), benzyl dimethyl N‐hexadecyl ammonium chloride, and hexadecyl trimethyl ammonium bromide by direct melt intercalation were studied. The organoclay loading was varied from 1 to 5 wt %. The organoclays were characterized with X‐ray diffraction (XRD) to compute the crystallographic spacing and with thermogravimetric analysis to study the thermal stability. Detailed investigations of the mechanical and thermal properties as well as a dispersion study by XRD of the PBT/clay nanocomposites were conducted. X‐ray scattering showed that the layers of organoclay were intercalated with intercalating agents. According to the results of a differential scanning calorimetry analysis, clay acted as a nucleating agent, affecting the crystallization. The PBT nanocomposites containing clay treated with CPC showed good mechanical properties because of intercalation into the polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microcompounding of organoclay–ABS/PA6 blend‐based nanocomposites

In this study, acrylonitrile–butadiene–styrene (ABS) and polyamide‐6 (PA6) were blended in the presence of an olefin‐based compatibilizer and organoclays. The effects of ABS to PA6 ratio, clay content, and screw speed of the microcompounder were examined by performing morphological (i.e., XRD, SEM, and TEM) and tensile tests. The average aspect ratio of the clay platelets after processing was obtained by applying semiautomatic image analysis method. SEM analysis showed that addition of the compatibilizers to the ABS/PA6 blend system resulted in a decrease in diameter of dispersed phase when one of the phases was continuous. The addition of 5 wt% compatibilizer altered the dispersed morphology to cocontinuous morphology when the weight percentage of ABS was equal to that of PA6. The results of XRD analysis implied that clays were exfoliated in the presence of PA6. It was observed in TEM micrographs that clays were selectively dispersed in PA6 phase. Aspect ratio of the platelets increased as the PA6 content increased. Moduli of the nanocomposites were improved by enriching blend with PA6 and increasing screw speed. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Clay distribution and crystalline structure evolution in polyamide 6/montmorillonite composites prepared by activated anionic polymerization

Nanostructured polymer composites (NPC) based on polyamide 6 (PA6) are prepared by activated anionic ring‐opening polymerization (AAROP) of mixtures of ε‐caprolactam (ECL) and organically treated montmorillonite (o‐MMT). The polymerization is performed in bulk, at 165°C, i.e., below the melting point of the resulting APA6, the reaction time being in the range of 10–15 min. The o‐MMT content is varied in the 0.5–10% range. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) show that exfoliated NPC can be produced with clay loads of 0.5–1.0%. Larger clay amounts lead to various degrees of intercalation of the MMT layers. FT‐IR imaging proves that all NPCs contain MMT aggregates with sizes in the 10–20 µm range. The formation of the matrix crystalline structure is followed directly by performing AAROP of an activated ECL/o‐MMT blend in a synchrotron beamline. Irrespective of the o‐MMT type and concentration, it is the α‐PA6 that forms first and in larger amounts. The γ‐PA6 polymorph can be found in predominating amounts only after melting and recrystallization of the already produced polymer matrix. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1228‐1238, 2013     

Thermal–oxidative degradation and accelerated aging behavior of polyamide 6/epoxy resin‐modified montmorillonite nanocomposites

Polyamide 6 (PA6) nanocomposites based on epoxy resin‐modified montmorillonite (EP‐MMT) were prepared by melt processing using a typical twin‐screw extruder. X‐ray diffraction combined with transmission electron microscopy was applied to elucidate the structure and morphology of PA6/EP‐MMT nanocomposites, suggesting a nearly exfoliated structure in the nanocomposite with 2 wt % EP‐MMT (PA6/2EP‐MMT) and a partial exfoliated‐partial intercalated structure in PA6/4 wt %EP‐MMT nanocomposite (PA6/4EP‐MMT). The thermogravimetric analysis under air atmosphere was conducted to characterize the thermal–oxidative degradation behavior of the material, and the result indicated that the presence of EP‐MMT could inhibit the thermal‐oxidative degradation of PA6 effectively. Accelerated heat aging in an air circulating oven at 150°C was applied to assess the thermal–oxidative stability of PA6 nanocomposites through investigation of reduced viscosity, tensile properties, and chemical structure at various time intervals. The results indicated that the incorporation of EP‐MMT effectively enhanced the thermal–oxidative stability of PA6, resulting in the high retention of reduced viscosity and tensile strength, and the low ratio of terminal carboxyl group to amino group. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40825.     

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