Study on the dynamic self‐organization of montmorillonite in two phases

Polycarbonate (PC)/acrylonitrile–butadiene–styrene (ABS) polymer alloy/montmorillonite (MMT) and nylon 6 (PA6)/ABS polymer alloy/MMT nanocomposites were prepared using the direct melt intercalation technique. Their structures were characterized by XRD and TEM. The results of TEM show that the silicate layers dispersed differently in two phases. In the PC/ABS/MMT nanocomposite, the silicate layers were self‐organized in the ABS phase, whereas in the PA6/ABS/MMT nanocomposite, the silicate layers were dispersed in both phases but mainly in the PA6 phase. Furthermore, the PC/MMT nanocomposite was melt‐mixed with pure ABS, and the changed morphology of the hybrid with the change of melt‐mixing time was characterized by XRD and TEM, to study the dynamic self‐assembly of clay layers in two phases. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1457–1462, 2004     

Crystalline forms in melt‐crystallized syndiotactic polystyrene/clay nanocomposites

X‐ray diffraction methods and polarized optical microscopy have been used to investigate the structural change of syndiotactic polystyrene/clay nanocomposites. The nanocomposite has prepared by mixing an sPS polymer solution with organically modified montmorillonite. Both X‐ray diffraction and transmission electron microscopy results indicate that most of the swellable silicate layers are exfoliated and randomly dispersed into the sPS matrix. The X‐ray diffraction data also show the presence of polymorphism in sPS/clay nanocomposites, which is strongly dependent on the thermal history of the nanocomposites from the melt and on the content of clay. In this study, the effect of premelting temperatures and crystallization temperatures of sPS and sPS/clay nanocomposites on their crystalline phases is discussed.     

Effects of process conditions and mixing protocols on structure of extruded polypropylene nanocomposites

Polymer melt‐direct intercalation or exfoliation is a promising approach for the preparation of nanocomposites. The structure of nanoclay platelets in the nanocomposites depends not only on the properties of polymer matrix and nanoclay, but also on the operating conditions during processing. The objective of the present work is to investigate the effects of clay chemical modifiers, mixing protocols, and operating conditions upon the clay structure in nanocomposites prepared with a corotating twin‐screw extruder. Two mixing methods were used for the nanocomposite preparation: two‐step mixing and one‐step mixing. Experimental results obtained from melt flow index and complex viscosity measurements suggest that nanoclay C15A is more exfoliated than C30B in a polypropylene homopolymer containing a maleic anhydride grafted PP (PB) as compatibilizer. The two‐step mixing method results in better exfoliation for the nanofillers than the one‐step mixing method. A numerical simulation has been carried out to evaluate the mean residence time and shear rate in different screw configurations under various process conditions. X‐ray diffraction experiments indicate that the residence time is a dominant factor in producing satisfactory nanocomposites in extruders. However, high shear rate coupled with long residence time might result in poor exfoliation of clay. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1891–1899, 2004     

New polylactide-layered silicate nanocomposites. 2. Concurrent improvements of material properties, biodegradability and melt rheology

Our continuing research on the preparation, characterization, materials properties, and biodegradability of polylactide (PLA)-layered silicate nanocomposites has yielded results for PLA-montmorillonite nanocomposites. Montmorillonite modified with trimethyl octadecylammonium cation was used as an organically modified layered silicate for the nanocomposites preparation. The internal structure of the nanocomposites in the nanometer range has been established by using wide-angle X-ray diffraction and transmission electron microscope analyses. All the nanocomposites exhibited superior improvement of practical materials properties such as storage modulus, flexural modulus, flexural strength, heat distortion temperature, and gas barrier property as compared to that of neat PLA. The biodegradability of neat PLA and a representative nanocomposite was also studied under compost, and the rate of biodegradation of neat PLA significantly increased after nanocomposites preparation. The melt rheology of neat PLA and various PLACNs was also studied.     

Effect of order of mixing on morphology and thermal properties of the compatibilized PBT and ABS alloys/OMT nanocomposites

Poly(butylene terephthalate) (PBT) and acrylonitrile–butadiene–styrene terpolymers (ABS) alloys/organically modified montmorillonite (OMT) nanocomposites using terpolymers of random ethylene, methyl acrylate, and glycidyl methacrylate as the reactive compatibilizer were prepared by different melt‐mixing sequences. The microstructures were characterized by scanning electron microscopy, X‐ray diffraction, transmission electron microscopy, and high‐resolution electron microscopy. It was found that order of mixing affects the dispersion state of OMT in the alloy matrix. The crystallization behavior of PBT in the compatibilized PBT and ABS alloys/OMT nanocomposites was studied by wide angle X‐ray diffraction. It revealed that order of mixing has influence on the preferential crystal growing direction of PBT owing to the antagonistic effect of ABS and OMT. Thermogravimetric analyses and differential scanning calorimetry also showed order of mixing changes the thermal property of the compatibilized PBT and ABS alloys/OMT nanocomposites. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2130–2139, 2007     

Electrical and mechanical properties of acrylonitrile‐butadiene‐styrene/multiwall carbon nanotube nanocomposites prepared by melt‐blending

The electrical properties in polymer/carbon nanotube (CNT) nanocomposites are governed not only by the degree of dispersion but also to a greater extent on the aspect ratio of the CNTs in the final composites. Melt‐mixing of polymer and CNTs at high shear rate usually breaks the CNTS that lowers the aspect ratio of the nanotubes. Thus, homogeneous dispersion of CNTs while retaining the aspect ratio is a major challenge in melt‐mixing. Here, we demonstrate a novel method that involves melt‐blending of acrylonitrile‐butadiene‐styrene (ABS) and in situ polymerized polystyrene (PS)/multiwalled CNT (MWCNT) nanocomposites, to prepare electrically conducting ABS/MWCNT nanocomposites with very low CNT loading than reported. The rationale behind choosing PS/MWCNT as blending component was that ABS is reported to form miscible blend with the PS. Thus, (80/20 w/w) ABS/(PS/MWCNT) nanocomposites obtained by melt‐blending showed electrical conductivity value ≈1.27 × 10^?6 S cm^?1 at MWCNT loading close to 0.64 wt %, which is quite lower than previously reported value for ABS/MWCNT system prepared via solution blending. Scanning electron microscopy and differential scanning calorimetry analysis indicated the formation of homogenous and miscible blend of ABS and PS. The high temperature (100°C) storage modulus of ABS (1298 MPa) in the nanocomposites was increased to 1696 MPa in presence of 0.64 wt % of the MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and characterization of polymer/organosilicate nanocomposites based on unmodified LDPE

Low‐density polyethylene (LDPE)/silicate nanocomposites were prepared by the melt compounding and solution blend methods using unmodified LDPE polymer and layered silicates with different aspect ratio. X‐ray diffraction (XRD) analysis performed on composites obtained by dispersing the organosilicates in molten LDPE evidenced an exfoliated or partially exfoliated structure for the low aspect ratio silicate (laponite) in contrast to the high aspect ratio silicate (montmorillonite), which led to the formation of intercalated nanocomposites. With regard to the preparation method, the melt compounding method was more effective in forming exfoliated/highly intercalated LDPE nanocomposites compared with the solution blend method (using CCl₄ as a solvent). A gradual increase in crystallization temperatures (T_c) with increasing laponite content for LDPE‐organolaponite nanocomposites was revealed by differential scanning calorimetry (DSC) measurements. Thermogravimetric analysis and tensile measurements results indicated that thermal stability and elastic modulus increment were more prevalent for nanocomposites prepared using organomontmorillonite as filler. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

嵌入法制备聚合物/层状硅酸盐纳米复合材料的研究进展

本文介绍和对比了嵌入法制备聚合物／层状硅酸盐纳米复合材料的三种类型,与溶液嵌入法（包括单体嵌入聚合法和聚合物溶液嵌入法）相比,熔融嵌入法具有更广泛的适用性。并从热力学和动力学角度出发,分析了影响嵌入过程的各种因素。     

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.

     

Investigation of polyethylene/sisal whiskers nanocomposites prepared under different conditions

In this work, sisal nanowhiskers (SNWs) extracted from sisal fibers were used to reinforce high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE). The nanocomposites were prepared by solution casting from toluene and melt mixing, both followed by melt pressing. In the case of melt mixing, the surfaces of the SNW were also chemically modified with 1 phr of vinyl triethoxy silane to improve their dispersibility and compatibility with the matrices. The SNW had an average length of 197 nm and diameter of 12 nm, and a crystallinity index of 89%. Fourier transform infrared confirmed the surface chemical modification of the SNW. The whiskers were fairly well dispersed in the matrices, regardless of the treatment or preparation method. The presence of whiskers, as well as nanocomposite preparation method, had an observable influence on the storage modulus of LDPE, but very little influence on that of HDPE. There was, however, no significant influence on the degradation behavior of both polymers. The crystallization behavior of the polymers was found to strongly depend on their morphologies. The melting and crystallization behavior of the LDPE nanocomposites were almost unchanged, while an increase in crystallinity was observed for all the HDPE nanocomposites. The tensile properties depended on the type of polymer, the treatment, and the preparation method. Generally there was an improvement in tensile modulus, and a decrease in elongation at break, but the stress at break only improved for the HDPE nanocomposites. POLYM. COMPOS., 35:2221–2233, 2014. © 2014 Society of Plastics Engineers     

Melt spinning of conductive textile fibers with hybridized graphite nanoplatelets and carbon black filler

In this study, two different carbon fillers: carbon black (CB) and graphite nanoplatelets (GNP) are studied as conductive fillers for the preparation of conductive polypropylene (PP) nanocomposites. In order to obtain a homogenous dispersion of GNP, GNP/PP composites were prepared by two different methods: solid state mixing (SSM) and traditional melt mixing (MM). The result shows that MM is more efficient in the dispersion of GNP particles compared to SSM method. PP nanocomposites containing only one conductive filler and two fillers were prepared at different filler concentrations. Based on the analysis of electrical and rheological properties of the prepared nanocomposites, it shows that a hybridized composite with equal amounts of GNP and CB has favorable processing properties. Conductive fibers with a core/sheath structure were produced on a bicomponent melt spinning line. The core materials of these fibers are the hybridized GNP/CB/PP nanocomposite and the sheath is pure polyamide. It was found that GNPs were separated during melt and cold drawing which results in the decrease of conductivity. However, the conductivity could partly be restored by the heat treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2579–2587, 2013     

Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process

In this study, polymer‐clay nanocomposites of various concentrations were prepared by ultrasonically assisted polymerization and melt‐mixing processes. A sonication process using power ultrasonic waves was employed to enhance nano‐scale dispersion during melt‐mixing of polymer blends and organically modified clay. We expected enhanced breakup of layered silicate bundles and further reduction in the size of the dispersed phase, with better homogeneity compared to the different immiscible blend pairs. X‐ray diffraction (XRD) and Transmission Electron Microscopy (TEM) were used to characterize the structures of the nanocomposites. The rheological behaviors of the obtained nanocomposites were measured with parallel plate rheometry. It was found that the ultrasound‐assisted process successfully generated exfoliated nanocomposites and promoted in‐situ compatibilization of the matrix comprising an immiscible pair of polymers in a blend. The resulting nanocomposite exhibited superior thermal stability and elastic modulus compared to the base polymer. Polym. Eng. Sci. 44:1198–1204, 2004. © 2004 Society of Plastics Engineers.     

New polylactide/layered silicate nanocomposites. 5. Designing of materials with desired properties

Understanding the structure/property relationship in polymer/layered silicate nanocomposites is of great importance in designing materials with desired properties. In order to understand these relations, a series of polylactide (PLA)/organically modified layered silicate (OMLS) nanocomposites have been prepared using a simple melt extrusion technique. Four different types of OMLS have been used for the preparation of nanocomposites, three were modified with functionalized ammonium salts while fourth one was a phosphonium salt modified OMLS. The structure of the nanocomposites in the nanometer scale was characterized by using wide-angle X-ray diffraction and transmission electron microscopic observations. Using four different types of layered silicates modified with four different types of surfactants, the effect of OMLS in nanocomposites was investigated by focusing on four major aspects: structural analysis, thermal properties and spherulite morphology, materials properties, and biodegradability. Finally, we draw conclusions about the structure/property relationship in the case of PLA/OMLS nanocomposites.     

层状硅酸盐 /聚合物纳米复合材料的研究现状与前景

基于1996年以后的40余篇文献和作者的研究成果，综述了层状硅酸盐／聚合物纳米复合材料在制备技术、新品种、新性能、相关理论及应用等方面的最新研究进展，并总结出了以下观点：（1）粘土的有机化是制备纳米复合材料的第一关键要素，单体、预聚体、聚合物熔体与有机土的相容性是制备纳米复合材料的必要条件，外界剪切力可提供帮助；（2）剥离型结构最能体现层状硅酸盐／聚合物纳米复合材料的性能优势，是层状硅酸盐／聚合物纳米复合材料的制备方向；（3）聚合物熔体插层法为简单，是重要的发展方向，要形成剥离型结构，需要同时考虑热力学和动力学因素，基体或相容剂与层间环境的相容性要适中；（4）聚合物乳液共混共凝法有利于传统的制备方法，适合于具有乳液形成的聚合物；（5）在聚合物中原位生成硅酸盐片层的方法具有新意；（6）层状硅酸盐／聚合物纳米复合材料的主要特点是高刚性、高强度、高耐热性、高阻隔性、较好的阻燃性、质轻，目前，该的制备研究正向所有的聚合物品种扩展。汽车部件、包装材料将是层状硅酸盐／聚合物纳米复合材料先应用的两大领域；（7）层状硅酸盐／聚合物纳米复合材料的理论研究进展延慢。界面区状态以及结构－性能间的关系是理论研究的两个主题。     

碳纳米管/橡胶复合材料的制备与性能研究进展

介绍了碳纳米管/橡胶复合材料的直接共混、溶液共混、乳液共混、熔融共混、原位聚合制备工艺,综述了碳纳米管/橡胶复合材料的加工性能、力学性能和电性能,指出今后的发展方向是开发新的碳纳米管制备技术、探索碳纳米管的纯化和改性方法、研究碳纳米管/橡胶复合材料的制备技术及其结构与性能的关系.     

Microstructure, tensile properties, and biodegradability of aliphatic polyester/clay nanocomposites

Novel biodegradable aliphatic polyester (APES)/organoclay nanocomposites were prepared through melt intercalation method. Two kinds of organoclays, Cloisite 30B and Cloisite 10A with different ammonium cations located in the silicate gallery, were chosen for the nanocomposites preparation. The dispersion of the silicate layers in the APES hybrids was characterized by using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Tensile properties and the biodegradability of the APES/organoclay nanocomposites were also studied. APES/Cloisite 30B hybrids showed higher degree of intercalation than APES/Cloisite 10A hybrids due to the strong hydrogen bonding interaction between APES and hydroxyl group in the gallery of Cloisite 30B silicate layers. This leads to higher tensile properties and lower biodegradability for APES/Cloisite 30B hybrids than for the APES/Cloisite 10A hybrids.     

Recycled PET‐organoclay nanocomposites with enhanced processing properties and thermal stability

Preparation of thermally stable recycled PET‐organoclay nanocomposites with improved processing and mechanical properties is a challenging task from the environmental as well as industrial and commercial point of view. In this work, both modification of sodium‐type montmorillonite with 1,2‐dimethyl‐3‐octadecyl‐1H‐imidazol‐3‐ium chloride and additional treatment with [3‐(glycidyloxy)propyl]trimethoxysilane was performed. Thermal stability of the organoclays and nanocomposites prepared by melt compounding was tested by thermogravimetric analysis, differential scanning calorimetry, and melt rheology. In comparison with the organoclays modified with quaternary ammonium compounds, the prepared clays showed substantial suppression of matrix degradation during melt mixing. The increase in interlayer distance of silicate platelets and homogeneity of dispersions in the recycled and virgin PET matrices have been evaluated by transmission electron microscopy and wide‐angle X‐ray scattering. The higher degree of delamination in the nanocomposites filled with imidazole organoclays was in a good agreement with improved rheological characteristics and led to significant enhancement in mechanical properties and thermal stability. A difference in structure (besides the level of delamination and homogeneity of silicate platelets) of recycled versus virgin PET nanocomposites was detected by X‐ray diffraction patterns. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly(lactic acid) and layered silicate nanocomposites prepared by melt mixing: Thermomechanical and morphological properties

Poly(lactic acid) (PLA) nanocomposites were prepared by melt mixing technique in a Haake batch mixer. The clay dispersion within the PLA matrix during melt mixing was well explained through the morphological characterization. Morphological characterizations were studied by X‐ray diffraction and transmission electron microscopy. The exfoliation/intercalation of the clay particles within the polymer matrix during melt mixing depends on the mixing torque generated during the preparation of nanocomposites. The significance of processing temperature and the mixing time in melt mixing were studied for PLA/C93A and PLA/C30B nanocomposites. The structure and properties of the nanocomposites were also characterized by differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, and mechanical properties by standard tensile testing. The incorporation of nanoclays into the PLA matrix enhanced the mechanical properties and thermal stability of the PLA nanocomposites. This may be due to the reinforcing effect of nanoclays within the polymer matrix. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Chlorosulfonated polypropylene: preparation and its application as a coupling agent in polypropylene-clay nanocomposites

Polypropylene nanocomposites containing organophilic layered silicate were prepared by melt mixing. In order to increase polypropylene polarity, Cl and SO₂Cl groups were introduced by reaction with sulfuryl chloride under UV irradiation. Chlorosulfonated polypropylene was subsequently melt-compounded with organophilized montmorillonite clay to produce a masterbatch. The masterbatch was then blended with commercial isotactic polypropylene. An organophilized silicate (Cloisite 15A) and three chlorosulfonated polypropylenes with different degrees of functionalization were used in this study. The effect of various processing procedures was examined as well. The morphology of nanocomposites obtained was examined using TEM and X-ray diffraction. It has been shown that the presence of polar groups leads to an increased gallery distance and partial exfoliation. Nevertheless, full exfoliation of clay platelets has not been achieved. The observed morphologies affected the resulting tensile mechanical behaviour: both stiffness and strength significantly increased.     

Preparation of poly(acrylonitrile–butadiene–styrene)/montmorillonite nanocomposites and degradation studies during extrusion reprocessing

In this study, the preparation of organically modified montmorillonite/poly(acrylonitrile–butadiene–styrene) (ABS) nanocomposites was studied by melt blending in a twin‐screw extruder. The composite material was subjected to a series of five extrusion cycles, and the effect of reprocessing on the material's structural properties was investigated. More specifically, chemical changes were studied with attenuated total reflectance/Fourier transform infrared analysis, the thermal response was recorded by differential scanning calorimetry experiments, and the thermal stability was detected with thermogravimetric analysis. Also, the rheological properties of these blends were investigated via melt flow index tests as a measure of their processability during melt mixing and molding processes. Furthermore, the mechanical strength of the obtained mixtures was explored, and the observed interactions were interpreted in terms of the influence of each component on the functional properties of the final mixture. This attempt enriched our knowledge about the recycling of ABS, with the additional aspect of the use of collected data from more complex systems, that is, composite materials, where the montmorillonite nanoparticles play a role in the interactions initiated by repeated processing. The experimental results of this study show that the reprocessing of ABS/montmorillonite induced oxidation products, but the rheological, mechanical, and thermal properties and the thermal and color stabilities of the composites remained almost stable. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009