聚乙烯醇/氟基蒙脱土纳米复合材料的合成及性能研究

采用水热方法,在493 K条件下反应72小时,合成了氟基蒙脱土(F-MMT),在这种F-MMT中,硅酸盐结构中的一些OH-被F-取代。采用溶液插层方法,制备了聚乙烯醇/F-MMT纳米复合材料(PVA/F-MMT)。采用X 射线衍射、扫描电镜和透射电镜对F-MMT 和 PVA/F-MMT纳米复合材料进行了表征;结果表明,片状结构的F-MMT均匀分散于PVA中,形成了层离结构的纳米复合材料。热重分析、力学性能和紫外可见光谱的测试结果表明,在没有牺牲光学性能情况下,PVA/F-MMT纳米复合材料的热稳定性和力学性能都得到了提高。力学和热学性能的提高归功于F-MMT均匀而好的分散于聚合物基体中,以及PVA中的 OH- 和F-MMT 中F-之间强的氢键作用。     

GO/PVA nanocomposites with significantly enhanced mechanical properties through metalion coordination

In this study, a simple and efficient way is demonstrated to create strong interfacial interaction between graphene oxide(GO) filler and poly(vinyl alcohol)(PVA) matrix through metal ion coordination. The coordination bonding provides efficient load transfer during the tensile process, and enhances the mechanical properties of the nanocomposites significantly. After being coordinated with Cu(Ⅱ) ions, GO/PVA composites show much higher Young's moduli and yield stresses than pure PVA and noncoordinated GO/PVA. UV–vis and FTIR spectra are performed to confirm the successful coordination between GO and PVA. Ethylene diamine tetraacetic acid disodium salt(EDTA-2 Na) is used to confirm the important role of coordination in enhancing the composites. This research provides a new approach to manufacture polymer-matrix nanocomposites with significantly improved mechanical performances.     

Surface modified graphene oxide/poly(vinyl alcohol) composite for enhanced hydrogen gas barrier film

A series of novel polyethyleneimine (PEI) modified graphene oxide (PEI-mGO) filled poly(vinyl alcohol) (PVA) nanocomposite (PEI-mGO/PVA) films were prepared by solution-casing for hydrogen gas barrier applications. Hydrophilic PEI was used to simultaneously reduce and modify graphene oxide sheets, thereby facilitating a homogeneous dispersion of PEI-mGO in the PVA matrix. The effects of PEI-mGO on the morphology and properties of the nanocomposite films were examined by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis and field emission scanning electron microscopy. Analogous GO/PVA composites were also prepared and characterized for comparative purposes. The PEI-mGO/PVA nanocomposites showed higher thermal and mechanical stability as well as remarkable improvement in hydrogen gas barrier properties compared to the PVA film; specifically, the PEI-mGO/PVA film having 3.0 wt% of PEI-mGO content exhibited almost 95% decrease in GTR and permeability values compared to PVA film.     

热塑性淀粉/聚乙烯醇/蒙脱土三元纳米复合材料

用熔融挤出的方法制备了甘油塑化热塑性淀粉（TPS）/聚乙烯醇（PVA）/蒙脱土（MMT）纳米复合材料,添加蒙脱土和聚乙烯醇用以提高热塑性淀粉材料的力学性能。 在相对湿度50%的条件下,复合材料的XRD衍射谱图和透射电子显微镜测试表明,MMT以剥离状态均匀分布在TPS/PVA基体中;力学测试表明,当MMT的质量分数从0％增至5％时,复合材料的力学性能明显提高。 当蒙脱土的质量分数为3%时,复合材料最大抗张强度达到13.24 MPa,杨氏模量达到61.46 MPa。 这说明蒙脱土在复合材料中可以起到物理交联点的作用,提高了复合材料的力学性能。     

PREPARATION AND CHARACTERIZATION OF SOY PROTEIN ISOLATE(SPI)/MONTMORILLONITE(MMT) BIONANOCOMPOSITES

 The bionanocomposites of soy protein isolate (SPI)/montmorillonite (MMT) have been prepared successfully via simple melt mixing, in which MMT was used as nanofiller and glycerol was used as plasticizer. Their structures and properties were characterized with X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM), thermogravimetric analysis and tensile testing. XRD、TEM and SEM results indicated that the MMT layers could be easily intercalated by the SPI matrix even by simple melt processing. The exfoliated MMT layers were randomly dispersed in the protein matrix as MMT content was low (less than 5 wt%), an incomplete exfoliation was evident from SEM results, and some primary particles were observed as the MMT content was high (from 5 wt% to 9 wt%). A significant improvement of the mechanical strength and thermal stability of SPI/MMT nanocomposites has been achieved. Our work suggests that simple melt processing is an efficient way to prepare SPI/MMT nanocomposites with exfoliated structure.     

Thermal,mechanical and water barrier properties of graphene oxide/polyvinyl alcohol/polyol composite films

The novel polymer composite of polyvinyl alcohol (PVA), polyol(PO) and graphene oxide (GO) was used to prepare the PVA/PO and GO/PVA/PO with different weight percents of GO (0.5 and 1% denoted as (0.5 wt%)GO/PVA/PO and (1 wt%)GO/PVA/PO, respectively) through solution casting blend technique. The structure–properties of all used films were confirmed by scanning electron microscope (SEM), Transmission Electron Microscope (TEM), X-ray powder diffraction (XRD), thermogravimetric analysis (TGA) and mechanical properties. The SEM results exhibited the uniform and homogeneous dispersion of GO in the PVA/PO blend matrix. The TEM and XRD analysis confirmed the structure and exfoliation of GO nanosheets, respectively. Thermal stability suggested that (0.5 wt%)GO/PVA/PO and (1 wt%) GO/PVA/PO films are more stable than PVA/PO. The tensile strength of (0.5 wt%)GO/PVA/PO and (1 wt%)GO/PVA/PO films reached 270.5% and 1349.6%, respectively, which are higher than that of the PVA/PO film. The decrease in the water absorption (WA) of GO/PVA/PO was found from 110.5 to 38.4%. The physico-mechanical properties of used films suggested that the prepared GO/PVA/PO blend composite films can be applied in food packaging areas.     

氧化石墨烯对聚乙烯醇/硼酸水凝胶流变性能的影响

研究了氧化石墨烯(GO)对聚乙烯醇(PVA)/硼酸(borate)水凝胶线性及非线性流变性能的影响。 通过扫描电子显微镜、硼谱核磁共振波谱以及流变研究了水凝胶的流变性能。 结果表明,GO质量浓度在稀溶液区时,GO片层与PVA链间通过硼酸根离子形成了具有弹性活性的缔合点,有效地提高了水凝胶的平台模量、松弛时间和零切粘度;当GO进一步增加到亚浓溶液区,部分的交联剂被GO的团聚体捕获并处于非弹性活性的缔合状态,处于有效缔合状态的交联剂变少,导致平台模量、松弛时间和零切粘度降低。 稳态剪切测试下,样品在剪切增稠区的粘度增加随着GO添加量的增加明显加强,这与剪切场下取向的氧化石墨烯片层参与网络结构的重排有关。     

Ionic liquid functionalized graphene oxide for enhancement of styrene‐butadiene rubber nanocomposites

Ionic liquid 1‐allyl‐3‐methyl‐imidazolium chloride (AMICl) is used to fine‐tune the surface properties of graphene oxide (GO) sheets for fabricating ionic liquid functionalized GO (GO‐IL)/styrene‐butadiene rubber (SBR) nanocomposites. The morphology and structure of GO‐IL are characterized using atomic force microscope, X‐ray diffraction, differential scanning calorimetry, X‐ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, UV‐vis spectra and Raman spectra. The interaction between GO and AMICl molecules as well as the effects of GO‐IL on the mechanical properties, thermal conductivity and solvent resistance of SBR are thoroughly studied. It is found that AMICl molecules can interact with GO via the combination of hydrogen bond and cation–π interaction. GO‐IL can be well‐dispersed in the SBR matrix, as confirmed by X‐ray diffraction and scanning electron microscope. Therefore, the SBR nanocomposites incorporating GO‐IL exhibit greatly enhanced performance. The tensile strength, tear strength, thermal conductivity and solvent resistance of GO‐IL/SBR nanocomposite with 5 parts per hundred rubber GO‐IL are increased by 505, 362, 34 and 31%, respectively, compared with neat SBR. This method provides a new insight into the fabrication of multifunctional GO‐based rubber composites. Copyright © 2016 John Wiley & Sons, Ltd.     

Effect of pullulan/poly(vinyl alcohol) blend system on the montmorillonite structure with property characterization of electrospun pullulan/poly(vinyl alcohol)/montmorillonite nanofibers

Nanofibers of the composite of pullulan (PULL), poly(vinyl alcohol) (PVA), and montmorillonite clay (MMT) were prepared using electrospinning method in aqueous solutions. Pullulan is an interesting natural polymer for many of its merits and good properties. Because of biocompatibility and non-toxicity of PVA, it could be used in numerous fields. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FTIR), X-ray diffraction (XRD), and thermal gravimetric analysis (TGA) were done to characterize the PULL/PVA/MMT nanofibers morphology and properties. XRD patterns and FTIR data demonstrated that there were good interactions between PULL and PVA caused by possibly hydrogen bonds. Moreover, XRD data and TEM images indicated that intercalated and exfoliated MMT nanoplatelets can be obtained within the PULL/PVA/MMT nanofibers depending on the PULL/PVA blend ratios. Furthermore, the thermal stability and mechanical property (tensile strength) of PULL/PVA/MMT nanofibers could be enhanced more by exfoliated MMT nanoplatelets than intercalated structures of that nanoplatelets.     

STRUCTURAL EVOLUTION AND COMPOSITION CHANGE IN THE SURFACE REGION OF POLYPROPYLENE/CLAY NANOCOMPOSITES ANNEALED AT HIGH TEMPERATURES

A model experiment was done to clear the formation mechanism of protective layers during combustion of polypropylene(PP)/organically modified montmorillonite(OMMT) nanocomposites.The investigation was focused on the effects of annealing temperature on the structural changes and protective layer formation.The decomposition of OMMT and degradation of PP/OMMT nanocomposites were characterized by means of thermogravimetric analysis(TGA).The structural evolution and composition change in the surface region of...     

Preparation and nonisothermal crystallization behavior of polyamide 6/montmorillonite nanocomposites

Polyamide 6 (PA6)/montmorillonite (MMT) nanocomposites were prepared via melt intercalation. The structure, mechanical properties, and nonisothermal crystallization kinetics of PA6/MMT nanocomposites were investigated by X‐ray diffraction (XRD), tensile and impact tests, and differential scanning calorimetry (DSC). Before melt compounding, MMT was treated with an organic surfactant agent. XRD traces showed that PA6 crystallizes exclusively in γ‐crystalline structure within the nanocomposites. Tensile measurements showed that the MMT additions are beneficial in improving the strength and the stiffness of PA6, at the expense of tensile ductility. Impact tests revealed that the impact strength of PA6/MMT nanocomposites tended to decrease with increasing MMT content. The nonisothermal crystallization DSC data were analyzed by Avrami, Ozawa, modified Avrami‐Ozawa, and Nedkov methods. The validity of these empirical equations on the nonisothermal crystallization process of PA6/MMT nanocomposites is discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2878–2891, 2004     

Facile regulation of glutaraldehyde-modified graphene oxide for preparing free-standing papers and nanocomposite films

Colloidal suspensions of glutaraldehyde (GA) crosslinked or grafted graphene oxide (GO) sheets were fabricated by simply tailoring the feed sequence. The different structures were confirmed by Fourier transform infrared spectra and X-ray diffraction. As demonstration of the utilities, the different colloidal suspensions were used to prepare free-standing papers by flow-directed filtration and poly(vinyl alcohol) (PVA)-based nanocomposite films by casting. Free-standing papers from GA crosslinked GO sheets exhibited better mechanical properties than unmodified GO paper, while nanocomposite films from GA grafted GO exhibit higher tensile strength and Young’s modulus.     

乳液聚合法制备剥离型PS/MMT纳米复合材料

以阳离子表面活性剂十八烷基三甲基氯化铵(OTAC)和烯丙基十八烷基二甲基氯化铵(ATAC)为插层处理剂改性蒙脱土(MMT),原位乳液聚合分别制备了PS/C18MMT和PS/AC18MMT两种纳米复合材料.XRD和TEM分析表明,MMT均被剥离成单个或几个片层无规的分散在PS基体中,TGA分析表明,MMT的加入提高了材料的耐热性能,当PS基体与有机化处理的MMT片层发生一定的化学连接后,PS/AC18MMT纳米复合材料表现出更好的耐热性能.动态力学分析表明,MMT的加入提高了PS的玻璃态储能模量,降低了材料的动态损耗;PS/AC18MMT纳米复合材料的玻璃化温度较PS有所提高,而PS/C18MMT的玻璃化温度与PS相比略有降低.     

In situ Synthesis of Poly(methyl methacrylate)/Graphene Oxide Nanocomposites Using Thermal-initiated and Graphene Oxide-initiated Polymerization

A facile and cost-effective method to prepare poly(methyl methacrylate) (PMMA)/graphene oxide (GO) nanocomposites was developed by in situ polymerization. By using thermal-initiated and GO-initiated polymerization of methyl methacrylate (MMA), no extra radical initiator was added during the reaction. Without any pre-functionalization of GO, PMMA chains were covalently bonded to its surface, which was confirmed by Fourier-transform infrared, atomic force microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy investigations. TGA analysis showed that the mass ratio of grafted PMMA and GO was as high as 1.7. Transmission electron microscopy and X-ray powder diffraction investigations demonstrated that the grafting of PMMA chains to GO surfaces resulted in homogeneous dispersion of GO sheets in PMMA matrix, which led to a commendable performance on its mechanical and thermal properties. Dynamic mechanical analysis showed that, at a loading level of just 0.5 wt% for the nanocomposites, the storage modulus of the nanocomposites was improved 14%, and the glass transition temperature was increased 12°C in comparison with that of neat PMMA. Thermogravimetric analysis showed that the onset degradation temperature of the nanocomposites was increased 13°C with a GO content of 0.25 wt%.     

Poly(vinyl alcohol) Chains Grafted onto the Surface of Copper Oxide Nanoparticles: Application in Synthesis and Characterization of Novel Optically Active and Thermally Stable Nanocomposites Based on Poly(amide-imide) Containing N-trimellitylimido-L-valine Linkage

Green polymer nanocomposites (NCs) show unique properties of combining the advantages of nanofillers and organic polymers. In this study, in order to control the dispersion of nanoparticles (NPs) in a polymer matrix, first, poly(vinyl alcohol) (PVA) as a green modifier was grafted on the surface of the CuO NPs to obtain CuO-PVA nanohybrid. Then poly(amide-imide) (PAI) was synthesized by the direct step growth polymerization of N-trimellitylimido-L-valine and 4,4′-methylenebis(3-chloro-2,6-diethylaniline) in ionic liquid medium. Finally, CuO-PVA hybrids were incorporated into the PAI matrix using ultrasonic technique for the preparation of PAI/CuO-PVA NCs. The obtained PAI/CuO-PVA NCs were characterized by different methods. The results of thermogravimetric analysis showed that thermal stability of the NCs was enhanced by incorporation of CuO-PVA nanohybrid compared to the pure PAI.     

Enhancement of tensile,electrical and thermal properties of epoxy nanocomposites through chemical hybridization of polypyrrole and graphene oxide

This paper presents the properties of epoxy nanocomposites, prepared using a synthesized hybrid Polypyrrole-Graphene Oxide (PPy-GO) filler, via in-situ chemical polymerization, at various filler loadings (i.e., 0.5–2 w. t %). The microstructures and properties of the PPy-GO hybrids and epoxy nanocomposites were studied via Fourier transform infrared (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), mechanical (Tensile Properties), electrical, Dynamic mechanical thermal analysis (DMTA) and thermogravimetric analyses (TGA). Morphological study demonstrated that varying the nanofiller nature (PPy-GOs, PPy or GO) lead to different states of dispersion. Mechanical, electrical and thermal analysis demonstrated that the hybrid concentration and its architecture (PPy:GO ratio) are interesting factors significantly affected the properties of the epoxy based nanocomposites. On the other hand, the mechanical performance of the cured nanocomposites outperformed the PPy-GO, with enhancements of 78% and 51% of Young's modulus and strength, respectively. Here it has been established that the embedding of PPy-GO hybrids into pristine epoxy endows optimum dispersion of PPy and GO as well as better interfacial adhesion between the fillers and matrix, which results in a significant improvement in load transfer effectiveness. Electrical conductivity measurements showed that conductivity of epoxy filled nanocomposites increased up 10⁻⁴ S/cm for Epoxy/PPy-GO nanocomposites. DMTA test indicated that incorporation of PPy-GO resulted in a significantly increase in Tg of the resultant nanocomposites, which is attributed to the highly exfoliation structure and the stronger interfacial interaction. The PPy-GO particles enhanced electrical, thermal and mechanical properties of nanocomposites, confirming the synergistic effect of PPy-GO as multifunctional filler.     

Effect of montmorillonite treatment with supercritical CO2 on the morphology and properties of polypropylene nanocomposites

The effects of montmorillonite (MMT) treatment with supercritical carbon dioxide (SC-CO₂) on clay morphology and the properties of polypropylene nanocomposites were investigated by wide-angle X-ray diffraction, transmission electron microscopy, scanning electron microscopy, dynamic mechanical analysis, and differential scanning calorimetry. The use of poly(propylene glycol) (PPG) was evaluated. The results showed that the MMT morphology (structure formation, dispersion, and orientation) was affected by treatment with SC-CO₂, and the use of PPG, or the use of CO₂ in the liquid state. Consequently, different reinforcement measurements were obtained. The relationship between structure and properties was reported.     

Electrospinning and characterization of poly(vinyl alcohol)/chitosan oligosaccharide/clay nanocomposite nanofibers in aqueous solutions

Submicron fibers of the composite of poly(vinyl alcohol) (PVA), chitosan oligosaccharide [COS, (1→4)2-amino-2-deoxy-β-d-glucose], and montmorillonite clay (MMT) were prepared using electrospinning method with aqueous solutions. Scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), thermal gravimetric analyzer, and tensile strength testing machine (Zwick) were utilized to characterize the PVA/COS/MMT nanofiber mats morphology and properties. The PVA/COS ratio and MMT concentration play important roles in nanofiber mat properties. XRD and TEM data demonstrated that exfoliated MMT layers were well-distributed within nanofiber. It was also found that the mechanical property and thermal stability were increased with COS and MMT contents.     

The influence of multiple modified MMT on the thermal and fire behavior of poly (lactic acid) nanocomposites

This work reported the preparation and physical properties of biodegradable nanocomposites fabricated using polylactic acid (PLA) and multiple organic modified montmorillonite (MMT). In order to improve the chemical compatibility between PLA and Na‐MMT, the surface of Na‐MMT was first organically modified by cetyl trimethyl ammonium bromide (CTAB) and resorcinol bis(diphenyl phosphate) (RDP) using ion‐exchange and adsorption technique. Both Fourier transform infrared and X‐ray diffraction (XRD) results indicated that CTAB and RDP molecules were intercalated into the galleries of MMT sheets to enlarge the interlayer spacing. Then, the PLA/MMT nanocomposites were prepared by a simple melt‐blending method. The XRD and TEM results of the nanocomposites indicated that the PLA polymer chains inserted into the galleries of co‐modified MMT (C‐MMT) and contained disorderedly intercalated layered silicate layers within a PLA matrix. The C‐MMT nanolayers were homogenously dispersed in PLA matrix, resulting in various property enhancement. The fabricated PLA/C‐MMT nanocomposites with 5.0 wt% addition showed significant enhancements (176%) in the storage modulus compared to that of neat PLA. The thermal stability and fire resistance were also remarkably improved. These improvements are probably because of both the physical barrier effect of the MMT nanosheets and charring effect of the C‐MMT. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and characterization of rigid poly(vinyl chloride)/MMT nanocomposites. II. XRD,morphological and mechanical characteristics

A Haake torque rheometer equipped with an internal mixer is used to study the influence of the amount of sodium montmorillonite (Na⁺‐MMT) and organically modified MMT (O‐MMT) on X‐ray diffraction (XRD), morphology, and mechanical characteristics of rigid poly (vinyl chloride) (PVC)/Na⁺‐MMT and PVC/O‐MMT nanocomposites, respectively. Results of XRD and transmission electron microscopy (TEM) indicate that MMT is partially encapsulated and intercalated in the rigid PVC/Na⁺‐MMT nanocomposites. However, results of XRD and TEM show MMT is partially intercalated and exfoliated in the rigid PVC/O‐MMT nanocomposites. Tensile strength, yield strength, and elongation at break of the rigid PVC/MMT nanocomposites were improved simultaneously with adding 1–3 wt % Na⁺‐MMT or O‐MMT with respect to that of pristine PVC. However, the addition of Na⁺‐MMT or O‐MMT should be kept as not more than 3 wt % to optimize the mechanical properties and the processing stability of the rigid PVC/MMT nanocomposites. SEM micrographs of the fractured surfaces of the rigid PVC/Na⁺‐MMT and PVC/O‐MMT nanocomposites both before and after tensile tests were also illustrated and compared. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2145–2154, 2006