马来酸酐接枝聚乙烯/石墨导电纳米复合材料的研究

用溶液插层法制备了马来酸酐接枝聚乙烯(MGPE)/膨胀石墨(EG)导电纳米复合材料,以熔体混合法作对照,通过电导率测试和X射线衍射、透射电镜、扫描电镜和光学显微分析,研究了复合材料的制备方法-形态结构-导电性能关系和导电通路形成机理。溶液插层法复合材料的逾渗阈值(1.65%体积)仅约为熔体混合法复合材料(3.03%体积)的一半。上述复合材料的导电行为和差异可用统计逾渗理论结合材料的形态结构特征来说明。     

Preparation and characterization of polyethylene‐g‐maleic anhydride–styrene/montmorillonite nanocomposites

It is difficult to prepare polyethylene/montmorillonite by direct melt mixing because of the difference in character between polyethylene and montmorillonite. Therefore, it is necessary to modify polyethylene with polar groups, which can increase the hydrophilicity of polyethylene. At the same time, the inorganic montmorillonite should be modified with long‐chain alkyl ammonium to increase the basing space between the interlayers. Thus, through the grafting of the polar monomer onto the main chain of polyethylene by reactive extrusion, polyethylene/montmorillonite nanocomposites can be prepared by the melt mixing of the grafter and organic montmorillonite. Fourier transform infrared has been used to prove that the monomers are grafted onto polyethylene. X‐ray diffraction and transmission electron microscopy have been employed to characterize the nanocomposites. Furthermore, thermogravimetric analysis measurements show that the thermal stability of the nanocomposites is improved in comparison with that of the virgin materials. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 805–809, 2006     

Effect of the graft yield of maleic anhydride on the rheological behaviors,mechanical properties,thermal properties,and free volumes of maleic anhydride grafted high‐density polyethylene

The rheological behavior, thermal properties, and molecular mobility of a series of maleic anhydride (MA) grafted high‐density polyethylenes were characterized and evaluated. The rheological behavior was studied with a Haake minilaboratory. The viscosity of the samples in their melt state decreased with an increase in the graft yield, and this could be attributed to the higher molecular mobility for samples with a higher degree of grafting. The thermal properties were investigated with dynamic mechanical analysis and differential scanning calorimetry. Positron annihilation lifetime measurements were used to study the effect of the degree of grafting on the chemical environment and the atomic‐scale free‐volume properties. It was found that the grafted MA group played a significant chemical inhibition role in positronium formation when the graft yield was low. The results also indicated that the higher the degree of grafting was, the broader the free‐volume distribution was. The relationship between the microstructure and rheological behavior is discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and properties of polyethylene/montmorillonite nanocomposites by in situ polymerization

Polyethylene (PE)/montmorillonite (MMT) nanocomposites were prepared by in situ coordination polymerization using a MMT/MgCl₂/TiCl₄ catalyst activated by Al(Et)₃. The catalyst was prepared by first diffusing MgCl₂ into the swollen MMT layers, followed by loading TiCl₄ on the inner/outer layer surfaces of MMT where MgCl₂ was already deposited. The intercalation of MMT layers by MgCl₂ and TiCl₄ was demonstrated by the enlarged interlayer spacing determined by WAXD. The nanoscale dispersion of MMT layers in the polyethylene matrix was characterized by WAXD and TEM. As a consequence, the crystallinity of the nanocomposite decreased sharply, whereas the tensile strength was significantly improved compared to that of virgin polyethylene of comparable molecular weight. The confinement of the nanodispersed MMT layers to molecular chain and the strong interaction between the nanoscale MMT layers and the resin matrix were thought to account for the decrease of crystallinity and the remarkable enhancement of strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3680–3684, 2003     

线性低密度聚乙烯/有机蒙脱土纳米复合材料的制备及性能研究

通过熔融共混法制备了线性低密度聚乙烯／有机蒙脱土（LLDPEtOMMT）纳米复合材料,采用X-射线衍射分析（XRD）和透射电镜（TEM）对材料的结构进行表征,研究了OMMT的用量对LLDPE／OMMT纳米复合材料力学性能及阻燃性能的影响。结果表明,当OMMT的用量为30％（重量百分比）8寸,材料的极限氧指数（LOI）从180％提高到23．8％,热释放速率峰值（PHRR）从LLDPE的771．9kW／m2下降到5113kW／m2,下降幅度高达33．8％,表现出较好的阻燃性能;同时材料也呈现出良好的力学性能。     

Effect of silane grafting on the microstructure of high‐density polyethylene/organically modified montmorillonite nanocomposites

Organically modified montmorillonite (org‐MMT) and high‐density polyethylene (HDPE) grafted with silane groups (HDPE‐g‐silane) were melt compounded to give HDPE‐g‐silane‐blend‐org‐MMT nanocomposites. X‐ray diffractometry was performed to investigate the intercalation effect. Transmission electron microscopy was applied to observe the dispersion of org‐MMT layers in HDPE matrices. The results indicate that an intercalated structure can be easily obtained in HDPE‐g‐silane‐blend‐org‐MMT nanocomposites. Furthermore, positron annihilation lifetime spectroscopy was used to characterize the microstructure of the composites. It is found that the ortho‐positron (o‐Ps) intensity for HDPE‐g‐silane is decreased by approximately 10% with a narrower lifetime distribution than that for HDPE. With increasing org‐MMT concentration, the o‐Ps intensity I₃ increases for HDPE‐g‐silane‐blend‐org‐MMT nanocomposites; however, for HDPE‐blend‐org‐MMT composites I₃ decreases. It is found that HDPE composites with good dispersion can be obtained following appropriate modification of the HDPE. And silane grafting has an effect on the free volume of the HDPE nanocomposites. Copyright © 2007 Society of Chemical Industry     

High‐density polyethylene/ultrahigh‐molecular‐weight polyethylene blend. I. The processing,thermal, and mechanical properties

Various blend ratios of high‐density polyethylene (HDPE) and ultrahigh‐molecular‐weight polyethylene (UHMWPE) were prepared with the objective of determining their suitability as biomaterials. Although the presence of HDPE in the blends enabled melt processing, the presence of UHMWPE helped to improve the toughness of the resulting blends. The processability of the blends was investigated with the Brabender torque, which was used as an indication of the optimum blend conditions. The blends were characterized with differential scanning calorimetry. The mechanical tests performed on the blends included tensile, flexural, and impact tests. A 50:50 (w/w) blend yielded optimum properties in terms of the processability and mechanical properties. The tensile property of the 50:50 blend was intermediate between those of HDPE and UHMWPE, but the strain at break increased 200% in comparison with that of both neat resins. The energy at break of the 50:50 blend revealed an improvement in the toughness. The fracture mechanism was also investigated with scanning electron microscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 413–425, 2005     

Effect of exfoliation and dispersion on the yield behavior of melt‐compounded polyethylene–montmorillonite nanocomposites

The yield behavior of melt‐mixed nanocomposites containing 5 wt % organically modified montmorillonite in matrices of a linear low‐density polyethylene (LLDPE) or a modified polyethylene was studied as a function of the temperature and strain rate. In the melt‐mixed LLDPE nanocomposite, the montmorillonite showed a slight increase in the clay spacing, which suggested that the clay was at best intercalated. Transmission electron microscopy (TEM) images showed that the dispersion in this nanocomposite was poor. The use of the modified polyethylene promoted exfoliation of the clay tactoids in the nanocomposite, as assessed by X‐ray diffraction and TEM. In both nanocomposites, the yield mechanisms were insensitive to the addition of the organoclay, even though modest increases in the modulus were produced. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3044–3049, 2006     

Effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on thermal properties,morphology, and tensile properties of low‐density polyethylene (LDPE) and corn starch blends

The effects of polyethylene‐grafted maleic anhydride (PE‐g‐MA) on the thermal properties, morphology, and tensile properties of blends of low‐density polyethylene (LDPE) and corn starch were studied with a differential scanning calorimeter (DSC), scanning electron microscope (SEM), and Instron Universal Testing Machine, respectively. Corn starch–LDPE blends with different starch content and with or without the addition of PE‐g‐MA were prepared with a lab‐scale twin‐screw extruder. The crystallization temperature of LDPE–corn starch–PE‐g‐MA blends was similar to that of pure LDPE but higher than that of LDPE–corn starch blends. The interfacial properties between corn starch and LDPE were improved after PE‐g‐MA addition, as evidenced by the structure morphology revealed by SEM. The tensile strength and elongation at break of corn starch–LDPE–PE‐g‐MA blends were greater than those of LDPE–corn starch blends, and their differences became more pronounced at higher starch contents. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2904–2911, 2003     

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     

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     

Effects of screw configurations on the grafting of maleic anhydride grafted low-density polyethylene in reactive extrusion

The effects of screw configurations, that is, the staggering angles and disc widths of the kneading blocks, on grafting reactive extrusion for maleic anhydride grafted low-density polyethylene were investigated in a corotating twin-screw extruder. Samples were collected from three positions along the screw and the die exit. The grafting degree (GD) of the specimens was evaluated by titration. It was found that the kneading block configurations had a significant influence on the grafting reactive extrusion. In addition, another three groups of extrusion experiments were performed to explore the intrinsic relationship between the GD, the degree of fill in the screw channel, the residence time distribution (RTD), and the mixing intensity in various screw configurations. The experimental results indicated that the location of the melting endpoint significantly affected the position at which the reaction began; the degree of fill, RTD, and mixing performance of the screw played important roles in the grafting reaction. The reverse kneading blocks with a narrow disc width, which had a high degree of fill and good mixing capacity, enhanced the increase in GD along the screw during the reactive extrusion. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Use of purified and modified bentonites in linear low‐density polyethylene/organoclay/compatibilizer nanocomposites

Polyethylene‐based ternary nanocomposites were prepared with different clay structures, obtained by the modification of purified Resadiye bentonite as the reinforcement, a random terpolymer of ethylene, butyl acrylate, and maleic anhydride with the trade name Lotader3210 as the compatibilizer, and linear low‐density polyethylene (LLDPE) as the polymer matrix in an intensive batch mixer. The quaternary ammonium/phosphonium salts used for the modification of bentonite were dimethyldioctadecyl ammonium (DMDA) chloride (Cl), tetrakisdecyl ammonium (TKA) bromide (Br), and tributylhexadecyl phosphonium (TBHP) Br. The effects of the physical properties and structure of the organoclay on the clay dispersion were studied at different clay contents (2 and 5 wt %) and at a compatibilizer/organoclay ratio of 2.5. The extent of organoclay dispersion was determined by X‐ray diffraction (XRD) and was verified by transmission electron microscopy (TEM), mechanical testing, and rheological analysis. XRD analysis showed that the nanocomposite with the organoclay DMDA contained intercalated silicate layers, as also verified by TEM. The TEM analysis of the nanocomposites with TBHP exhibited intercalated/partially exfoliated clay dispersion. TKA, with a crowded alkyl environment, sheltered and hindered the intercalation of polymer chains through the silicate layers. In comparison to pure LLDPE, nanocomposites with a 33–41% higher Young's modulus, 16–9% higher tensile strength, and 75–144% higher elongation at break were produced with DMDA and TBHP, respectively (at 5 wt % organoclay). The storage modulus increased by 807–1393%, and the dynamic viscosity increased by 196–339% with respect to pure LLDPE at low frequencies for the samples with DMDA and TBHP (at 5 wt % organoclay). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Biodegradation of montmorillonite filled oxo‐biodegradable polyethylene

Oxo‐biodegradation of polyethylene has been well studied with different pro‐oxidants and it has been shown that pro‐oxidants have limited role in the oxidation of polyethylene and do not have any role in microbial growth. However, in few recent studies, montmorillonite clay has been reported to promote the growth of microbes by keeping the pH of the environment at levels conducive to growth. In an attempt to improve the overall oxo‐biodegradation of polyethylene, montmorillonite nanoclay has been used in this study along with a pro‐oxidant. Film samples of oxo‐biodegradable polyethylene (OPE) and oxo‐biodegradable polyethylene nanocomposite (OPENac) were subjected to abiotic oxidation followed by microbial degradation using microorganism Pseudomonas aeruginosa. The progress of degradation was followed by monitoring the chemical changes of the samples using high‐temperature gel permeation chromatography (GPC) and infrared spectroscopy (FTIR). The growth of bacteria on the surface of the polymer was monitored using environmental scanning electron microscopy. GPC data and FTIR results have shown that the abiotic oxidation of polyethylene is influenced significantly by the pro‐oxidant but not by nanoclay. But, the changes in molecular weight distribution and FTIR spectra for the biodegraded samples indicate that the growth rate of P. aeruginosa on OPENac is significantly greater than that on OPE. It indicates that nanoclay, by providing a favourable environment, helps in the growth of the microorganism and its utilisation of the polymer surface and the bulk of the polymer volume. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of linear low‐density polyethylene/low‐density polyethylene/TiO2 membranes

Because of their special functions, the application of nanoscale powders has recently attracted both industrial and theoretical interest. In this study, nanoscale TiO₂, which exhibited a special UV absorption and consequent antibacterial function, was added to a low‐density polyethylene/linear low‐density polyethylene hybrid by melt compounding to yield functional composite membranes. TiO₂ exhibited an apparent induced nucleation effect on the crystallization of polyethylene, and the size of the crystallites decreased while the number increaed with the introduction of TiO₂; however, the crystallinity of polyethylene changed little. Also, TiO₂ exhibited an ideal dispersion in the membrane with an average size less than 100 nm, and this excellent dispersion provided the membranes extra UV absorption; moreover, the transparency of the membranes was maintained to satisfy common requirements. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 216–221, 2005     

Crystalline morphology at the interface between polyethylene‐grafted glass and polyethylene

Adhesion measurements performed on a polyethylene (PE)‐grafted‐glass interface showed that the structure of the PE free chains (matrix) was an important parameter. The fracture energy was higher for interfaces prepared from a linear matrix, such as high‐density polyethylene (HDPE), than for those from a branched PE [low‐density polyethylene (LDPE)]. Therefore, the microstructure of the grafted PE/PE matrix interface or interphase was investigated as a function of the molar masses of the connectors and the structure (linear or branched) of the free PE matrix chains. As the grafted chains were linear, a cocrystalline structure with free chains of the HDPE matrix was generated. PE connecting chains led to a low capacity for cocrystallization with LDPE. Cocrystallization was studied with blends based on functionalized PE chains and PE matrices. These blends were assumed to be miscible, as substantiated by a single differential scanning calorimetry (DSC) peak. The DSC analyses were confirmed by wide‐angle X‐ray scattering, which revealed a crystalline orientation of the chains in the interphase, that is, in the vicinity of the glass surface. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 214–229, 2003     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Preparation and characterization of polypropylene/clay nanocomposites with polypropylene‐graft‐maleic anhydride

Polypropylene (PP)/montmorillonite (MMT) nanocomposites were prepared by the esterification of propylene‐g‐maleic anhydride (MAPP) with MMT modified with α,ω‐hydroxyamines. The structural characterization confirmed the formation of ester linkages and the interaction between the silicate layers. In particular, X‐ray diffraction patterns of the modified clays and MAPP/MMT composites showed 001 basal spacing enlargement as great as 0.14–0.62 nm according to the type of α,ω‐hydroxyamine. Thermal characterization by thermogravimetric analysis for the composites revealed increased onset temperatures of thermal decomposition. The melting peak temperature decreased, and the crystallization peak temperature increased; this indicated that MMT retarded the crystallization of MAPP. Compounding PP with MAPP/MMT composites enhanced the tensile modulus and tensile strength of PP. However, the elongation at break decreased drastically even when the MMT content was as low as 0.4–2.0 wt %. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1229–1234, 2005     

Mechanical and antibacterial properties of modified nano‐ZnO/high‐density polyethylene composite films with a low doped content of nano‐ZnO

Nano‐ZnO/high‐density polyethylene (HDPE) composite films were prepared via melt blending and a hot compression‐molding process. The properties, including ultraviolet absorption, mechanical and antibacterial properties of the films, and plasticizing behavior of the composites, were investigated. The results show that the absorbance in the ultraviolet region of the HDPE films was enhanced after the addition of modified nano‐ZnO to the HDPE matrix. Also, we found that improvement in the HDPE films of the tensile strength and elongation at break was achieved by the incorporation of modified ZnO nanoparticles up to 0.5 wt % in contrast with the original nano‐ZnO/HDPE composite films. Antibacterial testing was carried out via plate counting, and the results indicate that the HDPE films doped with modified ZnO nanoparticles showed favorable antibacterial activity, especially for Staphylococcus aureus. However, the low doped content of modified nano‐ZnO in the HDPE matrix made the balance torque of the composites increase slightly. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Physical properties of polyethylene/silicate nanocomposite blown films

Maleated polyethylene/silicate nanocomposite and maleated polyethylene/SiO₂ blown films were prepared by melt extrusion. The silicate and SiO₂ significantly affected the physical properties of the films. The former films showed higher tensile strength than the latter films. This high reinforcement effect seemed to be attributable to the strong interaction between the matrix and silicate as well as the uniform dispersion of silicate layers in the polymer matrix. The addition of silicate beyond a certain content gave a worse Elmendorf tear strength than SiO₂. The silicate did not increase the falling dart impact strength at all. The worst Elmendorf strength apparently originated from the orientation of anisotropic silicate rather than the orientation of lamellae of the polymer matrix, and the silicate made the films more brittle. The well‐dispersed silicate layers in the polymer matrix gave almost the same optical properties as the pure polymer despite the increase in the silicate content. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2131–2136, 2003