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1.
Multi‐walled carbon nanotubes (MWCNTs)/polyethylene (PE) nanocomposites were prepared via in situ polymerization with MWCNTs supported Bis‐ (cyclopentadienyl) zirconium dichloride (Cp2ZrCl2) catalyst. X‐ray photoelectron spectroscopy (XPS) and field emission scanning electron microscope (FESEM) results implied that Cp2ZrCl2 catalyst was immobilized in the surface of the MWCNTs supports via a bridge of methylaluminoxane (MAO). The efficient dispersion of MWCNTs in PE matrix and the strong compressive forces associated with PE on the MWCNTs were demonstrated by means of transmission electron microscope (TEM), FESEM and Raman spectra. With introducing 0.2 wt% MWCNTs, both the tensile strength and elongation of MWCNTs/PE nanocomposite were improved by factors of 1.6 (from 29 to 45 MPa) and 1.5 (from 909% to 1360%) comparing with the pure PE, respectively. Morphology observation of fractured surface revealed that the PE firmly adhered to the nanotubes, which was responsible for the significant improvement of the mechanical properties of nanocomposites. Thermal stabilities of the nanocomposites were significantly improved. In addition, the MWCNTs/PE nanocomposites showed very high ultraviolet (UV) shielding property, which could increase photooxidative stability of the PE. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers  相似文献   

2.
Preparation of novel polyethylene/carbon nanotubes (CNTs) nanocomposites with core–shell structure was presented. The method involved in situ ethylene polymerization in which nanotube surface was treated with Grignard Agent, followed by reacting with active transition metal compound, TiCl4. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerize ethylene to form polymer nanocomposite. MWCNTs were homogeneously dispersed within polymer matrix, and as expected, the resultant nanocomposites featured core–shell structure which was confirmed by HRTEM. For the nanocomposite, the microscopic examination of the cryogenically fractured surface not only ensured a good distribution of carbon nano-particles in the PE matrix but also revealed the ductile-like fracture. The Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed for the study of covalent sidewall functionalization and chemical bonding environment of MWCNTs, also indicated effective immobilization of titanium catalyst on the MWCNTs surface. The crystalline properties, dielectric property and thermal stability of the nanocomposites were determined by WAXD, impedance analyzer and TGA. The dielectric result showed a slight decline of the dielectric constant of the nanocomposites with increase of the polymerization time, and lower dielectric loss was also observed.  相似文献   

3.
The preparation of thermoplastic nanocomposites of waterborne polyurethane (WBPU) and multiwall carbon nanotubes (MWCNTs) via an in situ polymerization approach is presented. The effects of the presence and content of MWCNTs on the morphology and thermal, mechanical and electrical properties of the nanocomposites were investigated. Carbon nanotubes were modified with amide groups in order to enhance their chemical affinity towards WBPU. Thermogravimetric studies show enhanced thermal stability of the nanocomposites. Scanning and transmission electronic microscopy images prove that functionalized carbon nanotubes can be effectively dispersed in WBPU matrix. Mechanical properties reveal that Young's modulus and tensile strength tend to increase when appropriate amounts of MWCNTs are loaded due to the reinforcing effect of the functionalized carbon nanotubes. Thermal properties show an increase in the glass transition temperature and storage modulus with an increase in MWCNT content. X‐ray diffraction reveals better crystallization of the WBPU in the presence of MWCNTs. The WBPU/MWCNT nanocomposite film containing 1 wt% of MWCNTs exhibits a conductivity nearly five orders of magnitude higher than that of WBPU film. © 2017 Society of Chemical Industry  相似文献   

4.
We investigated the structure and properties of strands of high-density polyethylene (HDPE), containing multi-walled carbon nanotubes (MWCNTs) extruded from a capillary rheometer. Surprisingly, we found that the MWCNTs enhanced the chain orientation of HDPE, and that in the absence of MWCNTs, orientation relaxation occurred in the HDPE immediately after passing through the die. Conventional differential scanning calorimetry measurements indicated that MWCNT acts as a nucleating agent and raises the crystallization temperature 2–4 °C under quiescent condition. In the flow field, oriented MWCNTs behave like polymeric chain extended crystals “shish” and greatly accelerate the flow-induced crystallization of the HDPE “kebab.” Consequently, the modulus was significantly increased in the flow direction. These findings demonstrate that the addition of MWCNTs is an effective method of enhancing the rigidity of HDPE. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48010.  相似文献   

5.
Poly(ε-caprolactone)-coated (covalently grafted and physisorbed) multi-walled carbon nanotubes (MWCNTs) were synthesized by ring-opening polymerization (ROP) of ε-caprolactone initiated from primary amines grafted on the MWCNT surface through the exposure to atomic nitrogen generated in a microwave-induced plasma. The morphology of the recovered nanohybrids and the amount of grafted polymer chains were studied by transmission electron microscopy (TEM) and thermogravimetric analysis (TGA), respectively. These nanohybrids were used as highly filled masterbatches to be dispersed within either poly(ε-caprolactone) (PCL) or high-density polyethylene (HDPE) matrices in the molten state. The thermal behavior as well as the electrical properties of the so-produced nanocomposites were characterized and correlated to their morphology. The HDPE filled with PCL-coated MWCNTs nanohybrids showed better electrical properties than HDPE filled with non-modified MWCNTs. The electrical properties improvement was associated to a better dispersion of the PCL-coated MWCNTs and, also, to the exclusive presence of PCL coating in tunneling junction between the nanotubes.  相似文献   

6.
引言聚烯烃是国民生活和现代国防不可或缺的基础原材料,但与ABS、PC等工程塑料相比,其刚性不足,低温脆性也较明显,因此很难作为结构材料使用。纳米技术的出现为聚烯烃材料性能的提高提供了广阔的空间[1],其中,纳米复合材料中存在纳米尺寸效应、超大的比表面积以及很强的界面相互作用,具有比强度高、可设计性强、抗疲劳性好等优点,因此,纳米复合聚乙烯中含少量纳米材料便能极大增强材料本身的性能,同时聚合物中纳米材料的低含量也大大减少了无机载体在聚合物中的灰分,有利于聚合物材料高性能的保持,这引起了研究工作者的广泛关注。  相似文献   

7.
Nanocomposites based on poly(methyl methacrylate) (PMMA) and poly(methyl methacrylate‐co‐octadecyl methacrylate) (M/O) matrices and four different types of multiwall carbon nanotubes: pristine, oxidized (MWCNT–COOH), methyl ester (MWCNT–COOCH3), and dodecyl ester (MWCNT–COOC12H25) functionalized, were prepared in situ by radical (co)polymerization. The effectiveness of preparation of nanocomposites regarding dispersion and distribution of various MWCNT in polymer matrices was sized by Scanning electron microscopy. In case of PMMA matrix, the best dispersion and distribution were accomplished for MWCNT–COOCH3 due to their chemical resemblance with polymer matrix. After the introduction of 10 mol % of octadecyl methacrylate in polymer matrix a fairly good dispersion and distribution of MWCNT–COOCH3 were retained. The addition of 1 wt % of MWCNTs caused a significant reduction in the degree of polymerization of the PMMA matrix. But at the same time, the present MWCNTs increased storage modulus of PMMA nanocomposites except for dodecyl ester functionalized MWCNT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46113.  相似文献   

8.
In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H2SO4/HNO3 (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm?1) and G (1583 cm?1) bands. For the untreated MWCNTs, the ID/IG ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the Tgs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

9.
The purpose of this study was to investigate the influence of aging on the properties of high-density polyethylene (HDPE) reinforced with multi-wall carbon nanotubes (MWCNTs). Nanocomposites were prepared with nanotubes at 0, 1, 3, and 5 wt%. The long-term durability of the prepared materials was evaluated by thermo-oxidative aging test. Test bodies were aged at 110°C for up to 10 weeks. The nanocomposites were characterized by differential scanning calometry, thermogravimetric analysis (TGA), 13C-NMR, elongation at break, and transmission electron microscopy. The aging mainly occurred on the surface of the samples and the neat HDPE showed a strong yellowing after the aging. A strong reduction in elongation at break was seen. For neat HDPE, the elongation at break was reduced from roughly 1400–25%. When HDPE was reinforced with the nanotubes, the reduction was less dramatic.  相似文献   

10.
The introduction of carbon nanotubes in a polymer matrix can markedly improve its mechanical properties and electrical conductivity, and much effort has been devoted to achieve homogeneous dispersions of carbon nanotubes in various polymers. Our group previously performed successfully fluorine‐grafted modification on the sidewalls of multi‐walled carbon nanotubes (MWCNTs), using homemade equipment for CF4 plasma irradiation. As a continuation of our previous work, in the present study CF4 plasma‐treated MWCNTs (F‐MWCNTs) were used as a nanofiller with poly(ethylene terephthalate) (PET), which is a practical example of the application of such F‐MWCNTs to prepare polyester/MWCNTs nanocomposites with ideal nanoscale structure and excellent properties. As confirmed from scanning electron microscopy observations, the F‐MWCNTs could easily be homogeneously dispersed in the PET matrix during the in situ polymerization preparation process. It was found that a very low content of F‐MWCNTs dramatically altered the crystallization behavior and mechanical properties of the nanocomposites. For example, a 15 °C increase in crystallization temperature was achieved by adding only 0.01 wt% F‐MWCNTs, implying that the well‐dispersed F‐MWCNTs act as highly effective nucleating agents to initiate PET crystallization at high temperature. Meanwhile, an abnormal phenomenon was found in that the melt point of the nanocomposites is lower than that of the pure PET. The mechanism of the tailoring of the properties of PET resin by incorporation of F‐MWCNTs is discussed, based on structure–property relationships. The good dispersion of the F‐MWCNTs and strong interfacial interaction between matrix and nanofiller are responsible for the improvement in mechanical properties and high nucleating efficiency. The abnormal melting behavior is attributed to the recrystallization transition of PET occurring at the early stage of crystal melting being retarded on incorporation of F‐MWCNTs. Copyright © 2009 Society of Chemical Industry  相似文献   

11.
In this study, preparation of high-density polyethylene (HDPE)/clay nanocomposite by in situ polymerization of ethylene using a zirconocene catalyst (bis-(cyclopentadienyl) zirconium dichloride (Cp2ZrCl2)) was investigated. To obtain higher efficiency, nanoclay particles (Na-montmorillonite) were modified by ammonia (NH3), NH3/methylaluminoxane (MAO), NH3/dodecylamine (DDA), and NH3/MAO/DDA systems. The results showed that the activity of the catalyst supported on the nanoclay particles modified by NH3/MAO (762 gp/mmol (Zr) t [atm]) was higher than that of the one supported on the unmodified nanoclay as well as the other prepared modified nanoclay-supported catalyst systems. The catalyst activities versus MAO concentration in NH3/MAO treatment system and versus DDA concentration in NH3/DDA system showed a maximum. Unexpectedly, a very low catalyst activity (180 gp/mmol(Zr) t [atm]) was obtained using NH3/MAO/DDA system. X-ray diffraction patterns showed that the HDPE/clay nanocomposites prepared by NH3/MAO/DDA treatment system had less intercalated structure. Fourier transform infrared (FTIR) spectroscopy confirmed that water molecules of the nanoclay particles were reduced by NH3 modification. DSC results revealed that crystallinity of the HDPE/clay nanocomposites increased with the modification of the nanoclay particles. The maximum degree of crystallinity of 80.8% was obtained for HDPE/clay nanocomposites prepared by the nanoclay modified by NH3. In addition, nanoclay modification with NH3, NH3/MAO, and NH3/DDA systems resulted in higher thermal decomposition temperature (~30 °C higher than 480 °C of the unmodified one). Such increase was not observed for the NH3/MAO/DDA treatment system. Dynamic mechanical analysis showed an increase in the elastic modulus of the nanocomposite samples prepared by modified nanoclay particles, as well. Meanwhile, modification of the nanoclay particles by NH3 led to the highest elastic behavior compared to the other modification systems. It was about 4.6 GPa which was 28% higher than the elastic modulus of the nanocomposite prepared by unmodified nanoclay particles.  相似文献   

12.
Studies have proved that increasing polymer matrices by carbon nanotubes to form structural reinforcement and electrical conductivity have significantly improved mechanical and electrical properties at very low carbon nanotubes loading. In other words, increasing polymer matrices by carbon nanotubes to form structural reinforcement can reduce friction coefficient and enhance anti-wear property. However, producing traditional MWCNTs in polymeric materix is an extremely complicated process. Using melt-mixing process or in situ polymerization leads to better dispersion effect on composite materials. In this study, therefore, to simplify MWCNTs /HDPE composite process and increase dispersion, powder was used directly to replace pellet to mix and sinter with MWCNTs. The composite bulks with 0, 0.5, 1, 2 and 4% nanotube content by weight was analyzed under SEM to observe nanotubes dispersion. At this rate, a MWCNTs/HDPE composite bulk with uniformly dispersed MWCNTs was achieved, and through the wear bench (Pin-on-Disk), the wear experiment has accomplished. Accordingly, the result suggests the sintered MWCNTs/HDPE composites amplify the hardness and wear-resist property.  相似文献   

13.
In this study, polypropylene/carbon nanotube nanocomposites were prepared via in situ polymerization using a bi‐supported Ziegler ? Natta catalytic system. In this system, magnesium ethoxide and multiwall carbon nanotubes (MWCNTs) are jointly used as catalyst supports. SEM images reveal the distribution and quite good dispersion of MWCNTs throughout the polypropylene (PP) matrix. The thermal properties of the samples were examined using DSC and TGA tests. The results show that the crystallization temperature of the nanocomposites significantly increases while the melting point is not markedly affected. In addition, the thermal stability is improved. The melt rheological properties of PP/MWCNT nanocomposites in the linear and nonlinear viscoelastic response regions were studied. An increment of the complex viscosity (η*), storage modulus (G′) and loss modulus (G′′) and a decrement of the loss factor (tan δ) compared with neat PP are observed. Steady shear flow experiments show an increase in shear viscosity with increasing the MWCNT content. © 2013 Society of Chemical Industry  相似文献   

14.
The electrical conductivities (σ) of nanocomposites of single-walled carbon nanotubes (SWCNTs) and high density polyethylene (HDPE) have been studied for a large number of nanocomposites prepared in a SWCNT concentration range between 0.02 and 8 wt%. The values of σ obey a percolation power law with an SWCNT concentration threshold, pc = 0.13 wt%, the lowest yet obtained for any kind of carbon-polyethylene nanocomposites. Improved electrical conductivities attest to an effective dispersion of SWCNT in the polyethylene matrix, enabled by the fast quenching crystallization process used in the preparation of these nanocomposites. Characterization by scanning electron microscopy (SEM) and Raman spectroscopy consistently points to a uniform dispersion of separate small SWCNT bundles at concentrations near pc and increased nanotube clustering at higher concentrations. Near pc, high activation energies and geometries of long isolated rods suggest that electron transport occurs by activated electron hopping between nanotubes that are close to each other but still geometrically separate. The degree of SWCNT clustering given by Raman spectroscopy and the barrier energy for electrical conductivity are highly correlated. The nanotubes act as nucleants in the crystallization of the polyethylene matrix, and change the type of supermolecular aggregates from spherulites to axialitic-like objects. The size of crystal aggregates decreases with SWCNT loading, however, in reference to the unfilled polyethylene, the three-dimensional growth geometry extracted from the Avrami exponents remains unchanged up to 2 wt%. Consistency between SEM, Raman and electrical transport behavior suggests that the electrical conductivity is dominated by dispersion and the geometry of the SWCNT in the nanocomposites and not by changes or lack thereof in the HDPE semicrystalline structure.  相似文献   

15.
In this paper, we report interfacial crystallization in olefin block copolymer (OBC) with low crystallinity incorporated by multi‐walled carbon nanotubes (MWCNTs). A hybrid shish‐kebab (HSK) superstructure in nanocomposites is observed that MWCNTs act as central shish and OBC crystals grow perpendicular to the nanotubes axis. The mechanical properties of nanocomposites are significantly improved with incorporation of MWCNTs. The most ideal reinforcing and toughening effect is both observed in nanocomposites with MWCNTs content of 1 wt % that can increase tensile strength by 122% as well as elongation at break by 36%. Efficient load transfer are confirmed with in‐situ Raman spectra that G’ band of MWCNTs in OBC matrix exhibit a downshifting trend and symmetric broadening of line shape which reveals additional macroscale strain from axial extension of MWCNTs in nanocomposites, thus suggesting a certain load is carried by HSK superstructure. The structural evolution of OBC and nanocomposites are investigated by in‐situ wide‐angle X‐Ray Diffraction (WAXD). The Herman's orientation factor of nanocomposites with 2 wt % MWCNTs incorporation is lower than that of neat matrix at mall and intermediate strains, indicating a heterogeneous stress distribution and low compliance of HSK superstructure, which is consistent with in‐situ Raman results. Moreover, the nanocomposites presents significantly enhanced thermal stability. The onset decomposition temperature of nanocomposites with 3 wt % MWCNTs can be 60.2°C higher than that of neat OBC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42368.  相似文献   

16.
In this work, nanocomposites with simultaneous dispersion of multiwalled carbon nanotubes (MWCNT) and montmorillonite clays in an epoxy matrix were prepared by in situ polymerization. A high energy sonication was employed as the dispersion method, without the aid of solvents in the process. The simultaneous dispersion of clays with carbon nanotubes (CNT) in different polymeric matrices has shown a synergic potential of increasing mechanical properties and electrical conductivity. Two different montmorillonite clays were used: a natural (MMT‐Na+) and an organoclay (MMT‐30B). The nanocomposites had their electrical conductivity (σ) and dielectric constant (εr) measured by impedance spectroscopy. The sharp increase in electrical conductivity was found between 0.10 and 0.25 wt% of the MWCNTs. Transmission electron microscopy (TEM) of the samples showed a lower tendency of MWCNT segregation on the MMT‐30B clay surface, which is connected to intercalation/exfoliation in the matrix, that generates less free volume available for MWCNTs in the epoxy matrix. Data from electrical measurement showed that simultaneously adding organoclay reduces the electrical conduction in the nanocomposite. Moreover, conductivity and permittivity dispersion in low frequency suggest agglomeration of nanotubes surrounding the natural clay (MMT‐Na+) particles, which is confirmed by TEM. POLYM. COMPOS., 37:1603–1611, 2016. © 2014 Society of Plastics Engineers  相似文献   

17.
Yingjuan Huang  Jin-Yong Dong 《Polymer》2007,48(14):4005-4014
This paper discusses a strategy of enhancing the structure stability of polyethylene/montmorillonite (PE/MMT) nanocomposites prepared by intercalative polymerization technique. The chemistry centers on an in situ, controlled PE matrix functionalization that is made possible by engaging a reactive comonomer in the intercalative polymerization process to intentionally anchor in the formed PE matrix ready-to-functionalize reactive groups. Thus, ethylene polymerization was conducted in the presence of p-methylstyrene (p-MS) using an OMMT (organically modified MMT)-intercalated metallocene catalyst (Et[Ind]2ZrCl2 in combination with MAO), resulting in p-MS-containing PE/OMMT nanocomposites. Subsequent functionalization of the PE matrix then facilely and selectively occurred on the benzyl group in the p-MS unit, including a free radical maleation reaction and a butyllithium-initiated metallation reaction which was followed by an anionic graft-from polymerization of methyl methacrylate (MMA), under very mild reaction conditions. The in situ-incorporated functional groups, including the pendant maleic anhydride groups and the polar poly(methyl methacrylate) (PMMA) side chains, significantly improved miscibility between the PE matrix and laminated silicate layers of MMT, leading to effective stabilization of the nanocomposite structure against processing.  相似文献   

18.
Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (Tg) and decomposition (Td) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers  相似文献   

19.
Low density polyethylene (LDPE)/maleic anhydride grafted polyolefin elastomer (POE-g-MA) with multiwall carbon nanotubes (MWCNTs) wrapped by fumed silicon dioxide (SiO2) were prepared by melt mixing. The results revealed that SiO2 improved the dispersion of MWCNTs on matrix. SiO2 and MWCNTs both had a heterogeneous nucleation effect on matrix and the crystallinity of composites increased with adding SiO2, MWCNTs and MWCNTs/SiO2. The addition of MWCNTs modified by SiO2 increased tensile strength and elongation at break of composites compared with composite with raw MWCNTs. MWCNTs had a strong absorption effect, leading to an obvious decrease in reflectance at 1060 nm of composites.  相似文献   

20.
The homogenous nanocomposite films of UV/O3 oxidized multiwall carbon nanotubes (MWCNTs) subsequently modified with aniline moiety were synthesized with polymethylmethacrylate (PMMA) through free radical polymerization. The phenylamine functional groups present on the surface of MWCNTs providing an anchoring sites for deposition of Ag metal nanoparticles (NP).The in situ free radical polymerization of MMA in the presence of these well dispersed nanotubes gave a new class of radiation resistant nanocomposite films. The synthesized materials were characterized by FT‐IR, TGA, TEM, EDX, TC, DMA, universal testing machine, and optical microscopy to ascertain their structural morphologies, thermal stability, and mechanical strength. The microscopic and structural properties reflect the homogenous mixing of modified MWCNTs in polymer matrix contributing in enhancement of thermal stability, thermo‐mechanical strength, glass transition temperatures, and thermal conductivity of nanocomposites even at 0.25 wt% addition of modified nanofiller. Thermal and thermo‐mechanical behavior of pre‐ and post‐UV/O3 irradiated nanocomposite films have been compared with neat polymer. The results revealed that modified nanofiller network can effectively disperse the radiation and has a dramatic reinforcement effect on the nature of degradation of PMMA matrix. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers  相似文献   

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