UHMWPE/CNTs复合纤维的结晶行为研究

分别用DSC、X衍射、热台偏光显微镜对超高分子质量聚乙烯（UHMWPE）和UHMWPE／CNTs（碳纳米管）复合纤维的结晶行为进行了研究。结果表明：碳纳米管的加入使得复合材料的熔点较UHMWPE有所提高,碳纳米管起到了成核剂的作用。晶片厚度较UHMWPE增加。     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

二乙烯三胺改性碳纳米管对环氧树脂纳米复合材料力学性能影响研究

采用二乙烯三胺(DETA)对碳纳米管(MWNTs)进行改性,并用X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对其进行表征。发现DETA被有效地包覆在MWNTs表面。并将改性前后的MWNTs与环氧树脂进行复合,采用浇铸成型法制备了MWNTs/环氧树脂纳米复合材料,测试其力学性能,并采用透射电镜(TEM)研究其分散性,扫描电镜(SEM)对其断口进行了分析研究。结果表明,少量的改性MWNTs可以使复合材料的力学性能提高,具有明显的增韧作用。当MWNTs的含量为0.6%时,纳米复合材料的冲击强度与纯环氧体系相比,提高幅度达400%以上,弯曲强度和弯曲模量的提高幅度均达到了100%以上。     

Dispersion of carbon nanotubes in ultrahigh‐molecular‐weight polyethylene by melt mixing dominated by elongation stress

A novel melt‐mixing method and corresponding mixer for polymer materials are reported. The effects of carbon nanotube (CNT) loading, rotation rate and mixing time on the morphology and properties of CNTs/ultrahigh‐molecular‐weight polyethylene (UHMWPE) nanocomposites were experimentally investigated in detail using the mixer. Homogeneous dispersion of CNTs in intractable UHMWPE is successfully realized without the aid of any additives or solvents. Differential scanning calorimetry results showed that the crystallinity increases 13.8% when 1 wt% of CNTs is added into the composites. The maximum crystallinity increased 13.5% and then decreased slightly with increasing rotation rate. The mixing time had little effect on crystallinity. Rheological tests reveal that the effect of CNT loading on the storage modulus/complex viscosity is a result of competition between the viscosity decrease due to the selective adsorption of UHMWPE onto CNT surfaces and the viscosity increase caused by the formation of an interconnected polymer–nanotube network. The storage modulus/complex viscosity decreased with increasing rotation rate/mixing time. This is a synergic result of the selective adsorption of the long molecular chains onto the CNT surface and their thermomechanical degradation. The results showed that the mixing process dominated by elongation stress is a simple, efficient green way to prepare CNTs/UHMWPE nanocomposites via melt mixing. © 2018 Society of Chemical Industry     

Nanocomposites of poly(vinylidene fluoride) with multiwalled carbon nanotubes

The preparation and characterization of nanocomposites of poly(vinylidene fluoride), PVDF, with acid treated multiwalled carbon nanotubes (MWCNT) with a wide composition range, from 0.1 to 5.0% MWCNT by weight, is reported. Effect of uniaxial orientation by zone drawing on these nanocomposites is discussed and compared with unoriented compression molded films. Static room temperature two‐dimensional wide angle X‐ray scattering and Fourier transform infrared spectroscopy were used for phase identification. Differential scanning calorimetry, polarizing optical microscopy, dynamic mechanical analysis (DMA), and thermogravimetic analysis (TGA) were used to study the thermal and mechanical properties. Incorporation of MWCNT into PVDF has no obvious effect in forming beta phase crystal in the PVDF/MWCNT bulk films, while zone drawing cause a significant alpha to beta transition in PVDF/MWCNT. Results indicate that MWCNTs act as nucleation agent during crystallization and slightly increase the degree of crystallinity of PVDF/MWCNT bulk films. TGA indicates the thermal stability is improved when MWCNT concentration increases for unoriented PVDF/MWCNT film. The modulus also increases significantly when MWCNT concentration increases. The glass transition temperature measured by the peak position of tanδ from DMA does not change with MWCNT concentration, but a slightly higher glass transition can be obtained by zone drawing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

UHMWPE/CNTs冻胶体系的流变行为研究

研究了碳纳米管(CNTs)的加入对超高分子质量聚乙烯(UHMWPE)稳态表观粘度、粘流活化能、非牛顿指数和结构粘度指数的影响。结果表明:碳纳米管添加量小于或等于3ω时,UHMWPE/CNTs冻胶体系的粘流括化能降低,表观粘度都低于空白UHMWPE冻胶体系。CNTs的加入对UHMWPE冻胶体系的非牛顿指数和结构粘度指数影响不大。     

多壁碳纳米管的功能化及其应用研究

首先用混合酸纯化了原料碳纳米管,然后使用有机胺对碳纳米管进行了共价功能化。拉曼光谱和元素分析结果表明,烷基胺通过共价键接合于碳纳米管表面。从热重分析结果可知,碳纳米管表面附着有质量分数为6.9%～16.4%的有机物。透射电镜照片显示,在碳纳米管的外壳上覆盖有厚度为几纳米的无定形的材料,形成核—壳结构。力学性能结果表明,加入质量分数为1%的功能化纳米碳管可使环氧树脂的断裂韧性提高35%。     

Preparation,structure and properties of thermoplastic olefin nanocomposites containing functionalized carbon nanotubes

The morphology and properties of multiwalled carbon nanotube modified polypropylene (PP)/ethylene–octene copolymer blends were studied. Polypropylene chains are covalently grafted onto the surface of carbon nanotubes (CNTs) in order to improve their interaction with the polymer matrix. It is observed that functionalization of CNTs improves their dispersion and increases the interfacial bonding between CNTs and polymer matrix. The functionalized CNTs are selectively distributed in the continuous polypropylene phase. The size of the dispersed elastomer phase decreases after the addition of CNTs. Functionalized CNTs act as a nucleating agent and increase the crystallinity of the polypropylene. More importantly, an important increase in impact strength, stiffness and toughness can be achieved through introducing functionalized CNTs. Copyright © 2011 Society of Chemical Industry     

A convenient route to modified multiwall carbon nanotubes with liquid crystal molecules via covalent functionalization

A novel nanocomposite of the rod‐like liquid crystal (LC) molecules' waist positions anchored on the surface (sidewalls and ends) of multiwall carbon nanotubes (MWNTs) was prepared by using a dissolving metal reduction method for the first time. The MWNTs carbanion complexes of lithium were first synthesized in tetrahydrofuran with an electron transfer from lithium naphthalene radical anion on the surface of MWNTs. Then the novel material (LC‐MWNTs) was obtained by treating the carbanion complexes with bromic liquid crystalline aromatic amide compound. The formation of the LC‐MWNTs was confirmed by both Raman and FTIR spectroscopies. HRTEM demonstrates that the rod‐like LC molecules are anchored on the surface of MWNTs via covalent attachment, with a wrapped thickness approximately 3‐4 nm. The loss‐weight fraction of the LC layers for the LC‐MWNTs can be roughly estimated as 23% by TGA. The experiments of solubility exhibit that the LC‐MWNTs forms a stable suspension solution in polar solvents such as dimethylformamide. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry     

Effective reinforcement of carbon nanotubes in polypropylene matrices

This study describes an attempt to mechanically reinforce polypropylene (PP) using multi‐wall carbon nanotubes (MWNTs) through a melt compounding process followed by hot‐pressing and solid state drawing. The effect of a high density polyethylene (HDPE) coating on MWNTs and melt flow index (MFI) of PP on the dispersion of MWNTs and composite properties are studied by means of mechanical tests, transmission electron microscopy (TEM), scanning electron microscope (SEM), differential scanning calorimetry (DSC), and wide angle x‐ray diffraction (WAXD). Highly orientated composite tapes are prepared to fully utilize the properties of MWNTs in uniaxial direction. Highly aligned MWNTs are shown by SEM, while highly oriented polymer chains are characterized by WAXD. Composite theory is used to analysis the results and indicate that effective reinforcement of PP by MWNTs is highest at relatively low filler content and draw ratios. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Processing and properties of syntactic foams reinforced with carbon nanotubes

This article presents synthesis and mechanical characterization of carbon nanotube (CNT)‐reinforced syntactic foams. Following a dispersion approach (comprising ultrasonic, calendering, and vacuum centrifugal mixing), single‐ and multi‐walled functionalized CNTs (FCNTs) were incorporated into two foam composites containing various commercially available microballoon grades (S38HS, S60HS, and H50 from 3M). The FCNT‐reinforced composites were tested for compressive strength and apparent shear strength before and after hot/wet conditioning. The results showed that the FCNT‐reinforced composites' mechanical properties depended on the vacuum pressure used during processing. Compared with pristine and commercially available syntactic foam (EC‐3500 from 3M), the FCNT‐reinforced composites processed at high vacuum (0.2 kPa) showed significant increase in compressive strength and apparent shear strength before and after hot/wet conditioning. Dynamic mechanical analysis showed an increase of about 22°C in glass transition temperature for composites processed at high vacuum with 0.5 wt % FCNT and 45 wt % S38HS–5 wt % S60HS microballoons. Thermogravimetric analysis indicated water absorption and lower decomposition temperature for the FCNT‐reinforced composite mixed at atmospheric pressure, whereas no significant change was observed for the compound processed at high vacuum. Fracture analysis showed matrix failure for the composite processed at high vacuum and microballoon crushing for the composite mixed at atmospheric pressure. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hybrid modification of high‐density polyethylene with hyperbranched polyethylene‐functionalized multiwalled carbon nanotubes and few‐layered graphene

Herein, a facile method has been reported to efficiently prepare debundled multiwalled carbon nanotubes (MWCNT) and few‐layered graphene using a hyperbranched polyethylene (HBPE), and as hybrid fillers, their modification effects on high‐density polyethylene (HDPE) are well demonstrated. Stable dispersions of debundled MWCNT and graphene in chloroform were respectively obtained by sonication using the HBPE as stabilizer, and MWCNT/graphene/HDPE ternary nanocomposites were then fabricated by solution‐assisted premixing and subsequent melt mixing, at a fixed mass ratio of MWCNT/graphene of 3:1 and serially changed filler loadings. It is found that the MWCNT and graphene have good dispersibility in the composites, and as hybrid fillers, they can effectively form composite net‐like structure, which makes them show better modification effects on both the electrically and thermally conductive properties of HDPE, as compared to the single MWCNT. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44848.     

Preparation and characterization of poly(vinylidene fluoride) nanocomposites containing multiwalled carbon nanotubes

Poly(vinylidene fluoride) (PVDF) nanocomposites with different loadings of multiwalled carbon nanotubes (MWNT) were prepared by melt‐compounding technique. A homogeneous dispersion of MWNT throughout PVDF matrix was observed on the cryo‐fractured surfaces by scanning electron microscopy. Thermogravimetric analysis results indicated that the thermal stability of neat PVDF was improved with the incorporation of MWNT. Dynamic mechanical analysis showed a significant improvement in the storage modulus over a temperature range from ?125 to 75°C with the addition of MWNT. The melt‐rheological studies illustrated that incorporating MWNT into PVDF matrix resulted in higher complex viscosities (|η*|), storage modulus (G′), loss modulus (G″), and lower loss factor (tan δ) than those of neat PVDF. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal conductivity of carbon nanotubes and graphene in epoxy nanofluids and nanocomposites

We employed an easy and direct method to measure the thermal conductivity of epoxy in the liquid (nanofluid) and solid (nanocomposite) states using both rodlike and platelet-like carbon-based nanostructures. Comparing the experimental results with the theoretical model, an anomalous enhancement was obtained with multiwall carbon nanotubes, probably due to their layered structure and lowest surface resistance. Puzzling results for functionalized graphene sheet nanocomposites suggest that phonon coupling of the vibrational modes of the graphene and of the polymeric matrix plays a dominant role on the thermal conductivities of the liquid and solid states.PACS: 74.25.fc; 81.05.Qk; 81.07.Pr.     

Nitrogen-doped carbon nanotubes synthesized with carbon nanotubes as catalyst

Nitrogen-doped carbon (CN_x) nanotubes were synthesized with carbon nanotubes (CNTs) as catalyst by detonation-assisted chemical vapor deposition. CN_x nanotubes exhibited compartmentalized bamboo-like structure. Electron energy loss spectroscopy and elemental mapping studies indicated that the synthesized tubes contained high concentration of nitrogen (ca. 17.3 at.%), inhomogeneously distributed with an enrichment of nitrogen within the compartments. X-ray photoelectron spectroscopy analysis revealed the presence of pyridine-like N and graphitic N incorporated into the graphitic network. The catalytic activity of CNTs for CN_x nanotube growth was ascribed to the nanocurvature and opening edges of CNT tips, which adsorbed C_n/CN species and assembled them into CN_x nanotubes.     

Silica supported single‐walled carbon nanotubes as a modifier in polyethylene composites

Composites have been made from single‐wall carbon nanotubes in a polyethylene (PE) matrix, in which different methods of preparation were used to disperse the nanotubes. The study includes using either the refined pure nanotubes (P‐NT) as the source, or the original silica supported nanotubes (SS‐NT). SS‐NT contained nanotubes still incorporated in and around the silica as originally grown. Composites were then made by (1) coprecipitation from a suspension of P‐NT or SS‐NT in a PE solution, or (2) by forming a polymerization catalyst from the SS‐NT, and using it to polymerize ethylene, which ruptures and expands the silica as polymer builds up in the pores. Extrusion was also studied as a method of additional dispersion. Nanotubes were found to have a powerful effect on the melt rheology, increasing the low shear viscosity dramatically. Increasing the nanotube concentration also increased the flexural and tensile moduli, decreased the elongation, and increased the electrical conductivity. Consistent trends were observed from all of these diverse properties: SS‐NT had a stronger effect than P‐NT, and within the SS‐NT group the choice of silica type also had a major effect. Polymerization was generally preferred as the method of dispersing the nanotubes. The conductivity, which in some cases was quite high, was found to be pressure sensitive. Conductive NT/PE composites could be molded into films or extruded into other shapes, or comolded with other PE. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Polymer adsorption in the grafting reactions of hydroxyl terminal polymers with multi-walled carbon nanotubes

Melt stirring of non-functional polymers such as poly(ethylene oxide) dimethylether (PEO-Me) and polystyrene (PS-H) with multiwalled carbon nanotubes (MWNTs) in the absence of solvent for 48 h induced a substantial amount of polymer adsorption on the MWNTs. The chloroform extraction of the reaction products using centrifugation yielded black colored solutions exhibiting UV absorbance corresponding to the presence of MWNTs. The adsorption of polymer was confirmed on the surfaces of solvent washed residual and recovered MWNTs from the reactions using thermogravimetric analysis (TGA) and FT-IR spectroscopy. Covalent grafting reactions carried out using hydroxyl-terminated PEO-OH and PS-OH with acid chloride containing MWNTs under identical melt stirring condition produced similar results. The presence of polymer on the residual and recovered MWNTs irrespective of the nature of the terminal groups indicates that the adsorption of polymers poses a problem in accurately determining the grafting efficiency. FT IR spectra of the PEO-g-MWNTs shows a substantial shift in CH stretching vibrations indicating a plausible weak intermolecular interaction with π electrons of the MWNTs.     

Shear enhanced interfacial interaction between carbon nanotubes and polyethylene and formation of nanohybrid shish-kebabs

In this work, raw multiwalled carbon nanotubes (MWNTs) without any pre-treatment were blended with linear low density polyethylene (LLDPE), then molded via a so-called Dynamic Packing Injection Molding (DPIM) technique, in which oscillatory shear was exerted on the prepared composites during the stage of cooling solidification. The injection molded samples were extracted by xylene to remove LLDPE, and the remained MWNTs were collected and characterized. Shear enhanced interfacial adhesion between MWNTs and LLDPE was confirmed by dissolution experiment and Fourier transform infrared. The former a longer mixing time in xylene for remained MWNTs compared with raw MWNTs, while in the latter an increased intensity of characteristic LLDPE peak for MWNTs subjected to dynamic packing injection molding. More importantly, SEM images showed a formation of MWNTs/LLDPE nanohybrid shish-kebab, in which MWNTs served as shish, and LLDPE lamellae as kebab and periodically decorated on MWNTs. A simultaneously improved tensile strength and elongation of LLDPE have been achieved by adding the LLDPE-decorated MWNTs. Our work provides a new way for the modification of MWNTs, particularly a convenient way for the enhancement of interfacial adhesion in polymer/MWNT composites via realistic molding processing.