A Simple and Facile Approach to Synthesize Water-Soluble Multiwalled Carbon Nanotubes Wrapped by Poly(4-Vinylpyridine)

By simple grinding, water-soluble linear polymers poly(4-vinylpyridine) (PVP) wrapped around multiwalled carbon nanotubes (MWCNTs) and thus rendered them reversibly soluble in water, ethanol, and DMF. The structure and properties of the resulting nanocomposite, CNTs wrapped by PVP, were evaluated by SEM, AFM, TGA, and FTIR spectroscopy. Individual tubes are clearly observed after PVP-wrapped nanotubes were spin-coated onto a silicon wafer as determined by SEM and AFM. Subsequently, a novel and facile approach to attach high-density and uniform size gold nanoparticles on individual multiwalled carbon nanotubes was achieved by in situ reduction of HAuCl₄ in the homogeneous aqueous solution of MWCNTs–PVP.     

Influence of the electronic distribution of polymers in the spatial conformation of polymer grafted carbon nanotube composites

In this work we report the covalent functionalization of multiwalled carbon nanotubes (MWCNTs) with polyacrylonitrile (PAN) and polyvinylpyridine (PVP) by the graft from method. Differences in the electronic distribution of both polymers resulted in different interaction between polymers and the nanotubes. It was found that PVP chains wrapped the nanotubes while nanotubes functionalized with PAN presented PAN chains forming amorphous entanglements on the nanoscale linked to the MWCNTs. Differences in the conformation between both polymers and the MWCNTs can be attributed to interactions between the aromatic groups in PVP and the MWCNTs through π–π stacking. The absence of aromatic groups in the case of the PAN chains favours the interaction between them. The functionalization efficiency was characterized using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and UV–vis spectroscopy, while morphological changes were characterized by high resolution transmission electron microscopy.     

Preparation and characterization of amphiphilic multi-walled carbon nanotubes

Multiwalled carbon nanotubes (MWCNTs, average diameter 8 nm) functionalized by N-vinyl pyrrolidone (NVP) were synthesized by radical polymerization and characterized by Fourier transform infrared and Raman spectroscopies, thermogravimetric analysis and transmission electron microscopy. These NVP–MWCNTs exhibit remarkable solubility in water, ethanol and dimethyl formamide. The polyvinyl pyrrolidone can be attached onto the surface of the MWCNTs and the degree of functionalization is affected by NVP content. The functionalization causes possible grafting reaction and solid physical coating between MWCNTs and PVP.     

Poly(N-vinyl carbazole)-grafted multiwalled carbon nanotubes: Synthesis via direct free radical reaction and optical limiting properties

In this work, samples of poly(N-vinyl carbazole) (PVK)-grafted multiwalled carbon nanotubes (MWCNTs) were synthesized via free radical reaction. The ready-made PVK was allowed to react directly with MWCNTs at 70 °C in the presence of azo-bis-isobutyronitrile (AIBN). The purified deep grey products, which can dissolve in common organic solvents such as chloroform and 1,2-dichlorobenzene (DCB), were then characterized by FTIR spectra, TEM, TGA, elemental analysis, XPS, UV-vis spectra and Raman spectra. It was confirmed that PVK chains were grafted onto the surface of the carbon nanotubes (CNTs). The optical limiting properties of these PVK-grafted MWCNTs samples were investigated by open-aperture z-scan method. All of the samples of PVK-modified carbon nanotubes in chloroform showed optical limiting behavior better than that of C₆₀ in toluene.     

Functionalization of multiwalled carbon nanotubes for reinforcing of poly(l-lactide-co--caprolactone) biodegradable copolymers

Up to now, synthetic polymers and biomacromolecules have been grafted or assembled onto the convex surface of carbon nanotubes (CNTs) via covalent bonds or chemisorptions. In this research, poly(l-lactide-co--caprolactone)-functionalized multiwalled carbon nanotubes (MWCNT-OH-g-PCLA)s are synthesized by in situ ring-opening copolymerization of l-lactide (LA) and -caprolactone (CL) using stannous octanoate and hydroxylated MWCNTs (MWCNT-OHs) as the initiating system. The pristine MWCNTs are modified to possess carboxyl groups and then hydroxyl groups. MWCNT-OHs are used as coinitiators to polymerize LA and CL by the surface-initiated ring-opening polymerization. The FT-IR spectra, SEM and TEM micrographs revealed that the PCLA grafted form the sidewall of MWCNTs strongly. The TGA analysis indicates that about 75 wt% of functionalized MWCNTs with PCLA belongs to grafted PCLA and the remaining 25 wt% to the initial MWCNT-OH.     

Sol-Gel Synthesis of Multi-Walled Carbon Nanotubes Reinforced Alumina-Silica Fibers

Multi-walled carbon nanotubes (MWCNTs) reinforced alumina-silica fibers were prepared by the sol-gel dry-spinning method. Aluminum isopropoxide (AIP), aluminum nitrite (AN), and tetraethyl orthosilicate (TEOS) were used as starting materials to prepare spinnable aluminosilicate sols in aqueous media. Polyvinylpyrrolidone (PVP) was used as dispersant agent to homogeneous disperses MWCNTs in the spinnable aluminosilicate sol through an in-situ process. The structure and mechanical properties of the MWCNTs reinforced alumina-silica fibers were studied. The results revealed that homogeneous dispersion of MWCNTs in alumina-silica fibers improved their mechanical properties considerably. The addition of only 0.5 wt% acid-treated MWCNTs into alumina-silica fibers result in a 60% increase in tensile strength to 398 ± 45 MPa.     

超声技术在高分子材料中应用研究进展

本文综述了检测超声和功率超声在高分子检测,高分子加工,高分子化学方面应用的最新进 展。阐明了超声与高分子材料的作用原理,以及影响超声作用的因素。展望了研究高分子熔体中声化 学的重要性。     

A plasmonic and SERS dual-mode iodide ions detecting probe based on the etching of Ag-coated tetrapod gold nanostars

Journal of Nanoparticle Research - Multiwalled carbon nanotubes (MWCNTs) were grafted with poly(AMPS–co–AM) by free-radical polymerization of acrylamide (AM) and...     

Nanotitania-coated multi-walled carbon nanotube composite by facile colloidal processing route for photocatalytic applications

Multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanocomposites (MWCNTs/TiO₂) were fabricated by a simple novel colloidal processing route and tested as a photocatalyst for degradation of methylene blue under UV irradiation. The novel idea behind this work is to make MWCNTs and TiO₂ nanoparticle suspensions separately highly oppositely charged and utilize the electrostatic force of attraction between two entities to deposit nanotitania onto MWCNTs surface. Particle charge detector, scanning electron microscopy, transmission electron microscope, energy dispersive X-rays, X-rays diffraction (XRD), and Raman spectroscopy were used to characterize the composite. XRD and Raman spectroscopic analysis showed the crystalline structure of deposited TiO₂ over MWCNTs surface structure as anatase phase. It was found that MWCNTs/TiO₂ composite structure have much higher photocatalytic activity compared to TiO₂ nanoparticles. The composite material developed may find potential applications in the degradation of organic pollutants in aqueous medium under UV irradiation.     

γ射线辐照下多壁碳纳米管结构转变过程研究

采用60Coγ射线辐照纯净的多壁碳纳米管,用高分辨透射电镜和拉曼光谱,研究了多壁碳纳米管由石墨结构向无定形结构转变的演化过程.发现在γ射线辐照下,碳纳米管的外部石墨层逐渐失去最初的有序结构而向无定形结构转变.而且,随着γ射线辐照剂量的增加,无定形结构不断推进,而石墨层结构则不断减小,直至使整个碳纳米管变为一个中空的无定形纳米线结构.用原子位移理论和溅射机理对这种转变过程进行了分析.γ射线轰击碳纳米管击出碳原子,碳原子停留在晶格的间隙位置上产生间隙原子,在它原来的平衡位置则留下一个空位.当轰击粒子动能足够大时导致碰撞级联效应,无序结构增加.多数空位和间隙原子可能相互复合而彼此退火,但仍有少数原子作为间隙原子而造成晶格进一步缺陷.辐射也可以引起碳原子的溅射,溅射出来的碳原子沉积在碳纳米管的外壁上形成一层无定形碳结构.     

The use of calcination in exposing the entrapped Fe particles from multi-walled carbon nanotubes grown by chemical vapour deposition

Multi-walled carbon nanotubes (MWCNTs) were synthesized a by chemical vapour deposition method. The effect of calcination at temperatures ranging from 300 to 550°C in exposing the metal nanoparticles within the nanotube bundles was studied. The degree of degradation of the structural integrity of the MWCNTs during the thermal process was studied by Raman spectroscopy, X-ray diffraction analysis, field-emission scanning electron microscopy, and transmission electron microscopy. The thermal behaviour of the as-prepared and calcined samples was investigated by thermogravimetric analysis. Calcination in air, at 400°C for 1 h, was found to be an efficient and simple method to extract metallic impurities from the amorphous carbon shells with minimal damage to the tube walls and lengths. The nanotubes were observed to be damaged at temperatures higher than 450°C.     

Functional multi-walled carbon nanotube/polysiloxane composite films as supports of PtNi alloy nanoparticles for methanol electro-oxidation

We demonstrate the use of molecular monolayers to enhance the nucleation of electrocatalytically active PtNi alloy nanoparticles onto the multi-walled carbon nanotubes (MWCNTs). After the siloxane was polymerized on the nanotube surfaces, the carbon nanotubes were embedded within the polysiloxane shell with a hydrophilic amino group situated outside. Subsequent deposition of PtNi nanoparticles led to high density of 3-10 nm diameter PtNi alloy nanoparticles uniformly deposited along the length of the carbon nanotubes. The presence of MWCNTs and PtNi in the composite films was confirmed by transmission electron microscopy (TEM), X-ray diffraction (XRD) and energy dispersion X-ray spectra analysis (EDS). The electrocatalytic activity of the PtNi-modified MWCNT/polysiloxane (PtNi/Si-MWCNT) composite electrode for electro-oxidation of methanol was investigated by cyclic voltammetry (CV), and excellent electrocatalytic activity can be observed.     

Effects of enhanced hydrogen bonding on the mechanical properties of poly (vinyl alcohol)/carbon nanotubes nanocomposites

In this study, poly (vinyl alcohol) (PVA) composites reinforced by multiwall carbon nanotubes (MWCNTs) functionalized with either phenolic hydroxyl groups (MWCNTs-f-OH) or PVP molecule (PVP@MWCNTs) were fabricated. The objective was to elucidate the effect of different MWCNTs surface functionalization on the mechanical properties of the nanocomposites. It was found that both of PVP@MWCNTs and MWCNTs-f-OH had a good dispersion in PVA matrix. However, the MWCNTs-f-OH had stronger effective interfacial interaction with PVA matrix than PVP@MWCNTs, owe to the formation of hydrogen bonds between MWCNTs-f-OH and PVA. The stress-strain measurements showed that the Young’s modulus and tensile strength of MWCNTs-f-OH/PVA with only 1.0 wt.% contents increased by 200 and 100% compare with that of PVA, respectively. The findings of this experimental study emphasized the critical role of MWCNTs surface morphology in determining the mechanical properties of nanocomposites, and shed new light on understanding and advancing the properties of carbon nanotube based composites.     

Effects of corona discharge on the surface structure, morphology and properties of multi-walled carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were modified by corona discharge and then heat treated in the air. The influences of corona discharge parameters such as treatment time and processing power were investigated. The results of energy dispersive X-ray analysis (EDX) and thermogravimetric analysis (TGA) indicated the introduction of oxygen-containing functional groups onto the surface of the MWCNTs after heat treatment. The water contact angle tests showed that the hydrophobicity of the MWCNTs was decreased to some extent. The static water contact angle was reduced from 146° to 122° when the time of the corona discharge treatment reached 3 min at the processing power of 200 W. The enhanced thermomechanical and mechanical properties of epoxy nanocomposites filled with the corona discharge treated MWCNTs were observed. The modified MWCNTs conferred better properties on the composites than the pristine MWCNTs because of the improved dispersion of MWCNTs in matrix and the enhanced interfacial interaction between the treated MWCNTs and epoxy.     

MWCNTs Supported N,N′-Dicyclohexyl-1,5-diamino-2,6-naphthalenedicarboxamide: A Novel β-Nucleating Agent for Polypropylene

N,N′-Dicyclohexyl-1,5-diamino-2,6-naphthalenedicarboxamide (NA), a highly efficient and selective β-nucleating agent for isotactic polypropylene (iPP), was synthesized and chemically supported on the surface of multiwall carbon nanotubes (MWCNTs) via an amidation reaction. The β-nucleation ability of NA, itself, is superior to the commonly used, highly efficient, and selective β-nucleating agents, e.g., commercial rare earth WBG-and aryl amide derivative TMB-5, as proved by the results of wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The effect of MWCNTs supported NA (MWCNT-NA) on the crystallization and melting behavior of iPP was investigated by means of WAXD and DSC. The results show that the MWCNTs supported NA can effectively induce the formation of β-crystals in iPP/MWCNT-NA, although the grafting degree of NA onto the surface of MWCNTs could still to be improved.     

超声处理有机废水的现状与进展

从超声降解有机废水的机理入手,对当前单频和多频(二维正交和三维)超声以及超声技术与其他技术联用降解污水的原理、影响因素和效果和国内外研究现状进行了总结和回顾,同时对该技术在处理有机废水方面的研究趋势进行了展望。     

Nonlinear finite-element modeling of graphene and single- and multi-walled carbon nanotubes under axial tension

An effective finite-element (FE) approach for modeling the structure and the deformation of single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs) is presented. An individual tube was modeled using a frame-like structure with beam elements. The effect of van der Waals forces, crucial in MWCNTs, was modeled by spring elements. The success of this new carbon nanotube (CNT) modeling approach was verified by comparing the simulation results for single- and multi-walled nanotubes and graphene with other experimental and computational results available in the literature. Simulations of final deformed configurations were in excellent agreement with the atomistic models for various deformations. The proposed approach successfully predicts the experimentally observed values for mechanical behavior of SWCNTs and MWCNTs. The results demonstrated that the proposed FE technique could provide a valuable tool for studying the mechanical behavior of different types of nanotubes, as well as their effectiveness as load-bearing entities in nanocomposite materials.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Rheological Behaviors of Poly(Vinylidene Fluoride)/“Bud-Branched” Nanotubes Nanocomposites

Bud-branched nanotubes, fabricated by growing metal particles on the surfaces of multiwall carbon nanotubes (MWCNTs), were used to prepare poly(vinylidene fluoride) (PVDF)-based nanocomposites. The melt viscoelastic behaviors of PVDF and its nanocomposites were characterized. The results showed that the introduction of both the MWCNTs and bud-branched nanotubes (MWCNTs-B) increased the storage modulus, loss modulus, and complex viscosity of the nanocomposites. However, the bud-branched nanotubes were more efficient to increase the elasticity than the MWCNTs that have relatively smooth surfaces. In particular, it was observed that the bud-branched nanotubes caused an increase of normal force and crossover modulus, while for MWCNTs, no variation in the normal force and a decrease of the crossover modulus were observed.     

In situ polyphenyl derivatisation and the effect of thermal decomposition of adsorbed and chemisorbed polyphenyls on the structure of multi-wall carbon nanotubes

This study presents the exploitation of an alternative reaction route of deamination of arylamines to perform in situ derivatisation of multi-walled carbon nanotubes (MWCNTs) with polyphenyl (PPh) species of various masses. As a result of consecutive derivatisation, high conversion of PPh grafting of the MWCNTs was realised with the collateral outgrowth of physical modification with adsorbed additional PPhs. Applied derivatisation process exceeds the monolayer coverage related superficial saturation limitations in the overall grafting yield of the nanotubes. Thus, a linear relationship was recognized between the overall quantities of chemisorbed PPhs composed of D₅-phenylene oligomers and the applied excess of diazonium activated reagents, corresponding to ²H MAS NMR spectroscopy results. According to mass spectrometry (MS) investigations, uniform thermal decomposition of the chemisorbed PPhs modified MWCNTs was found besides the more intense and altered decomposition characteristic-featured adsorbate-chemisorbate PPhs contained MWCNTs during sequential pyrolysis under inert atmosphere. This is attributed to the pyrolysis provoked isomerisation, decomposition and the formation of adsorbed and chemisorbed PPh moieties. As a result, a mediated and an even more pronounced degradation in the order of graphitic lattice of the MWCNTs were evidenced in the adsorbate-chemisorbate and the chemisorbate PPhs contained samples by FT-Raman spectroscopy and transmission electron microscopy (TEM), respectively. ²H MAS NMR supplied results of relevant amount of deuterium in the chemisorbate PPh contained sample without traces of aromatic related MS detected volatile products, these allow us to conclude about a thermally stable derivatisation that is interpreted as an endohedral modification of the nanotubes.