Study of interactions in carbon nanotubes systems by using Raman and SERS spectroscopy

We present results obtained on carbon nanotube systems by means of Raman scattering and surface enhanced Raman scattering (SERS). Such systems consist of single-walled nanotubes (SWNTs), multi-walled nanotubes (MWNTs), or polymer/nanotubes composites. In particular, we have focused our studies on the interactions taking place in these compounds which lead to an upshift of the radial breathing mode (RBM) in the case of SWNTs, either when they are arranged in bundles or embedded in polymers. Similar calculations has allowed us to interpret the low frequency Raman modes observed in purified MWNTs. We show that they come from the RBM of individual tubes. From intensity calculations performed to simulate Raman spectra, we demonstrate the importance of two experimental parameters, namely the diameter of internal tubes and the number of shells which constitute the MWNTs, such parameters being extracted experimentally from high resolution transmission electron microscopy images.     

Effect of multi-walled carbon nanotubes on tribological properties of lubricant

After purified by mixture of sulfuric acid and nitric acid, the multi-walled carbon nanotubes(MWNTs) were modified with stearic acid(SA). The modified carbon nanotubes as lubricant additive were utilized to prepare lubricant, and the effects of carbon nanotubes on the tribological properties were investigated by using a pin-on-plate wear tester. The surface structure of MWNTs was examined by transmission electron microscopy, Raman spectroscopy and infrared spectroscopy. The results show that the surfaces of MWNTs are coated with a modified layer of SA. Furthermore, the modified MWNTs as lubricant additive can effectively improve the friction-reduction and antiwear ability of lubricant. The friction coefficient of base lubricant decreases by about 10% and the wear loss of base lubricant decreases by 30%-40% when the concentration of modified MWNTs in lubricant is 0.45 %. In addition,the mass ratio of SA to MWNTs influences the friction-reduction and anti-wear ability of the modified MWNTs as lubricant additive. The optimum mass ratio of MWNTs to stearic acid is about 3 : 8 - 1 : 2.     

Carbon nanotube/polyaniline core-shell nanowires prepared by in situ inverse microemulsion

By the in situ inverse microemulsion, we prepared multi-walled carbon nanotubes/polyaniline composites (MWNTs/PANI). Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) showed that the nanotubes were coated with a PANI layer. Fourier transform infrared (FT-IR) spectra suggested that the π-bonded surface of the carbon nanotubes (CNTs) interact strongly with the conjugated structure of the PANI shell layer. The thermal stability and electrical conductivity of the MWNTs/PANI composites were examined by thermogravimetric analysis (TGA) and conventional four-probe method. In comparison with the pure PANI, the decomposition temperature of the MWNTs/PANI (1 wt% MWNTs) composites increased from 360 to 400 °C and the electrical conductivity of MWNTs/PANI (1 wt% MWNTs) composites was increased by one order of magnitude.     

Synthesis of MWNT-based composite materials with inorganic coating

Multiwalled carbon nanotube (MWNT) based metal oxide composites were prepared by an impregnation method using organometallic compounds as precursor. Aluminium isopropoxide (AlIP), tetraethyl orthosilicate (TEOS), and tetraethyl orthotitanate (TEOTi) were used as inorganic sources and decomposed by hydrolysis on the surface of carbon nanotubes. The composites were subsequently investigated by transmission electron microscopy and their coverage was compared. A direct, solvent-free impregnation technique turned out to be the most successful for all organometallic compounds and provided homogeneous inorganic cover layer on the surface of purified MWNTs.     

多壁碳纳米管载镍对镁基合金储氢性能影响

采用化学法制备多壁碳纳米管载镍催化剂(Ni/MWNTs),并将其加入到镁粉中,结合氢化燃烧合成(HydridingCombustionSynthesis,HCS)和机械球磨(MechanicalMilling,MM),即HCS+MM复合技术制备Mg85-Nix/MWNTs15-x(x代表质量百分数,x=3,6,9,12)合金。通过X射线衍射仪、透射电子显微镜、扫描电镜以及气体反应控制器研究了材料的晶体结构、微观形貌和吸放氢性能。结果表明:Mg85-Ni9/MWNTs6合金具有最佳综合吸放氢性能,其在373K,吸氢量达到5.68%(质量分数,下同),且在100s内就基本达到饱和吸氢量;在523K,1800s内的放氢量达到4.31%。Ni/MWNTs催化剂的添加,不但起到催化的作用,而且MWNTs具有优异的纳米限制作用,使得催化剂的粒径限制在纳米级,有利于限制产物中Mg2NiH4颗粒的长大。另外Ni与MWNTs存在协同催化作用,当它们达到一定比例时,对合金的吸放氢促进作用达到最优化,明显改善了合金的吸放氢性能。     

Electroless deposition of Cu on multiwalled carbon nanotubes

Copper has been deposited on the surface of multiwailed carbon nanombes （MWNTs） and inside MWNTs by electroless deposition. The as-prepared Cu-MWNT composite materials have been characterized by X-ray diffractometer （XRD）, transmission electron microscopy （TEM）, and electrochemical measurement. XRD analyses showed that Cu was a face-centered cubic （fcc） structure. The average size of Cu was calculated by Scherrer＇s formula from XRD data, and it was 11 nm. TEM revealed that Cu grains on the surface of MWNTs were uniform with the sizes of about 30-60 nm. The electrochemical measurement indicated that Cu-MWNT composite materials possessed fine electron conductivity.     

碳纳米管/聚酰亚胺纳米复合材料的制备及动态力学性能和介电性能

依次用混强酸和SOCl2对多壁碳纳米管(MWNTs)进行改性,解决其在有机溶剂的溶解性和在基体聚酰亚胺中分散性问题,并采用光电子能谱(XPS)和透射电镜(TEM)对改性前后的MWNTs进行表征.以4,4'-二氨基二苯醚(ODA)和3,3',4,4'-二苯甲酮四羧酸二酐(BTDA)为原料,以原位聚合法将改性碳纳米管掺杂聚酰亚胺(PI),制备MWNTs/PI纳米复合材料.通过热重分析(TGA)、动态力学分析(DMA)和电容测试对材料的热性能、动态力学和介电性能进行表征.结果表明:加入MWNTs后,材料仍有很好的热稳定性,材料的动态力学性能随MWNTs增加而增强,在50℃和10%(质量分数)MWNTs时储能模量为2.307 GPa,比纯聚酰亚胺(PI)提高23.1%;材料的介电常数随着MWNTs含量的增加明显提高,在IMHz和10%时介电常数为66.7,是纯PI的18.6倍.制备的碳纳米管/聚酰亚胺材料是一种具有优良的热学、动态力学力学和介电性能性能的纳米复合材料.     

Mechanical properties of hard Cr-MWNT composite coatings

Chromium-multiwalled carbon nanotubes (Cr-MWNT) composite coatings are electrodeposited from “environmentally acceptable” trivalent Cr electrolytes containing MWNTs under ultrasonic agitation. The structures, hardness and tribological behaviors are investigated using the transmission electron microscope (TEM), field-emission scanning electron microscope (FE-SEM), Vickers hardness indenter, tribology tester and three-dimensional profile tester, respectively. Results show that MWNTs are dispersed evenly in Cr matrix. The introduction of MWNTs obviously improved the hardness, toughness and tribological performance of Cr coatings.     

Synthesis and properties of multi-walled carbon nanotubes coated with inorganic nanoparticles

Rare earth fluoride EuF3 and TbF3 were coated on the multi-walled carbon nanotubes (MWNTs) via the intermediate of noncovalent hydrophobic interactions of the MWNTs surface with sodium dodecyl sulfate (SDS).They were characterized by X-ray diffraction (XRD) and transmission electron microscope (TEM). The nanoparticle sizes of metal fluorides and sulfides on MWNTs are less than 20 nm. The photo physical properties of the composites were investigated, which indicated the composites exhibited the optical transitions within the 4f shell of the rare earth ions.     

Preparation and magnetic property of multi-walled carbon nanotube/a-Fe2O3 composites

In order to attain new functional nanomaterials with good magnetic property, multi-walled carbon nanotubes/hematite (MWNTs/α-Fe₂O₃) composites were synthesized using the co-deposition method. MWNTs/α-Fe₂O₃ composites were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy(TEM), Raman spectroscopy and vibrating sample magnetometry (VSM). The experimental results show that the structure and magnetic properties of the MWNTs/α-Fe₂O₃ composites are related to the heat treatment temperature. MWNTs are modified by α-Fe₂O₃ nano-particles and α-Fe₂O₃ nanorods with a diameter of 10?50 nm after being treated at 450 °C. When the heat treatment temperature exceeds 600 °C, MWNTs are only modified by Fe₃O₄ particles. Furthermore, the MWNTs composites treated at 450 °C and 600 °C have good magnetic behaviour.     

核壳型碳微球和碳纳米管的制备及其阻燃性能

为改善碳微球(CMSs)/碳纳米管(MWNTs)与聚对苯二甲酸乙二醇酯(PET)基体相容性,采用原位聚合法对CMSs和MWNTs分别进行表面修饰,制成核壳型结构的PET@CMSs(PCMSs)和PET@MWNTs(PMWNTs),并通过熔融共混法制备了PCMSs/PMWNTs/PET复合材料,对其阻燃性能进行探讨。使用TEM、SEM、FTIR、TGA、CONE等测试手段,表征了PCMSs与PMWNTs的结构及与PET基体的相容性,并测试了PCMSs/PMWNTs/PET的力学性能、阻燃性能、热稳定性和燃烧行为等。结果表明,与修饰前的CMSs/MWNTs相比,PCMSs/PMWNTs与PET基体具有更好的分散相容性,在PCMSs\PMWNTs添加的质量分数为1%,PCMSs与PMWNTs的质量比为1∶2时,PCMSs/PMWNTs/PET比CMSs/MWNTs/PET的抗拉强度提高的最大,可达26.1%;与纯PET、CMSs/MWNTs/PET相比,PCMSs/PMWNTs作为阻燃材料添加到PET中,具有较好的热稳定性、且有效延长了PET的点燃时间、增大FPI指数,从而降低火灾危险性,阻燃效果较好,其LOI值为28.1%,熔滴数为3 d/min,UL-94阻燃级别可达到V-0级。     

Polypyrrole coated carbon nanotubes: Synthesis,characterization, and enhanced electrical properties

We describe a simple approach to the synthesis of MWNT/polypyrrole nanotubes by the in situ chemical polymerization of pyrrole on the carbon nanotubes using ferric chloride as an oxidant. The effects of pyrrole concentration on the coating and properties of the resulting complex nanotubes were studied by Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction, and thermal gravimetric analysis. The coated PPy layers could be controlled easily by adjusting a feed ratio of pyrrole to MWNTs. FT-IR results suggested an existence of interaction between the –COOH groups of chemically modified MWNTs and NH groups of the PPy. SEM and TEM studies indicated that each individual MWNT could be coated with PPy. The resultant nanotubes enhanced electrical conductivity compared to PPy and MWNT which was strongly influenced by the feed ratio of pyrrole to MWNTs.     

Behavior of mixed multi-walled carbon nanotube/P3HT monolayer at the air/water interface

The sidewall structure of multi-walled carbon nanotubes (MWNTs) was successfully functionalized with poly(3-hexylthiophene) (P3HT) by a non-covalent bond method. P3HT plays an important role in dispersing MWNTs, and assists them to have a stable existence at the air/water interface. The behavior of mixed MWNT/P3HT monolayer at the air/water interface was investigated after obtaining a homogeneously dispersed solution. The effect of MWNT concentration on the mixed MWNT/P3HT monolayer was investigated using the pressure–area (π–A) isotherm, relaxation curve and transmission electron microscopy (TEM). The mixed MWNT/P3HT monolayer was transferred onto a solid substrate using the Langmuir–Blodgett (LB) technique with horizontal or vertical deposition. The multilayer film was delicately fabricated by repeated deposition of the ultra-thin film. Scanning electron microscopy (SEM) images revealed non-uniformity in morphology of the ultra-thin MWNT/P3HT films. The absorption intensity at 250 nm by UV/vis spectroscopy illustrates that a uniform formation of mixed MWNT/P3HT monolayer into multilayer film was successfully obtained by horizontal deposition. The current–voltage characteristic of the ultra-thin MWNT/P3HT film shows that the current increases linearly with the increasing voltage, which indicates that MWNT/P3HT film forms an ohmic contact with gold. And, the electric current was estimated to be mainly contributed by MWNTs.     

Effect of hydroxyl radical on the structure of multi-walled carbon nanotubes

In this research, we present the systematic investigation of the effect of hydroxyl radical (HO) on the structure of multi-walled carbon nanotubes (MWNTs) via Fenton oxidation treatment in given conditions: molar ratio of hydrogen peroxide (H₂O₂) and ferrous ion (Fe²⁺) is approximately equal to 10 and pH value is controlled at 3 ± 0.5. Fenton oxidation process was followed and characterized by using Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The experimental results showed that the original graphene structure was disordered/destroyed by the newly generated oxygen-containing functional groups including OH, COOH and quinone groups, which were introduced while MWNTs was treated by Fenton reagents (Fe²⁺–H₂O₂). Moreover, two attackable routes for possible mechanism of interactions between HO and MWNTs were assumed by spectral changes and properties of reactive species, which were described as follows: (l) a preferred attack on defect sites existing in the purified MWNTs sample (2) a synchronous or succedent attack on unsaturated bonds of CC on the sidewalls of MWNTs by electrophilic addition reaction. The possible mechanism indicated that introduction of those functional groups into the structure of MWNTs could be regarded as the results of attacks of HO with double properties of oxidizability and electrophilic addition on defect sites and unsaturated bonds of CC in the MWNTs sample, which were consistent with spectral changes in infrared spectroscopy and Raman spectroscopy.     

Fabrication of Pt nanoparticles decorated PPy–MWNTs composites and their electrocatalytic activity for methanol oxidation

Here we report the synthesis and characterization of a catalyst material constituted of Pt, polypyrrole (PPy) and multi-walled carbon nanotubes (MWNTs). The catalyst supports (PPy–MWNTs nanocomposites) were synthesized via in situ chemical polymerization in advance, in which MWNTs were regarded as the matrix material. The supports were characterized by SEM & TEM, elemental analysis, XRD, FTIR and conductivity measurements. Then the catalysts were synthesized by a chemical reduction using sodium borohydride (NaBH₄) as reducing agent and acetic acid buffer (pH = 4) containing trace K₂C₂O₄ as reaction media. FTIR spectra showed that there existed relations between PPy and MWNTs during in situ polymerization. SEM and TEM micrographs of the catalyst samples exhibited that the existence of PPy layer which was evenly wrapped on the surface of MWNTs resulted in significant improvement in helping Pt particles well dispersed. XRD results showed that higher Pt(1 1 1) content in the catalyst deposited on PPy–MWNTs supports than that on MWNTs. The cyclic voltammetry (CV) tests of methanol electrocatalytic oxidation demonstrated that the electrode modified by Pt/PPy–MWNTs ternary composite catalyst showed higher catalytic stability than Pt/MWNTs binary catalyst, due to the synergic interaction between Pt and the carrier.     

Dispersion of multiwalled carbon nanotubes in aluminum powders

Multiwalled carbon nanotubes (MWNTs) were treated with the reflux within the concentrated nitric acid for 0-25 h to purify and disperse the tangled MWNTs. The effect of reflux time on the morphology and the weight loss of MWNTs were investigated. Meanwhile,the dispersion of MWNTs with 0-2.0 wt.% in 2024Al powders using mechanical stirring with an assisting ultrasonic shaker in ethanol was also studied. The results show that the reflux time markedly affects the morphology of MWNTs. The weight loss of MWNTs i...     

Synthesis and characterization of the carbon nanotube-based composite materials with poly(3,4-ethylenedioxythiophene)

We report a procedure to prepare a conducting nano-composites composed of multi-walled carbon nanotubes (MWNTs) and PEDOT by using a poly(sodium 4-styrenesulfonate) (PSSNa) as a inter-linking molecule between MWNT and PEDOT. When PSSNa chains are introduced on the MWNTs via physicochemical interaction, the surface of MWNT becomes negatively charged, and PSS-modified MWNTs promote the effective association of the positively charged PEDOT chains. The resulting MWNT-PSS/PEDOT composites are characterized by a better interconnection between MWNT and PEDOT components.     

The electrochemical hydrogen storage of CNTs synthesized by CVD using LaNi5 alloy particles as catalyst and treated with different temperature in nitrogen

The multi-wall carbon nanotubes (MWNTs) were synthesized by chemical vapor deposition (CVD) using LaNi₅ alloy particles as catalyst. The effect of 40–60 nm MWNTs treated with different temperature in nitrogen on the electrochemical properties of CNTs–Ni electrode were investigated. Three-electrode system was introduced for testing electrochemical hydrogen storage of the electrode. The CNTs–Ni electrodes were used as the working electrode, which were prepared by mixing MWNTs and Ni powder in a weight ratio of 1:10 (MWNTs:Ni). Ni(OH)₂/NiOOH worked as the counter electrode and Hg/HgO as the reference electrode. A 6 mol/L KOH solution acted as the electrolyte. MWNTs treated with different temperature in nitrogen ambient represented a great discrepancy in the electrochemical hydrogen storage capability under the same testing condition. The CNTs–Ni electrodes with 40–60 nm diameter CNTs which were treated in a temperature of 800 °C in nitrogen has the best electrochemical hydrogen storage capacity of 588.1 mAh/g and a corresponding discharging plateau voltage of 1.18 V. From 500 to 800 °C, the higher temperature the MWNTs treated, the better the electrochemical hydrogen storage property of them is. This shows that the temperature of treatment is an important factor that influences electrochemical hydrogen storage performance of MWNTs.     

Synthesis and characterization of MWNTs with narrow diameter over nickel catalyst by MPCVD

Multi-walled carbon nanotubes (MWNTs) were synthesized on silicon substrates using nickel catalyst with thickness varied from 2 to 30 nm by microwave plasma chemical vapor deposition technique. The characterization results show that the diameter of produced MWNTs decreases with decreasing thickness of nickel catalyst layer. The MWNTs with narrow diameter of 8 nm have been obtained at the nickel catalyst thickness of 2 nm.     

Morphological development of nanofibrillar composites of polyaniline and carbon nanotubes

Nanofibrillar composite of polyaniline (PANI)/multi-walled carbon nanotubes (MWNTs) is readily synthesized by means of conventional in situ polymerization process. It is found that the MWNT loading during polymerization has a significant influence on both the micro- and macro-scale morphological properties of the composites. At low MWNT loadings, PANI/MWNTs are formed as individual nanofibers, similar to that of the neat PANI in the absence of MWNTs. With the increase in MWNT loading, the composite exhibits granular form and becomes a continuous porous matrix at higher MWNT loadings. A possible mechanism is proposed to account for the structural variation of the composites caused by MWNTs at the different loadings.