A facile method for preparing CNT-grafted carbon fibers and improved tensile strength of their composites

Carbon nanotube (CNT)-grafted carbon fibers (CFs) have emerged as new reinforcements for improving the mechanical properties of CF-reinforced composites but such enhancement in macroscale composites has not been realized. This paper reports a facile method for preparing CNT-grafted CFs and improving the tensile strength of their composites. A CNT/polyacrylonitrile solution was sprayed onto the surface of the CF woven fabrics, and the CNTs were grafted by a thermal treatment at 300 °C. CNT-grafted CF composites were fabricated using the CNT-grafted CF woven fabrics using a vacuum-assisted resin transfer molding process with epoxy resin. The CNT-grafted CF composite exhibited 22% enhancement in the tensile strength compared to that of the pristine CF composite. Fracture surfaces of the CNT-grafted CF composites showed that the grafted CNTs obstructed the propagation of micro-cracks and micro-delamination around the CFs and also yarn boundaries, resulting in improved tensile strength of CNT-grafted CF composites.     

多壁碳纳米管的化学修饰及其增强环氧树脂复合材料的性能

研究原生多壁碳纳米管和己二胺修饰的多壁碳纳米管分别对环氧树脂的增强作用。用SEM、FT-IR及XPS对修饰前后的碳纳米管进行的表征表明,所用的方法可以在碳纳米管的表面接上己二胺。研究发现,修饰后的碳纳米管比原生碳纳米管对环氧树脂有更明显的增强作用。修饰后的碳管含量为2%时,拉伸强度、断裂伸长率和冲击强度比纯环氧树脂分别提高79.7%、160.4%和188.2%。     

Electro-active shape memory properties of poly(ε-caprolactone)/functionalized multiwalled carbon nanotube nanocomposite

One type of electroactive shape memory nanocomposite was fabricated, including cross-linked poly(ε-caprolactone) (cPCL) and conductive multiwalled carbon nanotubes (MWNTs). The cross-linking reaction of the pristine poly(ε-caprolactone) (PCL) was realized by using benzoyl peroxide (BPO) as an initiator. The raw MWNTs (Raw-M) were prefunctionalized by acid-oxidation process and covalent grafting with poly (ethylene glycol) (PEG), respectively. Three kinds of nanocomposites containing cPCL/Raw-M, cPCL/acid-oxidation MWNTs (AO-M) and cPCL/PEG grafted MWNTs (PEG-M) were obtained, and the mechanical, electrical and shape memory properties were further investigated. The influence of in vitro degradation on their shape memory and mechanical properties was also evaluated. The methyl thiazolyl tetrazolium (MTT) assay was performed to estimate their biocompatibility. The results displayed that these nanocomposites could perform favorable shape memory recovery both in hot water at 55 °C and in electric field with 50 V applied voltage. In addition, compared with cPCL/Raw-M and cPCL/AO-M, cPCL/PEG-M composite possessed more favorable properties such as mechanical, biocompatible, and electroactive shape memory functions. Therefore, the nanocomposite may be potential for application as smart bioactuators in biomedical field.     

Synthesis and thermal behavior of poly(ε-caprolactone) grafted on multiwalled carbon nanotubes with high grafting degrees

Poly(ε-caprolactone) (PCL) was grafted onto multiwalled carbon nanotubes (MWNTs) with high grafting degrees. The surface of MWNTs was first modified by 2-hydroxyethyl benzocyclobutene (BCB-EO) via a [2 + 4] cyclo-addition reaction. Polymerization of ε-caprolactone was conducted in the presence of BCB-EO modified MWNTs and the catalyst stannous octoate. Alternatively, the grafted-BCB-EO first reacted with CpTiCl₃ and then the reactant was used to catalyze polymerization of ε-caprolactone. The grafting degrees of PCL prepared from BCB-EO modified MWNTs can reach at least 94%, much higher than those prepared by other two conventional methods. TEM result shows that the morphology and thickness of the grafted PCLs strongly depend on the grafting degree and grafting method. The crystallization and melting behaviors of the MWNTs-grafted PCL were investigated. MWNTs can exert both nucleation and confinement effects on crystallization of the grafted PCL, leading to lower crystallinity but higher crystallization temperature (T_c) and melting temperature (T_m) of the grafted PCLs. It is found that crystallinity of the grafted PCLs increases with the grafting degree, but T_c and T_m also depend on the molecular weight.     

Multi-walled carbon nanotube/silver nanoparticles used for thermal transportation

A green method was applied to prepare composites of multi-walled carbon nanotubes (MWNTs) decorated with silver nanoparticles (Ag-NPs). MWNTs were functionalized using ball milling technology in the presence of ammonium bicarbonate, and the traditional method of silver mirror was used to decorate MWNTs to obtain Ag/MWNT composite. The obtained Ag/MWNT composites were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transmission infrared spectroscopy, and Brunauer–Emmet–Teller (BET) surface area analysis. SEM characterization showed that Ag-NPs distributed uniformly on the walls of MWNTs. The content and size of Ag-NPs could be controlled by adjusting the redox time. XRD patterns demonstrated that the Ag-NPs are composed of pure Ag and crystallized well. BET analysis indicated that the specific surface areas of Ag/MWNT decrease with increasing the content of Ag-NPs, and this result is similar to that of the literature. The measurement results of the thermal property showed that the thermal conductivity of the nanofluid containing Ag/MWNT composites was higher than that of nanofluid containing pristine or functionalized MWNTs.     

Design of an Assembly of Poly(benzimidazole), Carbon Nanotubes,and Pt Nanoparticles for a Fuel‐Cell Electrocatalyst with an Ideal Interfacial Nanostructure

A newly designed and fabricated novel nanocomposite composed of multiwalled carbon nanotubes (MWNTs), poly(benzimidazole) (PBI), and Pt nanoparticles. This composite is fabricated by the preparation of PBI‐wrapped MWNTs (MWNT/PBI), followed by Pt loading onto the MWNT/PBI. As a result of the PBI wrapping, the loading efficiency of the Pt nanoparticles onto the MWNTs is dramatically improved up to 58.8% compared to that of the pristine MWNTs (41.0%). The process also allows homogeneous Pt immobilization onto the surface of MWNTs without any strong oxidation process for the MWNTs that is typically used for metal supporting on carbon nanotubes. Far‐IR spectroscopy of the composite shows a peak from the Pt? N bonding, indicating that these improvements are derived from the coordination of the Pt ion with the PBI molecules. Cyclic voltammogram measurements reveal that the Pt nanoparticles deposited on the MWNT/PBI shows higher utilization efficiency (74%) for electrocatalysts compared to that on the pristine MWNT (39%).     

壳聚糖-氧化石墨烯/热塑性聚氨酯复合材料的原位溶液聚合及性能

为了制备高力学性能、阻隔性能和导热性能的热塑性聚氨酯(TPU)复合材料,采用改进的原位溶液聚合法,将壳聚糖改性的氧化石墨烯(CS-GO)与TPU预聚体接枝,再经扩链反应得到CS-GO/TPU复合材料。利用FTIR、XRD、FESEM对CS-GO进行表征,并采用万能试验机、氧气透过仪和导热仪对CS-GO/TPU复合材料的性能进行测试分析。结果表明:CS与GO之间存在氢键作用,CS-GO在TPU基体中的分散性优于GO。CS-GO的均匀分散有效阻隔了O₂的渗透,提高了CS-GO/TPU复合材料的阻隔性能。CS-GO与TPU基体之间的相互作用有利于应力载荷的传递和导热网络的形成,与纯TPU相比,当CS-GO含量为1wt%时,CS-GO/TPU复合材料的拉伸强度和断裂伸长率分别提高了106.8%和111.2%,导热系数提高了1.55倍。      

Preparation and Thermal Properties of Grafted CNTs Composites

Oleylamine(G18) and octanol(G8) were grafted onto the surfaces of the multi-walled carbon nanotubes(CNTs).The grafted CNTs were dispersed into palmitic acid(PA) and paraffin wax(PW) to prepare phase change composites.The heat storage/retrieval experiments showed that the composites kept stable after repeating melting and solidification for 80 times.The structure of the G18-CNT/PA and G8-CNT/PA was homogenous compared with the pristine CNT(P-CNT)/PA.The latent heat capacity(Ls) of solid liquid phase change of G18-CNT/PW was higher than that of PW while those of the G8-CNT/PW and P-CNT/PW were lower than that of PW.Compared with PA,all PA based composites with both P-CNTs and grafted CNTs decreased Ls evidently.The Ls values of G18-CNT composites in both matrices were higher than that of the counterparts of G8-CNT.The thermal conductivities of all the PA based composites in the study were higher than that of PA,as well as those of all the PW based composites.However,the thermal conductivities of the G18-CNT composites in both matrixes were lower than those of the G8-CNT composites in both matrixes at all measured temperatures.     

Effect of pyrene-modified multiwalled carbon nanotubes on the properties of epoxy composites

The block polymer of poly(styrene-b-pyrene) (PS-b-PAH) containing pyrene units was successfully applied on the surface of multiwalled carbon nanotubes (MWNTs) and the properties of nanocomposites were enhanced. The morphology of the modified MWNTs was characterized by transmission electron microscopy (TEM), and the results showed that PS-b-PAH helped effectively the MWNTs to disperse well in epoxy matrices, and these dispersed MWNTs were stabilized by the pyrene modifier. The mechanical properties of the composites, such as impact toughness and flexural strength, and the electrical conductivity of the nanocomposites, are improved significantly after the treatment of the MWNTs using PS-b-PAH. The results show that the mechanical and electrical properties of the modified MWNTs/epoxy composites with PS-b-PAH are obviously superior to those of pristine MWNTs/epoxy composites. The enhanced interfacial interactions lead to good dispersion of MWNTs in epoxy matrices, thus enhancing the mechanical and electrical properties of the nanocomposites.     

Polypropylene-clay composite prepared from Indian bentonite

In the present work, a set of experimental polypropylene (PP) clay composites containing pristine bentonite clay of Indian origin has been prepared and then characterized. The polymer clay composites are processed by solution mixing of polypropylene with bentonite clay using a solvent xylene and high speed electric stirrer at a temperature around 130°C and then by compression molding at 170°C. The mechanical properties of PP-clay composites like tensile strength, hardness and impact resistance have been investigated. Microstructural studies were carried out using scanning electron microscope and transmission electron microscope and the thermal properties were studied using differential scanning calorimeter. Mechanical properties of the prepared composites showed highest reinforcing and toughening effects of the clay filler at a loading of only 5 mass % in PP matrix. Tensile strength was observed to be highest in case of 5 mass % of clay loading and it was more than 14% of that of the neat PP, while toughness increased by more than 80%. Bentonite clay-PP composite (5 mass %) also showed 60% increase in impact energy value. However, no significant change was observed in case of hardness and tensile modulus. Higher percentages of bentonite clay did not further improve the properties with respect to pristine polypropylene. The study of the microstructure of the prepared polymer layered silicate clay composites showed a mixed morphology with multiple stacks of clay layers and tactoids of different thicknesses.     

Growth of multi-amine terminated poly(amidoamine) dendrimers on the surface of carbon nanotubes

An in situ repetitive divergent polymerization strategy was employed to grow multi-amine poly(amidoamine) dendritic macromolecules on the surfaces of multiwalled carbon nanotubes (MWNTs), affording novel three-dimensional (3D) molecular nanocomposites. The crude MWNTs were oxidized using H(2)SO(4)/HNO(3) = 3:1?(v/v) and then reacted with thionyl chloride, resulting in MWNTs functionalized with chlorocarbonyl groups (MWNT-COCl). MWNT-COCl, when reacted with an excess of ethylenediamine, produced amine-functionalized MWNT supported initiators (MWNT-NH(2)). Using the MWNT-NH(2) as the growth supporter and methylacrylate/ethylenediamine as building blocks, multi-amine dendritic poly(amidoamine) macromolecules were covalently grafted onto the sidewalls and ends of MWNTs via Michael addition reaction and amidation. Thermal gravimetric analysis (TGA) measurements showed that the weight ratio of the as-grown dendritic polymers on the MWNT surfaces lay in the 10%-50% range. The products were also characterized by Fourier transform infrared (FTIR), Raman, nuclear magnetic resonance (NMR), and transmission electron microscopy (TEM) analysis. The results indicate that the dendrimers are grafted onto the surface of MWNTs. The as-prepared nanocomposites exhibit excellent dispersibility in water.     

Characterizing the surface properties of carbon nanotubes by inverse gas chromatography

Inverse gas chromatography (IGC) was used to characterize the surface properties of pristine multi-walled carbon nanotubes (MWNTs), as well as the poly(acrylic acid) sidewall covalently functionalized MWNTs (PAA-g-MWNTs) and hydroxyl group directly grafted MWNTs (MWNTols). The dispersive component of the surface energy ( ) and the acid/base character of these samples’ surfaces were estimated by the retention time with different non-polar and polar probes at infinite dilution region. The specific free energy (ΔG ^AB) and the enthalpy (ΔH ^AB) of adsorption corresponding to acid–base surface interactions were determined. By correlating ΔH ^AB with the donor and acceptor numbers of the probes, the acidic (K _A) and the basic K _D parameters of the samples’ were calculated. The results show that chemical modification successfully reduces the dispersive component of the surface energy of MWNTs. Furthermore, MWNTs grafted with hydroxyl groups exhibit a more basic character, while MWNTs grafted with poly(acrylic acid) show a more acidic character. Overall, IGC provides useful complementary information on the changes resulted from the chemical modifications of the surface.     

Surface-functionalized MWNTs with emeraldine base: preparation and improving dielectric properties of polymer nanocomposites

A comparative study of the dielectric properties of poly(vinylidene fluoride) (PVDF) based nanocomposites with pristine multiwalled carbon nanotubes (MWNTs) and surface-modified MWNTs with core/shell structure (denoted as MEB) as fillers, was reported. Compared with MWNTs/PVDF composites, the MEB/PVDF composites exhibited lower loss tangent and higher dielectric permittivity. It is suggested that the conductive/nonconducting core/shell structure of the MEB filler is the main cause of the improved dielectric properties. Percolation based MWNTs networks is in charge of the improvement of dielectric permittivity, and the nonconducting emeraldine base layer of the MEB filler supports the low loss tangent and low conductivity in the MEB/PVDF composites.     

Synthesis,characteristic, and flammability of modified carbon nanotube/poly(ethylene-<Emphasis Type="Italic">co</Emphasis>-vinyl acetate) nanocomposites containing phosphorus and silicon

A novel flame retardant containing phosphorus–silicon, spirocyclic pentaerythritol bisphosphorate disphosphorylchloride/9,10-dihydro-9-oxa-10-phosphaphanthrene-10-oxide/vinyl methyl dimethoxysilane (SPDV), has been used to modify multiwalled carbon nanotubes (MWNTs) and the m-MWNTs (MWNTs-g-SPDV) was obtained by the covalent grafting of SPDV onto the surfaces of MWNTs. And then the according poly(ethylene-co-vinyl acetate) nanocomposites were prepared via melt blending. Transmission electron microscopy (TEM) results showed that a core–shell nanostructure with MWNTs as the hard core and SPDV as the soft shell was formed, and the resultant m-MWNTs can achieve better dispersion than pristine MWNTs in EVM matrix. Cone calorimeter results showed that better flame retardancy was obtained for EVM/m-MWNTs nanocomposites. Mechanical measurements showed that the Young’s modulus increases due to the presence of MWNTs or m-MWNTs. The flammability and mechanical properties of the nanocomposites are strongly dependent on the dispersion state of nanotubes.     

接枝物包覆合成云母填充聚丙烯复合材料的界面形态及性能

采用不同用量配比马来酸酐接枝均聚聚丙烯(iPP-MA)及马来酸酐接枝聚烯烃弹性体(POE-MA)对合成云母进行包覆后,填充到均聚聚丙烯(iPP)中制备复合材料,对包覆云母沉降行为及复合材料断面形态、性能进行研究。结果表明,固定接枝物用量,随着POE-MA含量的增多,复合材料界面结合呈现改善趋势。iPP-MA对材料屈服前比基本断裂功(We,y)的提高有利,而POE-MA对材料屈服前比非基本断裂功(β′Wp,y)提高有利。     

高岭土接枝流滴剂/聚乙烯复合材料的制备及性能

通过表面接枝技术将流滴剂十八烷基二乙醇胺丙烯酸单酯（AAM）接枝到高岭土（Ka）表面,制得Ka与AAM接枝物（Ka-g-AAM）;将Ka-g-AAM与线性低密度聚乙烯（LLDPE）熔融挤出,制备了Ka-g-AAM/LLDPE复合材料;利用FTIR、SEM、DSC和加速流滴仪等对Ka-g-AAM/LLDPE复合材料的结构和性能进行了表征。结果表明,与AAM/LLDPE和Ka-AAM/LLDPE复合材料相比,Ka-g-AAM/LLDPE复合材料中LLDPE的熔融温度、结晶温度和力学性能变化不大;Ka-g-AAM/LLDPE复合材料薄膜在60℃加速流滴期达23天,比AAM/LLDPE复合材料延长了4天。      

PA6(MWNTs)纳米纤维增强PMMA透光复合材料

以尼龙6(PA6)为载体,结合同轴共纺技术将多壁碳纳米管(MWNTs)均匀包裹在PA6/PMMA体系的芯层中,再利用热压成型技术将壳层聚甲基丙烯酸甲酯(PMMA)熔融,从而制备出PA6(MWNTs)均匀分散的增强透光复合材料.实验中分别考察不同含量的MWNTs对复合材料形貌、力学性能的影响.结果表明,采用同轴共纺工艺能...     

Fabrication of polypropylene/carbon nanotubes composites via a sequential process of (rotating solid-state mixing)-plus-(melt extrusion)

In this study, a simple but effective method to realize excellent comprehensive performances in polypropylene (PP)/multi-walled carbon nanotubes (MWNTs) was developed. Before melt extrusion, solid-state iPP powders and MWNTs were pre-mixed upon high-speed rotating. By this way, the dispersion extent of nanotubes was significantly improved as comparing to the common one-step melt extrusion strategy. As validated by scanning electron microscopy, most of MWNTs exist as a form of filament bundles with size of hundreds nanometers; no obvious agglomerate was found even at high MWNTs content, 5%. The improvements of the major mechanical properties and electric conductivity were much efficient for the composites obtained via the two-step process of rotating solid-state mixing (RSSM)-plus-melt extrusion. The tensile strength, Young’s modulus and impact strength at 5% MWNTs content were enhanced for 35%, 42% and 45%, respectively, indicating an excellent strength-rigidity-toughness balance, which was hardly achieved in polyolefin/carbon nanotubes composite. It is believed that the method developed in this study is so far the most effective and convenient for efficiently dispersing nanotubes into the nonpolar, intractable thermoplastics and resulting in good properties, among a variety of fabrication method suggested in the previous researches. Importantly, the used RSSM equipment is a kind of frequently used dispersion machine, thus it has tremendous potential to be applied in industrial producing immediately.     

Dispersions of carbon nanotubes/polyhedral oligomeric silsesquioxanes hybrids in polymer: the mechanical,electrical and EMI shielding properties

A hybrid was synthesized by grafting polyhedral oligomeric silsesquioxane (POSS) to multiwalled carbon nanotubes (MWCNTs). The MWCNT/polymer composites produced using silsesquioxane grafted MWCNTs as a filler had a high electromagnetic interference shielding effectiveness. Homogeneous dispersion of silsesquioxane grafted MWCNTs occurred throughout the polymer without any aggregation, while a pristine MWCNT aggregate that integrated several nanotube domains existed in the polymer matrix. A comparative study of the optical transmittance, electrical, and electromagnetic interference shielding properties of poly(l-lactide) (PLLA)/MWCNT composites based on pristine MWCNTs and silsesquioxane grafted MWCNTs was carried out. A high electromagnetic interference shielding effectiveness (15–16 dB) was obtained in the 36–50 GHz range at a relatively low filler loading (4 wt%) in the PLLA/silsesquioxane grafted MWCNT composite.     

Synthesis of nano-carbon (nanotubes,nanofibres, graphene) materials

In the present study, we report the synthesis of carbon nanotubes (CNTs) using a new natural precursor: castor oil. The CNTs were synthesized by spray pyrolysis of castor oil-ferrocene solution at 850°C under an Ar atmosphere. We also report the synthesis of carbon nitrogen (C-N) nanotubes using castor oil-ferrocene-ammonia precursor. The as-grown CNTs and C-N nanotubes were characterized through scanning and transmission electron microscopic techniques. Graphitic nanofibres (GNFs) were synthesized by thermal decomposition of acetylene (C₂H₂) gas using Ni catalyst at 600°C. As-grown GNFs reveal both planar and helical morphology. We have investigated the structural and electrical properties of multi-walled CNTs (MWNTs)-polymer (polyacrylamide (PAM)) composites. The MWNTs-PAM composites were prepared using as purified, with ball milling and functionalized MWNTs by solution cast technique and characterized through SEM. A comparative study has been made on the electrical property of these MWNTs-PAM composites with different MWNTs loadings. It is shown that the ball milling and functionalization of MWNTs improves the dispersion of MWNTs into the polymer matrix. Enhanced electrical conductivity was observed for the MWNTs-PAM composites. Graphene samples were prepared by thermal exfoliation of graphite oxide. XRD analysis confirms the formation of graphene.