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.     

Studying the growth of carbon nanotubes on carbon fibers surface under different catalysts and electrochemical treatment conditions

A special electrochemical anodic oxidation (EAO) method was applied to modify the surface of carbon fibers (CFs) with fatty alcohol polyoxyethylene ether phosphate (O₃P), triethanolamine (TEA), fatty alcohol polyoxyethylene ether ammonium phosphate (O₃PNH₄), and ammonium bicarbonate (NH₄HCO₃) used as the electrolyte respectively. Then different catalysts, including Ni, Co, and Cu, were used to catalyze the growth of carbon nanotubes (CNTs) on the surface of CFs. The variation regulation of structure and property of CNTs on CFs surface was investigated by different methods. The results showed that the optimal effect of surface modification of CFs was achieved when O₃PNH₄ served as an electrolyte and the optimal electrochemical treatment intensity (ETI) was 100C/g. Also, with temperature variety, there are different microstructure changes for CNTs that adopt different catalysts. Through the experiment, a uniform catalyst coating was obtained on the surface of CFs after reduction process, which laid the foundation for the growth of uniform and regular CNTs.     

A one-step hot pressing molding method of polyacrylonitrile carbon fibers: influence on surface morphology,microstructure and mechanical property

Carbon fibers (CFs) have been the most popular material for decades and compound into various materials because of their excellent performance. Herein, a novel one-step hot pressing molding is proposed to prepare polyacrylonitrile (PAN) CFs, eliminating the time-consuming and energy-consuming thermal stabilization stage. The fibers are tiled and pressed tightly between the two plates. The unit is then carbonized in a tubular furnace. Hot pressing enforced the fiber structure to be cyclized and reduces the damage of fibers by mitigating the escape of heteroatoms gas. The thermoplasticity of PAN fibers is innovatively utilized in the preparation of carbon fibers by hot pressing, which is able to improve density and repair the cracks. The density and tensile strength of fibers at 900 °C have reached to 1.70 g cm^?3 and 1.1GPa. The CFs obtained by hot pressing molding have not only a smooth surface morphology, but also a high degree of microstructure cyclization. Hot pressing molding can not only realize the function of thermal stability stage, but also simplify the process, save energy and time, and reduce the cost.

     

乙炔热裂解沉积对PAN基炭纤维性能的影响

利用有机溶剂去除PAN基炭纤维表面的集束剂与染剂.然后通过乙炔热裂解沉积对其进行表面改性,以期获得兼具高机械强度和优良导电性的高性能PAN基炭纤维.采用SEM、AFM、XRD、Raman等方法对PAN基炭纤维在改性前后的微观结构、结晶性、抗拉强度、弹性模量、导电性等进行了分析.研究结果表明采用化学气相沉积法可以提高或者明显改善石墨化处理后的PAN基炭纤维的力学性能(抗拉强度为2GPa,弹性模量为270GPa)和导电性(5×10-4Ω·cm).     

Interfacially reinforced methylphenylsilicone resin composites by chemically grafting multiwall carbon nanotubes onto carbon fibers

Both silane and multiwall carbon nanotubes (CNTs) were grafted successfully onto carbon fibers (CFs) to enhance the interfacial strength of CFs reinforced methylphenylsilicone resin (MPSR) composites. The microstructure, interfacial properties, impact toughness and heat resistance of CFs before and after modification were investigated. Experimental results revealed that CNTs were grafted uniformly onto CFs using 3-aminopropyltriethoxysilane (APS) as the bridging agent. The wettability and surface energy of the obtained hybrid fiber (CF-APS-CNT) were increased obviously in comparison with those of the untreated-CF. The CF-APS-CNT composites showed simultaneously remarkable enhancement in interlaminar shear strength (ILSS) and impact toughness. Moreover, the interfacial reinforcing and toughening mechanisms were also discussed. In addition, Thermogravimetric analysis and thermal oxygen aging experiments indicated a remarkable improvement in the thermal stability and heat oxidation resistance of composites by the introduction of APS and CNTs. We believe the facile and effective method may provide a novel interface design strategy for developing multifunctional fibers.     

Carbon nanotube reinforced small diameter polyacrylonitrile based carbon fiber

Polyacrylonitrile (PAN) and PAN/carbon nanotube (CNT) composite (99/1) based carbon fibers with an effective diameter of about 1 μm have been processed using island-in-a-sea bi-component cross-sectional geometry and gel spinning. PAN/CNT (99/1) based carbon fibers processed using this approach exhibited a tensile strength of 4.5 GPa (2.5 N/tex) and tensile modulus of 463 GPa (257 N/tex), while these values for the control PAN-based carbon fiber processed under the similar conditions were 3.2 GPa (1.8 N/tex) and 337 GPa (187 N/tex), respectively. Properties of these 1 μm diameter carbon fibers have been compared to the properties of the larger diameter (>6 μm) PAN and PAN/CNT based carbon fibers.     

Correlation between electrokinetic potential, dispersibility, surface chemistry and energy of carbon nanotubes

This paper proposes the correlation between the electrokinetic potential, dispersibility in solvents, surface energy and oxygen content of carbon nanotubes (CNTs) affected by functionalization. Colloidal systems consisting of CNTs with varying degrees of dispersion are prepared and characterized to evaluate CNT dispersibility and suspension stability in solvents with different polarities. The results show that an absolute value of zeta potential at about 25 mV is closely related to the micro- and macroscopic dispersion of CNTs, whereas a high absolute value of 40 mV is regarded as an indication of high quality CNT dispersion with much enhanced suspension stability in solvents. The absolute zeta potential value increases consistently with increasing degree of CNT functionality, the increase being most pronounced in a hydrophilic liquid such as water. A linear correlation is established between the surface energy of a CNT film and the oxygen to carbon ratio of CNT surface. The CNT dispersibility in a liquid is determined not only by their physical states, but also by the hydrophilicity and surface functionality of CNTs, all of which are reflected by zeta potential.     

Role of carbon atoms in plasma-enhanced chemical vapor deposition for carbon nanotubes synthesis

The role of carbon atoms in a dc plasma-enhanced chemical vapor deposition for carbon nanotubes (CNTs) synthesis was investigated. It was observed that at 1.33 kPa pressure of CH₄ gas in plasma, a high value of the ratio between the intensities of the graphite peak (G peak) and the disorder peak (D peak) in the Raman spectrum corresponds to the maximum value of the excited C number density in the vicinity of the Si substrate. It was found that a CH₄ gas pressure higher than 1.33 kPa leads to an increase of the relative density of the C₂, C₃ molecules and the clusters, and to a decrease of the C excited atom number density in plasma. The presence of a high amount of sp²-graphite in the composition of CNTs observed in Raman spectrum was also confirmed by the measurement of the IR-active G peak at 1584 cm^- 1 in the transmission spectrum.     

Selective-catalyst formation for carbon nanotube growth by local indentation pressure

We studied the selective formation of Co catalyst particles as a function of indentation pressure. We subjected a Co (8 nm thickness)/Si substrate pre-annealed at 600 °C to indentation processing. The catalytic function was confirmed in the indentations by the selective growth of carbon nanotubes (CNTs) at 800 °C. The number density of CNTs against the indentation pressure was investigated against indentation loads for two types of indenter: a Berkovich indenter with a ridge angle of 115° and a Berkovich indenter with a ridge angle of 90°. The pressures above 7 GPa applied by the former indenter enhanced Co atomization acting as a catalyst function for CNT growth (35 CNTs in one indentation). In contrast to this, the number of CNTs was markedly reduced when the latter indenter was used with pressures less than 3 GPa. The pop-out phenomenon was observed in unloading curves at pressures above 7 GPa. These results indicate that metastable Si promotes the self-aggregation of catalyst particles (Co) leading to the selective growth of CNTs within indentations at pressures above 7 GPa.     

Fabrication of carbon papers using polyacrylonitrile fibers as a binder

Carbon papers (CPs) have been fabricated using wet-laying carbon fibers (CFs) and polyacrylonitrile (PAN) fibers. Scanning electron microscopy revealed that the PAN fibers tightly interconnected the CF junctions with the pores between the fibers. The tensile strength of the carbon webs (CWs) increased as the fraction of PAN fibers used as the binder increased. The CW fabricated with 0.15 wt% PAN fibers had a tensile strength six times greater than that of the CW without PAN fibers. Moreover, by mixing the CFs with PAN fibers in water, the CFs separated from each other in the webs due to the interruption of hydrophobicity between the CFs. After mixing with PAN fibers, the CWs were carbonized at 1200 °C in the presence of a phenolic resin. The PAN fibers maintained their morphology due to their high carbon content after carbonization. The electrical resistivity of the CPs with high PAN fiber content was significantly lower than that of a CP without PAN fibers due to the interconnection of the CFs by the carbonized PAN fibers.     

Effect of a multiscale reinforcement by carbon fiber surface treatment with graphene oxide/carbon nanotubes on the mechanical properties of reinforced carbon/carbon composites

An effective carbon fiber/graphene oxide/carbon nanotubes (CF-GO-CNTs) multiscale reinforcement was prepared by co-grafting carbon nanotubes (CNTs) and graphene oxide (GO) onto the carbon fiber surface. The effects of surface modification on the properties of carbon fiber (CF) and the resulting composites was investigated systematically. The GO and CNTs were chemically grafted on the carbon fiber surface as a uniform coating, which could significantly increase the polar functional groups and surface energy of carbon fiber. In addition, the GO and CNTs co-grafted on the carbon fiber surface could improve interlaminar shear strength of the resulting composites by 48.12% and the interfacial shear strength of the resulting composites by 83.39%. The presence of GO and CNTs could significantly enhance both the area and wettability of fiber surface, leading to great increase in the mechanical properties of GO/CNTs/carbon fiber reinforced composites.     

Characteristics of powder metallurgy pure titanium matrix composite reinforced with multi-wall carbon nanotubes

By using pure titanium powder coated with un-bundled multi-wall carbon nanotubes (MWCNTs) via wet process, powder metallurgy (P/M) titanium matrix composite (TMC) reinforced with the CNTs was prepared by spark plasma sintering (SPS) and subsequently hot extrusion process. The microstructure and mechanical properties of P/M pure titanium and reinforced with CNTs were evaluated. The distribution of CNTs and in situ formed titanium carbide (TiC) compounds during sintering was investigated by optical and scanning electron microscopy (SEM) equipped with EDS analyzer. The mechanical properties of TMC were significantly improved by the additive of CNTs. For example, when employing the pure titanium composite powder coated with CNTs of 0.35 mass%, the increase of tensile strength and yield stress of the extruded TMC was 157 MPa and 169 MPa, respectively, compared to those of extruded titanium materials with no CNT additive. Fractured surfaces of tensile specimens were analyzed by SEM, and the uniform distribution of CNTs and TiC particles, being effective for the dispersion strengthening, at the surface of the TMC were obviously observed.     

Mechanical characterization of copper coated carbon nanotubes reinforced aluminum matrix composites

In this investigation, carbon nanotube (CNT) reinforced aluminum composites were prepared by the molecular-level mixing process using copper coated CNTs. The mixing of CNTs was accomplished by ultrasonic mixing and ball milling. Electroless Cu-coated CNTs were used to enhance the interfacial bonding between CNTs and aluminum. Scanning electron microscope analysis revealed the homogenous dispersion of Cu-coated CNTs in the composite samples compared with the uncoated CNTs. The samples were pressureless sintered under vacuum followed by hot rolling to promote the uniform microstructure and dispersion of CNTs. In 1.0 wt.% uncoated and Cu-coated CNT/Al composites, compared to pure Al, the microhardness increased by 44% and 103%, respectively. As compared to the pure Al, for 1.0 wt.% uncoated CNT/Al composite, increase in yield strength and ultimate tensile strength was estimated about 58% and 62%, respectively. However, in case of 1.0 wt.% Cu-coated CNT/Al composite, yield strength and ultimate tensile strength were increased significantly about 121% and 107%, respectively.     

A study on the tensile response and fracture in carbon nanotube-based composites using molecular mechanics

A study on the mechanical properties of polyethylene and carbon nanotube (CNT) based composites is presented using molecular mechanics simulations. The systems being investigated consist of amorphous as well as crystalline polyethylene (PE) composites with embedded single-walled CNTs. All the systems are subjected to quasi-static tensile loading, with the assumption that no cross-link chemical bonds exist between the CNT and polyethylene matrix in the case of nanocomposites. Based on the numerical simulations, we report Young’s moduli (C₃₃) of 212–215 GPa for crystalline PE, which closely match the experimental measurement. Furthermore, elastic stiffness of 3.19–3.69 GPa and tensile strength of 0.21–0.25 GPa are obtained for amorphous PE. The tensile responses are found to be highly isotropic. In the case of crystalline PE reinforced by long through CNTs, moderate improvements in the tensile strength and elastic stiffness are observed. However, the results differ from the predictions using the rule of mixtures. On the other hand, although significant increase in the overall tensile properties is observed when amorphous PE is reinforced by long through CNTs, the load transfer at the nanotube/polymer interface has negligible effect. Finally, degradations in both tensile strength and elastic stiffness are reported when amorphous PE is reinforced by embedded CNTs. The study presented indicates the importance of specific CNT and polymer configurations on the overall properties of the nanocomposite.     

A Novel Multiscale Reinforcement by In-Situ Growing Carbon Nanotubes on Graphene Oxide Grafted Carbon Fibers and Its Reinforced Carbon/Carbon Composites with Improved Tensile Properties

In-situ growing carbon nanotubes(CNTs)directly on carbon?bers(CFs)always lead to a degraded tensile strength of CFs and then a poor?ber-dominated mechanical property of carbon/carbon composites(C/Cs).To solve this issue,here,a novel carbon?ber-based multiscale reinforcement is reported.To synthesize it,carbon?bers(CFs)have been?rst grafted by graphene oxide(GO),and then carbon nanotubes(CNTs)have been in-situ grown on GO-grafted CFs by catalytic chemical vapor deposition.Characterizations on this novel reinforcement show that GO grafting cannot only nondestructively improve the surface chemical activity of CFs but also protect CFs against the high-temperature corrosion of metal catalyst during CNT growth,which maintains their tensile properties.Tensile property tests for unidirectional C/Cs with different preforms show that this novel reinforcement can endow C/C with improved tensile properties,32% and 87%higher than that of pure C/C and C/C only doped with in-situ grown CNTs.This work would open up a possibility to fabricate multiscale C/Cs with excellent global performance.     

A systematic investigation into a novel method for preparing carbon fibre–carbon nanotube hybrid structures

By electrospraying solvent dispersed carbon nanotubes (CNTs) with a binder onto carbon fibre (CF), hybrid structures, with an end aim to improve interfacial bonding in composites, were formed. The electrospray parameters controlling the modification of the CNT morphologies were studied. High-speed camera observations found applied voltage was critical for determining spray mode development. Electric field simulations revealed a concentrated electric field region around each fibre. Both voltage and distance played an important role in determining the CNT morphology by mediating anchoring strength and electric field force. The forming mechanism investigation of different surface morphologies suggested that binder with appropriate wetness gives freedom to the CNTs, allowing them to orientate radially from the CF surface. Linear density (LD) measurements and thermogravimetric analysis revealed that a 10 min coating increased the LD of a single CF filament by up to 31.7% while a 1 h treatment increased fibre bundle mass by 1%.     

Microstructure of carbon nanotubes/PET conductive composites fibers and their properties

Poly(ethylene terephthalate) (PET) resin has been compounded with carbon nanotubes (CNTs) using a twin-screw extruder. The composites of 4 wt% CNTs in PET had a volume electrical resistance of 10³ Ω cm, which was 12 orders lower than pure PET. The volume electrical conductivity of CNTs/PET composites with different CNTs containing followed a percolation scaling law of the form σ = κ(ρ − ρ_c)^t well. Scanning electron microscopy (SEM) micrograph showed that CNTs had been well dispersed in PET matrix. Optical microscopy micrograph showed that discontinuity of conductive phase existed in some segments of composite fiber. Rheological behavior of CNTs/PET composites showed that the viscosity of CNTs/PET composites containing high nanotube loadings exhibited a large decrease with increasing shear frequency. Crystallization behavior of CNTs/PET composites was studied by differential scanning calorimetry (DSC) and the nucleating effect of CNTs in the cooling crystallization process of PET was confirmed. Composite fiber was prepared using the conductive CNTs/PET composites and pure PET resin by composite spinning process. Furthermore, cloth was woven by the composite fiber and common terylene with the ratio 1:3. The cloth had excellent anti-static electricity property and its charge surface density was only 0.25 μC/m².     

Improving mechanical and electrical properties of oriented polymer-free multi-walled carbon nanotube paper by spraying while winding

In this study, a new method is introduced for fabricating carbon nanotube (CNT) paper, in which the solvent is sprayed on the CNT sheet while it is wound on a rotating mandrel. As the solvent evaporated, the capillary force pulls CNT closer together, resulting in a CNT paper with a high degree of alignment and a high packing density. Three batches of multi-walled CNTs with different wall thicknesses, tube diameters and lengths are utilized for synthesizing highly oriented CNT papers. It is found that CNTs with smallest diameter of 8 nm form strongest CNT paper with a tensile strength of 563 MPa and a tensile modulus of 15 GPa, while that made with CNTs of 10 nm diameter shows the highest electrical conductivity of 5.5 × 10⁴ S/m.     

Free standing thin webs of porous carbon nanofibers of polyacrylonitrile containing iron-oxide by electrospinning

We present for the first time a novel strategy of producing carbon nanofibers (CNFs) using polyacrylonitrile (PAN)-incorporated with iron oxide particles using electrospinning method. The successfully electrospun iron oxide-incorporated PAN thin white web was stabilized in air. Formation of iron oxide nanoparticles resulted in the formation of porous structure on the web. Following heat treatment to the stabilized fibers to about 1000 °C in an N₂ atmosphere resulted in CNFs with specific surface areas, which ranged from 310, 420, and 550 m² g^− 1, for PAN containing 1, 2 and 3 wt.% iron oxide, respectively.     

Enhancement of field emission property from hills-like carbon nanotubes film

Improved field emission property of carbon nanotubes (CNTs) is achieved by using NiTi alloy film as catalyst under optimized condition. The NiTi alloy films are prepared by magnetron co-sputtering process and the CNTs films are synthesized by thermal chemical vapor deposition. With the increase of the Ni/Ti ratio from 19 at.% to 95 at.%, the CNTs density increases from discrete cluster to dense network, and the optimized field emission property of CNTs film is found at the medium density. However, the field emission property is significantly enhanced when the Ni/Ti ratio is about 76 at.%, and it is supposed to attribute to the combined effect of the hills-like surface enhancement and the intrinsic emission properties of CNTs.