Growth of carbon nanotubes on carbon fibers using the combustion flame oxy-acetylene method

Multi-walled carbon nanotubes (MWCNTs) were directly grown on carbon fibers (CFs) using the combustion flame oxy-acetylene method. Ferrocene deposited on the fiber surface acts as a catalyst for carbon nanotubes (CNTs) growth. The effects of ferrocene concentration on the morphology of the CNTs coating were investigated. Growth temperature ranges from 500 to 650 °C at atmospheric pressure, while growth surface is a continuous 10 × 1000 mm² tape. CNTs are produced with a dense entanglement, covering the CFs uniformly. Tube outer diameters are in the range of 20–40 nm. Tube length is quite long (about 4–5 μm) and uniform. Particularly, growth times are very short: about 0.3–0.6 s. Growth morphology and other characteristics of the as-grown tubes were examined by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Energy dispersive X-ray (EDX) and by Raman spectroscopy.     

Effect of pyrolysis temperature on cobalt phthalocyanine supported on carbon nanotubes for oxygen reduction reaction

Cobalt phthalocyanine (CoPc)-impregnated functionalized multi-walled carbon nanotubes (CNTs) were used as nonprecious electrocatalysts for oxygen reduction reaction (ORR). The electrocatalysts were thermally treated at temperatures ranging from 450 to 850 °C, and the effect of pyrolysis temperature and their relationship to the electrocatalytic activity for ORR were investigated. Thermo gravimetric analysis, X-ray diffraction, and electron microscopy were used to study the thermal stability, crystal structure, and morphology of these catalysts. Cyclic voltammetry and rotating disk electrode results showed that CoPc/CNTs pyrolyzed at a temperature of 550 °C had the highest electrocatalytic activity for ORR, and the catalytic activity decreased with further increase in pyrolysis temperature. X-ray photoelectron spectroscopy showed decrease in functional groups at a temperature higher than 550 °C, correlating with the decreased catalytic activity. The result suggests that oxygen functional groups introduced by acid oxidation for anchoring the CoPc on CNT plays a major role in determining the electrocatalytic activity.     

Growth of carbon nanotubes on the surface of carbon fiber using Fe–Ni bimetallic catalyst at low temperature

This article provides a method for growing carbon nanotubes(CNTs) on carbon fibers(CFs) using iron and nickel as catalysts at low temperatures. This series of experiments was conducted in a vacuum chemical vapor deposition(CVD)furnace. It is found that Fe–Ni catalysts, which have a certain thickness and can be better combined with resins when manufacturing composite materials, are more ideal for the growth of CNTs than single metal catalysts. At the same time, it is proved that the CVD process worked best at 450 °C. The mechanical property test proved the reinforcing effect of CNTs on carbon fiber, the single-filament tensile strength of CFs obtained by using Fe–Ni catalyst at 450 °C was 11% higher than that of Desized CFs. The bonding strength of carbon fiber and resin has also been significantly improved. When synthesized at low temperature, CNTs exhibited a hollow multi-wall structure.     

The effect of temperature on the morphology and chemical surface properties of nitrogen-doped carbon nanotubes

One of the most effective ways to tune the physical and chemical properties of CNTs is to dope them with a foreign element, such as nitrogen. Nitrogen atoms that are incorporated into the CNT structure can drastically change the properties of CNTs. The properties of nitrogen-doped carbon nanotubes (N-CNTs) originate from their structure; thus, it is practical to create a desired structure during synthesis. We have investigated the effects of synthesis parameters, mainly temperature, on various characterizations of N-CNTs, such as their morphologies, dimensions (diameter and length), defects, nitrogen inclusions and thermal stability. The results revealed strong correlations between the synthesis parameters and the properties of the synthesized N-CNTs. XPS characterization indicated that the percentage of nitrogen inclusion decreased with increasing synthesis temperature up to 850 °C and then increased at 950 °C. Raman spectroscopy showed a decrease in the number of defects in the N-CNT structure with increasing synthesis temperature. Finally TGA demonstrated a trend of increasing thermal stability of N-CNTs with increasing synthesis temperature, up to 850 °C then a reduced thermal stability at 950 °C. Based on these results, one can control the properties of N-CNTs and obtain materials with the desired characteristics by choosing the appropriate synthesis conditions.     

Influence of CVD parameters on Co-TiO2/CNT properties: A route to enhance energy harvesting from sunlight

Carbon nanotubes (CNTs) have been employed to enhance the photoactivity of titanium dioxide (TiO₂). In this work, CNTs were deposited by chemical vapor deposition (CVD) onto the surface of anodized Co-TiO₂ nanotubes. The influence of CVD parameters (time and temperature) on the Co-TiO₂/CNT structure and properties was investigated. We studied three synthesis times (10, 20, and 30 min) and two synthesis temperatures (700 and 800°C). The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and X-ray diffraction (XRD). The photocurrent performance of the electrodes was determined by linear voltammetry. The results showed the successful formation of Co-TiO₂/CNT hybrid structures. The shortest synthesis time produced higher quality CNTs. The samples synthesized at 700 and 800°C for 10 min exhibited a current density of 1.13 mA.cm⁻² and 7.84 mA.cm⁻², respectively, which is 9 and 65 times greater than the Co-TiO₂ sample. The synergistic effect of the CNT deposition and the crystalline phase composition significantly improved the photoresponse of TiO₂. The proper choice of synthesis parameters allowed the control of the sample structure, leading to the production of electrodes with better light-harvesting performance.     

High resolution transmission electron microscopy study on polyacrylonitrile/carbon nanotube based carbon fibers and the effect of structure development on the thermal and electrical conductivities

Polyacrylonitrile (PAN) and PAN/carbon nanotube (CNT) based carbon fibers at various CNT content have been processed and their structural development was investigated using high resolution transmission electron microscope (HR-TEM). In CNT containing carbon fibers, the CNTs act as templating agents for the graphitic carbon structure development in their vicinity at the carbonization temperature of 1450 °C, which is far below the graphitization temperature of PAN based carbon fiber (>2200 °C). The addition of 1 wt% CNT in the gel spun precursor fiber results in carbon fibers with a 68% higher thermal conductivity when compared to the control gel spun PAN based carbon fiber, and a 103% and 146% increase over commercially available IM7 and T300 carbon fibers, respectively. The electrical conductivity of the gel spun PAN/CNT based carbon fibers also showed improvement over the investigated commercially available carbon fibers. Increases in thermal and electrical conductivities are attributed to the formation of the highly ordered graphitic structure observed in the HR-TEM images. Direct observation of the graphitic structure, along with improved transport properties in the PAN/CNT based carbon fiber suggest new applications for these materials.     

Development of multiwalled‐carbon‐nanotube‐welded carbon fibers and evaluation of the interfacial strength in epoxy composites

Multiwalled carbon nanotube (MWCNT)‐welded carbon fibers (CFs) were prepared by a three‐step process, which included polyacrylonitrile (PAN) coating, MWCNT absorption, and heat treatment. The structure of these materials was characterized by scanning electron microscopy, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. The MWCNTs were uniformly assembled on the surface of the PAN‐coated CFs and welded by a PAN‐based carbon layer after heat treatment. The contact angle of the MWCNT‐welded CFs in the epoxy resins was 41.70°; this was 22.35% smaller than that of the unsized CFs. The interfacial shear strength (IFSS) of the MWCNT‐welded CF–epoxy composite was 83.15 MPa; this was 28.89% higher than that of the unsized CF–epoxy composite. The increase in the IFSS was attributed to the enhancement of adhesions between the CFs and polymer matrix through the welding of the MWCNTs on the CFs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45027.     

CVD growth and field electron emission of aligned carbon nanotubes on oxidized Inconel plates without addition of catalyst

Direct growth of carbon nanotubes (CNTs) on Inconel 600 sheets was investigated using plasma enhanced hot filament chemical vapor deposition in a gas mixture of methane and hydrogen. The Inconel 600 sheets were oxidized at different temperatures (800 °C, 900 °C, 1000 °C, and 1100 °C) before CNT deposition. The structure and surface morphology of the pre-treated substrate sheets and the deposited CNTs were studied by scanning electron microscopy (SEM) and X-ray diffraction. The field electron emission (FEE) properties of the CNTs were also tested. The SEM results show that well aligned CNTs have been grown on the pre-treated Inconel sheets without addition of any catalysts and the higher treatment temperature resulted in CNTs with better uniformity, indicating that the oxidation pre-treatment of the substrate is effective to enhance the CNT growth. FEE testing shows that CNTs with better height uniformity exhibit better FEE characteristics.     

Synthesis and characterisation of silica–carbon nanotube hybrid microparticles and their effect on the electrical properties of poly(vinyl alcohol) composites

Hybrid silica–carbon nanotube (CNT) particles with a radial symmetry were produced by the growth of nanotubes onto spherical, mesoporous silica gel particles using the floating catalyst chemical vapour deposition (FC-CVD) method. Characterisation of the hybrid particles, using electron microscopy, Raman spectroscopy and thermogravimetry showed the geometry and porosity of the silica particles to influence the alignment and density of the CNTs produced. CNT growth initiated in the pores of the gel particles and three hours of CVD growth were required to get extensive surface coverage. In the early stages of growth, the reactants diffused inside the mesoporous silica and consequently the CNTs grew mainly within the silica gel rather than on the surface. Some indication of catalyst templating was observed within the smaller (<10 nm) pores, but this templating did not result in aligned CNTs. Composite films of hybrid silica–CNT particles in poly(vinyl alcohol) were cast and their impedance measured. An electrical percolation threshold of 0.62 wt.% was found for the hybrid particles, of which 0.20 wt.% were CNTs.     

Low temperature graphitization of interphase polyacrylonitrile (PAN)

Ordered polyacrylonitrile (PAN) interphase structures were formed in solution-cast PAN/carbon nanotube (CNT) composite films by enhancing polymer crystallization conditions and processing parameters for five types of CNTs. All film samples were heat-treated using similar stabilization and carbonization (up to 1100 °C) processes. Both the precursor and carbonized materials were characterized by electron microscopy and X-ray spectroscopy. Highly ordered graphitic structure was formed predominantly in the carbonized materials at 1100 °C (i.e., ∼1500 °C lower than the temperature used in a commercial graphitization process). The ordering of the graphite structure formed at 1100 °C was further improved by heat treatment up to 2100 °C. Multiple characterization results indicate that the early onset of PAN conversion to graphite is directly related to the polymer interphase formation as well as the CNT type. Based on the stabilization and carbonization parameters used in this study, PAN/single-wall carbon nanotube (SWNT) samples showed more prevalent graphite formation at 1100 °C. This work demonstrates the influence of CNT type regarding interfacial confinement toward this low-temperature polymer-to-graphite conversion process.     

Thermal properties of hyperbranched polyborate functionalized multiwall carbon nanotube/polybenzoxazine composites

Using a noncovalent functionalization strategy, hyperbranched polyborate (HBb) acts as a solubilizer for carbon nanotubes (CNTs), and a stable HBb‐CNT dispersion in N‐methyl‐pyrrolidone was produced. The thermal properties of the resulting HBb‐CNT/polybenzoxazine (B‐BOZ) composites and their carbonized structures were investigated. Scanning electron microscopy demonstrated that the fracture surface of HBb‐CNT/B‐BOZ composites was rather rough and plenty of plastic deformation was exhibited. Thermogravimetric analysis indicates an improvement in the thermal stability of the composite with CNTs, especially that of 2.0 wt% CNT modified composite. The increase in the thermal stability is due to the good nanotube dispersion and the effective polymer‐CNT interaction. Graphite‐like boron carbonitride ceramic compounds were found after the composites were carbonized at 1,100°C for 2 h, and there was more B‐C, B‐N, and C‐N bonds in the carbonized HBb‐CNT/B‐BOZ composite than that of HBb/B‐BOZ composite. The result implied that CNTs can promote the ceramic process of HBb/B‐BOZ composite, and the strategy of introducing ceramic precursor into polymer composites may be useful to improve their ablation properties. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Purity-controllable growth of bamboo-like multi-walled carbon nanotubes over copper-based catalysts

The growth of bamboo-like multi-walled carbon nanotubes (CNTs) without the formation of amorphous carbons was performed using copper-based catalysts by catalytic chemical vapour deposition (CVD) with diluted ethylene at 700–900 °C. The as-grown CNT soot was characterised by transmission electron microscopy, thermogravimetric analysis and Raman spectroscopy. The weak metal–support interaction of a sulphate-assisted copper catalyst (CuSO₄/SiO₂) can provide high-purity growth with remarkable yields of CNTs (2.24–6.10 CNT/g Cu·h) at 850–900 °C. Additionally, hydrogen-assisted CVD can activate inert copper catalysts, e.g., Cu(NO₃)₂/SiO₂ or Cu(CH₃COO)_2/SiO₂, for the growth of CNTs.     

Low temperature growth mechanisms of vertically aligned carbon nanofibers and nanotubes by radio frequency-plasma enhanced chemical vapor deposition

Using radio frequency-plasma enhanced chemical vapor deposition (RF-PECVD), carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were synthesized at low temperature. Base growth vertical turbostratic CNFs were grown using a sputtered 8 nm Ni thin film catalyst on Si substrates at 140 °C. Tip growth vertical platelet nanofibers were grown using a Ni nanocatalyst in 8 nm Ni films on TiN/Si at 180 °C. Using a Ni catalyst on glass substrate at 180 °C a transformation of the structure from CNFs to CNTs was observed. By adding hydrogen, tip growth vertical multi-walled carbon nanotubes were produced at 180 °C using FeNi nanocatalyst in 8 nm FeNi films on glass substrates. Compared to the most widely used thermal CVD method, in which the synthesis temperature was 400–850 °C, RF-PECVD had a huge advantage in low temperature growth and control of other deposition parameters. Despite significant progress in CNT synthesis by PECVD, the low temperature growth mechanisms are not clearly understood. Here, low temperature growth mechanisms of CNFs and CNTs in RF-PECVD are discussed based on plasma physics and chemistry, catalyst, substrate characteristics, temperature, and type of gas.     

Structure and properties of aeronautical composites using carbon nanotubes/epoxy dispersion as nanocomposite matrix

The structure and properties of hybrid multiscale composites containing carbon nanotubes (CNTs) was reported. CNTs were dispersed in epoxy by using high energy ultrasonication, followed by the fabrication of CNT hybrid composites via resin transfer molding (RTM) processing. The processability of CNTs/epoxy systems was explored by a capillary experiment. The dependences of mechanical and electrical properties of the hybrid composites on CNT content were investigated. Microscopic observation confirms the formation of CNTs percolation network. The different roles of CNT networks in mechanical reinforcement and electrical amelioration were analyzed. One explanation based on the dispersion and distribution of CNTs is proposed. It is found that the variations of the hybrid composites with respect to mechanical and electrical properties are attributed to the hierarchical structure in the hybrid composites. As far as the hybrid multiscale composites produced via RTM process is concerned, the formation of CNT percolation network, subjected to dynamic impregnation, is hindered by the presence of continuous fibrous reinforcement. The hierarchical structure influenced by several competing factors reveals great potential in being able to tailor the structural and functional performance of the CNT hybrid composites. The effects of CNTs on the dimensional stability of polymer based composites are also assessed. POLYM. COMPOS., 34:1690–1697, 2013. © 2013 Society of Plastics Engineers     

Effect of functional groups of carbon nanotubes on the cyclization mechanism of polyacrylonitrile (PAN)

The cyclization mechanism of polyacrylonitrile (PAN) in PAN/functionalized carbon nanotube (CNT) composites was examined. The surface functionalization of CNTs was carried out by using diazonium reagents with 4-substituted aniline. The results strongly suggest that the type of functional groups on the CNTs strongly influences the cyclization mechanism of PAN during the stabilization process. The nitrile of PAN in F–Ph–CNT/PAN composite was cyclized through the free radical reaction during thermal stabilization whereas nitrile of PAN in COOH–Ph–CNT/PAN composite underwent cyclization via the ionic reaction due to the acid groups on the surfaces of the CNTs. The fluoro functional groups on the CNTs can act as effective external initiators for nitrile cyclization in homo PAN, in contrast to acid functional groups. Consequently, a lower cyclization temperature (265 °C) and enthalpy value (688 J/g) of F–Ph–CNT were shown compared to those of homo PAN.     

Plasma sprayed graphene/carbon nanotube reinforced lanthanum-cerate hybrid composite coating

Lanthanum cerate (LC: La₂Ce₂O₇) is a potential material for thermal barrier coating, whose improved toughness is a crucial necessity for the pathway of its industrialization. Herein, we demonstrated a promising approach to develop graphene/carbon nanotube hybrid composite coating using a large throughput and atmospheric plasma spraying method. Graphene nanoplatelets (GNP: 1 wt %) and carbon nanotube (CNT: 0.5 wt %) reinforced lanthanum cerate (LCGC) hybrid composite coatings were deposited on the Inconel substrate. Addition of 1 wt % GNP and 0.5 wt % CNT in LC matrix has significantly increased its relative density, hardness, and elastic modulus up to 97.2%, 2–3 folds, 3–4 folds, respectively. An impressive improvement of indentation toughness (8.04 ± 0.2 MPa m^0.5) was observed on LCGC coating, which is ～8 times higher comparing the LC coating. The toughening was attributed to the factors: such as the distribution of GNPs and CNTs in the LC matrix, synergistic toughening offered by the GNPs and CNTs; (i) GNP/CNT pull-out, (ii) crack bridging and arresting, (iii) splat sandwiching, mechanical interlocking, etc. Finally, this improved toughness offered an exceptional thermal shock performance up to 1721 cycles at 1800 °C, without any major failure on the coating. Therefore, the GNP and CNT-reinforced LC hybrid composite coating can be recommended to open a path for turbine industries.     

碳纳米管在炭纤维表面的可控自组装

采用催化化学气相沉积法将碳纳米管(CNTs)原位生长于炭纤维(CF)表面并自组装成不同形貌的CNTs/CF杂化结构。使用扫描电子显微镜、拉曼光谱仪对制备的纳米/微米杂化结构进行微观形貌分析和结构表征。结果显示,随着温度的升高,碳纳米管在炭纤维表面由均匀分布状态转变为取向生长状态,并且长度及石墨化程度均不断增加。结合碳纳米管结构参数的变化,使用纳米悬臂梁模型解释了这一杂化结构的形成机理。模型分析表明,杂化结构的形貌转变是由不同温度下在炭纤维表面生长的碳纳米管的结构参数不同所造成的,因此可以通过调整相关结构参数控制碳纳米管在炭纤维表面的自组装过程。     

The effect of carbon nanotubes on the thermal expansion isotropy of injection molded carbon fiber reinforced thermoplastics

Plastics have a weight advantage over metals but they lack their strength, stiffness, dimensional stability, and electrical conduction. Fiber reinforced plastics have been used to bridge this properties gap, specifically engineering thermoplastics including carbon fibers (CFs). These composites are light, strong and stiff, electrostatically dissipating, and relatively easy to process by injection molding. However, the high aspect ratio and rigidity of the CFs cause orientation and anisotropy, especially when injection molded, thus reducing dimensional stability on the final product and limiting its use in precision components. In this study, polymer composite formulations of polyether imide containing CFs and carbon nanotubes (CNTs) were compounded and injection‐molded following a design of experiments (DOE) methodology. The coefficient of thermal expansion (CTE) in the polymer flow direction and perpendicular to the flow direction was used to evaluate thermal expansion isotropy. The electrical resistivity, impact strength, and morphological structure were also investigated. It was found that the addition of CNT caused a significant reduction in the thermal expansion anisotropy of the parts without compromising the impact strength. Also, it was found that CNTs are significantly more efficient than CFs for reducing the electrical resistivity. The conclusions of this study can be used to fine‐tune polymer composites with high dimensional thermal stability, electrostatic dissipation, and good mechanical properties, suitable for high‐performance devices. POLYM. COMPOS. 34:1367–1374, 2013. © 2013 Society of Plastics Engineers     

Direct measurement of grafting strength between an individual carbon nanotube and a carbon fiber

Hierarchical structures consisting of carbon nanotubes (CNTs) grafted onto a carbon fiber (CF) have the potential to improve the performance of fiber/polymer composites. The strength between a CNT and a CF is a key factor that influences the load-transfer behavior and inter-laminar properties. Here, we directly measured the grafting strength of a chemically bonded CNT–CF hierarchical structure by detaching individual CNT from the CF substrate and simultaneously recording the force–displacement characteristics in a scanning electron microscopy equipped with a nano-manipulator. We observed a relatively wide distribution of the maximum forces at complete detachment for different grafted CNTs, which ranges from below the van der Waals (vdW) force existing at the CNT–CF interface up to 7 times higher than that. For a typical configuration where a CNT is partially anchored on a CF, we obtained grafting strengths in the range of 5–90 MPa, which are dominated by the vdW force as well as other factors such as chemical bonding. Our results, based on the measurements at individual nanostructure level, might be useful for designing and fabrication of high performance hierarchical composites.     

SiOCN Functionalized Carbon Nanotube Gas Sensors for Elevated Temperature Applications

Silicon Oxycarbonitride (SiOCN) functionalization is proposed for stable, reproducible, reliable, and enhanced gas‐sensing properties in carbon nanotube (CNT) gas sensors. The process is very simple: liquid precursor completely coats the surfaces of the CNTs without requiring any surface modification and a thin layer of semiconductor ceramic SiOCN is created on the CNTs after heat treatment. This new kind of conductometric gas sensors can detect 10 ppm NH₃ and 2 ppm NO₂ at temperatures up to 350°C. The stability of the functionalized CNT sensor is verified up to 520°C, while the CNT sensor without the SiOCN coating lost conductance after 250°C due to the structural modification. SiOCN functionalization of CNT changes the recovery from irreversible to reversible and the recovery time decreases from 60 min at 100°C to 19 min at 350°C.