A layer-by-layer deposition mechanism for producing a pyrolytic carbon coating on carbon nanotubes

Pyrolytic carbon (PyC) was deposited on carbon nanotubes (CNTs) in order to modify them by introducing defects to their surface. The deposition of PyC was carried out at temperature between 800 and 1000 °C using propane as carbon source with or without a hydrogen carrier gas at low pressure of 20 kPa. The structure of PyC coatings was examined using transmission electron microscopy. The PyC coating could be distinguished from the original CNT walls due to the difference of the structure, with the coating showing a less orderly layer structure. When H₂ was introduced during deposition, PyC coating started to form at 900 °C, and the deposition rate increased rapidly with increasing temperature. Without H₂, PyC coating with a thickness of a few layers could be formed at temperatures between 800 and 900 °C in 10 min. The outmost layer of the PyC coating showed a structure of rough and curved carbon fragment. A layer-by-layer mechanism is proposed for the deposition consisting of alternating fragment formation (nucleation) and lateral growth to layer.     

A mullite/SiC oxidation protective coating for carbon/carbon composites

To protect carbon/carbon (C/C) composites against oxidation, a mullite coating was prepared on SiC precoated C/C composites by a hydrothermal electrophoretic deposition process. The phase composition, microstructure and oxidation resistance of the prepared mullite/SiC coatings were investigated. Results show that hydrothermal electrophoretic deposition is an effective route to achieve crack-free mullite coatings. The mullite/SiC coating displays excellent oxidation resistance and can protect C/C composites from oxidation at 1773 K for 322 h with a weight loss rate of only 4.89 × 10^?4 g/cm² h. The failure of the multi-layer coatings is considered to be caused by the volatilization of silicate glass layer, the formation of microholes and microcracks on the coating surface and the formation of penetrative holes between the SiC bonding layer and the C/C matrix at 1773 K. The corresponding high temperature oxidation activation energy of the coated C/C composites at 1573–1773 K is calculated to be 111.11 kJ/mol.     

Microstructure and oxidation resistance of C-AlPO4–mullite coating prepared by hydrothermal electrophoretic deposition for SiC-C/C composites

Oxidation resistant C-AlPO₄–mullite coating for SiC pre-coated carbon/carbon composites (SiC-C/C) was prepared by a novel hydrothermal electrophoretic deposition process. The phase composition, surface and cross-section microstructure of the as-prepared multi-layer coatings were characterized by X-ray Diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The influence of deposition voltage on phase composition, microstructure and oxidation resistance of the as-prepared coatings was particularly investigated. Results show that the outer layer coating mainly composed of C-AlPO₄ and mullite phase can be achieved after the hydrothermal electrophoretic deposition. The thickness, density and anti-oxidation property of the C-AlPO₄–mullite coating was improved with the increase of deposition voltage from 160 V to 200 V. The multi-layer coating prepared at a voltage of 200 V exhibit excellent anti-oxidation property, which can effectively protect C/C composites from oxidation in air at 1773 K for 324 h with a weight loss of 1.01%. The failure of the multi-layer coatings is due to the generation of cross-holes in the coating, which cannot be self-cured by the metaphosphate and silicate glass layer after long time oxidation at 1773 K.     

The production of a corrosion resistant graphene reinforced composite coating on copper by electrophoretic deposition

We report the fabrication of a robust graphene reinforced composite coating with excellent corrosion resistance by aqueous cathodic electrophoretic deposition (EPD). At optimum EPD conditions, a coating thickness of around 40 nm is obtained at 10 V and deposition time of 30 s. The surface morphological characterization are carried out by scanning electron microscopy which clearly shows reduced graphene oxide (rGO) with sizes ranging from 1 to 2 μm uniformly coated on the copper sheet. The composite coating is shown to significantly increase the resistance of the metal to electrochemical degradation. Tafel analysis confirms that the corrosion rate exhibited by composite coating is an order of magnitude lower than that of bare copper. It is expected that this simple EPD technique for producing a graphene-reinforced composite coating can open a new avenue especially for marine engineering materials where resistance to salt water is of paramount importance.     

Electrophoretic deposition of carbon nanotubes and bioactive glass particles for bioactive composite coatings

The production of bioactive coatings consisting of 45S5 Bioglass^® and mutli-walled carbon nanotubes (CNTs) by electrophoretic deposition (EPD) was investigated. In addition to pure Bioglass^® coatings, the co-deposition and sequential deposition of Bioglass^® particles (size <5 μm) and CNTs on stainless steel substrates were carried out in order to fabricate bioactive, nanostructured composite layers. The optimal experimental conditions were determined using well-dispersed suspensions by means of a trial-and-error approach by varying the relevant EPD parameters: applied voltage and deposition time. SEM images demonstrated the successful fabrication of Bioglass^®/CNT composites by revealing their morphology and topography. The co-deposition of Bioglass^® particles and CNTs resulted in homogenous and dense coatings exhibiting the presence of well-dispersed CNTs placed in-between micron-sized Bioglass^® particles. This network of high-strength CNTs embedded in the glass layer could act as reinforcing element leading to higher mechanical stability of the coatings. The coatings obtained by sequential deposition offered a two-dimensional nanostructured fibrous mesh of CNTs covering the Bioglass^® layer thus providing a controlled (ordered) nano-topographical surface. This surface nanostructure has the potential to promote the attachment and growth of osteoblast cells and to benefit the formation of bone-like nanosized hydroxyapaptite crystals in contact with body fluids.     

Electrophoretic deposition of MnO2-coated carbon nanotubes on a graphite sheet as a flexible electrode for supercapacitors

A flexible electrode was prepared by microwave heating deposition of manganese oxide (MnO₂) on carbon nanotubes (CNTs) followed by electrophoretic deposition of the MnO₂-coated CNTs on a flexible graphite sheet (FGS). The prepared MnO₂-coated CNTs were characterized by scanning and transmission electron microscopy, and X-ray diffraction. A uniformly thin nano-scale MnO₂ coating was formed on the surface of the CNTs. The MnO₂-coated CNTs–FGS electrode showed highly capacitive behaviour in the 0.5 M Na₂SO₄ aqueous solution, with a specific capacitance of 442.9 F/g based on MnO₂ at 2 mV/s. It exhibited an excellent cycling stability with no more than 1.1% capacitance loss after 1000 cycles at 50 mV/s.     

An innovative fabrication of nano-HA coatings on Ti-CaP nanocomposite layer using a combination of friction stir processing and electrophoretic deposition

In the present study, a combination of friction stir processing and electrophoretic deposition was used to fabricate nano-hydroxyapatite coatings on the Ti-CaP nanocomposite surface layer. A constant tool rotation rate of 250 rpm, travel speed of 16 mm/min and plunge depth of 1.2 mm with a tool tilt angle of 3° were used to incorporate nano-hydroxyapatite particles into Ti–6Al–4V substrates. Microstructure of the stir zone was analyzed using optical and scanning electron microscopy. Microhardness profile and AFM analysis of substrates were then studied. The electrophoretic deposition of nano-HA particles was carried out at constant voltage of 30 V after 60 s. The as-deposited nano-HA coating was characterized employing scanning electron microscope and X-ray diffraction. The results of adhesion test and potentiodynamic polarization measurements showed that Ti-CaP nanocomposite layer could effectively increase the bonding strength between coating and substrate as well as corrosion resistance.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

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 of bamboo-like carbon nanotubes on a copper foil by catalytic chemical vapor deposition from ethanol

Bamboo-like carbon nanotubes (CNTs) were synthesized on a copper foil by catalytic chemical vapor deposition (CVD) from ethanol. The effects of temperature (700–1000 °C) and duration (5–60 min) on the growth of CNTs were investigated. Morphology and structure of the CNTs were characterized by scanning and transmission electron microscopy and Raman spectroscopy. The yield and size of the CNTs increased with temperature. Those prepared at 700 °C had a copper droplet tip and those at 800–900 °C had a copper nanoparticle inside. An amorphous carbon film consisted of a porous and non-porous layer was observed on the surface of the copper substrate, and the CNTs were really grown from this carbon film. The thickness of the carbon film increased from 187 to 900 nm when the duration increased from 5 to 60 min. It was also found that the copper foil became porous after ethanol CVD treatment. The growth mechanism of the CNTs, carbon film and motion of copper catalyst were discussed. It is proposed that a carbon film first deposited on the top surface of the copper foil while the top surface of the copper foil partially melted and migrated across the carbon film, where CNTs formed.     

Graphene oxide/hydroxyapatite composite coatings fabricated by electrophoretic nanotechnology for biological applications

Graphene oxide (GO) was firstly employed as nanoscale reinforcement fillers in hydroxyapatite (HA) coatings by a cathodic electrophoretic deposition process, and GO/HA coatings were fabricated on pure Ti substrate. The transmission electron microscopy observation and particle size analysis of the suspensions indicated that HA nanoparticles were uniformly decorated on GO sheets, forming a large GO/HA particle group. The addition of GO into HA coatings could reduce the surface cracks and increase the coating adhesion strength from 1.55 ± 0.39 MPa (pure HA) to 2.75 ± 0.38 MPa (2 wt.% GO/HA) and 3.3 ± 0.25 MPa (5 wt.% GO/HA), respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that the GO/HA composite coatings exhibited higher corrosion resistance in comparison with pure HA coatings in simulated body fluid. In addition, superior (around 95% cell viability for 2 wt.% GO/HA) or comparable (80–90% cell viability for 5 wt.% GO/HA) in vitro biocompatibility were observed in comparison with HA coated and uncoated Ti substrate.     

Effect of co-deposited SiC nanowires and carbon nanotubes on oxidation resistance for SiC-coated C/C composites

To protect carbon/carbon composites (C/Cs) against oxidation, SiC coating toughened by SiC nanowires (SiCNWs) and carbon nanotubes (CNTs) hybrid nano-reinforcements was prepared on C/Cs by a two-step technique involving electrophoretic co-deposition and reactive melt infiltration. Co-deposited SiCNWs and CNTs with different shapes including straight-line, fusiform, curved and bamboo dispersed uniformly on the surface of C/Cs forming three-dimensional networks, which efficiently refined the SiC grains and meanwhile suppressed the cracking deflection of the coating during the fabrication process. The presence of SiCNWs and CNTs contributed to the formation of continuous glass layer during oxidation, while toughed the coating by introducing toughing methods such as bridging effect, crack deflection and nanowire pull out. Results showed that after oxidation for 45 h at 1773 K, the weight loss percentage of SiC coated specimen was 1.35%, while the weight gain percentage of the SiCNWs/CNTs reinforced SiC coating was 0.03052% due to the formation of continuous glass layer. After being exposed for 100 h, the weight loss percentage of the SiCNWs/CNTs reinforced SiC coating was 1.08%, which is relatively low.     

Synthesis,processing, characterization,and applications of red mud/carbon nanotube composites

In the present study, red mud/carbon nanotube (RM/CNT) composites were synthesized by decomposition of hydrocarbon gas using the chemical vapor deposition (CVD) method. Red mud, a by-product of the Bayer process of alumina production, was used as a catalyst in this process. Synthesis was done at different growth temperatures (600, 700, 750 and 850 °C). The microstructure and morphology of the synthesized nanocomposite was characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), Simultaneous Thermal Analysis (STA), and Raman spectra analysis.The prepared nanocomposite, which was prepared at 750 °C, was used for Pb (II) adsorption. The adsorption characteristics of the nanocomposite for Pb (II) removal were investigated as a function of pH, adsorbent dose, and contact time. The best result was obtained with 0.05 g of adsorbent at a pH=5 with 40 min of contact time. The results proved that RM/CNT composites are a good adsorbent for lead ions in comparison with unprocessed RM or pristine CNTs.     

Synthesis,morphology and physical properties of multi-walled carbon nanotube/biphenyl liquid crystalline epoxy composites

We have developed multi-walled carbon nanotube/liquid crystalline epoxy composites and studied the effects of incorporation carbon nanotubes (CNTs) on the morphology, thermal and mechanical properties of the composites. The CNTs are functionalized by liquid crystalline (LC) 4,4′-bis(2,3-epoxypropoxy) biphenyl (BP) epoxy resin for the ease of dispersion and the formation of long range ordered structure. The epoxy functionalized CNT (ef-CNT) were dispersed in the LC BP epoxy resin that can be thermal cured with an equivalent of 4,4′-diamino-diphenylsulfone to form composite. The curing process was monitored by polarized optical microscopy. The results indicate the LC resin was aligned along the CNTs to form fiber with dendritic structure initially then further on to obtain micro-sized spherical crystalline along with fibrous crystalline. With homogeneous dispersion and strong interaction between nanotubes and matrix, the composite containing 2.00 wt.% ef-CNT exhibits excellent thermal and mechanical properties. When the amount of ef-CNT exceeds 2.00 wt.%, vitrification stage of curing is fast reached, which lowers the degree of conversion. As compared with the neat resin, the composite containing 2.00 wt.% ef-CNT increases the glass transition temperature by 70.0 °C, the decomposition temperature by 13.8 °C, the storage modulus by 40.9%, and the microhardness by 63.3%.     

Constrained sintering of YSZ/Al2O3 composite coatings on metal substrates produced from eletrophoretic deposition

Yttria stabilized zirconia/alumina (YSZ/Al₂O₃) composite coatings were prepared from electrophoretic deposition (EPD), followed by sintering. The constrained sintering of the coatings on metal substrates was characterized with microstructure examination using electron microscopy, mechanical properties examination using nanoindentation, and residual stress measurement using Cr³⁺ fluorescence spectroscopy. The microstructure close to the coating/substrate interface is more porous than that near the surface of the EPD coatings due to the deposition process and the constrained sintering of the coatings. The sintering of the YSZ/Al₂O₃ composite coating took up to 200 h at 1250 °C to achieve the highest density due to the constraint of the substrate. When the coating was sintered at 1000 °C after sintering at 1250 °C for less than 100 h, the compressive stress was generated due to thermal mismatch between the coating and metal substrate, leading to further densification at 1000 °C because of the ‘hot pressing’ effect. The relative densities estimated based on the residual stress measurements are close to the densities measured by the Archimedes method, which excludes an open porosity effect. The densities estimated from the hardness and the modulus measurements are lower than those from the residual stress measurement and the Archimedes method, because it takes account of the open porosity.     

Fabrication and electromagnetic interference shielding effectiveness of carbon nanotube reinforced carbon fiber/pyrolytic carbon composites

Carbon nanotube reinforced carbon fiber/pyrolytic carbon composites were fabricated by precursor infiltration and pyrolysis method and their electromagnetic interference shielding effectiveness (EMI SE) was investigated over the frequency range of 8.2–12.4 GHz (X-band). Carbon nanotubes (CNTs) were in situ formed through catalyzing hydrocarbon gases evaporating out of phenolic resin with nano-scaled Ni particles. The content of CNTs increased with the increase of Ni loadings (0.00, 0.50, 0.75 and 1.25 wt.%) in phenolic resin. Thermal gravimetrical analysis results showed that the carbon yield of phenolic resin increased with the addition of Ni catalyst. With the formation of CNTs, the EMI SE increased from 28.3 to 75.2 dB in X-band. The composite containing 5.0 wt.% CNTs showed an SE higher than 70 dB in the whole X-band.     

Nanoindentation-induced deformation behaviour of tetrahedral amorphous carbon coating deposited by filtered cathodic vacuum arc

The nanoindentation-induced deformation behaviour of a ta-C (tetrahedral amorphous carbon) coating deposited on to a silicon substrate by a filtered vacuum cathodic vapour arc technique was investigated. The 0.17-μm-thick ta-C coating was subjected to nanoindentation with a spherical indenter and the residual indents were examined by cross-sectional transmission electron microscopy. The hard (~ 30 GPa) ta-C coatings exhibited very little localized plastic compression, unlike the softer amorphous carbon coatings deposited by plasma-assisted chemical vapour deposition. However, neither through-thickness cracks nor delamination was observed in the coating for the loads studied. Rather, the silicon substrate exhibited plastic deformation for indentation loads as low as 10 mN and at higher loads it showed evidence of both phase transformation and cracking. These microstructural features were correlated to the observed discontinuities in the load-displacement curves. Further, it was observed that even a very thin coating can modify the primary deformation mechanism from phase transformation in uncoated Si to predominantly plastic deformation in the underlying substrate.     

Synthesis of nanodiamond-reinforced aluminum metal matrix composites using cold-spray deposition

A dense nanodiamond–aluminum (ND–Al) composite coating was successfully produced by low pressure cold spray (CS) deposition of ball-milled powders containing 10 wt% ND. High-energy ball milling is a feasible means for the synthesis of composite feedstock powders as it provides excellent control over particle size distribution, crystal size, and the dispersion of ND agglomerates. The resulting CS coatings were characterized with respect to deposition efficiency, particle velocity and mechanical properties. It was found that the CS deposition produced dense, ND–Al composite coatings with increases in both hardness and elastic modulus as compared to the feedstock powders. The coating hardness of the 0.5 h-milled ND–Al composite that has the highest DE (14.2%) in ND–Al composites is 3.02 GPa, an 175% increase over the pristine as-received Al (1.10 GPa). The highest elastic modulus of the composite coatings is 98.3 GPa, a 51.5% increase over the as-received Al powder.     

One-step synthesis of a multi-functional anti-oxidation protective layer on the surface of carbon/carbon composites

A multi-functional anti-oxidation (AO) protective coating is produced in one-step synthesis on the surface of the carbon/carbon (C/C) composite by a novel electrically induced liquid infiltration (EILI) method. The AO coating involves several protective layers which have different anti-oxidation mechanisms. In this study phosphorus acid is applied as active-site poisoning agents to inhibit oxidations by forming stable glassy complex barriers that decrease oxygen diffusion. Simultaneously silicon carbide (SiC) or SiC/silica layers are formed on the surface of C/C composites that act as physical protection barriers for oxygen penetration. It is proved that under the optimum conditions the acid groups survive the high temperature EILI process. Oxidation tests reveal that formed coatings effectively protect C/C composite from oxidation: average percent of weight losses decrease from 30 to 1 wt.% and from 69 to 5 wt.% for the thermal (1150 K) and catalytic (920 K) oxidation tests, respectively.     

Enhanced field emission properties from titanium-coated carbon nanotubes

The effect of titanium (Ti) coating over the surface of carbon nanotubes (CNTs) on field emission characteristics was investigated. Vertically aligned CNTs were grown by inductively-coupled plasma-enhanced chemical vapor deposition (ICP-CVD). In order to reduce the screening effect of electric field due to densely packed CNTs, as-grown CNTs were partly etched back by DC plasma of N₂. Ti with various thicknesses from 5 nm to 150 nm was coated on CNTs by a sputtering method. Since thick Ti coating with thickness of 100 nm or more resulted in the shape of a metal post by merging an individual CNT in a bundle, it was inadequate to a field emission application. On the other hand, thin Ti-coated CNTs with thickness of 10 nm or less showed a lower turn-on field, a higher emission current density, and improved emission uniformity compared with pristine CNTs. The improved emission performance was mainly attributed to the low work function of Ti and the reliable and lower resistance contact between CNTs and substrates.