Pressureless sintering of carbon nanotube–Al2O3 composites

Alumina ceramics reinforced with 1, 3, or 5 vol.% multi-walled carbon nanotubes (CNTs) were densified by pressureless sintering. Commercial CNTs were purified by acid treatment and then dispersed in water at pH 12. The dispersed CNTs were mixed with Al₂O₃ powder, which was also dispersed in water at pH 12. The mixture was freeze dried to prevent segregation by differential sedimentation during solvent evaporation. Cylindrical pellets were formed by uniaxial pressing and then densified by heating in flowing argon. The resulting pellets had relative densities as high as ～99% after sintering at 1500 °C for 2 h. Higher temperatures or longer times resulted in lower densities and weight loss due to degradation of the CNTs by reaction with the Al₂O₃. A CNT/Al₂O₃ composite containing 1 vol.% CNT had a higher flexure strength (～540 MPa) than pure Al₂O₃ densified under similar conditions (～400 MPa). Improved fracture toughness of CNT–Al₂O₃ composites was attributed to CNT pullout. This study has shown, for the first time, that CNT/Al₂O₃ composites can be densified by pressureless sintering without damage to the CNTs.     

Carbon nanotube toughened aluminium oxide nanocomposite

This paper describes the mechanical properties of carbon nanotube-reinforced Al₂O₃ nanocomposites fabricated by hot-pressing. The results showed that compared with monolithic Al₂O₃ the fracture toughness, hardness and flexural strength of the nanocomposites were improved by 94%, 13% and 6.4% respectively, at 4 vol.% CNT additions. For 10 vol.% CNT additions, with the exception of the fracture toughness, which was improved by 66%, a decrease in mechanical properties was observed when compared with those for monolithic Al₂O₃. The toughening mechanism is discussed, which is due to the uniform dispersion of CNTs within the matrix, adequate densification, and proper CNT/matrix interfacial connections.     

Microstructure and physicomechanical properties of pressureless sintered multiwalled carbon nanotube/alumina nanocomposites

Multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites containing CNT from 0.15 vol.% to 2.4 vol.% have been successfully fabricated by simple wet mixing of as-received commercial precursors followed by pressureless sintering. Extent of densification of nanocomposites sintered at low temperature (e.g. 1500 °C) was <90%, but increased up to ∼99% when sintered at 1700 °C and offered superior performance compared to pure Al₂O₃. Nanocomposites containing 0.3 vol.% MWCNT and sintered at 1700 °C for 2 h in Argon led to ∼23% and ∼34% improvement in hardness and fracture toughness, respectively, than monolithic Al₂O₃. In addition, the highest improvement (∼20%) in bending strength was obtained for 0.15 vol.% MWCNT/Al₂O₃ nanocomposite compared to pure Al₂O₃. Weibull analysis indicated reliability of nanocomposites increased up to 0.3 vol.% MWCNT, whereas, beyond that loading consistency was the same as obtained for pure Al₂O₃. Detailed microstructure and fractographic analysis were performed to assess structure-property relationship of present nanocomposites.     

Development of Carbon Nanotube Reinforced Bulk Polycrystalline Ceramics with Intragranular Carbon Nanotube Reinforcement

In the bulk polycrystalline ceramic–carbon nanotube (CNT) composites developed to date, reinforcing CNTs have been present just at the matrix grain boundaries, with the grain interiors being nearly completely devoid of CNT; thus severely limiting the improvements achieved in fracture and wear properties. Against this backdrop, bulk polycrystalline Al₂O₃‐based composites, having multi‐walled CNTs (MWCNTs) present within the matrix grain interiors (not just at grain boundaries), have been developed in this work for the first time. Such microstructure development has been rendered possible by an innovative, but facile, wet‐chemical synthesis route (sans ball‐milling) involving incorporation of well‐dispersed MWCNTs directly into matrix sol, followed by rapid gelation (within a few seconds) and sintering (inclusive of crystallization step). Intragranular MWCNT reinforcements (in “sol–gelled” composites) led to significant improvements in indentation‐induced crack propagation resistances and abrasive wear resistances, as compared to “conventionally” prepared Al₂O₃–MWCNT composites (i.e., “ball‐milled” counterpart) having the same contents of MWCNT, but present only at grain boundaries. Wear rates recorded with the “sol–gelled” Al₂O₃‐2.5 vol%MWCNT are lower than those for monolithic Al₂O₃ and “ball‐milled” counterpart by ~95% and ~90%, respectively. Such improvements, as never achieved before, are a consequence of reinforcing the matrix grain interiors with MWCNTs.     

Remarkable improvement in tribological behavior of plasma sprayed carbon nanotube and graphene nanoplatelates hybrid reinforced alumina nanocomposite coating

Addition of 0.5?wt% of graphene nanoplatelates (GNPs) and 1?wt% carbonnanotube (CNTs) in plasma sprayed Al₂O₃ coating showed the reduction of 93.25% in wear volume loss and 90.94% in wear rate. This could be attributed to the simultaneous effect of enhanced densification, presence of the transferred layer from the counterpart, strong interface between Al₂O₃, GNP and CNTs and toughening offered by the GNPs and CNTs. The lowest COF value of 0.27 was recorded on addition of 0.5?wt% of GNP in Al₂O₃ coating, which could be attributed to the graphitic lubrication on the worn track during the wear.     

Tribological behavior of plasma sprayed carbon nanotubes reinforced TiO2 coatings

Intrinsic structural limitations of plasma-spray TiO₂ coating deteriorate its wear resistance. Herein, CNTs are incorporated in the coating to assess their effects on the microstructure and tribological properties. Structurally, degradation degree of CNTs in TiO₂ matrix during plasma spraying was revealed by Raman spectroscopy. And high resolution transmission electron microscopy manifested that TiO₂/CNT interface was well bonded along with presence of notable interfacial carbothermic product Ti_nO_2n-1 at atomic scale. The phenomenon indicates a beneficial effect for transferring stress from matrix to CNTs effectively. Then, the influence of CNTs on coating’s friction behavior was investigated by zirconia ball-on-disk tribometer under dry-sliding condition. As compared to TiO₂ coating, the nanocomposite coating exhibited a moderate decrease in friction coefficient and an enormous reduction (～93.6%) in wear volume. The remarkable advance in tribological properties of the reinforced coating can be attributed to four kinds of frictional effects of CNTs: tribo-reorientation, tribo-protruding, tribo-film and tribo-degradation.     

Formation of carbon nanotubes through ethylene decomposition over supported Pt catalysts and silica-coated Pt catalysts

Ethylene decomposition was performed over supported Pt catalysts to fabricate composites of Pt metal nanoparticles and carbon nanotubes (CNTs). All supported Pt catalysts (Pt/carbon black, Pt/CNT, Pt/MgO, Pt/Al₂O₃ and Pt/SiO₂) showed catalytic activity for ethylene decomposition at 973 K to form CNTs. Pt metal particles were found at tips of CNTs. These results indicate that Pt metal particles have catalytic activity for growth of CNTs through hydrocarbon decomposition. A broad range (5-50 nm) of CNT diameters were formed from the use of supported Pt metal catalysts although Pt metal particles in the catalysts before ethylene decomposition were relatively uniform in size (2-5 nm). These results imply that Pt metal particles in the catalysts aggregated during ethylene decomposition at 973 K. Aggregation of Pt metal particles in catalysts during ethylene decomposition could be suppressed by covering catalysts with silica layers that were a few nanometers thick. Silica-coated Pt catalysts showed high activity for ethylene decomposition to form CNTs with uniform diameters (8-10 nm) despite the uniform coverage of Pt metal particles with silica layers.     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Effect of Y2O3 addition on tribological properties of plasma sprayed Al2O3-13% TiO2 coating

The effect of Y₂O₃ addition on structure, mechanical properties and tribological properties of Al₂O₃-13 wt% TiO₂ coating was investigated. The addition of 20 wt% Y₂O₃ resulted in better densification, stabilization of alpha (α) alumina phase and improvement in fracture toughness of Al₂O₃-13 wt% TiO₂ coating. Abrasive wear tests were performed over a range of loads and sliding speeds. The stabilization of α alumina phase further increased with an increase in severity of wear test conditions, as noted from X-Ray Diffraction (XRD) and X-Ray Photoelectron Spectroscopy (XPS) analysis of worn coatings. Al₂O₃-13 wt% TiO₂-20 wt% Y₂O₃ coating displayed lower friction coefficient and lower abrasive wear rate than Al₂O₃-13 wt% TiO₂ coating, which was due to synergistic effect of α alumina phase and formation of magneli phase oxide of titanium; Ti₂O₃. Friction energy map was used to rationalize observed wear rates, to identify different regimes of wear and degradation modes of coatings.     

Carbon nanotubes improve the adhesion strength of a ceramic splat to the steel substrate

A scratch technique was used to measure the adhesion strength of plasma sprayed carbon nanotube (CNT) reinforced aluminum oxide (Al₂O₃) splat on the steel substrate. The effect of adding carbon nanotube on the adhesion strength of a single splat was studied by varying the CNT content as 0, 4 and 8 wt.% in the Al₂O₃ matrix. Higher lateral force was required by the nanoindenter tip to detach CNT reinforced Al₂O₃ splats as compared to Al₂O₃ splat. The adhesion strength increased significantly from 0.52 ± 0.05 MPa for Al₂O₃ splat to 4.21 ± 0.49 MPa for Al₂O₃-4 wt.% CNT splat and 7.36 ± 3.96 MPa for Al₂O₃-8 wt.% CNT splat. A high variation in the adhesion strength of Al₂O₃-8 wt.% CNT splat was due to varying degree of CNT dispersion in the matrix. A significant increase in the adhesion strength of Al₂O₃-CNT splat was attributed to its better mechanical interlocking with the substrate as a result of enhanced melting and spreading caused by the higher thermal conductivity of nanotubes. CNTs also form anchors between the splat and the substrate resulting in higher adhesion strength.     

Tribological and electrical properties of ceramic matrix composites with carbon nanotubes

Tribological behaviur of carbon fibrous phases (nanofibers and nanotubes) containing composites with Si₃N₄, ZrO₂ and Al₂O₃ matrices was studied by pin-on-disk technique in conditions of dry sliding. Coefficients of friction and wear rates were measured, wear damage mechanisms were observed and identified. The resulting tribological behaviur was related to microstructure and mechanical properties of respective materials. Electrical conductivity was measured in wide range of frequencies by two-point method and effect of volume fraction and distribution of CNTs and CNFs on percolation threshold was evaluated. Both coefficient of friction and electrical resistivity decreased with increasing amount of carbon phases, in both cases the nanofibers were more efficient than the nanotubes. The wear resistance in most cases decreased but for Si₃N₄–CNT composite a certain optimum (～5 wt.% CNT) was found.     

Bimodal microstructure toughens plasma sprayed Al2O3-8YSZ-CNT coatings

Current work pursues generating controlled bimodal microstructure by plasma spraying of micrometer-sized Al₂O₃ and nanostructured spray-dried agglomerate with reinforcement of 20 wt% of 8 mol % yttria stabilized zirconia (8YSZ) and 4 wt% carbon nanotube (CNT) as potential thermal barrier coating (TBC) on the Inconel 718 substrate. Composite coatings exhibit bimodal microstructure of: (i) fully melted and resolidified microstructured region (MR), and (ii) partially melted and solid state sintered nanostructured regions (NR). Reinforcement with 8YSZ has led to an increase in hardness from ∼12.8 GPa (for μ-Al₂O₃) to ∼13.9 GPa in MR of reinforced Al₂O₃-YSZ composite. Further, with the addition of CNT in Al₂O₃-8YSZ reinforced composite, hardness of MR has remained similar ∼13.9 GPa (8YSZ reinforced) and ∼13.5 GPa (8YSZ-CNT reinforced), which is attributed to acquiescent nature and non-metallurgical bonding of CNT with MR. Indentation fracture toughness increased from 3.4 MPam^0.5 (for μ-Al₂O₃) to a maximum of 5.4 MPam^0.5 (8YSZ- CNT reinforced) showing ∼57.7% improvement, which is due to crack termination at NR, retention of t-ZrO₂ (∼3.3 vol%) crack bridging, and CNT pull-out toughening mechanisms. Modified fractal models affirmed that the introduction of bimodal microstructure (NR) i.e., nanometer-sized- Al₂O₃, nanostructured 8YSZ and CNTs in the μ-Al₂O₃ (MR) contributes ∼44.6% and ∼72% towards fracture toughness enhancement for A8Y and A8YC coatings. An enhanced contribution of nanostructured phases in toughening microstructured Al₂O₃ matrix (in plasma sprayed A8YC coating) is established via modified fractal model affirming crack deflection and termination for potential TBC applications.     

Influence of different introduction modes of metal Ag into plasma sprayed Al2O3 coating on tribological properties

Al₂O₃ coating and Al₂O₃/Ag (10%) composite coating were prepared on the surface of GH4169 superalloy by the atmospheric plasma spraying technology. And an in-situ synthesis method was applied to introduce the Ag particles into a part of Al₂O₃ coatings to obtain Al₂O₃/Ag(synthesis) composite coating. Then, the microstructure and mechanical properties of these three Al₂O₃-based coatings were systematically studied in this work. In order to reveal the lubrication characteristics of Ag, their friction tests were carried out at room temperature (RT), 400 °C, 600 °C and 800 °C, respectively. The results showed that both microstructure and mechanical properties of Al₂O₃/Ag(synthesis) composite coating were better than that of Al₂O₃/Ag (10%) composite coating because many pores and cracks produced during the direct spraying. Although the friction coefficients of two kinds of composite coatings were close to that of Al₂O₃ coatings at RT, their wear rates were both greatly decreased due to the introduction of Ag. In addition, the lubricating performance of Ag was not enough to reduce their friction coefficients when friction temperature is lower than 600 °C. However, the friction coefficients of these composite coatings were both reduced to about 0.3 at 800 °C . At this time, the Al₂O₃/Ag(synthesis) composite coating also exhibited a lower wear rate because of its dense microstructure and excellent mechanical properties.     

Mechanical properties and electrical conductivity in a carbon nanotube reinforced silicon nitride composite

The influence of carbon nanotubes (CNTs) addition on basic mechanical, thermal and electrical properties of the multiwall carbon nanotube (MWCNT) reinforced silicon nitride composites has been investigated. Silicon nitride based composites with different amounts (1 or 3 wt%) of carbon nanotubes have been prepared by hot isostatic pressing. The fracture toughness was measured by indentation fracture and indentation strength methods and the thermal shock resistance by indentation method. The hardness values decreased from 16.2 to 10.1 GPa and the fracture toughness slightly decreased by CNTs addition from 6.3 to 5.9 MPa m^1/2. The addition of 1 wt% CNTs enhanced the thermal shock resistance of the composite, however by the increased CNTs addition to 3 wt% the thermal shock resistance decreased. The electrical conductivity was significantly improved by CNTs addition (2 S/m in 3% Si₃N₄/CNT nanocomposite).     

Tribological properties of Al2O3 nanoparticles as lubricating oil additives

Nano-scale Al₂O₃ spherical particles, prepared via a hydrothermal method and modified by silane coupling agent, can be well-dispersed in lubricating oil. The tribology properties of Al₂O₃ nanoparticles as lubricating oil additives have been studied by four-ball and thrust-ring friction test, which illustrate that the modified Al₂O₃ nanoparticles can effectively improve the lubricating behaviors compared to the base oil. When the added concentration is 0.1 wt%, the friction coefficient and the wear scar diameter are both smallest. The lubrication mechanism is that a self-laminating protective film is formed on the friction surface and the wear behavior changes from sliding friction to rolling friction.     

Role of interface on electrical conductivity of carbon nanotube/alumina nanocomposite

Interface of multiwalled carbon nanotube (MWCNT)/alumina (Al₂O₃) nanocomposites have been studied using TEM. At low sintering temperature (T_sin=1500 °C), a 3–5 nm thick amorphous interface region was noticed. Nanocomposite sintered at 1700 °C possessed a well-defined graphene layer coating on matrix grains as the interface between CNT and Al₂O₃. A mechanism of such layered interface formation has been proposed. No traceable chemical reaction product was observed at the interface even after sintering at 1700 °C. It was noticed that while DC electrical conductivity (σ_DC) of 1500 °C sintered 2.4 vol% MWCNT/Al₂O₃ nanocomposite was only~0.02 S/m, it raised to ~21 S/m when sintering was done at 1700 °C. Such 10³ times increase in σ_DC of present nanocomposite at a constant CNT loading was not only resulted from the exceptionally high electron mobility of CNT but the well-crystallized graphene interface on insulating type Al₂O₃ grains also significantly contributed in the overall increase of electrical performance of the nanocomposite, especially, when sintering was done at 1700 °C.     

Effects of micro-grooves on tribological behaviour of plasma-sprayed alumina-13%titania coatings

This study was aimed at investigating the effects of micro-grooves on the tribological behaviour of a plasma-sprayed Al₂O₃ – 13%TiO₂ coating. A combined surface profile with non-regular depths and micro-groove texture was successfully developed by using a Nd:YVO₄ laser system. The surface condition and characterisation of the Al₂O₃ – 13%TiO₂ coating was conducted using a VPSEM and a 3D microscope. A pin-on-disc test was then carried out to measure the effectiveness of the micro-grooves in reducing the wear rates of the Al₂O₃ – 13%TiO₂ coatings under non-lubricated conditions. It was noted that the textured coatings gradually decreased the wear rate with only a slight reduction on the friction coefficient due to the entrapment of the wear debris within the grooves. It was proven that the combined surfaces successfully reduced the wear rate up to 44.7% and 61.5% for 10 N and 20 N of load respectively.     

Mechanical properties and sliding wear behaviour of Al2O3-SiC nanocomposites with 3–20 vol% SiC

Al₂O₃/SiC composites containing different volume fractions (3, 5, 10, 15, and 20 vol%) of SiC particles were produced by conventional mixing of alumina and silicon carbide powders, followed by hot pressing at 1740 °C for 1 h under the pressure of 30 MPa in the atmosphere of Ar. The influence of the volume fraction and size of SiC particles (two different powders with the mean size of SiC particles 40 and 200 nm were used), and final microstructure on mechanical properties and dry sliding wear behaviour in ball-on-disc arrangement were evaluated. The properties of the composites were related to a monolithic Al₂O₃ reference. Microstructure of the composites was significantly affected by the volume fraction of added SiC, with the mean size of alumina matrix grains decreasing with increasing content of SiC particles. The addition of SiC moderately improved the Vickers hardness. Fracture toughness was lower with respect to monolithic Al₂O₃, irrespective of the volume fraction and size of SiC particles. Al₂O₃/SiC nanocomposites conferred significant benefits in terms of wear behaviour under the conditions of mild dry sliding wear. Wear resistance of the alumina reference was poor, especially at the applied load of 50 N. The wear rates of composites markedly decreased with increasing volume fraction of SiC. Wear of the composites was also influenced by the material of counterparts, especially their hardness, with softer counterparts resulting in lower wear rates. All composites wore by a combination of grain pull-out with plastic deformation associated with grooving and small contribution of mechanical wear (micro-fracture). No influence of SiC particle size on wear rate or mechanism of wear was observed in the materials with identical volume fractions of SiC.     

Growth and electrical characterization of high-aspect-ratio carbon nanotube arrays

The remarkable properties of carbon nanotubes (CNTs) make them attractive for microelectronic applications, especially for interconnects and nanoscale devices. In this paper, we describe a microelectronics compatible process for growing high-aspect-ratio CNT arrays with application to vertical electrical interconnects. A lift-off process was used to pattern catalyst (Al₂O₃/Fe) islands to diameters of 13 or 20 μm. After patterning, chemical vapor deposition (CVD) was involved to deposit highly aligned CNT arrays using ethylene as the carbon source, and argon and hydrogen as carrier gases. The as-grow CNTs were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CNTs have high purity, and form densely-aligned arrays with controllable array size and height. Two-probe electrical measurements of the CNT arrays indicate a resistivity of ∼0.01 Ω cm, suggesting possible use of these CNTs as interconnect materials.     

Growth of conformal single-walled carbon nanotube films from Mo/Fe/Al2O3 deposited by electron beam evaporation

We discuss growth of high-quality carbon nanotube (CNT) films on bare and microstructured silicon substrates by atmospheric pressure thermal chemical vapor deposition (CVD), from a Mo/Fe/Al₂O₃ catalyst film deposited by entirely electron beam evaporation. High-density films having a tangled morphology and a Raman G/D ratio of at least 20 are grown over a temperature range of 750-900 °C. H₂ is necessary for CNT growth from this catalyst in a CH₄ environment, and at 875 °C the highest yield is obtained from a mixture of 10%/90% H₂/CH₄. We demonstrate for the first time that physical deposition of the catalyst film enables growth of uniform and conformal CNT films on a variety of silicon microstructures, including vertical sidewalls fabricated by reactive ion etching and angled surfaces fabricated by anisotropic wet etching. Our results confirm that adding Mo to Fe promotes high-yield SWNT growth in H₂/CH₄; however, Mo/Fe/Al₂O₃ gives poor-quality multi-walled CNTs (MWNTs) in H₂/C₂H₄. An exceptional yield of vertically-aligned MWNTs grows from only Fe/Al₂O₃ in H₂/C₂H₄. These results emphasize the synergy between the catalyst and gas activity in determining the morphology, yield, and quality of CNTs grown by CVD, and enable direct growth of CNT films in micromachined systems for a variety of applications.