Mechanical and electrical properties of carbon nanotube buckypaper reinforced silicon carbide nanocomposites

The nanocomposite was produced via phenolic resin infiltrating into a carbon nanotube (CNT) buckypaper preform containing B₄C fillers and amorphous Si particles followed by an in-situ reaction between resin-derived carbon and Si to form SiC matrix. The buckypaper preform combined with the in-situ reaction avoided the phase segregation and increased significantly the volume fraction of CNTs. The nanocomposites prepared by this new process were dense with the open porosities less than 6%. A suitable CNT–SiC bonding was achieved by creating a B₄C modified interphase layer between CNTs and SiC. The hardness increased from 2.83 to 8.58 GPa, and the indentation fracture toughness was estimated to increase from 2.80 to 9.96 MPa m^1/2, respectively, by the reinforcing effect of B₄C. These nanocomposites became much more electrically conductive with high loading level of CNTs. The in-plane electrical resistivity decreased from 124 to 74.4 μΩ m by introducing B₄C fillers.     

Microstructure and mechanical properties of hot-pressed B4C/TiC/Mo ceramic composites

Boron carbide (B₄C)/TiC/Mo ceramic composites with different content of TiC were produced by hot pressing. The effect of TiC content on the microstructure and mechanical properties of the composites has been studied. Results showed that chemical reaction took place for this system during hot pressing sintering, and resulted in a B₄C/TiB₂/Mo composite with high density and improved mechanical properties compared to monolithic B₄C ceramic. Densification rates of the B₄C/TiC/Mo composites were found to be affected by additions of TiC. Increasing TiC content led to increase in the densification rates of the composites. The sintering temperature was lowered from 2150 °C for monolithic B₄C to 1950 °C for the B₄C/TiC/Mo composites. The fracture toughness, flexural strength, and hardness of the composites increased with increasing TiC content up to 10 wt.%. The maximum values of fracture toughness, flexural strength, and hardness are 4.3 MPa m^1/2, 695 MPa, and 25.0 GPa, respectively.     

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.     

Additive-free superhard B4C with ultrafine-grained dense microstructures

A unique combination of high-energy ball-milling, annealing, and spark-plasma sintering has been used to process superhard B₄C ceramics with ultrafine-grained, dense microstructures from commercially available powders, without sintering additives. It was found that the ultrafine powder prepared by high-energy ball-milling is hardly at all sinterable, but that B₂O₃ removal by gentle annealing in Ar provides the desired sinterability. A parametric study was also conducted to elucidate the role of the temperature (1600–1800 °C), time (1–9 min), and heating ramp (100 or 200 °C/min) in the densification and grain growth, and thus to identify optimal spark-plasma sintering conditions (i.e., 1700 °C for 3 min with 100 °C/min) to densify completely (>98.5%) the B₄C ceramics with retention of ultrafine grains (∼370 nm). Super-high hardness of ∼38 GPa without relevant loss of toughness (∼3 MPa m^1/2) was thus achieved, attributable to the smaller grain size and to the transgranular fracture mode of the B₄C ceramics.     

Densification behaviour and mechanical properties of B4C–SiC intergranular/intragranular nanocomposites fabricated through spark plasma sintering assisted by mechanochemistry

High-performance B₄C–SiC nanocomposites with intergranular/intragranular structure were fabricated through spark plasma sintering assisted by mechanochemistry with B₄C, Si and graphite powders as raw materials. Given their unique densification behaviour, two sudden shrinkages in the densification curve were observed at two very narrow temperature ranges (1000–1040 °C and 1600–1700 °C). The first sudden shrinkage was attributed to the volume change in SiC resulting from disorder–order transformation of the SiC crystal structure. The other sudden shrinkage was attributed to the accelerated densification rate resulting from the disorder–order transformation of the crystal structure. The high sintering activity of the synthesised powders could be utilised sufficiently because of the high heating rate, so dense B₄C–SiC nanocomposites were obtained at 1700 °C. In addition, the combination of high heating rate and the disordered feature of the synthesised powders prompted the formation of intergranular/intragranular structure (some SiC particles were homogeneously dispersed amongst B₄C grains and some nanosized B₄C and SiC particles were embedded into B₄C grains), which could effectively improve the fracture toughness of the composites. The relative density, Vickers hardness and fracture toughness of the samples sintered at 1800 °C reached 99.2±0.4%, 35.8±0.9 GPa and 6.8±0.2 MPa m^1/2, respectively. Spark plasma sintering assisted by mechanochemistry is a superior and reasonable route for preparing B₄C–SiC composites.     

Mechanical properties and deformation mechanisms of B4C–TiB2 eutectic composites

Samples of B₄C–TiB₂ eutectic are laser processed to produce composites with varying microstructural scales. The eutectic materials exhibit both load dependent and load independent hardness regimes with a transition occurring between 4 and 5 N indentation load. The load-independent hardness of eutectics with a microstructural scale smaller than 1 μm is about 31 GPa, and the indentation fracture toughness (5–10 N indenter load) of the eutectics is 2.47–4.76 MPa m^1/2. Indentation-induced cracks are deflected by TiB₂ lamellae, and indentation-induced spallation is reduced in the B₄C–TiB₂ eutectic compared to monolithic B₄C. Indentation-induced amorphization in monolithic B₄C and the B₄C phase of the eutectic is detected using Raman spectroscopy. Sub-surface damage is observed using TEM, including microcracking and amorphization damage in B₄C and B₄C–TiB₂ eutectics. Dislocations are observed in the TiB₂ phase of eutectics with an interlamellar spacing of 1.9 μm.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

Reinforcement of precursor-derived Si–C–N ceramics with carbon nanotubes

Nanocomposites consisting of precursor-derived Si–C–N ceramics incorporated with carbon nanotubes (CNTs) were successfully prepared by casting of a mixture of CNTs and a liquid precursor polymer followed by cross-linking and thermolysis. The effect of CNTs on the fracture toughness of these nanocomposites was investigated by a thermal loading technique. The results reveal a dependence of the fracture toughness on the type of the CNTs. One type shows a significant increase of the fracture toughness at CNT contents of only 1–2 mass%, whereas the other one exhibits no effect. The microstructural effects of CNTs observed at the fracture surfaces of the nanocomposites by scanning electron microscope (SEM) and transmission electron microscope (TEM) can be correlated with the observed fracture toughness behavior.     

Microstructures and mechanical properties of B4C–SiC intergranular/intragranular nanocomposite ceramics fabricated from B4C,Si, and graphite powders

B₄C–SiC intergranular/intragranular nanocomposites with high hardness and high toughness were fabricated through mechanochemical processing with B₄C, Si, and graphite powders and subsequent hot pressing without any sintering aid. The milled powders are composed of stacking-disordered SiC and nanocrystalline B₄C. Most nano/micron-sized SiC particles are homogeneously dispersed in B₄C matrix, and some nano-sized SiC and B₄C particles are embedded into B₄C grains to form an intergranular/intragranular structure. The disordered characteristic of the milled powders is the essential factor for the formation of the intragranular structure, sudden densification within the narrow temperature range (1700–1900 °C), and the preparation of dense samples under a relatively low temperature (1900 °C). The relative density, Vickers hardness, and fracture toughness of the samples sintered at 1950 °C are 98.6%, 34.3 GPa, and 6.0 MPa m^1/2, respectively. The intergranular/intragranular structure plays an important role in improving fracture toughness and hardness of the composites.     

Microstructure development,hardness, toughness and creep behaviour of pressureless sintered alumina/SiC micro–nanocomposites obtained by slip-casting

Al₂O₃–SiC micro–nanocomposites are much more resistant materials than monolithic alumina regarding some mechanical properties. In order to study the possibility of obtaining creep resistant alumina/SiC micro–nanocomposites using inexpensive forming methods, alumina 1 and 5 vol% SiC materials were produced by slip-casting and pressureless sintering. Well-densified alumina–SiC pressureless sintered materials were obtained at 1700 °C for 2 h and attained 97–99% of the theoretical density. The microstructure, hardness and toughness were examined and 4-point flexure creep tests were performed at 1200 °C and 100 MPa in air. Compared with pure alumina materials, the creep resistance, toughness and hardness were enhanced drastically in materials containing 5 vol% of SiC.     

Bulk boron carbide nanostructured ceramics by reactive spark plasma sintering

Bulk boron carbide (B₄C) ceramics was fabricated from a boron and carbon mixture by use of one-step reactive spark plasma sintering (RSPS). It was also demonstrated that preliminary high-energy ball milling (HEBM) of the B+C powder mixture leads to the formation of B/C composite particles with enhanced reactivity. Using these reactive composites in RSPS permits tuning of synthesized B₄C ceramic microstructure. Optimization of HEBM + RSPS conditions allows rapid (less than 30 min of SPS) fabrication of B₄C ceramics with porosity less than 2%, hardness of ~35 GPa and fracture toughness of ~ 4.5 MPa m ^1/2     

Microstructure and densification of ZrB2–SiC composites prepared by spark plasma sintering

ZrB₂–SiC composites were prepared by spark plasma sintering (SPS) at temperatures of 1800–2100 °C for 180–300 s under a pressure of 20 MPa and at higher temperatures of above 2100 °C without a holding time under 10 MPa. Densification, microstructure and mechanical properties of ZrB₂–SiC composites were investigated. Fully dense ZrB₂–SiC composites containing 20–60 mass% SiC with a relative density of more than 99% were obtained at 2000 and 2100 °C for 180 s. Below 2120 °C, microstructures consisted of equiaxed ZrB₂ grains with a size of 2–5 μm and α-SiC grains with a size of 2–4 μm. Morphological change from equiaxed to elongated α-SiC grains was observed at higher temperatures. Vickers hardness of ZrB₂–SiC composites increased with increasing sintering temperature and SiC content up to 60 mass%, and ZrB₂–SiC composite containing 60 mass% SiC sintered at 2100 °C for 180 s had the highest value of 26.8 GPa. The highest fracture toughness was observed for ZrB₂–SiC composites containing 50 mass% SiC independent of sintering temperatures.     

Microstructure and mechanical properties of B4C based ceramics with Fe3Al as sintering aid by spark plasma sintering

B₄C based ceramics were fabricated with different Fe₃Al contents as sintering aids by spark plasma sintering at relatively low temperature (1700 °C) in vacuum by applying 50 MPa pressure and held at 1700 °C for 5 min. The effect of Fe₃Al additions (from 0 to 9 wt%) on the microstructure and mechanical properties of B₄C has been studied. The composition and microstructure of as-prepared samples were characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe microanalyzer (EPMA) equipped with WDS (wavelength dispersive spectrometry) and EDS. The mixtures of B₄C and Fe₃Al underwent a major reaction in which the metal borides and B₄C were encountered as major crystallographic phases. The sample with 7 wt% of Fe₃Al as a sintering aid was found to have 32.46 GPa Vickers hardness, 483.40 MPa flexural strength, and 4.1 MPa m^1/2 fracture toughness which is higher than that of pure B₄C.     

Effect of post-sintering heat-treatment on thermal and mechanical properties of Si3N4 ceramics sintered with different additives

To improve the thermal conductivity of Si₃N₄ ceramics, elimination of grain-boundary glassy phase by post-sintering heat-treatment was examined. Si₃N₄ ceramics containing SiO₂–MgO–Y₂O₃-additives were sintered at 2123 K for 2 h under a nitrogen gas pressure of 1.0 MPa. After sintering, the SiO₂ and MgO could be eliminated from the ceramics by vaporization during post-sintering heat-treatment at 2223 K for 8 h under a nitrogen gas pressure of 1.0 MPa. Thermal conductivity of 3 mass% SiO₂, 3 mass% MgO and 1 mass% Y₂O₃-added Si₃N₄ ceramics increases from 44 to 89 Wm⁻¹ K⁻¹ by the decrease in glassy phase and lattice oxygen after the heat-treatment. Relatively higher fracture toughness (3.8 MPa m^1/2) and bending strength (675 MPa) with high hardness (19.2 GPa) after the heat-treatment were achieved in this specimen. Effects of heat-treatment on microstructure and chemical composition were also observed, and compared with those of Y₂O₃–SiO₂-added and Y₂O₃–Al₂O₃-added Si₃N₄ ceramics.     

Processing,microstructure, and mechanical properties of zirconium diboride-boron carbide ceramics

The processing, microstructure, and mechanical properties of zirconium diboride-boron carbide (ZrB₂-B₄C) ceramics were characterized. Ceramics containing nominally 5, 10, 20, 30, and 40 vol% B₄C were hot-pressed to full density at 1900 °C. The ZrB₂ grain size decreased from 4 to 2 µm and B₄C inclusion size increased from 3 to 5 µm for B₄C additions of 5 and 40 vol% B₄C, respectively. Elastic modulus decreased from 525 to 515 GPa and Vickers hardness increased from 15 to 21 GPa as the B₄C content increased from 5 to 40 vol%, respectively, following trends predicted using linear rules of mixtures. Flexure strength and fracture toughness both increased with increasing B₄C content. Fracture toughness increased from 4.1 MPa m^½ at 5 vol% B₄C to 5.3 MPa m^½ at 40 vol% B₄C additions. Flexure strength was 450 MPa with a 5 vol% B₄C addition, increasing to 590 MPa for a 40 vol% addition. The critical flaw size was calculated to be ~30 µm for all compositions, and analysis of the fracture surfaces indicated that strength was controlled by edge flaws generated by machining induced sub-surface damage. Increasing amounts of B₄C added to ZrB₂ led to increasing hardness due to the higher hardness of B₄C compared to ZrB₂ and increased crack deflection. Additions of B₄C also lead to increases in fracture toughness due to increased crack deflection and intergranular fracture.     

Toughening of super-hard ultra-fine grained B4C densified by spark-plasma sintering via SiC addition

Toughening of super-hard B₄C ceramics with ultra-fine grained microstructures via the addition of SiC (15 wt.%) or the simultaneous addition of SiC (15 wt.%) and graphite (2 wt.%) is reported. The ultra-fine grained B₄C–SiC and B₄C–SiC–C composites prepared by spark-plasma sintering from powder mixtures subjected to high-energy co-ball-milling are found to be remarkably tougher (i.e., ～65% and 50%) than the pure B₄C ceramic with a coarsened microstructure. Crack bridging by the homogenously dispersed SiC grains can give an explanation for the improvement in toughness. Also, the addition of SiC to the B₄C matrix was found to change the fracture mode from purely transgranular to a mixture of intergranular and transgranular fracture. This is derived from the weakness of the B₄C–SiC interfaces due to the existence of residual thermo-elastic stresses. It was also found that despite SiC is softer than B₄C, the B₄C–SiC are yet extremely hard if densified appropriately, with the hardness even reaching 36 GPa.     

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.     

Properties of Si3N4–TiN composites fabricated by spark plasma sintering by using a mixture of Si3N4 and Ti powders

Si₃N₄–TiN composites were successfully fabricated via planetary ball milling of 70 mass% Si₃N₄ and 30 mass% Ti powders, followed by spark plasma sintering (SPS) at 1250–1350 °C. The sintering mechanism for SPS was a hybrid of dissolution–reprecipitation and viscous flow. The electrical resistivity decreased with increasing sintering temperature up to a minimum at 1250 °C and then increased with the increasing sintering temperature. The composites prepared by SPS at 1250–1350 °C could be easily machined by electrical discharge machining. Composite prepared by SPS at 1300 °C showed a high hardness (17.78 GPa) and a good machinability.     

Carbon nanotube/boehmite-derived alumina ceramics obtained by hydrothermal synthesis and spark plasma sintering (SPS)

Preparation, structure and properties of hydrothermally treated carbon nanotube/boehmite (CNT/γ-AlOOH) and densification with spark plasma sintering of Al₂O₃ and CNT/Al₂O₃ nanocomposites were investigated. Hydrothermal synthesis was employed to produce CNT/boehmite from an aluminum acetate (Al(OH)(C₂H₃O₂)₂) and multiwall-CNTs mixture (200 °C/2 h.). TEM observations revealed that the size of the cubic shape boehmite particles lies around 40 nm and the presence of the interaction between surface functionalized CNTs and boehmite particles acts to form ‘nanocomposite particles’. Al₂O₃ and CNT/Al₂O₃ compact bodies were formed by means of spark plasma sintering (SPS) at 1600 °C for 5 min using an applied pressure of 50MPa resulting in the formation of stable α-Al₂O₃ phase and CNT–alumina compacts with nearly full density. It was also found that CNTs tend to locate along the alumina grain boundaries and therefore inhibit the grain coarsening and cause inter-granular fracture mode. The DC conductivity measurements reveal that the DC conductivity of CNT/Al₂O₃ is 10^?4 S/m which indicate that there is a 4 orders of magnitude increase in conductivity compared to monolithic Al₂O₃. The results of the microhardness tests indicate a slight increase in hardness for CNT/Al₂O₃ (28.35 GPa for Al₂O₃ and 28.57 GPa for CNT/Al₂O₃).     

Hard polycrystalline eutectic composite prepared by spark plasma sintering

A polycrystalline eutectic B₄C–TiB₂ composite was prepared by spark plasma sintering. The starting eutectic powder was obtained by mechanical grinding of the directionally solidified eutectic B₄C–TiB₂ alloy. The microstructure of the polycrystalline composite exhibited randomly oriented eutectic grains with an average size of about 50–100 μm. Eutectic grains consisted of boron carbide matrix reinforced by titanium diboride inclusions. The secondary eutectic structure in the grain boundary is formed at sintering temperature higher than 1700 °C. XRD analysis revealed that the eutectic B₄C–TiB₂ composite consist mainly of B₄C and TiB₂ phases. The measured Vickers hardness was in the range of 32.35–54.18 GPa and the average fracture toughness of the samples was as high as 4.81 MPa m^1/2. The bending strengths of the composite evaluated at room temperature and at 1600 °C were 230 and 190 MPa, respectively.