Microstructure,mechanical properties and machining performance of spark plasma sintered Al2O3–ZrO2–TiCN nanocomposites

The effect of addition of nanocrystalline ZrO₂ and TiCN to ultrafine Al₂O₃ on mechanical properties and microstructure of the composites developed by spark plasma sintering (SPS) was investigated. The distribution of the nanoparticles was dependent on their overall concentration. Maximum hardness (21 GPa) and indentation toughness (5.5 MPa m^1/2) was obtained with 23 vol% nanoparticles, which was considered as the optimum composition. The Zener pinning criteria were also satisfied at this composition with grain size of the restraining nanoparticles ～63–65 nm. Hardness of the composites follows the rule of mixtures; crack deflection and crack arrest by nanoparticles at grain boundaries along with mixed fracture mode led to high toughness in the nanocomposites. Cutting tool inserts were developed by SPS with the optimized composition and their machining performance was compared with commercial alumina based inserts. Increased toughness in the nanocomposite inserts reflects in the machining performance as the tool life improves drastically compared to that of the commercial inserts at high cutting speeds ≥500 m min^?1. This was attributed to differences in their failure modes; the commercial inserts fail catastrophically by fracture due to their low toughness whereas the nanocomposite inserts reach the tool failure criteria by crater wear at all machining conditions.     

Electrical properties and microstructural evolution of ZrO2–Al2O3–TiN nanocomposites prepared by spark plasma sintering

Electroconductive ZrO₂–Al₂O₃–25 vol% TiN ceramic nanocomposites were prepared by spark plasma sintering at 1200 °C for 3 min. The electrical resistivity of the composites decreased from 4.5 × 10^?4 Ω m to 3 × 10^?5 Ω m as the Al₂O₃ content in the ZrO₂–Al₂O₃ matrix increased from 0 to 100 vol%. SEM images graphically presented the microstructural evolution of the composites and a geometrical percolation model was applied to investigate the relationship between the electrical property and the microstructure. The results indicated that the addition of Al₂O₃ to ZrO₂–TiN improved the electrical conductivity of the material by tailoring the structure from “nano–nano” type for ZrO₂–TiN to “micro–nano” type for ZrO₂–Al₂O₃–TiN.     

Creep behaviour of Al2O3–SiC nanocomposites

Compared with monolithic fine grained Al₂O₃, Al₂O₃ nanocomposites reinforced with SiC nanoparticles display especially high modulus of rupture as well as reduced creep strain. Taking into account the fracture mode change, the morphology of ground surfaces showing plastic grooving, the low sensitivity to wear and the low dependence of erosion rate with grain size, it can be reasonably assumed that the strength improvement is associated with an increase of the interface cohesion (due to bridging by SiC particles) rather than with a grain size refinement involving substructure formation (as initially suggested by Niihara). In the present work, creep tests have been performed and the results agree with such a reinforcement of the mechanical properties by SiC particle bridging Al₂O₃–Al₂O₃ grain boundaries. Indeed, particles pinning the grain boundaries hinder grain boundary sliding resulting in a large improvement in creep resistance. In addition, SiC particles, while counteracting sliding, give rise to a recoverable viscoelastic contribution to creep. Because of the increased interface strength, the samples undergoing creep support stress levels, greater than the threshold value required to activate dislocation motion. The high stress exponent value as well as the presence of a high dislocation density in the strained materials suggests that a lattice mechanism controls the deformation process. Finally, a model is proposed which fits well with the experimental creep results.     

Microstructure,hardness and fracture toughness of spark plasma sintered ZrB2–SiC–Cf composites

The combined effects of SiC particles and chopped carbon fibers (C_f) as well as sintering conditions on the microstructure and mechanical properties of spark plasma sintered ZrB₂-based composites were investigated by Taguchi methodology. Analysis of variance was used to optimize the spark plasma sintering variables (temperature, time and pressure) and the composition (SiC/C_f ratio) in order to enhance the hardness of ZrB₂–SiC–C_f composites. The sintering temperature was found as the most effective variable, with a significance of 83%, on the hardness. The hardest ZrB₂-based ceramic was achievable by adding 20 vol% SiC and 10 vol% C_f after spark plasma sintering at 1850 °C for 6 min under 30 MPa. Fracture toughness improvement were related to the simultaneous presence of SiC and C_f phases as well as the in-situ formation of nano-sized interfacial ZrC particles. Crack deflection, crack branching and crack bridging were detected as the toughening mechanisms. A Vickers hardness of 14.8 GPa and an indentation fracture toughness of 6.8 MPa m^1/2 were measured for the sample fabricated at optimal processing conditions.     

Dielectric and electrical conductivity properties of multi-stage spark plasma sintered HA–CaTiO3 composites and comparison with conventionally sintered materials

One of the different issues limiting the wider application of monolithic hydroxyapatite (HA) as an ideal bone replacement material is the lack of reasonably good electrical transport properties. The comprehensive electrical property characterization to evaluate the efficacy of processing parameters in achieving the desired combination of electroactive properties is considered as an important aspect in the development of HA-based bioactive material. In this perspective, the present work reports the temperature (RT-200 °C) and frequency (100 Hz–1 MHz) dependent dielectric properties and AC conductivity for a range of HA–CaTiO₃ (HA–CT) composites, densified using both conventional pressureless sintering in air as well as spark plasma sintering in vacuum. Importantly, the AC conductivity of spark plasma sintered ceramics [～upto 10^?5 (Ω cm)^?1] are found to be considerably higher than the corresponding pressureless sintered ceramics [～upto 10^?8 (Ω cm)^?1]. Overall, the results indicate the processing route dependent functional properties of HA–CaTiO₃ composites as well as related advantages of spark plasma sintering route.     

Fabrication and microstructure of Al2O3–ZrO2(3Y)–SiC nanocomposites

Al₂O₃–ZrO₂(3Y)–SiC composite powder was prepared by the heterogeneous precipitation method. Calcinating temperature of the powder was important to obtain dense sintered body. The nanocomposites were got by hot-pressing, and addition of ZrO₂ did not raise the sintering temperature. Some Al₂O₃ grain shape was elongated, and Al₂O₃ grain size was about μm. Nano SiC particles were observed uniformly distributing throughout the composites, and most of them were located within the matrix grains. Because SiC particles located within ZrO₂ grains influenced the phase transformation of ZrO₂, the sintering of nanocomposites, which controlled grain size and transformable ZrO₂ amount, become important to get high performance. The strength of 80 wt% Al₂O₃–15 wt% ZrO₂–5 wt% SiC nanocomposites was 555 MPa, and toughness was 3·8 MPa m^1/2, which were higher than those of monolithic Al₂O₃ ceramics. ©     

Microstructure analysis and mechanical properties of a new class of Al2O3–WC nanocomposites fabricated by spark plasma sintering

We report the synthesis of a new class of Al₂O₃–WC nanocomposites for the first time by using metal–organic chemical vapor deposition process in a spouted bed followed by spark plasma sintering technique. The microstructure and mechanical properties of these prepared nanocomposites have been analyzed for various sintering parameters. From microstructure observation, it is found that the nanosized WC particles are dispersed within alumina matrix grains and intergrains. The microstructure of transgranular and step-wise fracture surface are found in these nanocomposites. The basic mechanical properties like density, hardness, and toughness also have been analyzed and the results are interpreted by correlating with that of corresponding microstructures.     

TEM characterization of spark plasma sintered ZrB2–SiC–graphene nanocomposite

The interfacial behavior of spark plasma sintered ZrB₂–SiC nanocomposite doped with graphene nano-platelets was investigated by transmission electron microscopy (TEM). A powder mixture including ZrB₂ matrix, 20?vol% SiC and 10?vol% graphene was used as the starting material. X-ray diffraction analysis did not exhibit any in situ phase formation in the prepared nanocomposite. TEM observations verified the diffusion-controlled sintering. This study clarifies that graphene nano-platelets additive in the prepared nanocomposite did not engage in reactive sintering process, unlike many previous research studies addressing reactive sintering role for carbon additives.     

Development and evaluation of TiB2–AlN ceramic composites sintered by spark plasma

Titanium diboride (TiB₂) is a ceramic material with high mechanical resistance, chemical stability, and hardness at high temperatures. Sintering this material requires high temperatures and long sintering times. Non-conventional sintering techniques such as spark plasma sintering (SPS) can densify materials considered difficult to sinter. In this study, TiB₂–AIN (aluminum nitride) composites were sintered by using the SPS technique at different sintering temperatures (1500 °C, 1600 °C, 1700 °C, 1800 °C, and 1900 °C). x-ray diffraction was used to identify the phases in the composites. mechanical properties such as hardness and indentation fracture toughness was obtained using a vickers indenter. Different toughening mechanisms were identified, and good densification results were obtained using shorter times and lower temperatures than those previously reported.     

Development of spark plasma sintered conductive SiC–TiB2 composites for electrical discharge machining applications

Highly dense electrically conductive silicon carbide (SiC)–(0, 10, 20, and 30 vol%) titanium boride (TiB₂) composites with 10 vol% of Y₂O₃–AlN additives were fabricated at a relatively low temperature of 1800°C by spark plasma sintering in nitrogen atmosphere. Phase analysis of sintered composites reveals suppressed β→α phase transformation due to low sintering temperature, nitride additives, and nitrogen sintering atmosphere. With increase in TiB₂ content, hardness increased from 20.6 to 23.7 GPa and fracture toughness increased from 3.6 to 5.5 MPa m^1/2. The electrical conductivity increased to a remarkable 2.72 × 10³ (Ω cm)^–1 for SiC–30 vol% TiB₂ composites due to large amount of conductive reinforcement, additive composition, and sintering in nitrogen atmosphere. The successful electrical discharge machining illustrates potential of the sintered SiC–TiB₂ composites toward extending the application regime of conventional SiC-based ceramics.     

In-situ fabrication of Al2O3–SiC nanocomposites using B2O3 as sintering aid

Al₂O₃–SiC nanocomposites with 5 and 10 vol% SiC have been in-situ fabricated by sol-gel method followed by carbothermal reduction of alumina–silica gel using B₂O₃ as sintering aid. Green bodies were formed by cold isostatic pressing of calcined gel, which was prepared by an aqueous sol-containing aluminum chloride, TEOS, sucrose and boric acid. Pressureless sintering was carried out in Ar–12%H₂ atmosphere at 1700 °C. Addition of B₂O₃ (1 or 3 wt%) was an effective densification aid in the Al₂O₃–5 vol% SiC composites, while the densification of Al₂O₃–10 vol% SiC composites was not affected by adding B₂O₃. The composite material containing 5 vol% SiC doped with 3 wt% B₂O₃ reached 98.7% of full density. Nano-sized β-SiC particles were formed in-situ by means of a reaction between mullite and carbon at 1600 °C. Scanning electron microscopy revealed that the spherical in-situ synthesized SiC nanoparticles were well distributed through the composite and located predominantly to the interior of alumina matrix grains.     

Synthesis,microstructure and electrical conductivity of carbon nanotube–alumina nanocomposites

Carbon nanotube–alumina (CNT–Al₂O₃) nanocomposites have been synthesized by direct growth of carbon nanotubes on alumina by chemical vapor deposition (CVD) and the as-grown nanocomposites were densified by spark plasma sintering (SPS). Surface morphology analysis shows that the CNTs and CNT bundles are very well distributed between the matrix grains creating a web of CNTs as a consequence of their in situ synthesis. Even after the SPS treatment, the CNTs in the composite material are still intact. Experimental result shows that the electrical conductivity of the composites increases with the CNT content and falls in the range of the conductivity of semiconductors. The nanocomposite with highest CNT content has electrical conductivity of 3336 S/m at near room temperature, which is about 13 orders of magnitude increase over that of pure alumina.     

Electrical resistivity of Cr–Al2O3 and ZrxAly–Al2O3 composites with interpenetrating microstructure

AC and DC resistivity of Cr–Al₂O₃ and Zr_xAl_y–Al₂O₃ composites with varying metal content were measured. A strong percolation behavior was observed in the Cr–Al₂O₃ system, where the AC resistivity varied nine orders of magnitude close to the percolation threshold of 28 vol.%. AC measurements were less dependant on the contact resistance than DC measurements. The best reproducibility was obtained at a frequency of 100 kHz. AC resistivity values of insulating composites differed from DC values and may also be frequency-dependant. DC measurements up to 600 °C indicate that the intermetallic phases ZrAl₃ and ZrAl are PTC conductors. The electrical properties of Zr_xAl_y–Al₂O₃ samples with a metal content of 29 vol.% were anisotropic, with a much higher resistivity in the pressing direction.     

Mechanical and functional properties of Al2O3–ZrO2–MWCNTs nanocomposites

Multi-walled carbon nanotubes (MWCNTs) are often reported as additives improving mechanical and functional properties of ceramic composites. However, despite tremendous efforts in the field in the past 20 years, the results are still inconclusive. This paper studies room temperature properties of the composites with polycrystalline alumina matrix reinforced with 0.5–2 vol.% MWCNTs (composites AC) and zirconia toughened alumina with 5 vol.% of yttria partially stabilised zirconia (3Y-PSZ) containing 0.5–2 vol.% of MWCNTs (composites AZC). Dense composites were prepared through wet mixing of the respective powders with functionalised MWCNTs, followed by freeze granulation, and hot-pressing of granulated powders. Room temperature bending strength, Young's modulus, indentation fracture toughness, thermal and electrical conductivity of the composites were studied, and related to their composition and microstructure. Slight increase of Young's modulus, indentation fracture toughness, bending strength, and thermal conductivity was observed at the MWCNTs contents ≤1 vol.%. At higher MWCNTs contents the properties were impaired by agglomeration of the MWCNTs. The DC electrical conductivity increased with increasing volume fraction of the MWCNTs.     

Mechanical properties and thermal conductivity of dense β-SiAlON ceramics fabricated by two-stage spark plasma sintering with Al2O3-AlN-Y2O3 additives

Fully dense β-SiAlON ceramics with excellent mechanical properties and good thermal conductivity were fabricated by two-stage spark plasma sintering (SPS) processes without and with applying pressure respectively, using α-Si₃N₄ powder and 6 Al₂O₃-3 AlN-6 Y₂O₃ (in wt.%, label with 636), 424 and 422 additives. In the first stage SPS process without pressure, the relative dense β-SiAlON ceramics with interlock microstructures of elongated grains and density of 3.14˜3.18 g cm⁻³, hardness of 14.00˜14.82 GPa and fracture toughness of 6.00˜6.63 MPa m^1/2 were obtained by sintering at about 1600 °C for 20 min. In the second stage SPS process at about 1425 °C for 5 min under pressure of 24 MPa, the fully dese β-SiAlON ceramics with density of 3.22˜3.24 g cm⁻³, high hardness of 15.68˜15.95 GPa, high fracture toughness of 6.38˜7.03 MPa m^1/2 and thermal conductivity of 13.5˜19.6 Wm^-1K^-1 were obtained. The reaction between the samples and the graphite mold can be avoided in this fabrication method.     

Particle occlusion and mechanical properties of Ni–Al2O3 nanocomposites

Polycrystalline alumina, doped with MgO below the solubility limit, was reinforced with sub-micron particles of Ni by infiltration of Ni-nitrate into fired alumina green bodies, followed by reduction and sintering. The Ni particle size and location were monitored both after reduction and after sintering by transmission electron microscopy. Particle occlusion was found to increase with sintering time and temperature, and is correlated with experimentally detected Mg segregation to the Ni–alumina interfaces, resulting in partial depletion of Mg at the alumina grain boundaries and thus their increased mobility. Occlusion of Ni particles reduces the fracture strength and Weibull modulus of the composites, indicating that particle location is a key microstructural parameter for reaching high fracture strengths, and that this can be controlled via grain boundary and interface adsorption.     

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.     

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.     

Reactive,nonreactive, and flash spark plasma sintering of Al2O3/SiC composites—A comparative study

The influence of different SPS-based methods, that is, conventional spark plasma sintering (SPS), flash SPS (FSPS), and reactive SPS (RSPS) on the properties of Al₂O₃/SiC composite was investigated. It was shown that the application of preliminary high energy ball milling of the powders significantly enhances the sinterability of the ceramics. It was also demonstrated that FSPS provides unique conditions for rapid, that is, less than a minute, consolidation of refractory ceramics. The Al₂O₃-20 wt% SiC composite produced by FSPS possesses the highest relative density (~99%), fracture toughness (7.5 MPa m^1/2), hardness (20.3 GPa) and wear resistance among all ceramics produced by other SPS-based approaches with dwelling time 10 minutes. The RSPS ceramics hold the highest Young's modulus (390 GPa). Substitution of micron-sized Al₂O₃ particles by nano alumina does not lead to measurable enhancement of the mechanical properties.     

A novel approach for preparation of dense TiC–SiC nanocomposites by sol–gel infiltration and spark plasma sintering

Dense TiC–SiC nanocomposite ceramics were prepared by infiltration of porous TiC scaffolds with a SiOC sol, followed by spark plasma sintering (SPS). The porous nano TiC scaffold was first synthesized by direct carbothermal reduction of a monolithic TiOC precursor obtained from a controlled sol–gel process. The TiC scaffold was infiltrated with a SiOC sol and then the sample was aged in a container for 48 h at 80 °C to convert the sol into gel. After this, the sample was heated at 550 °C to remove the organic components and then 1350 °C to convert the SiOC gel to SiC by carbothermal reduction reaction. The cycle of the infiltration and carbothermal reduction was repeated several times to obtain relatively dense TiC–SiC composite samples. Dense TiC–SiC composite with a uniform nano-sized grain microstructure was obtained by spark plasma sintering at 1800 °C for 5 min under 40 MPa uniaxial pressure. Compared with conventional powder mixing methods, the sol–gel infiltration approach has shown distinct advantages of achieving dense TiC–SiC composites with uniform nano-sized grain structures.