Mechanical Properties and Microstructure of Nano-SiC–Al2O3 Composites Densified by Spark Plasma Sintering

Heterogeneous precipitation method has been used to produce 5 vol% SiC–Al₂O₃ powder, from aqueous suspension of nano-SiC, aqueous solution of aluminium chloride and ammonia. The resulting gel was calcined at 700°C. Nano-SiC–Al₂O₃ composites were densified using spark plasma sintering (SPS) process by heating to a sintering temperature at 1350, 1400, 1450, 1500 and 1550°C, at a heating rate of 600 °/min, with no holding time, and then fast cooling to 600°C within 2–3 min. High density composites could be achieved at lower sintering temperatures by SPS, as compared with that by hot-press sintering process. Bending strength of 5 vol% SiC–Al₂O₃ densified by SPS at 1450°C reached as high as 1000 MPa. Microstructure studies found that the nano-SiC particles were mainly located within the Al₂O₃ grains and the fracture mode of the nanocomposites was mainly transgranular fracture.     

Mechanical behavior of zirconium diboride–silicon carbide ceramics at elevated temperature in air

The mechanical properties of zirconium diboride–silicon carbide (ZrB₂–SiC) ceramics were characterized from room temperature up to 1600 °C in air. ZrB₂ containing nominally 30 vol% SiC was hot pressed to full density at 1950 °C using B₄C as a sintering aid. After hot pressing, the composition was determined to be 68.5 vol% ZrB₂, 29.5 vol% SiC, and 2.0 vol% B₄C using image analysis. The average ZrB₂ grain size was 1.9 μm. The average SiC particles size was 1.2 μm, but the SiC particles formed larger clusters. The room temperature flexural strength was 680 MPa and strength increased to 750 MPa at 800 °C. Strength decreased to ～360 MPa at 1500 °C and 1600 °C. The elastic modulus at room temperature was 510 GPa. Modulus decreased nearly linearly with temperature to 210 GPa at 1500 °C, with a more rapid decrease to 110 GPa at 1600 °C. The fracture toughness was 3.6 MPa·m^½ at room temperature, increased to 4.8 MPa·m^½ at 800 °C, and then decreased linearly to 3.3 MPa·m^½ at 1600 °C. The strength was controlled by the SiC cluster size up to 1000 °C, and oxidation damage above 1200 °C.     

Direct coagulation casting of silicon nitride suspension via a dispersant reaction method

A direct coagulation casting method for silicon nitride suspension via dispersant reaction was reported. Tetramethylammonium hydroxide (TMAOH) was used as dispersant to prepare silicon nitride suspension with high solid loading and low viscosity. Influences of TMAOH and pH value on the dispersion of silicon nitride powder were investigated. Glycerol diacetate (GDA) was used to coagulate the silicon nitride suspension. Influences of the concentration of glycerol diacetate on the viscosity and pH value of the suspension were investigated. It was indicated that high viscosity sufficient to coagulate the suspension was achieved by adding 1.0–2.0 vol% glycerol diacetate at 40–70 °C. The coagulation mechanism was proposed that the silicon nitride suspension was destabilized by dispersant reacting with acetic acid which was hydrolyzed from glycerol diacetate at elevated temperature. Coagulated samples could be demolded without deformation by treating 50 vol% silicon nitride suspensions with 0.2 wt% tetramethylammonium hydroxide and 1.0–2.0 vol% glycerol diacetate at different temperatures. Dense silicon nitride ceramics with relative density above 98.8% had been prepared by this method using glycerol diacetate as coagulating agent sintered by different methods.     

Microstructure evolution and wear resistance of nitride/aluminide coatings on the surface of Ti-coated 2024 Al alloy during plasma nitriding

A duplex surface treatment consisting in depositing a Ti film followed by plasma nitriding was adopted to improve the wear resistance of 2024 Al alloys. Nano-grained Ti films were firstly deposited on the substrate surface by using magnetron sputtering, then plasma nitrided for 8 h at 400 °C, 430 °C, 460 °C and 490 °C, in a gas mixture of 40% N₂+60% H₂. Duplex coatings composed of three sublayers (i.e. the outmost TiN_0.3 layer, the intermediate Al₃Ti layer and the inside Al₁₈Ti₂Mg₃ layer) were obtained at nitriding temperature higher than 460 °C. The coatings obtained at 400 °C and 430 °C consisted of mainly α-TiN_0.3 with (002) preferred orientation. The surface hardness of the coatings increased at higher nitriding temperature, reaching the maximum of 500 HV at 490 °C, which was about 8 times higher than that of the uncoated alloy. The friction coefficients of 2024 Al alloy decreased in the coatings prepared at higher nitriding temperature, reaching the lowest values of 0.31 at 490 °C. The wear rate of the coated samples decreased by 56% compared with the uncoated ones. The analysis of worn surface indicated that the nitrided samples exhibited severe adhesive wear at 400 °C that changed to predominant abrasive wear at increased nitriding temperature.     

Facile synthesis of nanorods of tetragonal barium titanate using ethylene glycol

Tetragonal barium titanate (BaTiO₃) nanorods were synthesized from hydroxide precursor by a hydrothermal/solvothermal method with 10 vol% ethylene glycol as solvent. The hydroxide precursor slurry was prepared by the addition of 10 M NaOH to a mixed solution of BaCl₂ and TiCl₄. When the above aqueous slurry was heated with water only at 200 °C, cubic BaTiO₃ nanocrystals formed, whereas tetragonal BaTiO₃ nanorods were obtained when heated with 10 vol% ethylene glycol. The crystallization of cubic BaTiO₃ via dissolution–reprecipitation of precursor could be suppressed by the addition of ethylene glycol, resulting in the formation of tetragonal BaTiO₃ under hydrothermal treatment at 200 °C.     

Catalytic dehydration of glycerol to acrolein over sulfuric acid-activated montmorillonite catalysts

For the development of efficient solid acid catalysts for the catalytic dehydration of glycerol to acrolein, catalysts made from montmorillonitic clay activated by sulfuric acid were investigated. Montmorillonite was activated in diluted sulfuric acid in the concentration range of 5–40 wt.%. The effects of sulfuric acid treatment on the structure of the montmorillonite were characterized by X-ray diffraction, measurements of acidity, N₂ adsorption–desorption isotherms, and Fourier transform infrared spectroscopy. The catalytic behavior of sulfuric acid-activated montmorillonite catalysts in the gas-phase dehydration of glycerol were investigated under varying conditions, including the reaction temperature, the feed rate, and the concentration of glycerol. After montmorillonitic clay was activated by sulfuric acid, the layered structural features of montmorillonite remained nearly intact. Ca^2 +-montmorillonite was changed to H⁺-montmorillonite by ion exchange reaction during activation. The optimal catalytic glycerol dehydration reaction conditions were found to be: temperature at 320 °C, liquid hourly space velocity (LHSV) = 18.5 h^− 1, concentration of glycerol solution = 10 wt.%, and the flow rate of N₂ carrier gas = 10 mL/min. A conversion of 54.2% of glycerol and a yield of 44.9 wt.% acrolein were achieved over the montmorillonite catalyst activated by an aqueous 10 wt.% sulfuric acid solution. The H⁺ in the interlayer space of acid-activated montmorillonite catalysts played a critical role in the catalytic dehydration of glycerol. The temperature, the LHSV, and the concentration of glycerol affected the performance of the catalysts through their influence on the reaction mechanism, the contact time, and the reaction equilibrium.     

Strength of hot pressed ZrB2–SiC composite after exposure to high temperatures (1000–1700 °C)

Residual strength (room temperature strength after exposure in air at high temperatures) of hot pressed ZrB₂–SiC composites was evaluated as function of SiC contents (10–30 vol%) as well as exposure temperatures for 5 h (1000–1700 °C). Multilayer oxide scale structures were found after exposures. The composition and thickness of these multilayered oxide scale structure was dependent on exposure temperature and SiC contents in composites. After exposure to 1000 °C for 5 h, the residual strength of ZrB₂–SiC composites improved by nearly 60% compared to the as-hot pressed composites with 20 and 30 vol% SiC. On the other hand, the residual strength of these composites remained unchanged after 1500 °C for 5 h. A drastic degradation in residual strength was observed in composites with 20 and 30 vol% SiC after exposure to 1700 °C for 5 h in ZrB₂–SiC. An attempt was made to correlate the microstructural changes and oxide scales with residual strength with respect to variation in SiC content and temperature of expsoure.     

Effect of graphite nanoplatelets on the mechanical properties of alumina-based composites

Al₂O₃-based composites using exfoliated graphite nanoplatelets (xGnPs) have been developed by powder metallurgy (PM) route using both conventional as well as spark plasma sintering (SPS) processes. Al₂O₃-0.2, 0.5, 0.8, 3 and 5 vol% xGnP composites have been developed, and the effect of the addition of xGnP on the density, hardness, fracture toughness and wear behaviour of the various Al₂O₃-xGnP composites have been analyzed. Conventional sintering was done at a temperature of 1650 °C for 2, 3 and 4 h in inert atmosphere, whereas SPS was carried out at 1450 °C under 50 MPa pressure for 5 min. A uniform dispersion of the xGnP in the Al₂O₃ matrix was observed in the composites upto the addition of 3 vol% xGnP. Results indicate that a significant improvement in hardness, wear resistance and fracture toughness of the composites could be achieved by using xGnP as nanofiller. The hardness and fracture toughness of the composites developed by both conventional sintering and SPS show an increase upto the addition of 3 and 0.8 vol% xGnP respectively. The wear resistance of the composites also shows significant improvement upto the addition of 3 vol% xGnP. The composites developed by SPS have been found to possess superior mechanical properties as compared to the composites developed by conventional sintering. The improvement in the mechanical properties can be attributed to the strong interaction between the xGnP and the Al₂O₃ matrix at the interfaces and to the toughening mechanisms such as crack bridging and crack deflection.     

High temperature erosion behavior of spark plasma sintered ZrB2-SiC composites

Damage of structural components of hypersonic vehicles by atmospheric particles demands thorough understanding on their wear behavior. In the present work, dense ZrB₂-SiC (10, 20, and 30 vol%) composites are prepared by spark plasma sintering at 55 MPa in two stages: 1400 °C for 6 min followed by 1600 °C for 2 min. With increase in SiC content, microstructures of sintered composites reveal strongly bonded ZrB₂ grains with SiC particles. A combination of maximum hardness of 23 GPa, elastic modulus of 398 GPa and fracture toughness of 5.4 MPa m^1/2 are obtained for the composite containing 30 vol% SiC particles. It is found that cracks are bridged or deflected by SiC particles in the composites. When the composites are subjected to SiC particle erosion at 800 °C, a 14% decrease in erosion rate is obtained with increase in SiC content from 10 to 30 vol%. The formation of large extent of boro-silicate rich viscous surface on eroded surfaces is attributed to reduced fracture or removal of ZrB₂ grains of the composites with increased SiC content.     

UHTC–carbon fibre composites: Preparation,oxyacetylene torch testing and characterisation

Current generation carbon–carbon (C–C) and carbon–silicon carbide (C–SiC) materials are limited to service temperatures below 1800 °C and materials are sought that can withstand higher temperatures and ablative conditions for aerospace applications. One potential materials solution is carbon fibre-based composites with matrices composed of one or more ultra-high temperature ceramics (UHTCs); the latter are intended to protect the carbon fibres at high temperatures whilst the former provides increased toughness and thermal shock resistance to the system as a whole. Carbon fibre–UHTC powder composites have been prepared via a slurry impregnation and pyrolysis route. Five different UHTC compositions have been used for impregnation, viz. ZrB₂, ZrB₂–20 vol% SiC, ZrB₂–20 vol% SiC–10 vol% LaB₆, HfB₂ and HfC. Their high-temperature oxidation resistance has been studied using a purpose built oxyacetylene torch test facility at temperatures above 2500 °C and the results are compared with that of a C–C benchmark composite.     

Direct coagulation casting of yttria-stabilized zirconia using magnesium citrate and glycerol diacetate

Direct coagulation casting via controlled release of high valance counter ions (DCC-HVCI) has been reported in recent years. In this paper, concentrated yttria-stabilized zirconia (YSZ) suspensions were coagulated using DCC-HVCI method with magnesium citrate as coagulating agent assisted by pH shift in the presence of glycerol diacetate. The effect of ammonium polyacrylate (PAA-NH₄) on the dispersibility of YSZ powder was investigated. The influence of concentrations of glycerol diacetate and magnesium citrate on pH and viscosities of YSZ suspensions was studied. The results indicate that concentrated YSZ suspensions can be coagulated by adding 2 vol% glycerol diacetate and magnesium citrate above 0.5 wt% at room temperature for 2–5 h. The compressive strength of coagulated wet samples is above 2.0 MPa. YSZ ceramics sintered at 1450 °C show homogeneous microstructures with relative densities of 98.9–99.2%. Flexural strength of YSZ ceramics is 869±84 MPa.     

High temperature mechanical properties of Al2O3/TiC micro–nano-composite ceramic tool materials

A type of Al₂O₃-based composite ceramic tool material simultaneously reinforced with micro-scale and nano-scale TiC particles was fabricated by the hot-pressing technology with different contents of cobalt additive. The effects of cobalt on the ambient temperature mechanical properties and high temperature flexural strength were investigated. The flexural strength and fracture toughness of the composite with 3 vol% cobalt as a function of temperature were investigated. Cobalt greatly enhanced the ambient temperature flexural strength and fracture toughness, while further increasing the content of cobalt led to a dramatic strength degradation, especially at high temperature. The flexural strength of the composite containing 3 vol% cobalt decreased as the temperature increased from 20 to 1200 °C, and the fracture toughness decreased as a function of the temperature up to 1000 °C but increased at 1200 °C. The degradation of high temperature flexural strength was ascribed to the change of the fracture mode, the grain and grain boundary oxidation, the decrease of elastic modulus and the grain boundary sliding.     

Tribological behavior of Ti3SiC2 and Ti3SiC2/Pb composites sliding against Ni-based alloys at elevated temperatures

The Ti₃SiC₂ and Ti₃SiC₂/Pb composites were tested under dry sliding conditions against Ni-based alloys (Inconel 718) at elevated temperatures up to 800 °C using a pin-on-disk tribometer. Detailed tribo-chemical changes of Pb on sliding surface were discussed. It was found that the tribological behavior were insensitive to the temperature from 25 °C (RT) to 600 °C (friction coefficient ≈0.61–0.72, wear rate ≈10⁻³ mm³ N m⁻¹). An amount of Pb in the composites played a key role in lubricating with the temperature below 800 °C. The friction coefficient (≈0.22) and wear rate (≈10⁻⁷ mm³ N m⁻¹) at elevated temperatures were both decreased by the added PbO. The wear mechanisms of Ti₃SiC₂/Pb-Inconel 718 tribo-pair at elevated temperatures were believed to be the combined effect of abrasive wear and tribo-oxidation wear. During the sliding, two oxidization reactions proceed, 2Pb+O₂=2PbO (below 600 °C) and 6PbO+O₂=2Pb₃O₄ (800 °C). The friction coefficient and wear rate of the composites were reduced due to the self-lubricating effect of the tribo-oxidation products.     

Wear mechanisms of TiN–TiB2 ceramic in sliding against alumina from room temperature to 700 °C

TiN–TiB₂ ceramic was prepared by the reactive hot-pressing method using titanium and BN powders as raw materials. The friction and wear properties of TiN–TiB₂ ceramic were evaluated in sliding against alumina ball from room temperature to 700 °C in air. The TiN–TiB₂ ceramic has a relative density of 98.6%, a flexural strength of 731.9 MPa and a fracture toughness of 8.5 MPa m^1/2 at room temperature. The TiN–TiB₂ ceramic exhibits a distinct decrease in friction coefficient at 700 °C as contrasted with the friction data obtained at room temperature and 400 °C. Wear mechanisms of TiN–TiB₂ ceramic depend mainly upon testing temperature at identical applied loads. Lubricious oxidized products caused by thermal oxidation provide excellent lubrication effects and greatly reduce the friction coefficient of TiN–TiB₂ ceramic at 700 °C. However, abrasive wear and tribo-oxidation are the dominant wear mechanisms of TiN–TiB₂ ceramic at 400 °C. Mechanical polishing effect and removal of micro-fractured grains play important roles during room-temperature wear tests.     

Wear damage of Si3N4-graphene nanocomposites at room and elevated temperatures

Mechanical and tribological properties of nanocomposites with silicon nitride matrix with addition of 1 and 3 wt.% of multilayered graphene (MLG) platelets were studied and compared to monolithic Si₃N₄. The wear behavior was observed by means of the ball-on-disk technique with a silicon nitride ball used as the tribological counterpart at temperatures 25 °C, 300 °C, 500 °C, and 700 °C in dry sliding. Addition of such amounts of MLG did not lower the coefficient of friction. Graphene platelets were integrated into the matrix very strongly and they did not participate in lubricating processes. The best performance at room temperature offers material with 3 wt.% graphene, which has the highest wear resistance. At medium temperatures (300 °C and 500 °C) coefficient of friction of monolithic Si₃N₄ and composite with 1%MLG reduced due to oxidation. Wear resistance at high temperatures significantly decreased, at 700 °C differences between the experimental materials disappeared and severe wear regime dominated in all cases.     

Ball milling assisted hydrothermal synthesis of ZrO2 nanopowders

The formation of ZrO₂ nanopowders under various hydrothermal conditions such as temperature, time, autoclave rotation speed, heating rate and particularly assistance of ball milling during reaction was investigated. Full ZrO₂ formation (with monoclinic phase) from zirconium solution was completed at shorter times with increasing temperature such as after 4 h at 150 °C, 2 h at 175 °C and less than 2 h at 200 °C. Crystallite size increased from 2.9 to 4 nm with increasing reaction temperature from 125 °C to 200 °C, respectively. Ball milling assisted hydrothermal runs were performed to understand the effect of mechanical force on phase formation, crystallinity and particle size distribution. Monoclinic ZrO₂ was formed in both milled and non-milled runs when zirconium solution was used. Mean particle size for the 2 M solution was measured to be 94 nm for the milled and 117 nm for the non-milled powders. However, when amorphous aqueous zirconia gels (precipitated at pH 5.8) were used, tetragonal phase was also formed in addition to monoclinic phase. Mean particle size was measured to be 0.7 μm (d₉₀≅1.3 μm) for the milled and 7.9 μm (d₉₀≅13 μm) for the non-milled powders. Ball milling during hydrothermal reactions of both zirconium solution and aqueous zirconium gel resulted in smaller crystallite size and mean particle size and, at the same time, effectively controlled particle size distribution (or agglomeration) of nanopowders.     

Thermal stability and mechanical properties of HVOF/PVD duplex ceramic coatings produced by HVOF and cathodic vacuum arc

Duplex ceramic coatings, consisting of an inner NiCr-Cr₃C₂-based coating and an outmost AlCrN film, were produced on the steel substrate in succession by velocity oxygen-fuel spraying (HVOF) and cathodic vacuum arc methods, and then isochronally annealed at annealing temperatures below 900 °C for 2 h. The thermal stability and mechanical properties of the annealed samples were systematically studied by means of X-ray diffraction, Optical microscope and transmission electron microscope, in association with mechanical property measurements. The results show that the microstructure, phase evolution and mechanical properties of duplex ceramic coatings are significantly dependent on the annealing temperature. Metastable fcc-AlCrN solid solution in AlCrN film first decomposes to rich-Al and rich-Cr domains by spinodal decomposition at 700 °C, leading to a notable increase in hardness due to its smaller grain size and high elastic strain field, and then to equiaxed hcp-AlN and Cr₂N by the nucleation and growth at 900 °C, leading to a notable decrease in hardness due to the recrystallization and the formation of hcp-AlN. Meanwhile, the both decarburization of Cr₃C₂ to Cr₇C₃ occurs at 800 °C, but becomes more intensive at 900 °C, leading to a notable loss in hardness. In addition, the dissolution of Cr₃C₂ produces high density of porosity, which also reduces the hardness. The hardness tests show the following ordering of load-bearing capacity for the duplex ceramic coatings: 700 °C>As-deposited >800 °C>900 °C. Tribological property measurements demonstrate that the wear resistance of the tested duplex ceramic coatings obeys the following ordering: 700 °C>As-deposited >800 °C>900 °C. The improved wear resistance is due to high surface hardness, load-bearing capacity and thermal stability. In addition, the wear mechanisms are shown.     

Corrosive wear behavior of chromium carbide coatings deposited by air plasma spraying

The corrosive wear behavior of chromium carbide coatings deposited by air plasma spraying was studied, through wet pin-on-disk wear experiments. During the wear tests, the samples were immersed in corrosive environments consisting of watery hydrochloric acid with the acid concentrations of 5, 10 and 15 vol%. The wear tests were performed at both room temperature and 80 °C. The results showed that the wet environment significantly increased the wear rate. In addition, the increase of the acid concentration and temperature considerably deteriorated the wear resistance of the coated samples. It was also realized that, compared to the dry condition, the wear mechanism changed from abrasive to adhesive in the wet environment where a tribochemical wear was observed.     

Effect of temperature and heating rate on the sintering performance of SiC-Al2O3-Dy2O3 and SiC-Al2O3-Yb2O3 systems

Samples of SiC+10 vol%(Al₂O₃+Dy₂O₃) and SiC+10 vol%(Al₂O₃+Yb₂O₃) mixtures were obtained by cold isostatic pressing and sintered for one hour in a dilatometer at 1800 °C and 1900 °C, applying heating rates of 10, 20 and 30 °C/min. The results of the complete sintering cycle indicated that the heating rates do not significantly influence the shrinkage, but that temperature and total sintering time may be relevant factors. The compacts sintered at 1900 °C shrank on average 9% more than those sintered at 1800 °C, and it was found that the sintering time can be reduced by 40–50% at faster heating rates. The maximum shrinkage rates occurred at temperatures lower than those of the sintering thresholds for the two mixtures, two temperatures and three heating rates. It was also found that after formation of the liquid, the mechanisms of particle rearrangement and solution-precipitation were not as fast as reported in the literature, even at high heating rates, for example 30 °C/min, but they are responsible for much of the shrinkage occurring throughout the sintering cycle.     

Diamond wear properties in cold plasma jet

Cold plasma jet is applied to control the contact interface and restrain the diamond wear when cutting ferrous metals. A new generation device was developed to generate stable cold plasma jet under atmospheric pressure. Friction & wear tests and thermal analysis experiments were conducted on a mirror steel NAK80/diamond friction pair in atmospheres of air, nitrogen, and nitrogen cold plasma jet (NPJ), respectively. The friction and diamond graphitization rules were determined through the experiments. Results proved that the friction pair exhibited the best friction and wear properties in NPJ atmosphere. When the rotation speed was ≥ 300 r/min, the nitrogen cold plasma atmosphere was found to reduce the friction coefficient of the friction pair, and the friction coefficient tended to be stable when the load was ≥ 50 N. Moreover, the graphitization temperature of diamond increased from 885 °C to 1185 °C after NPJ treatment.