Processing of nanocrystalline 8 mol% yttria-stabilized zirconia by conventional, microwave-assisted and two-step sintering

Manufacturing of near full dense (>97%) 8 mol% yttria-stabilized zirconia (8YSZ) nanopowder (15–33 nm) compacts was manipulated using conventional sintering (CS), two-step sintering (TSS) and microwave-assisted sintering methods. Microwave firing was performed via two different heating rates, i.e. 5 and 50 °C min⁻¹. Although, the lower rate microwave sintering (LMS) was found to yield the higher densities at lower temperatures, this regime ultimately did not provide higher final densities compared to the other methods. The higher rate microwave sintering (HMS) on the other hand managed to suppress the accelerated grain growth and resulted to a finer microstructure (0.9 μm) than LMS (2.35 μm) and CS (2.14 μm). In spite of the great capability of TSS method in fabricating the specimens with ultra-fine grains (0.29 μm), microstructural inhomogeneity and the long total sintering time (>20 h) in comparison with HMS (29 min) set restrictions on the application of TSS method. Based on the effect of grain size on the mechanical properties of ceramics, the specimens produced by TSS exhibited higher fracture toughness (3.16 ± 0.06 MPa m^1/2) than those obtained from CS (1.61 ± 0.07 MPa m^1/2) and LMS (1.9 ± 0.09 MPa m^1/2), due to their finer grain size. The proximity in the fracture toughness values of TSS and HMS (3.17 ± 0.10 MPa m^1/2) samples stems from the higher microstructural homogeneity caused by HMS, while having a larger grain size.     

Hard iron boride (Fe2B) on 99.97 wt% pure iron

Some properties such as hardness and fracture toughness of boride formed on the 99.97 wt% pure iron were investigated. Boronizing was carried out in a solid medium, consisting of Ekabor powders of 5% B₄C as donor, 5% KBF₄ as an activator and 90% SiC as diluent at 800 °C for 2, 4 and 8 h. The dominant phase formed on the substrate was found to be Fe₂B that had a finger-like shape morphology. The hardness of boride on the 99.97% pure iron was over 1700HVN, while the hardness of pure iron was about 130HVN. It was found that the fracture toughness of boride formed on surfaces of 99.97% pure iron, depending on the process time, ranged from 3.59 to 3.83 MPa m^1/2. Depending on process time and temperature, the depth of the boride layer ranges from 22 to 43 μm, leading to a diffusion-controlled process.     

The effects of multiwalled carbon nanotubes on the hot-pressed 3 mol% yttria stabilized zirconia ceramics

The bulk composites of 3 mol% yttria stabilized zirconia ceramics reinforced by multiwalled carbon nanotubes were prepared by ball milling, spray-drying and hot-pressing processes. The effects of MWCNTs’ contents and heterocoagulation pretreatment on the mechanical properties of 3Y–ZrO₂/MWCNTs’ composites were investigated at room temperature. Experimental results showed that the heterocoagulation pretreatment played a vital role in homogeneous dispersion of MWCNTs in the ceramic matrix. The flexural strength of 989.8 ± 20.0 MPa and fracture toughness of 5.77 ± 0.06 MPa M^1/2 were obtained for the composite with 1.0 wt.% of MWCNTs’ content, which were 135.3 MPa (or 8.4%) higher in flexural strength and 0.92 MPa M^1/2 (or 21.1%) higher in fracture toughness than those of blank 3Y–ZrO₂, respectively. The mechanisms of strengthening and toughening of the composites could be attributed to the synergic effects of bridging, pulling out of MWCNTs and their promotive effects on the phase transformation of the ceramics.     

Rapid densification and reaction sequences in self-reinforced Y-α-SiAlON ceramics with barium aluminosilicate as an additive

Y-α-SiAlON (Y_1/3Si₁₀Al₂ON₁₅) ceramics with 5 wt.%BaAl₂Si₂O₈ (BAS) as an additive were synthesized by spark plasma sintering (SPS). The kinetic of densification, phase transformation sequences and grain growth during sintering process were investigated. Full densification could be achieved by 1600 °C without holding and using a heating rate of 100 °C min⁻¹, but the transformation from α-Si₃N₄ to α-SiAlON is not completed simultaneously with the densification process. The equilibrium phase assemblage could be reached after SPS at 1800 °C for 5 min and the resultant material possesses self-reinforced microstructure with high hardness of 19.2 GPa and fracture toughness of 6.8 MPa m^1/2. The complete crystallization of BAS is beneficial to the high temperature mechanical properties. The obtained could maintain the room strength up to 1300 °C.     

Fabrication of silicon carbide composites with carbon nanofiber addition and their fracture toughness

The authors have examined the fabrication conditions of SiC composites containing carbon nanofiber, i.e., vapor-grown carbon nanofiber (VGCF), to enhance the fracture toughness. Commercially available ultrafine SiC powder (specific surface area: 47.5 m² g⁻¹) was mixed with VGCF and sintering aid in the Al₄C₃–B₄C system. Approximately 1.5 g of the mixture was uniaxially pressed at 50 MPa to obtain a compact with a diameter of 20 mm and a thickness of approximately 1.5 mm. The resulting compact was hot-pressed at 1800 °C for 1 h in Ar atmosphere under a pressure of 62 MPa. The relative density of hot-pressed SiC composite decreased from 98.0 to 96.3%, whereas the fracture toughness was enhanced from 3.8 to 5.2 MPa m^1/2, as the amount of VGCF increased from 0 to 6 mass%. Furthermore, an acid treatment of VGCF was conducted to enhance its dispersibility within the SiC matrix, owing to the formation of COO⁻ groups on the VGCF surface. As a result of this treatment, the relative density and fracture toughness of hot-pressed SiC composite with 6 mass% acid-treated VGCF addition increased to 99.0% and 5.7 MPa m^1/2, respectively.     

Mechanical and dielectric properties of porous Si3N4–SiO2 composite ceramics

In order to prepare a structural/functional material with not only higher mechanical properties but also lower dielectric constant and dielectric loss, a novel process combining oxidation-bonding with sol–gel infiltration-sintering was developed to fabricate a porous Si₃N₄–SiO₂ composite ceramic. By choosing 1250 °C as the oxidation-bonding temperature, the crystallization of oxidation-derived silica was prevented. Sol–gel infiltration and sintering process resulted in an increase of density and the formation of well-distributed micro-pores with both uniform pore size and smooth pore wall, which made the porous Si₃N₄–SiO₂ composite ceramic show both good mechanical and dielectric properties. The ceramic with a porosity of 23.9% attained a flexural strength of 120 MPa, a Vickers hardness of 4.1 GPa, a fracture toughness of 1.4 MPa m^1/2, and a dielectric constant of 3.80 with a dielectric loss of 3.11 × 10⁻³ at a resonant frequency of 14 GHz.     

Spark plasma sintering of UHTC powders obtained by self-propagating high-temperature synthesis

Fully dense ZrB₂–SiC and HfB₂–SiC ultra-high-temperature ceramics (UHTCs) composites are fabricated by first synthesizing via self-propagating high-temperature synthesis (SHS) the composite powders from B₄C, Si, and Zr or Hf reactants, and subsequently consolidating the product by spark plasma sintering (SPS) without the addition of any sintering aid. It was found that the SHS technique leads to the complete conversion of reactants to the desired products and the SPS allows for the full consolidation (>99.5% relative density) under the optimal operating conditions of 1800 °C/20 min/20 MPa and 1800 °C/30 min/20 MPa, for the cases of ZrB₂–SiC and HfB₂–SiC, respectively. Based on the results reported in this work, it can be stated that the combination of SHS and SPS methods represents a particularly rapid and convenient preparation route (lower sintering temperature and processing time) for UHTCs as compared to the techniques available in the literature for the fabrication of analogous products.     

Mechanical and thermal properties of AlN–BN–SiC ceramics

Mechanical and thermal properties were characterized for two AlN:BN:SiC composite ceramics produced from BN with different particle sizes. The ceramics were hot pressed at temperatures from 1950 to 2100 °C to 97% relative density. For both materials, the matrix (90:10 vol% SiC:AlN) had a grain size of 0.4 μm, and the BN grains (10 vol%) were crystallographically aligned. Microhardness values were between 20 and 22 GPa, while fracture toughness values were between 2.5 and 3.1 MPa m^1/2. Other properties were found to be dependent on testing direction. Elastic moduli were between 260 and 300 GPa and strengths were 630 MPa for small particle BN additions. Thermal conductivity was calculated to be between 25 and 37 W/m K at room temperature and 17 and 25 W/m K at 900 °C. The low values compared to traditional SiC ceramics were attributed to AlN–SiC solid solution formation and sub-micron matrix grain sizes.     

Threshold stress intensity factor for delayed hydride cracking in Zr–2.5%Nb pressure tube alloy

Delayed hydride cracking (DHC) velocity was determined at 203, 227, 250 and 283 °C using 17 mm width curved compact toughness specimens machined from an unirradiated Zr–2.5 wt.% Nb pressure tube spool, gaseously charged with 60 ppm of hydrogen by weight. Single CT specimen was used to determine DHC velocity at a constant temperature for a range of stress intensity factor (K_I) obtained by load drop method. For a given temperature and K_I > 15 MPa m^1/2, DHC velocity was found to be practically independent of K_I. For 15 > K_I > 10 MPa m^1/2, DHC velocity decreased significantly with decrease in stress intensity factor and extrapolation of the data suggested the threshold stress intensity factor to be about 9–11 MPa m^1/2 in the aforementioned temperature range. The activation energy associated with DHC was observed to be 35.1 kJ/mol.     

Microstructure–mechanical properties relations in SiC–TiB2 composite

Densification and mechanical properties (fracture toughness, flexural strength and hardness) of SiC–TiB₂ composite were studied. Pressureless sintering experiments were carried out on samples containing 0–50 vol% of TiB₂ created by in situ reaction between TiO₂, B₄C and carbon. Al₂O₃ and Y₂O₃ were used as sintering additives to create liquid phase and promote densification at sintering temperature of 1940 °C. The sintered samples were subsequently heat treated at 1970 °C. It was found that the presence of TiB₂ serves as an effective obstacle to SiC grain growth as well as crack propagation thus increasing both strength and fracture toughness of sintered SiC–TiB₂ composite. The subsequent heat treatment of sintered samples promoted the elongation of SiC matrix and further improved mechanical properties of the composite. The best mechanical properties were measured in heat-treated samples containing 12–24 vol% TiB₂. The maximum flexural strength of ∼600 MPa was obtained in samples with 12 vol% TiB₂ whereas the maximum fracture toughness of 6.6 MPa m^1/2 was obtained in samples with 24 vol% TiB₂. Typical microstructures of samples with the mentioned volume fractions of TiB₂ consist of TiB₂ particles (<5 μm) uniformly dispersed in a matrix of elongated SiC plates.     

Strength and toughness of cellular SiC at elevated temperature

Bending strength and toughness of β-SiC foams were measured from ambient temperature to 1400 °C. It was found that SiC was able to maintain the mechanical properties up to 1200 °C even after long-term exposure at this temperature. Creep deformation was not detected and the negative effects of oxidation at this temperature were balanced by the healing effect induced by the formation of SiO₂. Nevertheless, the mechanical properties were rapidly degraded at 1400 °C as a consequence of massive oxidation of SiC.     

Reactive and dense sintering of reinforced-toughened B4C matrix composites

Reactive hot-press (1800-1880 °C, 30 MPa, vacuum) is used to fabricate relatively dense B₄C matrix light composites with the sintering additive of (Al₂O₃ +Y₂O₃). Phase composition, microstructure and mechanical properties are determined by methods of XRD, SEM and SENB, etc. These results show that reactions among original powders B₄C, Si₃N₄ and TiC occur during sintering and new phases as SiC, TiB₂ and BN are produced. The sandwich SiC and claviform TiB₂ play an important role in improving the properties. The composites are ultimately and compactly sintered owing to higher temperature, fine grains and liquid phase sintering, with the highest relative density of 95.6%. The composite sintered at 1880 °C possesses the best general properties with bending strength of 540 MPa and fracture toughness of 5.6 MPa m^1/2, 29 and 80% higher than that of monolithic B₄C, respectively. The fracture mode is the combination of transgranular fracture and intergranular fracture. The toughening mechanism is certified to consist of crack deflection, crack bridging and pulling-out effects of the grains.     

Microwave dielectric properties and sintering behavior of nano-scaled (α + θ)-Al2O3 ceramics

The dielectric properties at microwave frequencies and the microstructures of nano (α + θ)-Al₂O₃ ceramics were investigated. Using the high-purity nano (α + θ)-Al₂O₃ powders can effectively increase the value of the quality factor and lower the sintering temperature of the ceramic samples. Grain growth can be limited with θ-phase Al₂O₃ addition and high-density alumina ceramics can be obtained with smaller grain size comparing to pure α-Al₂O₃. Relative density of sintered samples can be as high as 99.49% at 1400 °C for 8 h. The unloaded quality factors Q × f are strongly dependent on the sintering time. Further improvement of the Q × f value can be achieved by extending the sintering time to 8 h. A dielectric constant (_r) of 10, a high Q × f value of 634,000 GHz (measured at 14 GHz) and a temperature coefficient of resonant frequency (τ_f) of −39.88 ppm/°C were obtained for specimen sintered at 1400 °C for 8 h. Sintered ceramic samples were also characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).     

Fabrication and mechanical properties of monolithic MoSi2 by spark plasma sintering

Fine MoSi₂ powders containing a small amount of Mo₅Si₃ have been prepared by self-propagating high-temperature synthesis (SHS), followed by spark plasma sintering (SPS) for 10 min at 1200-1500°C and 30 MPa. Dense MoSi₂ materials, in which the grain size is ∼7.5 μm, have been fabricated at 1300°C. They exhibit excellent mechanical properties: Vicker’s hardness H_v (10.6 GPa), fracture toughness K_IC (4.5 MPa m^1/2), and bending strength σ_b (560 MPa). The strength of 325 MPa can be retained up to 1000°C.     

Processing,microstructure and properties of in-situ reinforced SiC matrix composites

SiC matrix composites were fabricated by in-situ formation of transition metal boride and carbide particles from oxide powders by carbothermal reactions. Dense composites with various microstructures were produced by pressureless sintering and additional hot-isostatic pressing. The microstructures and mechanical properties of the composites were dependent upon the pressureless-sintering temperature. The use of submicron-sized TiO₂ lead to fine and equiaxial TiB₂ particulates. The composites exhibited high flexural strengths (>700 MPa). At higher sintering temperatures, the grain growth of SiC swept the boride into clusters with larger sizes and anisotropic shapes, which improved the fracture toughness of the composite at the expense of strength.     

Microstructure and mechanical properties of ZrB2-SiC composites

A ZrB₂-based composite containing 20 vol.% nanosized SiC particles (ZSN) was fabricated at 1900 °C for 30 min under a uniaxed load of 30 MPa by hot-pressing. The microstructure and mechanical properties of the composite were investigated. It was shown that the grain growth of ZrB₂ matrix was effectively suppressed by submicrosized SiC particles located along the grain boundaries. In addition, the mechanical properties of ZSN composite were strongly improved by incorporating the nanosized SiC particles into a ZrB₂ matrix, especially for flexural strength (925 ± 28 MPa) and fracture toughness (6.4 ± 0.3 MPa•m^1/2), which was much higher than that of monolithic ZrB₂ and ZrB₂-based composite with microsized SiC particles, respectively. The formation of intragranular nanostructures plays an important role in the strengthening and toughening of ZrB₂ ceramic.     

Hot-pressed ZrB2–SiC–YSZ composites with various yttria content: Microstructure and mechanical properties

ZrB₂–10 vol%SiC–20 vol%YSZ composites were prepared by hot-pressed sintering with yttria content ranging from 2 mol% to 8 mol% in YSZ. The phase constitution, microstructure and mechanical properties of the composites were found to be strongly dependent on the yttria content. The average grain size became bigger for the composites with higher yttria content. When the yttria content was below 3 mol%, there is no cubic zirconia in the polished surface of composites, and the flexural strength of the composites was above 740 MPa. With the increase in yttria content, the fracture toughness fell down from 6.4 MPa m^1/2 to 5.6 MPa m^1/2. Vickers’ hardness of the hot-pressed composites varied above 18 GPa without obvious effect of the yttria content.     

Fabrication and thermal shock resistance of HfB2-SiC composite with B4C additives

A HfB₂ based ceramic matrix composite containing 20 vol.% SiC particles with 2 vol.% B₄C as sintering additives was fabricated by hot-pressed sintering. The microstructure and properties, especially the thermal shock resistance of the composite were investigated. Results showed that the addition of B4C improved the powder sinterability and led to obtaining nearly full dense composite. The flexural strength and fracture toughness of the composite were 771 MPa and 7.06 MPam^1/2, respectively. The thermal shock resistance tests indicated that the residual strength decreased significantly when the thermal shock temperature difference was higher than 600 °C. The large number of microcracks on the sample surface was the main reason for the catastrophic failure.     

The thermal shock resistance of the ZrB2–SiC–ZrC ceramic

In the present work, the thermal shock resistance of the ZrB₂–SiC–ZrC ceramic was estimated by the water quenching method and the flexural strength of the quenched specimen was measured. The measured critical temperature difference of the ZrB₂–SiC–ZrC ceramic was significantly greater than that of the ZrB₂–15 vol.% SiC ceramic. The improvement in thermal shock resistance was attributed to its higher fracture toughness (6.7 MPa m^1/2) and lower flexural strength (526 MPa) relative to the ZrB₂–15 vol.% SiC ceramic (4.1 MPa m^1/2 and 795 MPa) based on Griffith fracture criterion. Furthermore, the temperature and thermal stress distributions in the specimen during instantaneous water quenching were simulated by Finite element analysis.