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.     

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.     

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.     

Microstructure and mechanical properties of TiC–WC–(Ti,W)C–Ni cermets

(Ti_0.93W_0.07)C solid-solution powder is synthesized via high-energy milling and carbothermal reduction. When the solid-solution carbide is sintered after blending with Ni and commercial single-phase carbides such as TiC and WC, a complex microstructure is developed, typically featuring a core–rim structure along with the initial solid-solution phase. Furthermore, an increase in total volume of the solid-solution phase with (Ti_0.93W_0.07)C in the cermets results in significantly enhanced mechanical properties: fracture toughness (K_1C) is 7.5–12.7 MPa m^1/2 and hardness (H_v) is 11.9–14.1 GPa. These properties are in contrast with those of conventional cermets, which yield K_1C = 6 MPa m^1/2 and H_v = 12.6 GPa.     

Mechanical and thermal properties of silicon-carbide composites fabricated with short Tyranno® Si-Zr-C-O fibre

Silicon carbide (SiC) composites reinforced with 10–50 mass% (10.5–51.2 vol%) of short Tyranno® Si-Zr-C-O fibre (average length 0.5 mm) and 0–10 mol% of Al₄C₃as a sintering aid were fabricated using the hot-pressing technique. Firstly, the effect of Si-Zr-C-O fibre addition on the relative density (bulk density/true density) of the SiC composite hot-pressed at 1800 °C for 30 min was examined by fixing the amount of Al₄C₃to be 5 mol%. Although the relative density was reduced to 87.4% for 10 mass% of Si-Zr-C-O addition, further increases in the amount of Si-Zr-C-O fibre increased density to a maximum of 92.8% at 40 mass% of fibre addition. Secondly, the effect of varying the amount of Al₄C₃addition on the relative density was examined by fixing the amount of Si-Zr-C-O fibre to be 40 mass%. The optimum amount of Al₄C₃addition for the fabrication of dense SiC composite was found to be 5 mol%. The fracture toughness of the hot-pressed SiC composites with 20–40 mass% of Si-Zr-C-O fibre addition (amount of Al₄C₃: 5 mol%) was 3.2–3.4 MPa · m^1/2and approximately 1.5 times higher than that (2.39 MPa · m^1/2) of the hot-pressed SiC composite with no Si-Zr-C-O fibre addition. SEM observation showed evidence of Si-Zr-C-O fibre debonding and pull-out at the fracture surfaces. The hot-pressed SiC composite with 5 mol% of Al₄C₃and 40 mass% of Si-Zr-C-O fibre additions showed excellent heat-resistance at 1300 °C in air due to the formation of a SiO₂layer at and near exposed surfaces.     

Structure and up-conversion luminescence in sol–gel derived Er–Yb co-doped SiO2:PbF2 nano-glass–ceramics

Transparent oxyfluoride nano-glass–ceramics 90(SiO₂)10(PbF₂) co-doped with 0.3 Yb³⁺ and 0.1 Er³⁺ (mol%) have been prepared by thermal treatment of precursor sol–gel glasses. X-ray diffraction and high resolution transmission electron microscopy analysis pointed out a precipitation of cubic β-PbF₂ nanocrystals of certain diameter in nano-glass–ceramics varying from 10 to 20 nm depending on heat treatment conditions. The incorporation of Yb³⁺ and Er³⁺ dopants in these nanocrystals has been confirmed by signatures of luminescence spectroscopy. Up-conversion luminescence pumped at 980 nm has been detected. Colour tuneability of up-conversion luminescence varying pump power has been analyzed in terms of standard chromaticity diagram. This tuneability opens applications for up-conversion phosphors and three-dimensional optical recording.     

Preparation of nanocrystalline YSZ powders by the plasma technique

A plasma synthesis method has been devised to produce nanosize YSZ powders with various yttria contents. The powders are synthesized by introducing a mixture of coarse-grained zirconia and yttria into an r.f. inductively coupled plasma flame. The average particle size of the as-prepared powders is in the range 20–40 nm and the specific surface area is 18–50 m²g^–1. The phase and granulometric composition of the produced powders depend on the degree of evaporation of raw powders, reagent concentration in the gas flow and quenching rate, and on the content of Y₂O₃. Up to 5.5 mol% yttria, the major phase of nanosize powders is tetragonal ZrO₂, mostly as the non-transformable (t) form. For yttria contents higher than 6 mol%, the major phase is cubic ZrO₂.     

Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> co-stabilized ZrO<Subscript>2</Subscript>-WC composites

Y₂O₃ + Nd₂O₃ co-stabilized ZrO₂-based composites with 40 vol% WC were fully densified by pulsed electric current sintering (PECS) at 1350 °C and 1450 °C. The influence of the PECS temperature and Nd₂O₃ co-stabilizer content on the densification, hardness, fracture toughness and bending strength of the composites was investigated. The best combination of properties was obtained for a 1 mol% Y₂O₃ and 0.75 mol% Nd₂O₃ co-stabilized composite densified for 2 min at 1450 °C under a pressure of 62 MPa, resulting in a hardness of 15.5 ± 0.2 GPa, an excellent toughness of 9.6 ± 0.4 MPa.m^0.5 and an impressive 3-point bending strength of 2.04 ± 0.08 GPa. The hydrothermal stability of the 1 mol% Y₂O₃ + 1 mol% Nd₂O₃ co-stabilized ZrO₂-WC (60/40) composites was compared with that of the equivalent 2 mol% Y₂O₃ stabilized ceramic. The double stabilized composite did not degrade in 1.5 MPa steam at 200 °C after 4000 min, whereas the yttria stabilized composite degraded after less than 2000 min. Moreover, the (1Y,1Nd) ZrO₂-WC composites have a substantially higher toughness (~9 MPa.m^0.5) than their 2Y stabilized equivalents (~7 MPa.m^0.5).     

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.     

Processing and properties of Al–Li–SiCp composites

Al–Li–SiC_p composites were fabricated by a modified version of the conventional stir casting technique. Composites containing 8, 12 and 18 vol% SiC particles (40 μm) were fabricated. Hardness, tensile and compressive strengths of the unreinforced alloy and composites were determined. Ageing kinetics and effect of ageing on properties were also investigated. Additions of SiC particles increase the hardness, 0.2% proof stress, ultimate tensile strength and elastic modulus of Al–Li–8%SiC and Al–Li–12%SiC composites. In case of the composite reinforced with 18% SiC particles, although the elastic modulus increases the 0.2% proof stress and compressive strength were only marginally higher than the unreinforced alloy and lower than those of Al–Li–8%SiC and Al–Li–12%SiC composites. Clustering of SiC particles appears to be responsible for reduced the strength of Al–Li–18%SiC composite. The fracture surface of unreinforced 8090 Al-Li alloy (8090Al) shows a dimpled structure, indicating ductile mode of failure. Fracture in composites occurs by a mixed mode, giving rise to a bimodal distribution of dimples in the fracture surface. Cleavage of SiC particles was also observed in the fracture surface of composites. Composites show higher peak hardness and lower peak ageing time compared with unreinforced 8090Al alloy. Macro- and microhardness increase significantly after peak ageing. Ageing also results in considerable improvement in strength of the unreinforced 8090Al alloy and its composites. This is attributed to formation of δ^′ (Al₃Li) and S^′ (Al₂CuMg) precipitates during ageing. Per cent elongation, however, decreases due to age hardening. Al–Li–12%SiC, which shows marginally lower UTS and compressive strength than the Al–Li–8%SiC composite in extruded condition, exhibits higher strength than Al–Li–8%SiC in peak-aged condition.     

Influence of Cu addition on the self-propagating high-temperature synthesis of Ti5Si3 in Cu–Ti–Si system

The self-propagating high-temperature synthesis (SHS) reactions can take place in Cu–Ti–Si systems with Cu additions of 10–50 wt.%, and the products only consist of Ti₅Si₃ and Cu phases, without any transient phase. In Ti–Si system, most of the Ti₅Si₃ grains synthesized exhibit the polygon-shaped coarse appearance with an obviously sintered morphology. When Cu content increases from 10 to 50 wt.%, however, the Ti₅Si₃ exhibits cobblestone-like shape with a relatively smooth surface, and its average size decreases significantly from 15 to 2 μm or less. The formation mechanism of Ti₅Si₃ in Cu–Ti–Si system is characterized by the solution, reaction and precipitation processes. Furthermore, the addition of Cu has a great influence on the volume change between green and reacted preforms. The volume change increases with Cu content increasing from 0 to 20 wt.%, and then decreases with the content further increasing from 20 to 50 wt.%. The addition of Cu to Ti–Si system significantly decreases the onset temperature of the reaction during differential scanning calorimetry process, which is even much lower than the α → β transition temperature of Ti (882 °C), suggesting that the reaction could be greatly facilitated by Cu addition. As a result, the role of Cu serves not only as a diluent but also as a reactant and participates in the self-propagating high-temperature synthesis reaction process.     

High-temperature stability of the mechanical and optical properties of Si–B–C–N films prepared by magnetron sputtering

Quaternary Si–B–C–N materials are becoming increasingly attractive due to their possible high-temperature and harsh-environment applications. In this work, amorphous Si–B–C–N films with two compositions (Si₃₄B₉C₄N₄₉ and Si₃₆B₁₃C₇N₄₀) and low contamination level (H + O + Ar < 4 at.%) were deposited on silicon substrates by reactive dc magnetron co-sputtering using two different targets and gas mixtures. Thermal stability of these films was investigated in terms of composition, bonding structure, as well as mechanical and optical properties after annealing in helium up to a 1300°C substrate limit. Films with a high nitrogen content (Si₃₄B₉C₄N₄₉, i.e. N/[Si + B + C]~ 1.0) were found to be stable up to 1300°C. After annealing, the hardness and elastic recovery of those films slightly increased up to 27 GPa and 84%, respectively, and the reduced Young's modulus remained practically constant (~ 170 GPa). The refractive index and the extinction coefficient at 550 nm were evaluated at 2.0 and 5 × 10^− 4, respectively, and the optical band gap was approximately 3.0 eV. In contrast, films with a lower nitrogen content (Si₃₆B₁₃C₇N₄₀, i.e. N/[Si + B + C]~ 0.7) were stable only up to 1200°C. Both Si–B–C–N materials studied here exhibited extremely high oxidation resistance in air up to the 1300°C substrate limit.     

Structural evolution and its influence on luminescence of SiO2–SrF2–ErF3 glass ceramics prepared by sol–gel method

Er³⁺ doped SrF₂–SiO₂ transparent glass ceramics were prepared by sol–gel method and heat treatment. The decomposition of Sr²⁺–CF₃COO⁻ and the formation of SrF₂ nano-crystals were found to proceed synchronously in the xerogel. After crystallization of the xerogel, SrF₂ nano-crystals with 8–10 nm in size distributed homogenously among the glassy matrix, and the microstructure of the glass ceramic was stable under and at the temperature of 800 °C probably due to interfacial interaction between nano-crystals and glassy matrix. When heat-treated at 800 °C, the chemically bonded water in the sample was eliminated, resulting in the appearance of the visible luminescence bands of ²H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 transitions.     

Removal of trace level aqueous mercury by adsorption and photocatalysis on silica–titania composites

Silica–titania composites (STCs) were applied to trace level mercury solutions (100 μg/L Hg) to determine the degree of mercury removal that could be accomplished via adsorption and photocatalysis. STCs are a porous, high surface area silica substrate (>200 m²/g), manufactured using sol–gel methodology, impregnated with TiO₂ nanoparticles. The performance of this material along with its precursors, silica and Degussa P25 TiO₂ were compared. Under adsorption alone (no UV illumination), STCs were able to achieve approximately 90% removal of mercury, which is comparable to that of Degussa P25. Silica without TiO₂ performed poorly in comparison and was minimally affected by UV illumination. Contrary to expectations, the performance of Degussa P25 was not largely changed by UV irradiation and the STC was detrimentally affected under the same conditions. It was concluded that elemental mercury was formed under UV irradiation with or without the presence of TiO₂ due to photochemical reactions, decreasing the mercury removal by STC. Additionally, the primary particle size of the STC was reduced to increase mass transfer. The result was improved Hg removal under adsorption and photocatalysis conditions. Improved adsorption kinetics were also achieved by altering the STC pore size and TiO₂ loading.     

Microstructural characterization of precipitates in Cu–10 wt.%Al–0.8 wt.%Be shape-memory alloy

Microstructural characterization of α₁-plate and γ₂ phase precipitated in hypoeutectoid Cu–10 wt.%Al–0.8 wt.%Be shape-memory alloy (SMA) aged at 200 °C for different periods of time (20–160 h) is researched in this study. High-resolution transmission electron microscope (HRTEM) was employed to investigate the α₁-plate with 18R long period stacking order structure (LPSO) in the SMA aged for 20 h. According to the atomic shuffling revealed in HRTEM-micrograph, the atomic model of the 18R LPSO is proposed. The quantitative mapping of electron energy loss spectrometry shows that the α₁-plates in the SMA aged for 160 h contain lower aluminum concentration than the parent phase matrix. The lattice image of the nanometer-sized γ₂ phase precipitated homogeneously in the SMA aged for 160 h is also revealed by using HRTEM. Precipitation of the nanometer-sized γ₂ phase cannot be impeded by means of the addition of beryllium and quenching, and such precipitate does not grow up in the SMA aged for periods of time less than 160 h.     

Microstructure and high temperature deformation characteristics of sol–gel derived aluminium titanate–mullite composites

Aluminium titanate (AT)–mullite composites with varying compositions were processed by sol–gel technique. The influence of mullite on the microstructure and creep deformation of AT–mullite composites was investigated. In the composites mullite addition was varied from 0 to 100 vol.%. The AT-80 vol.% mullite composite sintered at 1600 °C resulted in fine-grained microstructure with an average grain size of 2.5 μm. From the steady-state creep analysis of the different AT–mullite composites, the activation energies for the creep deformation and stress exponents were determined. The activation energies in the range 655–874 kJ mol⁻¹ were obtained for various the sol–gel derived AT–mullite composites. Similarly stress exponent values were found in the range 1.5–1.9.     

Preparation of TeO2 based thin films by nonhydrolytic sol–gel process

To solve the problem of the extremely high hydrolytic reactivity of tellurium alkoxides in hydrolytic sol–gel method, the nonhydrolytic sol–gel process has been applied as a novel route for producing TeO₂ based thin films. The transition of nonhydrolytic sol–gel was monitored by means of ¹H NMR, FT-IR and Raman techniques. These results show that the formation of Te–O–Te bonds in gel networks mainly resulted from the nonhydrolytic cross-condensation reaction between different Te–OR groups. The decomposition process and structure evolution of the nonhydrolytic gel products were investigated and managed. Results from DTA and XRD analyses show that metallic tellurium, β-TeO₂ and α-TeO₂ phase appeared in the film during heat-treatment process at around 300, 350 and 400 °C, respectively. The formation of metallic tellurium can be alleviated through preheating the gel films under O₂ atmosphere or by additions of the second component. Crystallization of α-TeO₂ could be retarded by additions of TiO₂ or Al₂O₃, and the transparent, homogeneous amorphous TeO₂ based thin films were obtained by the methods above. The nonhydrolytic sol–gel process developed in this study offers a simple and practical method for fabricating TeO₂ based thin film devices.     

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.     

Synthesis and magnetic properties of Ni–SiO2 nanocomposites

Nanocomposite Ni_(1 − x)/(SiO₂)_x soft magnetic materials were synthesized by a simple sol–gel combined hydrogen reduction method. The crystal structure of the particles was determined by X-ray diffraction (XRD). The shapes and sizes of the metal particles embedded in the SiO₂ matrix were determined by transmission electron microscopy (TEM), and magnetic properties were measured by the vibrating samples magnetometer (VSM). The obtained nanocomposite material is composed of nanoparticles coated with a thin SiO₂ layer, and with the content of the silicon increase, the thickness of the silica shells increase and the saturation magnetization decrease. The diameter of Ni particle in the sample is about 30–40 nm. The influence of the Ni content and preparation conditions on the microstructures and magnetic properties were discussed.