Processing and mechanical properties of ZrO2–TiB2 composites

In this paper, a strategy is described to develop high toughness yttria-stabilised tetragonal zirconia polycrystalline (Y-TZP) composites reinforced with hard TiB₂ particles. The experimental results revealed that fully dense Y-TZP composites with 30 vol.% TiB₂ can be obtained with a moderate hardness of 13 GPa, a high strength up to 1280 MPa and an excellent indentation toughness up to 10 MPa m^1/2 by hot pressing in vacuum at 1450 °C. The toughness of the composites can be tailored between 4 and 10 MPa m^1/2 by varying the yttria stabiliser content of the ZrO₂ matrix between 3 and 2 mol%. An optimum composite toughness was achieved for a ZrO₂ matrix with an overall yttria content of 2.5 mol%, obtained by mixing pure monoclinic and 3 mol% Y₂O₃ co-precipitated ZrO₂ starting powders. An important observation is that the thermal residual tensile stress in the ZrO₂ matrix due to the TiB₂ addition, needs to be taken into account when optimising the transformability of the ZrO₂ matrix in order to develop high toughness Y-TZP composites.     

Failure investigation of carbon nanotube/3Y-TZP nanocomposites

3Y-TZP matrix composites containing 0.1–1 wt.% of multi-wall (MWCNT) and single-wall (SWCNT) carbon nanotubes were fabricated by spark plasma sintering technique. The sintered composites reached full density. Hardness and fracture toughness were measured using Vickers indention method. The hardness of the composite decreased with increasing weight content of the MWNT. The fracture toughness was 5.52 MPa m^0.5 when the amount of MWCNTs was 0.5 wt.%, however it decreased to 4.5 MPa m^0.5 when the content was raised to 1.0 wt.%. The composite containing 0.5 wt.% SWCNTs showed similar fracture toughness as that of matrix. The incorporation of CNTs into 3Y-TZP matrix led to no prominent improvement on the mechanical properties. The failure mechanism was analyzed finally.     

Critical crack-healing condition for SiC whisker reinforced alumina under stress

Alumina reinforced by SiC whisker, called here “alumina(w)” was developed with the objective of improving fracture toughness and crack-healing ability. The composites were crack-healed at 1200 °C for 8 h in air under elevated static and cyclic stresses. The bending strength at 1200 °C of the crack-healed composites were investigated. The threshold static stress during crack-healing of alumina(w) has been determined to be 250 MPa, and the threshold cyclic stress was found to be 300 MPa. Considering that the crack growth is time-dependent, the threshold stress of every condition during crack-healing of alumina(w) was found to be 250 MPa. The results showed that the threshold stress intensity factor during crack-healing was 3.8 MPa m^1/2. The same experiment conditions were applied to specimens cracked and annealed at 1300 °C for 1 h in Ar, to remove the tensile residual stress at a tip of the crack. Thus, the threshold stress intensity factor during crack-healing was found to be 3.2 MPa m^1/2 for the specimens crack-healed with annealing. The threshold stress intensity factor during crack-healing of alumina(w) was chosen to be 3.2 MPa m^1/2 to facilitate comparison with the values of the threshold stress intensity factor during crack-healing. The residual stress was slightly larger than the intrinsic value.     

The fracture toughness and fatigue crack propagation behaviour of annealed PET

The fracture toughness of poly(ethylene terephthalate) (PET) is correlated with various morphologies produced upon annealing. Annealing PET at a Hoffman regime III crystallization temperature (120°C) or inducing solid-state polymerization result in materials of high fracture toughness (K_c = 8.7 MPa m^1/2 and 9.5 MPa m^1/2, respectively); these high toughness values are related to multiple-crazing mechanisms produced by high tie-molecule densities. Annealing fully dried PET at 200°C transforms the material to a Hoffman regime I/II structure, and the fracture toughness decreases to 6.5 MPa m^1/2. Hydrolysis also reduces the fracture toughness (K_c < 3 MPa m^1/2). In these low toughness materials, multiple crazing is not observed. In addition, the fatigue crack propagation response of PET is found to be superior in samples annealed to produce high fracture toughness as compared with samples annealed to produce low fracture toughness values.     

Piezospectroscopic measurement of the stress field around an indentation crack tip in ruby using SEM cathodoluminescence

Piezospectroscopy using stress-sensitive lines in the cathodoluminescence (CL) spectrum generated in response to excitation by the electron beam of an SEM has recently been shown to be a promising technique for submicron resolution stress measurements in alumina and other ceramics. This paper develops and applies the technique by mapping the wavelength shifts of the R₁ CL line around the tip of an indentation crack in a ruby single crystal. Accounting for crystallographic anisotropy, the shifts observed were quantitatively consistent with the classical crack tip stress field for all polar angles ahead of the crack tip and indicated a crack tip stress intensity factor of 1.0 MPa m^1/2. This is significantly lower than the fracture toughness of the crack plane (4.5 MPa m^1/2), and indicates the post-indentation development of lateral cracks and slow crack growth. The spatial resolution of the stress measurements was measured as 550 nm and the effects of specimen heating by the electron beam were shown to be negligible.     

Yb2O3 and Y2O3 co-doped zirconia ceramics

A suspension stabilizer-coating technique was employed to prepare x mol% Yb₂O₃ (x = 1.0, 2.0, 3.0 and 4.0) and 1.0 mol% Y₂O₃ co-doped ZrO₂ powder. A systematic study was conducted on the sintering behaviour, phase assemblage, microstructural development and mechanical properties of Yb₂O₃ and Y₂O₃ co-doped zirconia ceramics. Fully dense ZrO₂ ceramics were obtained by means of pressureless sintering in air for 1 h at 1450 °C. The phase composition of the ceramics could be controlled by tuning the Yb₂O₃ content and the sintering parameters. Polycrystalline tetragonal ZrO₂ (TZP) and fully stabilised cubic ZrO₂ (FSZ) were achieved in the 1.0 mol% Y₂O₃ stabilised ceramic, co-doped with 1.0 mol% Yb₂O₃ and 4.0 mol% Yb₂O₃, respectively. The amount of stabilizer needed to form cubic ZrO₂ phase in the Yb₂O₃ and Y₂O₃ co-doped ZrO₂ ceramics was lower than that of single phase Y₂O₃-doped materials. The indentation fracture toughness could be tailored up to 8.5 MPa m^1/2 in combination with a hardness of 12 GPa by sintering a 1.0 mol% Yb₂O₃ and 1.0 mol% Y₂O₃ ceramic at 1450 °C for 1 h.     

Microstructures and mechanical properties of 8Y-FSZ ceramics with BaTiO3 additive

The microstructure and mechanical properties of 8 mol% Y₂O₃ fully stabilized zirconia (8Y-FSZ) with BaTiO₃ additive were investigated. The introduction of BaTiO₃ additive would significantly increase the density and the grain size of 8Y-FSZ ceramics. XRD, Raman spectroscopy, and dielectric measurement were performed. A rhombohedral Ba(Ti_1−xZr_x)O₃ ferroelectric phase resulted in the composite with 5 mol% additive, while for those with higher additive content, the secondary phase changes to cubic Ba(Ti_1−xZr_x)O₃. The fracture toughness of the xBaTiO₃/(1−x)8Y-FSZ composites reached a maximum and then decreased with increasing the amount of additive. The highest value reached 6.1 MPa m^1/2 for 0.05BaTiO₃/0.95(8Y-FSZ) sintered at 1475 °C for 3 h, where the piezoelectric/ferroelectric secondary phase toughening played an important role. Moreover, the fracture toughness of the composites increased firstly and then decreased with increasing sintering temperature.     

Thermal stability of tungsten carbide in 7 mol.% calcia–zirconia solid solution matrix heat treated in argon

Zirconia polycrystals stabilised with 7 mol.% CaO containing 10 vol.% WC particles (Ca-PSZ/WC) were obtained by using zirconia nanopowder and WC micropowder. Cold isostatically pressed samples were pressureless sintered in argon at 1350–1950 °C. The influence of the sintering temperature and the incorporation of WC particles on the phase composition and mechanical properties of the composites were studied. Decomposition of WC due to the reaction with the zirconia matrix was found. W₂C and metallic tungsten were detected as decomposition products when heat treated below 1750 °C. At higher temperatures, ZrC is formed. The mechanism of WC decomposition was discussed. The zirconia polycrystals modified with in situ formed W and W₂C inclusions showed a bending strength of 417 ± 67 MPa, a fracture toughness of 5.2 ± 0.3 MPa m^0.5 and a hardness of 14.6 ± 0.3 GPa.     

Strengthening interfaces between biaxial oriented PET and PSMA: Effects of nitrogen plasma and bonding treatments

The fracture toughness, G_c, of the interface between a nitrogen plasma-treated poly(ethylene terephthalate) (PET) film and a poly(styrene-co-maleic anhydride) (PSMA) substrate was measured by using asymmetric double cantilever beam method. The effects of plasma treatment condition on PET films and post-plasma bonding treatment of the bi-material on the adhesion and the failure mechanism were investigated. For a given plasma pressure and energy, the amount of incorporated nitrogen on the PET surface as determined from X-ray photoelectron spectrometry (XPS) increased with increasing plasma treatment time and reached a plateau value of 7.7 at.%. XPS measurement showed that the incorporated nitrogen was primarily in the form of amine and amide. For bonding temperatures between 130 °C and 160 °C, the fracture toughness increased with increasing nitrogen incorporation on PET surface and reached a saturation G_c which significantly depended on the bonding temperature. The saturation G_c increased from 10 J/m² at 130 °C to 40 J/m² at 140 °C, reached a maximum of 120 J/m² at 150 °C, and then decreased to 60 J/m² at 160 °C. The location of failure also changed drastically with the bonding temperature. SEM and XPS measurements showed that for bonding temperature < 140 °C, failure occurred at the PET/PSMA interface. For bonding temperature = 150 °C, the interfacial adhesion exceeded that of the cohesive strength of PET film and failure occurred within the PET film. At the bonding temperature of 160 °C, failure occurred within PSMA bulk material. XPS measurement was used to measure the areal joint density, Σ_cross of PSMA chains pinned on the functionalized PET film surface. A transition in areal joint density below which G_c scales linear with Σ_cross and above which G_c scales with was found. The transition was identified as the transition from the pure chain scission of in situ formed copolymers to plastic deformation of the interface.     

ß-sialon ceramics with TiN particle inclusions

Fully dense composites of 0–30 wt% discrete TiN particles distributed in a ß-sialon matrix of overall composition Si_5·5Al_0·5O_0·5N_7·5 have been prepared by hot isostatic pressing at 1650 and 1750°C. Pressureless sintering at 1775°C gave materials with an open porosity. Typical sizes of the TiN particles were 1–3 μm, and no intergranular glassy phase was observed in the prepared materials. The grain size of ß-sialon was below 1 μm in the materials HIPed at 1650°C, and 1–2 μm at 1750°C. The Vickers hardness was fairly constant for the TiN-ß-sialon composites with up to 15 wt% TiN added: H_v10 around 17·5 GPa for materials HIPed at 1650° and around 17 GPa at 1750°C, whereas at higher TiN contents the hardness decreased to around 16 GPa. The indentation fracture toughness of the ß-sialon ceramic increased approximatively from 3 to 4 MPam^1/2 at an addition of 15 wt% TiN particulates. The fracture toughness could be further increased to 5 MPam^1/2 by addition of small amounts of Y₂O₃ and A1N to a ß-sialon composite with 30 wt% TiN.     

R-curve behaviour of 2Y-TZP with submicron grain size

Nanocrystalline powders were used to prepare fracture test specimens of 2Y-TZP with average grain sizes between 150 and 900 nm. Crack extension and attendant R-curve behaviour were studied in both air and vacuum. The plateau values in air and vacuum increase linearly with grain size from 3.1 to 5.1 MPa m^1/2 and from 4.7 to 6.7 MPa m^1/2, respectively. The size of the process zone was quantified using Raman microscopy and the results correlated to both the plateau values and the shape of the R-curve as a function of grain size.     

Microstructure development and properties of novel Ba-doped phase Sialon ceramics

Herein, we report the microstructure and properties of the newly developed near monophasic S-Sialon ceramic, based on the composition of Ba₂Si_12−xAl_xO_2+xN_16−x (x = 20.2). Appropriate amount of the precursor powders (BaCO₃, -Si₃N₄, AlN, Al₂O₃) with a targeted composition of BaAlSi₅O₂N₇ was ball milled and hot pressed to full density in the temperature range of 1600–1750 °C for 2 h in nitrogen atmosphere. Extensive transmission electron microscopy (TEM) study has been conducted to understand the microstructure development and characterise the various morphological features in hot pressed S-Sialon. The sintering mechanism is based on the liquid phase sintering route, which involves the formation of a Ba–Al silicate liquid (<5%) with dissolved nitrogen at intergranular pockets. The experimental observation suggests that the S-phase crystallises in elongated platelet morphology with preferred growth parallel to the orthorhombic ‘c’ axis and primary facet planes parallel to (1 0 0) and (0 1 0). The Ba-S-phase ceramic has an acoustically measured Young modulus of 210–230 GPa, a hardness of 13 GPa and a fracture toughness of 4 MPa m^1/2, little lower than typical of a ceramic with morphologically anisotropic grains contributing to bridging and pullout mechanisms.     

Cresol novolac–epoxy networks: properties and processability

Linear controlled molecular weight ortho-cresol novolac oligomers were crosslinked with epoxies to form tough, flame retardant networks with enhanced processability and reduced moisture uptake. At the networks' optimum stoichiometry, the fracture toughness, assessed by the critical stress intensity factor (K_IC), was slightly higher for the cresol novolac–epoxy networks (1.1 MPa m^1/2) than for similar phenolic novolac–epoxy networks (0.85 MPa m^1/2). Cresol novolac–epoxy networks exhibited improved processability under melt conditions relative to phenolic novolac–epoxy materials, and this was attributed to the presence of a methyl group adjacent to the hydroxyl group on cresol repeat units, which reduced the rate of reaction between phenol and epoxy. The use of cresol novolac oligomers also reduced the network equilibrium water absorption, and this was likely due to the presence of the additional methyl on each repeat unit. The equilibrium water absorption for all cresol novolac containing compositions was between 1.7 and 2.1 wt%, comparable to epoxy networks. Cone calorimetry showed that the flame retardance of cresol novolac–epoxy networks was lower than that for the phenolic novolac–epoxy materials, but was far superior to the control epoxy networks.     

Microhardness and Fracture Toughness Anisotropy in Cubic Zirconium Oxide Single Crystals

Vickers and Knoop indentation tests have been used to study the fracture and deformation characteristics of 9.4-mol%-Y₂O₃-stabilized ZrO₂ single crystals. K_c is anisotropic, with values of 1.9 and 1.1 MPa·m^1/2 for radial cracks propagating along (100) and (110), respectively. The toughness for these two orientations was also determined using the single-edge notched-beam geometry, and yielded values of 1.9 and 1.5 MPa·m^1/2.     

The Study on Carbon Nanofiber (CNF)-Dispersed B4C Composites

Carbon nanofiber (CNF)-dispersed B₄C composites have been synthesized and consolidated directly from mixtures of elemental raw powders by pulsed electric current pressure sintering (1800°C/10 min/30 MPa). A 15 vol% CNF/B₄C composite with ∼99% of dense homogeneous microstructures (∼0.40 μm grains) revealed excellent mechanical properties at room temperature and high temperatures: a high bending strength (σ_b) of ∼710 MPa, a Vickers hardness ( H _v) of ∼36 GPa, a fracture toughness ( K _{I C} ) of ∼7.9 MPa m^1/2, and high-temperature σ_b of 590 MPa at 1600°C in N₂. Interfaces between the CNF and the B₄C matrix were investigated using high-resolution transmission electron microscopy, EDS, and electron energy-loss spectroscopy.     

Zirconia stabilized with a mixture of the rare earth oxides

A hydrothermal technique was used to prepare micropowders of ZrO₂ solid solutions stabilized by the mixture of rare earth oxides and yttria (Ln₂O₃) recovered from phosphogypsum. Phase compositions and particle sizes of the powders were measured. Zirconia solid solutions of cubic and tetragonal symmetry are the major phases. A larger Ln₂O₃ concentration promotes a greater cubic phase content. Powders having low Ln₂O₃ concentrations have small amounts of monoclinic phase present.

The phase composition, fracture toughness (K_Ic) and Vickers hardness of samples sintered at temperatures ranging from 1250 to 1350°C were measured. Tetragonal and, in some cases, monoclinic zirconia solid solutions are found in the microstructure of the sintered bodies. Two ordered phases with the formulae Ln₂Zr₂O₇ and Ce₂Zr₃O₁₀ were also detected in the system. Tetragonal zirconia polycrystals (TZP) with high (10 MPaM^0·5) fracture toughness were found.     

In-situ growth of needlelike LaAl11O18 for reinforcement of alumina composites

In situ growth of needlelike LaAl₁₁O₁₈ grains reinforcing Al₂O₃ composites can be fabricated by a coprecipitation method using La(NO₃)₃√6H₂O and Al(NO₃)₃√9H₂O as starting materials. The new two-step process involved firstly preparing needlelike LaAl₁₁O₁₈ grains distributed homogeneously in Al₂O₃ powder and then pressureless sintering the composite powders. The Al₂O₃/25 vol.%LaAl₁₁O₁₈ samples pressureless sintered at 1550°C for 4 h achieve relative density up to 96.5% and exhibit a bending strength of 420±30 MPa and a fracture toughness of 4.3±0.4 MPa m^1/2.     

Grain growth inhibition and mechanical property enhancement by adding ZrO2 to Al2O3 matrix

The critical amount and critical size of ZrO₂ for effective dragging of grain boundary migration occurred at 8 vol% addition for Al₂O₃ ceramic composite, pressureless-sintered at 1600°C for 2h. The fracture toughness was increased from 4·1 to 5·4 MPa m^1/2, and the flexural strength from 290 to 410 MPa at optimal conditions. The enhancement of mechanical properties is attributed to the stress-induced phase transformation toughening when ZrO₂ particles were located intergranularly. Al₂O₃ grain growth is inhibited by ZrO₂ particles pinning at the grain boundaries.     

Processing Temperature Effects on Molybdenum Disilicide

A series of MoSi₂ compacts were fabricated at increasing hot-pressing temperatures to achieve different grain sizes. The materials were evaluated by Vickers indentation fracture to determine room-temperature fracture toughness, hardness, and fracture mode. From 1500° to 1800°C, MoSi₂ had a constant 67% transgranular fracture and linearly increasing grain size from 14 to 21 μm. Above 1800°C, the fracture percentage increased rapidly to 97% transgranular at 1920°C (32-μm grain size). Fracture toughness and hardness decreased slightly with increasing temperature. MoSi₂ processed at 1600°C had the highest fracture toughness and hardness values of 3.6 MPa.m^1/2 and 9.9 GPa, respectively. The effects of SiO₂ formation from oxygen impurities in the MoSi₂ starting powders and MoSi₂–Mo₅Si₃ eutectic liquid formation were studied.     

Microemulsion synthesis of MgO-supported LaMnO3 for catalytic combustion of methane

Catalysts with 20% LaMnO₃ supported on MgO have been prepared via CTAB-1-butanol-iso-octane-nitrate salt microemulsion. The preparation method was successfully varied in order to obtain different degrees of interaction between LaMnO₃ and MgO as shown by TPR and activity tests after calcination at 900 °C. Activity was tested on structured catalysts with 1.5% CH₄ in air as test gas giving a GHSV of 100,000 h⁻¹. The activity was greatly enhanced by supporting LaMnO₃ on MgO compared with the bulk LaMnO₃. After calcination at 1100 °C both the surface area and TPR profiles were similar, indicating that the preparation method is of little importance at this high temperature due to interaction between the phases. Pure LaMnO₃ and MgO were prepared using the same microemulsion method for comparison purposes. Pure MgO showed an impressive thermal stability with a BET surface area exceeding 30 m²/g after calcination at 1300 °C. The method used to prepare pure LaMnO₃ appeared not to be suitable since the surface area dropped to 1.1 m²/g already after calcination in 900 °C.