Evaluation of the Thermal Resistance of Structural Ceramics in Testing Notched Prismatic Samples

The considered approach to determining thermal resistance in structural ceramics involves thermal cycling of samples with a special notch. The proposed thermal resistance characteristics include the loss of crack resistance after a thermal shock, the insensitivity of the material structure to defects formed at the notch apex as the result of a thermal shock, and the degree of defect accumulation at the notch apex. The testing results of ceramics made of Al₂O₃, ZrO₂, partly stabilized Y₂O₃ (molar part 3%), and cermet ZrO₂ – Y₂O₃ (molar part 3%) with metallic chromium additive (50 vol.%) are indicated.     

Heat resistance of alumina ceramics

A method for evaluating the heat resistance of structural ceramics according to which the thermally stressed state is created by blowing a directed air flow into the tip of a notch in a heated prismatic specimen is presented. For this purpose a special complexly shaped notch is formed in order to provide free inflow of the air to its tip. The radius of curvature of the notch in alumina ceramics is 5 Μm. In blowing, the heat is removed predominantly from a local volume at the tip of the notch, thus providing a “local” thermal shock. The heat resistance of alumina ceramics obtained by sintering and reaction bonding is studied. The mechanical properties of Al₂O₃ tend to improve after a local thermal shock. The tendency is proved by testing a statistically reliable sample of unnotched specimens by the conventional method for determining the heat resistance. This tendency can be explained by “curing” of some of the defects (commensurable with the elements of the substructure) in densely sintered ceramics under the effect of thermal stresses. This was established due to the low scattering of the values of the mechanical properties measured in testing a sample of specimens with a special notch. It cannot be detected in tests of unnotched specimens within the same sample. A heat cycle of “850‡C-water” worsens the mechanical properties of notched and unnotched specimens due to the initiated microfracture. Translated from Ogneupory i Tekhnicheskaya Keramika, Nos. 1–2, pp. 14–19, January–February, 1999.     

A structural study of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-partially stabilized zirconia ceramics

Partially stabilized zirconia ceramics ZrO₂ (Y₂O₃) of different structures and phase compositions are tested for thermal stability and thermal shock. The ceramics can be used as solid electrolytes in oxygen activity sensors for fluid heat transfer agents (lead).__________Translated from Novye Ogneupory, No. 10, pp. 56 – 59, October, 2004.     

Some methodological features of determination of crack resistance in ceramic materials

The known methods for forming stress concentrators (cracks and notches) in ceramic specimens in order to determine their crack resistance are described. A method for forming a notch with a tip curvature radius of at most 10 µm is suggested. The notch is first formed in the process of pressing the specimen in a specially designed mold and then the green specimen is cut additionally from the tip of the notch by a steel blade with a thickness of 0.1 mm and a grinding angle of 14°. After sintering, this specimen does not contain induced defects that are possible when sintered specimens are notched by a diamond disk by the conventional method. It is shown for a ZrO₂ ceramics partially stabilized by 12 mol.% CeO₂ and an Al₂O₃ ceramics with 0.5 wt.% MgO possessing a layered granular structure that an incorrect choice of the tip curvature radius can result in an erroneous evaluation of the optimality of the structure of the material and an incorrect choice of the technological parameters for its production. Notching by the suggested method made it possible to establish the discrete nature of fracture of the layered granular structure of the ceramics from strain diagrams and the mechanisms of crack propagation causing this kind of fracture.Translated from Ogneupory i Tekhnicheskaya Keramika, No. 9, pp. 26 – 30, September, 1996.     

Toughening of laminated ZrB2-SiC ceramics with residual surface compression

Laminated ZrB₂-SiC ceramics with residual surface compression were prepared by stacking layers with different SiC contents. The maximum apparent fracture toughness of these laminated ZrB₂-SiC ceramics was 10.4 MPam^1/2, which was much higher than that of monolithic ZrB₂-SiC ceramics. The theoretical predictions showed that the apparent fracture toughness was strongly dependent on the position of the notch tip, which was confirmed by the SENB tests. Moreover, laminated ceramics showed a higher fracture load when the notch tip located in the compressive layer, whereas showed a lower fracture load as the notch tip within the tensile layer. The toughening effect of residual compressive stresses was verified by the appearance of crack deflection and pop-in event. The influence of geometrical parameters on the apparent fracture toughness and residual stresses was analyzed. The results of theoretical calculation indicated that the highest residual compressive stress did not correspond to the highest apparent fracture toughness.     

Accurate measurement of fracture toughness in structural ceramics

The measured values of fracture toughness for ceramics are closely correlated with the sharpness of notch tips, which in turn influences the accurate measurement of fracture toughness. Here, typical structural ceramics, i.e., 3 mol% yttria-stabilized tetragonal zirconia polycrystal (3Y-TZP), ZrB₂, ZrB₂-SiC and ZrB₂-SiC-Grapite, were used for the measurement of fracture toughness, and the effect of notch tip radius on the fracture toughness values of these typical structural ceramics was investigated. Ultra-sharp notches with a tip radius less than 1 μm can be fabricated by laser, lower than the critical notch tip radius in ceramics below which the fracture toughness value almost remains constant, and improved accuracy and consistency of fracture toughness measurement can be obtained by this method compared with traditional method.     

Enhanced ionic conductivity and thermal shock resistance of MgO stabilized ZrO2 doped with Y2O3

The present work focused on the effect of Y₂O₃ co-doping on the phase composition, microstructure, ionic conductivity and thermal shock resistance of 8 mol% MgO stabilized ZrO₂ (Mg-PSZ) electrolyte ceramics for high temperature applications. The addition of Y₂O₃ could promote the process of monoclinic-to-cubic/tetragonal phase transformation and became the metastable phase at room temperature. Meanwhile, the grain size of Mg-PSZ decreased. It was demonstrated that an appreciable increase in the ionic conductivity and compressive strength occurred on substituting MgO with Y₂O₃ in the Mg-PSZ electrolyte ceramics across the measured temperature range. Moreover, the Y₂O₃ addition could restrain the adverse effect of the cyclic thermal shock on the ionic conductivity and compressive strength of Mg-PSZ. The main reason was that the increase of the amount of monoclinic phase caused by cubic/tetragonal-to-monoclinic phase transformation by the cyclic thermal shock was restrained after the Y₂O₃ addition.     

Fabrication and characterization of highly transparent Er:Y2O3 ceramics with ZrO2 and La2O3 additives

In this study, we report highly transparent Er:Y₂O₃ ceramics (0–10 at% Er) fabricated by a vacuum sintering method using compound sintering additives of ZrO₂ and La₂O₃. The transmittance, microstructure, thermal conductivity and mechanical properties of the Er:Y₂O₃ ceramics were evaluated. The in-line transmittance of all of the Er:Y₂O₃ ceramics (1.2 mm thick) exceeds 83% at 1100 nm and 81% at 600 nm. With an increase in the Er doping concentration from 0 to 10 at%, the average grain size, microhardness and fracture toughness remain nearly unchanged, while the thermal conductivity decreases slightly from 5.55 to 4.89 W/m K. A nearly homogeneous doping level of the laser activator Er up to 10 at% in macro-and nanoscale was measured along the radial direction from the center to the edge of a disk specimen, which is the prominent advantage of polycrystalline over single-crystal materials. Based on the finding of excellent optical and mechanical properties, the compound sintering additives of ZrO₂ and La₂O₃ are demonstrated to be effective for the fabrication of transparent Y₂O₃ ceramics. These results may provide a guideline for the application of transparent Er:Y₂O₃ laser ceramics.     

Fabrication and thermal conductivity of AlN/BN ceramics by spark plasma sintering

Aluminum nitride/boron nitride (AlN/BN) ceramics with 15–30 vol.% BN as secondary phase were fabricated by spark plasma sintering (SPS), using Yttrium oxide (Y₂O₃) as sintering aid. Effects of Y₂O₃ content and the SPS temperature on the density, phase composition, microstructure and thermal conductivity of the ceramics were investigated. The results revealed that with increasing the amount of starting Y₂O₃ in AlN/BN, Yttrium-contained compounds were significantly removed after SPS process, which caused decreasing of the residual grain boundary phase in the sintered samples. As a result, thermal conductivity of AlN/BN ceramics was remarkably improved. By addition of Y₂O₃ content from 3 wt.% to 8 wt.% into AlN/15 vol.% BN ceramics, the thermal conductivity increased from 110 W/m K to 141 W/m K.     

Development of stabilized zirconia–alkali salts dual membranes for carbon dioxide capture

Molten Na₂CO₃–K₂CO₃ (NKC, 56–44 mol%) eutectic compositions were vacuum-impregnated, at the eutectic temperature, into two porous ZrO₂:8.6 mol% MgO (magnesium-partially stabilized zirconia, MgPSZ) and ZrO₂:8 mol% Y₂O₂ (yttria-fully stabilized zirconia, 8YSZ) ceramics. Thermogravimetric analyses were performed in mixtures of that composition with MgPSZ and 8YSZ ceramic powders. Before impregnation, porosity was achieved in the two compounds by addition and thermal removal of 30 vol.% NKC. To ascertain the carbonates had filled up through the ceramic body, both sides of the parallel and fracture surfaces of the disk-shaped impregnated compositions were observed in a scanning electron microscope and analyzed by energy-dispersive X-ray spectroscopy. The electrical conductivity of the two ceramics, before and after impregnation, was evaluated by electrochemical impedance spectroscopy in the 5 Hz–13 MHz frequency range from approximately 530 to 740°C. The permeation of the carbonate ions through the membranes via the eutectic composition was assessed by the threshold temperatures of the onset of the carbonate ion percolation. The objectives were to prepare dual-phase membranes for the separation of carbon dioxide and for the development of carbon dioxide sensors.     

Effect of Y2O3 on the oxidation properties of ZrSi2/SiC coating prepared by SAPS on the carbon-carbon composites

In order to improve the oxidation resistance of carbon-carbon (C/C) composites at high temperature, different content of Y₂O₃ modified ZrSi₂/SiC coating for C/C composites were prepared by pack cementation and supersonic atmosphere plasma spraying (SAPS). Microstructure observation and phase identification of the coatings were analyzed by SEM, XRD, DSC/TG and EDS. Experimental results shown that the coating with 10?wt% Y₂O₃ effectively protected C/C composites from oxidation at 1500?°C in air for 301?h with a mass loss of 0.13% and experienced 18 thermal shock times from room temperature (RT) to 1500?°C. First, Y₂O₃ could restrain the phase transition of ZrO₂ to reduce the formation of thermal stresses of the coating; second, the random distribution of ZrO₂ ceramic particles and the formation of ZrSiO₄ enhanced the stability of the SiO₂; third, the formation of Y₂Si₂O₇ and Y₂SiO₅ could relieve the thermal mismatch between ZrSi₂-Y₂O₃ outer layer and the inner layer.     

High-gravity activated SHS of large bulk Al2O3/ZrO2 (Y2O3) nanocrystalline composites

Large bulk Al₂O₃/ZrO₂ (Y₂O₃) composites were in-situ prepared by SHS under varied high-gravity from ZrO₂ + Y₂O₃powder blends with an added thermit mixture. Investigated was the effect of high gravity on the microstructure, crystal growth, and properties of synthesized materials. The XRD data suggest that high gravity did not bring about any change in the phase constitution of the composite ceramics and that the ceramic matrix was composed of α-Al₂O₃, t-ZrO₂, and m-ZrO₂. SEM and EDS data show that, with increasing level of high gravity, the morphology of the ceramic microstructures transformed from the cellular eutectics to the rodshaped colonies, and the volume fraction and aspect ratio of the rod-shaped colonies increased while the rodshaped colonies were refined. Above 200 g, the microstructures of composite ceramics developed as the randomlyorientated rod-shaped colonies with a symmetrical triangular dispersion of tetragonal ZrO₂ fibers of 300 nm in the average diameter. Relative density, hardness, flexural strength and fracture toughness simultaneously reached the highest values of 98.6%, 18.6 GPa, 1248 MPa, and 15.6 MPa m^1/2 as the maximum high-gravity level of 250 g was achieved. An increase in the relative density and hardness of the ceramics with increasing gravity level was attributed to the acceleration of gas escape from SHS melts and the elimination of shrinkage cavity in the ceramics under the action of high-gravity field. The increase in fracture toughness results from the enhancement of the coupled toughening mechanisms while the increase in flexural strength comes from the refinement of the microstructures, decrease in critical defect size, and achievement of high fracture toughness.     

Fracture characteristics of ceramic and cermet cutting tools

This paper deals with the fracture characteristics of ceramic and cermet cutting materials on the basis of Al₂O₃+ZrO₂, Al₂O₃+ZrO₂+MgO, WC-Co and WC-TiC-Co. The influence of defects on the bend strength and the relationship between the structure, fracture micromechanisms and the fracture toughness are studied. The knowledge gained will help in making suggestions for variations in production technology of these tools with the aim of improving their properties.     

Study on thermal shock resistance of Sc2O3 and Y2O3 co-stabilized ZrO2 thermal barrier coatings

In order to reveal the effect of Sc₂O₃ and Y₂O₃ co-doping system on the thermal shock resistance of ZrO₂ thermal barrier coatings, Y₂O₃ stabilized ZrO₂ thermal barrier coatings (YSZ TBCs) and Sc₂O₃–Y₂O₃ co-stabilized ZrO₂ thermal barrier coatings (ScYSZ TBCs) were prepared by atmospheric plasma spraying technology. The surface and cross-section micromorphologies of YSZ ceramic coating and ScYSZ ceramic coatings were compared, and their phase composition before and after heat treatment at 1200 °C was analyzed. Whereupon, the thermal shock experiment of the two TBCs at 1100 °C was carried out. The results show that the micromorphologies of YSZ ceramic coating and ScYSZ ceramic coating were not much different, but the porosity of the latter was slightly higher. Before heat treatment, the phase composition of both YSZ ceramic coating and ScYSZ ceramic coating was a single T′ phase. After heat treatment, the phase composition of YSZ ceramic coating was a mixture of M phase, T phase, and C phase, while that of ScYSZ ceramic coating was still a single T′ phase, indicating ScYSZ ceramic coating had better T′ phase stability, which could be attributed to the co-doping system of Sc₂O₃ and Y₂O₃ facilitated the formation of defect clusters. In the thermal shock experiment, the thermal shock life of YSZ TBCs was 310 times, while that of ScYSZ TBCs was 370 times, indicating the latter had better thermal shock resistance. The difference in thermal shock resistance could be attributed to the different sintering resistance of ceramic coatings and the different growth rates of thermally grown oxide in the two TBCs. Furthermore, the thermal shock failure modes of YSZ TBCs and ScYSZ TBCs were different, the former was delamination, while the latter was delamination and shallow spallation.     

Coating Y2O3 nano-particles with ZrO2-additive via precipitation method for colloidal processing of highly transparent Y2O3 ceramics

In the present work, transparent Y₂O₃ ceramics were prepared via colloidal processing method using ZrO₂-coated nano-sized Y₂O₃ powders. The chemical precipitation method was adopted for the coating of Y₂O₃ raw powder. The evolution of the coated-ZrO₂ layer upon calcination was studied. The rheological behaviors of the slurries of Y₂O₃ powders coated with different content of ZrO₂-additive were investigated. The pH_IEP of ZrO₂-coated Y₂O₃ powders shows intermediate values between that of raw Y₂O₃ and ZrO₂ powders. As the ZrO₂-coating concentration increased from 0 to 5.0 at%, the magnitude of the negative zeta potential at pH > pH_IEP shows a general trend of increment, whereas it decreased at pH < pH_IEP. The viscosity decreases pronouncedly with the increase of ZrO₂ content from 0.5 at% to 3.0 at%. The suspensions with low viscosity and high stability was achieved for a solid loading of 35.0 vol% using Y₂O₃ powders coated with 5.0 at% ZrO₂. The dispersed suspensions were consolidated by centrifugal casting method and the green bodies shown improved homogeneity. Transparent Y₂O₃ ceramics were fabricated by vacuum sintering at 1800 ℃ for 5 h. Transmittance at wavelength 800 nm (1.0 mm thick) reached 80.8%, close to the theoretical value of Y₂O₃.     

Enhancement of thermal shock and slag corrosion resistance of MgO–ZrO2 ceramics by doping CeO2

The purpose of this paper was to develop ceramics materials with high thermal shock resistance and corrosion resistance for preparing gas blowing components. In this paper, MgO-rich MgO–ZrO₂ ceramics were obtained by using MgO powder and ZrO₂ powder as starting materials and CeO₂ as an additive. Changes in the properties in terms of thermal shock resistance, mechanical properties, and slag corrosion-resistance with chemical compositions were examined correlated to microstructure and phase changes. Especially, the effect of doping CeO₂ on phase transition of zirconia in MgO-rich system was discussed. The results showed that doping amount of CeO₂ significantly improved properties of MgO–ZrO₂ ceramics. Especially when doping amount of CeO₂ was 2 wt%, residual strength ratio was enhanced over 100% after thermal shock testing. In samples doped with CeO₂, ZrO₂ was stable in cubic or tetragonal form due to complete solution of CeO₂, which was important reason for the improvement of various properties of MgO–ZrO₂ ceramics.     

ZrO2-doped Y2O3 transparent ceramics via slip casting and vacuum sintering

Commercial Y₂O₃ powder was used to fabricate highly transparent Y₂O₃ ceramics with the addition of ZrO₂ via slip casting and vacuum sintering. The effects of ZrO₂ addition on the transparency, grain size and lattice parameter of Y₂O₃ ceramics were studied. With addition of ZrO₂ the transparency of Y₂O₃ ceramics increased markedly and the grain size of Y₂O₃ ceramics decreased markedly by cation diffusivity mechanism and the lattice parameter of Y₂O₃ ceramics slightly decreased. The highest transmittance (at wavelength 1100 nm) of the 5.0 mol% ZrO₂–Y₂O₃ ceramic (1.0 mm thick) sintered at 1860 °C for 8 h reached 81.7%, very close to the theoretical value of Y₂O₃.     

An investigation of conductivity,microstructure and stability of HfO2–ZrO2–Y2O3–Al2O3 electrolyte compositions for high-temperature oxygen measurement

In search of better ionically conducting ceramics for high temperature oxygen fuel cells and sensors, the conductivity and microstructure of the HfO₂–ZrO₂–Y₂O₃ system with 15 mol% of Y₂O₃ and the HfO₂–ZrO₂–Y₂O₃–Al₂O₃ system with 50 mol% of Al₂O₃ have been investigated with X-ray diffractometry (XRD), scanning electron microscopy (SEM) and conductivity measurements as a function of temperature. The stability of electrolyte compositions was studied by continuously monitoring conductivity as a function of time at 1000°C. A majority of the investigated samples exhibited linear Arrhenius plots of the lattice conductivity as a function of temperature. In the HfO₂–ZrO₂–Y₂O₃–Al₂O₃ electrolyte systems the parameter pe′ was measured at a temperature range of 1000–1400°C. The HfO₂–ZrO₂–Y₂O₃–Al₂O₃ electrolyte systems have also showed better thermal shock resistance than the ZrO₂–Y₂O₃ systems. A comparison between the ageing of ZrO₂- and HfO₂-based electrolyte systems, as a result of long time annealing at a temperature of 1000°C, indicated that the degradation of the HfO₂-based system at a temperature of 1000°C and above is 1.5 times lower than the degradation of the ZrO₂-based systems.     

Low Thermal Conductivity of SnO2‐Doped Y2O3‐Stabilized ZrO2: Effect of the Lattice Tetragonal Distortion

Considering the phonon scattering effect and the stability of t′ zirconia, Sn⁴⁺ ion is recognized as an appropriate dopant to achieve the best combination of thermal insulating capability and durability of yttria‐stabilized zirconia thermal barrier coatings (TBCs). In this research, unusual lattice expansion and strong structural disordering were observed in a series of SnO₂‐doped Y₂O₃‐stabilized ZrO₂ compounds, which are caused by the tetragonal distortion of oxygen coordination. Phonon scattering due to the structural disordering rather than point defects of Sn⁴⁺ substitutions predominates in reducing the thermal conductivity. However, deterioration of the thermal properties was observed at high doping content, which may be attributed to the t‐m phase transformation during the measurements. Considering the structure stability and thermal properties, SnO₂‐doped Y₂O₃‐stabilized ZrO₂ compounds can be promising candidates for TBCs.     

Some thermomechanical properties of pure oxide ceramics

Conclusions The proposed vacuum furnace makes it possible to determine the deformation temperature under load and the coefficient of thermal expansion to high temperatures.Ceramics of pure oxides, Al₂O₃, ZrO₂, MgO, and BeO, have high temperatures of softening under load. The temperature of initial softening of Al₂O₃ ceramics containing additives lies in the range 1860–1930°C. The magnesia and beryllia specimens show high softening temperatures under load, but in vacuum at high temperatures they are very volatile. The initial softening temperature of ZrO₂ is about 2250°C.The linear expansion of pure-oxide ceramics reaches 2–3% at 1800–2000°C. Values obtained for the average coefficients of expansion for Al₂,O₃, ZrO₂, MgO, and BeO are little different from those in the literature.The compressive strength and bending strength of pure oxides at high temperatures are relatively low. The highest o_bend at high temperatures is possessed by specially pure zirconia, stabilized with MgO. Magnesia and beryllia in compressive strength at high temperatures exceed the other oxides.The highest spalling resistance is shown by beryllia ceramics. The combined addition to alumina of 1% TiO₂ and 5% ZrO₂ leads to a reduction in sintering temperature and an increase in thermal shock resistance. Ceramics based on specially pure zirconia stabilized with an optimum amount of CaO and MgO show a high thermal shock resistance.