Mechanical Properties of ZrO_2 Ceramic Stabilized by Y_2O_3 and CeO_2

ZrO2 ceramic was made from evenly dispersed ( Y, Ce)-ZrO2 powder with different compositions , which was prepared by the chemical coprecipitation, and stabilized by compound additions through appropriate techniques. And its mechanical property that is related to the phase content and its microstructwe was studied by X-ray diffraction(XRD) , scan electron microscope( SEM). The results show that Y2O3 has stronger inhibition to the growth of ZrO2 crystal than CeO2 has. Therefore, within an appropriate composition range of Y2 O3 and CeO2, the higher the content of Y2O3, the lower the content of CeO2 , the smaller ZrO2 crystal. Combining this feature and the stabilization technique with complex additions instead of simple addition, ZrO2 ceramic with high density and excellent mechanical properties can be made under normal conditions. It is concluded that the improvement of mechanical properties originates from the toughening of microcrack, phase transformation and the effect of grain e-vulsions.     

Preparation of Al2O3-SiO2-TiO2-ZrO2 Composite Ceramic Membranes by Sol-Gel Method

Al2O3-SiO2- TiO2-ZrO2 supported membranes were prepared by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al2O3, TiO2 ( anatase ), Al2 SiO5 , and ZrO2 in these membranes. Changing the molar ratio of Al:Si: Ti : Zr ,the kinds and content of crystal phases of composite membranes could be different, which may lend to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investigated by XRD, SEM, AFM, EPMA. The effects of additives and heat treatments on the surface nanoscale topography and microstracture of composite ceramic membranes were also analyzed.     

Investigation on plasma-sprayed ZrO2 thermal barrier coating on nickel alloy substrate

The thermal barrier coatings with NiCrAlY alloy bonding layer, NiCrAlY-Y₂O₃ stabilized ZrO₂ transition layer and Y₂O₃ stabilized ZrO₂ ceramic layer are prepared on nickel alloy substrates using the plasma spray technique. The relationship among the composition, structure and property of the coatings are investigated by means of optical microscope, scanning electronic microscope and the experiments of thermal shock resistance cycling and high temperature oxidation resistance. The results show that the structure design of introducing a transition layer between Ni alloy substrate and ZrO₂ ceramic coating guarantees the high quality and properties of the coatings; ZrO₂ coatings doped with a little SiO₂ possesses better thermal shock resistance and more excellent hot corrosion resistance as compared with ZrO₂ coating materials without SiO₂; the improvement in performance of ZrO₂ coating doped with SiO₂ is due to forming more dense coating structure by self- closing effects of the flaws and pores in the ZrO₂ coatings. Biography of the first author: LU An-xian, Ph.D, professor, born in Jan. 1960, majoring in inorganic non-metal materials.     

Properties of plasma sprayed NiCrAlY+(ZrO2+Y2O3) coating on refractory steel surface

NiCrAlY+(ZrO₂+Y₂O₃) thermal barrier coating was prepared on the surface of refractory steel 1Cr18Ni9Ti with plasma spraying technique. The phases and microstructure of the thermal barrier coating were determined by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results show that the bonding between thermal barrier coating and substrate is sound. The surface hardness of 1Cr18Ni9Ti reaches up to 1 000 HV, but that of substrate is only 300 HV. The patterns sprayed with CoNiCrAlY+(ZrO₂+Y₂O₃) ceramic coating have a good heat insulation effect at 800 °C for heat insulation temperature difference reaches 54 °C, which increases the operating temperature and service life of refractory steel. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education     

Progress on RE<Subscript>2</Subscript>O<Subscript>3</Subscript>-Mo/W matrix secondary emitter materials

Two types of secondary emitter materials, the rare earth oxides (RE₂O₃) doped Mo cermet cathodes and the Y₂O₃-W matrix pressed cathode, are introduced in this paper. According to the calculation results, Y₂O₃ exhibits the best secondary emission property among Y₂O₃, La₂O₃, CeO₂ and Lu₂O₃. The rare earth oxides co-doped Mo cathodes in which Y₂O₃ is the main active substance exhibit better secondary emission property than single RE₂O₃ doped Mo cathode. The results obtained by the Monte-Carlo calculation method show that the secondary electron emission property is strongly related to the grain size of the cathode. The decreasing of the grain size reduces the positive charge effect of the rare earth oxide due to the electrons supplement from the metal to the rare earth oxide, whereby the secondary electrons are easier to escape into the vacuum. Y₂O₃ is introduced into Ba-W cathode to fabricate a pressed Y₂O₃-W matrix dispenser cathode. The result indicates that the secondary emission yield of the Ba-W cathode increases from 2.13 to 3.51 by adding Y₂O₃, and the thermionic emission current density (J ₀) could reach 4.18 A/cm² at 1050 °Cb.     

Valence electron structure and properties of stabilized ZrO2

To reveal the properties of stabilizers in ZrO₂ on nanoscopic levels, the valence electron structures of four stable ZrO₂ phases and c-ZrO₂ were analyzed on the basis of the empirical electron theory of solids and molecules. The results showed that the hybridization levels of Zr atoms in c-ZrO₂ doped with Ca and Mg dropped from B17 to B13, the hybridization levels of Zr atoms in c-ZrO₂ doped with Y and Ce dropped from B17 to B15, and that the four stabilizing atoms all made the hybridization levels of O atoms drop from level 4 to level 2. The numbers of covalent electrons in the strongest covalent bond in the descending order are c-ZrO₂>Zr_0.82Ce_0.18O₂>Zr_0.82Y_0.18O_1.91>Zr_0.82Mg_0.18O_1.82>Zr_0.82Ca_0.18O_1.82. The bond energies of the strongest covalent bond and the melting points of the solid solutions in the descending order are Zr_0.82Ce_0.18O₂> c-ZrO₂>Zr_0.82Y_0.18O_1.91>Zr_0.82Mg_0.18O_1.82>Zr_0.82Ca_0.18O_1.82. The percentages of the total number of covalent electrons in the descending order are c-ZrO₂>Zr_0.82Y_0.18O_1.91> Zr_0.82Ce_0.18O₂>Zr_0.82Mg_0.18O_1.82> Zr_0.82Ca_0.18O_1.82. From the above analysis, it can be concluded that the stabilizing degrees of the four stabilizers in the descending order are CaO> MgO>Y₂O₃>CeO₂. Supported by the Major Project of the National Natural Science Foundation of China (Grant No. 90505015)     

Preparation and mechanical properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Al laminated ceramic matrix composites

Three series of Al2O3/Al laminated ceramic matrix composites,named SPA,SPV and HP,were fabricated by different methods.SPA and SPV were prepared using Al2O3 slices and Al slurry via screen printing and subsequent heat treatment in air or vacuum.HP samples were made by hot pressing the layered stack of Al foils and Al2O3 slices.SEM and XRD were applied to analyze the microstructure and the interlayer crystal phase.The bending strength,fracture toughness and fracture work of the samples made by the three methods were measured and compared.The results show that the composites have much better toughness and higher fracture work than the Al2O3 slice.Among the samples made by the three methods,the samples made by hot pressing have the optimum mechanical performance.The displacement-load curves and fracture mechanism were analyzed.     

Synthesis,characterization and thermal stability of CeO<Subscript>2</Subscript> stabilized ZrO<Subscript>2</Subscript> ultra fine nanoparticles via a sol-gel route

CeO₂ stabilized ZrO₂ ultra fine nanoparticles were successfully synthesized via a simple and effective sol-gel synthetic approach by using zirconylchloride octahydrate, cerium nitrate hexahydrate, and citric acid as starting materials. A series of techniques, including X-ray diffraction (XRD), thermogravimetry (TG), differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and N₂-sorption analysis, were used to characterize the structure and morphology of the as-prepared samples. XRD studies indicate that the as-synthesized sample is of well crystallized tetragonal phase of CeO₂ stabilized ZrO₂ with high purity. TEM images show that the as-synthesized sample is composed of a large number of fine dispersive nanoparticles with an average size about 10 nm. The as-synthesized tetragonal CeO₂ stabilized ZrO₂ sample was heated at different temperatures in order to evaluate its thermal stability. The exprimental results reveal that the as-synthesized tetragonal CeO₂ stabilized ZrO₂ sample exhibits excellent stability without the occurrence of phase transformation.     

Structure and properties of CaO-MgO-SiO2 inorganic glass fiber with additives (Al2O3, Y2O3)

Structure, crystallization and dissolution properties of CaO-MgO-SiO2 inorganic glass fiber in the presence of additives (Al2O3, Y2O3) were investigated by DTA, XRD, FTIR and ICP-AES techniques. The results show that with the addition of Al2O3 and Y2O3, the glass network structure is strengthened and the precipitation of crystals is inhibited for heat-treated fibers. Compared with Y2O3 doped fibers, Al2O3 presents more significant effects on the enhancement of silica network and the inhibition of crystallization in fibers. As for dissolution properties in physiological fluids, though the weight losses, changes of pH values and leached ions concentration lower slightly with the addition of Al2O3 and Y2O3 for the intensified network structure, and fibers still present high dissolution rates.     

The effect of alumina content on fracture property of all-ceramics zirconia

The purpose of the present study was to evaluate the effect of Al2O3 content on the fracture property of all-ceramics ZrO2. To improve the all-ceramics ZrO2 restoration mechanics properity ,96 samples containing 0,5,10 and 15 wt% of Al2O3 particles were prepared by cold isostatic pressing (200 MPa) and 1 550 ℃ sintered .The phase was analyzed by X-ray diffraction analysis and the bulk densities of the samples were made using Archimedes principle. Samples were randomly divided into four groups. In each group, 24 specimens were prepared so that the angle between notch and specimen’s long axis is 90o and 60o. Notch depths were 1 mm for all samples. Samples were loaded with three-point bending method. 90° cut samples were used to measure fracture toughness while 60°cut samples were used to observe fracture curve by taking points on the fracture extension path under microscope, plotting points on coordinates, generating fitting curve by software "Origin", and analyzing the microstructure of the specimen fracture surfaces by scanning electron microscopy (SEM).The results show that the increment of Al2O3 has insignificant effect on the densification of all-ceramic ZrO2.XRD analysis shows that the specimen is comprised of t-ZrO2 and α- Al2O3 before fracture while fracture surface is m-ZrO2, t-ZrO2 and a-Al2O3. ZrO2 containing 10% Al2O3 has the optimum mechanical properties and unconspicuous crack propagation and distribution. The observations may provide a reference for the materials selection, shape design , and production process of all-ceramic crown and bridge.     

Effect of sintering additives on properties of Si3N4-BN composites fabricated via die pressing and precursor infiltration and pyrolysis route

The Si3N4-BN composites have been prepared via die pressing and precursor infiltration and pyrolysis route using borazine as precursor, and the effect of sintering additives on properties of the composites has been investigated. After sintering additives are adopted, the α to β phase transition of Si3N4 and the mechanical properties of the composites at both room temperature and high temperature are all increased with small extent. When using Y2O3+Al2O3 as additives, the phase transition of Si3N4 and the mechanical properties of the composites have better results. The β-Si3N4 content is 17.47%. The fl exural strength, elastic modulus and fracture toughness of the composites are 188.74 MPa, 84.34 GPa and 2.96 MPa?m1/2, respectively. After exposed at 1 000 ℃ in the air for 15 min, the fl exural strength of the composites is 154.62 MPa with a residual ratio of 81.92%. The elongated β-Si3N4 grains appear in all composites with different sintering additives. Relatively more rod like β-Si3N4 grains can be observed in composites with Y2O3+Al2O3 as additives, making it to possess better mechanical properties.     

Comparative study of β-Si3N4 powders prepared by SHS sintered by spark plasma sintering and hot pressing

β-Si3N4 powders prepared by self-propagating high-temperature synthesis (SHS) with additions of Y2O3 and Al2O3 were sintered by spark plasma sintering (SPS). The densification, microstructure, and mechanical properties of Si3N4 ceramics prepared using this method were compared with those obtained by hot pressing process. Well densified Si3N4 ceramics with finer and homo- geneous microstructure and better mechanical properties were obtained in the case of the SPS technique at 200°C lower than that of hot pressing. The microhardness is 15.72 GPa, the bending strength is 716.46 MPa, and the fracture toughness is 7.03 MPa?m1/2.     

Modification of LiCo1/3Ni1/3Mn1/3O2 cathode material by CeO2-coating

LiCo_1/3Ni_1/3Mn_1/3O₂ was coated by a layer of 1.0 wt% CeO₂ via sol-gel method. The bared and coated LiMn_1/3Co_1/3Ni_1/3O₂ was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammogram (CV) and galvanotactic charge-discharge test. The results show that the coating layer has no effect on the crystal structure, only coating on the surface; the 1.0 wt% CeO₂-coated LiCo_1/3Ni_1/3Mn_1/3O₂ exhibits better discharge capacity and cycling performance than the bared LiCo_1/3Ni_1/3Mn_1/3O₂. The discharge capacity of 1.0 wt% CeO₂-coated cathode is 182.5 mAh·g⁻¹ at a current density of 20 mA·g⁻¹, in contrast to 165.8 mAh·g⁻¹of the bared sample. The discharge capacity retention of 1.0 wt% CeO₂-coated sample after 12 cycles reaches 93.2%, in comparison with 86.6% of the bared sample. CV results show that the CeO₂ coating could suppress phase transitions and prevent the surface of cathode material from direct contact with the electrolyte, thus enhance the electrochemical performance of the coated material.     

Effects of nucleating additives on crystallization and properties of CaO-B2O3-SiO2 glass-ceramics

ZrO₂, TiO₂ and P₂O₅ were doped in CaO-B₂O₃-SiO₂ glass-ceramics as nucleating additives. Effects of different nucleating additives on the phase separation and crystalline behaviors were investigated by using gradient temperature furnace, DTA and XRD. Then, sintering process of the glass-ceramics was investigated by testing sintering shrinkage, dielectric constant and loss. The experimental results shows that the glass-ceramics doped with nucleating additives represents higher crystallization, with ZrO₂ as an exceptional effective dopant to promote the precipitation of wollastonite crystal. Finally, ZrO₂ containing glass-ceramics was chosen to study the influence of sintering temperature and soaking time with the help of X-ray diffraction analysis and density measurement. The glass-ceramics can be well consolidated at 850 °C for 10 min, with low dielectric constant (5.87) and loss (3.21 × 10⁻⁴), which is desirable for LTCC application.     

Effect of nucleating agents and heat treatments on the crystallization of magnesium aluminosilicate transparent glass-ceramics

The crystallization behavior and transparent property of MgO-Al2O3-SiO2 (MAS) glasses with TiO2 and TiO2+ZrO2 as nucleating agents were discussed by differential thermal analysis, X-ray diffraction, field emission-environment scanning electron microscope, energy dispersive spectrum and UV-VIS-NIR scanning spectrophotometer. It was found that the glass crystallized at 950 ℃ with ZrO2 less than 3% could obtain transparent glass ceramic, which presented purple to colorless. With the nucleating agent additives (5% TiO2+3% ZrO2), the colorless transparent glass-ceramics with spinel as the main crystal phase could be prepared, and the transmittance reached about 80% . As the crystallized temperature increase to 1 000 ℃, besides spinel(MgAl2O4), sapphirine (Mg3.5Al9Si1.5O20) and ZrTiO4 precipitated from matrix glass, and the transmitance of glass-ceramic decreased.     

Corrosion resistance of plasma sprayed NiCrAl+(ZrO2+Y2O3) thermal barrier coating on 18-8 steel surface

The corrosion resistance of NiCrAl+(ZrO₂+Y₂O₃) thermal barrier coating, formed with the plasma spraying technique, on the 18 - 8 steel surface was investigated. The phase structure and morphology of the coating were analyzed by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). The electrochemical corrosion behavior of the coating in 1.0 mol/L H₂SO₄ solution was studied by using electrochemical measurement methods. The results show that the gradient plasma spraying coating is composed of the NiCrAlY coating and the (ZrO₂+Y₂O₃) top coating, and the coating thickness is 360 μm. The microhardness of coating reaches 1 100 HV. The corrosion resistance of the plasma sprayed coating of the 18 - 8 steel surface is about 5 times as great as that of the original pattern. The corrosion resistance of the coating is enhanced notably. Foundation item: Project (5040202140) supported by Scientific Research Common Program of Beijing Municipal Commission of Education     

Fabrication and characterization of composite YSZ-La9.33Si6O26 oxygen-ion conductor

To improve the conductivity of Y₂O₃-stabilized ZrO₂ (YSZ) based oxygen-ion conductor, Zr_0.85Y_0.15O_1.925-La_9.33Si₆O₂₆ (YSZ-LSO) composite ceramics with the mass fraction of La_9.33Si₆O₂₆ (LSO) of 15% were prepared by using a modified coprecipitation method. The phases, microstructures and conductivities of the YSZ, LSO and YSZ-LSO were investigated by X-ray diffraction, electron microscopy and complex impedance, respectively. The results show that the as-calcined powder of YSZ-LSO composite has the grain size less than 10 nm, and the as-sintered composite ceramics are composed of YSZ and LSO phases. The conductivity can be enhanced obviously by composite method. At 700 °C, the conductivity of the composite ceramic is 0.125 S/cm, which is one order in magnitude higher than that of the YSZ ceramic and two orders in magnitude higher than that of LSO ceramic. By analyzing the impedance spectra and modulus spectra, the interfacial effect on the conductivity improvement was proposed.     

Phase Structure and Dielectric Properties of Doped BaTiO3 Ceramics

The effects of two rare earth oxides such as CeO2 and Sm2O3 on the phase structure and dielectric properties of BaTiO3 ceramic were investigated. Results indicate that the dielectric constant of this system will increase greatly with the increasing content of these two oxides, and Ce^4＋ substitutes for Ba^2＋ located at A-site in ABO3 structure. Quantitative XRD analysis shows that c/a ratio in the sample with addition of CeO2 will increase, which implies the increase of tetragonality in system, causing the augment of dielectric constant, and the decrease of the crystal＇s geometrical symmetry results in curie-temperature moving towards low temperature; Sm^3＋（0.096 nm） substitutes for Ba^2＋（0.135 nm） possessing larger radius in A-site and the electrovalency in A-site increases, the mutual effect is strengthened, so the polarization is enhanced, and the dielectric constant increases notablely.     

Microstructures and characteristics of deep trap levels in ZnO varistors doped with Y2O3

In this paper discussions on ZnO based varistor ceramics doped with different ratios of Y₂O₃ are presented. Analysis on the phase and microstructures of the samples indicates that an additional phase is detected in the samples doped with Y₂O₃, and the average grain size of the specimens decreases from about 9.2 μm to 4.5 μm, with an increase in the addition of Y₂O₃ from 0 mol% to 3 mol%. The corresponding varistor’s voltage gradient markedly increases from 462 V/mm to 2340 V/mm, while the nonlinear coefficient decreases from 22.3 to 11.5, respectively. Furthermore, the characteristics of deep trap levels in these ZnO samples are investigated by measuring their dielectric spectroscopies. The trap energy level and capture cross section evaluated by relaxation peak of the Cole-Cole plot vary slightly as the addition of Y₂O₃ increases. These traps may be ascribed to the intrinsic defects of ZnO lattice.