Processing and properties of zirconia-toughened alumina ceramics

Al₂O₃:ZrO₂ ceramics have been prepared from physically mixed pure oxide powders. The results indicate that careful processing of the starting powders and a two-stage sintering process can avoid expensive processing methods like hot pressing/hot isostatic pressing used for achieving high densification. The mechanical properties were measured and the resultant microstructure studied to explain the toughening behaviour of this material.     

Effects of TiO2 doping on microstructure and properties of directed laser deposition alumina/aluminum titanate composites

ABSTRACT

Al₂O₃-based composite ceramics have excellent high temperature performance and are ideal materials for preparing hot end components. However, poor fracture toughness and thermal shock resistance limit its applications. Based on the excellent low thermal expansion characteristics and thermal shock resistance of Al₂TiO₅ ceramic, different composition ratios of Al₂O₃/Al₂TiO₅ composite ceramics were prepared by directed laser deposition (DLD) technology. Effects of TiO₂ doping amount on microstructure and properties of the composite ceramics were investigated. Results show that α-Al₂O₃ phase is discretely distributed in the continuous aluminum titanate matrix when TiO₂ doping amount between 2 and 30?mol%. With the increase of TiO₂ doping amount, content of Al₂O₃ gradually decreases and its morphology changes from cellular to dendritic. When TiO₂ doping amount reaches 43.9?mol%, the microstructure transforms into fine Al₂TiO₅/Al₆Ti₂O₁₃ eutectic structure. Property test results show that Al₂O₃/Al₂TiO₅ composite ceramics have good comprehensive mechanical properties when TiO₂ doping amount between 2 and 6?mol%.     

Non-protective alumina growth in sulfur-doped NiAl(Zr)

Abstract

The 1,200°C oxidation behavior of NiAl was examined at various levels of sulfur and zirconium dopants to test the possibility of a critical S/Zr ratio required for adhesion. Cyclic furnace testing for 200 1-h cycles and interrupted testing for 500 h were used as screening tests. Pure NiAl and NiAl(Zr) with 0.14 at. % Zr were chosen as model base compositions; they exhibited normal, slow-growing scales (3 mg/cm²) with excellent adhesion for the Zr-doped alloys. NiAl with about 120 ppma S exhibited a substantial weight loss (?20 mg/cm²) in cyclic tests and a very large weight gain (+60 mg/cm²) in interrupted tests. The major surface phase remained as α-Al₂O₃. Sulfur doping the NiAl(Zr) alloy caused massive weight gains of 80–100 mg/cm², swelling, cracking, and nearly complete conversion into NiAl₂O₄ and α-Al₂O₃. The initial objective of determining critical S/Zr ratios for adhesion was therefore unattainable. Initiation of the catastrophic attack was examined after a 10 h exposure, revealing a few sites of broad, raised, and cracked ridges. In cross-section, the ridges appeared as nodular intrusions, with a complex, fractal, oxide–metal interface. They were primarily alumina (with occasional entrapped islands of NiAl₂O₄ or pure Ni metal). They possessed a unique microstructure consisting of 0.3 μm lamellae, separated by 0.1 μm open channels. This allowed for rapid growth controlled by gaseous diffusion. The microstructure is discussed in terms of SO₂ evolution and a sulfur-driven depassivation process.     

Effect of TiO2 addition on the sintering behavior, hardness and fracture toughness of an ultrafine alumina

The effect of TiO₂ addition (0–4.0 wt%) on the sintering behavior and mechanical properties of an ultrafine (150 nm) alumina–5 wt% zirconia powder has been investigated. TiO₂ is a beneficial additive, resulting in lower sintering temperature and higher sintered density. The grain growth is shown to be enhanced simultaneously after TiO₂ addition. At higher amounts of TiO₂ addition and at higher sintering temperature, the formation of secondary phases of ZrTiO₄ or Al₂TiO₅, which has lower elastic moduli compared with alumina, reduces the hardness of the sintered bulk from 19.3 to 17.9 GPa. The lager grain size and the transition of fracture mode to fully intergranular due to the TiO₂ addition seem to improve the toughness from 4.4 to 5.2 MPa m^1/2.     

Tensile strength and microstructure of Al2O3-ZrO2 hypo-eutectic fibers

Al₂O₃-ZrO₂(Y₂O₃) eutectic materials possess good fracture strengths and creep resistance. Increased Al₂O₃ content is one means to further improve creep resistance. The objective of this study is to examine fracture strength of Al₂O₃-rich (hypoeutectic) compositions at varying Y₂O₃ contents. Fibers 160-220 μm in diameter with 68 m/o Al₂O₃ and 1.1-7.6 m/o Y₂O₃ (30.5 to 16 m/o ZrO₂) were directionally solidified at 0.11 mm/s using the laser-heated float-zone process. Defect populations increased in size and severity with higher Y₂O₃ contents. However, fibers maintained 1 GPa fracture strength in the presence of numerous pores and shrinkage cavities, which extend with crack-like morphology along the fiber axis.     

Enhancement of titania by doping rare earth for photodegradation of organic dye (Direct Blue)

Lanthanide ions (La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, and Yb³⁺)/doped TiO₂ nanoparticles were successfully synthesized by sol–gel method. Their photocatalytic activities were evaluated using Direct Blue dye (DB53) as a decomposition objective. The structural features of TiO₂ and lanthanide ions/TiO₂ were investigated by XRD, SEM, UV-diffuse reflectance, and nitrogen adsorption measurements. Our findings indicated that XRD data characteristic anatase phase reflections and also XRD analysis showed that lanthanides phase was not observed on Lanthanide ions/TiO₂. The results indicated that Gd³⁺/TiO₂ has the lowest bandgap and particle size and also the highest surface area and pore volume (V_p) as well. Lanthanide ions can enhance the photocatalytic activity of TiO₂ to some extent as compared with pure TiO₂ and it was found that Gd³⁺/TiO₂ is the most effective photocatalyst. The photocatalytic tests indicate that at the optimum conditions; illumination time 40 min, pH ∼4, 0.3 g/L photocatalyst loading and 100 ppm DB53; the dye removal efficiency was 100%. Details of the synthesis procedure and results of the characterization studies of the produced lanthanide ions/TiO₂ are presented in this paper.     

Fracture behavior under mixed-mode loading of ceramic plasma-sprayed thermal barrier coatings at ambient and elevated temperatures

The fracture behavior under modes I and II loading of ceramic plasma-sprayed thermal barrier coatings was determined in air at 25 and 1316 °C in asymmetric four-point flexure. The mode I fracture toughness was found to be K_Ic = 1.15 ± 0.07 and 0.98 ± 0.13 MPa , respectively, at 25 and 1316 °C. The respective ‘nominal’ mode II fracture toughness values were K_IIc = 0.73 ± 0.10 and 0.65 ± 0.04 MPa . The empirical mixed-mode fracture criterion best described the coatings’ fracture behavior under mixed-mode loading. The angle of crack propagation was in reasonable agreement with the minimum strain energy density criterion.     

Kinetics of Fe(3)O(4)-CoO/Al(2)O(3) catalytic ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid

The presence of Fe(3)O(4)-CoO/Al(2)O(3) can improve degradation efficiency significantly during the ozonation of the herbicide 2-(2,4-dichlorophenoxy) propionic acid (2,4-DP). The main factors affecting degradation efficiency, such as pH, the catalyst concentration and addition of the scavenger, were investigated. The kinetics of the catalytic ozonation are also discussed. The results indicate that two factors, the oxidation after adsorption of 2,4-DP and the oxidation of hydroxyl radicals (OH), lead to a great enhancement in ozonation efficiency during the catalytic ozonation of 2,4-DP in the presence of Fe(3)O(4)-CoO/Al(2)O(3), in which the oxidation of the OH plays an important role. Under controlled conditions, the apparent reaction rate constants for the degradation of 2,4-DP were determined to be 2.567 × 10(-4)s(-1) for O(3) and 1.840 × 10(-3)s(-1) for O(3)/Fe(3)O(4)-CoO/Al(2)O(3). The results from the analysis of the reaction kinetics using the relative method showed that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) possessed a larger R(ct) (R(ct) is defined as the ratio of the ·OH exposure to the O(3) exposure, R(ct) = ∫C(t)(OH) dt/C(t)O(3)dt) than O(3), indicating that O(3)/Fe(3)O(4)-CoO/Al(2)O(3) produced more hydroxyl radicals.     

Novel plasma generating systems for advanced materials processing

Material processing using nano-technology is now advancing towards a more precise and controllable “smart” stage and plasma systems with high performance are being required for advanced thermal processing. One such unique plasma generator, a high speed plasma accelerator is capable of generating high energy plasma flows of required composition within a large range of plasma parameters. Another gas tunnel type plasma system also exhibits high energy density and high efficiency. Its application to the plasma spraying of ceramics proved that the characteristics of these ceramic coatings are superior to conventional ones. Various types of plasma accelerators are described here with emphasis on a MagnetoPlasma Compressor of Compact Geometry (MPC-CG) which was used to investigate plasma flow interaction with solid silicon surfaces. Different types of submicron structure were obtained due to the compression plasma flow action? The plasma produced by a gas tunnel type plasma source was used for the surface modification of Titanium, TiN films being formed in a relatively short time of 5 s. Plasma sprayed ZrO₂/Al₂O₃ coatings were also investigated, and the results showed that the ZrO₂/Al₂O₃ composite system has the possibility for the development of high functionally graded thermal barrier coating (TBC), which exhibits excellent mechanical properties and oxidation resistance.     

Thermo-optic properties of TiO2, Ta2O5 and Al2O3 thin films for integrated optics on silicon

The direct measurement of the thermo-optic coefficients of aluminium oxide, tantalum pentoxide and titanium dioxide thin films is presented. Using ellipsometry on monolithically integrated permutations of the layers of silicon, silicon dioxide and the material under test, allows the direct measurement of the overall thermo-optic coefficient accounting for thermally induced changes in the dielectric permittivity and density of the materials as well as the elasto-optic effect due to the non-matching thermal expansion coefficients of the different materials.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

The etching characteristics of Al2O3 thin films in an inductively coupled plasma

In this study, the etching characteristics of ALD deposited Al₂O₃ thin film in a BCl₃/N₂ plasma were investigated. The experiments were performed by comparing the etch rates and the selectivity of Al₂O₃ over SiO₂ as functions of the input plasma parameters, such as the gas mixing ratio, the DC-bias voltage, the RF power, and the process pressure. The maximum etch rate was obtained at 155.8 nm/min under a 15 mTorr process pressure, 700 W of RF power, and a BCl₃ (6 sccm)/N₂ (14 sccm) plasma. The highest etch selectivity was 1.9. We used X-ray photoelectron spectroscopy (XPS) to investigate the chemical reactions on the etched surface. Auger electron spectroscopy (AES) was used for the elemental analysis of the etched surfaces.     

Use of oxygen isotope to study the transport mechanism during high temperature oxide scale growth

Abstract

The examination of high temperature (HT) oxide scale growth mechanisms was performed using secondary ion mass spectrometry (SIMS) and secondary neutral mass spectrometry (SNMS), in conjunction with ¹⁶O₂/¹⁸O₂ HT oxidation experiments. Cr₂O₃, NiO, ZrO₂ and Al₂O₃ were studied because they constitute excellent representative thermally grown oxide scales: they grow by cationic diffusion (Cr₂O₃, NiO), anionic diffusion (ZrO₂) or mixed anionic-cationic diffusion (Al₂O₃). The oxidation tests were performed first in ¹⁶O₂ and subsequently in ¹⁸O₂ at several temperatures (600–1000°C for NiO, 600°C for ZrO₂, 1000°C for Cr₂O₃ and 1100°C for Al₂O₃). The oxygen isotope distribution observed by SIMS and SNMS profiles are discussed and related with the HT oxidation mechanisms proposed in the literature.     

Effect of pH on solar photocatalytic reduction and deposition of Cu(II), Ni(II), Pb(II) and Zn(II): speciation modeling and reaction kinetics

The present study is targeted on the effect of pH on solar photocatalytic removal of metal ions from wastewater. Photoreductive deposition and dark adsorption of metal ions Cu(II), Ni(II), Pb(II) and Zn(II), using solar energy irradiated TiO(2), has been investigated at pH values 2, 4, 7, 8 and 10. Modeling of metal species at the studied pH values has been performed and speciation is used as a tool for discussing the photodeposition. The decreasing order of metal deposition at pH 2 and 4 was found to be Pb(II)>Cu(II)>Ni(II) congruent with Zn(II). In the neutral and alkaline pH conditions (pH 7, 8 and 10) the order was Cu(II)>Zn(II)>Ni(II)>Pb(II).     

Failure morphologies of cyclically oxidized ZrO2-based thermal barrier coatings

Abstract

Advanced and baseline thermal barrier coatings (TBCs) were thermal cycle tested in air at 1163°C until delamination or spallation of the ceramic top coat. The top coat of the advanced TBC’s consisted of ZrO₂ with various amounts of Y₂O₃, Yb₂O₃, Gd₂O₃, or Nd₂O₃ dopants. The composition of the top coat of the baseline TBC was ZrO₂-8wt.%Y₂O₃. All top coats were deposited by air plasma spraying. A NiCrAlY or NiCoCrAlY bond coat was deposited by low pressure plasma spraying onto a single-crystal, Ni-base superalloy. The TBC lifetime for the baseline coatings was approximately 190 cycles (45 minutes at 1163°C per cycle) while the lifetime for the advanced coatings was as high as 425 cycles. The fracture surfaces and sample cross sections were examined after TBC failure by SEM and optical microscopy, and the top coats were further examined by X-ray diffraction. These post-test studies revealed that the fracture path largely followed splat boundaries with some trans-splat fracture. However, there were no obvious distinguishing features which explained the difference in TBC lifetimes between some of the advanced and baseline coatings.     

Synthesis and photocatalytic oxidation properties of titania hollow spheres

The hollow spheres of anatase TiO₂ with higher photocatalytic activity have been fabricated by spherical CaCO₃ nanoparticles as a template, and titanium sulfate (Ti(SO₄)₂) as a precursor, and the CaCO₃ templates were dissolved subsequently in dilute HNO₃ solution. The TiO₂ hollow spheres samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and N₂ adsorption-desorption isotherms. The characterization results indicate that as prepared TiO₂ hollow spheres sample was transformed to anatase phase in calcined at 400 °C, and the anatase TiO₂ hollow spheres have a higher specific surface area and show much better photocatalytic activity than commercial P25 in the photodegradation of Rhodamine B under the UV irradiation.     

Transparent conducting Nb-doped anatase TiO2 (TNO) thin films sputtered from various oxide targets

Transparent conducting Nb-doped anatase TiO₂ (TNO) epitaxial films were sputtered from TiO₂-, Ti₂O₃-, and Ti-based targets at various oxygen partial pressures (Po₂). Using the TiO₂- and Ti₂O₃-based targets, highly conductive films showing a resistivity (ρ) of ~ 3 × 10^− 4 Ω cm could be formed without postdeposition treatment. In the case of the TNO films formed from the Ti-based target, reductive annealing had to be carried out at a temperature of 600 °C to achieve similar resistivity values. Thus, the use of oxide targets is preferable to obtain as-grown transparent conducting TNO films. In particular, the Ti₂O₃-based target is practically advantageous, because it offers a wide range of optimal Po₂ values at which ρ values of the order of 10^− 4 Ω cm are achievable.     

Utilization of Chemically Synthesized Fine Powders of SiC/Al2O3 Composites for Sintering

Fine powders of (Al₂O₃)_100–x(SiC)_x (0 ≤ x ≤ 50) composites were prepared by chemical route (named as pyrophoric technique) to achieve a uniform mixture of SiC in an alumina matrix. The chemically synthesized fine SiC/Al₂O₃ composite powders were sintered to form composites at 1450°C which is well below the sintering temperature of SiC. Sintering was performed in an argon atmosphere. Highly dense SiC/Al₂O₃ microstructures were achieved. An improvement in bulk density and hardness has been achieved for SiC/Al₂O₃ composites with 20 wt% of SiC. Hexagonal-shaped grains have been obtained in (Al₂O₃)₅₀(SiC)₅₀ composite with well-connected grain boundaries. The peak position of alumina in SiC/Al₂O₃ composites shifts toward lower wavenumbers in Fourier transform infrared spectroscopy and higher wavenumbers in Raman spectroscopy due to the incorporation of SiC in the composites. The optical band gap decreases with the addition of SiC and the composite behaves more like a semiconductor rather than an insulator. These properties make SiC/Al₂O₃ composites attractive for various industrial applications.     

Fabrication of nanostructure Al2O3/ZrO2 (Y2O3) eutectic by combustion synthesis melt-casting under ultra-high gravity

A novel method for preparing Al₂O₃/ZrO₂ (Y₂O₃) eutectic was developed by combining combustion synthesis with melt-casting under ultra-high gravity (CSMC-UHG). The application of UHG = 800 g resulted in a high relative density of 99.8%, and an orientation-growth along the UHG direction. The microstructure was composed of aligned growth regimes containing a triangular dispersion of orderly ZrO₂ rods in Al₂O₃ matrix with a spacing of 300 nm. The eutectic had a high fracture toughness up to 17.9 MPa·m^1/2, which was mainly attributed to the nanostructure and the elastic bridge effects of the aligned ZrO₂ rods.     

Structure and property changes of ZrO2/Al2O3/ZrO2 laminate induced by low-temperature NH3 annealing applicable to metal-insulator-metal capacitor

Phase transformation and morphology evolution of ZrO₂/Al₂O₃/ZrO₂ laminate induced by the post-deposition NH₃ annealing at 480 °C were studied and the effect on the electrical property of the TiN/ZrO₂/Al₂O₃/ZrO₂/TiN capacitor module was evaluated in dynamic random access memory cell. Experimental results indicated N could indeed be incorporated into the dielectric laminate by the low-temperature NH₃ annealing, resulting in tetragonal-to-cubic phase transformation and small crystallites in the ZrO₂ layers. The C residue and Cl impurity in the ZrO₂/Al₂O₃/ZrO₂ laminate, which derived from the dielectric film formation and capping TiN layer deposition, respectively, could also be reduced by the nitridation process. As a result of the better surface morphology and less impurity content, lower dielectric leakage current and longer reliability lifetime were observed for the nitrided ZrO₂/Al₂O₃/ZrO₂ capacitor. This study demonstrates the low-temperature NH₃ annealing on ZrO₂/Al₂O₃/ZrO₂ dielectric can be applicable to the metal-insulator-metal capacitor structure with nitride-based electrode, which brings advantages over mass production-wise property improvements and extends the practical applicability of the ZrO₂/Al₂O₃/ZrO₂ dielectric.