Composites with a functional gradient in the systems Si3N4−Al2O3−Y2O3−TiC

Composites with a functional gradient in the system Si₃N₄−Al₂O₃−Y₂O₃−TiC were made by laminating and sintering ceramic films obtained by tape casting. The films had high contents of TiC and Al₂O₃ and were of different thicknesses. Materials with a high density and high fracture toughness (K_1c≈9.3 MPa·m^1/2) were obtained. Warsaw Polytechnic Institute. Translated from Poroshkovaya Metallurgiya, Nos. 7–8(408), pp. 1–7, July–August, 1999.     

Nitrogen Ceramics: Liquid Phase Sintering

Abstract

The role of a minor silicate eutectic liquid phase as a transport medium in sintering hot–pressed silicon nitride (β Si₃N₄) ceramics was identified in the 1970s. A similar mechanism is applicable to hot–pressed Si–Al–O–N ceramic alloys which offer an advantage in control of the final liquid volume and hence in superior high temperature mechanical properties. By increasing the liquid volume it is possible to densify ceramic alloys without application of pressure at the sintering temperature and hence to fabricate components of complex shape. The Lucas Syalon ceramics typify the new range of pressureless–sintered ceramics based on the β Si₃N₄ structure. They are fabricated from the ultrafine compound powders α Si₃N₄, SiO₂, Al₂O₃, Y₂O₃, and a polytypoid phase (a substitute for A1N). The ceramics consist of submicrometre solid solution crystals of general composition Si_3?xAl_xO_xN_4?x(x < 1) within a minor matrix phase which may be either a glassy Y–Si–Al oxynitride or be crystallized to form yttrogarnet. Analysis of matrix glass compositions shows them to be residues of liquids near to a ternary eutectic in the Y₂O₃–SiO₂–Al₂O₃ system which is well below the sintering temperature of ～ 1800°C. Sintering models, based on particle rearrangement due to dissolution of the major α Si₃N₄ component in the eutectic liquid and its reprecipitation as a β Si₃N₄ solid solution, are discussed. Properties and current applications of Syalon ceramics are surveyed briefly. PM/0266     

Al2O3/TiCN-0.2% Y2O3 Composite Prepared by HP and Its Cutting Performance

Al₂O₃/TiCN-0.2% Y₂O₃ composites were fabricated by hot pressing sintering. The effect on mechanical property and microstructure of the sample composition and HP temperate was investigated. The results of Al₂O₃/TiCN-0.2% Y₂O₃ were satisfied. The bending strength, fracture toughness, Vickers hardness was respectively 1015 MPa, 6.89 MPa·m^1/2 20.82 MPa at 1650 °C for 20 min. Good wear resistance was found for the kind of ceramic material when used as cutting tools in the machining of the hardened carbon steel. By the compared experiment for the cutting performances, it could be seen that the performance of this composite material was better than that of the ceramic tool material YT15 for continuously cutting quenched steel. This kind of composite tool material is suitable for continuously cutting quenched steel No.45, especially intermittently cutting quenched steel.     

Phase composition and mechanical properties of a zirconium dioxide based ceramic obtained by high temperature sintering in a vacuum

Changes in phase composition and mechanical properties of sintered ZrO₂ + 3% (mole) Y₂O₃ specimens were examined after annealing in air and after various mechanical operations. Compacted ceramic specimens containing T and T′ phase were obtained by sintering in a vacuum at 1800°C. Ceramics containing T and T′ phases have excellent toughness (K_1c up to 15 MPa·m^1/2), bend strength up to 800 MPa and HV hardness up to 13 GPa.     

Effects of Behaviors of Aluminum Nitride Ceramics with Rare Earth Oxide Additives

The effects of three types of additives, Y₂O₃, Nd₂O₃ and Er₂O₃ on the behaviors of AlN ceramics were investigated. The experimental results showed that the sintering temperature could be decreased and the mechanical behavior could be improved by adding rare earth oxide in AlN ceramics. The highest strength and fracture toughness of AlN ceramics with 2% Y₂O₃ addition were 311 MPa and 3.5 MPa·m^1/2, respectively. Second phase of AlN ceramics with Y₂O₃ addition was identified as Y₃Al₅O₁₂ formed by the reaction with Al₂O₃, meanwhile that with Nd₂O₃ was identified as NdAlO₃. The fracture behavior of AlN ceramics with Y₂O₃ and Nd₂O₃ were a mixed mode of transgranular fracture and intergranular fracture. Because of the high evaporation rates of Er₂O₃ (1.2 × 10⁻⁵ g·cm⁻²), no aluminium erbium oxide was found in the AlN ceramics doped with Er₂O₃. So the dielectric loss tanger(tanδ) and thermal conductivity of AlN ceramics doped with Er₂O₃ were best.     

Physico-Chemical Investigation of Component Interactions of the Si ― Al ― O ― N ― Ti System in the Region Si3N4 ― AlN ― Al2O3 ― SiO2 ― TiN ― TiO2. Part 1. Subsystems Si3N4 ― Al2O3, Si3N4 ― TiN,and Al2O3 ― TiN

Using the methods of differential thermal and x-ray diffraction analysis an investigation was made of component reactions in the Si Al O N Ti system, particularly between the compounds Si ₃N₄ Al₂O₃, Si₃N₄ TiN, and Al₂O TiN under conditions approximating those used in the hot pressing of composites. It was established that in the reaction of Si₃N₄ with Al₂O₃, -sialon, SiO₂, AlN, and the intermediate reaction products (mullite and X-phase) are formed. In the reaction of Si₃N₄ with TiN, as a result of the decomposition of Si₃N₄ at 1650-1900°C titanium disilicide is produced, which forms eutectics with free silicon and residual TiN at 1320 and 1280°C, respectively. The reaction of Al₂O₃ with TiN similarly leads to the formation of a eutectic between Al₂O₃ and spinel at 1850°C. The presence of eutectic liquids in the specimens after sintering promotes densification of the material, and improves certain of its mechanical properties.     

Nanocrystalline Powders Based on ZrO2 for Biomedical Applications and Power Engineering

An 80 mass% ZrO₂ ― 20 mass% Al₂O₃ powder was produced using a complex method which integrates sol-gel technology and hydrothermal synthesis. The specific surface areas of the powder varied from 39 to 5.3 m²/g depending on the thermal treatment conditions. Metastable F-ZrO₂ formed after powder annealing at 400°C. The phase transformation F-ZrO₂ → T-ZrO₂ (traces of M-ZrO₂) occurred under powder thermal treatment from 700 to 1000°C. Only Θ-Al₂O₃ was detected under experimental conditions. The powder was characterized by sintering activity. Operating the processes under powder thermal treatment in the ZrO₂ ― Y₂O₃ ― CeO₂ ― Al₂O₃ system will allow one to produce a variety of ceramic microstructures from fine-grained to “self-reinforced.” These powders can be used in manufacturing surgical cutting tools as well as in ceramic passive bioimplants and solid electrolytes for fuel elements.     

High-Temperature Corrosion of AlN-Based Composite Ceramic in Air and in Combustion Products of Commercial Fuel. Part 1. Corrosion of Ceramic Composites in the AlN – SiC System in Air and in Combustion Products of Kerosene and Diesel Fuel

We have established that scale formed upon oxidation of ceramic composites in the AlN – SiC system in air at temperatures up to 1550°C contains mullite 3Al₂O₃·2SiO₂ as the major phase of the outer layer, which provides its high protective properties. The inner layer of the scale contains β-SiO₂, α-Al₂O₃, and a fairly small amount of the oxynitride Al₁₀N₈O₂. In dry air, even at 1500°C with a long holding time (50 h), material of 50 mass% AlN – 50 mass% SiC retains extremely high corrosion resistance. We have shown that upon prolonged (up to 240 h) oxidation of the indicated ceramic in the combustion atmosphere of S- and Na-containing fuels (kerosene and marine diesel fuel) at 1200-1300°C, along with mullite in the scale we see formation (due to reaction of β-cristobalite with Al₂O₃ and gaseous Na₂O and NaOH) of low-viscosity silicate glass Na₂SiO₃ and NaAlSiO₄. Together with impurity Fe₂O₃ and gaseous Na₂SO₄, it partially destroys the protective mullite layer and leads to degradation of the protective properties of the scale.     

A comparison research on replacements of Ba2+ by Lu3+ and Ba2+-Si4+ by Lu3+-Al3+ in BaSi2O2N2:Eu phosphors

As a cyan-emitting oxonitridosilicate phosphor,BaSi₂O₂N₂:Eu²⁺can be used as a competent cyan compensator to improve the color rendering index of white light-emitting diodes(WLEDs).However,low luminescence efficiency and poor thermal stability of this type of phosphor seriously suppress its actual application in full-spectrum lighting.The replacements of Ba²⁺by Lu³⁺and Ba²⁺-Si⁴⁺by Lu³⁺-Al³⁺can greatly increase the luminescence intensity and improve the thermal stability at the same time.With Lu³⁺doping,the internal quantum efficiencyηIQE Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺is 24.08%higher than that of Ba_0.97Si₂O₂N₂:0.03 Eu²⁺.After Al³⁺co-doping,theηIQE is further increased by 10.31%compared to Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺.When the temperature rises to 473 K,the luminescence intensity of Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺maintains 62.32%of that at room temperature,which increases by 17.35%in relative to the Ba_0.97Si₂O₂N₂:0.03 Eu²⁺,while the luminescence intensity of Ba_0.925Si_1.97O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺,0.03 Al³⁺keeps 73.87%of the initial value,which increases by18.52%compared to Ba_0.925Si₂O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺.The mechanisms for luminescence and thermal stability improvement are proposed.The Ba_0.925Si_1.97O₂N₂:0.03 Eu²⁺,0.045 Lu³⁺,0.03 Al³⁺cyan phosphor,Y3 Al5 O12:Ce3+yellow phosphor and CaAlSiN3:Eu²⁺red phosphor are mixed thoroughly and coated on a blue LED(450 nm)to assemble a WLED.The WLED demonstrates a color rendering index(Ra)of 97.1 at150 mA,and the R1-R15 values are all above 90.The results indicate that as an effective cyan compensator in WLED,the BaSi₂O₂N₂:Eu²⁺,Lu³⁺,Al³⁺phosphor has great application prospect in the field of full-spectrum lighting.     

Electric-discharge sintering of TiN-AlN nanocomposites

The structurization and properties of TiN-AlN and TiN-AlN-Y₂O₃ nanocomposites consolidated by electric-discharge sintering are examined. TiN-AlN composites with a relative density of about 98 to 99% are produced. Their structure is not homogenous and consists of TiN and AlN grains of about 200 nm in size. There are also large spherical grains of titanium nitride of 2 to 10 µm. This effect is probably caused by microdischarges between particles of the conducting phase and subsequent meltback of the interacting surfaces. The effect of yttrium oxide additives on the material structure and properties is investigated. It is shown that TiN-AlN composites consolidated by electric-discharge sintering have high hardness (HV ～ 25 GPa) and fracture toughness (K_1c ～ 6 MPa · m^1/2).     

Evaluation of Microstructure and Mechanical Properties of Nano-Y2O3-Dispersed Ferritic Alloy Synthesized by Mechanical Alloying and Consolidated by High-Pressure Sintering

In this study, an attempt has been made to synthesize 1.0 wt pct nano-Y₂O₃-dispersed ferritic alloys with nominal compositions: 83.0 Fe-13.5 Cr-2.0 Al-0.5 Ti (alloy A), 79.0 Fe-17.5 Cr-2.0 Al-0.5 Ti (alloy B), 75.0 Fe-21.5 Cr-2.0 Al-0.5 Ti (alloy C), and 71.0 Fe-25.5 Cr-2.0 Al-0.5 Ti (alloy D) steels (all in wt pct) by solid-state mechanical alloying route and consolidation the milled powder by high-pressure sintering at 873 K, 1073 K, and 1273 K (600°C, 800°C, and 1000°C) using 8 GPa uniaxial pressure for 3 minutes. Subsequently, an extensive effort has been undertaken to characterize the microstructural and phase evolution by X-ray diffraction, scanning and transmission electron microscopy, and energy dispersive spectroscopy. Mechanical properties including hardness, compressive strength, Young’s modulus, and fracture toughness were determined using micro/nano-indentation unit and universal testing machine. The present ferritic alloys record extraordinary levels of compressive strength (from 1150 to 2550 MPa), Young’s modulus (from 200 to 240 GPa), indentation fracture toughness (from 3.6 to 15.4 MPa√m), and hardness (from13.5 to 18.5 GPa) and measure up to 1.5 through 2 times greater strength but with a lower density (~7.4 Mg/m³) than other oxide dispersion-strengthened ferritic steels (<1200 MPa) or tungsten-based alloys (<2200 MPa). Besides superior mechanical strength, the novelty of these alloys lies in the unique microstructure comprising uniform distribution of either nanometric (~10 nm) oxide (Y₂Ti₂O₇/Y₂TiO₅ or un-reacted Y₂O₃) or intermetallic (Fe₁₁TiY and Al_9.22Cr_2.78Y) particles' ferritic matrix useful for grain boundary pinning and creep resistance.     

Creep and microstructure of electrical discharge machinable Si3N4 composites

The compression creep behaviour of silicon nitride sintered with the aid of Y₂O₃ and Al₂O₃ and containing TiN particles was studied between 1260 and 1340°C at stresses ranging from 100 to 300 MPa. The volume fraction Φ of TiN particles was varied from 0 to about 40 vol % and two particle sizes: 1 μm and 2.5 μm were studied. The dominant creep mechanism of the matrix was viscous creep (n = 1) up to 1340°C and 200 MPa. The effect of the TiN addition on the creep behaviour was marked by a decrease of the creep strength with increasing volume fraction and decreasing particle size of TiN. In the same way, the steady state creep rate increased as the ratio Φ/d. In the microstructure, cavities and microcracks along particle/matrix interfaces show that a cavitational mechanism develop from the particles in the composite.     

Structure and Certain Properties of Hot-Pressed Boron Carbide-Based Ceramic with Calcium-Silicon Additive

The influence which the composition of powder mixtures, the treatment conditions which the mixtures are subjected to, and the conditions under which the hot-pressed composite materials B₄C – (5-10 mass%) calcium-silicon are fabricated exert on the structure, nature of failure, and mechanical properties of these materials is investigated. Optimum properties are possessed by material containing 10 mass% of addition. It is shown that the structure, morphology, and dispersivity, as well as the nature of the distribution of the components that are added to the composite material (secondary phase) vary as the temperature of hot pressing changes. Maximal mechanical characteristics of the composite material (σ_bend = 560 MPa, K _1c = 4.7 MPa·m^1/2, HV = 37 GPa) are attained at hot-pressing temperatures in the range 2000-2100°C.     

thermodynamics of nitrogen in BaO-TiOx melts

Using a gas-slag-metal equilibration technique, nitrogen contents in BaO-TiO^ slags and nitrogen and titanium contents in liquid Cu were measured at 1823, 1873, and 1923 K under controlled partial pressures of oxygen(@#@ P_{O 2} = 10^-11.5 ≈ 10^-13.7 atm) and nitrogen(@#@ P_{N 2} = 0.9 atm). The nitride capacity, C_(N) [=(mass pct N) · PO₂/3/4, (mass pct Ti³⁺)/(mass pct Ti⁴⁺) ratio, and solubility of TiN in BaO-TiO₂-TiO_1.5 slags were obtained as a function of slag com-position(@#@ X_BaO = 0.20 = 0.43) and temperature. Activity coefficients of TiN were estimated, using the values for activity coefficients of Ti in liquid Cu which were calculated from the results of a TiN saturation experiment. Free energy of dissolution of nitrogen into liquid Cu was derived as °GG_N ^o = 32,400 + 46.17 ± 1400 (J/g · atom).     

Low-Temperature Densification Sintering and Properties of Monoclinic-SrAl2Si2O8 Ceramics

The dense monoclinic-SrAl₂Si₂O₈ ceramics have been prepared by a two-step sintering process at a sintering temperature of 1173 K (900 °C). Firstly, the pre-sintered monoclinic-SrAl₂Si₂O₈ powders containing small SiO₂·Al₂O₃ crystal phases were obtained by continuously sintering a powder mixture of SrCO₃ and kaolin at 1223 K (950 °C) for 6 hours and 1673 K (1400 °C) for 4 hours, respectively. Subsequently, by the combination of the pre-sintered ceramic powders with the composite flux agents, which are composed of a SrO·3B₂O₃ flux agent and α-Al₂O₃, the low-temperature densification sintering of the monoclinic-SrAl₂Si₂O₈ ceramics was accomplished at 1173 K (900 °C). The low-temperature sintering behavior and microstructure evolvement of the monoclinic-SrAl₂Si₂O₈ ceramics have been investigated in terms of Al₂O₃ in addition to the composite flux agents. It shows that due to the low-meting characteristics, the SrO·3B₂O₃ flux agent can urge the dense microstructure formation of the monoclinic-SrAl₂Si₂O₈ ceramics and the re-crystallization of the grains via a liquid-phase sintering. The introduction of α-Al₂O₃ to the SrO·3B₂O₃ flux agent can apparently lead to more dense microstructures for the monoclinic-SrAl₂Si₂O₈ ceramics but also cause the re-precipitation of SiO₂·Al₂O₃ compounds because of an excessive Al₂O₃ content in the SrO·3B₂O₃ flux agent.     

Catalytic combustion of toluene on Pt/Al2O3 and Pd/Al2O3 catalysts with CeO2,CeO2-Y2O3 and La2O3 as coatings

CeO₂,La₂O₃,and CeO₂-Y₂O₃ oxides were coated on the surface of spherical granular AI₂O₃(3-5 mm)through impregnation method,and proved as better supports of Pd and Pt catalysts.The influences of rare earth metal doping on the adsorption rates of Pd and Pt ions,as well as the catalytic performance,were investigated.Results show that the H₂PtCl₆·6H₂O adsorption rates of the Al     

Effects of Y2O3 and transition-metal nitrates on phase,microstructures and PL properties of N-containing Ce2Si2.5Al0.5O3.5N3.5 melilite

N-containing Ce₂Si_2.5Al_0.5O_3.5N_3.5 (CeSiAlON) melilite was synthesized at 1550 and 1600 °C for 5 h from CeO₂, Si, Al, and Al₂O₃ in nitrogen by using Y₂O₃ and transition-metal nitrates (Co(NO₃)₂∙6H₂O and Ni(NO₃)₂∙6H₂O) as additives. The effects of Y₂O₃ and transition-metal nitrates on the phase, microstructures and photoluminescence properties of CeSiAlON melilite were studied. The incorporation of Y₂O₃ can promote the reaction of raw materials to a low degree, and results in a unit cell shrinkage of CeSiAlON due to the smaller radius of Y atom than that of Ce atom. The transition-metal nitrates can accelerate the reaction clearly and facilitate the formation of CeSiAlON fibers. The photoluminescence (PL) properties of CeSiAlON melilite presents a board violet emission band because of the 5d-4f transitions of Ce³⁺, and the additives can enhance the PL emission intensities of specimen significantly.     

Vacuum Carbothermic Production of Aluminum and Al-Si Alloys From Kaolin Clay: A Thermodynamic Study

Examination of the thermodynamic constraints for the carbothermic reduction of iron-free kaolinite, Al₂Si₂O₅(OH)₄, or of its calcination product mullite, Al₆Si₂O₁₃, either at atmospheric pressure or under vacuum of 10^?3 to 10^?5 bar, indicates the conditions required at equilibrium to produce either elementary Al or Al-Si alloys. At atmospheric pressure, a very high temperature of 3200 K would be required to obtain from Al₂Si₂O₅(OH)₄ + 9C an Al-Si alloy with 39 wt.% Si. At 10^?4 bar and 1800 K, the predicted Al-Si alloy would contain 2.4 wt.% Si. From mullite, the reaction of Al₆Si₂O₁₃ + 13C at 10^?4 bar and either 1800 K or 2200 K should produce an Al-Si alloy with 0.65 or 24 wt.% Si. The CO produced by the carbothermic reactions may be by water-gas shift converted to syngas, and further either to methanol or by a Fischer–Tropsch reaction to liquid fuels or chemical intermediates. Concentrated solar energy may be used to supply the required process heat of these high-temperature reactions.     

Preliminary characterization of the room temperature fracture behavior of monolithic and composite FeAl3-Fe2Al5

A monolithic FeAl₃-Fe₂Al₅ alloy exhibited a predominantly transgranular cleavage fracture mode and a fracture toughness value of about 1.1 MPa m^1/2 at room temperature. It is suggested that the low fracture toughness value for the alloy is a result of its complex crystal structure (intrinsic). The incorporation of 10 vol % Al₂O₃ or Y₂O₃ particles into the matrix increased the fracture toughness to 3.4 to 3.8 MPa m^1/2. The increase in fracture toughness is attributed to crack deflection by the particles. As a result, due to their excellent high temperature creep strength and oxidation resistance coupled with low material costs, intermetallics based upon FeAl₂, Fe₂Al₅ and FeAl₃ may be excellent candidates for high temperature applications if their ductility and toughness at room temperature can be improved.     

Cathodic reduction process of Al–Cu–Y alloy in fluoride-oxide eutectic system via molten salt electrolysis

Al-Cu-Y alloys were prepared by molten salt electrolysis in fluoride-oxide system composed of electrolyte(Na_3 AlF_6-AlF_3-LiF-MgF_2) and oxide(Al_2 O_3-CuO-Y_2 O_3). Cathodic reduction process of Al_2 O_3,CuO and Y_2 O_3 were analyzed by cyclic voltammetry and chronoamperometry. Components and phase composition of alloy samples prepared by potentiostatic electrolysis were characterized by scanning electron microscopy and energy dispersive spectroscopy. The results show that the Al-Cu-Y alloy can be prepared in the AIF_3-NaF-5 wt%LiF-5 wt%MgF2(NaF/AlF_3 = 2.2, molecular ratio) eutectic system with mixed oxide(Al_2 O_3-CuO-Y_2 O_3) through 2 h at the conditions of a temperature of 1208 K, cell voltage3.0 V, cathode current density 0.7 A/cm~2. Al(Ⅲ) and Cu(Ⅱ) ions can be reduced to zero valence Al(0) and Cu(0) directly on carbonaceous electrode surface by instantaneous nucleation, respectively, the reduction process is controlled by diffusion. The reduction potential of Y(Ⅲ) ions is close to the active ions of fluoride melts, but strengthened phase AI3 Y can be formed through electrochemical reduction and alloyed process with active Al(Ⅲ) and Cu(Ⅱ) ions, meanwhile, the Al_2 Cu and Al_3 Y phases are distributed at the grain boundary of Al matrix.