Effect of bimodal microstructure on high-temperature properties of nano-reinforced Al2O3–MgO–C refractories

The beneficial effects of adding nanostructured expandable graphite (EG) hybridized yttrium aluminium garnet (EG\YAG) powder as a composite reinforcement in improving the oxidation resistance, hot-strength, and microstructure development in Al₂O₃–MgO–C refractories were studied. The refractory components reinforced with EG\YAG exhibited more than 60% of oxidation resistance enhancement and as high as 200% increase in hot-strength performance over the standard refractories, formulated without EG\YAG. Correlating the damage parameter (D_E) calculations based on ultrasonic measurements with residual strength data (R_c, R_b) showed that there was a progressive increase in R_c and R_b values with consistent reduction in the oxidative damage of EG\YAG reinforced refractories. Analysis indicated that these beneficial features were majorly ascribed to the in-situ development of bimodal microstructure with EG\YAG sintered framework throughout the refractory interior in these new class of reinforced systems. Additionally, the mechanism of toughening and implications of these results to materials design are discussed.     

Sintering,microstructure and mechanical properties of Al2O3–Y2O3–ZrO2 (AYZ) eutectic composition ceramic microcomposites

We report on how the mechanical properties of sintered ceramics (i.e., a random mixture of equiaxed grains) with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition compare with those of rapidly or directionally solidified Al₂O₃–Y₂O₃–ZrO₂ eutectic melts. Ceramic microcomposites with the Al₂O₃–Y₂O₃–ZrO₂ eutectic composition were fabricated by sintering in air at 1400–1500 °C, or hot pressing at 1300–1400 °C. Fully dense, three phase composites of Al₂O₃, Y₂O₃-stabilized ZrO₂ and YAG with grain sizes ranging from 0.4 to 0.8 μm were obtained. The grain size of the three phases was controlled by the size of the initial powders. Annealing at 1500 °C for 96 h resulted in grain sizes of 0.5–1.8 μm. The finest scale microcomposite had a maximum hardness of 19 GPa and a four-point bend strength of 282 MPa. The fracture toughness, as determined by Vickers indentation and indented four-point bending methods, ranged from 2.3 to 4.7 MPa m^1/2. Although strengths and fracture toughnesses are lower than some directionally or rapidly solidified eutectic composites, the intergranular fracture patterns in the sintered ceramic suggest that ceramic microcomposites have the potential to be tailored to yield stronger, tougher composites that may be comparable with melt solidified eutectic composites.     

Effect of different corundum sources on microstructure and properties of Al2O3–Cr2O3 refractories

Al₂O₃–Cr₂O₃ refractories are completely substitutional solid solutions and exhibit better corrosion and abrasion resistance. To enable the comprehensive utilization of it, the microstructure and properties of Al₂O₃–Cr₂O₃ samples with different corundum sources were investigated in this study. The starting sources of corundum sources included sintered tabular corundum, fused white corundum, or brown corundum with minor impurities of β-Al₂O₃ and TiO₂. The results of mechanical test showed that the introduction of white corundum deteriorates the physical structure, while brown corundum acts in an opposite manner. The optimum bonding strength of the Al₂O₃–Cr₂O₃ brick was reached by combining white and brown corundum, whereby rapid neck growth occurred via surface diffusion during solid-phase sintering.     

Thermodynamic calculation and microstructure characterization of spinel formation in MgO–Al2O3–C refractories

In this paper, by simulating the gas phase conditions inside the MgO–Al₂O₃–C refractories during continuous casting process and combining with thermodynamic analysis, as well as SEM analysis, the gas-gas and gas-solid formation of MA spinel were clarified in carbon containing refractories. Thermodynamic calculations showed that gas partial pressure of CO, O₂ and Mg could meet the formation and stable existence conditions of MA spinel in MgO–Al₂O₃–C refractories under service environment, and nitrogen could not affect the formation of MA spinel at 1550 °C in the thermodynamic condition. The formation processes of MA spinel were analyzed experimentally under embedding carbon atmosphere. The carbon-coated alumina powders in MgO–Al₂O₃–C refractories prevented the direct contact between magnesia and alumina. Mg gas was formed by carbon thermal reaction, then reacted with alumina (gas-solid) and gas containing aluminum (gas-gas) to generate MA spinel. Through gas-gas or gas-solid reaction, the formation of MA spinel was effectively controlled. By means of SEM analysis, a two-layer structure with dense outer spinel layer and loose inner layer was formed in MgO–Al₂O₃–C refractories.     

Multicomponent synergistically affected mechanical properties,microstructure, and oxidation resistance of Zr–Al(Si)–C based composites

Herein, in-situ Zr₃[Al(Si)]₄C₆-based composites with 10–40 vol% ZrB₂–SiC (2-to-1 molar ratio) were prepared by hot-pressing sintering at 1850 °C. The simultaneously incorporated ZrB₂–SiC constitute multicomponent reinforcements and has a synergistic effect on the matrix, which improves the sinterability, mechanical properties, and oxidation resistance of materials. It is found that both of the toughness and strength increase first and then decrease with the increasing content of ZrB₂–SiC, while the hardness increases near linearly. Zr₃[Al(Si)]₄C₆–ZrB₂–SiC shows high strength (623 MPa), toughness (7.59 MPa m^1/2), and hardness (18.6 GPa), which can be ascribed to the synergistic mechanisms of the binary ZrB₂–SiC including fine-grained strengthening, particle reinforcement, intragranular microstructure, grain's pull-out and crack bridging, etc. In addition, the oxidation kinetics of as-prepared materials follow the parabolic law, and the composite shows a low oxidation rate of 0.87 × 10⁻⁵ kg² m⁻⁴ s⁻¹ when oxidized at 1400 °C.     

Effect of Al(H2PO4)3/Zn/B4C doped resin on properties and microstructure of unfired Al2O3–C slide plate materials

The unfired Al₂O₃–C slide plates have the advantages of energy saving, environment friendly, efficiency and relatively low-cost. However, the decomposition and oxidation of the phenol-formaldehyde (PF) resin at elevated temperatures deteriorate the properties and decrease service life of the unfired slide plates. In order to improve the property of resin, the doped PF resin is prepared by incorporating Al(H₂PO₄)₃, Zn and B₄C powders. The effects of the doped resin on medium-high temperature properties and microstructure of the unfired slide plate materials have been investigated. The results show that Zn and B₄C doped resin contributes to notable increasing the density and strength properties at medium temperature, because Zn and B₄C easily oxide and thus protect resin from oxidation, leading to form a dense structure. Zn and B₄C doped resin can significantly improve hot modulus of rupture of the materials at 1400 °C, which is due to Zn and B₄C react with oxidative gases leading to increase in concentration of C(g), CO and N₂, Al and Si would react with C(g), CO(g) and N₂(g) to form AlN and SiC whiskers creating strengthening effect. Specimens with Zn and B₄C doped resin addition have good oxidation resistance at 1500 °C, because Zn and B₄C in the surface of the material react with O₂ to form ZnAl₂O₄ or mullite containing dense glass film, which would retard O₂ diffusion into the inner of the specimens.     

Microstructure and mechanical properties of Al2O3–Ti(C,N)–cBN composites prepared by a novel hot-forging process

Al₂O₃–cBN has received considerable attention in the field of ceramic cutting tools due to its high hardness, high wear resistance, and low cost, but poor interfacial bonding affects the performance of the composite. In this study, a novel hot-forging process was used to prepare high-performance Al₂O₃–cBN composites using Ti(C,N) as a binder. The evolution of the morphology, phase, and microstructure of the hot-forged Al₂O₃–Ti(C,N)–cBN composites was determined, and the mechanical properties were measured. The relative density of the composites increases significantly after hot forging, and the deformation of the composites increases with the hot-forging temperature. The highest performing Al₂O₃–Ti(C,N)–cBN composite was prepared by hot forging at 1600°C and has a hardness of 20 GPa, a bending strength of 647 MPa and a fracture toughness of 5.37 MPa m^1/2, which are superior to those of a directly hot-pressed sintered composite. However, at hot-forging temperatures higher than 1700°C, Al₅O₆N and TiB₂ are formed in the composite. In the composite hot forged at 1800°C, serrated grain boundaries promote the strength and toughness of the composite to 877 MPa and 6.76 MPa m^1/2, respectively. Therefore, the novel hot-forging process is expected to enhance material properties.     

Tribological properties of NiCr–ZrO2(Y2O3)–SrSO4 composites at elevated temperatures

The effect of SrSO₄ content on the tribological properties of NiCr–30wt%ZrO₂(Y₂O₃) (NC30Z) cermet was evaluated over a wide temperature range from room temperature to 1000 °C. The results indicated that the inclusion of SrSO₄ effectively improved the friction coefficients and wear rates of NC30Z cermet above 400 °C. NC30Z–5SrSO₄ composite against alumina ball exhibited satisfactory tribological performance, which was attributed to synergistic lubrication of pseudocubic-SrZrO₃ and NiCr₂O₄ between 400 °C and 800 °C and cubic-SrZrO₃, NiCr₂O₄, NiO and Cr₂O₃ at 1000 °C.     

Fabrication and microstructure of Al2O3–ZrO2(3Y)–SiC nanocomposites

Al₂O₃–ZrO₂(3Y)–SiC composite powder was prepared by the heterogeneous precipitation method. Calcinating temperature of the powder was important to obtain dense sintered body. The nanocomposites were got by hot-pressing, and addition of ZrO₂ did not raise the sintering temperature. Some Al₂O₃ grain shape was elongated, and Al₂O₃ grain size was about μm. Nano SiC particles were observed uniformly distributing throughout the composites, and most of them were located within the matrix grains. Because SiC particles located within ZrO₂ grains influenced the phase transformation of ZrO₂, the sintering of nanocomposites, which controlled grain size and transformable ZrO₂ amount, become important to get high performance. The strength of 80 wt% Al₂O₃–15 wt% ZrO₂–5 wt% SiC nanocomposites was 555 MPa, and toughness was 3·8 MPa m^1/2, which were higher than those of monolithic Al₂O₃ ceramics. ©     

Improved thermal shock resistance of low-carbon Al2O3–C refractories fabricated with C/MgAl2O4 composite powders

The addition of C/MgAl₂O₄ composite powders can improve the thermal shock resistance of low-carbon Al₂O₃–C refractories attribute to the formation of microcracks in the agglomerated structure, thus consuming more thermal stress and strain energy. Moreover, C/MgAl₂O₄ composite powders additive promote the formation of short fibrous ceramic phases in the refractories, which suggest a bridging role in the interior of the refractories and increase its toughness. Furthermore, the C/MgAl₂O₄ composite powders also result in a remarkable enhancement of the slag corrosion resistance in the refractories.     

Designing low-carbon MgO–Al2O3–La2O3–C refractories with balanced performance for ladle furnaces

In order to achieve high-quality and stable production of special steel, the performance of low-carbon MgO-C refractories needs to be further optimized. For this purpose, low-carbon MgO–Al₂O₃–La₂O₃–C refractories with enhanced thermal shock resistance and slag resistance were designed and successfully prepared by introducing Al₂O₃ as a reinforcer and La₂O₃ as a modifier. The results showed that the refractory samples with additives show better overall performance than those without additives. When 10 wt% of Al₂O₃ and La₂O₃ were added, the oxidation resistance, thermal shock resistance and slag resistance of the refractory samples coked at 1400 °C are increased by 13.57%, 17.75% and 43.09%, respectively. The analysis found that this can be mainly attributed to the formation of MgAl₂O₄, Mg₂SiO₄, and 2CaO·4La₂O₃·6SiO₂ and the consequent volume expansion effect and intergranular phase enhancement effect. Therefore, a low-cost and enforceable reinforcement strategy for low-carbon MgO-C refractories is proposed, which is expected to be applied in steelmaking.     

Mechanical properties of (TixW1−x)C–Co cermet prepared by carbothermal reduction of high energy ball milled TiO2–WO3–C

A series of solid–solution carbides, (Ti_xW_1−x)C (x=0.9, 0.8, 0.7, 0.6), was prepared by the high-energy milling of TiO₂–WO₃–C mixtures via subsequent carbothermal reduction. With high-energy milling, only the size reduction of the constituent powders was apparent without any chemical reaction. The milled mixture powder was transformed to a single–phase (Ti_xW_1−x)C solid solution by heat treatment in a vacuum at 1200 °C. (Ti_xW_1−x)C–Co cermets were consolidated by isothermal sintering at 1300, 1400, and 1500 °C. The powders were fully densified by liquid-phase sintering at 1500 °C because the Co melted at 1430 °C. The mechanical properties of the (Ti_xW_1−x)C–Co cermet (H_v: ~24 GPa) were significantly better than those of the conventional WC–Co (H_v: ~13 GPa) or TiC–Co cermets (H_v: ~16 GPa). The use of a solid–solution carbide instead of conventional WC almost doubled its hardness values without a loss of toughness. It is indicated that the improved hardness of the (Ti_xW_1−x)C–Co cermet originates from the high hardness of (Ti_xW_1−x)C, and the solid–solution carbide would be a valuable substitute for conventional carbide cermets.     

Effect of CuO on self-lubricating properties of ZrO2(Y2O3)–Mo composites at high temperatures

In this paper, ZrO₂ matrix high-temperature self-lubricating composites with addition of CuO as lubricant were prepared using a hot-pressing method by tailoring the content of CuO. The wear and friction behaviour of the composites were investigated from 700 °C to 1000 °C. The composites sliding against an Al₂O₃ ceramic ball exhibited excellent self-lubricating and anti-wear properties at high temperatures. The low friction and wear mechanisms were investigated in detail.     

SiO2–Al2O3–CaO glass-ceramics: Effects of CaF2 on crystallization,microstructure and properties

The effects of fluorine content on the nucleation and crystallization behavior of SiO₂–Al₂O₃–CaO glass ceramics system have been investigated. The crystalline phases were determined by X-ray diffraction (XRD). The crystallization kinetics was determined by differential thermal analysis (DTA). The microstructures were examined by using scanning electron microscope (SEM). Fourier transformed infrared spectra (FTIR) analysis was used to study the glass structure. The results showed that by increasing the fluorine content, both the crystallization peak temperature (T_p) and activation energy (E) decreased. Wollastonite, anorthite and gehlenite are the main crystalline phases that exist in the glass ceramics system. The study shows that fluorine promoted initial crystallization of glass and can be used as an effective nucleating agent in the SiO₂–Al₂O₃–CaO system.     

Microstructure and mechanical properties of multi-walled carbon nanotubes containing Al2O3–C refractories with addition of polycarbosilane

Carbon nanotubes (CNTs) are a promising reinforcement for fabricating Al₂O₃–C refractories. However, CNTs are prone to agglomerate or react with antioxidants or reactive gaseous phases such as Al (g), Si (g) and SiO (g), etc. at high temperatures. To overcome the problems above, polycarbosilane (PCS) and multi-walled carbon nanotubes (MWCNTs) were firstly mixed with micro-alumina powder in a liquid medium and then incorporated into Al₂O₃–C refractories. Then the microstructure and mechanical properties of Al₂O₃–C refractories fired in the temperature range from 800 °C to 1400 °C were investigated in this work. The results showed that the MWCNTs were well dispersed in the specimens with addition of PCS in contrast to the specimens without PCS due to the PCS adsorption on the surface of MWCNTs during the mixing process. And the mechanical properties, such as cold modulus of rupture (CMOR), flexural modulus (FM), forces and displacements of Al₂O₃–C refractories with PCS were much higher than those without PCS, which was attributed to more homogeneous dispersion of MWCNTs, more residual MWCNTs as well as different morphologies of ceramic whiskers. Meanwhile, the oxidation resistance of Al₂O₃–C refractories with PCS was improved greatly, which was supposed that the in situ formed SiC_xO_y coating prevented the oxidation of MWCNTs to some extent.     

Preparation of AlN–Al2O3 composites exhibiting antibacterial and water purification properties

This study aimed to develop new antibacterial and water purification materials without heavy metal contamination. Herein, AlN–Al₂O₃ composites were prepared by changing the content of AlN in raw material. The results showed that AlN, Al₂O₃, aluminum oxynitride, and yttrium aluminum garnet phases were generated by adjusting the AlN: Al₂O₃ ratio. The difference in the ability of AlN and aluminum oxynitride to release substances such as ammonium ions and aluminum hydroxide when reacting with water resulted in remarkably different pH values of the sample immersion solution, which led to an increase in the material antibacterial efficiency with the addition of AlN. Similar results were also obtained with zinc ion absorption. Therefore, AlN–Al₂O₃ composite ceramics can potentially be used as novel antibacterial and water purification materials without heavy metal contamination through the release of ammonium ions for conferring antibacterial effects and of aluminum hydroxide for absorbing heavy metals and suspended impurities.     

Phase evaluation during high temperature long heat treatments in the Y2O3–Al2O3–SiO2 system

The effect of high temperature long heat treatments on the microstructure of the eutectic glass composition in the Y₂O₃–Al₂O₃–SiO₂ system was examined. The qualitative and quantitative phase analyses were conducted by using scanning electron microscopy combined with energy dispersive analysis and electron microprobe. Simultaneous thermal analyses were carried out to determine the transition temperatures and enthalpies. The crystallization behavior of these glasses was monitored with X-ray powder diffraction. A needle like X-phase was observed in the structure of this eutectic composition after long heat treatment at 1350 °C.     

Nonlinear optical properties of (1−x) CaFe2O4–xBaTiO3 composites

In this paper, we report nonlinear optical properties of a composite nanostructure with the general formula (1−x) CaFe₂O₄–(x) BaTiO₃ (x=0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1) prepared by sol–gel and conventional solid-state reaction methods. Structural properties and chemical compositions of the samples were characterized using XRD and HRTEM. Basic optical constants, band gap energy and linear absorption coefficient were calculated through optical absorbance measurements. The nonlinear optical properties were investigated using the single-beam open aperture Z-scan technique. The obtained nonlinearity fits to Two-photon absorption process and all samples display high nonlinear absorption effect. The incorporation of BaTiO₃ into CaFe₂O₄ systems show a significant improvement in the nonlinear optical properties. These composite that exhibit efficient optical limiting can have potential applications in photonic devices.     

Phase composition,microstructure and luminescent property evolutions in “light-scattering enhanced” Al2O3-Y3Al5O12: Ce3+ ceramic phosphors

Classic transparent ceramics for laser gain medium and window materials may benefit from their distinctive features of structural homogeneity and high transparency at large scales. However, this has restricted the ability of the ceramics for local light management. Herein, a strategy for ceramic-phosphor design was conducted in the present work via introducing light-scattering centers into single phased YAG: Ce³⁺ transparent ceramics, and an enhancement of light extraction was experimentally realized through the control of Al₂O₃ grain size. UV–vis-NIR diffuse reflectance spectra further confirmed the important roles of the excrescent Al₂O₃ grains. More importantly, PL characterization shows orange-white light emission with high brightness at high temperature. The results highlight that the unique configuration enables simultaneous control of light propagation, luminous efficiency and thermal stability of luminescence, and the design strategy may create great opportunities for laser lighting and displays with high laser power density.