Effect of nano-AlN addition on thermal diffusivity and mechanical strength of porous AL2O3 ceramic composites

In a properly made porous abrasive composite, the vitrified bond should ideally cover the grains and form a continuous network of bridges, and thus part of the heat energy from the grinding process is also transferred to the vitrified bond. Until recently, most studies on the design of composite properties have focused mainly on improving their mechanical strength and wear resistance, but increasingly the very important aspect of their thermal properties is noticed. The vitrified Al₂O₃ composites were made from Al₂O₃ grains, vitrified bond of Na₂OK₂OAl₂OB₂O₃SiO₂ and AlN nanopowder. The increase in porosity in the tested composites is the effect of the AlN decomposition reaction. Crystalline phases were identified in both composites - α-Al₂O₃ and NaAl₁₁O₁₇, but with a different percentage share in individual composites. In composites doped with AlN nanopowder, the proportion of NaAl₁₁O₁₇ crystalline phase decreases, due to its high susceptibility to reduction by Al, obtained from the AlN decomposition reaction. The product of the redox reaction is also Na⁺ ions, which may participate in the formation of the glass phase and thus increasing the fraction of the residual glass phase. As a result of the partial reduction of NaAl₁₁O₁₇ phase, an increase in α-Al₂O₃ content is observed. A higher proportion of α-Al₂O₃ phase with high thermal conductivity can be a factor that increases the rate of heat removal from the work zone.     

Mechanical properties of solid oxide fuel cell glass-ceramic sealants in the system BaO/SrO-MgO-B2O3-SiO2

Planar solid oxide fuel cells (p-SOFCs) require materials that can satisfy the high mechanical demands related to their utilization in stationary and, especially, in mobile applications. Two suitable glass-ceramic sealants based on the system BaO/SrO-MgO-B₂O₃-SiO₂ have been characterized with respect to their mechanical properties such as hardness, Young’s modulus, flexural strength at room and elevated temperature, fracture toughness as well as creep behavior at relevant operation temperatures (800 °C). Fracture toughness was calculated from crack opening displacements (COD) and the results were compared with fracture toughness measured by bending tests of notched bar samples. The mechanical behavior has been discussed regarding different thermal aging times of the glass-ceramics and their microstructural evolution. The glass-ceramics containing SrO revealed a better mechanical behavior than glass-ceramics with BaO. In particular, several superior properties were found in comparison to previously reported materials for this application.     

Microstructure and mechanical properties of CaAl12O19 reinforced Al2O3-Cr2O3 composites

Al₂O₃-Cr₂O₃ refractories have excellent slag corrosion resistance and can adapt to the oxidation/reduction atmosphere in the smelting reduction ironmaking furnace. However, Al₂O₃-Cr₂O₃ refractories have poor mechanical properties and sintering properties. In order to improve the mechanical properties of Al₂O₃-Cr₂O₃ materials, the CaAl₁₂O₁₉ reinforced Al₂O₃-Cr₂O₃ composites were prepared by pressureless sintering process, and the influences of CaO content on the sintering properties, mechanical properties, and microstructure evolution of the composites were studied. The results show that a small amount of CaO can significantly improve the compactness of the composites, which is mainly due to the formed sheet-like CA6 fill the gap between the solid solutions, and reduces the porosity of the composites. In addition, the sheet-like CA6 makes the connection between solid solutions closer, and the intergranular fracture gradually transforms into a mixed mode of intergranular and transgranular fracture. The best mechanical propertie is observed at S4 with the CaO content of 2 wt.%. Compared with sample S0 without CaO, the hardness, compressive strength and flexural strength of the S4 were increased by 35.19 %, 49.69 %, and 68.34 %, respectively. The addition of excessive CaO will deteriorate the mechanical properties of the composites, because the formation of a large number of layered CA6 increases the porosity of the composites. Furthermore, a small amount of CaO addition can significantly improve the thermal shock resistance of the composites. After 10 and 20 thermal shock cycles, the strength loss rates of S4 are only 5.83 % and 8.74 %, respectively.     

Preparation of porous Al2O3 ceramics with enhanced properties by SLS using Al2O3 poly-hollow microspheres (PHMs) coated with CaSiO3 sintering additive

The mechanical properties of porous ceramics prepared by poly-hollow microspheres (PHMs) is usually low because of the weak bonding between different ceramic PHMs. In this paper, CaSiO₃ were coated to the surface of Al₂O₃ PHMs through co-precipitation method as sintering additive to improve the properties of Al₂O₃ poly-hollow microsphere ceramics (Al₂O₃ PHM ceramics). The influence of different amount of CaCl₂ solution on properties of the Al₂O₃ PHM ceramics such as phase composition, microstructure, porosity and mechanical properties were studied. The porosity of the Al₂O₃ PHM ceramics decreased from 77.03% to 68.16% with the increase of CaCl₂ solution amount, while compressive strength increased 29 times from 0.29 MPa to 8.39 MPa. The addition of the CaSiO₃ could decrease the sintering temperature of Al₂O₃ PHM ceramics and significantly improve the mechanical properties of Al₂O₃ PHM ceramics, which is beneficial for preparing highly porous Al₂O₃ PHM ceramics with high mechanical properties and complex shapes.     

Strengthening of Al2O3-C slide gate plate refractories with microcrystalline graphite

The novel carbon sources (including nano-carbon black, carbon nanotubes and graphene oxide nanosheets, etc.) have been extensively researched in low carbon Al₂O₃-C refractory systems. In the present work, ultrafine microcrystalline graphite (UMCG) and nickel-loaded ultrafine microcrystalline graphite (NMCG) were added into low carbon Al₂O₃-C slide gate plate refractories to partially replace graphite flake (GF), respectively. The mechanical properties, phase compositions and microstructures were investigated by three-point bending test, X-ray diffraction, scanning electron microscopy, transmission electron microscopy and energy dispersive X-ray spectroscopy. Also, the reaction mechanisms of in-situ formed ceramic phases were discussed by thermodynamic analysis. The results indicate that the existence of UMCG powders can facilitate the in-situ formation of intertwined ceramic whiskers, leading to increased densification and mechanical properties of low carbon Al₂O₃-C slide gate plate. Moreover, multi-walled carbon nanotubes and ceramic phases intensively interlock with each other in the Al₂O₃-C refractories containing NMCG powders, which results in their better mechanical properties; the cold modulus of rupture are 36.03±0.12 MPa and 32.14±0.17 MPa for the specimens after coking at 1200 °C and 1350 °C, respectively. This work puts forward a practical application for the microcrystalline graphite as a candidate carbon source in Al₂O₃-C slide gate plate refractories.     

Effect of Al4B2O9 and Al18B4O33 whiskers synthesized in situ on the evolution of microstructure and mechanical properties of white fused alumina and Cubitron glass-ceramic composites

The present paper reports on the influence of in situ crystallization of aluminum borate whiskers on the evolution of the microstructure and mechanical properties of electrocorundum (white fused alumina) and microcrystalline alumina (Cubitron 321?) glass-ceramic porous composites. The investigated composites were obtained by sintering the white fused alumina (WFA) and Cubitron 321? abrasive grains, glass-ceramic bond and various amounts of precursor for whisker growth. The results showed that in the presented technology, the crystallization of the composite reinforcing phases proceeds differently in both types of composites, which affects their microstructure and mechanical properties. An increase in the mechanical tensile strength of 36% was observed for both types of composites; however, depending on the type of abrasive grain, the composites with the highest tensile strength differed in the amount of whisker precursor added. A significant increase in the Young's modulus values was also observed for composites containing 40 wt% precursor: by 45% for WFA and by 52% for Cubitron 321?.     

Improvement in structural,dielectric and energy-storage properties of lead-free niobate glass-ceramic with Sm2O3

Phase evolution, microstructure, dielectric performance, polarization, breakdown strength as well as energy-storage behaviors for the lead-free niobates glass-ceramics with Sm₂O₃ were systematically investigated. Two crystallographic structures of tetragonal tungsten bronze and orthorhombic perovskite complex phases were obtained and Sm³⁺ entered into the crystalline phases. The optimal microstructure of the glass-ceramic was obtained with Sm₂O₃ of 2 mol%. Both dielectric constant and polarizability were enhanced with increasing Sm₂O₃. The breakdown strength and energy-storage behaviors of the glass-ceramics were also improved by increased Sm₂O₃. The highest breakdown field of 21.2 kV/mm, the highest charged (0.74 J/cm³) and discharged energy density (0.45 J/cm³) were obtained in the glass-ceramic with 2 mol% Sm₂O₃. It is due to the reduced interfacial polarization in this particular composition.     

Microstructure evolution,mechanical and tribological properties of Ti3(Al,Sn)C2/Al2O3 composites

In this paper, in situ formed Ti₃(Al,Sn)C₂/Al₂O₃ composites were fabricated by sintering the mixture of Ti₃AlC₂ and SnO₂. The Al atoms could diffuse out of the Ti₃AlC₂ layered structure to react with SnO₂, resulting in the formation of Ti₃(Al,Sn)C₂ solid solution and Al₂O₃. When the SnO₂ content was 20?wt.%, the sintered Ti₃(Al,Sn)C₂/Al₂O₃ composite exhibited the best overall mechanical properties, because of the optimized cooperative strengthening effect of solution strengthening and Al₂O₃ enhancement. When the SnO₂ content increased up to 30?wt.%, the flexural strength and fracture toughness of Ti₃(Al,Sn)C₂/Al₂O₃ composite dramatically decreased on account of the large accumulation of generated Al₂O₃. Moreover, according to the SiC ball-on-flat wear tests, it was found that the wear resistance of Ti₃(Al,Sn)C₂/Al₂O₃ composites was significantly improved as the SnO₂ content increased.     

Selective laser sintering of porous Al2O3-based ceramics using both Al2O3 and SiO2 poly-hollow microspheres as raw materials

Porous Al₂O₃-based ceramics with improved mechanical strength and different pore size were fabricated using Al₂O₃ and SiO₂ poly-hollow microspheres (PHMs) as raw materials by selective laser sintering (SLS). The effects of different contents of SiO₂ PHMs on phase compositions, microstructures, mechanical properties and pore size distribution of the prepared ceramics were investigated. It is found that moderate content of SiO₂ PHMs (≤30 wt%) could work as a sintering additive, which could enhance the bonding necks between Al₂O₃ PHMs. When the content of SiO₂ PHMs increased from 0 wt% to 30 wt%, the compressive strength of Al₂O₃-based ceramics increased from 0.3 MPa to 4.0 MPa, and the porosity decreased from 77.0% to 65.0% with open pore size decreased from 52.0 μm to 38.3 μm. However, SiO₂ PHMs could provide pores by keeping its integrity when the content of SiO₂ PHMs increased to 40 wt%, which could result in the porosity increasing to 66.8% and pore size decreasing to 30.1 μm. Selective laser sintering of different kinds of ceramic PHMs is a feasible method to fabricate porous ceramics with complex shape, controllable pore size and improved properties.     

Enhancing mechanism of improved slag resistance of Al2O3-spinel castables added with pre-synthesized (Al,Cr)2O3 micro-powder

In order to enhance the slag resistance of Al₂O₃-spinel castables, (Al,Cr)₂O₃ is added into Al₂O₃-spinel system as a pre-synthesized micro-powder. Firstly, (Al,Cr)₂O₃ micro-powder is synthesized by sintering under reduction conditions to prevent the formation of hexavalent chromium. The Al₂O₃-spinel castables are prepared using tabular alumina, fused spinel, α-Al₂O₃ micro-powder, calcium aluminate cement and (Al,Cr)₂O₃ micro-powder as the raw materials. The bulk density, porosity, mechanical properties, and slag resistance of the samples are tested. Afterward, the effects of (Al,Cr)₂O₃ micro-powder (0–3 wt%) on the slag resistance and microstructures of the Al₂O₃-spinel castables are assessed by X-ray diffraction (XRD) and energy-dispersive (SEM-EDS) analysis. The results show that the addition of (Al,Cr)₂O₃ micro-powder can could inhibit the deteriorating effects of Cr³⁺ on the mechanical properties of the samples. The microstructure results also shows that with the addition of the (Al,Cr)₂O₃ micro-powder, a secondary solid solution of Ca(Al,Cr)₁₂O₁₉ formed, causing the unit cell to become larger. In the slag erosion area, CA₆ crystals formed with network-like interwoven structures, high density, and greater thickness. These characteristics significantly reduce the erosion and permeability indices of the castables, and improve the slag erosion resistance of the material.     

Effects of AlN inorganic binder on the properties of porous Si3N4 ceramics prepared by selective laser sintering

Porous Si₃N₄ ceramics are widely used in the aerospace field due to its lightweight, high-strength, and high wave transmission. Traditional manufacturing methods are difficult to fabricate complex structural and functional ceramic parts. In this paper, selective laser sintering (SLS) technology was applied to prepare porous Si₃N₄ ceramics using AlN as an inorganic binder. And the effects of AlN content on the properties of the obtained ceramic samples were explored. As the AlN content increased, nano-Al₂O₃ and nano-SiO₂ formed the eutectic liquid phase, enhancing the sintering densification and phase transformation of Si₃N₄ poly-hollow microspheres (PHMs). The island-like partial densification structures in Si₃N₄ green bodies increased. During the high-temperature sintering, the eutectic liquid phase partially transformed into the mullite phase or reacted with AlN and Si₃N₄ to form the Sialon phase. With the increase of AlN content, the fracture mode of Si₃N₄ ceramics changed from fracturing along PHMs to fracturing across PHMs. The bonding depth between PHMs increased and the connection between the grains was tighter, so the Si₃N₄ ceramics became denser. With the increase of AlN addition, the total porosity of the porous Si₃N₄ ceramics tended to decrease and the flexural strength gradually increased. When AlN content was 20 wt%, the total porosity and the flexural strength were 33.6% and 23.9 MPa, respectively. The addition of AlN inorganic binder was carried out to develop a novel way to prepare high-performance porous Si₃N₄ ceramics by SLS.     

Improvement on thermophysical and mechanincal properties of LaMgAl11O19 magnetoplumbite by Nd2O3 and Sc2O3 co-doping

LaMgAl₁₁O₁₉-type magnetoplumbite holds great promise to be used above 1300 °C as thermal barrier coatings (TBCs), but its practical application has been restricted because of inferior thermophysical properties. Herein, we focus on optimizing the thermophysical properties of LaMgAl₁₁O₁₉ by simultaneously substituting La³⁺ and Al³⁺ ions with Nd³⁺ and Sc³⁺ ions, respectively. Results show that the effects of co-substitution on reducing thermal conductivity are pronounced. The thermal conductivities of La_1-xNd_xMgAl_11-xSc_xO₁₉ (x = 0, 0.1, 0.2, 0.3) ceramics decrease progressively with dopant concentration and a lowest thermal conductivity of 2.04 W/(m·K) is achieved with x = 0.3 at 1000 °C, which is a value superior to pure LMA and even lower than YSZ. The mechanisms behind the lowered thermal conductivity are investigated. Increase of the thermal expansion coefficient is also realized (8.53 × 10⁻⁶ K⁻¹ for pure LMA, 9.07 × 10⁻⁶ K⁻¹ for x = 0.3, 1300 °C). Most importantly, Nd³⁺ and Sc³⁺ combination doping indeed facilitates mechanical properties of La_1-xNd_xMgAl_11-xSc_xO₁₉ solid solutions as well. It should be noted that Sc³⁺ doping at Al³⁺ site plays more effective role in improving thermal properties than Nd³⁺ does at La³⁺ site. This work provides a path to simultaneously integrate low thermal conductivity, good phase stability, moderate thermal expansion behavior and excellent mechanical properties on LMA for the next generation TBCs.     

Effect of Ge on microstructure and mechanical properties of Ti3SiC2/Al2O3 composites

Owing to the good physicochemical compatibility and complementary mechanical properties of Ti₃SiC₂ and Al₂O₃, Ti₃SiC₂/Al₂O₃ composites are considered as ideal structural materials. However, TiC and TiSi₂ typically coexist during the synthesis of Ti₃SiC₂/Al₂O₃ composites through an in-situ reaction, which adversely affects the mechanical properties of the resulting composites. In this study, Ti₃SiC₂/Al₂O₃ composites were prepared via in-situ hot pressing sintering at 1450 °C. Ge, which was used as a sintering aid, improved the purity and mechanical properties of the Ti₃SiC₂/Al₂O₃ composites. This is because Ge replaced some of the Si atoms to compensate the evaporation loss of Si to form Ti₃(Si_1-xGe_x)C₂, which showed a crystal structure similar to that of Ti₃SiC₂. Furthermore, the molten Ge accelerated the diffusion reaction of the raw materials, increasing the overall density of the Ti₃SiC₂/Al₂O₃ composites. The optimum Ge amount for improving the mechanical properties of the composites was found to be 0.3 mol. The flexural strength, fracture toughness, and microhardness of the composite with the optimum Ge amount were 640.2 MPa, 6.57 MPa m^1/2, and 16.21 GPa, respectively. The formation of Ti₃(Si_1-xGe_x)C₂ was confirmed by carrying out X-ray diffraction, energy dispersive spectroscopy, and transmission electron microscopy analyses. A model crystal structure of Ti₃(Si_1-xGe_x)C₂ doped with 0.3 mol Ge was established by calculating the solid solubility of Ge.     

Comparison of sintering behavior and reinforcing mechanisms between 3Y-TZP/Al2O3(w) and 12Ce-TZP/Al2O3(w) composites: Combined effects of lanthanide stabilizer and Al2O3 whisker length

The densification behavior, microstructural development, toughening and strengthening mechanisms of Al₂O₃ whisker-reinforced 3Y-TZP and 12Ce-TZP composites were systematically and comparatively investigated with varying whisker lengths. Compared with 3Y-TZP/A_w composites, the presence of a Ce-Al-Si-O amorphous phase, caused by the addition of Al₂O₃ whiskers, promoted the densification and grain growth of 12Ce-TZP/A_w composites. Crack deflection and bridging are proposed as the primary toughening mechanisms for 3Y-TZP/A_w composites, while the t-m martensitic transformation would dominate the toughening and strengthening processes of 12Ce-TZP/A_w composites. Changes in Al₂O₃ whisker length would vary the distributions of internal stress and amorphous phase within the ceria-stabilized ZrO₂ matrix, and hence affect the toughening and strengthening results. It indicates that effective toughening and strengthening of the Al₂O₃ whisker-reinforced TZP composites can be achieved by taking advantage of collaborative engineering control on the reinforcement morphology and the interface chemistry/structure.     

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.     

A glass-ceramic approach to prepare porous TiO2 with self-supported nano-flakes: The phase evolution and the thermal stability of the product

A porous TiO₂ material consisting of self-supported nano-flakes with mixed anatase/rutile phases was prepared by acid-etching of a glass-ceramic derived from 20MgO?24CuO?32TiO₂?24P₂O₅ phosphate glass frit. The analysis showed that selective dissolution of components of CuO, Mg₃(PO₄)₂, MgTi₄(PO₄)₆ in the crystallized sample first occurred, followed by the growth of TiO₂ nano-flakes and the formation of Ti(HPO₄)₂?2H₂O phase due to the supply of Ti⁴⁺ and [PO4]^3- released form the dissolved crystallites. The sample acid-treated for 17 h had the best crystallization of anatase and rutile phases, and the smallest band gap. In addition, the porous skeleton showed excellent thermal stability and a large surface area. The present study provided a new method which could be used for the scale-up production of porous TiO₂.     

Structure and magnetic properties of BeO-Fe2O3-Al2O3-TeO2 glass-ceramic composites

In this work, glass-ceramics in the xBeO–20Fe₂O₃–(80-x)TeO₂ system with x = 0–25 mol% were synthesized by the traditional melt quenching route and studied by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, confocal microscopy, infrared and Raman spectroscopy. BeO addition was found to support the crystallization process of Fe₂O₃ during melting, and an increased BeO content was associated with an increased fraction of the crystalline Fe₂O₃ phase and an increased size of these crystallites. Furthermore, samples doped with BeO exhibit an increasing polymerization of the residual tellurite glass network compared to the undoped sample. The magnetic properties and specific heat of all synthesized materials were measured, and the results show that all studied samples behave as spin-glasses. Also, the Morin transition of hematite was observed at 260 K with intensity depending on the material content in Fe₂O₃ crystalline phase, the formation of which correlates with the amount of added BeO.     

Effect of Y2O3-stabilized ZrO2 whiskers on the microstructure,mechanical and wear resistance properties of Al2O3 based ceramic composites

The aim of this study was to improve the mechanical properties of Al₂O₃ ceramics by the addition of Y₂O₃-stabilized ZrO₂ whiskers (designated as Al₂O₃/YSZ_W composite) through the flux method and hot-pressing technology. The effect of YSZ_W content on their microstructure, phase composition and transformability, mechanical properties, and wear resistance was systematically investigated. The Al₂O₃/YSZ_W composites containing 10 wt% YSZ_W exhibited the best mechanical performance, including the highest content of YSZ_W tetragonal phase and transformability as well as the largest values in their relative density (99.5%), hardness (1969 HV), fracture toughness (9.57 MPa m^1/2) and flexural strength (855 MPa). The strengthening and toughening of the Al₂O₃/YSZ_W composites were attributed to the YSZ_W tetragonal-monoclinic phase transformation as well as the whiskers reinforcing effect. Furthermore, the Al₂O₃/YSZ_W composites also showed the highest friction and wearing properties.     

Fabrication and microstructure of porous SiC ceramics with Al2O3 and CeO2 as sintering additives

In the present study, porous silicon carbide ceramics were prepared via spark plasma sintering at relatively low temperatures using Al₂O₃ and CeO₂ as sintering additives. Sacrificial template was selected as the pore forming mechanism, and gelcasting was used to fix the slurry in a short time. The evolution process of the microstructures during different steps was observed by SEM. The influence of the sintering temperature and sintering additives on the shrinkage and porosity of the samples was studied. The microstructures of different samples were characterized, and the mechanical properties were also evaluated.     

Microstructures,thermophysical properties and thermal cyclic behaviors of Nd2O3 and Sc2O3 co-doped LaMgAl11O19 thermal barrier coating deposited by plasma spraying

In this study, La_1-xNd_xMgAl_11-xSc_xO₁₉ (x = 0.1, 0.2, 0.3; abbreviated as LNMAS-1, 2, 3) coatings which are supposed to possess better properties than LaMgAl₁₁O₁₉ (LMA) were plasma-sprayed and their high-temperature performance were comparatively investigated. Results show that addition of Nd³⁺ and Sc³⁺ as dopants to LMA endows corresponding coatings with reduced thermal conductivity and enhanced thermal expansion coefficient, while maintaining advantageous phase stability, although still being subjected to amorphization in plasma flame and following crystallization upon high-temperature service. Furthermore, the doping could cause adherence increasing between topcoat/bondcoat, benefiting from improved melting condition, especially in LNMAS-2 and LNMAS-3 coatings, which is related to the specific powder morphology and lowered melting point. During exposure to 1350°C, mechanical performance and structure integrity of doped free-standing LNMAS coatings can be well preserved even after 400 h aging. In thermal cyclic fatigue test, LNMAS-2 and LNMAS-3 coatings undertake thermal cycling lifetime of ～181 and 191 cycles at 1100°C, respectively, 40% durable than that of LMA coating. These preliminary results suggest that LNMAS-2, 3 might be promising candidates for advanced thermal barrier coating applications.