Joining ZTA ceramic by using Dy2O3-Al2O3-SiO2 glass ceramic filler

In this paper, a novel Dy₂O₃-Al₂O₃-SiO₂ (DAS) glass ceramic was designed and prepared for joining zirconia toughened alumina (ZTA) ceramic. The crystallization, thermal expansion behavior and wetting behavior of the DAS glass filler were studied. The effect of cooling rate and joining temperature on the microstructure and flexural strength of joints was investigated. The results show that slow cooling rate (15 °C/min) leads to crystallization of brazing seam, which causes the formation of pores in the joints due to the large density difference between the glass and the crystalline phases. The dissolution of ZrO₂ from ZTA substrate into the filler during joining process improves the mismatch of the coefficient of thermal expansion (CTE) between the brazing seam and substrate. The maximum flexural strength of 535 MPa is obtained when the joining temperature and cooling rate are 1475 °C and 50 °C/min, respectively.     

Interfacial evolution mechanism of MgAl2O4/MgAl2O4 joints bonded with lanthanum glass

The La₂O₃-SiO₂-B₂O₃ (LSB) glass filler with high softening temperature was first used to join MgAl₂O₄ ceramic. An interfacial layer composed of Al₂O₃ was formed due to the solubility difference of MgO and Al₂O₃ in the LSB glass filler. As a result, the addition of Al₂O₃ into the LSB glass filler caused the increase of interfacial layer thickness. On the contrary, the addition of MgO into the LSB glass filler led to the decrease of interfacial layer thickness. When the adding content of MgO was 6 wt%, the interfacial layer disappeared and completely amorphous brazing seam was obtained. The in-line transmittance of joints decreased with the increase of the thickness of interfacial layer. The optimal in-line transmittance of joint bonded with La₂O₃-SiO₂-B₂O₃-MgO (LSB6M) glass filler reached 82.9% at 1000 nm. Meanwhile, the average flexural strength of joints was about 196.2 MPa, which was equal to the strength of MgAl₂O₄ substrate.     

Gel-casting of MgAl2O4 transparent ceramics using a common dispersant

The ethanolaminic salt of citric acid (commercial name Dolapix CE 64) has commonly been used as a dispersant for colloidal based ceramic forming process. In this paper, a surprise was presented that MgAl₂O₄ spinel slurries consisting of MgAl₂O₄ spinel nanoparticles and Dolapix CE 64 gelled in air at room temperature spontaneously. The MgAl₂O₄ spinel slurries with high solid loading (54 vol%) were prepared with Dolapix CE 64 and the green body with up to 57% relative density was obtained. MgAl₂O₄ transparent ceramics with small grain size (0.92 μm) and high transmittance (81.7% at 600 nm) were fabricated after pre-sintering at 1500°C and hot-isostatic sintering at 1550°C.     

Solid Solution Effects on the Thermal Properties in the MgAl2O4–MgGa2O4 System

Solid solution effects on thermal conductivity within the MgO–Al₂O₃–Ga₂O₃ system were studied. Samples with systematically varied additions of MgGa₂O₄–MgAl₂O₄ were prepared and the laser flash technique was used to determine thermal diffusivity at temperatures between 200°C and 1300°C. Heat capacity as a function of temperature from room temperature to 800°C was also determined using differential scanning calorimetry (DSC). Solid solution in the MgAl₂O₄–MgGa₂O₄ system decreases the thermal conductivity up to 1000°C. At 200°C thermal conductivity decreased 24% with a 5 mol% addition of MgGa₂O₄ to the system. At 1000°C, the thermal conductivity decreased 13% with a 5 mol% addition. Steady‐state calculations showed a 12.5% decrease in heat flux with 5 mol% MgGa₂O₄ considered across a 12 inch thickness.     

High strength and high light transmittance sapphire/sapphire joints bonded using a La2O3-Al2O3-SiO2 glass filler

A novel La₂O₃-Al₂O₃-SiO₂ (LAS) glass was used as filler to join transparent sapphire for obtaining high strength and high light transmittance joints. The results show that the LAS glass filler had compatible coefficient of thermal expansion (CTE) with sapphire and excellent wetting ability on sapphire. During the joining process, no interfacial reaction occurred and the brazing seams were in a completely amorphous state under fast cooling conditions (~50 °C/min). With increased joining temperature, the mutual dissolution and diffusion between sapphire and the LAS filler were enhanced. The flexural strength of joints first increased and then decreased with an increase in the joining temperature from 1400 °C to 1550 °C. The optimal flexural strength of joint reached 325 MPa, which almost was the same as the strength of sapphire substrate. At 500 nm, the in-line transmittance of this joint was 80.5%, which was close to that of sapphire (84.2%).     

Effect of heat treatment conditions on the growth of MgAl2O4 nanoparticles obtained by sol-gel method

MgAl₂O₄ nanoparticles (NPs) were prepared by sol–gel method using aluminium nitrate, magnesium nitrate and citric acid as starting materials, phenolic formaldehyde resin and carbon black as additives. Growth of MgAl₂O₄ NPs in different heat treatment conditions (temperature, atmosphere, carbon additives and in Al₂O₃-C system) was investigated. MgAl₂O₄ NPs were formed at 600 °C in air atmosphere with serious agglomeration of nanoparticles having diameter of approximate 30 nm. The size of MgAl₂O₄ NPs increased greatly from 40 to 50 nm to several hundreds of nanometres as the temperature was raised from 800 °C to 1400 °C. Partial sintering of NPs was observed upon heating at temperatures higher than 1200 °C in air. In reducing atmosphere, the size of MgAl₂O₄ NPs (about 30–50 nm) changed slightly with increasing temperature. This was attributed to the dispersion of carbon inclusions in the MgAl₂O₄ grain boundaries, inducing a steric hindrance effect and inhibiting the growth of particles. MgAl₂O₄ NPs (30–50 nm) in the Al₂O₃-C system were in-situ formed at high temperatures with the use of dried precursor gels. MgAl₂O₄ NPs can contribute to improving the thermal shock resistance of Al₂O₃-C materials.     

Joining of alumina using magnesium- or calcium-aluminosilicate glass–ceramic fillers

Magnesium- and calcium-aluminosilicate (MAS and CAS) glass–ceramics were used to join alumina with six different compositions. The fillers were applied onto the alumina by screen-printing, and then joining was performed slightly below and above the filler melting temperature (T_m). The evolution of various intermediate compounds upon heat treatment between the filler itself and at the joining interface was compared. MgAl₂O₄ and CaO·6Al₂O₃ was the main crystalline phase presented at the joining interface for the MAS and CAS system, respectively, while more intermediate compounds were observed when only filler was heat-treated. The formation of MgAl₂O₄ and CaO·6Al₂O₃ was attributed to the diffusion of Al ions from the alumina base, which is desirable for obtaining a sound joint due to the similar coefficient of thermal expansion to the base alumina. The maximum joint strength of 250 ± 41 and 301 ± 48 MPa was obtained for MAS and CAS filler system, respectively, after joining at T ≥ T_m due to complete interfacial wetting.     

Effect of MgAl2O4 nanoparticles addition on the densification and properties of MgO-CaO refractories

MgAl₂O₄nanoparticles were added to MgO–CaO refractory ceramic composites in the range of 0–8 wt%. Refractory specimens were obtained by sintering at 1650 °C for 3 h in an electric furnace. Refractory specimens were characterized by measurements of bulk density, apparent porosity, hydration resistance, cold crushing strength, crystalline phase formation, and microstructural analysis. Results show that with additions of MgAl₂O₄ nanoparticles the bulk density of the samples increased. But the apparent porosity and cold crushing strength decreased and increased, respectively with addition MgAl₂O₄ nanoparticles up to 6 wt% and for further MgAl₂O₄ nanoparticles, due to the thermal expansion mismatch, the results is reversed. Also, the hydration resistance of the samples was appreciably improved by the addition of MgAl₂O₄ nanoparticles due to its effect on decreasing the amount of free CaO in the refractory composite and promotion of densification by creating a dense microstructure.     

Synthesis and characterization of MgAl2O4 spinel precursor sol prepared by inorganic salts

Magnesium aluminate (MgAl₂O₄) spinel precursor sol was prepared using aluminum nitrate and magnesium nitrate as the precursors for alumina and magnesia, respectively. The obtained sol owned a translucent, homogenous, and stable appearance with a density of 1.19 g/cm³, and at the temperatures above 60 °C, converted to a soft and clear gel. The measured pH of sol was in the range of 3–4, and at the calcination temperature of 1000 °C, the solid content of 6% was reached. TGA/DSC analysis was utilized to study the thermal behavior of the sol. Fourier transforms infrared spectroscopy (FTIR) was applied to recognize the existing bounds in the dried and calcined sol. X-ray diffraction patterns revealed the formation of single-phase MgAl₂O₄ up to 600 °C. According to the FESEM images, the grain size for the sol calcined at 1000 °C was estimated at around 50 nm.     

Joining of Porous Alumina with a CaO–Al2O3–SiO2 Glass‐Ceramic

A CaO–Al₂O₃–SiO₂ (CAS)‐based glass interlayer was developed for joining of porous alumina membrane tubes with dense alumina in this work. The results indicated that the interfacial microstructure of the joint was highly sensitive to the quench rate from the joining temperature, which rendered crystallization of CaTiSiO₅ at a fast quench rate but CaAl₂Si₂O₈ at a slow quench rate due to the interfacial reaction between the CAS glass interlayer and the substrate. An extra crystallization treatment during quench, i.e., dwelling at 800°C–900°C for 2 h, produced a multiphase interlayer consisting of LiAlSi₂O₆, CaTiSiO₅, and CaAl₂Si₂O₈. All joints were evaluated by the thermal shock test. The results showed that the LiAlSi₂O₆‐containing joint interlayer had much lower thermal shock resistance than those without LiAlSi₂O₆.     

Microstructure evolution and mechanical properties of porous Si3N4 and dense Si3N4 joints bonded using CaO–Li2O-Al2O3–SiO2 glass-ceramic

A novel CaO-Li₂O-Al₂O₃-SiO₂ (CLAS) glass was developed for the joining of porous Si₃N₄ and dense Si₃N₄. A multiphase interlayer consisting of CaAl₂Si₂O₈, LiAlSi₂O₆ and CaSiO₃ phases was formed in joint, which possessed matched CTE with the Si₃N₄ substrates. In addition, the infiltrated layer with bilayer structure in the porous Si₃N₄ substrate was observed. The effects of joining temperature and cooling rate on microstructure, phase evolution and shear strength of joints were studied carefully. The results showed that the kinds of precipitated phases remained invariable with the joining temperature increased, but the crystallinity in the interlayer was improved remarkably as the cooling rate reduced. The maximum shear strength of 45 MPa was obtained when the joining temperature and cooling rate were 1100 °C and 5 °C/min, respectively. Moreover, fracture during the shear test occurred mainly within porous Si₃N₄ side, indicating superior joining of dense Si₃N₄/glass-ceramic/porous Si₃N₄.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Preparation,characterisation, and growth mechanism of mesoporous petal-like MgAl2O4 spinel

Petal-like MgAl₂O₄ spinel was successfully prepared using a novel inorganic salt-assisted nonhydrolytic sol-gel method without a template and was employed as absorbent in the removal of the Congo red (CR). The effects of the inorganic salt type, heat-treatment temperature, and dwelling time on the morphology and phase composition of the petal-like MgAl₂O₄ spinel were investigated systematically. Results indicated that when Na₂MoO₄ was employed as the salt and the heat-treatment temperature and dwelling time were 600 °C and 5 h, respectively, the as-obtained petal-like MgAl₂O₄ spinel exhibited a highly uniform morphology with a thickness of 19–23 nm and a length of 240–280 nm. The N₂ adsorption-desorption results revealed that the petal-like MgAl₂O₄ exhibited a large BET specific surface area of 161 m²g^-1 with a pore volume of 0.24 cm³g^-1. The growth mechanism of the petal-like MgAl₂O₄ is believed to be the formation of a two-dimensional layered network structure by the coordination between the condensation product of the magnesium aluminium bimetallic alkoxides and the ions in the salt. The as-prepared MgAl₂O₄ petal exhibited an effective adsorption capacity toward anionic dyes CR. The maximum adsorption capacity of CR onto the mesoporous MgAl₂O₄ petal was found to be 572.01 mg/g, it is showed the petal-like MgAl₂O₄ exhibit huge potential of application in the field of environmental remediation.     

Characterization of single crystalline a-TiO2 films on MgAl2O4(100) substrates by MOCVD

Anatase phase TiO₂ (a-TiO₂) films have been deposited on MgAl₂O₄(100) substrates at the substrate temperatures of 500–650 °C by the metal organic chemical vapor deposition (MOCVD) method using tetrakis-dimethylamino titanium (TDMAT) as the organometallic (OM) source. The structural analyses indicated that the TiO₂ film prepared at 600 °C had the best single crystalline quality with no twins. The out-of-plane and in-plane epitaxial relationships of the film were a-TiO₂(001)||MgAl₂O₄(100) and TiO₂[100]||MgAl₂O₄[100], respectively. A uniform and compact surface with stoichiometric composition was also obtained for the 600 °C-deposited sample. The average transmittance of all the TiO₂ films in the visible range exceeded 91% and the optical band gap of the films varied from 3.31 to 3.41 eV.     

Restructuring-diffusion mechanism of calcium alumino-titanate in CaAl12O19–MgAl2O4–Al2O3 castables

Calcium alumino-titanate (CAT), a secondary material obtained from ferrotitanium slag, was used as a hibonite source to prepare CaAl₁₂O₁₉–MgAl₂O₄–Al₂O₃ castables. The restructuring effect of CAT aggregate was compared by replacing tabular alumina aggregates with CAT aggregates of different particle sizes. The effects of CAT particle size on cold mechanical strength and thermal shock resistance of CaAl₁₂O₁₉–MgAl₂O₄–Al₂O₃ castables were studied. The results showed that CAT aggregates with particle size of 5–3 or 3–1 mm led to more internal cracks or pores and reduced the cold mechanical strength of the castable samples fired at 1600 °C for 3 h. The use of CAT aggregates with particle size of 1–0 mm led to the formation of a well-bonded CAT aggregate and matrix, improving the cold mechanical strength and thermal shock resistance of the castable samples fired at 1600 °C for 3 h. The enhancement mechanism of fine CAT aggregates in this process was proposed based on the sintering of the matrix–aggregate interface with the formation of Ca(Al, Mg, Ti)₁₂O₁₉.     

Fabrication and characterization of IR-transparent Fe2+ doped MgAl2O4 ceramics

Initial investigations on the preparation of highly transparent Fe²⁺:MgAl₂O₄ ceramics using nanopowders synthesized in a laser plume were carried out. For the first time, dense Fe²⁺:MgAl₂O₄ ceramics with high transmission in the mid-IR range were fabricated at a temperature as low as 1300°C and with a short sintering time (1 hour). The obtained Fe²⁺:MgAl₂O₄ ceramics contain a secondary (MgO)_0.91(FeO)_0.09 phase with a low wt% content, causing a substantial decrease in transmittance in the visible range. The transmittance increases with an increase in wavelength due to a decrease in Rayleigh scattering and reaches 85.6% at λ = 4 μm, which is close to the theoretical value. The absorption cross section of divalent iron ions was estimated to be σ = (1.66 ± 0.14) × 10⁻²⁰ cm².     

Joining of Al2O3 to ZTA using a B2O3–Al2O3–SiO2 glass with in-situ precipitated whiskers

A novel B₂O₃–Al₂O₃–SiO₂ (BAS) glass filler was first developed to join Al₂O₃ and zirconia toughened alumina (ZTA) ceramics. The microstructure, crystallization products, and interfacial reaction layer of the joint were all studied. Detailed growth process and the microstructural evolution mechanism of aluminum borate (Al₁₈B₄O₃₃ and Al₄B₂O₉) crystal whiskers were revealed through controlling the joining temperature and the holding time. The results showed that the Al₁₈B₄O₃₃ and Al₄B₂O₉ whiskers formed at the interfaces and in the joining seam, owing to the reaction between the substrates and the BAS glass system, and the precipitation out of the glass, respectively. Finally, bonded with this BAS glass filler at 1400 °C for one hour, the joints exhibited a maximum shear strength of 42 MPa at room temperature and good mechanical performance after thermal cycling.     

Fabrication of transparent MgAl2O4 ceramics by gelcasting and cold isostatic pressing

Highly transparent MgAl₂O₄ ceramics have been fabricated by aqueous gelcasting combined with cold isostatic pressing (CIP), pressureless sintering and hot isostatic pressing (HIP) from high purity spinel nanopowders. The gelling system used AM and MABM as monomer and gelling agent. The influences of dispersant and PH on the rheological behavior of the MgAl₂O₄ slurries were investigated. The spinel slurry with low solids loading (25 vol%) and low viscosity (0.15 Pa s) was obtained by using 6 wt% Duramax-3005 (D-3005) as dispersant. After CIP, the green body had a relative density of 48% with a narrow pore size distribution. The influence of sintering temperature on densification and microstructure was studied, choosing 1500 °C as the sintering temperature. After HIP (1650 °C/177 MPa/5 h), transparent MgAl₂O₄ ceramic with the thickness of 3 mm was obtained, whose in-line transmittance was 86.4% at 1064 nm and 79.8% at 400 nm, respectively. The ceramic exhibited a dense microstructure with the average grain size of 23 μm. The Vickers hardness and flexure strength of the sample reached 13.6 GPa and 214 MPa, respectively.     

A two-step heating strategy for low-temperature fabrication of high sinterability and fine MgAlON powder with MgAl2O4 as Mg source

Based on the reaction sequence during synthesis of MgAlON powder by solid-state reaction, a two-step heating strategy is proposed to low-temperature fabricate fine MgAlON powder of high sinterability by using MgAl₂O₄ as Mg source, respectively together with AlON and Al₂O₃+AlN. By introduction of an additional dwelling at 1550 °C to the first heating step, more α-Al₂O₃ dissolve into the solid solution at this temperature. By this way, overlarge particles of Al₂O₃ by agglomeration could be avoided in the next heating step to enable fast full reaction at a lower temperature. By dwelling 30 min at 1550 °C followed by 60 min at 1700 °C, single phase MgAlON powders were successfully prepared by solid-state reaction of all the two batches. The fine MgAlON powder synthesized by MAS+Al₂O₃+AlN batch exhibited high sinterability as the MgAlON ceramics pressureless sintered by this powder at 1880 °C without dwelling showed a transmittance up to 68.3%. The phase assemblage and morphology evolution of the mixture during solid-state reaction were monitored, which verified the effectiveness of the proposed two-step heating strategy. The low synthesis temperature of the two-step heating scheme benefits to prepare pure MgAlON powder with small particle size.     

Experimental phase relations between MgO-saturated magnesium-aluminate spinel (MgAl2O4) and CuOx-rich liquid

Experimental phase equilibrium data for the Cu-O-Al₂O₃-MgO system is required to improve the performance of MgAl₂O₄-containing refractories and slagging in non-ferrous smelting. In this work, the phase relations of MgAl₂O₄ in the Cu-O-Al₂O₃-MgO system were studied experimentally in air within a temperature range of 1100–1400 °C using the equilibration and quenching method. The chemical compositions of the phases in the quenched samples were determined using electron probe microanalysis (EPMA). Less than 1 wt% of Al₂O₃ or MgO were found in the oxide liquid phase, whereas the solid MgAl₂O₄ and MgO phases contained up to 23 wt% and 30 wt% of ‘Cu₂O’, respectively. Discrepancies between these results and the corresponding calculated values generated by the MTDATA 6.0 software and Mtox database Version 8.2 ranged from 3 wt% to 19 wt%. The results of this work indicate that the MgAl₂O₄ spinel is chemically stable in the presence of a CuO_x-rich liquid under the conditions studied.