Microstructure evolution of SiC/SiC joints during ultrasonic-assisted air bonding using a Sn–Zn–Al alloy

Direct soldering of SiC ceramic in air at 230 °C was achieved using a Sn–9Zn–2Al alloy assisted by ultrasonic wave within seconds. Experimental results indicated that a sound metallurgical bond was formed between the SiC ceramic and Sn–9Zn–2Al alloys. The dependence of interfacial microstructure evolution on ultrasonic action duration time was investigated. Two types of interfacial structures at the interface were observed as the ultrasonic action duration time increased. An amorphous SiO₂ layer was identified at the interface for ultrasonic exposures of 1 s, which was the oxide layer formed on the SiC ceramic surface during heating. A layer of amorphous alumina with a thickness of ~ 6.8 nm formed at the interface under ultrasonic action for over 4 s. The shear strength of joints could reach up to 44 MPa. The formation of the alumina layer at the interface was attributed to the redox reaction of Al from the filler metal and SiO₂ on the SiC ceramic surface under the action of ultrasonic waves. The rapid interfacial reaction was principally induced by the acoustic cavitation and streaming effects at the liquid/solid interface.     

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.     

Effect of P2O5 on evolution of microstructure of MgO–Al2O3–SiO2 glass ceramics

Abstract

MgO–Al₂O₃–SiO₂ (MAS) cordierite based glass ceramics were prepared by volume crystallisation. X-ray diffraction, Scanning electron microscopy and Energy diffraction scanning were used to investigate crystallisation behaviour and the influence of P₂O₅ on microstructure MAS based glass ceramics. The results showed that P⁵⁺ could promote the phase separation of MAS glass and that the glass was divided into two areas, such as Mg₄Al₂Ti₉O₂₅ and the containing P⁵⁺ area at <900°C. Mg₄Al₂Ti₉O₂₅ and Mg₃(PO₄)₂ in the area were both advantageous to the precipitation of μ cordierite, which further transformed to α cordierite due to P⁵⁺ in the residual glassy phase. However, P⁵⁺ inhibited the presence of cordierite when the heat treatment temperature was >900°C.     

Microstructure–thermal properties of Cu/Al2O3 bilayer prepared by direct bonding

The thermal conductivity of Cu/Al₂O₃ bilayers prepared by a direct-bonding technique was determined. The direct-bonding process started with the pre-oxidation treatment of a Cu plate at a temperature less than 600 °C. Though a thin oxide layer was located on the surface of the plate after treatment, the oxygen solutes began to diffuse into the interior of Cu plate prior to bonding. Bonding occurred by a eutectic liquid formed at 1075 °C. No reaction interphase was observed at the Cu–Al₂O₃ interface. The thermal resistance of the Cu/Al₂O₃ interface is very low. The extremely low thermal resistance can be related to the clean interface between the two materials.     

Fabrication and properties of macro-porous SiC using Al2O3–Y2O3–SiO2 as bonding additives

Macro-porous SiC was fabricated without using pore-forming agents by an in situ reaction bonding process. A bonding additive, Al₂O₃–Y₂O₃–SiO₂, with a low melting temperature was mixed with SiC particles and sintered at 1500 °C and 1600 °C for 1 h in Ar. Macro-porous SiC with a porosity of 32.7–45.9%, a pore size of 3.4–4.2 μm, and a relatively narrow and uniform pore size distribution was fabricated by varying the amount of bonding additive. The flexural strength of macro-porous SiC prepared at 1500 °C increased from 47.2 MPa to 71.2 MPa while the porosity decreased from 45.9% to 42.8%, respectively. When the sintering temperature of the macro-porous SiC was increased to 1600 °C, the flexural strengths were significantly reduced to 32.6–35.6 MPa, along with a reduction in porosity and pore size. The permeability of macro-porous SiC prepared at 1500 °C varied from 1.59 × 10^?12 m² to 1.26 × 10^?12 m², depending on the porosity. As the sintering temperature increased from 1500 °C to 1600 °C, the permeability decreased to less than 1.00 × 10^?12 m² because of the reduced porosity and average pore size. The electrical resistivity of macro-porous SiC prepared at 1500 °C and 1600 °C varied from 2.7 × 10⁸ Ω-cm to 1.4 × 10⁹ Ω-cm and from 1.3 × 10⁸ Ω-cm to 1.7 × 10⁹ Ω-cm, respectively, with increasing volume percent of bonding additives. The relatively high electrical resistivity was apparently due to neck bonding phase between SiC particles formed by phases consisting of Y₂Si₂O₇, YAG, and residual Al₂O₃.     

Microstructure and properties of SiCf/SiC composite joints with CaO–Y2O3–Al2O3–SiO2 interlayer

Using CaO, Y₂O₃, Al₂O₃, and SiO₂ micron-powders as raw materials, CaO–Y₂O₃–Al₂O₃–SiO₂ (CYAS) glass was prepared using water cooling method. The coefficient of thermal expansion (CTE) of CYAS glass was found to be 4.3 × 10^?6/K, which was similar to that of SiC_f/SiC composites. The glass transition temperature of CYAS glass was determined to be 723.1 °C. With the increase of temperature, CYAS glass powder exhibited crystallization and sintering behaviors. Below 1300 °C, yttrium disilicate, mullite and cristobalite crystals gradually precipitated out. However, above 1300 °C, the crystals started diminishing, eventually disappearing after heat treatment at 1400 °C. CYAS glass powder was used to join SiC_f/SiC composites. The results showed that the joint gradually densified as brazing temperature increased, while the phase in the interlayer was consistent with that of glass powder heated at the same temperature. The holding time had little effect on phase composition of the joint, while longer holding time was more beneficial to the elimination of residual bubbles in the interlayer and promoted the infiltration of glass solder into SiC_f/SiC composites. The joint brazed at 1400 °C/30 min was dense and defect-free with the highest shear strength of about 57.1 MPa.     

Microstructure and characterization of interfacial phases of sapphire/sapphire joint bonded using Bi2O3–B2O3–ZnO glass

Bismuth borate zinc glass, 50Bi₂O₃–30B₂O₃–20ZnO (mol.%), was used as a braze intended to join sapphire. Thermal properties of the glass were all experimentally determined. The wettability of the glass on sapphire was investigated. The contact angle not greater than 11.3° was obtained in air at temperatures of ≥700 °C. Subsequently, sapphire was successfully joined to themselves at 700 °C for 20 min. The microstructure of the joint was studied and the interfacial phases were characterized. The results showed that the ZnAl₂O₄ phase was formed as a result of the reaction between the sapphire substrate and ZnO from the glass. The mechanical integrity of the joints was investigated. The joints with an average room shear strength of 70 MPa were achieved. The fracture analysis indicated that the fracture occurred within the glass interlayer rather than at the sapphire/glass interface, hence indicating a good bonding of the glass with sapphire.     

Pressure-less joining of SiCf/SiC composites by Y2O3–Al2O3–SiO2 glass: Microstructure and properties

In this study, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass was prepared from Y₂O₃, Al₂O₃, and SiO₂ micron powders. Thermal expansion coefficient of as-obtained YAS glass was about 3.9 × 10⁻⁶, matching-well with that of SiC_f/SiC composites. SiC_f/SiC composites were then brazed under pressure-less state by YAS glass and effects of brazing temperature on microstructures and properties of resulting joints were investigated. The results showed that glass powder in brazed seam sintered and precipitated yttrium disilicate, cristobalite, and mullite crystals after heat treatment. With the increase in temperature, joint layer gradually densified and got tightly bonded to SiC_f/SiC composite. The optimal brazing parameter was recorded as 1400 °C/30 min and shear strength of the joint was 51.7 MPa. Formation mechanism of glass-ceramic joints was proposed based on combined analysis of microstructure and fracture morphology of joints brazed at different temperatures. Thermal shock resistance testing of joints was also carried out, which depicted decline in shear strength with the increase of thermal shock times. The strength of the joint after three successive thermal shock cycles at 1200 °C was 35.6 MPa, equivalent to 69% of that without thermal shock.     

The formation mechanism of pores and unbonding in the Al2O3/Al2O3 joints brazed by 50Bi2O3–35B2O3–15ZnO glass

50Bi₂O₃–35B₂O₃–15ZnO (mol. %) glass referred to as Bi50 glass, was used to braze Al₂O₃ ceramics. The phase transformations and wettability of the Bi50 glass on Al₂O₃ substrates at different temperatures were investigated. The results showed that the chemical compatibility of Bi50 glass and Al₂O₃ substrates at 650 °C was excellent. However, Al₂O₃/Al₂O₃ joints having a considerable volume fraction of pores and unbonding were obtained when the joining procedures were carried out by a one-step brazing method. Based on the experiments and simulation results, the prime determinants responsible for the presence of the pores and unbonding within the brazing joints can be divided into two aspects: (i) the intrinsic causes leading to the formation of closed pores (ii) the external factors causing the failure of pores and glass separation. Ultimately, an advanced joining procedure named two-step brazing was proposed, and joints nearly free of defects were acquired.     

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.     

Thermal evolution of Al2O3–CaO–Cr2O3 castables in different atmospheres

Al₂O₃–CaO–Cr₂O₃ castables are required for various furnaces linings due to their excellent corrosion resistance. However, toxic and water-soluble Cr(VI) could be generated in these linings during service. In this study Al₂O₃–CaO–Cr₂O₃ castables were prepared and heated at 300–1500 °C in air and coke bed to simulate actual service conditions. The formations of various phases were investigated by XRD and SEM-EDS. The Cr(VI) compounds CaCrO₄ and Ca₄Al₆CrO₁₆ formed in air at 300–900 °C and 900–1300 °C respectively, while C₁₂A₇ and CA₂ were generated rather than forming Cr(VI) compounds in coke bed at 700–1300 °C. However, at 1500 °C, nearly all the chromium existed in the form of (Al_1-xCr_x)₂O₃ solid solution in both atmosphere. As a result, the specimens treated in air contained 185.0–1697.8 mg/kg of Cr(VI) at 500–1300 °C but only 17.2 mg/kg of Cr(VI) at 1500 °C, whereas specimens treated in coke bed exhibited extremely low Cr(VI) concentration in the whole temperature range studied. Moreover, in coke bed, the mutual diffusion between Cr₂O₃ and Al₂O₃ was suppressed and a trace of Cr₂O₃ would even be reduced to form chromium-containing carbides on its surface, which would hindered the sintering process and hence lower the density as well as strength of the castables.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Joining MgAl2O4 ceramics using ZnO–Al2O3–SiO2 glass ceramic with precipitated ZnAl2O4

In this work, crystallization, thermal expansion and wetting behavior of ZnO–Al₂O₃–SiO₂ (ZAS) glass were first investigated. The results showed that ZnAl₂O₄ was precipitated from ZAS glass after crystallization treatment. Crystallization increased the coefficient of thermal expansion (CTE) of ZAS glass ceramic due to the high CTE of ZnAl₂O₄. In addition, ZAS glass exhibited good wettability on the surface of MgAl₂O₄ substrate. On this basis, ZAS glass was used to join MgAl₂O₄ ceramic, and the microstructure and mechanical properties of joints obtained with different cooling methods were investigated. The flexural strength of joints was related to the content of ZnAl₂O₄ crystals in the brazing seams. Additional nucleation and crystallization treatment during cooling process improved the crystallinity of brazing seam, resulting in better matching of the CTE of brazing seam with that of MgAl₂O₄ ceramic. The maximum flexural strength of joints reached 201 MPa, which was equivalent to the strength of MgAl₂O₄ ceramic.     

Microstructure and mechanical properties of Al2O3 ceramic and TiAl alloy joints brazed with Ag–Cu–Ti filler metal

Al₂O₃ ceramic was reliably joined to TiAl alloy by active brazing using Ag–Cu–Ti filler metal, and the effects of brazing temperature, holding time, and Ti content on the microstructure and mechanical properties of Al₂O₃/TiAl joints were investigated. The typical interfacial microstructure of joints brazed at 880 °C for 10 min was Al₂O₃/Ti₃(Cu,Al)₃O/Ag(s.s)+AlCu₂Ti+Ti(Cu,Al)+Cu(s.s)/AlCu₂Ti+AlCuTi/TiAl alloy. With increasing brazing temperature and time, the thickness of the Ti₃(Cu,Al)₃O reaction layer increased, and the blocky AlCu₂Ti compounds aggregated and grew gradually. The Ti dissolved from the TiAl substrate was sufficient to react with Al₂O₃ ceramic to form a thin Ti₃(Cu,Al)₃O layer when Ag–Cu eutectic alloy was used, but the dissolution of TiAl alloy was inhibited with an increase in Ti content in the brazing filler. Ti and Al dissolved from the TiAl alloy had a strong influence on the microstructural evolution of the Al₂O₃/TiAl joints, and the mechanism is discussed. The maximum shear strength was 94 MPa when the joints were brazed with commercial Ag–Cu–Ti filler metal, while it reached 102 MPa for the joint brazed with Ag–Cu+2 wt% TiH₂ at 880 °C for 10 min. Fractures propagated primarily in the Al₂O₃ substrate and partially along the reaction layer.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

Effect of CaO doping on the properties and crystallization behavior of Y2O3–Al2O3–SiO2 glass

Nowadays, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass joining is considered to be a promising scheme for nuclear-grade continuous silicon carbide (SiC) fiber reinforced SiC matrix composites (SiC/SiC). CaO has great potential for nuclear applications since it has low reactivity and low decay rate under nuclear irradiation. In this paper, the effect of CaO doping on the structure, thermophysical properties, and crystallization behavior of YAS glass was systematically studied. As the CaO doping content increased, the number of bridge oxygens and the viscosity at high temperatures reduced gradually. After heat treatment at 1400 °C, the main phases in YAS glass were β-Y₂Si₂O₇, mullite, and SiO₂ (coexistence of crystalline and glass phases), while that with 3.0% CaO doping turned into a single glassy phase under the same treatment conditions. Moreover, a structural model and the modification mechanism were proposed, which provided a theoretical basis for the subsequent component design and optimization.     

Microstructure and mechanical properties of Al2O3/Cu joints brazed with Ag–Cu–Ti+Zn composite fillers

In this study, Al₂O₃ ceramic and Cu bars were brazed with newly designed Ag–Cu–Ti(ABA)+Zn composite fillers. Systematic analysis of the microstructure of the brazed joints indicated that the volatilization of Zn atoms during the brazing process could promote the spreading of liquid brazing fillers on the surface of the Al₂O₃ ceramic, resulting in a uniform dendritic interfacial structure. The typical interfacial structure was an Al₂O₃/TiO/(Cu, Al)₃Ti₃O+Ag(s, s)/Cu interface. Notably, the tensile strength was improved to 20.89 MPa for Al₂O₃/Cu joint brazed with ABA+Zn composite fillers at 900 °C for 20 min, approximately 67.6% higher than the sample brazed without Zn foil. In this case, the fracture model was straight and sharp-angled inside the Al₂O₃ ceramic. In addition, the joint strength decreased with increased brazing temperatures from 900 to 940 °C.     

Microstructure and mechanical properties of Al2O3–YSZ spherical polycrystalline composites

The mechanical behavior and microstructure of highly densified, spherically shaped, polycrystalline Al₂O₃–YSZ composites, processed from pseudoboehmite powders by sol–gel is reported here. Processing was carried out by combining nanometric sized α-Al₂O₃ (120 nm) seeds and YSZ particles of tetragonal structure. The YSZ particles were homogeneously distributed in a coarse-grained matrix of alumina, both inside grains and along grain boundaries. Fracture surfaces, achieved by impact tests showed toughening effects of the zirconia particles. The tetragonality of the YSZ phase stability even after fracture events and fracture toughness measurements by Vickers indentation, where the crack tip interacts with YSZ particles, are all provided and discussed. The local mechanical properties, such as elastic modulus, indentation hardness and the onset of plastic deformation or fracture contact pressure of both YSZ particles and the Al₂O₃ matrix were quantified by nanoindentation. Evidence of coercive contact pressure was observed in YSZ from indentation stress–strain curves.     

Some features of the surface modification of MgO–Al2O3–TiO2–SiO2 glass and glass ceramics by Ag diffusion

Diffusion of Ag species into the surface layers of the MgO–Al₂O₃–TiO₂–SiO₂ glass stimulates the crystallization processes therein during subsequent thermal treatment. It was found that the silver doping significantly increases the microhardness of glass and glass ceramics. The effect of the Ag diffusion and the subsequent high-temperature treatment (T > T_g) on the structure and luminescence properties of the MgO–Al₂O₃–TiO₂–SiO₂ glass was studied. The thermal evolution, structure and properties of the glass and glass ceramics were investigated by the DSC method, XRD analysis and luminescence spectroscopy. It was found that the Ag diffusion into the surface layers leads to the formation of numerous different luminescent molecular Ag_n clusters. The MgO–Al₂O₃–TiO₂–SiO₂ glass and glass ceramics subjected to the Ag diffusion can operate as effective down-converters of the radiation demonstrating the effective transformation of UV and blue light into the radiation of red and NIR spectral range.