Low leakage rate of silicate glass modified with Al2O3 for solid oxide fuel cell

The gas tightness of glass sealing materials is a big challenge for the solid oxide fuel cell (SOFC) stacks operating at high temperature. Thermal, sintering, crystallization behavior and gas tightness properties of the glass-based with two different Al₂O₃ contents sealants are evaluated and discussed. The study showed that the sealants avoid cracks at the interface on NiO-YSZ (NiO-yttria stabilized zirconia) and SUS430 stainless steel interconnect substrates. The Al₂O₃ embedded in the glass matrix as a second phase, and promoted crystallization of K[AlSi₃O₈] at the early stage. This may because some ultrafine Al₂O₃ particles whose structure is destroyed by prolonged high temperature treatment according XRD and TEM analysis. Especially, the sealant containing 5 wt% Al₂O₃ undergoes a thermal cycle and maintains a stable leakage rate below 10^?4 sccm?cm^?1 for about 1000 h at 750 °C. The above results prove the possibility of using the Al₂O₃-doped sealing glass for SOFC stacks.     

Effect of the crystalline layer on the electrical behaviour of 17.7Li2O·5.2ZrO2·68.1SiO2·9.0Al2O3 glass ceramic monoliths

Li₂O–ZrO₂–SiO₂–Al₂O₃ (LZSA) glass ceramic systems are usually obtained from powder technology to obtain materials with a low thermal expansion coefficient (CTE). However, in these cases, there is a high residual porosity. An alternative to reduce the porosity involves the production of monoliths. Nevertheless, there is still a lack of crystallisation kinetics and the final properties of glass ceramic monoliths are affected such as electrical properties. This study aims to evaluate the electrical behaviour as function of the crystalline layer thickness formed on the monolith surface of a 17.7Li₂O·5.2ZrO₂·68.1SiO₂·9.0Al₂O₃ (molar basis) glass ceramic LZSA composition. Monoliths thermally treated at 750, 800, and 850 °C were chosen to evaluate based on the range of the crystalline layer growth. Electrochemical impedance spectroscopy was used for the electrical characterisation of LZSA glass and the glass ceramics. The resistivity increased with increasing thermal treatment temperature due to the formation of lithium-based crystalline phases. The electrical conductivity at 25 °C of the glass ceramic thermally treated at 850 °C decreased to 1.4 × 10^?13 S cm^?1 from 8.7 × 10^?11 S cm^?1 for LZSA glass. Based on the electrical behaviour, monoliths thermally treated at 850 °C can be considered potential for dielectric industrial applications.     

High gas tightness ZrO2-added silicate glass sealant with low thermal stress for solid oxide fuel cells

A low leakage rate sealant of 10 wt% ZrO₂-added CaO–K₂O–Na₂O–BaO silicate glass for SOFC has been studied. The structure of the sealant is stable at high temperatures with leakage rates less than 10⁻⁴ sccm∙cm⁻¹, and no crystal except for ZrO₂ is found in XRD analysis after heating at 800 °C for 100 h. ZrO₂ is distributed in the glass matrix and plays a supporting role in avoiding over-softening at operating temperature. Good compatibility in both oxidizing and reducing atmospheres between the sealant and SUS430 interconnect was proved by SEM at 750 °C for 100 h. A fully coupled 3D Multiphysics button SOFC is constructed for mechanical analyses. The results show that the increase of ZrO₂ in the sealant will decrease the stress and displacement in the SOFC. Besides, the width of the sealant also affects the stress value and distribution. The results show that GZ10 is a competitive sealing material compared with other ZrO₂-added sealants.     

Chemical compatibility of Al2O3-added glass sealant with bare and coated interconnect in oxidizing and reducing environments

Chemical compatibility in oxidizing and reducing environments between sealants and interconnects for planar solid oxide fuel cells (SOFC) are investigated. (Co,Mn)₃O₄, Co-Mn, and Al coatings were prepared on the FeCr-based ferritic-stainless-steel (SUS430). The (Co,Mn)₃O₄ coating exhibited water vapor bubble formation at the outer sealing edges when exposed to H₂, indicating reactions between the coating and sealant. Co-Mn metal coating was found readily oxidized in an oxidizing environment. The glass with 5 wt% Al₂O₃ addition helped mitigate the Cr diffusion into sealant based on bare SUS430 substrate. Moreover, the Al metal layer effectively blocked the diffusion of Cr into the sealant at the interface and environment for 100 h, with a thickness of only 1 µm. At the constant discharge current of 24 A, the voltage is stabilized at about 4.2 V for 48 h using H₂ as fuel gas in 5-cell stack.     

Design and development of SiO2-Al2O3-B2O3-Na2O based glass sealant for the glass-metal joint

SiO₂-Al₂O₃-B₂O₃-Na₂O based glass sealant compositions were designed for the development of GMJ using extreme vertices methodology. The effect of the glass sealant individual constituent on wettability, Glass transition temperature (T_g), Crystallization temperature (T_c), thermal conductivity, and density was analyzed with the help of analysis of variance technique (ANOVA). The increase in SiO₂ constituent in glass sealant decreased the spreading area (mm²) of glass sealant and increased the value of contact angle (θ) formed by glass sealant over the SS304 metal substrate. The T_g and T_c of glass sealant also increased as SiO₂ content increased. The addition of B₂O₃ and Na₂O in glass sealant system reduced the T_g and T_c of glass sealant. The developed regression model was validated and it was observed that the experimental and predicted results nearly matched with an error less than 5% in most of the cases.     

Crystallization behavior of BaO–CaO–SiO2–B2O3 glass sealant and adjusting its thermal properties for oxygen transport membrane joining application

In this work, the thermal stability of a BaO–CaO–SiO₂–B₂O₃ glass sealant, named “H”, was investigated by differential scanning calorimetry (DSC). The crystallization behavior of glass H as the sealant matrix was investigated by a combination of experimental X-ray diffraction (XRD) analysis and thermodynamic simulation with the FactSage package. A good agreement was found between the Rietveld refinement of XRD experiments and the FactSage simulation. Particular attention was also given to the influence of the Sr₂SiO₄ filler added to the glass matrix “H” on the thermal expansion and microstructures of glass-Sr₂SiO₄ composites by means of dilatometry and scanning electron microscopy (SEM). The reinforced 20 wt% Sr₂SiO₄ composite (HS2S20) showed excellent properties and, thus, its joining performance was investigated using SrTi_0.75Fe_0.25O_3-δ (STF25) and Aluchrom as promising oxygen transport membrane (OTM) and counterpart, respectively. The joining behaviors were investigated by comparing different joining temperatures. 920 °C is the best joining temperature for HS2S20 sealant.     

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.     

Novel Glass‐Ceramic Composition as Sealant for SOFCs

This work deals with the design, the characterization, and testing of a novel glass‐ceramic to be used as sealant for planar solid oxide fuel cells and its compatibility with Mn_1.5Co_1.5O₄‐coated Crofer22APU. Thermal, sintering, and crystallization behavior and thermo mechanical properties of the sealant are reviewed and discussed, indicating therefore that these compositions can be deposited at 850°C and provide an excellent compatibility with both the Mn_1.5Co_1.5O₄‐coated Crofer22APU and the anode‐supported electrolyte. In particular, Mn_1.5Co_1.5O₄‐coated Crofer22APU/sealant/anode‐supported‐electrolyte joined samples have been submitted to thermal tests (in air atmosphere) from RT to 800°C (SOFC operating temperature) up to 500 h. No interactions, cracks formation, or failure were observed at the Mn_1.5Co_1.5O₄‐coated Crofer22APU/sealant interface and between the glass‐ceramic and the anode‐supported‐electrolyte after 500 h of thermal tests in air atmosphere.     

Microstructure,mechanical and optical properties of MgAl2O4/MgAl2O4 joints bonded using CaO-Al2O3-SiO2 glass filler

Transparent MgAl₂O₄ ceramics were bonded by using CaO-Al₂O₃-SiO₂ (CAS) glass filler. The CAS glass filler exhibited the same thermal expansion behavior as MgAl₂O₄ ceramic and excellent wetting ability on the surface of MgAl₂O₄ ceramic. When the cooling rate of 15 °C/min was used, no interfacial reaction was observed and the amorphous brazing seam could be obtained. However, low joining temperature (1250 °C) led to the formation of pores and high joining temperature (1400 °C) resulted in the formation of cracks. Furthermore, the slow cooling rate of 5–10 °C/min induced the crystallization of CaAl₂Si₂O₈ and Mg₂Al₄Si₅O₁₈ due to the dissolution of MgAl₂O₄ substrate. The optimal flexural strength of 181–189 MPa was obtained when the joining temperature and cooling rate were 1300–1350 °C and 15 °C/min respectively. Moreover, the in-line transmittance of the joint at 1000 nm was 82.1%, which was slightly lower than that of MgAl₂O₄ ceramic (85.6%).     

Barium Borosilicate Sealing Glasses Synthesized by a Sol–Gel Process: Chemical Interactions with a Stainless Steel and Gas‐Tightness of a SOFC

Several glasses synthesized by sol–gel route and based on the BaO–B₂O₃–X–Al₂O₃–SiO₂ (X = CaO, MgO) glass system have been investigated to evaluate their applicability as sealant for solid oxide fuel cell (SOFC). Chemical interactions with K41X stainless steel and hydrogen‐tightness of these materials were evaluated after operations at high temperatures over 1,000 h in air atmosphere. Formation of a new phase at the steel–glass interface and formation of porosity in the glass were observed and determined as critical problems over mid‐term operations. The role of MgO is important to obtain a gas‐tight sealing. Application of the glass paste without binder addition was performed in order to avoid possible residual porosity related problems. The best glass was finally used as sealant between anodic and cathodic compartments in complete SOFCs operated at 760 and at 800 °C. Open circuit voltages and power densities of the cells were recorded during the first hours of operation.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

Glass-ceramics for joining oxide-based ceramic matrix composites (Al2O3f/Al2O3-ZrO2) operating under direct flame exposure

This work focuses on the joining processes of oxide-based ceramic matrix composites (Al₂O_3f /Al₂O₃-ZrO₂), which are used as radiant tube furnace components in the steel industry. These components have to operate in harsh environments, and under high temperatures, and they therefore have to resist corrosion, humidity, and combustion. Two glass-ceramics systems, which have Y₂Ti₂O₇ as their main crystalline phase, as well as specific and optimized properties to withstand severe operating conditions, including temperatures of 900 °C, are here proposed as joining materials. The adhesion of the glass-ceramics to the composite was found to be excellent after mechanical and thermal tests in which they were in direct contact with a 900 °C flame and thermal cycling of between 400 °C and 900 °C.     

Synthesis and characterization of LTCC compositions with middle permittivity based on CaO-B2O3-SiO2 glass/CaTiO3 system

CaTiO₃ ceramics with the addition of CaO-B₂O₃-SiO₂ (CBS) glass (45–55 wt%) composites were sintered at 830 °C, 850 °C, 875 °C and 900 °C. To illustrate influence mechanism of the different glass contents and sintering temperatures on the properties of the composites, we focused on the multiple performances of the composites by employing different qualitative and quantitative instruments. Composites with 50 wt% glass sintered at 875 °C presented fairly ideal performance: the bulk density was 3.20 g/cm³, the dielectric constant was 25.7 and the dielectric loss was 0.0009 at 7 GHz. Micro-Structure analysis of the composites showed a dense and pore-less microstructure except for few pores with size around 1 μm. In addition, the composite could meet the shrinkage requirement of Ag electrodes and could not possibly react with Ag electrodes any more. This makes them suitable for various dielectric applications at low sintering temperature.     

Carbon nanotube/graphene oxide‐added CaO‐B2O3‐SiO2 glass/Al2O3 composite as substrate for chip‐type supercapacitor

A CaO‐B₂O₃‐SiO₂ (CBS) glass/40 wt% Al₂O₃ composite sintered at 900°C exhibited a dense microstructure with a low porosity of 0.21%. This composite contained Al₂O₃ and anorthite phases, but pure glass sintered at 900°C has small quantities of wollastonite and diopside phases. This composite was measured to have a high bending strength of 323 MPa and thermal conductivity of 3.75 W/(mK). The thermal conductivity increased when the composite was annealed at 850°C after sintering at 900°C, because of the increase in the amount of the anorthite phase. 0.25 wt% graphene oxide and 0.75 wt% multi‐wall carbon nanotubes were added to the CBS/40 wt% Al₂O₃ composite to further enhance the thermal conductivity and bending strength. The specimen sintered at 900°C and subsequently annealed at 850°C exhibited a large bending strength of 420 MPa and thermal conductivity of 5.51 W/(mK), indicating that it would be a highly effective substrate for a chip‐type supercapacitor.     

Effects of Nb2O5 and Gd2O3 doping on boron volatility and activity between glass seals and lanthanum-containing cathode

In planar Solid Oxide Fuel Cells (SOFCs), the boron species volatilize from glass seals, and react with lanthanum-containing cathodes (i.e., La_0.6Sr_0.4Co_0.2Fe_0.8O_3 − δ, LSCF) to form LaBO₃ under cathodic polarization, which decomposes the perovskite structure and consequently decreases the electrochemical activity of cathode. In this study, Nb₂O₅ and Gd₂O₃ are added to an aluminoborosilicate glass to reduce the boron volatility from glass and the reaction between sealing glass and LSCF cathode. Both Nb₂O₅ and Gd₂O₃ doping increases the network connectivity, but Nb₂O₅ doping enhances the [BO₃] → [BO₄] transition and reduces the boron volatility from glass seals, thus effectively suppressing the deposition and poisoning of boron contaminants on the LSCF cathode. However, an obvious degradation of the electrocatalytic activity of LSCF occurs in the presence of Gd₂O₃-doped glass. The relationship between glass structure and glass/cathode interaction has been established to provide useful information for designing stable sealing materials for SOFC applications.     

Influence of boron substitution on the crystallisation behaviour of tetracalcium phosphate phase in the 4.5SiO2-3Al2O3-1.5P2O5-5CaO glass system

This study focuses on the effect of boron substitution on the crystallisation behaviour of an important bioceramic phase, tetracalcium phosphate (TTCP, Ca₄P₂O₉), in the 4.5SiO₂-3Al₂O₃-1.5P₂O₅-5CaO glass system. The influence of phase separation on the crystallisation activation energy as well as the microstructure is systematically analysed. The results indicate that increasing the extent of substitution of B for Al tends to lead to a decrease of the glass-transition temperature (T_g) and crystallisation temperature (T_p). When the substitution amount of B reaches 15 mol%, phase separation is observed. Weak phase separations during glass making can promote the nucleation of crystals due to heterogeneous nucleation with reduced nucleation activation energy. When 50 mol% B is substituted, serious phase separation is observed, with spherical-shaped TTCP phases appearing in the glass. The growth of striped-shaped TTCP crystals is largely suppressed even when a long holding time (1 h) at 900 °C is applied.     

Persistent luminescence of Eu/Dy-doped Sr2MgSi2O7 glass-ceramics processed by aerodynamic levitation

Glass beads of the Sr₂MgSi₂O₇ stoichiometric composition and a non-stoichiometric composition with higher SiO₂/SrO ratio doped with Eu₂O₃/Dy₂O₃ were prepared through aerodynamic levitation coupled to CO₂ laser heating. The glass beads were subsequently treated at 1100 ºC to produce glass-ceramics with Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ as the main crystalline phase. The doped glasses exhibit red emissions; after crystallisation, the corresponding glass-ceramics emit blue light under UV excitation. The starting glass composition considerably affects the crystallisation process, resulting in Sr₂MgSi₂O₇ glass-ceramics with very different microstructures which, in turn, have a significant influence on the luminescence properties. The photoluminescence emission spectra of the glass-ceramics under UV light show a broadband emission (λ = 400–500 nm) with a main peak assigned to the typical Eu²⁺ transition under excitation at 365 nm. Both the intensity of the emission and the persistence time significatively increase on decreasing temperature. Glass-ceramics from the non-stoichimetric glass composition co-doped with 1Eu₂O₃/0.5Dy₂O₃ (mol%.) provided the longest persistence times.     

The effect of Cr2O3 as a nucleating agent in iron-rich glass-ceramics

In this work, the effect of Cr₂O₃ as a nucleating agent, in iron rich glasses has been investigated by means of DTA, XRD and density measurements. By Cr₂O₃ addition, from 0·4 to 1·0 wt%, a lowering of the crystallisation peak temperature resulted in the DTA trace, the maximum effect corresponding to 0·7 wt%. By evaluating the degree of crystallisation of the glass at 0·7 wt% Cr₂O₃, the highest efficiency in the nucleation process also corresponds. The optimum values for the nucleation and crystallisation time and temperature, determined for 0·7 wt% Cr₂O₃ addition, have been 70 min at 630°C and 30  min at 800°C. The crystalline phases formed at different thermal treatment temperatures of the parent glass have been investigated by XRD; the spinel is the only phase after the nucleation; pyroxene is the major phase after the crystallisation. The results of this study have highlighted that a small percentage of Cr₂O₃ strongly affects the spinel formation thereby reducing the time and temperature of the thermal treatment and enhancing the degree of crystallisation of high iron content glasses. ©     

Self-organized nano-crystallisation of BaF2 from Na2O/K2O/BaF2/Al2O3/SiO2 glasses

In glasses with the compositions (100 ? x)(2Na₂O·16K₂O·8Al₂O₃·74SiO₂)xBaF₂ (with x = 0 to 6), the glass transition temperature decreases with increasing BaF₂-concentration. Samples with x = 6 were thermally treated at temperatures in the range from 500 to 600 °C for 5–160 h. This leads to the crystallisation of BaF₂. The quantity of crystalline BaF₂ increases with increasing time of thermal treatment, while the mean crystallite size remains constant within the limits of error. The glass transformation temperature of partially crystallised samples increases with increasing crystallisation time and approaches a value equal to the temperature, at which the samples were treated. This is explained by the formation of a highly viscous layer enriched in SiO₂ which is formed during crystallisation. This layer acts as a diffusion barrier and hinders further crystal growth.     

Tailoring the efficient laser-absorption-melting behavior of Bi2O3-B2O3-ZnO-Nd2O3 glass for the OLED encapsulation

The efficient 810 nm laser energy conversion of glass frit had been proven to be the key to the long-term hermetic encapsulation of Organic Light Emitting Display (OLED). A direct laser energy conversion laser-assisted Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ sealing glass material without extra laser absorbent such as carbon black, was designed and systematically investigated. The addition of Nd₂O₃, as glass modifiers with higher cationic field strength, could be conducive to enhancing the polymerization of glass network structure, manifesting that the glass-transition temperature Tg, onset-crystallization temperature Tc and thermal stability ΔT (ΔT = Tc-Tg) increased, while thermal expansion coefficient CTE dropped to 9.72×10⁻⁶/°C and advantageously matched with the glass substrate (8±1×10⁻⁶/°C). More importantly, the absorption rate of BBZ-Nd glass was more than 50 % between 800∼810 nm owing to the 4f-4f electron transition of Nd³⁺ ions, and yet the reflectivity and transmittance of the wavelength at 800–810 nm were lower. As optimal compositions, the addition of 3.0 wt% Nd₂O₃ in Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ glass frit with higher absorption coefficients (80 %) led to instantaneous bonding encapsulation between glass substrates without interfacial cracks or pores with the 808 nm wavelength of the laser at 20 W and 2.4 mm/s.