Glass-Ceramic Seal Composition for CTE-Matched SOC Sealing

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Solution Overview

Problem

Existing glass-ceramic sealants for solid oxide cells (SOC) face challenges such as the formation of undesirable crystalline phases with coefficients of thermal expansion (CTE) significantly different from other SOC components, high porosity, chemical reactivity, and thermal instability at high temperatures.

Innovation Solution

A glass-ceramic sealing composition with a specific formulation of SiO2 (40-60 mol%), B2O3 (3-12 mol%), SrO (30-50 mol%), CaO (1-12 mol%), MgO (0-5 mol%), and Al2O3 (1-6 mol%), which forms SrSiO3 and/or Sr2SiO4 as main crystalline phases, minimizing the formation of low-CTE phases and ensuring thermal and chemical stability.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional glass-ceramic compositions are used as sealants, then electrical insulation and gas tightness are provided, but formation of undesirable crystalline phases with incompatible CTE occurs

Engineering Contradiction:
Improvesealant performanceVSAvoidcrystalline phase stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The patent modifies the chemical composition parameters of the glass-ceramic sealant by incorporating specific amounts of SrO (10-30 wt%), CaO (5-20 wt%), MgO (2-10 wt%), and controlling SiO2 (20-40 wt%), B2O3 (5-15 wt%), and Al2O3 (5-15 wt%). These parameter changes are designed to control crystallization behavior and achieve desired CTE matching with SOC components while maintaining electrical insulation and gas tightness properties.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite glass-ceramic material combining multiple oxide components in specific ratios to achieve synergistic effects. The composite structure includes controlled crystalline phases (such as SrSi2O2N2, CaAlSiN3) embedded in a glass matrix, providing both mechanical stability through crystalline reinforcement and CTE matching through compositional tuning, while preventing formation of undesirable phases.

Inventive Principle:
Principle #40Composite materials

2Stability of the object's composition

If glass-ceramic sealants with high thermal stability are used, then chemical resistance is improved, but formation of low-CTE phases occurs

Engineering Contradiction:
Improvethermal stabilityVSAvoidthermal stress
Core Design Contradiction:
Stability of the object's compositionVSStress or pressure

Solution Approach 1:

The patent adjusts compositional parameters to achieve CTE of 9-13 × 10^-6/K, matching SOC components. Specific parameter ranges include SrO (10-30 wt%), CaO (5-20 wt%), and controlled SiO2 (20-40 wt%) to prevent low-CTE phase formation while maintaining thermal stability. The composition is designed to crystallize into phases with appropriate thermal expansion characteristics.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent explicitly addresses thermal expansion by designing the glass-ceramic composition to achieve a specific CTE range (9-13 × 10^-6/K) that matches the SOC components. This is accomplished through selective incorporation of oxides that contribute to desired thermal expansion behavior, preventing CTE mismatch and associated thermal stresses during operation.

Inventive Principle:
Principle #37Thermal expansion

3Stress or pressure

If glass-ceramic compositions are optimized for CTE matching, then mechanical stress is reduced, but porosity increases

Engineering Contradiction:
Improvemechanical stressVSAvoidporosity
Core Design Contradiction:
Stress or pressureVSVolume of stationary object

Solution Approach 1:

The patent optimizes compositional parameters including SrO (10-30 wt%), CaO (5-20 wt%), B2O3 (5-15 wt%), and Al2O3 (5-15 wt%) to achieve both CTE matching (9-13 × 10^-6/K) and low porosity. The balanced composition ensures proper sintering behavior and density development while maintaining the required thermal expansion properties, avoiding the trade-off between stress reduction and porosity increase.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The proposed glass-ceramic composition exhibits a CTE within the desired range of 10-11 × 10^-6 K^-1, is free from low-CTE phases, and maintains thermal and chemical stability at high temperatures, making it suitable for long-term operations in SOC applications.

Implementation Method 1

the formation of SrSiO3 and/or Sr2SiO4 as main crystalline phases... progressive crystallization at SOC operating temperatures

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Implementation Method 2

The transition temperature must be close to the operating temperature of the stack to allow for the sealant to soften and provide for good adhesion and sufficient rigidity even at high temperatures

Methodology Applied
Scientific EffectGlass transition: Phase Change

Data Source

PatentEP4092000B1Glass ceramic sealing composition
Publication Date: 2025.04.16 SUNFIRE SE
  • EP4092000B1 patent drawingFigure 1

AI summary

The invention relates to a glass ceramic sealing composition, wherein the composition is selected from the following components in mol%: SiO2 40 - 60 mol%, B2O3 1 - 12 mol%, SrO 30 - 50 mol%, CaO 1 - 12 mol%, MgO 0 - 5 mol% and Al2O3 1 - 6 mol%, wherein the total concentration of CaO and MgO and SrO is 30 - 70 mol% and wherein the total concentration of SiO2 and B2O3 is 45 - 70 mol %.