Zirconia-Toughened Glass Ceramics for Tetragonal Phase Stability

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Solution Overview

Problem

Existing transformation-toughened ZrO2 ceramics face challenges in maintaining a high fraction of the tetragonal phase due to thermal transitions during processing, which limits their fracture toughness and mechanical performance.

Innovation Solution

Development of ZrO2-toughened glass ceramics with high molar fractions of tetragonal ZrO2 and a lithium disilicate crystalline phase, optionally including additional phases for strengthening, achieved through controlled heat treatment and ion exchange processes.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Strength

If traditional ceramic processing techniques (hot pressing or sintering) are used to produce transformation-toughened ZrO2 ceramics, then the material can achieve high strength and toughness through phase transformation, but the thermal transition from tetragonal to monoclinic symmetry at about 950°C during processing causes the ZrO2 to transform to the monoclinic phase, producing a material comprising the 'transformed' monoclinic form that does not offer subsequent transformation toughening opportunity

Engineering Contradiction:
Improvefracture toughnessVSAvoidtetragonal phase stability
Core Design Contradiction:
StrengthVSStability of the object's composition

Solution Approach 1:

The patent modifies the chemical composition parameters of the glass ceramic system by incorporating specific oxide combinations (Al2O3: 0.1-10 wt%, TiO2: 0.1-10 wt%, P2O5: 0.1-10 wt%, B2O3: 0.1-10 wt%) that stabilize the tetragonal ZrO2 phase. These compositional changes lower the thermal transition temperature and prevent spontaneous transformation to monoclinic phase during processing, allowing the tetragonal phase to be maintained at lower processing temperatures where transformation toughening can subsequently occur.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite glass ceramic material comprising multiple phases including stabilized tetragonal ZrO2 crystals dispersed in a glass matrix. The glass matrix contains modified compositional elements that chemically interact with ZrO2 to stabilize the tetragonal phase, while the composite structure allows both the glass phase and ZrO2 crystals to contribute to the overall mechanical properties, achieving high fracture toughness through the combination of glass matrix toughness and ZrO2 phase transformation.

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If the ZrO2 fraction is substantially lower in glass ceramic composites compared to pure ceramic material, then the material can be processed more easily and achieve good toughness, but the fracture toughness and mechanical performance are limited by the lower ZrO2 content

Engineering Contradiction:
Improveprocessing easeVSAvoidfracture toughness
Core Design Contradiction:
Ease of manufactureVSStrength

Solution Approach 1:

The patent optimizes the ZrO2 content parameter within the glass ceramic composite to achieve a balance between processability and mechanical performance. By controlling the ZrO2 fraction and combining it with specific glass matrix compositions containing Al2O3, TiO2, P2O5, and B2O3, the patent achieves adequate toughness while maintaining ease of processing at lower temperatures compared to pure ZrO2 ceramics.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent develops a composite material where ZrO2 particles are dispersed in a specially formulated glass matrix. The glass matrix provides the bulk of the material's toughness and processability, while the ZrO2 particles contribute transformation toughening mechanisms. This composite approach allows the material to achieve good mechanical properties with lower ZrO2 content than pure ceramics, while maintaining ease of manufacture through the glass matrix's lower processing temperature requirements.

Inventive Principle:
Principle #40Composite materials

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 resulting glass ceramics exhibit enhanced fracture toughness of 1.8 to 10 MPa·m1/2 and improved mechanical properties, with the tetragonal ZrO2 phase contributing to crack deflection and toughening.

Implementation Method 1

The tetragonal ZrO2 phase transforms to the monoclinic phase under mechanical stress, which leads to toughening

Methodology Applied
Scientific EffectPhase transformation: Phase Change

Implementation Method 2

ZrO2 undergoes a thermal transition from tetragonal to monoclinic symmetry or structure at about 950°C

Methodology Applied
Scientific EffectThermal transition: Phase Change

Implementation Method 3

achieved through controlled heat treatment and ion exchange processes

Methodology Applied
Scientific EffectIon exchange: Ion Exchange

Data Source

PatentEP3475236B1Zirconia-toughened glass ceramics
Publication Date: 2025.10.08 CORNING INC
  • EP3475236B1 patent drawingFigure 1A~1B
  • EP3475236B1 patent drawingFigure 2A~2B
  • EP3475236B1 patent drawingFigure 2C~2D

AI summary

ZrO2-toughened glass ceramics having high molar fractions of tetragonal ZrO2 and fracture toughness value of greater than 1.8 MPa· m1/2. The glass ceramic may also include also contain other secondary phases, including lithium silicates, that may be beneficial for toughening or for strengthening through an ion exchange process. Additional second phases may also decrease the coefficient of thermal expansion of the glass ceramic. A method of making such glass ceramics is also provided.