Lead-Free Piezoelectric Ceramic Stabilization

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Solution Overview

Problem

Lead-free piezoelectric ceramic compositions face challenges with poor sinterability, moisture resistance, and abrupt property changes within the temperature range of -50°C to +150°C, limiting their practicality and performance compared to conventional lead-containing materials.

Innovation Solution

A lead-free piezoelectric ceramic composition comprising a first alkali niobate/tantalate type perovskite oxide and a second A-Ti-B-O composite oxide, with specific compositional formulas and ratios, which stabilizes the structure and enhances sinterability and insulating properties, preventing abrupt property changes across the desired temperature range.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Object-affected harmful factors

If lead-free piezoelectric ceramic composition (ANbO3) is used to eliminate lead, then environmental safety is improved, but sinterability and moisture resistance deteriorate

Engineering Contradiction:
Improvelead contentVSAvoidsinterability and moisture resistance
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The invention uses a composite material system consisting of KNN perovskite phase combined with K2SiF6 secondary phase. This composite structure allows the main KNN phase to provide piezoelectric functionality while the K2SiF6 phase acts as a stabilizing component that improves sinterability and moisture resistance without compromising the lead-free environmental benefit

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention optimizes specific compositional parameters including the ratio of K to Na in the A-site, the presence of Li and Ca dopants, and the controlled formation of the secondary K2SiF6 phase. These parameter adjustments transform the originally poor sinterability of pure KNN into excellent sinterability while maintaining lead-free composition

Inventive Principle:
Principle #35Parameter changes

2Reliability

If composition is optimized for high piezoelectric constant, then piezoelectric properties are improved, but phase transition point appears causing abrupt property changes

Engineering Contradiction:
Improvepiezoelectric constantVSAvoidproperty stability across temperature range
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The invention changes the compositional parameters by forming a composite system where the secondary K2SiF6 phase acts as a structural stabilizer. This phase suppresses the rhombohedral-to-tetragonal phase transition that occurs in pure KNN, thereby eliminating abrupt property changes while maintaining high piezoelectric constant through optimized KNN phase composition

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The composite structure of KNN perovskite phase with K2SiF6 secondary phase creates a synergistic effect where the K2SiF6 phase acts as a pinning phase that suppresses harmful phase transitions. This allows the KNN phase to maintain its high piezoelectric constant across the temperature range from -50°C to +150°C without abrupt changes

Inventive Principle:
Principle #40Composite materials

3Reliability

If lead-containing PZT materials are used, then piezoelectric properties are improved, but environmental safety deteriorates

Engineering Contradiction:
Improvepiezoelectric propertiesVSAvoidenvironmental safety
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention replaces the lead-containing PZT system with a lead-free KNN-based system that uses abundant, non-toxic elements (K, Na, Nb, Li, Ca). Although KNN alone has inferior properties, the composite approach with K2SiF6 phase creates a sustainable, environmentally friendly alternative that achieves comparable performance without the environmental burden of lead

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The invention changes the fundamental compositional parameters from Pb-based chemistry to alkali metal-based chemistry. By optimizing the K/Na ratio, adding Li and Ca dopants, and controlling the formation of K2SiF6 phase, the invention achieves piezoelectric properties comparable to PZT while completely eliminating lead content for environmental safety

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 composition achieves good piezoelectric properties without abrupt changes between -50°C and +150°C, offering improved sinterability and insulating properties, and can be produced at a low cost with high heat resistance and a higher Curie temperature.

Implementation Method 1

a first crystal phase of alkali niobate/tantalate type perovskite oxide having piezoelectric properties

Methodology Applied
Scientific EffectPiezoelectric effect: Piezoelectric Effect

Data Source

PatentEP2530060B1Lead-free piezoelectric ceramic composition
Publication Date: 2015.04.15 NITERRA CO LTD
  • EP2530060B1 patent drawingFigure 1~2
  • EP2530060B1 patent drawingFigure 3A
  • EP2530060B1 patent drawingFigure 3B~3C

AI summary

[Object] To provide a lead-free piezoelectric ceramic composition having good piezoelectric properties without abrupt properties changes between -50°C and +150°C. [Solution] A lead-free piezoelectric ceramic composition includes a first crystal phase of alkali niobate/tantalate type perovskite oxide having piezoelectric properties and a second crystal phase of A-Ti-B-O composite oxide (where the element A is an alkali metal; the element B is at least one ofNb and Ta; and the contents of the element A, the element B and Ti are not zero). Examples of the second crystal phase are those represented by A1-xTi1-xB1+xO5. It is preferable that x satisfies 0 ≤ x ≤ 0.15.