BaTiO3 Thermistor Stabilizing Na Ions for Humidity Resistance

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Semiconductor ceramics used in PTC thermistors degrade in high-humidity environments due to alkali metal ion elution, leading to resistance value variations and reliability issues.

Innovation Solution

A lead-free semiconductor ceramic with a perovskite structure, where part of Ba is replaced with Na, Bi, Ca, and a rare-earth element having an ionic radius smaller than Na, stabilizing Na ions in the A site and suppressing precipitation at grain boundaries, thereby maintaining resistance stability in high-humidity conditions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Temperature

If Na is added to increase Curie temperature, then Curie temperature is improved, but resistance stability in high-humidity atmosphere deteriorates due to Na ion elution

Engineering Contradiction:
ImproveCurie temperatureVSAvoidresistance stability
Core Design Contradiction:
TemperatureVSReliability

Solution Approach 1:

Ca serves as an intermediary element that stabilizes Na ions in the A site through ionic radius matching and electrostatic interaction. The Ca ions create a stabilizing environment that prevents Na ion elution while maintaining the high Curie temperature effect, thus mediating between the conflicting requirements of high temperature performance and humidity resistance

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent uses a composite doping strategy combining multiple elements (Na, Bi, Ca, and rare-earth elements) in the A site of the perovskite structure. This composite approach allows Na to provide high Curie temperature while Ca and rare-earth elements work together to suppress ion elution and stabilize the crystal structure in high-humidity environments

Inventive Principle:
Principle #40Composite materials

2Adaptability or versatility

If alkali metal elements are contained to achieve PTC characteristics, then PTC performance is improved, but reliability in high-humidity atmosphere deteriorates due to ion elution and grain boundary segregation

Engineering Contradiction:
ImprovePTC characteristicsVSAvoidresistance stability
Core Design Contradiction:
Adaptability or versatilityVSReliability

Solution Approach 1:

The patent applies local quality by creating different functional zones within the A site: Na and Bi provide the necessary PTC characteristics and high Curie temperature, while Ca and rare-earth elements provide local stabilization at grain boundaries and in the bulk structure. This spatial differentiation of functions allows simultaneous achievement of PTC performance and humidity resistance

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The patent changes the ionic radius parameter by selecting Ca (1.34 Å) and rare-earth elements with specific ionic radii to match and stabilize Na ions (1.39 Å). This parameter matching prevents Na ion elution while maintaining the electrical properties necessary for PTC characteristics

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 solution ensures high reliability and suppresses resistance degradation, maintaining a percentage change in resistivity of 30% or less even after exposure to an 85% RH high-humidity atmosphere for 1000 hours, ensuring stable PTC thermistor performance.

Implementation Method 1

A barium titanate (BaTiO3)-based semiconductor ceramic generates heat through the application of a voltage

Methodology Applied
Scientific EffectJoule heating: Joule Heating

Implementation Method 2

PTC characteristics in which the resistance value rapidly increases when the temperature exceeds the Curie temperature Tc at which phase transition is caused from a tetragonal crystal to a cubic crystal

Methodology Applied
Scientific EffectPhase transition: Phase Change

Data Source

PatentEP2377837B1Semiconductor ceramic and positive temperature coefficient thermistor
Publication Date: 2018.08.08 MURATA MFG CO LTD
  • EP2377837B1 patent drawingFigure 1~2
  • EP2377837B1 patent drawingFigure 3
  • EP2377837B1 patent drawing

AI summary

A semiconductor ceramic of the present invention includes a BamTiO3-based composition, as a main component, having a perovskite structure represented by general formula AmBO3, wherein part of Ba constituting an A site is replaced with Na, Bi, Ca, and a rare-earth element having an ionic radius smaller than that of the Na; the content of the rare-earth element when the total number of moles of the elements constituting the A site is 1 mole is 0.0005 to 0.015 on a molar ratio basis; and the content of the Ca when the total number of moles of the elements constituting the A site is 1 mole is 0.05 to 0.20 (preferably 0.125 or more and 0.175 or less) on a molar ratio basis. A PTC thermistor includes a component body 1 formed of the semiconductor ceramic. Accordingly, high reliability is achieved even if an alkali metal element is contained.