Multilayer Chromium-Nickel Coating for Zirconium Cladding Oxidation

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Solution Overview

Problem

Zirconium alloy claddings in nuclear reactors face significant oxidation challenges during accident conditions, leading to reduced mechanical properties, hydrogen release, and increased risks of rupture due to high temperatures and rapid oxidation mechanisms, which existing single-layer coatings fail to adequately address.

Innovation Solution

A multilayer material with a zirconium-based substrate coated with metallic layers composed of chromium, chromium alloys, or ternary Nb-Cr-Ti alloys, providing enhanced resistance to oxidation and hydrogen absorption, and maintaining mechanical integrity through a structured multilayer coating that limits oxidation and hydrogen uptake.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If a single-layer chromium coating is applied to zirconium alloy cladding, then resistance to low-temperature oxidation under nominal conditions is improved, but resistance to high-temperature oxidation under accident conditions remains insufficient

Engineering Contradiction:
Improveoxidation resistanceVSAvoidtemperature range coverage
Core Design Contradiction:
ReliabilityVSAdaptability or versatility

Solution Approach 1:

The coating is divided into multiple alternating layers of chromium and nickel, creating a multilayer structure that provides different protective functions at different temperature ranges, thereby resolving the contradiction between low-temperature and high-temperature oxidation resistance

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent uses a composite coating structure combining chromium and nickel layers, where chromium provides protection against low-temperature oxidation and nickel provides protection against high-temperature oxidation, achieving versatile temperature range coverage

Inventive Principle:
Principle #40Composite materials

2Object-affected harmful factors

If the cladding is exposed to high-temperature oxidation during accident conditions, then rapid deterioration occurs leading to hydrogen release and embrittlement, but existing coatings fail to provide adequate protection

Engineering Contradiction:
Improveoxidation damageVSAvoidsafety under accident conditions
Core Design Contradiction:
Object-affected harmful factorsVSReliability

Solution Approach 1:

The nickel layers are pre-applied to the cladding surface to create a protective barrier that prevents oxygen from reaching and oxidizing the zirconium alloy substrate during high-temperature accident conditions, thereby preventing hydrogen release and embrittlement before they can occur

Inventive Principle:
Principle #9Preliminary anti-action

Solution Approach 2:

The patent converts the harmful oxidation process into a beneficial protective mechanism by designing the coating to form a stable oxide layer on the nickel surface during high-temperature exposure, which actually protects the underlying zirconium alloy from further oxidation and hydrogen uptake

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Duration of action of stationary object

If oxidation thickness is limited to maintain mechanical properties, then service life is extended, but this requires effective oxidation protection that existing single-layer coatings cannot provide under accident conditions

Engineering Contradiction:
Improvecladding service lifeVSAvoidoxidation protection effectiveness
Core Design Contradiction:
Duration of action of stationary objectVSReliability

Solution Approach 1:

The multilayer coating structure segments the oxidation protection function across multiple layers, allowing the coating to maintain effectiveness over extended service periods by providing both low-temperature and high-temperature oxidation resistance, thereby extending cladding service life

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The coating is applied in advance to the cladding surface to establish a protective barrier before oxidation can occur, preventing oxygen penetration to the substrate throughout the entire service life, including during accident conditions

Inventive Principle:
Principle #10Preliminary action

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 multilayer coating significantly reduces oxidation and hydrogen absorption, maintaining mechanical strength and ductility, even under extreme conditions, thereby enhancing the safety and longevity of nuclear fuel claddings during both normal and accident scenarios.

Implementation Method 1

the zirconium alloy constituting the nuclear fuel cladding oxidizes on contact with the coolant

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 2

the proposed coating does not succeed in significantly limiting oxidation

Methodology Applied
Scientific EffectDiffusion: Diffusion

Implementation Method 3

hydrogen release; embrittlement of the cladding at high temperature, by oxidation or even, under certain conditions, hydriding of the cladding

Methodology Applied
Scientific EffectAbsorption: Absorption (physical)

Data Source

PatentEP2841264B1Multilayer material resistant to oxidation in a nuclear environment
Publication Date: 2024.01.24 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP2841264B1 patent drawingFigure 1~2
  • EP2841264B1 patent drawingFigure 3~4
  • EP2841264B1 patent drawingFigure 5

AI summary

The invention relates to a multilayer material including a zirconium substrate that is coated with a multilayer coating, the multilayer coating including metal layers consisting of identical or different materials selected from among chromium, a chromium alloy, and a ternary alloy of the Nb-Cr-Ti system. Such a material has improved resistance to oxidation in accident conditions of a nuclear reactor. The invention further relates to a multilayer coating, to a part entirely or partially consisting of the multilayer material or of the multilayer coating, as well as to the method for producing the multilayer material, e.g. a magnetron sputtering method.