Refractory Alloy Coating with Ternary Barrier Against Oxidation

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Solution Overview

Problem

Refractory alloy parts, such as molybdenum and TZM alloys, undergo significant oxidation and inter-diffusion issues during high-temperature manufacturing processes, leading to degradation of mechanical properties and performance in turbomachine blades.

Innovation Solution

A protective coating method using a treatment composition with a high mass proportion of active filler (40-66%) and a filler-to-polymer ratio ≥2, forming a continuous ternary alloy layer between the refractory alloy and ceramic layer, which reacts with the substrate to form a passivating oxide layer.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If refractory alloy parts are used without protective coating, then manufacturing process is simple, but oxidation occurs at high temperature leading to mass loss and mechanical property degradation

Engineering Contradiction:
Improvecoating process complexityVSAvoidoxidation resistance
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The refractory alloy part is pre-coated with a preceramic polymer composition containing active filler before the high-temperature consolidation process. This preliminary coating action creates a protective layer that prevents oxidation during subsequent thermal processing, allowing the part to maintain its mechanical properties without requiring complex post-processing or protective atmospheres.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

A preceramic polymer composition acts as an intermediary protective layer between the refractory alloy part and the oxidizing atmosphere. This intermediate coating transforms into a ceramic layer at high temperature, providing oxidation protection while the active filler within the composition reacts with the alloy surface to form a stable ternary alloy layer that further enhances protection.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of operation

If conventional low filler proportion coating is used, then coating application is easy, but discontinuous alloy layer forms providing insufficient protection

Engineering Contradiction:
Improvecoating application easeVSAvoidprotective layer continuity
Core Design Contradiction:
Ease of operationVSManufacturing precision

Solution Approach 1:

The mass proportion of active filler in the preceramic polymer composition is increased to at least 40%, and the active filler to preceramic polymer mass ratio is set to at least 2. This parameter change ensures sufficient active filler is available to react with the refractory alloy surface and form a continuous ternary alloy layer, transforming the coating from potentially discontinuous to continuously protective.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The coating composition is formulated as a composite material combining preceramic polymer with high proportion of active filler (such as silicon, aluminum, or boron). This composite structure ensures that upon heating, both the ceramic layer from polymer conversion and the continuous ternary alloy layer from filler-reaction are formed, providing redundant protective mechanisms.

Inventive Principle:
Principle #40Composite materials

3Temperature

If high temperature heat treatment is applied to convert polymer to ceramic, then protective ceramic layer is formed, but oxidation and inter-diffusion occur during the process

Engineering Contradiction:
Improveceramization temperatureVSAvoidoxidation and inter-diffusion
Core Design Contradiction:
TemperatureVSObject-affected harmful factors

Solution Approach 1:

The active filler in the preceramic polymer composition is specifically selected and proportioned to react with the refractory alloy surface before and during the ceramization process, forming a stable ternary alloy layer that acts as a diffusion barrier. This preliminary protective action prevents oxidation and inter-diffusion from occurring during the high-temperature heat treatment, even though the polymer is being converted to ceramic.

Inventive Principle:
Principle #9Preliminary anti-action

Solution Approach 2:

The high-temperature heat treatment that could potentially cause oxidation and inter-diffusion is transformed into a beneficial process by the presence of active filler. The filler reacts with the alloy surface at these elevated temperatures to form a protective ternary alloy layer, converting the harmful high-temperature exposure into a beneficial surface treatment that enhances protection rather than degrading it.

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

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 method effectively protects refractory alloy parts from oxidation and corrosion, enhancing their lifespan and mechanical properties by forming a continuous, thermally stable alloy layer that prevents oxidation and diffusion.

Implementation Method 1

heat treatment making it possible to at least partially convert the preceramic polymer to form a ceramic layer

Methodology Applied
Scientific EffectPyrolysis: Pyrolysis

Implementation Method 2

said active filler being chosen to form by solid or liquid diffusion, on the surface of said refractory alloy part, at least one ternary minimum alloy resulting from the co-reactivity of this active filler with the refractory alloy part

Methodology Applied
Scientific EffectDiffusion: Diffusion

Implementation Method 3

this ternary minimum alloy forming a continuous layer between the surface of said refractory alloy part and the ceramic layer obtained by conversion which protects said refractory alloy part from oxidation

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentEP4347153B1Method for coating a refractory alloy part, and the part thus coated
Publication Date: 2025.07.02 SAFRAN SA
  • EP4347153B1 patent drawingFigure 1~2
  • EP4347153B1 patent drawingFigure 3~4
  • EP4347153B1 patent drawingFigure 5~6

AI summary

The present invention relates to a method for coating a refractory alloy part (1), in particular based on molybdenum, and to the resulting part. The method comprises the coating of at least one zone of said part (1), using a treatment composition (2) comprising at least one type of preceramic polymer, a solvent and at least one active filler and heat treatment of the coated part (1) in order to at least partially convert the preceramic polymer to a ceramic layer (4). This method is noteworthy in that said treatment composition comprises, relative to its total weight, a weight proportion of between 40% and 66% of at least one active filler, in that the active filler/preceramic polymer weight ratio is greater than or equal to 2, in that said active filler is chosen to form, by solid or liquid diffusion, on the surface of said part (1), at least one continuous layer (3) of an at least ternary alloy resulting from the co-reactivity of this active filler with the refractory alloy part and the preceramic polymer and in that the heat treatment is carried out so as to form this continuous layer (3) of at least ternary alloy.