Bulk Metallic Glass Corrosion Resistance via Selective Anodization

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Solution Overview

Problem

Bulk metallic glasses (BMG) suffer from reduced corrosion resistance, particularly to pitting corrosion, due to the presence of non-passivable elements like copper and nickel, which hinder the formation of a stable passivation layer during conventional anodization, leading to aesthetic and structural issues.

Innovation Solution

An electrochemical anodic treatment with selective extraction of non-passivable elements and enrichment of passivable elements like zirconium, titanium, and aluminum, applied at specific current densities to enhance corrosion resistance while preserving the substrate's aesthetic.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional anodization is applied to BMG substrates containing non-passivable elements (Cu, Ni), then the substrate undergoes surface treatment, but the current density does not significantly decrease and a stable passivation layer is not formed

Engineering Contradiction:
Improvecorrosion resistanceVSAvoidpassivation layer formation
Core Design Contradiction:
ReliabilityVSManufacturing precision

Solution Approach 1:

The patent applies a two-stage anodization process with specific parameter changes: first stage at 10-100 mA/cm² for 5-30 minutes to remove non-passivable elements, then second stage at 1-10 mA/cm² for 10-60 minutes to form the passivation layer. This parameter modification enables successful passivation that conventional single-stage anodization cannot achieve.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The first anodization stage acts as a preliminary action to selectively remove non-passivable elements (Cu, Ni) from the BMG surface before the second stage forms the passivation layer. This preliminary removal of harmful elements is essential for subsequent successful passivation.

Inventive Principle:
Principle #10Preliminary action

2Strength

If BMG substrates contain non-passivable elements (Cu, Ni), then the alloy exhibits good mechanical properties, but the corrosion resistance is reduced due to inability to form stable passivation layer

Engineering Contradiction:
Improvemechanical propertiesVSAvoidcorrosion resistance
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent creates local quality differentiation by selectively removing non-passivable elements from the surface layer while preserving the bulk alloy composition. The surface becomes enriched in passivable elements (Zr, Ti, Al) forming a protective layer, while the bulk retains the original mechanical properties from Cu and Ni content.

Inventive Principle:
Principle #3Local quality

Solution Approach 2:

The first anodization stage extracts non-passivable elements (Cu, Ni) from the BMG surface through selective dissolution. This extraction removes the corrosive elements while preserving the beneficial mechanical properties contributed by these elements in the bulk material.

Inventive Principle:
Principle #2Taking out (Extraction)

3Shape

If the surface of BMG is polished to be fine (0.02 μm SiO2 abrasive), then the surface is smooth, but copper enrichment occurs with low resistance to pitting corrosion

Engineering Contradiction:
Improvesurface smoothnessVSAvoidpitting corrosion resistance
Core Design Contradiction:
ShapeVSReliability

Solution Approach 1:

The patent converts the harmful copper enrichment that occurs during fine polishing into a benefit by subsequently using controlled anodization to selectively remove this surface copper. The harmful copper-rich surface layer is transformed into a controlled process that ultimately creates a copper-depleted, corrosion-resistant surface.

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

4Productivity

If the current density is kept high during anodization of BMG, then the treatment is efficient, but non-passivable elements dissolve selectively and prevent stable passivation layer formation

Engineering Contradiction:
Improvetreatment efficiencyVSAvoidpassivation layer stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent uses periodic action by dividing the anodization process into two distinct stages with different current densities. The first stage uses high current density (10-100 mA/cm²) for efficient removal of non-passivable elements, then the second stage uses low current density (1-10 mA/cm²) for stable passivation layer formation. This periodic variation in current density achieves both efficiency and stability.

Inventive Principle:
Principle #19Periodic 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 process significantly improves the corrosion resistance of BMG alloys by forming a stable metal oxide layer enriched in passivable elements, reducing pitting corrosion and maintaining the substrate's visual integrity.

Implementation Method 1

an electrochemical anodic treatment applying a current density of from 0.2 mA.cm-2 to 200 mA.cm-2 for a duration of from 5 seconds to 2 hours

Methodology Applied
Scientific EffectElectrochemical dissolution: Electrolysis

Implementation Method 2

conventional anodisation on Vit105, the formation of a typical passivation layer is not usually achieved

Methodology Applied
Scientific EffectAnodization: Anodising

Implementation Method 3

forming a stable metal oxide layer enriched in passivable elements

Methodology Applied
Scientific EffectOxidation: Oxidation

Data Source

PatentEP3967791A1Enhanced corrosion resistance process for bulk metallic glass substrates
Publication Date: 2022.03.16 RICHEMONT INTERNATIONAL SA
  • EP3967791A1 patent drawingFigure 1~2
  • EP3967791A1 patent drawingFigure 3~4
  • EP3967791A1 patent drawingFigure 5~6

AI summary

The invention relates to a process for enhancing corrosion resistance of a metal-based glass substrate, wherein the metal of the metal-based glass is one or more of zirconium, titanium, hafnium, aluminium, magnesium, and gold, and wherein the process comprises a step of exposing the substrate to an electrochemical anodic treatment applying a current density from 0.5 mA.cm-2 to 1000 mA.cm-2.