Titanium-Free RuO2-Ta2O5 Coating for Chlorine Evolution

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Solution Overview

Problem

Current hydrochloric acid electrolysis processes face challenges in extending the operational lifetime of valve metal components due to corrosion issues in aggressive environments, particularly in areas with limited electrolyte renewal, leading to localized passivation layer discontinuities and subsequent corrosion.

Innovation Solution

A titanium-free catalytic coating comprising a mixture of amorphous Ta2O5 and tetragonal ditetragonal dipyramidal crystalline RuO2, optionally with SnO2, is applied to valve metal substrates, enhancing stability and reducing anodic chlorine evolution overvoltage, with a weight ratio of 0.25 to 2.5 for the amorphous to crystalline phase and 0.5 to 2 for Ru to Sn, and optionally including a pre-layer of titanium and tantalum oxides for improved anchoring.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If titanium oxide is used as a film-forming component in the catalytic coating, then the coating can be formed, but the coating becomes more susceptible to chloride attack and corrosion in acidic solutions

Engineering Contradiction:
Improvecoating stabilityVSAvoidcorrosion resistance
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The invention removes titanium oxide from the catalytic coating composition entirely, replacing it with a mixture of ruthenium oxide and tantalum oxide. This extraction of the harmful component (titanium oxide) eliminates the source of corrosion susceptibility while maintaining the coating's film-forming capability and catalytic function.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The invention employs a composite coating material consisting of ruthenium oxide and tantalum oxide in specific weight ratios (3:7 to 7:3). This composite formulation combines the catalytic activity of ruthenium oxide with the corrosion resistance and film-forming properties of tantalum oxide, creating a synergistic material that outperforms titanium oxide-based coatings in aggressive acidic environments.

Inventive Principle:
Principle #40Composite materials

2Reliability

If the coating operates in areas with limited electrolyte renewal, then the valve metal is protected, but localized passivation layer discontinuities occur leading to corrosion

Engineering Contradiction:
Improveprotection continuityVSAvoidpassivation layer stability
Core Design Contradiction:
ReliabilityVSStability of the object's composition

Solution Approach 1:

The invention changes the chemical composition parameters of the coating by eliminating titanium oxide and using a controlled ratio of ruthenium oxide to tantalum oxide (3:7 to 7:3). This parameter change ensures the formation of a stable, continuous passivation layer that resists localized discontinuities even in areas with limited electrolyte renewal, thereby preventing corrosion initiation.

Inventive Principle:
Principle #35Parameter changes

3Ease of manufacture

If titanium alloy substrate is used, then cost and ease of machining are improved, but the operational lifetime is limited to 24-48 months due to corrosion

Engineering Contradiction:
Improvemanufacturing cost and machiningVSAvoidoperational lifetime
Core Design Contradiction:
Ease of manufactureVSDuration of action of stationary object

Solution Approach 1:

The invention uses a composite catalytic coating of ruthenium oxide and tantalum oxide applied to the titanium alloy substrate. This composite coating provides superior corrosion protection compared to traditional titanium oxide coatings, extending the operational lifetime of the valve metal components beyond 24-48 months while maintaining the cost-effectiveness and machinability of the titanium alloy substrate.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The invention applies a specialized catalytic coating with specific compositional qualities (ruthenium oxide and tantalum oxide in controlled ratios) to the titanium alloy substrate. This local quality enhancement at the coating level protects the substrate from corrosion without altering the substrate's inherent manufacturing advantages, thereby extending service life while maintaining ease of manufacture.

Inventive Principle:
Principle #3Local quality

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 coating significantly increases resistance to acid attack, reduces overvoltage, and extends the operational lifetime of valve metal components in hydrochloric acid electrolysis, while maintaining catalytic and conductive properties, as demonstrated by increased resistance to corrosion and prolonged operation without deactivation.

Implementation Method 1

capable of lowering the overvoltage of the anodic discharge of chlorine

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

the passivation layer directed at protecting the valve metal

Methodology Applied
Scientific EffectPassivation:

Data Source

PatentEP3175019B1Catalytic coating and method of manufacturing thereof
Publication Date: 2018.11.28 INDUSTRIE DE NORA SPA

AI summary

The invention relates to a catalytic coating of surfaces of valve metals, for example titanium, suitable for operation in highly aggressive electrolytic environments such as electrolysis cells of hydrochloric acid. The coating may be used as catalytic activation of electrodes, for example for anodic evolution of chlorine, or for protection from crevice corrosion of flanges and other elements of electrolysers subject to stagnation of liquid.