SiC Refractory Blocks with Silicon Nitride Binder

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Solution Overview

Problem

Refractory blocks used in aluminum electrolysis cells face challenges such as high corrosion, oxidation, and mechanical stress due to exposure to hot molten cryolite and corrosive gases, with existing silicon carbide-based blocks being expensive and difficult to sinter, and having limited format and oxidation resistance.

Innovation Solution

Development of sintered refractory blocks based on silicon carbide with a silicon nitride binder, incorporating boron and calcium to enhance resistance to oxidation and corrosion, and a method involving a particulate mixture of silicon carbide granulate, boron, and calcium compounds, compacted, dried, and fired in a nitrogen atmosphere to form a stable nitride matrix.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If silicon carbide granulates are sintered at very high temperatures (2150°C) to improve resistance to attack, then oxidation resistance and mechanical strength are improved, but manufacturing cost becomes prohibitive and formatting is limited due to great shrinkage

Engineering Contradiction:
Improveresistance to attackVSAvoidmanufacturing cost and formatting
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent changes the sintering temperature parameter from conventional high temperatures (2150°C) to a lower range (1600-2000°C), making the process economically viable while maintaining satisfactory resistance to attack. This parameter modification resolves the contradiction between achieving high reliability and maintaining ease of manufacture.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite material system combining silicon carbide granulates with a silicon nitride binder phase. This composite approach allows the material to achieve improved oxidation resistance and mechanical strength through the synergistic combination of SiC and Si3N4 phases, while avoiding the need for extremely high sintering temperatures.

Inventive Principle:
Principle #40Composite materials

2Productivity

If block thickness is reduced to gain useful volume and facilitate heat evacuation, then productivity and energy efficiency are improved, but service life is affected due to reduced protection against corrosion and oxidation

Engineering Contradiction:
Improveheat evacuation efficiencyVSAvoidservice life
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The silicon nitride binder phase creates a composite structure that inherently provides superior oxidation resistance and mechanical strength. This allows thinner block designs to maintain adequate service life because the composite material itself is more resistant to degradation mechanisms, decoupling the relationship between thickness and service life.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent changes the material composition parameters by introducing a silicon nitride binder phase, which fundamentally alters the material's resistance properties. This enables the design of thinner blocks without compromising service life, as the new material composition provides enhanced protection against corrosion and oxidation even at reduced thickness.

Inventive Principle:
Principle #35Parameter changes

3Strength

If silicon carbide blocks are used to protect the metal envelope, then mechanical strength is improved, but oxidation resistance is insufficient compared to silicon nitride bonded materials

Engineering Contradiction:
Improvemechanical strengthVSAvoidoxidation resistance
Core Design Contradiction:
StrengthVSReliability

Solution Approach 1:

The patent creates a composite material where silicon carbide granulates are bound by a silicon nitride phase. The SiC provides mechanical strength and erosion resistance, while the Si3N4 binder phase provides superior oxidation resistance. This composite structure resolves the contradiction by combining the strengths of both materials.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent applies different material properties to different functional requirements: the SiC granulates provide mechanical strength and structural integrity, while the Si3N4 binder phase specifically addresses oxidation resistance. Each component is optimized for its local function, resolving the contradiction between strength and oxidation resistance.

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 solution provides improved resistance to oxidation and corrosion, dimensional stability, and thermal conductivity, allowing for thinner blocks with extended service life and reduced maintenance costs, suitable for high-temperature applications beyond electrolysis cells.

Implementation Method 1

Blocks are known which are obtained by reactive sintering of a mixture of silicon carbide and silicon, with nitrogen deriving from firing in a nitrogen atmosphere

Methodology Applied
Scientific EffectReactive sintering: Sintering

Implementation Method 2

firing in a nitrogen atmosphere to form a stable nitride matrix

Methodology Applied
Scientific EffectNitriding: Nitriding

Implementation Method 3

improve the compromise between oxidation resistance, mechanical strength (erosion), and thermal conductivity

Methodology Applied
Scientific EffectOxidation resistance: Oxidation

Implementation Method 4

allow sufficient heat to be evacuated to ensure temperature stabilization of the molten bath

Methodology Applied
Scientific EffectThermal conduction: Conduction (thermal)

Data Source

PatentEP2250141B2Use of a sintered refractory material based on silicon carbide with a silicon nitride binder
Publication Date: 2019.04.17 SAINT GOBAIN CENT DE RES & DEVS & DETUD EUROEN
  • EP2250141B2 patent drawingFigure 1~2
  • EP2250141B2 patent drawingFigure 3
  • EP2250141B2 patent drawing

AI summary

A sintered material based on silicon carbide (SiC) reactively sintered between 1,1000C and 1,7000C to form a silicon nitride binder (Si3N4), intended in particular for fabricating an aluminum electrolysis cell, including 0.05% to 1.5% of boron, the Si3N4/SiC weight ratio being in the range 0.05 to 0.45. Application, in particular, to an electrolysis cell.