Polysilazane Fiber Curing via Moisture and Free-Radical Crosslinking

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Current methods for crosslinking polysilazane green fibers to form silicon carbide fibers are expensive, environmentally hazardous, and prone to deformation due to high energy e-beam radiation or toxic gas exposure, and often result in the formation of films instead of fibers.

Innovation Solution

A combination of moisture and thermally activated cure processes is used to crosslink polysilazane fibers, increasing the softening point temperature without melting or deforming the fibers, eliminating the need for expensive e-beam facilities and incorporating a free-radical generator to enhance crosslinking.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If high energy e-beam radiation is used to crosslink polysilazane green fibers, then the fibers become infusible and maintain dimensional integrity, but the process is prohibitively expensive due to large capital investment and takes several hours

Engineering Contradiction:
Improvedimensional integrityVSAvoidcapital investment
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent replaces the mechanical/electromagnetic e-beam radiation system with a chemical crosslinking system using moisture and free-radical generators. The moisture cure process and free-radical initiated crosslinking achieve the same infusibility and dimensional integrity without requiring expensive e-beam equipment, thereby reducing capital investment while maintaining reliability.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The patent changes the crosslinking mechanism from physical radiation to chemical reactions. By introducing moisture and free-radical generators, the crosslinking process occurs through chemical bond formation rather than electromagnetic radiation, enabling the use of conventional heating equipment instead of expensive e-beam systems.

Inventive Principle:
Principle #35Parameter changes

2Reliability

If high energy e-beam radiation is used to crosslink polysilazane green fibers, then the fibers become infusible, but the process takes several hours due to the requirement that temperature not reach melting point

Engineering Contradiction:
Improvecrosslinking effectivenessVSAvoidcuring time
Core Design Contradiction:
ReliabilityVSLoss of time

Solution Approach 1:

The patent replaces the slow e-beam radiation process with a chemical crosslinking mechanism using free-radical generators and moisture. This chemical approach enables faster crosslinking at elevated temperatures without requiring the gradual dose delivery and cooling cycles necessary for e-beam processing, thereby significantly reducing curing time while maintaining crosslinking effectiveness.

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The e-beam process requires periodic interruption for cooling, creating a lengthy cyclic process. The chemical crosslinking method eliminates this periodic action by using moisture and free-radical generators that can operate continuously at elevated temperatures, achieving complete crosslinking in a single heating cycle without repeated cooling periods.

Inventive Principle:
Principle #19Periodic action

3Ease of manufacture

If moisture is used to crosslink polysilazane green fibers, then the process is simpler and less expensive, but the cross-linked fiber has high level of oxygen

Engineering Contradiction:
Improveprocess simplicityVSAvoidchemical composition
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent merges two crosslinking mechanisms: moisture cure and free-radical generator cure. The moisture provides initial crosslinking and infusibility, while the free-radical generator provides additional crosslinking that reduces oxygen content and improves chemical composition. This combination achieves both process simplicity and compositional precision.

Inventive Principle:
Principle #5Merging (Combining)

Solution Approach 2:

The free-radical generator acts as an intermediary substance that mediates between the moisture cure process and the desired final composition. It initiates additional crosslinking reactions that modify the fiber composition, reducing oxygen content while building upon the initial moisture-induced crosslinking structure.

Inventive Principle:
Principle #24Intermediary (Mediator)

4Reliability

If toxic gases such as ammonia, BCl3 or HSiCl3 are used to crosslink green fibers, then the fibers become infusible, but the process presents environmental health and safety challenges and is expensive

Engineering Contradiction:
ImproveinfusibilityVSAvoidenvironmental hazards
Core Design Contradiction:
ReliabilityVSObject-affected harmful factors

Solution Approach 1:

The patent converts the harmful effect of moisture (which normally introduces oxygen) into a beneficial crosslinking mechanism when combined with free-radical generators. The moisture cure provides the initial crosslinking structure, and the free-radical generator enhances this while controlling oxygen content, achieving infusibility without requiring toxic gases.

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

Solution Approach 2:

The patent replaces expensive and hazardous toxic gases with inexpensive, safe moisture and free-radical generators. These alternative reagents are non-toxic, environmentally benign, and can be used in conventional equipment, eliminating the need for specialized handling infrastructure while achieving the same infusibility.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

5Ease of manufacture

If films are formed instead of fibers, then melting of polymeric structures is acceptable and even desired, but this is not conducive to forming silicon carbide fibers that must maintain shape

Engineering Contradiction:
Improveprocessing flexibilityVSAvoidfiber shape
Core Design Contradiction:
Ease of manufactureVSShape

Solution Approach 1:

The patent applies local quality by creating different properties in different parts of the material. The fiber structure maintains its shape through localized crosslinking at the molecular level, while the overall fiber geometry is preserved. This allows the polymer to have sufficient rigidity to maintain fiber shape during processing while still allowing controlled melting behavior where needed.

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

This method provides a cost-effective and safe process for producing silicon carbide fibers that maintains their shape during pyrolysis, reducing capital investment and environmental hazards while ensuring robust crosslinking and fiber integrity.

Implementation Method 1

A moisture cure step is included in this process. The inherent moisture reactivity of the polysilazane polymer is used to increase the softening point temperature (Tsf) of the fiber

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Implementation Method 2

The inherent moisture reactivity of the polysilazane polymer is used to increase the softening point temperature (Tsf) of the fiber

Methodology Applied
Scientific EffectCondensation: Condensation

Implementation Method 3

a free-radical generator to enhance crosslinking

Methodology Applied
Scientific EffectFree-radical generation:

Implementation Method 4

curing the polysilazane fiber by exposing it to a temperature above the 1 hr half-life temperature of the free radical generator

Methodology Applied
Scientific EffectThermal activation: Heating

Implementation Method 5

curing the polysilazane fiber by exposing it to a temperature above the 1 hr half-life temperature of the free radical generator

Methodology Applied
Scientific EffectThermal decomposition: Pyrolysis

Data Source

PatentEP3110773B1Method for curing of green polysilazane-based silicon carbide precursor fibers
Publication Date: 2021.03.31 GENERAL ELECTRIC CO
  • EP3110773B1 patent drawingFigure 1A~1B
  • EP3110773B1 patent drawingFigure 2A~2E
  • EP3110773B1 patent drawingFigure 3A~3E

AI summary

Disclosed herein are methods of curing silicon carbide precursor polymer fibers, such as polysilazanes, using moisture and free radical generators, such as peroxides. Also disclosed are methods of forming, curing, and using silicon carbide precursor polymers that contain alkenyl groups and free radical generators, such as peroxides.