Preceramic Resin Stereolithography for Fully Dense Ceramics

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Solution Overview

Problem

Existing additive manufacturing techniques for ceramics result in porous structures with low strength due to porosity and inhomogeneity, limiting their application in high-temperature environments and complex shapes.

Innovation Solution

A preceramic resin formulation comprising molecules with C=X and C≡X bonds, photoinitiators, thermal initiators, and 3D-printing agents is used to create fully dense ceramic structures through UV-cure-based stereolithography, followed by thermal treatment.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Shape

If powder-based additive manufacturing techniques are used to create ceramic structures, then complex shapes can be fabricated, but the resulting structures are porous and have low strength

Engineering Contradiction:
Improvecomplex shapesVSAvoidstrength
Core Design Contradiction:
ShapeVSStrength

Solution Approach 1:

The invention changes the fundamental parameter of the starting material from ceramic powder to preceramic polymer resin. This parameter change enables the material to be deposited as a dense liquid that cures to form fully dense ceramic structures, eliminating the porosity inherent in powder-based methods while maintaining the ability to fabricate complex shapes through additive manufacturing

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention introduces preceramic polymer resin as an intermediary material between the additive manufacturing process and the final ceramic structure. The resin acts as a mediator that can be precisely deposited layer-by-layer to form dense green bodies, which are then converted to fully dense ceramics through pyrolysis, avoiding the porosity problems of direct powder sintering

Inventive Principle:
Principle #24Intermediary (Mediator)

2Ease of manufacture

If sintering is used to consolidate ceramic powders, then ceramic structures can be formed, but residual porosity is unavoidable and strength is severely decreased

Engineering Contradiction:
Improveconsolidation processVSAvoidstrength
Core Design Contradiction:
Ease of manufactureVSStrength

Solution Approach 1:

The invention inverts the conventional approach by instead of starting with powder and attempting to eliminate porosity through sintering, it starts with a liquid resin that cures to form a dense green body, then uses pyrolysis to convert the organic material to dense ceramic. This inversion of the process sequence eliminates residual porosity that plagues sintered parts

Inventive Principle:
Principle #13The other way round (Inversion)

Solution Approach 2:

The invention changes the consolidation mechanism from thermal sintering of particles to photopolymerization of resin followed by pyrolytic conversion. This parameter change in the consolidation process enables full density to be achieved without the porosity that is inherent in sintering processes

Inventive Principle:
Principle #35Parameter changes

3Shape

If conventional additive manufacturing processes are used for ceramics, then layer-by-layer fabrication is achieved, but fabrication rates are slow and binder removal is time-consuming

Engineering Contradiction:
Improvelayer-by-layer fabricationVSAvoidfabrication rate
Core Design Contradiction:
ShapeVSProductivity

Solution Approach 1:

The invention enables continuous photopolymerization of the preceramic resin during the additive manufacturing process, eliminating idle time between layers. The resin is deposited and cured in continuous operation, and the pyrolysis step consolidates the entire structure simultaneously, removing the time-consuming sequential binder removal process required by conventional methods

Inventive Principle:
Principle #20Continuity of useful action

4Ease of manufacture

If ceramic materials are processed by sintering or thin film deposition, then ceramic structures can be created, but flaws such as porosity and inhomogeneity are introduced that govern strength

Engineering Contradiction:
ImproveprocessingVSAvoidstrength
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The invention changes the processing parameters from high-temperature sintering of powders to photopolymerization of resins followed by controlled pyrolysis. This parameter change enables atomic-level homogeneity in the green body that translates to uniform dense ceramic structures after pyrolysis, eliminating the porosity and inhomogeneity that govern strength in conventionally processed ceramics

Inventive Principle:
Principle #35Parameter changes

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 produces fully dense, high-strength ceramic structures with minimal porosity and uniform shrinkage, suitable for complex shapes and high-temperature environments.

Implementation Method 1

UV-cure-based stereolithography

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Implementation Method 2

thermal treatment

Methodology Applied
Scientific EffectPyrolysis: Pyrolysis

Data Source

PatentEP4026817B1Polymer-derived ceramic materials
Publication Date: 2025.10.08 HRL LAB
  • EP4026817B1 patent drawingFigure 1
  • EP4026817B1 patent drawingFigure 2
  • EP4026817B1 patent drawingFigure 3

AI summary

This disclosure enables direct 3D printing of preceramic polymers, which can be converted to fully dense ceramics. Some variations provide a preceramic resin formulation comprising a molecule with two or more C=X double bonds or C=X triple bonds, wherein X is selected from C, S, N, or O, and wherein the molecule further comprises at least one non-carbon atom selected from Si, B, Al, Ti, Zn, P, Ge, S, N, or O; a photoinitiator; a free-radical inhibitor; and a 3D-printing resolution agent. The disclosed preceramic resin formulations can be 3D-printed using stereolithography into objects with complex shape. The polymeric objects may be directly converted to fully dense ceramics with properties that approach the theoretical maximum strength of the base materials. Low-cost structures are obtained that are lightweight, strong, and stiff, but stable in the presence of a high-temperature oxidizing environment.