Dual-Cure Photopolymer Composite for 3D Printing

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Solution Overview

Problem

Existing 3D printing technologies face challenges with materials that are prone to oxidation decomposition, emit toxic gases, have poor mechanical properties, and require high costs, as well as issues with rapid solidification and residual stress due to limited light penetration and non-uniform volume shrinkage in photopolymerization processes.

Innovation Solution

A dual-cure photopolymer composite material is developed, combining a polymer matrix with microcrystalline inorganic fillers and a system of co-initiating agents for photo- and thermal-polymerization, allowing for stable single-stage 3D printing with improved adhesion, reduced anisotropy, and enhanced mechanical performance by controlling the curing process through UV and thermal initiation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Speed

If photopolymerization is used for 3D printing, then curing speed is improved, but light penetration depth is limited causing non-uniform solidification

Engineering Contradiction:
Improvecuring speedVSAvoidlight penetration depth
Core Design Contradiction:
SpeedVSVolume of moving object

Solution Approach 1:

The patent divides the curing process into two distinct stages: first photopolymerization for rapid surface curing, then thermal polymerization for complete bulk curing. This segmentation allows each method to operate in its optimal range - UV light for quick surface hardening and heat for deep penetration throughout the material volume.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent changes the activation parameter from optical (UV light) to thermal (heat) to overcome the penetration depth limitation. By using a thermal initiator that activates at elevated temperatures, the curing process can proceed uniformly throughout the bulk material regardless of light penetration constraints.

Inventive Principle:
Principle #35Parameter changes

2Productivity

If photopolymerization is used for 3D printing, then curing efficiency is improved, but volume shrinkage is non-uniform causing residual stress and warpage

Engineering Contradiction:
Improvecuring efficiencyVSAvoiddimensional accuracy
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The curing process is segmented into two phases with different shrinkage characteristics. The rapid photopolymerization phase occurs first with controlled shrinkage, followed by the thermal polymerization phase that completes curing with additional uniform shrinkage. This staged approach allows stress management and reduces overall warpage compared to single-phase curing.

Inventive Principle:
Principle #1Segmentation

Solution Approach 2:

The patent ensures continuous curing action by immediately following photopolymerization with thermal polymerization. This continuous process prevents incomplete curing that would lead to residual stresses, while the gradual transition between curing mechanisms allows for more uniform stress distribution throughout the printed structure.

Inventive Principle:
Principle #20Continuity of useful action

3Adaptability or versatility

If cement-based materials are used for 3D printing, then material availability is improved, but solidification time is too long

Engineering Contradiction:
Improvematerial availabilityVSAvoidsolidification time
Core Design Contradiction:
Adaptability or versatilityVSLoss of time

Solution Approach 1:

The patent replaces the slow chemical setting mechanism of traditional cement with a dual-cure polymerization system. The photopolymerization component provides rapid initial setting (seconds to minutes) while thermal polymerization completes the process, dramatically reducing total solidification time compared to conventional cement-based materials.

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

Solution Approach 2:

The invention uses a composite material system combining photopolymerizable resins with thermal initiators and various fillers. This composite approach integrates the rapid curing capability of photopolymers with the structural properties needed for construction applications, achieving both speed and material performance.

Inventive Principle:
Principle #40Composite materials

4Ease of manufacture

If organic materials are used for 3D printing, then printability is improved, but mechanical properties of printed structures are poor

Engineering Contradiction:
ImproveprintabilityVSAvoidmechanical properties
Core Design Contradiction:
Ease of manufactureVSStrength

Solution Approach 1:

The patent employs composite materials combining organic photopolymer matrices with inorganic fillers and reinforcement elements. This composite structure provides both the printability of organic materials and the enhanced mechanical strength of inorganic components, creating structures suitable for load-bearing applications.

Inventive Principle:
Principle #40Composite materials

Solution Approach 2:

The patent changes the material state from purely organic to a hybrid organic-inorganic system. The dual-cure mechanism transforms the material properties during printing, with photopolymerization providing rapid structure formation and thermal polymerization enhancing final mechanical properties through complete crosslinking and potential phase transformations.

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 dual-cure technique reduces deformations, increases deposition speed and thickness, and enhances mechanical strength, enabling large-scale printing with reduced material consumption and improved layer adhesion, addressing issues of material scarcity, cost, and mechanical properties in 3D printing.

Implementation Method 1

a photopolymer composite resin, which comprises a polymer matrix, inorganic fillers and a system of co-initiating agents of photo- and thermal-polymerization

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Implementation Method 2

a system of co-initiating agents of photo- and thermal-polymerization

Methodology Applied
Scientific EffectThermal polymerization:

Data Source

PatentEP4013587B13D printing of a composite material via sequential dual-curing polymerization
Publication Date: 2024.10.02 MIGHTY BUILDINGS INC
  • EP4013587B1 patent drawingFigure 1
  • EP4013587B1 patent drawingFigure 2
  • EP4013587B1 patent drawingFigure 3

AI summary

A method of printing a 3D printing a photopolymer composite material includes providing a resin premix material including an acrylate monomer or an acrylate oligomer, an inorganic hydrate, a reinforcing filler, a co-initiator, and an ultraviolet (UV) initiator. A thermal initiator is mixed with the resin premix to form a photopolymer composite resin. The photopolymer composite resin is repeatedly extruded and dual-cured by a 3D printing system to create a photopolymer composite material. The 3D printing system includes a control system, a mixing system, a feeding system in fluid communication with the mixing system, a light curing module controlled by the control system, and a printing head controlled by the control system.