Ceramic Nanoparticle Transfer to Organic Slurry for Two-Photon Printing

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Solution Overview

Problem

Existing methods for two-photon polymerization of ceramic components face challenges with ceramic particle sizes below 150 nm, as they agglomerate in aqueous suspensions, leading to low viscosity, rapid drying, and poor resolution due to high vapor pressure, resulting in distortions and inhomogeneities.

Innovation Solution

Transfer ceramic nanoparticles from an aqueous medium to an organic medium with low vapor pressure, such as polyethylene glycol diacrylate (PEG-DA), using isopropanol dilution and concentration to create a stable, high-viscosity slurry suitable for two-photon polymerization.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If ceramic nanoparticles are suspended in aqueous medium for two-photon polymerization, then particle size can be kept below 150 nm, but the slurry viscosity is too low causing diffusion of photoactive monomers and loss of spatial resolution

Engineering Contradiction:
Improvespatial resolutionVSAvoidslurry viscosity
Core Design Contradiction:
Manufacturing precisionVSStability of the object's composition

Solution Approach 1:

The patent changes the solvent parameter from aqueous to organic medium, which fundamentally alters the slurry's viscosity characteristics. The organic solvent creates a more viscous environment that restricts monomer diffusion while maintaining nanoparticle stability and preventing agglomeration, thus resolving the contradiction between spatial resolution and slurry stability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite slurry system combining ceramic nanoparticles with organic photoactive monomers. This composite formulation achieves optimal viscosity by integrating the nanoparticle suspension with the organic medium, enabling both high spatial resolution through restricted diffusion and stable composition through improved slurry rheology

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If high particle load of more than 60 wt.% is achieved in aqueous environment, then ceramic content is sufficient for minimal shrinkage, but the slurry dries out quickly due to high vapor pressure of water

Engineering Contradiction:
Improveceramic particle loadVSAvoidslurry stability
Core Design Contradiction:
Quantity of substanceVSDuration of action of stationary object

Solution Approach 1:

The patent changes the fundamental parameter of the suspension medium from water to organic solvent. This parameter change dramatically reduces the vapor pressure of the slurry, preventing rapid evaporation and drying out. The organic medium maintains high ceramic particle load (60 wt.% or more) while providing long-term stability and preventing agglomeration during storage and processing

Inventive Principle:
Principle #35Parameter changes

3Illumination intensity

If ceramic particles are limited to approximately 150 nm maximum size for beam guidance, then transparency for two-photon polymerization is achieved, but the slurry viscosity is too low to achieve high spatial resolution on sub-micrometer scale

Engineering Contradiction:
Improvebeam guidance transparencyVSAvoidspatial resolution
Core Design Contradiction:
Illumination intensityVSManufacturing precision

Solution Approach 1:

The patent changes the medium parameter from aqueous to organic solvent, which increases the slurry viscosity without affecting the optical transparency. The organic medium provides sufficient viscosity to prevent monomer diffusion and maintain spatial resolution on sub-micrometer scale, while the nanoparticle size remains below 150 nm to ensure beam guidance transparency for two-photon polymerization

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

Achieves high particle loads of up to 80% by weight, enabling precise micrometer-scale structuring with reduced shrinkage and distortion, suitable for additive manufacturing of ceramic components with improved resolution and stability.

Implementation Method 1

the organic binder acts as the dispersion medium for the nanoparticles from the first liquid

Methodology Applied
Scientific EffectDispersion: Dispersion (of waves)

Implementation Method 2

By means of laser-induced two- or multi-photon absorption, a polymer network can be generated in a working volume in a location-selective manner

Methodology Applied
Scientific EffectPhotopolymerization: Photopolymerisation

Implementation Method 3

By means of laser-induced two- or multi-photon absorption, a polymer network can be generated in a working volume in a location-selective manner

Methodology Applied
Scientific EffectTwo-photon absorption:

Implementation Method 4

transferred into an organic medium which has a lower vapor pressure, is photocrosslinkable, and has a suitable viscosity to improve the production

Methodology Applied
Scientific EffectVapor pressure: Vapour Pressure

Data Source

PatentEP4001240B1Method for transferring suspended ceramic nanoparticles from an aqueous medium to an organic photocrosslinkable medium for obtaining a transparent ceramic slip with a defined nanoparticle size
Publication Date: 2025.08.20 BUNDESREPUBLIK DEUT VERTRETEN DURCH DEN BUNDESMINIST FUR WIRTSCHAFT & ENERGIE
  • EP4001240B1 patent drawingFigure 1~2
  • EP4001240B1 patent drawingFigure 3

AI summary

Sludge preparation process for the optically induced formation of a ceramic green body comprising: - Diluting an aqueous suspension of ceramic nanoparticles with iso-propanol to obtain a first liquid comprising dispersed ceramic nanoparticles; - Mixing the first liquid comprising dispersed ceramic nanoparticles with a second liquid, the second liquid comprising predominantly organic monomer, polymer, multiphoton polymerization initiator and organic crosslinker dissolved in iso-propanol to obtain an initial volume;- Concentration of the initial volume of the mixture of the first and second liquids by heating, stirring, and optionally subjecting the heated and stirred mixture to a reduced pressure relative to ambient pressure and/or a temperature increase relative to an initial temperature of the mixture, wherein the concentration of the initial volume is carried out down to a final volume, and the final volume is characterized by the produced slurry comprising ceramic nanoparticles, wherein the solid fraction of the ceramic nanoparticles in the final volume of the slurry is 50 to 95 wt%, preferably 60 to 90 wt%, more preferably 65 to 80 wt%.