Supramolecular Hydrogel Composition for Self-Supporting 3D Printing
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Solution Overview
Problem
Existing 3D printing technologies face challenges in integrating intelligent molecular systems with stimuli-responsive behavior, as self-assembled molecular systems are often too weak to be self-supportive and lack rapid self-healing properties, disrupting ordered superstructures during extrusion and limiting the control over macroscale 3D geometry.
Innovation Solution
A supramolecular polymer composition is used, comprising a solvent, a template molecule, and a reactive component that allows for co-assembly after 3D printing, forming a 3D structure with internal cavities and maintaining macrostructural form through viscoelastic properties, enabling hierarchical co-assembly to refine molecular features to the macroscale.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Adaptability or versatility
If self-assembled molecular systems are used in 3D printing, then molecular functions and stimuli-responsive behavior are achieved, but the materials are too weak to be self-supportive and lack rapid self-healing properties
Solution Approach 1:
The material system is segmented into two distinct components: self-assembled molecular systems (providing adaptability and molecular functions) and covalently crosslinked polymer networks (providing strength and self-supportive capability). This segmentation allows each component to fulfill its specific function without compromising the other.
Solution Approach 2:
The invention creates a composite material system combining self-assembled molecular systems with covalently crosslinked polymer networks. The self-assembled portion provides stimuli-responsive behavior and molecular functions, while the covalent crosslinked network provides mechanical strength and structural support, resolving the contradiction between adaptability and strength.
2Adaptability or versatility
If self-assembled molecular systems are used in 3D printing, then molecular features are achieved, but rapid self-healing properties are lost due to high kinetic barrier for reformation of superstructure
Solution Approach 1:
The material is segmented such that self-healing functionality is assigned to the self-assembled molecular component while the covalent network provides structural integrity. This segmentation enables rapid self-healing of the molecular component without being constrained by the kinetic barriers of the covalent network.
Solution Approach 2:
The self-assembled molecular systems act as an intermediary that facilitates rapid self-healing. These molecular assemblies can dynamically reorganize and heal defects quickly, mediating between the need for molecular functionality and the requirement for rapid self-healing, while the covalent network provides the stable framework.
3Productivity
If photo-crosslinking is performed during extrusion, then rapid prototyping is achieved, but control over assembled superstructures is limited due to disruption of ordered structures
Solution Approach 1:
The covalent crosslinked polymer network is formed preliminarily during the extrusion process, creating a stable framework that preserves the ordered superstructures. This preliminary action of crosslinking provides structural support that prevents disruption of the self-assembled molecular systems, allowing subsequent processing without loss of structural control.
Solution Approach 2:
The composite material system allows simultaneous achievement of rapid prototyping and manufacturing precision. The covalent crosslinked network enables rapid setting and prototyping, while the self-assembled molecular component maintains ordered superstructures and molecular features, resolving the contradiction between productivity and precision.
4Stability of the object's composition
If covalently linked polymer chains are formed, then structural stability is achieved, but molecular moieties are perturbed from assembling and dissembling cooperatively, resulting in loss of molecular features macroscopically
Solution Approach 1:
The material system is segmented into covalently crosslinked polymer chains (providing structural stability) and self-assembled molecular systems (providing molecular features). This segmentation allows the covalent network to provide stable structural support while the self-assembled component maintains its dynamic assembly and disassembly behavior, preserving molecular features at the macroscopic level.
Solution Approach 2:
The composite material combines covalently crosslinked polymer networks with self-assembled molecular systems. The covalent crosslinks provide structural stability and compositional integrity, while the self-assembled molecular component retains its ability to assemble and disassemble cooperatively, thereby maintaining molecular features macroscopically despite the presence of covalent bonds.
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 enables high-resolution 3D printing with hierarchical porous structures, dynamic fluorescence color change, and macroscopic volume expansion/contraction, overcoming limitations of conventional 3D printing techniques by allowing monomers and templates to co-assemble and self-heal post-printing, resulting in functional monoliths with enhanced properties.
Implementation Method 1
the monomer is capable of hydrogen bonding with the template molecule to form a 1D supramolecular structure
Implementation Method 2
the monomer comprises least two pendant groups capable of covalent crosslinking
Implementation Method 3
The supramolecular polymer composition has a suitable viscoelastic property which allows for 3-D printing of the hydrogel
Data Source
AI summary
The invention provides a supramolecular polymer composition capable of co-assembly to maintain a three dimensional (3-D) macrostructural form after 3-D printing, made of a solvent, a template molecule; and a reactive component. The reactive component can be at least one monomer that is capable of hydrogen bonding with the template molecule to form a 1D supramolecular structure. The template may be an amphiphilic polymer. The monomer has at least two pendant groups capable of covalent crosslinking. The invention also includes a 3-D structure formed by crosslinking a 3-D printed supramolecular polymer composition, which optionally has a mesoporous structure. Also included is a method of manufacturing a 3-D structure by delivering a supramolecular polymer composition onto a surface of a substrate to form the 3-D structure.