Recycling of Load-Bearing 3D Printable Double Network Granular Hydrogels

Sustainable materials, such as recyclable polymers, become increasingly important as they are often environmentally friendlier than their one-time-use counterparts. In parallel, the trend toward more customized products demands for fast prototyping methods which allow processing materials into 3D objects that are often only used for a limited amount of time yet, that must be mechanically sufficiently robust to bear significant loads. Soft materials that satisfy the two rather contradictory needs remain to be shown. Here, the authors introduce a material that simultaneously fulfills both requirements, a 3D printable, recyclable double network granular hydrogel (rDNGH). This hydrogel is composed of poly(2-acrylamido-2-methylpropane sulfonic acid) microparticles that are covalently crosslinked through a disulfide-based percolating network. The possibility to independently degrade the percolating network, with no harm to the primary network contained within the microgels, renders the recovery of the microgels efficient. As a result, the recycled material pertains a stiffness and toughness that are similar to those of the pristine material. Importantly, this process can be extended to the fabrication of recyclable hard plastics made of, for example, dried rDNGHs. The authors envision this approach to serve as foundation for a paradigm shift in the design of new sustainable soft materials and plastics.

Mechanical Reinforcement of Hydrogels through Physical Crosslinks and Double Network Granular Architecture

Alvaro Lino Boris Charlet

Throughout nature, organisms fabricate a myriad of materials to sustain their lifestyle. Many of the soft materials are composed of water-swollen networks of organic molecules, so-called hydrogels. They generally contribute to the mechanical integrity of the organism, and act as scaffolds for living cells. The ability to fabricate synthetic hydrogels that mimic their natural counterparts would greatly benefit the biomedical field. In particular, synthetic hydrogels have the potential to revolutionize tissue engineering and to enable the fabrication of functional load-bearing soft implants. However, available hydrogels suffer from poor mechanical properties, as they are either too brittle or too soft. While great effort in the field of soft matter has been devoted to the development of hydrogels with improved mechanical properties, they are often not compatible with state-of-the art manufacturing techniques such as additive manufacturing.In this thesis, I present the mechanical reinforcement of hydrogels using two distinctive strategies, and demonstrate their potential as 3D printable materials. I first investigate the use of high functionality crosslinks in metal-coordinated hydrogels. I show that this crosslinking strategy greatly improves the solid-like mechanical properties of viscoelastic gels. I then present the use of hydrogel microparticles to fabricate double network granular hydrogels. I discovered that these materials exhibit an extraordinarily high strength and toughness. Furthermore, the jammed microparticle precursor ink enables the extrusion and 3D printing of this material. This allows the fabrication of hydrogels with locally varying compositions, which can be utilized for example to design stimuli responsive materials. I leverage the granular structure to design recyclable double network granular hydrogels. This is achieved by forming a percolating network that has reversible covalent bonds. I show that this method can be extended to the fabrication of degradable hard plastics. Finally, I conclude by presenting the key findings, and I present a few possible follow-up ideas to further develop the field of load-bearing hydrogels.

EPFL2022

Mechanical Reinforcement of Hydrogels through Physical Crosslinks and Double Network Granular Architecture

Alvaro Lino Boris Charlet

EPFL2022