Colloidal Clusters and Networks Formed by Oppositely Charged Nanoparticles with Varying Stiffnesses.

Colloidal clusters and gels are ubiquitous in science and technology. Particle softness has a strong effect on interparticle interactions; however, our understanding of the role of this factor in the formation of colloidal clusters and gels is only beginning to evolve. Here, we report the results of experimental and simulation studies of the impact of particle softness on the assembly of clusters and networks from mixtures of oppositely charged polymer nanoparticles (NPs). Experiments were performed below or above the polymer glass transition temperature, at which the interaction potential and adhesive forces between the NPs were significantly varied. Hard NPs assembled in fractal clusters that subsequently organized in a kinetically arrested colloidal gel, while soft NPs formed dense precipitating aggregates, due to the NP deformation and the decreased interparticle distance. Importantly, interactions of hard and soft NPs led to the formation of discrete precipitating NP aggregates at a relatively low volume fraction of soft NPs. A phenomenological model was developed for interactions of oppositely charged NPs with varying softnesses. The experimental results were in agreement with molecular dynamics simulations based on the model. This work provides insight on interparticle interactions before, during, and after the formation of hard-hard, hard-soft, and soft-soft contacts and has impact for numerous applications of reversible colloidal gels, including their use as inks for additive manufacturing.

Modification of Commercial 3D Fused Deposition Modeling Printer for Extrusion Printing of Hydrogels.

In this paper, we report a simple modification of a commercially available printer with fused deposition modeling (FDM) technology for the implementation of extrusion printing of hydrogels. The main difference between an FDM printer and a gel-extrusion printer is their material propulsion system, which has to deal with ether a solid rod or liquid. By application of plastic 3D printing on an FDM printer, specific details, namely, the plunger system and parts of the gel supply system, were produced and combined with a modified printer. Two types of printing of polymer hydrogels were optimized: droplet and filament modes. The rheological ranges suitable for printing for each method were indicated, and the resolution of the samples obtained and the algorithms for creating g-code via Python scripts were given. We have shown the possibility of droplet printing of microspheres with a diameter of 100 microns and a distance between spheres of 200 microns, as well as filament printing of lines with a thickness of 300-2000 microns, which is appropriate accuracy in comparison with commercial printers. This method, in addition to scientific groups, will be especially promising for educational tasks (as a practical work for engineering students or for the introduction of 3D printing into school classes) and industrial groups, as a way to implement 3D extrusion printing of composite polymer hydrogels in a time- and cost-effective way.