[n]Cycloparaphenylenes as Compatible Fluorophores for Melt Electrowriting.

Fluorescent probes are an indispensable tool in the realm of bioimaging technologies, providing valuable insights into the assessment of biomaterial integrity and structural properties. However, incorporating fluorophores into scaffolds made from melt electrowriting (MEW) poses a challenge due to the sustained, elevated temperatures that this processing technique requires. In this context, [n]cycloparaphenylenes ([n]CPPs) serve as excellent fluorophores for MEW processing with the additional benefit of customizable emissions profiles with the same excitation wavelength. Three fluorescent blends are used with distinct [n]CPPs with emission wavelengths of either 466, 494, or 533 nm, identifying 0.01 wt% as the preferred concentration. It is discovered that [n]CPPs disperse well within poly(ε-caprolactone) (PCL) and maintain their fluorescence even after a week of continuous heating at 80 °C. The [n]CPP-PCL blends show no cytotoxicity and support counterstaining with commonly used DAPI (Ex/Em: 359 nm/457 nm), rhodamine- (Ex/Em: 542/565 nm), and fluorescein-tagged (Ex/Em: 490/515 nm) phalloidin stains. Using different color [n]CPP-PCL blends, different MEW fibers are sequentially deposited into a semi-woven scaffold and onto a solution electrospun membrane composed of [8]CPP-PCL as a contrasting substrate for the [10]CPP-PCL MEW fibers. In general, [n]CPPs are potent fluorophores for MEW, providing new imaging options for this technology.

On the Stability of Electrohydrodynamic Jet Printing Using Poly(ethylene oxide) Solvent-Based Inks.

Electrohydrodynamic (EHD) jet printing of solvent-based inks or melts allows for the producing of polymeric fiber-based two- and three-dimensional structures with sub-micrometer features, with or without conductive nanoparticles or functional materials. While solvent-based inks possess great material versatility, the stability of the EHD jetting process using such inks remains a major challenge that must be overcome before this technology can be deployed beyond research laboratories. Herein, we study the parameters that affect the stability of the EHD jet printing of polyethylene oxide (PEO) patterns using solvent-based inks. To gain insights into the evolution of the printing process, we simultaneously monitor the drop size, the jet ejection point, and the jet speed, determined by superimposing a periodic electrostatic deflection. We observe printing instabilities to be associated with changes in drop size and composition and in the jet's ejection point and speed, which are related to the evaporation of the solvent and the resulting drying of the drop surface. Thus, stabilizing the printing process and, particularly, the drop size and its surface composition require minimizing or controlling the solvent evaporation rate from the drop surface by using appropriate solvents and by controlling the printing ambient. For stable printing and improved jet stability, it is essential to use polymers with a high molecular weight and select solvents that slow down the surface drying of the droplets. Additionally, adjusting the needle voltages is crucial to prevent instabilities in the jet ejection mode. Although this study primarily utilized PEO, the general trends observed are applicable to other polymers that exhibit similar interactions between solvent and polymer.

Cryo-Electrohydrodynamic Jetting of Aqueous Silk Fibroin Solutions.

The incorporation of 3D-printing principles with electrohydrodynamic (EHD) jetting provides a harmonious balance between resolution and processing speed, allowing for the creation of high-resolution centimeter-scale constructs. Typically, EHD jetting of polymer melts offers the advantage of rapid solidification, while processing polymer solutions requires solvent evaporation to transition into solid fibers, creating challenges for reliable printing. This study navigates a hybrid approach aimed at minimizing printing instabilities by combining viscous solutions and achieving rapid solidification through freezing. Our method introduces and fully describes a modified open-source 3D printer equipped with a frozen collector that operates at -35 °C. As a proof of concept, highly concentrated silk fibroin aqueous solutions are processed into stable micrometer scale jets, which rapidly solidify upon contact with the frozen collector. This results in the formation of uniform microfibers characterized by an average diameter of 27 ± 5 µm, a textured surface, and porous internal channels. The absence of instabilities and the notably fast direct writing speed of 42 mm·s-1 enable precise, fast, and reliable deposition of these fibers into porous constructs spanning several centimeters. The effectiveness of this approach is demonstrated by the consistent production of biologically relevant scaffolds that can be customized with varying pore sizes and shapes. The achieved degree of control over micrometric jet solidification and deposition dynamics represents a significant advancement in EHD jetting, particularly within the domain of aqueous polymer solutions, offering new opportunities for the development of intricate and functional biological structures.

Melt Electrowriting of Nylon-12 Microfibers with an Open-Source 3D Printer.

This study demonstrates how either a heated flat or cylindrical collector enables defect-free melt electrowriting (MEW) of complex geometries from high melting temperature polymers. The open-source "MEWron" printer uses nylon-12 filament and combined with a heated flat or cylindrical collector, produces well-defined fibers with diameters ranging from 33 ± 4 to 95 ± 3 µm. Processing parameters for stable jet formation and minimal defects based on COMSOL thermal modeling for hardware design are optimized. The balance of processing temperature and collector temperature is achieved to achieve auxetic patterns, while showing that annealing nylon-12 tubes significantly alters their mechanical properties. The samples exhibit varied pore sizes and wall thicknesses influenced by jet dynamics and fiber bridging. Tensile testing shows nylon-12 tubes are notably stronger than poly(ε-caprolactone) ones and while annealing has limited impact on tensile strength, yield, and elastic modulus, it dramatically reduces elongation. The equipment described and material used broadens MEW applications for high melting point polymers and highlights the importance of cooling dynamics for reproducible samples.

Designing Outside the Box: Unlocking the Geometric Freedom of Melt Electrowriting using Microscale Layer Shifting.

Melt electrowriting, a high-resolution additive manufacturing technology, has so far been developed with vertical stacking of fiber layers, with a printing trajectory that is constant for each layer. In this work, microscale layer shifting is introduced through deliberately offsetting the printing trajectory for each printed layer. Inaccuracies during the printing of sinusoidal walls are corrected via layer shifting, resulting in accurate control of their geometry and mechanical properties. Furthermore, more substantial layer shifting allows stacking of fiber layers in a horizontal manner, overcoming the electrostatic autofocusing effect that favors vertical layer stacking. Novel nonlinear geometries, such as overhangs, wall texturing and branching, and smooth and abrupt changes in printing trajectory are presented, demonstrating the flexibility of the layer shifting approach beyond the state-of-the-art. The practice of microscale layer shifting for melt electrowriting enables more complex geometries that promise to have a profound impact on the development of products in a broad range of applications.

Ultrafast 3D printing with submicrometer features using electrostatic jet deflection.

Additive manufacturing technologies based on layer-by-layer deposition of material ejected from a nozzle provide unmatched versatility but are limited in terms of printing speed and resolution. Electrohydrodynamic jetting uniquely allows generating submicrometer jets that can reach speeds above 1 m s-1, but such jets cannot be precisely collected by too slow mechanical stages. Here, we demonstrate that controlling the voltage applied to electrodes located around the jet, its trajectory can be continuously adjusted with lateral accelerations up to 106 m s-2. Through electrostatically deflecting the jet, 3D objects with submicrometer features can be printed by stacking nanofibers on top of each other at layer-by-layer frequencies as high as 2000 Hz. The fast jet speed and large layer-by-layer frequencies achieved translate into printing speeds up to 0.5 m s-1 in-plane and 0.4 mm s-1 in the vertical direction, three to four orders of magnitude faster than techniques providing equivalent feature sizes.