skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Vapor-induced phase-separation-enabled versatile direct ink writing
Abstract Versatile printing of polymers, metals, and composites always calls for simple, economic approaches. Here we present an approach to three-dimensional (3D) printing of polymeric, metallic, and composite materials at room conditions, based on the polymeric vapor-induced phase separation (VIPS) process. During VIPS 3D printing (VIPS-3DP), a dissolved polymer-based ink is deposited in an environment where nebulized non-solvent is present, inducing the low-volatility solvent to be extracted from the filament in a controllable manner due to its higher chemical affinity with the non-solvent used. The polymeric phase is hardened in situ as a result of the induced phase separation process. The low volatility of the solvent enables its reclamation after the printing process, significantly reducing its environmental footprint. We first demonstrate the use of VIPS-3DP for polymer printing, showcasing its potential in printing intricate structures. We further extend VIPS-3DP to the deposition of polymer-based metallic inks or composite powder-laden polymeric inks, which become metallic parts or composites after a thermal cycle is applied. Furthermore, spatially tunable porous structures and functionally graded parts are printed by using the printing path to set the inter-filament porosity as well as an inorganic space-holder as an intra-filament porogen.  more » « less
Award ID(s):
2315811
PAR ID:
10499623
Author(s) / Creator(s):
; ; ; ; ; ; ; ; ; ;
Publisher / Repository:
Nature Publishing Group
Date Published:
Journal Name:
Nature Communications
Volume:
15
Issue:
1
ISSN:
2041-1723
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Three-dimensional printing (3DP) of functional materials is increasingly important for advanced applications requiring objects with complex or custom geometries or prints with gradients or zones with different properties. A common 3DP technique is direct ink writing (DIW), in which printable inks are comprised of a fluid matrix filled with solid particles, the latter of which can serve a dual purpose of rheology modifiers to enable extrusion and functional fillers for performance-related properties. Although the relationship between filler loading and viscosity has been described for many polymeric systems, a thorough description of the rheological properties of three-dimensional (3D) printable composites is needed to expedite the creation of new materials. In this manuscript, the relationship between filler loading and printability is studied using model paraffin/photopolymer composite inks containing between 0 and 73 vol. % paraffin microbeads. The liquid photopolymer resin is a Newtonian fluid, and incorporating paraffin microbeads increases the ink viscosity and imparts shear-thinning behavior, viscoelasticity, and thixotropy, as established by parallel plate rheometry experiments. Using Einstein and Batchelor's work on colloidal suspension rheology, models were developed to describe the thixotropic behavior of inks, having good agreement with experimental results. Each of these properties contributes to the printability of highly filled ([Formula: see text]43 vol. % paraffin) paraffin/photopolymer composite inks. Through this work, the ability to quantify the ideal rheological properties of a DIW ink and to selectively control and predict its rheological performance will facilitate the development of 3D printed materials with tunable functionalities, thus, advancing 3DP technology beyond current capabilities. 
    more » « less
  2. Abstract 3D printing is a popular fabrication technique because of its ability to produce complex architectures. Melt‐based 3D printing is widely used for thermoplastic polymers like poly(caprolactone) (PCL), poly(lactic acid) (PLA), and poly(lactic‐co‐glycolic acid) (PLGA) because of their low processing temperatures. However, traditional melt‐based techniques require processing temperatures and pressures high enough to achieve continuous flow, limiting the type of polymer that can be printed. Solvent‐cast printing (SCP) offers an alternative approach to print a wider range of polymers. Polymers are dissolved in a volatile solvent that evaporates during deposition to produce a solid polymer filament. SCP, therefore, requires optimizing polymer concentration in the ink, print pressure, and print speed to achieve desired print fidelity. Here, capillary flow analysis shows how print pressure affects the process‐apparent viscosity of PCL, PLA, and PLGA inks. Ink viscosity is also measured using rheology, which is used to link a specific ink viscosity to a predicted set of print pressure and print speed for all three polymers. These results demonstrate how this approach can be used to accelerate optimization by significantly reducing the number of parameter combinations. This strategy can be applied to other polymers to expand the library of polymers printable with SCP. 
    more » « less
  3. Abstract Direct ink writing (DIW) using polymer‐particle composite inks is a new research area enabling a wide range of new functionalities. Despite extensive studies, there remains a need for a deeper understanding of how particle size and loading specifically influence printability, especially in the nano range. This work aims to systematically evaluate the effects of SiO2nanoparticle size (26–847 nm) and loading on printability within a polydimethylsiloxane (PDMS) matrix. For the single‐layer printing process, which is influenced by the substrate properties, a 3D printing line analysis (3D‐PLA) is developed to monitor the top and side views of printed lines. It is found that line width varies with ink composition and substrate, while the line height decreases with solvent evaporation, indicating a strong confinement effect from the substrate. For multilayer structures, dual‐layer printing analysis (DLPA) is utilized to evaluate the printability. It is shown that DLPA is independent of the substrate and can be used to compare the printabilities from different inks. Both 3D‐PLA and DLPA can be correlated to the rheological behavior of the ink through ink rheology analysis (IRA). Finally, this research defined the design space for DIW by benchmarking the minimum and maximum particle loadings for printable composite inks. 
    more » « less
  4. Additive manufacturing (AM) of polymer composites with continuous fibers could play a major role in the future of aerospace and beyond but will require printed materials to achieve new levels of reliability. This study characterized the strength distribution of selected thermoplastic matrix composites as a func- tion of printing via fused filament fabrication (FFF). Experimental and commercial composite filaments of continuous carbon or Kevlar fibers were printed with volume fraction (Vf) ranging from approximately 28 to 56 %. The strength was evaluated under uniaxial tension after specific stages of printing and Weibull statistics were applied to characterize the strength distribution. There was a significant reduction in strength of the printed material with respect to the unprinted condition, regardless of reinforcement type, fiber volume fraction or printer used. Damage introduced by feed extrusion of the filament, and fiber failures induced at material deposition were most detrimental. For carbon fiber filaments, the reduc- tion ranged from approximately 10 % for an experimental material to over 60 % for a commercial filament. There was no correlation in the strength degradation or variability with Vf. The prevention of process-related fiber damage is key to advancing AM for continuous fiber composite and application to designs intended for stress-critical applications. 
    more » « less
  5. Abstract Covalent adaptable network (CAN) polymers doped with conductive nanoparticles are an ideal candidate to create reshapeable, rehealable, and fully recyclable electronics. On the other hand, 3D printing as a deterministic manufacturing method has a significant potential to fabricate electronics with low cost and high design freedom. In this paper, we incorporate a conductive composite consisting of polyimine CAN and multi-wall carbon nanotubes into direct-ink-writing 3D printing to create polymeric sensors with outstanding reshaping, repairing, and recycling capabilities. The developed printable ink exhibits good printability, conductivity, and recyclability. The conductivity of printed polyimine composites is investigated at different temperatures and deformation strain levels. Their shape-reforming and Joule heating-induced interfacial welding effects are demonstrated and characterized. Finally, a temperature sensor is 3D printed with defined patterns of conductive pathways, which can be easily mounted onto 3D surfaces, repaired after damage, and recycled using solvents. The sensing capability of printed sensors is maintained after the repairing and recycling. Overall, the 3D printed reshapeable, rehealable, and recyclable sensors possess complex geometry and extend service life, which assist in the development of polymer-based electronics toward broad and sustainable applications. 
    more » « less