The exciting advancements in 3D-printing of soft materials are changing the landscape of materials development and fabrication. Among various 3D-printers that are designed for soft materials fabrication, the direct ink writing (DIW) system is particularly attractive for chemists and materials scientists due to the mild fabrication conditions, compatibility with a wide range of organic and inorganic materials, and the ease of multi-materials 3D-printing. Inks for DIW need to possess suitable viscoelastic properties to allow for smooth extrusion and be self-supportive after printing, but molecularly facilitating 3D printability to functional materials remains nontrivial. While supramolecular binding motifs have been increasingly used for 3D-printing, these inks are largely optimized empirically for DIW. Hence, this review aims to establish a clear connection between the molecular understanding of the supramolecularly bound motifs and their viscoelastic properties at bulk. Herein, extrudable (but not self-supportive) and 3D-printable (self-supportive) polymeric materials that utilize noncovalent interactions, including hydrogen bonding, host–guest inclusion, metal–ligand coordination, micro-crystallization, and van der Waals interaction, have been discussed in detail. In particular, the rheological distinctions between extrudable and 3D-printable inks have been discussed from a supramolecular design perspective. Examples shown in this review also highlight the exciting macroscale functions amplified from the molecular design. Challenges associated with the hierarchical control and characterization of supramolecularly designed DIW inks are also outlined. The perspective of utilizing supramolecular binding motifs in soft materials DIW printing has been discussed. This review serves to connect researchers across disciplines to develop innovative solutions that connect top-down 3D-printing and bottom-up supramolecular design to accelerate the development of 3D-print soft materials for a sustainable future.
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Viscoelastic and thixotropic characterization of paraffin/photopolymer composites for extrusion-based printing
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.
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- Award ID(s):
- 2103182
- NSF-PAR ID:
- 10432455
- Date Published:
- Journal Name:
- Physics of Fluids
- Volume:
- 34
- Issue:
- 9
- ISSN:
- 1070-6631
- Page Range / eLocation ID:
- 093106
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Demineralized bone matrix (DBM) has been widely used clinically for dental, craniofacial and skeletal bone repair, as an osteoinductive and osteoconductive material. 3D printing (3DP) enables the creation of bone tissue engineering scaffolds with complex geometries and porosity. Photoreactive methacryloylated gelatin nanoparticles (GNP-MAs) 3DP inks have been developed, which display gel-like behavior for high print fidelity and are capable of post-printing photocrosslinking for control of scaffold swelling and degradation. Here, novel DBM nanoparticles (DBM-NPs, ∼400 nm) were fabricated and characterized prior to incorporation in 3DP inks. The objectives of this study were to determine how these DBM-NPs would influence the printability of composite colloidal 3DP inks, assess the impact of ultraviolet (UV) crosslinking on 3DP scaffold swelling and degradation and evaluate the osteogenic potential of DBM-NP-containing composite colloidal scaffolds. The addition of methacryloylated DBM-NPs (DBM-NP-MAs) to composite colloidal inks (100:0, 95:5 and 75:25 GNP-MA:DBM-NP-MA) did not significantly impact the rheological properties associated with printability, such as viscosity and shear recovery or photocrosslinking. UV crosslinking with a UV dosage of 3 J/cm2 directly impacted the rate of 3DP scaffold swelling for all GNP-MA:DBM-NP-MA ratios with an ∼40% greater increase in scaffold area and pore area in uncrosslinked versus photocrosslinked scaffolds over 21 days in phosphate-buffered saline (PBS). Likewise, degradation (hydrolytic and enzymatic) over 21 days for all DBM-NP-MA content groups was significantly decreased, ∼45% less in PBS and collagenase-containing PBS, in UV-crosslinked versus uncrosslinked groups. The incorporation of DBM-NP-MAs into scaffolds decreased mass loss compared to GNP-MA-only scaffolds during collagenase degradation. An in vitro osteogenic study with bone marrow-derived mesenchymal stem cells demonstrated osteoconductive properties of 3DP scaffolds for the DBM-NP-MA contents examined. The creation of photoreactive DBM-NP-MAs and their application in 3DP provide a platform for the development of ECM-derived colloidal materials and tailored control of biochemical cue presentation with broad tissue engineering applications.
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Printable feedstocks that can produce lightweight, robust, and ductile structures with tunable and switchable conductivity are of considerable interest for numerous application spaces. Combining the specific properties of commodity thermoplastics with the unique electrical and redox properties of conducting polymers (CPs) presents new opportunities for the field of printed (bio)electronics. Here, we report on the direct ink write (DIW) printing of ink formulations based on polyaniline-dinonylnaphthalene sulfonic acid (PANI-DNNSA), which has been synthesized in bulk quantities (∼400 g). DNNSA imparts solubility to PANI up to 50 mg mL −1 , which allows the use of various additives to tune the rheological behavior of the inks without significantly compromising the electrical properties of the printed structures, which reach conductivities in the range of <10 −7 –10 0 S cm −1 as a function of ink formulation and post treatment used. Fumed silica (FS) and ultra-high molecular weight polystyrene (UHMW-PS) additives are leveraged to endow printability and shape retention to inks, as well as to compare the use of traditional rheological modifiers with commodity thermoplastics on CP feedstocks for tailored DIW printing. We show that the incorporation of UHMW-PS into these ink formulations is critical for obtaining high crack resistance in printed structures. This work serves as a guide for future ink designs of CPs with commodity thermoplastics and their subsequent DIW printing to yield conductive architectures and devices for various applications.more » « less
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Abstract Developing mechanically flexible composite materials with high electrical conductivity is currently hindered by the need to use high loading of conductive filler, which severely limits flexibility. Here, acoustic focusing is used to control arrangement of conductive particles in photopolymer matrices to create composites with both tunable conductivity and flexibility. Acoustophoresis patterns filler particles into highly efficient percolated networks which utilize up to 97% of the particles in the composite, whereas the inefficient stochastic networks of conventional dispersed‐fiber composites utilize
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Abstract Direct ink writing (DIW) process is a facile additive manufacturing technology to fabricate three-dimensional (3D) objects with various materials. Its versatility has attracted considerable interest in academia and industry in recent years. As such, upsurging endeavors are invested in advancing the ink flow behaviors in order to optimize the process resolution and the printing quality. However, so far, the physical phenomena during the DIW process are not revealed in detail, leaving a research gap between the physical experiments and its underlying theories. Here, we present a comprehensive analytical study of non-Newtonian ink flow behavior during the DIW process. Different syringe-nozzle geometries are modeled for the comparative case studies. By using the computational fluid dynamics (CFD) simulation method, we reveal the shear-thinning property during the ink extrusion process. Besides, we study the viscosity, shear stress, and velocity fields, and analyze the advantages and drawbacks of each syringe-nozzle model. On the basis of these investigations and analyses, we propose an improved syringe-nozzle geometry for stable extrusion and high printing quality. A set of DIW printing experiments and rheological characterizations are carried out to verify the simulation studies. The results developed in this work offer an in-depth understanding of the ink flow behavior in the DIW process, providing valuable guidelines for optimizing the physical DIW configuration toward high-resolution printing and, consequently, improving the performance of DIW-printed objects.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1063/5.0104157
