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We present a novel additive manufacturing method for NiTi-Nb micro-trusses combining (i) extrusion-based 3D-printing of liquid inks containing NiTi and Nb powders, solvents, and a polymer binder into micro-trusses with 0/90° ABAB layers of parallel, ∼600 µm struts spaced 1 mm apart and (ii) subsequent heat-treatment to remove the binder and solvents, and then bond the NiTi powders using liquid phase sintering via the formation of a transient NiTi-Nb eutectic phase. We investigate the effects of Nb concentration (0, 1.5, 3.1, 6.7 at.% Nb) on the porosity, microstructure, and phase transformations of the printed NiTi-Nb micro-trusses. Micro-trusses with the highest Nb content exhibit long channels (from 3D-printing) and struts with smaller interconnected porosity (from partial sintering), resulting in overall porosities of ∼75% and low compressive stiffnesses of 1-1.6 GPa, similar to those of trabecular bone and in agreement with analytical and finite element modeling predictions. Diffusion of Nb into the NiTi particles from the bond regions results in a Ni-rich composition as the Nb replaces Ti atoms, leading to decreased martensite/austenite transformation temperatures. Adult human mesenchymal stem cells seeded on these micro-trusses showed excellent viability, proliferation, and extracellular matrix deposition over 14 days in culture., Statement of Significance: Near-equiatomic NiTi micro-trusses are attractive for biomedical applications such as stents, actuators, and bone implants because of their combination of biocompatibility, low compressive stiffness, high surface area, and shape-memory or superelasticity. Extrusion-based 3D-printing of NiTi powder-based inks into micro-trusses is feasible, but the subsequent sintering of the powders into dense struts is unachievable due to low diffusivity, large particle size, and low packing density of the NiTi powders. We present a solution, whereby Nb powders are added to the NiTi inks, thus forming during sintering a eutectic NiTi-Nb liquid phase which bonds the solid NiTi powders and improves densification of the struts. This study investigates the microstructure, porosity, phase transformation behavior, compressive stiffness, and cytocompatibility of these printed NiTi-Nb micro-trusses., (Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

We introduce a new process that enables the ability to 3D-print high porosity materials and structures by combining the newly introduced 3D-Painting process with traditional salt-leaching. The synthesis and resulting properties of three 3D-printable inks comprised of varying volume ratios (25:75, 50:50, 70:30) of CuSO 4 salt and polylactide-co-glycolide (PLGA), as well as their as-printed and salt-leached counterparts, are discussed. The resulting materials are comprised entirely of PLGA (F-PLGA), but exhibit porosities proportional to the original CuSO 4 content. The three distinct F-PLGA materials exhibit average porosities of 66.6-94.4%, elastic moduli of 112.6-2.7 MPa, and absorbency of 195.7-742.2%. Studies with adult human mesenchymal stem cells (hMSCs) demonstrated that elevated porosity substantially promotes cell adhesion, viability, and proliferation. F-PLGA can also act as carriers for weak, naturally or synthetically-derived hydrogels. Finally, we show that this process can be extended to other materials including graphene, metals, and ceramics., Statement of Significance: Porosity plays an essential role in the performance and function of biomaterials, tissue engineering, and clinical medicine. For the same material chemistry, the level of porosity can dictate if it is cell, tissue, or organ friendly; with low porosity materials being far less favorable than high porosity materials. Despite its importance, it has been difficult to create three-dimensionally printed structures that are comprised of materials that have extremely high levels of internal porosity yet are surgically friendly (able to handle and utilize during surgical operations). In this work, we extend a new materials-centric approach to 3D-printing, 3D-Painting, to 3D-printing structures made almost entirely out of water-soluble salt. The structures are then washed in a specific way that not only extracts the salt but causes the structures to increase in size. With the salt removed, the resulting medical polymer structures are almost entirely porous and contain very little solid material, but the maintain their 3D-printed form and are highly compatible with adult human stem cells, are mechanically robust enough to use in surgical manipulations, and can be filled with and act as carriers for biologically active liquids and gels. We can also extend this process to three-dimensionally printing other porous materials, such as graphene, metals, and even ceramics., (Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

With the emergence of three-dimensional (3D)-printing (3DP) as a vital tool in tissue engineering and medicine, there is an ever growing need to develop new biomaterials that can be 3D-printed and also emulate the compositional, structural, and functional complexities of human tissues and organs. In this work, we probe the 3D-printable biomaterials spectrum by combining two recently established functional 3D-printable particle-laden biomaterial inks: one that contains hydroxyapatite microspheres (hyperelastic bone, HB) and another that contains graphene nanoflakes (3D-graphene, 3DG). We demonstrate that not only can these distinct, osteogenic, and neurogenic inks be co-3D-printed to create complex, multimaterial constructs, but that composite inks of HB and 3DG can also be synthesized. Specifically, the printability, microstructural, mechanical, electrical, and biological properties of a hybrid material comprised of 1:1 HA:graphene by volume is investigated. The resulting HB-3DG hybrid exhibits mixed characteristics of the two distinct systems, while maintaining 3D-printability, electrical conductivity, and flexibility. In vitro assessment of HB-3DG using mesenchymal stem cells demonstrates the hybrid material supports cell viability and proliferation, as well as significantly upregulates both osteogenic and neurogenic gene expression over 14 days. This work ultimately demonstrates a significant step forward towards being able to 3D-print graded, multicompositional, and multifunctional constructs from hybrid inks for complex composite tissue engineering. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 105A: 274-283, 2017., (© 2016 Wiley Periodicals, Inc.)