A single additive, a grafted copolymer, is designed to ensure the stability of suspensions of highly loaded iron oxide nanoparticles (IOPs) and to facilitate three-dimensional (3D) printing of these suspensions in the filament form. This poly (ethylene glycol)-grafted copolymer of N-[3(dimethylamino)propyl]methacrylamide and acrylic acid harnesses both electrostatic and steric repulsion to realize an optimum formulation for 3D printing. When used at 1.15 wt % (by the weight of IOPs), the suspension attains ∼81 wt % solid loading-96% of the theoretical limit as calculated by the Krieger-Dougherty equation. Rectangular, thick-walled toroidal, and thin-walled toroidal magnetic cores and a porous lattice structure are fabricated to demonstrate the utilization of this suspension as an ink for 3D printing. The electrical and magnetic properties of the magnetic cores are characterized through impedance spectroscopy (IS) and vibrating sample magnetometry (VSM), respectively. The IS indicates the possibility of utilizing wire-wound 3D printed cores as the inductive coils. The VSM verifies that the magnetic properties of IOPs before and after the ink formulation are kept almost unchanged because of the low dosage of the additive. This particle-targeted approach for the formulation of 3D printing inks allows embodiment of a fully aqueous system with utmost target material content.
Calcium aluminate cement (CAC) suffers from loss of workability in less than an hour (~15 minutes) after first touch of water. Current superplasticizers that are utilized to modify the viscosity of cement admixtures are designed to target ordinary Portland cement (OPC). The high affinity between these superplasticizers and cement particles were found to be detrimental in CAC systems. Utilization of a monomer that, instead, facilitates gradual adsorption of a superplasticizer provides workability retention. For the first time in literature, we report a superplasticizer that caters to the properties of CAC such as high rate of surface development and surface charge. While neat CAC was almost unworkable after 1 hour, with the addition of only 0.4% of the optimized superplasticizer, 90% fluidity retention was achieved.
The capabilities of additive manufacturing for fabrication of complex and thin-walled ceramic-based objects are restricted by the availability of ceramics inks. Formulations of current ink systems strictly depend on using a high content of organic additives (5−30 wt %). The high amounts of additives affect uniformity and dimensional accuracy of the final object. Here, we designed a single additive that enables printing of high aspect ratio and thin-walled structures (height/width = 58) from an ink of alumina nanoparticles that comprises very low organic content (i.e., 1.25 wt % of nanoparticles mass). In addition to the generally exploited electrostatic effect, this additive has purpose-driven tailoring to harness steric hindrance to control the viscoelastic response of ceramic suspensions and realize an optimum ink for extrusion-based 3D printing. We pursued a stepwise approach in developing such an additive through synthesis of series of copolymers with backbone monomers of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid and side chains of poly(ethylene glycol). When the optimized additive is used, the suspension attains ∼80 wt % solid loading99% of the theoretical limit calculated by the Krieger−Dougherty equation. The shrinkage and deflection of the printed patterns as well as compactness and sinter-ability of dried structures are monitored. The printed structures did not experience any deformation or deflection during printing and reached 68% of theoretical density (TD: 3.98 g/cm 3 ) after drying. This compactness allowed sintering at lower temperatures and improved dimensional control of the final product. Our approach to formulate ceramic inks enables the embodiment of fully aqueous systems with the utmost material content and has the potential to expand the limited portfolio of ceramic inks.
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