Merging Electrohydrodynamic Printing and Electrochemistry : Sub-micronscale 3D-printing of Metals

Sammanfattning: Additive manufacturing (AM) is currently on the verge of redefining the way we produce and manufacture things. AM encompasses many technologies and subsets, which are all joint by a common denominator; they build three dimensional (3D) objects by adding materials layer-upon-layer. This family of methods can do so, whether the material is plastic, concrete, metallic or living cells which can function as organs. AM manufacturing at the micro scale introduces new capabilities for the AM family that has been proven difficult to achieve with established AM methods at the macro scale. Electrohydrodynamic jet (E-jet or EHD jet) printing is a micro AM technique which has the ability to print at high resolution and speed by exploiting physical phenomena to generate droplets using the means of an electric field. However, when printing metallic materials, this method requires nanoparticles for deposition. To obtain a stable structure the material needs to be sintered, after which the deposited material is left with a porous structure. In contrary, electrochemical methods using the well-known deposition mechanism of electroplating, can deposit dense and pure structures with the downside of slow deposition. In this thesis, a new method is proposed to micro additive manufacturing by merging an already existing technology EHD with simple electrochemistry. By doing so, we demonstrate that it is possible to print metallic structures at the micro- and nanoscale with high speeds, without the need for presynthesized nanoparticles. To achieve this, a printing setup was designed and built. Using a sacrificial wire and the solvent acetonitrile, metallic building blocks such as lines, pillars and other geometric features could be printed in copper, silver, and gold with a minimum feature size of 200 nm. A voltage dependence was found for porosity, where the densest pillars were printed at 135-150 V and the most porous at 260 V. The maximum experimental deposition speed measured up to 4.1 µm · s−1 at 220 V. Faraday’s law of electrolysis could be used to predict the experimental deposition speed at a potential of 190 V with vexp = 1.8 µm · s−1 and vtheory = 0.8 µm · s−1. The microstructure of the pillars could be improved through lowering the applied voltage. In addition, given that Faraday’s law of electrolysis could predict experimental depositions speeds well, it gives further proof to reduction being the mechanism of deposition.