Tungsten Oxide Coated Liquid Metal Electrodes via Galvanic Replacement as Heavy Metal Ion Sensors.

Gallium liquid metals (LMs) like Galinstan and eutectic Gallium-Indium (EGaIn) have seen increasing applications in heavy metal ion (HMI) sensing, because of their ability to amalgamate with HMIs like lead, their high hydrogen potential, and their stable electrochemical window. Furthermore, coating LM droplets with nanopowders of tungsten oxide (WO) has shown enhancement in HMI sensing owing to intense electrical fields at the nanopowder-liquid-metal interface. However, most LM HMI sensors are droplet based, which show limitations in scalability and the homogeneity of the surface. A scalable approach that can be extended to LM electrodes is therefore highly desirable. In this work, we present, for the first time, WO-Galinstan HMI sensors fabricated via photolithography of a negative cavity, Galinstan brushing inside the cavity, lift-off, and galvanic replacement (GR) in a tungsten salt solution. Successful GR of Galinstan was verified using optical microscopy, SEM, EDX, XPS, and surface roughness measurements of the Galinstan electrodes. The fabricated WO-Galinstan electrodes demonstrated enhanced sensitivity in comparison with electrodes structured from pure Galinstan and detected lead at concentrations down to 0.1 mmol·L-1. This work paves the way for a new class of HMI sensors using GR of WO-Galinstan electrodes, with applications in microfluidics and MEMS for a toxic-free environment.

Two-Photon Polymerization of Nanocomposites for Additive Manufacturing of Transparent Magnesium Aluminate Spinel Ceramics.

Transparent polycrystalline magnesium aluminate (MAS) spinel ceramics are of great interest for industry and academia due to their excellent optical and mechanical properties. However, shaping of MAS is notoriously challenging especially on the microscale requiring hazardous etching methods. Therefore, a photochemically curable nanocomposite is demonstrated that can be structured using high-resolution two-photon lithography. The printed nanocomposites are converted intro transparent MAS by subsequent debinding, sintering, and hot isostatic pressing. The resulting transparent spinel ceramics exhibit a surface roughness Sq of only 10 nm and can be shaped with minimum feature sizes of down to 13 µm. This technology will be important for the production of microstructured ceramics used for optics, photonics, or photocatalysis.

In Situ Actuators with Gallium Liquid Metal Alloys and Polypyrrole-Coated Electrodes.

Gallium liquid metal alloys (GLMAs) such as Galinstan and gallium-indium eutectic (EGaIn) are interesting materials due to their high surface tensions, low viscosities, and electrical conductivities comparable to classical solid metals. They have been used for applications in microelectromechanical systems (MEMS) and, more recently, liquid metal microfluidics (LMMF) for setting up devices like actuators. However, their high tendency to alloy with the most common metals used for electrodes such as gold (Au), platinum (Pt), titanium (Ti), nickel (Ni), and tungsten-titanium (WTi) is a major problem limiting the scaleup and applicability, e.g., liquid metal actuators. Stable electrodes are key elements for many applications and thus, the lack of an electrode material compatible with GLMAs is detrimental for many potential application scenarios. In this work, we study the effect of actuating Galinstan on various solid metal electrodes and present an electrode protection methodology that, first, prevents alloying and, second, prevents electrode corrosion. We demonstrate reproducible actuation of GLMA segments in LMMF, showcasing the stability of the proposed protective coating. We investigated a range of electrode materials including Au, Pt, Ti, Ni, and WTi, all in aqueous environments, and present the resulting corrosion/alloying effects by studying the interface morphology. Our proposed protective coating is based on a simple method to electrodeposit electrically conductive polypyrrole (PPy) on the electrodes to provide a conductive alloying-barrier layer for applications involving direct contact between GLMAs and electrodes. We demonstrate the versatility of this approach by direct three-dimensional (3D) printing of a 500 µm microfluidic chip on a set of electrodes onto which PPy is electrodeposited in situ for actuation of Galinstan plugs. The developed protection protocol will provide a generic, widely applicable strategy to protect a wide range of electrodes from alloying and corrosion and thus form a key element in future applications of GLMAs.

Replicative manufacturing of metal moulds for low surface roughness polymer replication.

Tool based manufacturing processes like injection moulding allow fast and high-quality mass-market production, but for optical polymer components the production of the necessary tools is time-consuming and expensive. In this paper a process to fabricate metal-inserts for tool based manufacturing with smooth surfaces via a casting and replication process from fused silica templates is presented. Bronze, brass and cobalt-chromium could be successfully replicated from shaped fused silica replications achieving a surface roughnesses of Rq 8 nm and microstructures in the range of 5 µm. Injection moulding was successfully performed, using a commercially available injection moulding system, with thousands of replicas generated from the same tool. In addition, three-dimensional bodies in metal could be realised with 3D-Printing of fused silica casting moulds. This work thus represents an approach to high-quality moulding tools via a scalable facile and cost-effective route surpassing the currently employed cost-, labour- and equipment-intensive machining techniques.

Injection Molding of Magnesium Aluminate Spinel Nanocomposites for High-Throughput Manufacturing of Transparent Ceramics.

Transparent ceramics like magnesium aluminate spinel (MAS) are considered the next step in material evolution showing unmatched mechanical, chemical and physical resistance combined with high optical transparency. Unfortunately, transparent ceramics are notoriously difficult to shape, especially on the microscale. Therefore, a thermoplastic MAS nanocomposite is developed that can be shaped by polymer injection molding at high speed and precision. The nanocomposite is converted to dense MAS by debinding, pre-sintering, and hot isostatic pressing yielding transparent ceramics with high optical transmission up to 84 % and high mechanical strength. A transparent macroscopic MAS components with wall thicknesses up to 4 mm as well as microstructured components with single micrometer resolution are shown. This work makes transparent MAS ceramics accessible to modern high-throughput polymer processing techniques for fast and cost-efficient manufacturing of macroscopic and microstructured components enabling a plethora of potential applications from optics and photonics, medicine to scratch and break-resistant transparent windows for consumer electronics.