Gold electrodes are important in some devices and certain applications where an inert, highly conductive feature is required. An aqueous gold nanoparticle (AuNP) ink suitable for inkjet printing was synthesized and formulated using starch and microwave-assisted heating. By varying the hydrolysis conditions of starch, the size, yield, and stability of the AuNP suspension can be controlled and optimized to achieve a jettable ink. The optimized formulation has a very low starch loading of only 1.75 wt % relative to gold, forming a highly stable AuNP ink, which upon drying already forms a very conductive film and sinters at low temperature. The overall synthesis protocol thus provides a greener and cheaper alternative to other AuNP synthesis methods. The sintering behavior of the film was monitored, wherein, upon heating, starch is degraded, crystallite growth increased, and the morphology changed from individual nanoparticles to a network of fused particles. The film sheet resistance decreased concomitant with these physical changes. By heating the film to at least 200 °C, a sheet resistance of <1.0 Ω/□ is achieved. This aqueous-formulated ink, therefore, offers an alternative to the usual organic solvent ink formulations used in printed electronics. It proved printing of conductive films on various substrates for possible applications in flexible electronic devices.
Fused filament fabrication (FFF) is a 3D printing method that is attracting increased interest in the development of miniaturized electrochemical sensor systems due to its versatility, low cost, reproducibility, and capability for rapid prototyping. A key component of miniaturized electrochemical systems is the reference electrode (RE). However, reports of the fabrication of a true 3D-printed RE that exhibits stability to variations in the sample matrix remain limited. In this work, we report the development and characterization of a 3D-printed Ag|AgCl|gel-KCl reference electrode (3D-RE). The RE was constructed using a Ag|AgCl wire and agar-KCl layer housed in a watertight 3D-printed acrylonitrile butadiene styrene (ABS) casing. The novel feature of our electrode is a 3D-printed porous junction that protects the gel electrolyte layer from chloride ion leakage and test sample contamination while maintaining electrical contact with the sample solution. By tuning the 3D printing filament extrusion ratio (k), the porosity of the junction was adjusted to balance the reference electrode potential stability and impedance. The resulting 3D-RE demonstrated a stable potential, with a potential drift of 4.55 ± 0.46 mV over a 12-h period of continuous immersion in 0.1 M KCl, and a low impedance of 0.50 ± 0.11 kΩ. The 3D-RE was also insensitive to variations in the sample matrix and maintained a stable potential for at least 30 days under proper storage in 3 M KCl. We demonstrate the application of this 3D-RE in cyclic voltammetry and in pH sensing coupled with electrodeposited iridium oxide on a gold electrode. Our method offers a viable strategy for 3D printing a customizable true reference electrode that can be readily fabricated on demand and integrated into 3D-printed miniaturized electrochemical sensor systems.
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