Slip casting was used to prepare BaCe_xZr_0.9−xY_0.1O_3−d(BCZY)-NiO tubes with a diameter of ½ inches (1.25 cm) and ¾ inches (1.875 cm). Two compositions were studied: BCZY18 and BCZY27 for x = 0.1 and 0.2, respectively. The unfired tubes were then dip-coated with three layers of the BCZY electrolyte membrane. Solid-state reactive sintering was used, meaning that the support and membrane were prepared with the precursors (oxides and carbonates). After co-sintering at 1550 °C, a 20-micron thick dense BCZY layer was well-adhered to the 1 mm thick BCZY-NiO support, as confirmed by scanning electron microscopy. The sintered BCZY-NiO/BCZY tubes were sealed onto alumina or BCZY substrates using a silver-based braze (with TiO₂ and CuO additions). Gas tightness was achieved under 2 bar when covering the silver braze with a ceramic (Resbond) sealing layer. These slip cast tubes are intended for use as hydrogen electrodes in various protonic ceramic devices, and the advantages of short tubes for reactor design are discussed.

A novel process for producing thick protonic ceramics for use in hydrogen separation membrane reactors is demonstrated. Polymer clay bodies based on polyvinyl acetate (PVA) and mineral oil were formulated, and they permitted parts with complex architectures to be prepared by simple, low-pressure molding in the unfired, “green” state. Ceramic proton conductors based on doped barium zirconate/cerate, made by solid-state reactive sintering, are particularly well-suited for the polymer clay process. In this work, the ceramic proton conductor, BZCY755 (BaZr_0.75Ce_0.05Y_0.2O_3−d) was fabricated into a variety of shapes and sizes. Test coupons were produced to confirm that the polymer clay route leads to a high-quality ceramic material suitable for the demanding environment of high-temperature membrane reactors. It has been demonstrated that protonic ceramic specimens with the requisite properties are easily prepared at the laboratory scale. The polymer clay fabrication route opens up the possibility of high-volume, low-cost manufacturing at a commercial scale, by a process similar to how dinnerware and sanitary porcelain are produced today.