Development of solid state thick film zirconia oxygen gas sensors.

Aspects relating to and including the development of thick film amperometric zirconia oxygen sensors were investigated. These devices, which were operated in the range 550-950°C, had a laminated structure in which a cathode, an electrolyte and an anode were printed, in that order, onto a planar alumina substrate. The anode and electrolyte were porous and during sensor Operation also acted as a diffusion barrier, restricting the rate of oxygen diffusion to the cathode. A thick film platinum heater was also developed to maintain the sensor at its operating temperature while acting simultaneously as a résistance thermometer; it was screen-printed onto the substrate on the reverse side to the sensor. The individual components were characterised and optimised prior to assembly of complete sensors.
Zirconia films were deposited by screen-printing onto alumina substrates. Careful attention was paid to formulation of zirconia inks, drying and firing procedures. Temperatures above 1350°C were necessary to sinter the zirconia to a low (<0.1%) though not zero porosity. The high sintering temperatures were found to result in the diffusion of impurities from the 96% alumina Substrate into the zirconia film which accelerated grain growth. X-ray diffraction showed that the grain growth resulted in transformation of the metastable tetragonal zirconia to the monoclinic form: where this occurred frequency response analysis of the films showed the expected decrease in ionic conductivity. These effects were absent on high purity (99.6%) alumina substrates.
Platinum-zirconia cermets were investigated as possible electrodes. When screen-printed and fired at 1000°C for 1 hour and operated in the range 500-700°C, electrode activity was orders of magnitude greater than for pure porous platinum electrodes and increased substantially with increasing zirconia fractions provided electronic continuity was maintained within the film. High firing temperatures (>
1000°C), which were necessary for preparing a sensor with co-fired electrolyte and electrodes, decreased electrode activities although cermets remained greatly superior to pure platinum.
Planar amperometric zirconia oxygen sensors were prepared using thick-film technology exclusively. When a voltage (0.5-1.4 V) was applied between the electrodes, a current flowed which was directly proportional to the oxygen concentration in the range up to 21%; this has not previously been achieved with such sensors. Characteristics were shown to be dependent upon firing temperature
and substrate purity. Interestingly, temperature coefficients of the output were positive and negative for sensors fired at temperatures up to 1400 and above 1450°C respectively. Operation in the combustion products of a gas-burning flue demonstrated linear dependence upon calculated oxygen concentration.
Heaters, printed using either fritted or unfritted platinum inks, were given extended treatments in a furnace at elevated temperatures (1000-1300°C) to accelerate ageing effects. Measurements were made of résistance (at 20°C), platinum evaporation rate and film cross-sectional area and these were correlated with the microstructure. The variation of résistance (at 20°C) of the films was analysed using effective medium theory invoked in order to quantify the blocking effect of the non-metallic
fractions. During the initial phase (résistance decreasing) the governing factor was probably the high resistance of necks between contacting platinum particles. During the subsequent phase (resistance increasing) the resistance was controlled principally by the formation and growth of voids.

A thesis submitted to the Council for National Academic Awards in partial fulfilment of the requirements for the degree of Doctor of Philosophy.