Pores, porosity shrinkage

Intersection of grain boundaries Shrinkage of open pores Porosity decreases substantially Slow grain growth... 

The microstructure, properties, and performance of Ni-YSZ anodes depend sensitively on the microscopic characteristics of the raw materials (e.g., particles size and morphology of NiO and YSZ powders). The particle sizes of the starting YSZ powders vary usually from 0.2 to 0.3 pm, whereas those for the NiO powders are 1 pm. The Ni to YSZ volume ratio usually varies from 35 65 to 55 45. For example, the reported Ni to YSZ volume ratios include 34 66 [20, 21], 40 60 [24], 43 57 [22], and 55 45 [23], For a bilayer anode, the functional anode layer in contact with the electrolyte contains 45 to 50 vol% Ni, whereas the anode support layer has 35 to 40 vol% Ni [25, 26], A pore former is usually added to tailor the shrinkage (for the cofiring) and to achieve sufficient porosity (>30 vol%) in the anode or the anode support layer. 

The presence of a small amount of water vapor (up to pH20/pH2 = -0.03) in fuel reduces anode overpotential. For anode-supported cells, the use of pore formers is important to tailor the shrinkage during cofiring and to create adequate porosity for better performance. The difference in cell power output could differ by as much as 100% for cells as porosity changes from -30 to -50%. 

When the densified component is pore-free, Vflnai = VsoUds and Dr = 1.0. Anything less than this value indicates the presence of porosity. Control of Dr requires control of both the microstructure of the as-formed part and the firing, because both affect the sintering shrinkage. 

The atmosphere is also important in sintering. Gas trapped in closed pores will limit pore shrinkage unless the gas is soluble in the grain boundary and can diffuse from the pore. Alumina doped with MgO can be sintered to essentially zero porosity in hydrogen or oxygen atmospheres, which are soluble, but not in air, which contains insoluble nitrogen. The density of oxides sintered in air is commonly less than 98% and often only 92-96%. The sintering atmosphere is also important in that it may influence the sublimation or the stoichiometry of the principal particles or dopants. 

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