Large negative thermal expansion (NTE) has been discovered during the last decade in materials of various kinds, particularly materials associated with a magnetic, ferroelectric or charge-transfer phase transition. Such NTE materials have attracted considerable attention for use as thermal-expansion compensators. Here, we report the discovery of giant NTE for reduced layered ruthenate. The total volume change related to NTE reaches 6.7% in dilatometry, a value twice as large as the largest volume change reported to date. We observed a giant negative coefficient of linear thermal expansion α=−115 × 10−6 K−1 over 200 K interval below 345 K. This dilatometric NTE is too large to be attributable to the crystallographic unit-cell volume variation with temperature. The highly anisotropic thermal expansion of the crystal grains might underlie giant bulk NTE via microstructural effects consuming open spaces in the sintered body on heating.

The effects of iron doping on the giant negative thermal expansion (NTE) of Ca2RuO4−y ceramics are investigated. Fe-doped ruthenate ceramics exhibit a large NTE even though the crystallographic unit-cell volume shows no NTE. The anisotropic thermal strain of crystal grains consumes open spaces in the sintered body and causes giant bulk volume contraction on heating. This giant NTE is reproducible against repeated thermal cycling, indicating a tough microstructure. The thermal expansion of epoxy resin is fully suppressed below 400 K by the 56 vol % loading of the Fe-doped ruthenate ceramic powder, demonstrating tough microstructures and the capability of thermal expansion compensation of the ruthenate sintered body.

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