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Heat capacity of single-crystal and polycrystalline (0≤x≤0.20) from 110 to 600 K
Phys. Rev. B 43, 239 – Published 1 January, 1991
DOI: https://doi.org/10.1103/PhysRevB.43.239
Abstract
Heat-capacity C(T) data on the title materials, as well as on CuO for comparison, were obtained with use of a differential scanning calorimeter to a precision of ≃0.1–1%. The measurements were carried out (i) to characterize the thermal anomaly at the tetragonal-orthorhombic transition temperature of single-crystal and polycrystalline (0≤x≤0.20) and (ii) to search for thermal anomalies at the Néel temperature of (≃300 K). We find a cusp-shaped anomaly with a peak at 523 K (≊) for a single crystal of with =304 K and find the transition to be second order, consistent with previous neutron- and x-ray-diffraction measurements. was determined from measurements of the anisotropic magnetic susceptibility on the same crystal, which are also presented. The C(T) anomaly at is smeared out somewhat in polycrystalline .
The size of the anomaly decreases with x in polycrystalline until the anomaly is no longer observable for x≥0.10. For 0≤x≤0.08, decreases linearly with x at a rate /dx=-(2430±50) K. This variation of with x is consistent with that found previously using x-ray and neutron diffraction. No features in C(T) were observed at the Néel temperature of single-crystal or polycrystalline . This is consistent with the expectation that the magnetic entropy is very small at , since dynamic short-range intraplanar antiferromagnetic ordering, which begins at much higher temperatures, is well developed at . A calculation shows that the expected size of the anomaly at is well below the resolution of the measurements.
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