Manchado J, Romero F J, Gallardo M C, Del Cerro J, Darling T W, Taylor P A, Buckley A, Carpenter M A
Departamento de Física de la Materia Condensada, Instituto Mixto de Ciencia de Materiales CSIC-Universidad de Sevilla, Apartado 1065, 41080 Sevilla, Spain.
J Phys Condens Matter. 2009 Jul 22;21(29):295903. doi: 10.1088/0953-8984/21/29/295903. Epub 2009 Jul 3.
Conduction calorimetry has been used to determine with high precision the latent heat and variation in heat capacity which accompany the first order [Formula: see text] phase transition in perovskites with compositions (Ca(1-x)Sr(x))TiO(3), x = 0.65, 0.68, 0.74 (CST65, CST68, CST74). In CST65 (CST68), the latent heat is dissipated/absorbed over a temperature interval of ∼11 K (∼6 K), which is centred on ∼292 K (∼258 K) during cooling and ∼302 K (∼270 K) during heating. The magnitude of the latent heat diminishes with increasing SrTiO(3) content and was not detected in CST74. Integration of the latent heat and excess heat capacity yields small excess entropies, which are consistent with the structural changes being displacive rather than order-disorder in origin. Resonant ultrasound spectroscopy measurements on the same CST65 sample as used for dielectric and calorimetric measurements through the same temperature intervals have allowed quantitative correlations to be made with the bulk modulus, shear modulus and acoustic dissipation parameter, Q(-1). The dielectric anomaly and changes in Q(-1) can be understood as being linear combinations of the properties of the separate I4/mcm and Pbcm phases in proportion to their volume fractions across the two-phase field. A change of only ∼0.5-1 GPa has been detected in the bulk modulus but the shear modulus softens by ∼5-8 GPa as the transition interval is approached from above and below. This shear mode softening presumably reflects clustering and/or phonon softening in both the I4/mcm and Pbcm structures. This pattern of structure-property relations could be typical of first order transitions in perovskites where there is no group/subgroup relationship between the high and low symmetry phases.
传导量热法已被用于高精度地测定钙钛矿(组成为(Ca(1 - x)Sr(x))TiO(3),x = 0.65、0.68、0.74,即CST65、CST68、CST74)中伴随一级[公式:见正文]相变的潜热和热容变化。在CST65(CST68)中,潜热在约11 K(约6 K)的温度区间内耗散/吸收,冷却时该区间以约292 K(约258 K)为中心,加热时以约302 K(约270 K)为中心。潜热的大小随SrTiO(3)含量的增加而减小,在CST74中未检测到。潜热和过剩热容的积分产生了小的过剩熵,这与结构变化起源于位移型而非有序 - 无序型一致。通过与用于介电和量热测量相同的温度区间,对与CST65样品相同的样品进行共振超声光谱测量,得以与体积模量、剪切模量和声耗散参数Q(-1)建立定量关联。介电异常和Q(-1)的变化可理解为分别为I4/mcm相和Pbcm相的性质按其在两相区的体积分数比例的线性组合。体积模量仅检测到约0.5 - 1 GPa的变化,但当从上下两个方向接近转变区间时,剪切模量软化约5 - 8 GPa。这种剪切模式软化可能反映了I4/mcm相和Pbcm相结构中的团簇化和/或声子软化。这种结构 - 性质关系模式可能是钙钛矿中一级相变的典型特征,其中高对称相和低对称相之间不存在群/子群关系。