The crystal structure of the perovskite-like high-temperature protonic conductor SrCeO3 has been studied with single-crystal and powder X-ray diffraction. SrCeO3 crystallizes in the orthorhombic space group Pbnm, Z= 4, with the unit-cell parameters a= 6.0117(4)A, b= 6.1538(5)A and c= 8.5886(9)A. The structure was refined to a weighted R value of 0.0226 for the single-crystal data. The oxygen coordination around cerium is almost perfectly octahedral, whereas the SrO12 polyhedra are rather distorted. SrCeO3 is isostructural with another high-temperature protonic conductor, BaCeO3, but displays an appreciably higher degree of lattice distortion.

Crystal structure of the high-temperature protonic conductor SrCeO3

Local proton dynamics in several kinds of perovskite-type high-temperature protonic conductors were investigated by spectral hole burning spectroscopy. Spectral holes based on light-induced protonic motion were observed. By applying a temperature-cycling technique, the potential barriers for local protonic motion, which is responsible for hole burning, were estimated. The values were several times lower than the activation energies obtained by electric conductivity measurements. The relationship between elementally protonic motion and long-range conduction mechanism is discussed based on these results.

Local proton dynamics in perovskite-type protonic conductors by spectral hole burning spectroscopy

The temperature dependence of the crystal structure of the protonic conducting perovskite SrCe0.95Yb0.05Oξ (ξ ∼ 3) has been determined from Rietveld refinement of neutron time-of-flight powder diffraction data in 25 K steps from 373 K to 1273 K. In contrast to most SrBIVO3 perovskites which show a sequence of structural phase transitions from Pmcn – Incn – I4/mcm - \( Pm\overline 3 m \) with increasing temperature, SrCe0.95Yb0.05Oξ remains orthorhombic with space group Pmcn from 4.2 K to the highest temperature measured. Crystallographic results are presented graphically in the form of the magnitude of the seven unique symmetry adapted basis vectors of a hypothetical aristotype perovskite phase. Thermoelastic properties of SrCe0.95Yb0.05Oξ deduced from the temperature variation of the unit cell volume and Debye-Waller factors are compared with literature values derived from independent calorimetric, Raman and elastic measurements. Thermodynamically, SrCe0.95Yb0.05Oξ behaves as a Debye-like solid with an average Gruneisen parameter in the range 1.4–1.5, but with two characteristic temperatures, ∼200 K and ∼600 K, the lower temperature being more related to the cation vibrations, the higher to the anion vibrations.

Structural and thermoelastic study of the protonic conducting perovskite SrCe 0.95 Yb 0.05 O ξ (ξ ∼ 3) between 373 K and 1273 K

Low temperature molten salt synthesis of perovskite-type ACeO3(A=Sr, Ba) in eutectic NaCl-KCl

The temperature dependence of the crystal structure and the thermoelastic properties of SrCeO3 have been determined from Rietveld refinement of high resolution, neutron time-of-flight powder diffraction data collected in 5 K intervals between 1273 K and 1723 K. No evidence was found for critical behaviour in the amplitudes of the modes that soften in zone boundary phase transitions in perovskite-structured phases suggesting SrCeO3 may remain orthorhombic, space group Pbnm from 1.2 K up to the 1 atm melting point of 2266 K. The temperature variation of the crystal structure has been determined from mode decomposition techniques and the structural evolution has been inferred from the temperature-dependences of the spontaneous shear strain and the order parameter associated with the anti-phase tilt. Thermoelastic properties have been derived from the temperature variation of the unit cell, isobaric heat capacity, and atomic displacement parameters and shows good agreement with earlier work carried out on the lightly doped system SrCe0.95Yb0.05Oξ (ξ ∼ 3). Temperature-dependent corrections for the bond valence parameters for strontium and cerium are reported.

/pdf/thermoelastic-and-structural-properties-of-ionically-17e30kbf6x.pdf

Thermoelastic and structural properties of ionically conducting cerate perovskites: (II) SrCeO3 between 1273 K and 1723 K

アークイメージ浮遊帯法により陽イオン伝導体であるSrCeO3およびSrCe0.95Yb0.05O3-a結晶を育成し,それぞれの構造を粉末X線回折図形のRietveld解析により決定した。精密化には,Glazerが提案したひずんだペロブスカイト型構造モデルを使用して行った。SrCeO3は斜方晶のPnma(No.62)で,格子定数はa=6.1473(2),b=8.5803(5),c=6.0066(2)Åで,SrCe0.95Yb0.05O3-aではa=6.1409(2),b=8.5783(7),c=5.9997(4)Åであった。SrCeO3とSrCe0.95Yb0.05O3-aとの精密化された構造パラメーターは,誤差範囲内で一致し,イッテルビウムの固溶は構造そのものには影響を与えないことがわかった。また,陰イオン八面体は[100]軸および[001]軸に対して13.2℃,[010]軸に対して10.7℃傾斜し,かなり大きなひずみを生じているが,これはSrCeO3の許容因子tがO.91とペロブカイト型化合物の中では小さいためだと考えられる。育成した結晶内部には複雑な双晶構造がプリセッション写真および偏光顕微鏡写真から観察された。この構造は,育成後の段階的な相転移の際に生じたもので,陰イオン八面体の傾斜に対応していた。

Crystal growth and structure refinement of SeCeO3 protonic conductor.

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Crystal growth and structure refinement of SeCeO3 protonic conductor.