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The Ba2LnFeNb4O15 Tetragonal Tungsten Bronze: towards RT composite multiferroics

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 Added by Mario Maglione
 Publication date 2008
  fields Physics
and research's language is English




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Several Niobium oxides of formula Ba2LnFeNb4O15 (Ln = La, Pr, Nd, Sm, Eu, Gd) with the Tetragonal Tungsten Bronze (TTB) structure have been synthesised by conventional solid-state methods. The Neodymium, Samarium and Europium compounds are ferroelectric with Curie temperature ranging from 320 to 440K. The Praseodymium and Gadolinium compounds behave as relaxors below 170 and 300 K respectively. The Praseodymium, Neodymium, Samarium, Europium and Gadolinium compounds exhibit magnetic hysteresis loops at room temperature originating from traces of a barium ferrite secondary phase. The presence of both ferroelectric and magnetic hysteresis loops at room temperature allows considering these materials as composites multiferroic. Based on crystal-chemical analysis we propose some relationships between the introduction of Ln3+ ions in the TTB framework and the chemical, structural and physical properties of these materials.



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82 - Mikhail Smirnov 2013
Tetragonal tungsten bronze (TTB) oxides are one of the most important classes of ferroelectrics. Many of these framework structures undergo ferroelastic transformations related to octahedron tilting deformations. Such tilting deformations are closely related to the Rigid Unit Modes (RUMs). This paper discusses the whole set of RUMs in an ideal TTB lattice and possible crystal structures which can emerge owing to the condensation of some of them. Analysis of available experimental data for the TTB-like niobates lends credence to the obtained theoretical predictions.
We have synthesised ceramic specimens of the tetragonal tungsten bronze K3Li2Ta5O15 (KLT) and characterized its phase transition via X-ray, dielectric permittivity, ultrasonic spectroscopy and heat capacity measurements. The space group of KLT is reported as both P4/mbm or Cmmm with the orthorhombic distortion occurring when there are higher partial pressures of volatile K and Li used within the closed crucibles for the solid state synthesis. The data show strong relaxor behaviour, with the temperature at which the two dielectric relative permittivity peaks decreasing with 104 K $geqslant$ Tm1 $geqslant$ 69 K and 69 K $geqslant$ Tm2 $geqslant$ 46 K as probe frequency f is reduced from 1 MHz to 316 Hz. The data satisfy a Vogel-Fulcher model with an extrapolated freezing temperature for {epsilon} and {epsilon} of Tf1 = + 15.8 and - 11.8 K and Tf2 = - 5.0 and - 15.0 K for f $rightarrow$ 0 (tending to dc). Therefore by tuning frequency, the transition could be shifted to absolute zero suggesting KLT has a relaxor-type quantum critical point. In addition, we have reanalysed the conflicting literature for Pb2Nb2O7 pyrochlore which suggests that this is also a relaxor-type quantum critical point as the freezing temperature from Vogel-Fulcher fitting is below absolute zero. Since the transition temperature evidenced in the dielectric data at ca. 100 kHz shifts below zero Kelvin for very low frequencies, heat capacity data collected in the zero-frequency (dc) limit, should not indicate a transition. Both of these materials show promise as possible new relaxor-type quantum critical points within non-perovskite based structures as multiple compounds are reported with low-temperature transitions.
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Various phenomena related to inhomogeneous magnetoelectric interaction are considered. The interrelation between spatial modulation of order parameter and electric polarization, known as flexoelectric effect in liquid crystals, in the case of magnetic media appears in a form of electric polarization induced by spin modulation and vice versa. This flexomagnetoelectric interaction is also related to the influence of ferroelectric domain structure on antiferromagnetic vector distribution, and to the magnetoelectric properties of micromagnetic structures. The influence of inhomogeneous magnetoelectric interaction on dynamic properties of multiferroics, particularly magnon spectra is also considered.
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