Manipulation of polar order in the “empty” tetragonal tungsten bronzes: Ba4-xSrxDy0.671.33Nb10O30, x = 0, 0.25, 0.5, 1, 2, 3

JG would like to thank the EPSRC for provision of a studentship via the doctoral training grant (EP/K503162/1).A series of “empty” tetragonal tungsten bronze (TTB) ferroelectrics, Ba4-xSrxDy0.67□1.33 Nb 10O30 (x = 0, 0.25, 0.5, 1, 2, 3; □ = vacancy), is reported. With increasing x the unit cell contracts in both the ab plane and c-axis; x ≤ 1 compounds are normal ferroelectrics (FE) with decreasing TC as x increases, while x ≥ 2 are relaxor ferroelectrics (RFE) with associated frequency dependent permittivity peaks and with similar Tm and Tf (Vogel-Fulcher freezing temperatures) values. This observation is rationalised by differing cation occupancies: for x ≤ 1, Sr2+ principally occupies the A2-site (co-occupied by Ba2+ with the A1-site occupied by Dy3+ and vacancies); for x ≥ 2 significant Sr A1-site occupation leads to the observed RFE characteristics. This FE to RFE crossover is consistent with a previously proposed TTB crystal chemical framework where both a decrease in average A-site size and concurrent increase in A1-site tolerance factor (tA1) favour destabilization of long range polar order and relaxor behaviour. The effect of increasing tA1 as a result of Sr occupancy at the A1 site is dominant in the compounds reported here.PostprintPeer reviewe

Compositional variation in hybrid organic-inorganic lead halide perovskites : kinetically- versus thermodynamically-controlled synthesis

Authors thank the Chinese Scholarship Council and the University of St Andrews for Ph.D. Studentship support (to JT, CSC No. 201603780020).The formation and study of partial solid solutions in Az1-xFAxPbBr3, using reportedly similar sized cations azetidinium (Az+) and formamidinium (FA+), was explored via mechanosynthesis and precipitation synthesis. The composition and lattice parameters of samples from both syntheses were analyzed by 1H NMR and Rietveld refinement of powder X-ray diffraction. A clear mismatch in the composition of the perovskite was found between the precipitated samples and the corresponding solutions. Such a mismatch was not observed for samples obtained via mechanosynthesis. The discrepancy suggests products are kinetically-controlled during precipitation, compared to thermodynamically controlled mechanosynthesis. Furthermore, the cell volume as a function of composition in both hexagonal, 6H (Az-rich) and cubic, 3C (FA-rich) perovskite solid solutions suggests that FA+ is actually smaller than Az+, contradicting the literature. In the 3C (Az-poor) solid solutions, the extent of Az1-xFAxPbBr3 is unexpectedly smaller than in the corresponding methylammonium (MA+) system, Az1-xMAxPbBr3, which suggests that the extent of solid solution formation in these halide perovskites is predominantly dependent on the average A-cation size while the size mismatch plays a lesser role in comparison to oxides.PostprintPeer reviewe

Origin and stability of the dipolar response in a family of tetragonal tungsten bronze relaxors

A new family of relaxor dielectrics with the tetragonal tungsten bronze structure (nominal composition Ba6M3+Nb9O30, M3+ = Ga, Sc or In) were studied using dielectric spectroscopy to probe the dynamic dipole response and correlate this with the crystal structure as determined from powder neutron diffraction. Independent analyses of real and imaginary parts of the complex dielectric function were used to determine characteristic temperature parameters, TVF, and TUDR, respectively. In each composition both these temperatures correlated with the temperature of maximum crystallographic strain, Tc/a determined from diffraction data. The overall behaviour is consistent with dipole freezing and the data indicate that the dipole stability increases with increasing M3+ cation size as a result of increased tetragonality of the unit cell. Crystallographic data suggests that these materials are uniaxial relaxors with the dipole moment predominantly restricted to the B1 cation site in the structure. Possible origins of the relaxor behaviour are discussed.Comment: Main article 32 pages, 8 figures; Supplementary data 24 pages, 4 figure

POLICY OF INTERNATIONAL ECONOMIC RELATIONS AFTER SLOVENIA\u27S ACCESSION TO THE EU

With accession to the EU Slovenia will simultaneously become a member of customs union, meaning that it should abolish existing trade barriers with partner countries and that it should adapt its trade policy against third countries to the policy of the Union. As a member of the EU Slovenia is going to regulate relations with other EU-member countries by competition policy, and to regulate relations with non-member countries by trade policy. Slovenia should cede up the instruments of common commercial policy. Thus, in the future, policy of international economic relations is going to be carried out at three levels: national, European and international (e.g. WTO, OECD). Practical importance for Slovenia will be caused by loss of national sovereignity in the field of anti-dumping measures as well as concluding trade agreements, what will have a considerable effects on trade with countries in the area of former Yugoslavia

Towards novel multiferroic and magnetoelectric materials: dipole stability in tetragonal tungsten bronzes

authors thank the Engineering and Physical Science Research Council for funding (grant no. EP/F004133/1).We discuss the strategy for development of novel functional materials with the tetragonal tungsten bronze structure. From the starting composition Ba6GaNb9O30, the effect of A- and B-site substitutions on the dielectric properties is used to develop an understanding of the origin and stability of the dipolar response in these compounds. Both tetragonal strain induced by large B-site cations and local strain variations created by isovalent A-site substitutions enhance dipole stability but result in a dilute, weakly correlated dipolar response and canonical relaxor behaviour. Decreasing cation size at the perovskite A2-site increases the dipolar displacements in the surrounding octahedra, but insufficiently to result in dipole ordering. Mechanisms introducing small A-site lanthanide cations and incorporation of A-site vacancies to induce ferroelectricity and magnetism are presented.PostprintPeer reviewe

Structural and dielectric studies of the phase behaviour of the topological ferroelectric La1-xNdxTaO4

We thank the University of St Andrews and EPSRC (via DTG studentships to CALD and JG) for funding,The layered perovskite LaTaO4 has been prepared in its polar orthorhombic polymorphic form at ambient temperature. Although no structural phase transition is observed in the temperature interval 25° C < T < 500 °C, a very large axial thermal contraction effect is seen, which can be ascribed to an anomalous buckling of the perovskite octahedral layer. The non-polar monoclinic polymorph can be stabilised at ambient temperature by Nd-doping. A composition La0.90Nd0.10TaO4 shows a first-order monoclinic-orthorhombic (non-polar to polar) transition in the region 250° C < T < 350 °C. Dielectric responses are observed at both the above structural events but, despite the ‘topological ferroelectric’ nature of orthorhombic LaTaO4, we have not succeeded in obtaining ferroelectric P–E hysteresis behaviour. Structural relationships in the wider family of AnBnX3n+2 layered perovskites are discussed.Publisher PDFPeer reviewe

Relaxor-to-ferroelectric crossover and disruption of polar order in "empty" tetragonal tungsten bronzes

JG would like to thank the EPSRC for provision of a studentship via the doctoral training grant (EP/K503162/1). The research data (and/or materials) supporting this publication can be accessed at [http://dx.doi.org/10.17630/a7a9bc13-b5cb-485d-914a-923832f25190]Combined temperature-dependent structural and electrical characterization of a series of “empty” ferroelectric tetragonal tungsten bronzes (TTBs) of composition Ba4(La1- xNdx)0.67□1.33Nb10O30 are reported. The La-material exhibits a temperature dependent crossover from relaxor-ferroelectric to polar (but non-ferroelectric) to linear dielectric behavior. The loss of ferroelectric switching in the polar, non-ferroelectric phase is accompanied by disorder associated with structural relaxation due the significant vacancy concentration at the A1-perovskite-like site. In this disordered regime, large polarization can be re-established with application of sufficient electric field, however relaxation back into the disordered phase occurs on removal of the field as indicated by the loss of remenant polarization. The field against which “backswitching” (depolarization) occurs increases with temperature indicating increasing stability of the disordered regime. The disordered phase can be de-stabilized by substituting Nd for La at the A1-site and which reintroduces “normal” ferroelectric behavior.PostprintPeer reviewe

Preface : Thermophysical Aspects of Functional Materials and Surfaces (TAFCS)

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Themed issue on advances in solid state chemistry and its applications

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