Rietveld refinements using neutron powder profiles are reported for a series of samples (commonly known as PZT), with x ranging from to . Cation shifts, octahedral distortion and tilts are determined with varying composition across the ferroelectric rhombohedral regions, and , of the PZT phase diagram. These parameters are then used in conjunction with a simple Landau-Devonshire model to investigate the nature of the phase transition. It is found that the cation shifts, octahedral distortion and tilt angles decrease with increasing Ti content, but, surprisingly, the octahedral strain, as indicated by the rhombohedral angle, increases. This is in contrast to the case for all other known rhombohedral perovskites. Furthermore, the refined anisotropic displacement parameters of the cations are anomalous and cannot be accounted for by the average crystal structure. A model is presented in which a domain-type `local' structure is considered, containing `ordered' additional cation displacements, consistently with the reports of extra reflections observed in electron microscopy studies by Viehland et al, Dai et al and Ricote et al.

The crystal structure of the perovskite lead zirconate PbZrO 3 has been redetermined using single-crystal X-ray diffraction (MoKct radiation, 2--0.71069A).Single-crystal data at 100 K: space group. Pbam, a=5.884(1), b=11.787(3), c=8.231(2) (1). An investigation is made into previous contradicting reports of a possible disorder in the oxygens and their origin by examining the crystal pseudo-symmetry. Information distinguishing an ordered and disordered oxygen substructure is shown to reside in weak l odd reflections. Because of their extremely low intensities these reflections have not contributed sufficiently in previous X-ray structure investigations and hence, to date, conclusive evidence differentiating between ordered and disordered models has not been possible. By collecting single-crystal X-ray data at low temperature and by using exceptionally long scans on selected hkl, l odd, reflections, a new accurate structure determination is presented and discussed, showing the true ordered oxygen positions. Because of the large difference in scattering factors between lead and oxygen when using X-rays, a neutron diffraction Rietveld refinement using polycrystalline samples (D1A instrument, ILL, 2-1.90788 A) is also reported as further evidence to support the true ordered oxygen structure revealed by the low-temperature X-ray analysis.

Transmission electron microscopy and neutron diffraction have been used to characterize ceramics and single crystals from the rhombohedral region of the (x = 0.06-0.45) phase diagram. Electron diffraction patterns showed the existence of superlattice reflections of the type , where h = k = l, and , which are not observed by neutron powder diffraction. The analysis of these reflections also revealed satellite spots around the , which are associated with periodic antiphase boundaries. The origin of these superlattice reflections is explained by the existence of local regions presenting antiparallel cation displacements, and models for this are suggested

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The crystal structure of lead tetraborate, PbO.2B2O3, has been refined using single-crystal X-ray diffraction data (Mo Kα radiation, λ = 0.71069 Å). Crystal data at room temperature: Mr = 362.43, orthorhombic, P21 nm (C 7 2v ), a = 4.251 (2), b = 4.463 (3), c = 10.860 (3) Å, V = 206.04 Å3 with Z = 2, μ = 402.6 cm−1, Dx = 5.88 Mg m−3, F(000) = 316, final R = 0.022, wR = 0.025 over 655 reflections with I > 2.5σ(I). Atomic coordinates are in general agreement with those previously reported for the isostructural compound, SrO.2B2O3, by Perloff & Block [Acta Cryst. (1966), 20, 274–279]. All the borons are tetrahedrally coordinated with a three-dimensional network formed from O atoms that are common to either two or three tetrahedra. The tetrahedra show deformation because the B—O bonds involving the two-coordinated O atoms are much shorter than those involved with three-coordinated O atoms. The Pb atoms are situated in empty tunnels running along [010] left by the network of tetrahedra. The Pb atoms display a highly asymmetric distribution of Pb—O bonding, with the five shortest bonds covering the range 2.483 (5)–2.664 (5) Å, being all situated to one side of the Pb atom. Preliminary investigations of the non-linear optical behaviour of lead tetraborate are also discussed. The results indicate that doping with barium should lead to a new non-linear optical material that is both phase-matchable and has a high optical non-linearity.

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The room‐temperature crystal structure of the perovskite lead hafnate PbHfO3 is investigated using both low‐temperature single crystal X‐ray diffraction (Mo Kα radiation, λ = 0.71069 Å) and polycrystalline neutron diffraction (D1A instrument, ILL, λ = 1.90788 Å). Single crystal X‐ray data at 100 K: space group Pbam, a = 5.856 (1), b = 11.729 (3), c = 8.212 (2) Å, V = 564.04 Å3 with Z = 8, μ = 97.2 mm−1, F(000) = 1424, final R = 0.038, wR = 0.045 over 439 reflections with F >1.4σ(F). Polycrystalline neutron data at 383 K: a = 5.8582 (3), b = 11.7224 (5), c = 8.2246 (3) Å, V = 564.80 Å3 with χ2 = 1.62. Although lead hafnate has been thought to be isostructural with lead zirconate, no complete structure determination has been reported, as crystal structure analysis in both these materials is not straightforward. One of the main difficulties encountered is the determination of the oxygen positions, as necessary information lies in extremely weak l = 2n + 1 X‐ray reflections. To maximize the intensity of these reflections the X‐ray data are collected at 100 K with unusually long scans, a procedure which had previously been found successful with lead zirconate. In order to establish that no phase transitions exist between room temperature and 100 K, and hence that the collected X‐ray data are relevant to the room‐temperature structure, birefringence measurements for both PbZrO3 and PbHfO3 are also reported.

Single‐crystal X‐ray diffraction data (Mo Kα radiation) are used to re‐refine the structure of RbNbOB2O5, rubidium niobium oxo pyroborate. The structure is refined as an incommensurate modulated structure with superspace group symmetry Pmn21(0,0.4,0)s and lattice parameters a = 7.406 (2), b = 3.939 (2) and c = 9.475 (2) Å. Refinement on 3242 unique reflections converged to R = 0.031, while a previous conventional superstructure refinement led to R = 0.090. This lowering of the R factor goes hand‐in‐hand with a substantial reduction in the number of refined parameters. The refinement strongly suggests that the structure is effectively incommensurately modulated, despite an apparently rational magnitude of the primary modulation wavevector and overlap of satellite reflections.