John E. Daniels

Evolving morphotropic phase boundary in lead-free (Bi1/2Na1/2)TiO3–BaTiO3 piezoceramics

The correlation between structure and electrical properties of lead-free (1−x)(Bi1/2Na1/2)TiO3–xBaTiO3 (BNT-100xBT) polycrystalline piezoceramics was investigated systematically by in situ synchrotron diffraction technique, combined with electrical property characterization. It was found that the morphotropic phase boundary (MPB) between a rhombohedral and a tetragonal phase evolved into a morphotropic phase region with electric field. In the unpoled material, the MPB was positioned at the transition from space group R3m to P4mm (BNT-11BT) with optimized permittivity throughout a broad single-phase R3m composition regime. Upon poling, a range of compositions from BNT-6BT to BNT-11BT became two-phase mixture, and maximum piezoelectric coefficient was observed in BNT-7BT. It was shown that optimized electrical properties are related primarily to the capacity for domain texturing and not to phase coexistence.

Electric-field-induced phase transformation at a lead-free morphotropic phase boundary: Case study in a 93%(Bi0.5Na0.5)TiO3–7% BaTiO3 piezoelectric ceramic

The electric-field-induced strain in 93%(Bi0.5Na0.5)TiO3–7%BaTiO3 polycrystalline ceramic is shown to be the result of an electric-field-induced phase transformation from a pseudocubic to tetragonal symmetry. High-energy x-ray diffraction is used to illustrate the microstructural nature of the transformation. A combination of induced unit cell volumetric changes, domain texture, and anisotropic lattice strains are responsible for the observed macroscopic strain. This strain mechanism is not analogous to the high electric-field-induced strains observed in lead-based morphotropic phase boundary systems. Thus, systems which appear cubic under zero field should not be excluded from the search for lead-free piezoelectric compositions.

A high-specific-strength and corrosion-resistant magnesium alloy

Ultra-lightweight alloys with high strength, ductility and corrosion resistance are desirable for applications in the automotive, aerospace, defence, biomedical, sporting and electronic goods sectors. Ductility and corrosion resistance are generally inversely correlated with strength, making it difficult to optimize all three simultaneously. Here we design an ultralow density (1.4 g cm(-3)) Mg-Li-based alloy that is strong, ductile, and more corrosion resistant than Mg-based alloys reported so far. The alloy is Li-rich and a solute nanostructure within a body-centred cubic matrix is achieved by a series of extrusion, heat-treatment and rolling processes. Corrosion resistance from the environment is believed to occur by a uniform lithium carbonate film in which surface coverage is much greater than in traditional hexagonal close-packed Mg-based alloys, explaining the superior corrosion resistance of the alloy.

Two-stage processes of electrically induced-ferroelectric to relaxor transition in 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3

The stability of electrically induced long-range ferroelectric order in a relaxor 0.94(Bi1/2Na1/2)TiO3-0.06BaTiO3 ceramic material has been investigated by temperature-dependent X-ray diffraction and electrical property measurements. The depolarization and ferroelectric-to-relaxor transition are identified as separate and discrete processes. It is observed that the induced ferroelectric domains first lose their ferroelectric/ferroelastic texture coincident with a peak signal in the thermally induced depolarization current. With further increase in temperature, the detextured ferroelectric domains are dissociated into nanoscale entities. This fragmentation marks the ferroelectric-to-relaxor transition. It is suggested that the ferroelectric-to-relaxor transition has features of a second order phase transition.

Direct measurement of the domain switching contribution to the dynamic piezoelectric response in ferroelectric ceramics

The dynamic piezoelectric response of ferroelectric ceramics is comprised of both intrinsic (piezoelectric lattice strain) and extrinsic (non-180° domain wall motion) components. Here the authors report direct measurements of non-180° domain wall motion in ceramic lead zirconate titanate during application of subcoercive cyclic driving electric fields using an in situ stroboscopic neutron diffraction technique. During unipolar cycling at 1Hz and half of the coercive field, non-180° domain switching gives rise to approximately 34% of the measured d33 coefficient of 400pm∕V.

Electric-field-induced strain mechanisms in lead-free 94%(Bi1/2Na1/2)TiO3–6%BaTiO3

High resolution neutron diffraction has been used to investigate the structural origin of the large electric-field-induced remanent strain in 94(Bi1/2Na1/2)TiO3–6BaTiO3 ceramics. The virgin material was found to be a mixture of near-cubic phases with slight tetragonal and rhombohedral distortions of a0a0c+ and a−a−a− octahedral tilt type, respectively. Application of an electric field of 4.57 kV/mm transformed the sample to a predominantly rhombohedral a−a−a− modification with a significantly higher degree of structural distortion and a pronounced preferred orientation of the c-axis along the field direction. These electric field-induced structural effects contribute significantly to the macroscopic strain and polarization of this system.

High-energy X-ray diffraction using the Pixium 4700 flat-panel detector

The Pixium 4700 detector represents a significant step forward in detector technology for high-energy X-ray diffraction. The detector design is based on digital flat-panel technology, combining an amorphous Si panel with a CsI scintillator. The detector has a useful pixel array of 1910 x 2480 pixels with a pixel size of 154 microm x 154 microm, and thus it covers an effective area of 294 mm x 379 mm. Designed for medical imaging, the detector has good efficiency at high X-ray energies. Furthermore, it is capable of acquiring sequences of images at 7.5 frames per second in full image mode, and up to 60 frames per second in binned region of interest modes. Here, the basic properties of this detector applied to high-energy X-ray diffraction are presented. Quantitative comparisons with a widespread high-energy detector, the MAR345 image plate scanner, are shown. Other properties of the Pixium 4700 detector, including a narrow point-spread function and distortion-free image, allows for the acquisition of high-quality diffraction data at high X-ray energies. In addition, high frame rates and shutterless operation open new experimental possibilities. Also provided are the necessary data for the correction of images collected using the Pixium 4700 for diffraction purposes.

Speciation of Rare‐Earth Metal Complexes in Ionic Liquids: A Multiple‐Technique Approach

The dissolution process of metal complexes in ionic liquids was investigated by a multiple-technique approach to reveal the solvate species of the metal in solution. The task-specific ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf(2)N]) is able to dissolve stoichiometric amounts of the oxides of the rare-earth elements. The crystal structures of the compounds [Eu(2)(bet)(8)(H(2)O)(4)][Tf(2)N](6), [Eu(2)(bet)(8)(H(2)O)(2)][Tf(2)N](6) x 2 H(2)O, and [Y(2)(bet)(6)(H(2)O)(4)][Tf(2)N](6) were found to consist of dimers. These rare-earth complexes are well soluble in the ionic liquids [Hbet][Tf(2)N] and [C(4)mim][Tf(2)N] (C(4)mim = 1-butyl-3-methylimidazolium). The speciation of the metal complexes after dissolution in these ionic liquids was investigated by luminescence spectroscopy, (1)H, (13)C, and (89)Y NMR spectroscopy, and by the synchrotron techniques EXAFS (extended X-ray absorption fine structure) and HEXS (high-energy X-ray scattering). The combination of these complementary analytical techniques reveals that the cationic dimers decompose into monomers after dissolution of the complexes in the ionic liquids. Deeper insight into the solution processes of metal compounds is desirable for applications of ionic liquids in the field of electrochemistry, catalysis, and materials chemistry.

Characterization of domain structures from diffraction profiles in tetragonal ferroelastic ceramics

The underlying domain structures of ferroelastic ceramics have a large influence on their macroscopic electromechanical properties. The profile shape functions of certain pseudo-cubic peaks in diffraction patterns collected from these materials can provide a great deal of information about such domain structures. Using both constant-wavelength neutron and high-energy synchrotron x-ray diffraction, profile shape functions of the pseudo-cubic 002 reflection are evaluated in a soft, tetragonal PZT ceramic. Errors in the integrated intensity ratio, important for measuring the degree of domain boundary movement in these materials, are subject to further scrutiny. It is shown that an asymmetric Pearson VII type distribution, integrated numerically between reasonable limits, gives the most accurate value of relative domain populations in these materials. It is also shown that the diffuse scattering caused by ferroelastic domain walls may be used to estimate the amount of material that is affected by microstrains originating at these walls.

Structural origins of relaxor behavior in a 0.96(Bi1/2Na1/2)TiO3―0.04BaTiO3 single crystal under electric field

Diffuse x-ray scattering intensities from a single crystal of 0.96(Bi1/2Na1/2TiO3)–0.04(BaTiO3) have been collected at room temperature with and without application of an electric field along the [100] direction. Distinct features in the diffuse scattering intensities indicate correlations on a nanometer length scale. It is shown that locally correlated planar-like structures and octahedral tilt-domains within the room temperature rhombohedral R3c phase are both electrically active and are irreversibly affected by application of an electric field of 4.3 kV/mm. The field dependence of these nanoscale structures is correlated with the relaxor behavior of the material by macroscopic permittivity measurements.