In situ X-ray diffraction of CaO based CO2 sorbents

In situ X-ray diffraction coupled with Rietveld refinement has been used to study CO2 capture by CaO, Ca(OH)2 and partially hydrated CaO, as a function of temperature. Phase quantification by Rietveld refinement was performed to monitor the conversion to CaCO3 and the results were compared to those derived using thermogravimetric analysis (TGA). It was found that Ca(OH)2 converted directly to 100% CaCO3 without the formation of a CaO intermediate, at ca. 600 °C. Both pure CaO and partially hydrated CaO (33.6 wt% Ca(OH)2) reached the same capture capacity, containing approximately 65 wt% CaCO3 at 800 °C. It was possible to provide direct evidence of the capture mechanism. The stresses in the Ca(OH)2 phase of the partially hydrated CaO were found to be more than 20 times higher than its strength, leading to disintegration and the generation of nano-sized crystallites. The crystallite size determined using diffraction (75 × 16 nm) was in good agreement with the average crystallite size observed using TEM (of 83 × 16 nm). Electron diffraction patterns confirmed coexistence of CaO and Ca(OH)2. The analysis provides an explanation of the enhanced capture/disintegration observed in CaO in the presence of steam

Temperature Dependence of Domain Contributions as a Function of Ageing in Soft and Hard Lead Zirconate Titanate Piezoelectric Ceramics

The stress and temperature dependence of three different lead zirconate titanate ceramics have been measured at 48 h and 1 month after poling. The data were fit to a modified Rayleigh law in which a negative quadratic stress term accounts for a saturation of the domain wall contributions at higher stress. The relative changes to the fitting parameters can be explained by the materials possessing differences in the concentration of orientable defect dipoles, but with similar distributions of relaxation time constants

Expanding the application space for piezoelectric materials

The long history of innovation in the field of piezoelectric devices has, over the last 65 years, been predominantly rooted in a single material, the Pb(Zr, Ti)O3 ceramic, known as lead zirconate titanate (PZT). Despite enormous resources being dedicated in the last 20 years to identifying lead-free alternatives to PZT and developing a thriving, but limited, market in PbTiO3-relaxor single crystals, most device developments are still PZT based. However, more recently, solid solutions based on BiFeO3 have opened up new applications for active piezoelectric devices at high temperatures (to 600 ○C) and under high stress (exceeding 250 MPa), with applications in industrial ultrasound, aerospace, automotive, and micro-actuators. This perspective article examines how new materials are expanding the application space for piezoelectric materials

Strain-relief by single dislocation loops in calcite crystals grown on self-assembled monolayers

Most of our knowledge of dislocation-mediated stress relaxation during epitaxial crystal growth comes from the study of inorganic heterostructures. Here we use Bragg coherent diffraction imaging to investigate a contrasting system, the epitaxial growth of calcite (CaCO3) crystals on organic self-assembled monolayers, where these are widely used as a model for biomineralization processes. The calcite crystals are imaged to simultaneously visualize the crystal morphology and internal strain fields. Our data reveal that each crystal possesses a single dislocation loop that occupies a common position in every crystal. The loops exhibit entirely different geometries to misfit dislocations generated in conventional epitaxial thin films and are suggested to form in response to the stress field, arising from interfacial defects and the nanoscale roughness of the substrate. This work provides unique insight into how self-assembled monolayers control the growth of inorganic crystals and demonstrates important differences as compared with inorganic substrates

Electrocaloric enhancement near the morphotropic phase boundary in lead-free NBT-KBT ceramics

The electrocaloric effects (ECEs) of the morphotropic phase boundary (MPB) composition 0.82(Na0.5Bi0.5)TiO3-0.18(K0.5Bi0.5)TiO3 (NBT-18KBT) are studied by direct measurements. The maximum ECE DTmax¼0.73K is measured at 160 C under 22 kV/cm. This corresponds to an ECE responsivity (DT/DE) of 0.33 10 6 K m/V, which is comparable with the best reported values for lead-free ceramics. A comparison between the direct and indirect ECE measurements shows significant discrepancies. The direct measurement of both positive and negative electrocaloric effect confirms the presence of numerous polar phases near the MPB of NBT-based materials and highlights their potential for solid-state cooling based on high field-induced entropy changes

Electric-field-induced phase switching in textured Ba-doped bismuth ferrite lead titanate

The template grain growth technique was used to synthesis textured 60BiFeO3-PbTiO3 (60'40BFPT) by using platelets of BaTiO3 as template. Synchrotron measurement clearly showed textured 60'40BFPT. Moreover, in situ high energy synchrotron radiation was employed to investigate the influence of an external electric filed on crystallographic structure of mixed phase 60:40BFPT. Application of an electric field ≥ 1 kV/mm resulted in phase transformation from mixed rhombohedral/tetragonal phases (≈ 73.5% tetragonal / 26.5% rhombohedral) to predominately tetragonal phase (≈ 95%) at applied field of 6 kV/mm

Texture analysis of thick bismuth ferrite lead titanate layers

The template grain growth technique was used to synthesis textured 60BiFeO3-PbTiO3(60:40BFPT) by using platelets of BaTiO3 as template. Synchrotron measurement clearly showed textured 60:40BFPT. Moreover, in situ high energy synchrotron radiation was employed to investigate the influence of an external electric filed on crystallographic structure of mixed phase 60:40BFPT. Application of an electric field ≥ 1 kV/mm resulted in phase transformation from mixed rhombohedral/tetragonal phases (≈ 73.5% tetragonal / 26.5% rhombohedral) to predominately tetragonal phase (≈ 95%) at applied field of 6 kV/mm. A crystallographic texture refinement was done by using software package materials analysis using diffraction (MAUD) with a 4th order spherical harmonic orientation distribution function (ODF). This refinement was completed using a P4mm+Cm structure model. Texture coefficients were constrained such that the equivalent texture coefficients of each phase are the same. The resulting texture refinement determined that sample has a 1.3 multiples of random distribution (MRD) {100} crystallographic texture

Exceptionally large piezoelectric strains in BiFeO-(K Bi)TiO-PbTiO ceramics

Samples of (1-x-y)BiFeO-x(KBi) TiO-yPbTiO, where x = 0.15 and y = 0.275, were produced via a conventional mixed oxide method. Ceramics were characterized using X-ray diffraction, confirming an electric-field-induced phase change from predominantly rhombohedral to mixed phase tetragonal and rhombohedral structure upon poling. There was a remnant polarization of 34 μC cm and a total strain of 0.805% at 6.5 kV mm, the highest electric-field-induced strain reported in a polycrystalline material. A d of 205 pm V was measured and Rayleigh analysis was used to quantify the extrinsic contributions