Electrochemical characterisation of cement hydration and properties by alternating current impedance spectroscopy

The complexity of the chemical and microstructural evolution of cement during the hydration process can be evaluated using many different characterisation techniques. One of these techniques which has been demonstrated to be useful, but not yet fully accepted by the cement research community, is Alternating Current Impedance Spectroscopy (ACIS). However, although ACIS is a non-destructive, rapid, and easily implemented technique, it has been found in the past that it has several limitations such as electrode contact, electrode area dependence, ground coupling effects, complications due to inductance at high frequencies, and a lack of mathematical and physical rigour in much of the data interpretation. Please click Additional Files below to see the full abstract

Phase transitions, domain structure, and pseudosymmetry in La- and Ti-doped BiFeO3

The phase transitions and domain structure of the promising PbO-free solid solution series, (0.95-x)BiFeO3-xLaFeO3-0.05La2/3TiO3, were investigated. X ray diffraction(XRD) revealed a transition from a ferroelectricR3c to a PbZrO3-like (Pbam) antiferroelectric (AFE) structure at x = 0.15 followed by a transition to a paraelectric (PE, Pnma) phase at x > 0.30. The ferroelastic/ferroelectric twin domain width decreased to 10–20 nm with increasing x as the AFE phase boundary was approached but coherent antiphase tilted domains were an order of magnitude greater. This domain structure suggested the local symmetry (20 nm) is lower than the average structure (R3c, a−a−a−) of the tilted regions. The PE phase (x = 0.35) exhibited a dominant a−a−c+ tilt system with Pnma symmetry but diffuse reflections at ∼1/4{ooe} positions suggest that short range antipolar order is residual in the PE phase. The complex domain structure and phase assemblage of this system challenge the conventional interpretation of phase transitions based on macroscopic symmetry. Instead, it supports the notion that frustration driven by chemical distributions at the nanometric level influences the local or pseudo-symmetry as well as the domain structure, with XRD giving only the average macroscopic structure

p-type/n-type behaviour and functional properties of KxNa (1-x)NbO3 (0.49 <= x <= 0.51) sintered in air and N2

Abstract Potassium sodium niobate (KNN) is a potential candidate to replace lead zirconate titanate in sensor and actuator applications but there are many fundamental science and materials processing issues to be understood before it can be used commercially, including the influence of composition and processing atmosphere on the conduction mechanisms and functional properties. Consequently, KNN pellets with different K/Na ratios were sintered to 95% relative density in air and N2 using a conventional mixed oxide route. Oxygen vacancies (VO..) played a major role in the semi-conduction mechanism in low p(O2) for all compositions. Impedance spectroscopy and thermo-power data confirmed KNN to be n-type in low p(O2) in contradiction to previous reports of p-type behaviour. The best piezoelectric properties were observed for air- rather than N2-sintered samples with d33=125 pC/N and kp=0.38 obtained for K0.51Na0.49NbO3

The influence of excess K2O on the electrical properties of (K,Na)1/2Bi1/2TiO3 ceramics

The solid solution (KxNa0.50-x)Bi0.50TiO3 (KNBT) between Na1/2Bi1/2TiO3 (NBT) and K1/2Bi1/2TiO3 (KBT) has been extensively researched as a candidate lead-free piezoelectric material because of its relatively high Curie temperature and good piezoelectric properties, especially near the morphotropic phase boundary (MPB) at x ~ 0.10 (20 mol% KBT). Here we show low levels of excess K2O in the starting compositions, i.e. (Ky+0.03Na0.50-y)Bi0.50TiO3.015 (y-series), can significantly change the conduction mechanism and electrical properties compared to a nominally stoichiometric KNBT series (KxNa0.50-x)Bi0.50TiO3 (x-series). Impedance Spectroscopy measurements reveal significantly higher bulk conductivity (σb) values for y ≥ 0.10 samples (activation energy, Ea, ≤ 0.95 eV) compared to the corresponding x-series samples which possess band-gap type electronic conduction (Ea ~ 1.26 to 1.85 eV). The largest difference in electrical properties occurs close to the MPB composition (20 mol% KBT) where y = 0.10 ceramics possess b (at 300 oC) that is 4 orders of magnitude higher than x = 0.10 and the oxide-ion transport number in the former is ~ 0.70 – 0.75 compared to < 0.05 in the latter (between 600 and 800 oC). The effect of excess K2O can be rationalised on the basis of the (K + Na):Bi ratio in the starting composition prior to ceramic processing. This demonstrates the electrical properties of KNBT to be sensitive to low levels of A-site nonstoichiometry and indicates excess K2O in KNBT starting compositions to compensate for volatilisation can lead to undesirable high dielectric loss and leakage currents at elevated temperatures

Themed issue on advances in solid state chemistry and its applications

Peer reviewedPostprin

Field enhanced bulk conductivity of acceptor-doped BaTi1−xCaxO3−x ceramics

The electrical properties of Ca-doped BaTiO3 are very different when Ca substitutes onto Ba or Ti sites. The p-type semiconductivity of Ti-substituted ceramics increases reversibly by one to two orders of magnitude under a dc-bias voltage of 100 V cm−1, whereas Ba-substituted ceramics show little sensitivity to a dc bias. This increase in BaTi1−xCaxO3−x, studied over the temperature range 150–600 °C, is independent of electrode material and atmosphere and is attributed to ionization of underbonded O2− ions adjacent to acceptor-doped Ca2+ ions

Synthesis and characterisation of new bismuth phosphate sillenite materials

Sillenite compounds, Bi12MO20, where M = Ge, Si, Ti, P, Pb, B (Lobato et al., 2000; Valent and Suvorov, 2001; Valent and Suvorov, 2002; Wignacourt et al., 1991; Marinova et al., 2002) have been studied for their electro-optical, photoconductivity and dielectric properties

Temperature Stable and Fatigue Resistant lead-free ceramics for actuators

Lead-free ceramics with the composition 0.91K1/2Bi1/2TiO3–0.09(0.82BiFeO3-0.15NdFeO3-0.03Nd2/3TiO3) were prepared using a conventional solid state, mixed oxide route. The ceramics exhibited a high strain of 0.16% at 6 kV mm1, stable from room temperature to 175 C, with a variation of <10%. The materials were fabricated into multilayer structures by co-firing with Pt internal electrodes. The prototype multilayer actuator exhibited constant strains up to 300 C with a variation of 15%. The composition showed fatigue resistant behaviour in both monolithic and multilayer form after bipolar loading of 106 cycles