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Materials undergoing antiferroelectric/ferroelectric (AFE/FE) transitions are studied for possible applications that exploit the large volume, charge, and entropy differences between the two states, such as electrocaloric cooling, energy storage, and electromechanical actuators. Though certain compositions of PbZr1-xTixO3 codoped with La and Sn may withstand millions of electrically induced AFE/FE cycles, in other cases few thermally induced cycles and room temperature aging may cause noticeable changes in the material properties. This is particularly evident in the elastic moduli, which at room temperature can become as much as four times softer. In order to get more insight into the mechanisms involved in such elastic aging and full recovering with mild annealing at 600-800 K, the effect of La doping on PbZr0.954Ti0.046O3 is studied with anelastic measurements. Complete suppression of the time dependent phenomena is found after the transformation of the intermediate FE phase into incommensurate AFE by 2% La doping. This is discussed in terms of disappearance of the stress and electric fields at the FE/AFE interfaces, in the light of the thermally activated anelastic relaxation processes that are observed at high temperature and are due to mobile defects, presumably O vacancies. [ABSTRACT FROM AUTHOR]

We present the results of dielectric and anelastic spectroscopy measurements, together with X-ray diffraction investigations, which allow us to establish more precisely the phase diagram of Pb1-xLax(Zr0.9Ti0.1)1-x/4O3 (PLZT x/90/10) in the compositional range around the AFE/FE phase boundary (00.032 are antiferroelectric with orthorhombic Pbam structure. In-between, for compositions with 0.025⩽x⩽0.032, a coexistence of the AFE/FE phases is evidenced. The use of complementary dielectric and anelastic techniques allows to follow the phase transitions shifts throughout all the interesting composition range and to construct the temperature-composition phase diagram. The tilt instability line, separating the R3c and R3m low and high temperature phases, has been evidenced. Moreover, the new transition, associated with the onset of disordered tilting preceding the long range order of the R3c phase, previously found in Zr-rich Pb(Zr,Ti)O3, is confirmed in rhombohedral PLZT x/90/10 compositions. [ABSTRACT FROM AUTHOR]

The metal-insulator (MI) phase transition in Nd1-xEuxNiO3, 0⩽x⩽0.35, has been investigated through the pressure dependence of the electrical resistivity ρ(P, T) and measurements of specific heat CP(T). The MI transition temperature (TMI) increases with increasing Eu substitution and decreases with increasing pressure. Two distinct regions for the Eu dependence of dTMI/dP were found: (i) for x⩽0.15, dTMI/dP is nearly constant and ~-4.3 K/kbar; (ii) for x⩾0.15, dTMI/dP increases with x and it seems to reach a saturation value ~-6.2 K/kbar for the x=0.35 sample. This change is accompanied with a strong decrease in the thermal hysteresis in ρ(P, T) between the cooling and warming cycles, observed in the vicinity of TMI. The entropy change (ΔS) at TMI for the sample x=0, estimated by using the dTMI/dP data and the Clausius-Clapeyron equation, resulted in ΔS~1.2 J/mol K, a value in line with specific heat measurements. When the Eu concentration is increased, the antiferromagnetic (AF) and the MI transitions are separated in temperature, permitting that an estimate of the entropy change due to the AF/Paramagnetic transition be carried out, yielding ΔSM ~ 200 mJ/mol K. This value is much smaller than that expected for a s=½ spin system. The analysis of ρ(P, T) and CP(T) data indicates that the entropy change at TMI is mainly due to the electronic delocalization and not related to the AF transition. [ABSTRACT FROM AUTHOR]

We show that it is possible, by anelastic spectroscopy measurements, to identify beyond the intrinsic limits of other techniques such as diffraction, resistivity, or extended x-ray absorption fine structure, the nature of spurious and minority phases possibly present in the experimental samples. We will stress how the high selectivity of this spectroscopy can be useful in studying classes of materials such as colossal magnetoresistance manganites or other transition metal oxides where the characterization of the specimens assumes a crucial role. [ABSTRACT FROM AUTHOR]

The transition metals Nb, Ta and V have been known to be cubic at all temperatures, until recently the existence of a martensitic transformation has been reported, based on anomalies in the thermal expansion at low temperatures. Such a structural transformation would have passed unnoticed, because it would be hindered by small amounts of impurities. This finding is discussed in the light of anelastic measurements on Nb samples whose purities are comparable to those presenting the dilatometric anomalies. It results that the effects of the alleged transformation on the anelastic spectra would be at least three orders of magnitude smaller than in typical mar- tensitic transformations. A possible alternative explanation for the observed anomalies is proposed in terms of precipitation of unnoticed residual H. [ABSTRACT FROM AUTHOR]

A method is proposed for evaluating the potential piezoelectric response, that a ferroelectric material would exhibit after full poling, from elastic and dielectric measurements of the unpoled ceramic material. The method is based on the observation that the softening in a ferroelectric phase with respect to the paraelectric phase is of piezoelectric origin, and is tested on BaTiO3. The angular averages of the piezoelectric softening in unpoled ceramics are calculated for ferroelectric phases of different symmetries. The expression of the orientational average with the piezoelectric and dielectric constants of single crystal tetragonal BaTiO3 from the literature reproduces well the softening of the Young's modulus of unpoled ceramic BaTiO3, after a correction for the porosity. The agreement is good in the temperature region sufficiently far from the Curie temperature and from the transition to the orthorhombic phase, where the effect of fluctuations should be negligible, but deviations are found outside this region, and possible reasons for this are discussed. This validates the determination of the piezoelectric response by means of purely elastic measurements on unpoled samples. The method is indirect and, for quantitative assessments, requires the knowledge of the dielectric tensor. On the other hand, it does not require poling of the sample, and therefore is insensitive to inaccuracies from incomplete poling, and can even be used with materials that cannot be poled, for example, due to excessive electrical conductivity. While the proposed example of the Young's modulus of a ceramic provides an orientational average of all the single crystal piezoelectric constants, a Resonant Ultrasound Spectroscopy measurement of a single unpoled ceramic sample through the ferroelectric transition can in principle measure all the piezoelectric constants, together with the elastic ones. [ABSTRACT FROM AUTHOR]

A method is proposed for evaluating the potential piezoelectric response, that a ferroelectric material would exhibit after full poling, from elastic and dielectric measurements of the unpoled ceramic material. The method is based on the observation that the softening in a ferroelectric phase with respect to the paraelectric phase is of piezoelectric origin, and is tested on BaTiO3. The angular averages of the piezoelectric softening in unpoled ceramics are calculated for ferroelectric phases of different symmetries. The expression of the orientational average with the piezoelectric and dielectric constants of single crystal tetragonal BaTiO3 from the literature reproduces well the softening of the Young's modulus of unpoled ceramic BaTiO3, after a correction for the porosity. The agreement is good in the temperature region sufficiently far from the Curie temperature and from the transition to the orthorhombic phase, where the effect of fluctuations should be negligible, but deviations are found outside this region, and possible reasons for this are discussed. This validates the determination of the piezoelectric response by means of purely elastic measurements on unpoled samples. The method is indirect and, for quantitative assessments, requires the knowledge of the dielectric tensor. On the other hand, it does not require poling of the sample, and therefore is insensitive to inaccuracies from incomplete poling, and can even be used with materials that cannot be poled, for example, due to excessive electrical conductivity. While the proposed example of the Young's modulus of a ceramic provides an orientational average of all the single crystal piezoelectric constants, a Resonant Ultrasound Spectroscopy measurement of a single unpoled ceramic sample through the ferroelectric transition can in principle measure all the piezoelectric constants, together with the elastic ones. [ABSTRACT FROM AUTHOR]

The elastic response of (Ba,Ca)(Ti,Zr)O3 at compositions where the piezoelectric effect is maximized has been measured by different methods between 1 Hz and 250 kHz and compared with that of PZT at the middle of its morphotropic phase boundary. In all cases, the compliance is peaked at the border between the tetragonal (T) and the orthorhombic (O) phases, intermediate between the T and the low-temperature rhombohedral phase. The anomalies do not exhibit dependence on frequency and their relative amplitude is 200-300 times larger than the losses, demonstrating that they are intrinsic rather than due to the domain wall motion. This also demonstrates the role of an intermediate O or monoclinic phase in enhancing the transverse instability and piezoelectric coupling at a (morphotropic) phase boundary between R and T phases. [ABSTRACT FROM AUTHOR]

The effect of oxygen vacancies on the elastic properties of BaCe0.9Y0.1O3-δ is studied by measuring the complex Young’s modulus between 80 and 850 K varying the content of O vacancies from 0 to nearly 0.05. The Young’s modulus measured at a fixed temperature above 300 K may change by more than 20% but this is due to a shift of the rhombohedral-orthorhombic transition by 250 K and to proton and vacancy hopping. Below 100 K these effects are frozen and the filling of the O vacancies with OH ions increases the Young’s modulus by ∼1.3%. [ABSTRACT FROM AUTHOR]

Oxides RNiO3 (R = rare-earth, R ≠ La) exhibit a metal-insulator (MI) transition at a temperature TMI and an antiferromagnetic (AF) transition at TN. Specific heat (CP) and anelastic spectroscopy measurements were performed in samples of Nd1-xEuxNiO3, 0 ≤ x ≤ 0.35. For x = 0, a peak in CP is observed upon cooling and warming at essentially the same temperature TMI = TN ∼ 195 K, although the cooling peak is much smaller. For x ≥ 0.25, differences between the cooling and warming curves are negligible, and two well defined peaks are clearly observed: one at lower temperatures that define TN, and the other one at TMI. An external magnetic field of 9 T had no significant effect on these results. The elastic compliance (s) and the reciprocal of the mechanical quality factor (Q-1) of NdNiO3, measured upon warming, showed a very sharp peak at essentially the same temperature obtained from CP, and no peak is observed upon cooling. The elastic modulus hardens below TMI much more sharply upon warming, while the cooling and warming curves are reproducible above TMI. Conversely, for the sample with x = 0.35, s and Q-1 curves are very similar upon warming and cooling. The results presented here give credence to the proposition that the MI phase transition changes from first to second order with increasing Eu doping. [ABSTRACT FROM AUTHOR]