How to Make Porous Piezoelectrics? Review on Processing Strategies.

Ferroelectric ceramics are a technologically important class of materials that are currently exploited in actuators, sensors, transducers, and memory devices. The introduction of porosity into these materials has been proved to be an effective tool for tuning functional properties for specific applications, such as piezoelectric and pyroelectric devices and energy harvesters. In this review, a comprehensive description of the most widely used processing techniques able to produce porous ferroelectric ceramics is reported. In particular, the state-of-the-art production strategies including replica technique, direct foaming, sacrificial template method, and additive manufacturing used up to now for the realization of porous piezoelectric lead zirconate titanate (PZT)-based structures are critically reviewed and rationalized. Moreover, this work aims to give concrete indications on the more effective and actual production strategies that should be exploited for the development of porous PZT-based materials for the specific applications. Finally, two case studies are reported to remark the critical importance of material-processing-microstructure correlations on the functional properties of the designed devices.

A Glance at Processing-Microstructure-Property Relationships for Magnetoelectric Particulate PZT-CFO Composites.

In this work, we investigated the processing-microstructure-property relationships for magnetoelectric (ME) particulate composites consisting of hard ferromagnetic CoFe2O4 (CFO) particles dispersed in a Nb-doped PbZrxTi1-xO3 (PZT) soft ferroelectric matrix. Several preparation steps, namely PZT powder calcination, PZT-CFO mixture milling and composite sintering were tailored and a range of microstructures was obtained. These included open and closed porosities up to full densification, PZT matrices with decreasing grain size across the submicron range down to the nanoscale and well dispersed CFO particles with bimodal size distributions consisting of submicron and micron sized components with varying weights. All samples could be poled under a fixed DC electric field of 4 kV/mm and the dielectric, piezoelectric and elastic coefficients were obtained and are discussed in relation to the microstructure. Remarkably, materials with nanostructured PZT matrices and open porosity showed piezoelectric charge coefficients comparable with fully dense composites with coarsened microstructure and larger voltage coefficients. Besides, the piezoelectric response of dense materials increased with the size of the CFO particles. This suggests a role of the conductive magnetic inclusions in promoting poling. Magnetoelectric coefficients were obtained and are discussed in relation to densification, piezoelectric matrix microstructure and particle size of the magnetic component. The largest magnetoelectric coefficient α33 of 1.37 mV cm-1 Oe-1 was obtained for submicron sized CFO particles, when closed porosity was reached, even if PZT grain size remained in the nanoscale.

Lead-Free BNT-BT0.08/CoFe2O4 Core-Shell Nanostructures with Potential Multifunctional Applications.

Herein we report on novel multiferroic core-shell nanostructures of cobalt ferrite (CoFe2O4)-bismuth, sodium titanate doped with barium titanate (BNT-BT0.08), prepared by a two-step wet chemical procedure, using the sol-gel technique. The fraction of CoFe2O4 was varied from 1:0.5 to 1:1.5 = BNT-BT0.08/CoFe2O4 (molar ratio). X-ray diffraction confirmed the presence of both the spinel CoFe2O4 and the perovskite Bi0.5Na0.5TiO3 phases. Scanning electron microscopy analysis indicated that the diameter of the core-shell nanoparticles was between 15 and 40 nm. Transmission electron microscopy data showed two-phase composite nanostructures consisting of a BNT-BT0.08 core surrounded by a CoFe2O4 shell with an average thickness of 4-7 nm. Cole-Cole plots reveal the presence of grains and grain boundary effects in the BNT-BT0.08/CoFe2O4 composite. Moreover, the values of the dc conductivity were found to increase with the amount of CoFe2O4 semiconductive phase. Both X-ray photoelectron spectroscopy (XPS) and Mössbauer measurements have shown no change in the valence of the Fe3+, Co2+, Bi3+ and Ti4+ cations. This study provides a detailed insight into the magnetoelectric coupling of the multiferroic BNT-BT0.08/CoFe2O4 core-shell composite potentially suitable for magnetoelectric applications.

Damage from Coexistence of Ferroelectric and Antiferroelectric Domains and Clustering of O Vacancies in PZT: An Elastic and Raman Study.

It is often suggested that oxygen vacancies (V O ) are involved in fatigue and pinning of domain walls in ferroelectric (FE) materials, but generally without definite evidence or models. Here the progress of damage induced by the coexistence of FE and antiferroelectric (AFE) domains in the absence of electric cycling is probed by monitoring the Young's modulus, which may undergo more than fourfold softenings without significant changes in the Raman spectra, but may end with the disaggregation of PZT with ∼5% Ti. At these compositions, the FE and AFE phases coexist at room temperature, as also observed with micro-Raman, and hence the observations are interpreted in terms of the aggregation of V O at the interfaces between FE and AFE domains, which are sources of internal electric and stress fields. The V O would coalesce into planar defects whose extension grows with time but can be dissolved by annealing above 600 K, which indeed restores the original stiffness. The observed giant softening is interpreted by assimilating the planar aggregations of V O to flat inclusions with much reduced elastic moduli, due to the missing Zr/Ti-O bonds. A relationship between the coalescence of a fixed concentration of V O into planar defects and softening is then obtained from the existing literature on the effective elastic moduli of materials with inclusions of various shapes.

Probing the dielectric, piezoelectric and magnetic behavior of CoFe2O4/BNT-BT0.08 composite thin film fabricated by sol-gel and spin-coating methods.

We investigated in this paper a novel bilayer composite obtained by sol-gel and spin coating of the ferroelectric 0.92Na0.5Bi0.5TiO3-0.08BaTiO3 (abbreviated as BNT-BT0.08) and ferromagnetic CoFe2O4 phases, for miniature low-frequency magnetic sensors and piezoelectric sensors. This heterostructure, deposited on Si-Pt substrate (Si-Pt/CoFe2O4/BNT-BT0.08), was characterized using selected method such as: X-ray diffraction, dielectric spectroscopy, piezoelectric force microscopy, SQUID magnetometry, atomic force microscopy/magnetic force microscopy, and advanced methods of transmission electron microscopy. CoFe2O4/BNT-BT0.08 ferromagnetic-piezoelectric thin films show good magnetization, dielectric constant and piezoelectric response. The results of analyses and measurements reveal that this heterostructure can have applications in high-performance magnetoelectric devices at room temperature.

Combined use of Mössbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy for estimating incipient phase separation in lead titanate-based multiferroics.

The formation of separate phases in crystalline materials is promoted by doping with elements with different valences and ionic radii. Control of the formation of separate phases in multiferroics is extremely important for their magnetic, ferroelectric and elastic properties, which are relevant for multifunctional applications. The ordering of dopants and incipient phase separation were studied in lead titanate-based multiferroics with the formula (Pb0.88Nd0.08)(Ti0.98-xFexMn0.02)O3 (x = 0.00, 0.03, 0.04, 0.05) by means of a combination of Mössbauer spectroscopy, XPS, HRTEM, dielectric and anelastic spectroscopy. We found that Fe ions are substituted as Fe3+ at Ti sites and preferentially exhibit pentahedral coordination, whereas Ti ions have coexisting valences of Ti4+/Ti3+. Fe3+ ions are preferentially ordered in clusters, and there exists a transition temperature TC1, below which phase separation occurs between a tetragonal phase T1 free of magnetic clusters and a cubic phase, and a lower transition temperature TC2, below which the cubic phase rich in magnetic clusters is transformed into a tetragonal phase T2. The phase separation persists at the nanoscale level down to room temperature and is visible in HRTEM images as a mixing of nanodomains with different tetragonality ratios. This phase separation was observed over the whole studied concentration range of xFe values. It occurs progressively with the value of xFe, and the transition temperature TC2 decreases with the concentration from about 620 K (xFe = 0.03) to about 600 K (xFe = 0.05), while TC1 remains nearly constant.

Encapsulation of Piezoelectric Transducers for Sensory Augmentation and Substitution with Wearable Haptic Devices.

The integration of polymeric actuators in haptic displays is widespread nowadays, especially in virtual reality and rehabilitation applications. However, we are still far from optimizing the transducer ability in conveying sensory information. Here, we present a vibrotactile actuator characterized by a piezoelectric disk embedded in a polydimethylsiloxane (PDMS) shell. An original encapsulation technique was performed to provide the stiff active element with a compliant cover as an interface towards the soft human skin. The interface stiffness, together with the new geometry, generated an effective transmission of vibrotactile stimulation and made the encapsulated transducer a performant component for the development of wearable tactile displays. The mechanical behavior of the developed transducer was numerically modeled as a function of the driving voltage and frequency, and the exerted normal forces were experimentally measured with a load cell. The actuator was then tested for the integration in a haptic glove in single-finger and bi-finger condition, in a 2-AFC tactile stimulus recognition test. Psychophysical results across all the tested sensory conditions confirmed that the developed integrated haptic system was effective in delivering vibrotactile information when the frequency applied to the skin is within the 200⁻700 Hz range and the stimulus variation is larger than 100 Hz.

Field-induced phase transition and relaxor character in submicrometer-structured lead-free (Bi0.5Na0.5)0.94Ba0.06TiO3 piezoceramics at the morphotropic phase boundary.

Submicrometer-structured (Bi(0.5)Na(0.5))(0.94)Ba(0.06)TiO(3) ceramics ((G) < 720 nm) from nanopowders were studied. The real part of the optimum room temperature set of piezoelectric coefficients obtained from resonances of the BNBT6 dense ceramic disks and shear plates [d(31) = (-37 + 1.33i) pC·N(-1), d(15) = (158.3 - 8.31i) pC·N(-1), k(t) = 40.4%, k(p) = 26.8%, and k(15) = 40.2%] and d(33) (148 pC·N(-1)) can be compared with the reported properties for coarse-grained ceramics. Shear resonance of thickness-poled plates is observed at T = 140°C. Permittivity versus temperature curves of poled samples show relaxor character up to T(i) = 230°C on heating and T(i) = 210°C on cooling of the depoled samples. The phase transition from the room-temperature ferroelectric (FE) to a low-temperature non-polar at zero field (LTNPZF) phase can be observed as a sharp jump in ε(δ)(33)'(T) curves or, as the degree of poling decreases, as a soft change of slope of the curves at T(FE-LTNPZF) = T(d) = 100°C. This dielectric anomaly is not observed on cooling of depoled samples, because the FE phase is field-induced. The observed macroscopic piezoelectric activity above T(d) is a consequence of the coexistence of nanoregions of the FE phase in the interval between T(FE-LTNPZF) and T(i).

Nano-sized ceramic inks for drop-on-demand ink-jet printing in quadrichromy.

Nano-sized ceramic inks suitable for ink-jet printing have been developed for the four-colours CMYK (cyan, magenta, yellow, black) process. Nano-inks of different pigment composition (Co(1-x)O, Au(0), Ti(1-x-y)Sb(x)Cr(y)O2, CoFe2O4) have been prepared with various solid loadings and their chemicophysical properties (particle size, viscosity, surface tension, zeta-potential) were tailored for the ink-jet application. The pigment particle size is in the 20-80 nm range. All these nano-suspensions are stable for long time (i.e., several months) due to either electrostatic (high zeta-potential values) or steric stabilization mechanisms. Both nanometric size and high stability avoid problems of nozzle clogging from particles agglomeration and settling. Nano-inks have a Newtonian behaviour with relatively low viscosities at room temperature. More concentrated inks fulfil the viscosity requirement of ink-jet applications (i.e., < 35 mPa x s) for printing temperatures in between 30 and 70 degrees C. Surface tension constraints for ink-jet printing are fulfilled by nano-inks, being in the 35-45 mN x m(-1) range. The nano-sized inks investigated behave satisfactorily in preliminary printing tests on several unfired industrial ceramic tiles, developing saturated colours in a wide range of firing temperatures (1000-1200 degrees C).