Dr. Marius CIOANGHER

The synergistic piezoelectric and osteoconductive properties of barium titanate (BT) and hydroxyapatite (HA) could stir the development of a new generation of synthetic bone graft substitutes, with capability for rapid and safe osseointegration. The research focused on two concurrent approaches for coupling the BT and HA materials: (i) conventional sintering of BT-HA powder mixtures; and (ii) functionalization of pre-sintered BT with HA coatings using magnetron sputtering (MS). Irrespective of the BT/HA ratios ranging from 95/5 to 80/20 wt%, nanocrystalline or highly-crystallized nature of the powders, sub-micron- or micron-sized particle dimensions, and sintering temperature, it was observed that the BT-HA reactivity cannot be prevented above 800 degrees C. At higher temperatures in the range of 1000-1300 degrees C, HA undergoes decomposition and extensively reacts with BT, leading to the formation of several secondary phases such as CaTiO3, Ba2Ca(PO4)2, BaCa6(PO4)4O, BaCa(PO3)4, and beta-Ca2P2O7. As a consequence, the cytocompatibility assessed in fibroblast and osteoblast cell cultures, as well as the piezoelectric response, were significantly altered. Applying HA coatings by MS to the sintered BT ceramics successfully preserved their piezoelectric properties, while also providing an unaltered cytocompatible and osteogenic-prone surface. The HA coatings were fully crystallized at post-deposition annealing temperatures of 550 and 700 degrees C, achieving crystalline qualities comparable to HA powders sintered at 1100 and 1200 degrees C, respectively. No reactivity events between BT and HA were observed. Partial reactivity was only noticeable upon annealing at 1000 degrees C. Therefore, it is suggested that the HA coating of BT is effective in seamlessly coupling the piezoelectric and osteogenic properties of the two constituents without compromise.

This work was devoted to the first multi-parametric unitary comparative analysis of a selection of sintered piezoceramic materials synthesised by solid-state reactions, aiming to delineate the most promising biocompatible piezoelectric material, to be further implemented into macro-porous ceramic scaffolds fabricated by 3D printing technologies. The piezoceramics under scrutiny were: KNbO3, LiNbO3, LiTaO3, BaTiO3, Zr-doped BaTiO3, and the (Ba0.85Ca0.15)(Ti0.9Zr0.1)O-3 solid solution (BCTZ). The XRD analysis revealed the high crystallinity of all sintered ceramics, while the best densification was achieved for the BaTiO3-based materials via conventional sintering. Conjunctively, BCTZ yielded the best combination of functional properties-piezoelectric response (in terms of longitudinal piezoelectric constant and planar electromechanical coupling factor) and mechanical and in vitro osteoblast cell compatibility. The selected piezoceramic was further used as a base material for the robocasting fabrication of 3D macro-porous scaffolds (porosity of similar to 50%), which yielded a promising compressive strength of similar to 20 MPa (higher than that of trabecular bone), excellent cell colonization capability, and noteworthy cytocompatibility in osteoblast cell cultures, analogous to the biological control. Thereby, good prospects for the possible development of a new generation of synthetic bone graft substitutes endowed with the piezoelectric effect as a stimulus for the enhancement of osteogenic capacity were settled.

Novel (1-x) SrFe12O19 - x BNT-BT0.08 (x = 0; 0.5; 0.8; 1) nanocomposites were explored in this study. The samples were produced by sol-gel method and compacted by conventional sintering. The composition, morphology, local structure, dielectric and magnetic properties were investigated by X-ray diffraction, Transmission Electron Microscopy, Impedance Analysis, Mossbauer spectroscopy, and SQUID magnetometry. The desired composition and the presence of the magnetoplumbite SrFe12O19 and perovskite BNT-BT structures were verified by X-ray diffraction. Irregular morphology and large size distributions are evidenced in the electron microscopy micrographs. The reported room temperature dielectric constants in this study are the highest values obtained in multiferroic composites at room temperature: giant dielectric constants (similar to 1.3 x 10(6)) were obtained, relative to 0.13 x 10(4) in BNT-BT. The hyperfine parameters allowed the identification of the Wyckoff positions of the Fe ions corresponding closely to the theoretical case. The hard magnetic character of the SrFe12O19 phase is evidenced from the magnetic measurements. For the first time in multifermic composites, superdielectric characteristics are evidenced at room temperature.

The dielectric and electric properties of a core-shell SrFe12O19 - BNT-BT nanocomposite were explored in this study. The desired composition and the existence of the magnetoplumbite SrFe12O19 and perovskite BNT-BT structures were verified by X-ray diffraction. The dielectric constant values approached the case of BNT-BT due to the small amount of hexaferrite content. The electric properties were also derived.

Piezoelectric hard/soft effects of multivalence co-dopants (Sb and Mn) in correlation with their location in the lattice, were investigated in PZT ceramics, prepared by conventional ceramic technology, with the following compositions: Pb0.98Sr0.02 ((Ti0.49Zr0.51)(1-0.015-x)Mn0.015Sbx)O-3 with x = 0, 0.005, 0.01, 0.02, 0.03, where antimony was initially assumed to substitute for Ti/Zr ions. The antimony valence state was found to be +3 in all samples by X-ray Photoelectron Spectroscopy investigations. The Electron Paramagnetic Resonance spectra evidenced a steep enhancement of the Mn2+ concentration upon increasing antimony doping level, explained by a charge compensation mechanism, between the Sb3+ ions substituting Pb2+ at the A-sites and the Mn2+ ions, localized at the B-sites. The incorporation of Sb3+ at the A-site of the PZT lattice is also supported by the variation of the lattice parameters, determined by X-ray Diffraction, with the increasing Sb concentration. The investigation of the dielectric, electromechanical and ferroelectric properties evidenced a hard piezoelectric behavior, mainly attributed to the presence of large sized Mn2+ ions, localized at B-sites. Our results prove that the piezoelectric hard/soft response is decisively influenced by the interplay between multiple valence states and locations of the co-dopants, on one hand, and the charge compensation mechanisms, on the other hand. This provides indirect information about the location of some co-dopants which can substitute for both cationic sites in the PZT based ceramics.

A series of seven alkali-free silica-based bioactive glasses (SBG) with ZnO and/or SrO additives (in concentrations of 0-12 mol%) were synthesized by melt-quenching, aiming to delineate a candidate formulation possessing (i) a coefficient of thermal expansion (CTE) similar to the one of titanium (Ti) and its medical grade super alloys (crucial for the future development of mechanically adherent implant-type SBG coatings) and (ii) antibacterial efficiency, while (iii) conserving a good cytocompatibility. The SBGs powders were multi-parametrically evaluated by X-ray diffraction, Fourier transform infrared and micro-Raman spectroscopy, dilatometry, inductively coupled plasma mass spectrometry, antibacterial (against Staphylococcus aureus and Escherichia coli strains) suspension inhibition and agar diffusion tests, and human mesenchymal stem cells cytocompatibility assays. The results showed that the coupled incorporation of zinc and strontium ions into the parent glass composition has a combinatorial and additive benefit. In particular, the "Z6S4" formulation (mol%: SiO2-38.49, CaO-32.07, P2O5-5.61, MgO-13.24, CaF2-0.59, ZnO-6.0, SrO-4.0) conferred strong antimicrobial activity against both types of strains, minimal cytotoxicity combined with good stem cells viability and proliferation, and a CTE (similar to 8.7 x 10(-6) x degrees C-1) matching well those of the Ti-based implant materials.

Ba0.75Sr0.25TiO3 (BST) and PbZr0.68Fe0.14Nb0.14Ti0.04O3 (PZFNT) ceramic pellets were obtained by ceramic technology and their structural, ferroelectric and pyroelectric properties were investigated. The relative density of BST and PZFNT is about 93% and 90%, respectively, with an average grain size of 102 mu m and 6.45 mu m. Both materials have similar room temperature dielectric constants (similar to 2000), but PZFNT shows higher remnant polarization (similar to 15 mu C/cm(2)) and better pyroelectric properties (similar to 1.69 . 10(-4) C/m(2)K), which recommend it for pyroelectric detectors, infrared radiation- and laser pulse energy-meters.

Lead zirconate titanate doped with iron and niobium (PZFNT) was prepared by conventional processing technique, solid state synthesis method. The influence of dopants on the microstructure, ferroelectric and pyroelectric properties was investigated. XRD data reveals a perovskite structure near to the lead zirconate phase. The relative density of PZFNT is approximate 90%, with average grains size of 6.45 mu m.

Ceramic compounds of ferroelectric lead zirconate titanate (PZT) and ferroelectric barium titanate (BT) were prepared from nanopowders corresponding to the formula (1-x)PZT.xBT with x = 0; 0.1; 0.2 ... 0.9; 1. The samples were investigated by X-ray diffraction and electron microscopy and the piezoelectric properties were determined by means of an impedance analyzer. The sintering process is complex since samples densify at different temperatures depending on the composition resulting in different morphostructures. Accordingly, the piezoelectric properties show unusual behavior discussed in terms of different grain size and composition. A remarkably high enhancement of the relative dielectric constant, epsilon(r) coupled with maxima in both, piezoelectric charge constant d(33) and the piezoelectric voltage constant g(33), is observed for x = 0.4 while the values of the coupling coefficient kp are still high similar to those of pure PZT.

Pure BT and BT doped with 1 and 2 mol% Zr, with orthorhombic-tetragonal (O-T) phase transitions near room temperature were prepared, with different grain sizes, by conventional ceramic method, at various sintering temperatures. Intrinsic and extrinsic effects of Zr addition on structural, dielectric, piezoelectric and ferroelectric properties of BT ceramics, near O-T phase transition were studied. In coarse grained ceramics, the intrinsic effects manifested in low field measurements (dielectric and piezoelectric constants), were reduced by Zr addition, while the extrinsic effects which control the high field response (remanent polarization and coercive field) were significantly enhanced. Instead, in fine grains ceramics, of either pure or doped BT, the extrinsic effects related to increased domain wall and grain boundaries density were dominant in both low and high field measurements, overlapping Zr effects. The results were explained in terms of crystal anisotropy correlated with grain size effects.

The effect of 1 and 2 mol % V addition on sintering conditions, structural and functional properties of NbeLi co-doped PZT ceramics, prepared by conventional ceramic method, was systematically studied, by different experimental techniques. The reported results show that the increasing amount of vanadium, as a substitute for niobium, decreases the optimal sintering temperature with 100-150 degrees C, but slightly reduces the piezoelectric, ferroelectric, and electromechanical properties of these ceramics. In addition, the presence of vanadium increases the lattice tetragonality and grain size, promoting a harder piezoelectric behaviour, mostly in the absence of niobium. EPR spectra exhibit well-defined hyperfine splitting characteristics for V4+ state, dispersed in the lattice as VO2+ ion. Additionally, complex paramagnetic defects (charged oxygen vacancies and associated defects) are evidenced for 2 mol % vanadium addition. The results were explained by assuming that vanadium promotes the B-site Li substitution, compensated by oxygen vacancies, while niobium facilitates the A-site Li substitution with lead vacancies formation and partial reduction of V5+ to V4+. Thus, indirect information about lithium location is provided. (C) 2016 Elsevier B.V. All rights reserved.

Water splitting by means of semiconducting photoelectrodes and solar light represents a promising alternative to conventional fossil fuel economy. In this process the photoactive electrode absorb sunlight directly thus initiating the photochemical reaction which create excess electrons in the conduction band of the semiconducting electrode. Titanium doped iron oxide seems to be a promising semiconducting material for photoelectrodes. Consequently, we investigated the effect of Ti doping on the structure, electrical and photoelectrochemical properties alpha-Fe2O3. The Ti doped alpha-Fe2O3 were prepared by a slightly modified mixed oxide route, consisting in a prolonged mixing of the raw materials in a high energy planetary ball mill until the particles decreased to the nanometric sizes. Optimum results were obtained for samples doped with 5 at. % titanium and sintered at 1200 degrees C. Photocurrents as high as 8.4 mA/cm(2), for illumination from a 300 W xenon lamp, were recorded for such samples. It is hoped that such photoelectrodes show promise for water splitting.

Effects of Ni, Nb and Mn co-doping on microstructural, dielectric and electromechanical properties of lead titanate (PT) dense ceramics, obtained as a result of decreasing lattice anisotropy with increasing amount of co-dopants, were investigated. Different values of the average valence (AV) of Ni-Nb co-dopants were obtained by mutual valence compensation between these acceptor donor ions of various relative concentrations. Significantly higher amounts of Mn2+ (resulted by reduction of Mn4+ in presence of donor co-dopants) were found in materials with Ni-Nb AV >4+. These materials show higher coupling factors, correlated with higher mechanical quality factors, compared to the rest of materials. Hard-like piezoelectric behavior was manifested in materials with Ni-Nb AV 4+, and without manganese, turned out to have a soft-like behavior. Electromechanical properties of PT ceramics are discussed in terms of average valence of Ni-Nb co-dopants and multivalence state of manganese. (C) 2013 Elsevier Ltd. All rights reserved.

A high performance piezoceramic material of PZT type, doped with 6 atomic % W, was prepared in order to be used as sensing element for a vibration transducer used to equilibrate the motor-fan group of auto vehicles. The piezoelectric parameters of material showed high values which recommended it for the vibration transducer. The transducer consists of a ring shaped active element sandwiched between two steel blocks. The transducer works in quasistatic regime, at frequencies much lower than the resonance frequency, being tightly screwed in the measurement system by a metallic cover attached at the back end.

Three ceramic magnetic compositions within the CuZnTi ferrite system, having the Curie temperatures centered around 60 degrees C, 80 degrees C and 100 degrees C, respectively were investigated in order to determine the time-temperature stability of their main magnetic properties. Rates of changes of 33, 66 and 100 ppm/h of the maximum slopes of permeability were found for the samples aged at 60 degrees C, 80 degrees C and 100 degrees C, respectively. The samples aged at temperatures higher than 200 degrees C show a rather sudden decrease of the maximum slope of permeability, but no shift of the Curie temperature and the working point, corresponding to the temperature where the slope has the maximum value. The results are discussed in terms of the migration processes of the cations, especially Cu2+, from metastable positions on which they were frozen during the rapid cooling of the samples from the sintering temperature, to the more stable ones, namely the octahedral sites into the spinel lattice.

0.89(Na0.5Bi0.5)TiO3-0.11BaTiO(3), (BNT-BT0.11) thin film was fabricated by sol-gel/spin coating process, on platinized silicon wafer. Perovskite structure with random orientation of crystallites has been obtained at 700 A degrees C. Piezoelectric activity of BNT-BT0.11 thin film was detected using piezoresponse force microscopy (PFM). Effective piezoelectric coefficient d (33eff) of such film, recorded at 5 V applied dc voltage, was similar to 29 pm/V, which is similar to other BNT-BT (x) thin films. The complex refractive index and dielectric function of BNT-BT0.11 thin films were also investigated. The high leakage current density significantly influences the dielectric, ferroelectric, and piezoelectric properties of the BNT-BT0.11 films.

Due to its low resistivity and excellent thermal stability, IrO2 has attracted attention as an alternative for electrode material in ferroelectric integrated circuit applications. Oriented growth of IrO2 electrode film was investigated with the goal to control the texture of the PZT thin film. IrO2 films were prepared by DC reactive sputtering. PZT film was prepared by RF magnetron sputtering single target deposition method. The whole layer stack was grown onto amorphous thermal oxide of a silicon wafer. The results indicate that IrO2 thin film was preferentially (200) oriented when a TiO2 seeding layer was used. The orientation relationships along the whole PZT(111)/IrO2(200)/TiO2(200)/Ti structure was discussed.

The application area of piezoceramic materials and devices based on such materials is continuously extended. The working conditions for such devices and structures may be sometimes very hard such as low and high temperatures, nuclear radiation, high pressure and so on. Such conditions may affect to some extent the transducer performances due to the changes of the basic properties of piezoceramic materials used as sensors. In this regard we have investigated the changes of the main piezoelectric properties of two typically hard and soft piezoceramics within a large temperature range from 2 to 600 K. All parameters measured showed a rather steady increase or decrease with increasing temperature. The results were discussed in terms of intrinsic and domain wall contribution to the dielectric and piezoelectric response of materials.

Multiferroic composite materials, consisting of piezoelectric and piezomagnetic phases, show electric polarization in the presence of a magnetic field and magnetization on applying an electric field, i.e. piezomagnetic phase causes polarization while piezoelectric phase causes changes in magnetization. The figure of merit of such multiferroic particulate composites is the magnetoelectric voltage coefficient representing the amount of polarization induced by a given magnetic field. In the present investigation we prepared and studied the properties of bulk particulate composites made from cobalt ferrite (COF) and a soft piezoelectric material (PZT). Composite samples, according to the formula xCOF center dot(1-x)PZT with 0 <= x <= 1 were prepared by mixing the COF and PZT powders, pressing them as discs and then sintered at 1200 degrees C for 3 hours. Structural, magnetic, piezoelectric and magnetoelectric characteristics of the sintered composites were determined as a function of the mass fraction of COF into PZT and magnetic field. The ME coefficient shows a maximum value of about 70 mV/cm.Oe for composites containing 40 % COF and 60 % PZT, in a DC magnetic field of 3 kOe at a frequency of 1 KHz of the ac magnetic field. Some of the dielectric and piezoelectric properties of the composite samples, as a function of the mass fraction x, were also determined.

A high quality soft type PZT material was designed and produced in order to be used as sensor for a high intensity air siren, Two thin disks from this material were assembled into a parallel bimorph type sensor with an intermediate metallic plate for the siren. This assembly behaves like an acoustic resonator in the high frequency audio range. This structure transforms the radial mode of vibration into a flexural one, with a much lower frequency. A mechanical impedance adapter was used in order to assure a good match between the oscillating ceramic and the surrounding air. A theoretical approach was outlined, which allows the evaluation of the resonance frequency for the working transducer. The theoretical and experimental data agree to a satisfactory degree up to the input errors assumed by the model. Acoustical and impedance measurements were made in order to appreciate the influence of the metallic plate on the frequency. The bimorph necessary for making the siren was designed as a parallel structure and the corresponding transducer was measured and evaluated. In order to increase the acoustic emission a frontal cardboard horn was added to the resonator.

Lead free ceramics in the system (1-x)KNN x(Bi2O3,CaO,CuO) with 0.0 <= x <= 0.1 were synthesized by the usual solid state reaction and their structural and piezoelectric properties were investigated Dense samples with densities of about 4 68 g/cm(3) were prepared by sintering at an optimum temperature of 1150 degrees C for 6 h Only perovskite phase was detected by X-ray investigation in all samples A typical MPB where orthorombic-tetragonal phases coexist was detected for a doping level of 0.06 where the piezoelectric parameters showed maximum values Planar coupling factor, as much as 0.46, piezoelectric charge constant of 270 pC/N and mechanical quality factor Q(m) of 75 were recorded for the samples situated within the MPB.

Lead titanate (PT) ceramics co-doped with 8 to 13 mol% Ni-Nb, by substituting titanium ions, were prepared by conventional ceramic method and the influence of Ni-Nb doping level on their mopho-structural, electromechanical and dielectric properties was investigated. Dense tetragonal PT ceramics were obtained for 8 to 12 mol% Ni-Nb co-doping. Lattice anisotropy decreased from 1.053 to 1.046 with increasing doping level. Large thickness coupling factors of 0.4 were obtained for 8, 11, and 12 mol% Ni-Nb. Large electromechanical anisotropy of 10 was obtained for 8 mol% Ni-Nb. It was found that Ni-Nb co-doping has both softening and hardening effects as a function of donor or acceptor behavior of different amounts of Ni-Nb. For 13 mol% Ni-Nb, segregation of a small amount of a secondary phase occurs, lattice constants and tetragonality significantly decrease and the resulting ceramic becomes very hard.

Soft ferrites in the CuZnTi system, having the chemical composition Cu1-x-yZnxTiyFe2O4 with 0.5 <= x <= 0.7 and 0.00 <= y <= 0.05 were investigated as a function of composition, sintering temperature and cooling speed, in order to obtain materials with different Curie temperatures, between 30 and 180 degrees C and very high change rate of permeability with temperature around their Curie points. Such materials are well suited to use as high sensitive magnetic temperature sensors and transducers for temperature control. Zn and Ti additions to copper ferrite change the Curie temperature in a controllable manner, thus being possible to produce ferrite material with a fine control of the Curie point at any desired temperature. Most important was the behavior of magnetic permeability with temperature around the Curie point, where it may change with about 60 %/degrees C by a proper choice of the cooling speed of samples from the sintering temperature to room temperature. This makes such materials extremely attractive as magnetic temperature sensors of high sensitivity. Two applications Of Such materials as temperature sensors, namely an ultrathermostat and an on-off switch type relay were designed. Their functionality and performances are presented and discussed.

The displacement devices using piezoceramic sensors play an important role in many fields. Soft type piezoelectric materials used for such sensors arc more appealing because of their lower coercive field, relatively low modulus of elasticity, high electromechanical coupling factors and piezoelectric strain coefficients. We designed a PZT type material doped with niobium and nickel to increase the strain coefficient and still retaining a high coupling coefficient. The chemical formula was Pb0.9Ba0.08Nb0.03Ni0.06Zr0.46Ti0.40O3. The main piezoelectric parameters were: d(33)=680 pm/V. d(31)=-235 pm/V, k(p)=0.64 and k(31)=0.42. A unimorph transducer was made from a thin sheet of such a piezoceramic material, tightly bonded on a thin optically polished glass plate and mounted as a cantilever. The performance of this transducer was evaluated by means of a new optical method which makes use of the Moire deflectometry and provides high precision. The method is rather simply and consists mainly in the following: the Moire fringes rotate when the bimorph bends under the influence of the electric field and by measuring the rotating angle of the fringes one can easily determine the bimorph curvature and the free end displacement.

In order to determine the effect of sample shape, compacting pressure and green density gradients on the final shape and density of sintered bodies a study was made on a PZT type powder, pressed within a large range of shapes from long cylinders up to thin discs and at pressures ranging between 40 and 180 MPa. Important shape distorsion were found for both long cylinders and thin discs but surprisingly the final density was not essentially changed even if the green compacted density showed important changes with in the samples. Differences in the shrink age of diameter and thickness brought about by sintering for samples with different shapes were found.

A high quality PZT type material was designed and produced in order to be used as sensor for a high internsity siren. Two disks from this materials were assembled into a parallel bimorph type transducer with an intermediate metallic plate. This assembly behaves like an acoustic resonator in the high frequency audio range. The fundamental of the flexural mode for a free resonator is taken into account Its frequency dependence on the geometry of the system and on its material properties is computed using the results for a circular plate with clamped edges and an observation on the equivalence between the movement of a particular part of a resonator in a stationary state and the movement of that pari separated from the resonator but with the same border conditions. Acoustical and impedance measurements were made in order to appreciate the influence of the metallic plate on the frequency. In order to increase the acoustic emission a frontal cardboard horn was added to the resonator.

A study was made on the temperature behavior of the main piezoelectric parameters, namely the electromechanical coupling factor k(p), the mechanical quality factor Q, the dielectric permittivity (real and imaginary part), the loss tangent t(g) and the piezoelectric charge constants 6133 and d(31) of a soft type piezoelectric material. It was evidenced that temperatures under 150 degrees C do not influence these parameters, which means that every transducer made from this type of material may be successfully used up to this temperature. Between 150 degrees C and 250 degrees C, the piezoelectric properties undergo more or less important changes, mainly due to the depoling effect. After that, at temperatures over 250 degrees C, they degrade very rapidly, tending to zero.

Functionally graded materials represent a new class of composite type materials characterized by a continuous variation of properties through the thickness direction. Due to this they found numerous applications in aerospace, automobile, biomedical or nuclear industries. Bilayered structures made from typically hard and typically soft PZT type materials as well as plain hard and soft and intimately mixed hard and soft samples were prepared by green pressed powdersfollowed by sintering at different temperatures between 1000 and 1300 degrees C. The dielectric and piezoelectric properties of sintered compacts were determined in relation with the nature of the interdiffusion layer involved. Electron microscopy as well as X-Ray diffractometry was used to get an insight into the interfacial diffusion process. The composition and the width of the interdiffusion layer depend on temperature. The mechanism of the interdiffusion layer and materials properties were discussed in terms of the ionic diffusion coefficients and activation energies of the species which take place into the diffusion process.

Barium titanate was prepared by the advanced procedure of mechanochemical synthesis from barium and titanium oxides after 50 hours of milling. The X-ray examination of the milled powders showed the phase evolution during synthesis and the perovskite phase was initiated after 5 hours and was completed after 50 hours. Sintered samples from these nanopowders show different dielectric properties for fine and coarse grained ceramics. Samples with an average grain size of 2 mu m showed the highest dielectric constant of 5800 at room temperature. A sharp maximum of the dielectric constant with values of about 16000 was recorded at the Curie temperature.

The temperature behavior of the main piezoelectric parameters, such as the electromechanical coupling factor k(p), the mechanical quality factor Qm, the dielectric permittivity epsilon (real and imaginary part), the loss tangent tan delta, the piezoelectric charge constants d(33) and d(31) and the voltage constants 933 and 931 of a soft type piezoelectric material was investigated. The results showed that temperatures under 150 degrees C do not influence these parameters, which indicate that every transducer made from this type of material may be successfully used up to this temperature. Between 150 degrees C and 250 degrees C, the piezoelectric properties undergo more or less important changes, mainly due to the depoling effect and above that, at temperatures over 250 degrees C, they degrade very rapidly, tending to zero.

New PZT type ceramic materials, doped with Ni, were prepared by the usual solid state reaction. The best composition proved to be the one containing 6% atomic Ni and having the following chemical formula: Pb0.95Bi0.03Nb0.02Zr0.51 Ti0.43Ni0.06O3. Rectangular samples of this powder were pressed and sintered at 1200 OC for 4 hours and then it was cut in thin slices used to construct an efficient bimorph type ventilator to be used in miniaturized devices for cooling. Miniature ventilators made of PZT ceramics are preferred due to their smallness, high electromechanical efficiency and lack of rotating parts and last but not least of contiguous electrical contacts. We made such a device by using two thin ceramic PZT plates of the material with the best piezoelectric properties, assembled in a flexural oscillator through a proper bimorph association. The emerging doublet behaves itself very much like a bimetal system and possesses a good developed flexural mode. Attaching a metallic elastic plate to the bimorph produces a highly efficient miniature ventilator. A theoretical quantitative study of this flexural bimorph system with elastic plate attached was proposed.

A study was made to determine the effect of sample shape, compacting pressure and green density gradients on the final shape and density of sintered bodies. Experiments were carried out on a PZT type powder, pressed with a large range of shapes from long cylinders up to thin discs, at pressures ranging between 40 and 180 MPa. Important shape distorsion were found for both long cylinders and thin discs but surprisingly the final density was not essentially changed even if the green compacted density showed important changes within the samples. Differences in shrinkage of diameter and thickness brought about by sintering for samples with different shapes were found.

The new advanced procedure of mechanochemical synthesis was used to prepare barium titanate from barium and titanium oxides. The X-ray examination of the powders milled for different times showed the phase evolution during synthesis. The perovskite phase was initiated after 5 hours of milling and was completed after 50 hours. Sintered samples from these nanopowders show different dielectric properties depending on their morphostructure. Thus for samples with an average grain size of 2 mu m we obtained the highest dielectric constant of 5 800 at room temperature. A sharp maximum of the dielectric constant with values of about 16 000 was recorded at the Curie temperature.

In the present investigation we studied the effect of lead content on a hard type ceramics starting from lack to excess PbO. Specimens of Pb-x(Mn0.017Sb0.033Zr0.48Ti0.47)O-3 with 0.96 <= x <= 1.06 were prepared by conventional oxide mixing technique and sintered at temperatures between 1280 and 1350 degrees C. In samples with lower Ph concentration the pyrochlore phase appeared, while in those with higher Pb an excess of PbO phase was detected. These phases proved detrimental for the properties of sintered ceramics. The highest values of piezoelectric properties were observed only for samples with an excess lead of about 2% sintered at 1340 degrees C, indicating that it represents the optimum amount of PbO. For such samples, the density p was 7.77 g/cm (3). the remnant polarization P, was 37 mu C/cm(3) the planar coupling coefficient k(P) was 0.57 and the charge constant d(33) was 340 C-P/N. (c) 2007 Elsevier Ltd. All rights reserved.

Soft and hard type piezoceramic sintered samples were subjected to neutron irradiation in fluxes up to, 10(18) n/cm(2) and the changes of the basic properties brought about by irradiation were investigated. The results showed that intermediate irradiation levels of up to 10(15) n/cm(2) do not change significantly the properties, but higher levels changed them. Thus the electromechanical coupling factor, the dielectric permittivity and losses decreased while the mechanical quality factor increases with increasing neutron flux for both types of materials. Changes of the lattice constants a and c were also observed. The main defects produced by neutron irradiation are oxygen vacancies but they are not entirely responsible for the modification of the materials properties. Some other factors such as domain pinning and lattice deformation can contribute to the properties degradation.