Thermal transport properties of selected ferroelectrics, mixed valance perovskites and dielectric ceramics using photopyroelectric technique

Photothermal spectroscopy is a group of high sensitivity methods used to measure optical absorption and thermal characteristics of a sample.The basis of photothermal spectroscopy is a photo-induced change in the thermal state of the sample.Light energy absorbed and not lost by subsequent emission results in sample heating.This heating results in a temperature change as well as changes in thermodynamic parameters of the sample which are related to temperature.Measurements of the temperature,pressure,or density changes that occur due to optical absorption are ultimately the basis for the photothermal spectroscopic methods.This is a more direct measure of optical absorption than optical transmission based spectroscopies.Sample heating is a direct consequence of optical absorption and so photothermal spectroscopy signals are directly dependent on light absorption.Scattering and reflection losses do not produce photothermal signals.Subsequently,photothermal spectroscopy more accurately measures optical absorption in scattering solutions,in solids,and at interfaces.This aspect makes it particularly attractive for application to surface and solid absorption studies,and studies in scattering media.

Investigation of dielectric and elastic properties of selected dielectric ceramics and oxide glasses

The dielectric and elastic properties are of considerable significance to the science and technology of matter in the solid state. The study of these properties give information about the magnitude of the forces and nature of the bonding between the atoms. Our aim has been to investigate systematically the effect of doping of an appropriate element on the elastic and dielectric properties of selected dielectric ceramics and oxide glasses. These materials have got wide technological applications due to their interesting electrical, optical, thermal and elastic behaviour. Ultrasound propagation and capacitance measurement techniques have been employed for the systematic investigation of the elastic and dielectric properties of selected number of these materials. Details of the work done and results obtained are presented in this thesis.

Thermal characterisation of dye-intercalated K-10 montmorillonite ceramics using photoacoustic technique

Thermal diffusivity (TD) measurements were performed on some industrially important dyes – auramine O (AO), malachite green and methylene blue (MB) – adsorbed K-10 montmorillonites using photoacoustic method. The TD value for the dye-adsorbed clay mineral was observed to change with a variation in dye concentration. The contribution of the dye towards TD was also determined. The repeatedly adsorbed samples with MB and AO exhibited a lower TD than the single-adsorbed samples. TD values of sintered MB samples were also obtained experimentally. These sintered samples exhibit a higher TD, although they show a trend similar to that of non-sintered pellets. A variation in dye concentration and sintering temperature can be used for tuning the TD value of the clay mineral to the desired level

Piezoelectric Ultrasonic Micromotors

This report describes development of micro-fabricated piezoelectric ultrasonic motors and bulk-ceramic piezoelectric ultrasonic motors. Ultrasonic motors offer the advantage of low speed, high torque operation without the need for gears. They can be made compact and lightweight and provide a holding torque in the absence of applied power, due to the traveling wave frictional coupling mechanism between the rotor and the stator. This report covers modeling, simulation, fabrication and testing of ultrasonic motors. Design of experiments methods were also utilized to find optimal motor parameters. A suite of 8 mm diameter x 3 mm tall motors were machined for these studies and maximum stall torques as large as 10^(- 3) Nm, maximum no-load speeds of 1710 rpm and peak power outputs of 27 mW were realized. Aditionally, this report describes the implementation of a microfabricated ultrasonic motor using thin-film lead zirconate titanate. In a joint project with the Pennsylvania State University Materials Research Laboratory and MIT Lincoln Laboratory, 2 mm and 5 mm diameter stator structures were fabricated on 1 micron thick silicon nitride membranes. Small glass lenses placed down on top spun at 100-300 rpm with 4 V excitation at 90 kHz. The large power densities and stall torques of these piezoelectric ultrasonic motors offer tremendous promis for integrated machines: complete intelligent, electro-mechanical autonomous systems mass-produced in a single fabrication process.

Performance limitations of piezoelectric and force feedback electrostatic transducers in different applications

Current limitations in piezoelectric and electrostatic transducers are discussed. A force-feedback electrostatic transducer capable of operating at bandwidths up to 20 kHz is described. Advantages of the proposed design are a linearised operation which simplifies the feedback control aspects and robustness of the performance characteristics to environmental perturbations. Applications in nanotechnology, optical sciences and acoustics are discussed.

Osteoconductivity of modified fluorcanasite glass-ceramics for bone tissue augmentation and repair

Modified fluorcanasite glasses were fabricated by either altering the molar ratios of Na(2)O and CaO or by adding P(2)O(5) to the parent stoichiometric glass compositions. Glasses were converted to glass-ceramics by a controlled two-stage heat treatment process. Rods (2 mm x 4 mm) were produced using the conventional lost-wax casting technique. Osteoconductive 45S5 bioglass was used as a reference material. Biocompatibility and osteoconductivity were investigated by implantation into healing defects (2 mm) in the midshaft of rabbit femora. Tissue response was investigated using conventional histology and scanning electron microscopy. Histological and histomorphometric evaluation of specimens after 12 weeks implantation showed significantly more bone contact with the surface of 45S5 bioglass implants when compared with other test materials. When the bone contact for each material was compared between experimental time points, the Glass-Ceramic 2 (CaO rich) group showed significant difference (p = 0.027) at 4 weeks, but no direct contact at 12 weeks. Histology and backscattered electron photomicrographs showed that modified fluorcanasite glass-ceramic implants had greater osteoconductivity than the parent stoichiometric composition. Of the new materials, fluorcanasite glass-ceramic implants modified by the addition of P(2)O(5) showed the greatest stimulation of new mineralized bone tissue formation adjacent to the implants after 4 and 12 weeks implantation. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 94A: 760-768, 2010

COLOR STABILITY OF DENTAL CERAMICS SUBMITTED TO ARTIFICIAL ACCELERATED AGING AFTER REPEATED FIRINGS

Statement of problem. Color stability is an important factor to ensure the long-term clinical success of ceramic restorations. There is a lack of information on how color is affected by fabrication procedures, such as the number of firings. Purpose. The purpose of this study was to evaluate the effects that the number of firings and type of substrate have on the color stability of dental ceramic submitted to artificial accelerated aging. Material and methods. Sixty specimens were fabricated: 30 metal ceramic (Verabond II + IPS d.SIGN) and 30 all-ceramic (IPS d.SIGN). Specimens were divided into 3 groups (n=10), and submitted to 2, 3, or 4 firings (+/- 900 degrees C), respectively, according to the manufacturer`s instructions. Color readings were obtained with a spectro photometer before and after artificial accelerated aging, and L*, a*, and b* coordinates and total color variation (Delta E) were analyzed (2-way ANOVA, Bonferroni, (alpha=05). Results. For metal ceramic specimens, differences for the L* coordinates were significant (P<.05) only for the group submitted to 3 firings. With respect to the all-ceramic specimens, smaller L* coordinates were obtained for greater a* and b* coordinates, indicating that the greater the number of firings, the darker and more reddish/yellowish the specimen. All Delta E values, for all groups, were below 1.0. All-ceramic specimens submitted to 3 and 4 firings presented Delta E means differing statistically (P<.05) from those of the metal ceramic group. Conclusions. The type of substrate and number of firings affected the color stability of the ceramic material tested. Artificial accelerated aging did not produce perceptible color stability changes (Delta E<1.0). (J Prosthet Dent 2009-101:13-18)

The gas flow rate increase obtained by an oscillating piezoelectric actuator on a micronozzle

Micronozzles with piezoelectric actuator were fabricated and investigated. The micronozzles were fabricated in glass substrates using a powder-blasting technique, and the actuator is a bimorph structure made from a piezoelectric polymer. The actuator was located at the nozzle outlet, and was driven in an oscillating mode by applying an alternating voltage across the actuator electrodes. With a pressure difference between inlet and outlet, the gas flow rate through the device was increased. This effect was quantified, and compared to a similar micronozzle with no actuator. The increase in the flow rate was defined as the gas flow through the micronozzle with actuator oscillating minus the gas flow without actuator, was found to depend on the inlet pressure, the pressure ratio, and the nozzle throat diameter. (C) 2008 Elsevier B.V. All rights reserved.

Thermoluminescence dating of Brazilian indigenous ceramics

Two indigenous ceramics fragments, one from Lagoa Queimada (LQ) and another from Barra dos Negros (BN), both sites located on Bahia state (Brazil), were dated by termoluminescence (TL) method. Each fragment was physically prepared and divided into two fractions, one was used for TL measurement and the other for annual dose determination. The TL fraction was chemically treated, divided in sub samples and irradiated with several doses. The plot extrapolation from TL intensities as function of radiation dose enabled the determination of the accumulated dose (D(ac)), 3.99 Gy and 1.88 Gy for LQ and BN, respectively. The annual dose was obtained through the uranium, thorium and potassium determination by ICP-MS. The annual doses (D(an)) obtained were 2.86 and 2.26 mGy/year. The estimated ages were similar to 1375 and 709 y for BN and LQ ceramics, respectively. The ages agreed with the archaeologists` estimation for the Aratu and Tupi tradition periods, respectively.

Dating archeological ceramics from the Valley of Vitor, Arequipa by the TL method

The age of some ancient pottery from the Valley of Vitor in the region of Arequipa, Peru, is determined by the thermoluminescence (TL) method. For dating, a 325 degrees C TL peak was used and irradiation with -dose from 5 to 50Gy was carried out for the additive method, and from 0.4 to 5Gy for the regeneration method. For these dose values, the TL intensity is observed to grow linearly, obtaining an accumulated dose of 1.62 +/- 0.09Gy and 1.36 +/- 0.03Gy for the additive and regeneration methods, respectively. The age (A) of the sample was calculated by the two methods, being A=867 +/- 195 years after Christ (AC) for the additive method and A=1050 +/- 157 years AC for the regeneration method. Both results are within 800-1200 years AC, which is the period of the Wari culture.

In situ X-ray diffraction studies of phase transition in Pb1-x La x Zr0.40Ti0.60O3 ferroelectric ceramics

The temperature dependence of the crystalline structure and the lattice parameters of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric ceramic system with 0.00 x 0.21 was determined. The samples with x 0.11 show a cubic-to-tetragonal phase transition at the maximum dielectric permittivity, Tmax. Above this amount and especially for the x = 0.12 sample, a spontaneous phase transition from a relaxor ferroelectric state (cubic phase) to a ferroelectric state (tetragonal phase) is observed upon cooling below the Tmax. Unlike what has been reported in other studies, the x = 0.13, 0.14, and 0.15 samples, which present a more pronounced relaxor behavior, also presents a spontaneous normal-to-relaxor transition, indicated by a cubic to tetragonal symmetry below the Tmax. The origin of this anomaly has been associated with an increase in the degree of tetragonality, confirmed by the measurements of the X-ray diffraction patterns. The differential thermal analysis (DSC) measurements also confirm the existence of these phase transitions.

Microstructural, structural and dielectric properties of Er(3+)-modified BaTi(0.85)Zr(0.15)O(3) ceramics

The (micro)structural and electrical properties of undoped and Er(3+)-doped BaTi(0.85)Zr(0.15)O(3) ceramics were studied in this work for both nominal Ba(2+) and Ti(4+) substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 degrees C for 3 h. For those materials prepared following the donor-type nominal Ba(1-x)Er(x)(Ti(0.85)Zr(0.15))O(3) composition, especially, Er(3+) however showed a preferential substitution for the (Ti,Zr)(4+) lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O(3-delta)-like system, with a solubility limit below but close to 3 cat.% Er(3+). The overall phase development is discussed in terms of the amphoteric nature of Er(3+), and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials` grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er(3+) content. (C) 2008 Elsevier Ltd. All rights reserved.

Microstructural, structural and electrical properties of La(3+)-modified Bi(4)Ti(3)O(12) ferroelectric ceramics

Bi(4-x)La(x)Ti(3)O(12) (BLT) ceramics were prepared and studied in this work in terms of La(3+)-modified microstructure and phase development as well as electrical response. According to the results processed from X-ray diffraction and electrical measurements, the solubility limit (XL) of La(3+) into the Bi(4)Ti(3)O(12) (BIT) matrix was here found to locate slightly above x = 1.5. Further, La(3+) had the effect of reducing the material grain size, while changing its morphology from the plate-like form, typical of BIT ceramics, to a spherical-like one. The electrical results presented and discussed here also include the behavior of the temperature of the ferroelectric-paraelectric phase transition as well as the normal or diffuse and/or relaxor nature of this transition depending on the La(3+) content. (c) 2008 Elsevier Ltd. All fights reserved.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.