Characterization of Selected Photonic Materials and Systems Using Photoacoustic Technique

The photoacoustic investigations carried out on different photonic materials are presented in this thesis. Photonic materials selected for the investigation are tape cast ceramics, muItilayer dielectric coatings, organic dye doped PVA films and PMMA matrix doped with dye mixtures. The studies are performed by the measurement of photoacoustic signal generated as a result of modulated cw laser irradiation of samples. The gas-microphone scheme is employed for the detection of photoacoustic signal. The different measurements reported here reveal the adaptability and utility of the PA technique for the characterization of photonic materials.Ceramics find applications in the field of microelectronics industry. Tape cast ceramics are the building blocks of many electronic components and certain ceramic tapes are used as thermal barriers. The thermal parameters of these tapes will not be the same as that of thin films of the same materials. Parameters are influenced by the presence of foreign bodies in the matrix and the sample preparation technique. Measurements are done on ceramic tapes of Zirconia, Zirconia-Alumina combination, barium titanate, barium tin titanate, silicon carbide, lead zirconate titanateil'Z'T) and lead magnesium niobate titanate(PMNPT). Various configurations viz. heat reflection geometry and heat transmission geometry of the photoacoustic technique have been used for the evaluation of different thermal parameters of the sample. Heat reflection geometry of the PA cell has been used for the evaluation of thermal effusivity and heat transmission geometry has been made use of in the evaluation of thermal diffusivity. From the thermal diffusivity and thermal effusivity values, thermal conductivity is also calculated. The calculated values are nearly the same as the values reported for pure materials. This shows the feasibility of photoacoustic technique for the thermal characterization of ceramic tapes.Organic dyes find applications as holographic recording medium and as active media for laser operations. Knowledge of the photochemical stability of the material is essential if it has to be used tor any of these applications. Mixing one dye with another can change the properties of the resulting system. Through careful mixing of the dyes in appropriate proportions and incorporating them in polymer matrices, media of required stability can be prepared. Investigations are carried out on Rhodamine 6GRhodamine B mixture doped PMMA samples. Addition of RhB in small amounts is found to stabilize Rh6G against photodegradation and addition of Rh6G into RhB increases the photosensitivity of the latter. The PA technique has been successfully employed for the monitoring of dye mixture doped PMMA sample. The same technique has been used for the monitoring of photodegradation ofa laser dye, cresyl violet doped polyvinyl alcohol also.Another important application of photoacoustic technique is in nondestructive evaluation of layered samples. Depth profiling capability of PA technique has been used for the non-destructive testing of multilayer dielectric films, which are highly reflecting in the wavelength range selected for investigations. Eventhough calculation of thickness of the film is not possible, number of layers present in the system can be found out using PA technique. The phase plot has clear step like discontinuities, the number of which coincides with the number of layers present in the multilayer stack. This shows the sensitivity of PA signal phase to boundaries in a layered structure. This aspect of PA signal can be utilized in non-destructive depth profiling of reflecting samples and for the identification of defects in layered structures.

Comparison of polymers and ceramics in new and discarded electrical insulators: reuse and recycling possibilities

The expansion and maintenance of electricity distribution networks generates large amounts of waste, much of it in the form of discarded insulators that are not reused or recycled. This paper describes the results of tests on used and new ceramic and polymeric insulators to verify if their exposure to weathering justifies their replacement. In new and used ceramic insulators, properties such as contact angle, relative density, porosimetry, dilatometry and X-ray diffraction patterns showed no differences or the differences that were found could not be related to their use. The discarded ceramic material showed high thermal stability, an interesting characteristic for application as chamotte. It can also be reused to replace gravel used in substations. In polymeric insulators, thermogravimetry, differential scanning calorimetry and relative density test results suggest degradation of used material compared to new. This would justify their replacement and discard as waste, but they show little recycling potential.

Crystallographic characterization of silicon nitride ceramics sintered with Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) additions

Silicon nitride ceramics were sintered using Y(2)O(3)-Al(2)O(3) or E(2)O(3)-Al(2)O(3) (E(2)O(3) denotes a mixed oxide Of Y(2)O(3) and rare-earth oxides) as sintering additives. The intergranular phases formed after sintering was investigated using high-resolution X-ray diffraction (HRXRD). The use of synchrotron radiation enabled high angular resolution and a high signal to background ratio. Besides the appearance Of beta-Si(3)N(4) phase the intergranular phases Y(3)Al(5)O(12) (YAG) and Y(2)SiO(5) were identified in both samples. The refinement of the structural parameters by the Rietveld method indicated similar crystalline structure Of beta-Si(3)N(4) for both systems used as sintering additive. On the other hand, the intergranular phases Y(3)Al(5)O(12) and Y(2)SiO(5) shown a decrease of the lattice parameters, when E(2)O(3) was used as additive, indicating the formation of solid solutions of E(3)Al(5)O(12) and E(2)SiO(5), respectively. (C) 2007 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Characterization of a chromium-rich tannery waste and its potential use in ceramics

Leather industries which promote hide stabilization by the conventional chrome-tanning process are a major source of pollution because of the resultant chromium-rich wastes. In this work, an extensive characterization of such a chromium-rich waste sludge is presented, regarding its chemical composition (XRF), crystalline phase contents (XRD), organic carbon content (TOC), thermal behavior by thermogravimetry (TG) and differential scanning calorimetry (DSC), as well as its stability under chemical attack (the concentration of important ions in the leachates being determined by capillary electrophoresis) and when submitted to temperatures as high as 1100 degrees C, in air. The material showed the tendency to produce some undesirable, and previously non-detected hexavalent chromium when exposed to high temperatures, but after washing off the soluble salts and the elimination of the organic matter by firing, the resultant material was succesfully tested as a ceramic pigment in a conventional glaze composition usually employed in the ceramic the industry. (C) 2009 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Chemical characterization of tin-lead glazed ceramics from Aragon (Spain) by neutron activation analysis

Majolica pottery was the most characteristic tableware produced in Spain during the Medieval and Renaissance periods. A study of the three main production centers in the historical region of Aragon during Middle Ages and Renaissance was conducted on a set of 71 samples. The samples were analyzed by instrumental neutron activation analysis (INAA), and the resulting data were interpreted using an array of multivariate statistical procedures. Our results show a clear discrimination among different production centers allowing a reliable provenance attribution of ceramic sherds from the Aragonese workshops.

Preparation, Characterization and Dilectric Properties of Ceramics in the BaO-Nd2O3-TiO2 System

The dielectric ceramics BaNd2Ti3Oto, BaNd2Ti4O12 and BaNd2Ti5O14 have been prepared by Conventional solid state ceramic route. The sintered ceramic samples have been characterized by X-ray diffraction and Scanning Electron Microscopy (SEM). The dielectric properties in the microwave frequency range have been measured using conventional microwave dielectric resonator methods. The BaNd2Ti1O10, BaN2Ti4O12 and BaNd2Ti5O14 have dielectric constants (Er) ~ 60, 84 and 77 respectively. They have relatively high quality factors

Preparation, Characterization, and Microwave Properties of RETiNbO6 (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, and Yb) Dielectric Ceramics

Microwave ceramic dielectric resonators (DRs) based on RETiNbO6 (RE = Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Y, and Yb) have been prepared using the conventional solid -state ceramic route. The DR samples are characterized using XRD and SEM methods. The microwave dielectric properties are measured using resonant methods and a net work analyzer . The ceramics based on Ce, Pr, Nd, and Sin have dielectric constants in the range 32-54 and positive coefficient of thermal variation of resonant frequency (r,). The ceramics based on Gd, Tb, Dy, Y. and Yb have dielectric constants in the range 19-22 and negative Tf

Synthesis,Characterization and Properties of [REI_xREX]TiNb06 Dielectric Ceramics

Dielectric ceramics based on solid solution phases of [RE1_x= REr]TiNb06, where REI_s = Nd, Pr, Sm and RE' = Dy, Gd and Y, were prepared by the conventional solid-state ceramic route for values of x. The ceramic samples are characterized by X-ray diffraction and microwave methods. Ceramics based on RE (Pr, Nd and Sm) belonging to aeschynite group shows positive value of Tf and those based on RE (Gd, Dy and Y) belonging to euxenite group show negative value of r f. The solid solution phases between the aeschynite and the euxenite group shows intermediate dielectric constant and r f values. The results indicate the possibility of tailoring the dielectric properties by varying the composition of the solid solution phases. The range of solid solubility of euxenite in aeschenite and aeschenite in euxenite are different for different rare earth ions

Preparation, Characterization and Microwave Dielectric Properties of Ba (B1/2Nb1/2)03 [B' = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb and In] Ceramics

Microwave dielectric resonators (DRs) based on Ba(B1,2Nbi/2)03 [B' = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In] complex perovskites have been prepared by conventional solid state ceramic route. The dielectric properties (relative permittivity, Er; quality factor, Q; and resonant frequency, rr) of the ceramics have been measured in the frequency range 4-6 GHz using resonance methods. The resonators have relatively high dielectric constant in the range 36-45, high quality factor and small temperature variation of resonant frequency. The dielectric properties are found to depend on the tolerance factor (t), ionic radius (r), and lattice parameter (ap)

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Thermal characterization of nanocrystalline porous CePO4 ceramics

A laser-induced photoacoustic technique was employed to investigate thermal transport through nanocrystalline CePO4 samples prepared via the sol–gel route. Evaluation of thermal diffusivity was carried out using the one-dimensional model of Rosencwaig and Gersho for the reflection configuration of the photoacoustic method. Structural analyses of samples revealed that they are nanoporous in nature, possessing micron-sized grains. Analysis of results shows that thermal diffusivity value varies with sintering temperature. Results are explained in terms of the variation in porosity with sintering temperature and the effects of various scattering mechanisms on the propagation of phonons through the nanoporous ceramic matrix. Further analyses confirm that apart from porosity, grain boundary resistance and interface thermal resistance influence the effective value of thermal diffusivity of the samples under investigation.

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.