The printing of lead zirconate titanate (PZT, Pb(Zr,Ti)O 3 ) piezoelectric thick films on silicon substrates is being studied for potential use as microactuators, microsensors, and microtransducers. A fundamental challenge in the fabrication of useful PZT thick-film devices on silicon is to sinter the PZT to high density at sufficiently low temperature to avoid mechanical or chemical degradation of the silicon substrate. The goal of the present study is to develop and implement suitable electrodes and PZT sintering aids that yield attractive piezoelectric properties for devices while minimizing reactions between the silicon, the bottom electrode, and the PZT thick film. A B 2 O 3 -Bi 2 O 3 -CdO sintering aid has been found to be superior to borosilicate glass, and the use of a gold/platinum bilayer bottom electrode has resulted in better thermal stability of the electrode/film structure. Films sintered at 900°C for 1 h have relative permittivity of 970 (at 1 kHz), remnant polarization of 20 C/cm 2 , coercive field of 30 kV/cm, and weak-field piezoelectric coefficient d 33 of 110 pm/V.
The light-scattering performance of TiO 2 pigment depends intimately upon particle size, size distribution, shape and dispersion quality. TiO 2 particles exhibit complex shapes and have anisotropic optical constants, and particulate dispersions of TiO 2 are characterized by complicated microstructures such as aggregates and agglomerates. Despite this complexity, the theoretical understanding of light scattering by white pigment has been based upon Mie theory, which is restricted to the case of a single, optically isotropic sphere. We utilize a finite-element method which produces rigorous solutions to Maxwell's equations to determine computationally the light-scattering properties of complex particulate microstructures. This represents a significant step beyond the restrictions of Mie theory, providing a method to determine quantitatively the effects of particle shape, optical anisotropy, and interactions between neighboring particles upon the light-scattering properties of white pigments in coatings. In the present study, we use the finite-element method first to compute the light-scattering properties of a single, morphological rutile particle with a representative size and shape. These results are compared to the light-scattering properties of the optically isotropic, equivalent volume sphere using Mie theory. Neither the average index nor the weighted sum approximation offers clear advantages in this case. Second, the far-field lightscattering properties of two such particles interacting at near field are determined as a function of the interparticle separation. The agglomerated pair of particles exhibits a 20% decrease relative to the single particle in the scattering parameter associated with the hiding power of a paint film. The basis for this decrease is the same as for the crowding effect observed in extensive paint films. The results of both sets of computations are compared to Mie theory to determine the sizes of spherical particles with equivalent scattering cross sections. These comparisons highlight the inherent difficulties in using Mie theory to evaluate particle size by light-scattering methods.
Diverse device applications for lead zirconate titanate (PZT) ceramics in thick-film form are currently in active development. In the present study, the particle dispersion properties of thick-film ink formulations containing PZT powder have been determined using rheological measurements. Although all of the eight commercially available dispersants tested are more effective than the terpineol solvent alone in decreasing attractive interparticle forces in suspensions, the best dispersant identified for hard and soft PZT powders is a phosphate ester oligomer. This dispersant is extremely efficient, and its use in thick-film ink formulations results in viscosity decreases of 50% at low shear rates (10 s ؊1 ) and 30% at high shear rates (100 s ؊1 ) compared with current ink formulations containing no dispersant. The effects upon rheology of the order of addition of components in the processing of inks have been studied, with the most effective processing route using a fugitive solvent that probably facilitates uniform coverage of the particle surfaces by the dispersant molecules. Modeling of the rheological profiles of inks indicates that the use of a dispersant decreases the depth of the primary minimum in the interparticle potential by a factor of 3. Demonstrated advantages of the use of a dispersant in PZT thick-film inks include improved microstructural homogeneity in the green body and the ability to formulate printable inks with higher solids loadings. No adverse effects of the dispersant upon the dielectric and piezoelectric properties of bulk PZT samples are found following burnout and sintering.
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