Publications

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The microstructure and mechanical properties of niobium-modified lead zirconate titanate (PNZT) 95/5 ceramics, where 95/5 refers to the ratio of lead zirconate to lead titanate, were evaluated as a function of lead (Pb) stoichiometry. Chemically-prepared PNZT 95/5 is produced at Sandia National Laboratories by the Ceramics and Glass Processing Department (14154) for use as voltage elements in ferroelectric neutron generator power supplies. PNZT 95/5 was prepared according to the nominal formulation of Pb{sub 0.991+x}(Zr{sub 0.955}Ti{sub 0.045}){sub 0.982}Nb{sub 0.018}O{sub 3+x}, where x (-0.0274 {approx}< x {approx}< 0.0297) refers to the mole fraction of Pb and O that deviated from the stoichiometric value. The Pb concentrations were determined from calcined powders; no adjustments were made to Pb compositions due to weight loss during sintering. The microstructure (second phases, fracture mode and grain size) varied appreciably with Pb stoichiometry, whereas the mechanical properties (hardness, fracture toughness, strength and Weibull parameters) exhibited modest variation. Specimens deficient in Pb, 2.74% (x = -0.0274) and 2.15% (x = -0.02150), had a high area fraction of a zirconia (ZrO{sub 2}) second phase on the order of 0.02. As the Pb content in solid solution increased the ZrO{sub 2} content decreased; no ZrO{sub 2} was observed for the specimen containing 2.97% excess Pb (x = 0.0297). Over the range of Pb stoichiometry most specimens fractured predominately transgranularly; however, 2.97% Pb excess PNZT 95/5 fractured predominately intergranularly. No systematic changes in hardness or Weibull modulus were observed as a function of Pb content. Fracture toughness decreased slightly from 1.8 MPa{center_dot}m{sup 1/2} for Pb deficient specimens to 1.6 MPa{center_dot}m{sup 1/2} for specimens with excess Pb. Although there are microstructural differences with changes in Pb content, the mechanical properties did not vary substantially. However, the average failure stress and fracture toughness for PNZT 95/5 containing 2.97% excess Pb decreased slightly. It is expected that additional increases in Pb content would result in further mechanical property degradation. The decrease in mechanical properties for the 2.97% Pb excess ceramics could be the result of a weaker PbO-rich grain boundary phase present in the material. If better mechanical properties are desired, it is recommended that PNZT 95/5 ceramics are processed by a method whereby any excess Pb is depleted from the final sintered ceramic so that near-stoichiometric values of Pb concentration are reached. Otherwise, a PbO-rich grain boundary phase may exist in the ceramic which could potentially be detrimental to the mechanical properties of PNZT 95/5 ceramics.

The goal of this project was to identify a viable, non-destructive methodology for the detection of cracks in electrically poled piezoelectric ceramics used in neutron generator power supply units. The following methods were investigated: Impedance Spectroscopy, Scanning Acoustic Microscopy, Lock-in Thermography, Photo-acoustic Microscopy, and Scanned Vicinal Light. In addition to the exploration of these techniques for crack detection, special consideration was given to the feasibility of integrating these approaches to the Automatic Visual Inspection System (AVIS) that was developed for mapping defects such as chips, pits and voids in piezoelectric ceramic components. Scanned Vicinal Light was shown to be the most effective method of automatically detecting and quantifying cracks in ceramic components. This method is also very effective for crack detection in other translucent ceramics.

The hydrostatically induced ferroelectric(FE)-to-antiferroelectric(AFE) phase transformation for chemically prepared niobium modified PZT 95/5 ceramics was studied as a function of density and pore former type (Lucite or Avicel). Special attention was placed on the effect of different pore formers on the charge release behavior associated with the FE-to-AFE phase transformation. Within the same density range (7.26 g/cm3 to 7.44 g/cm3), results showed that ceramics prepared with Lucite pore former exhibit a higher bulk modulus and a sharper polarization release behavior than those prepared with Avicel. In addition, the average transformation pressure was 10.7% greater and the amount of polarization released was 2.1% higher for ceramics with Lucite pore former. The increased transformation pressure was attributed to the increase of bulk modulus associated with Lucite pore former. Data indicated that a minimum volumetric transformational strain of -0.42% was required to trigger the hydrostatically induced FE-to-AFE phase transformation. This work has important implications for increasing the high temperature charge output for neutron generator power supply units.

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We used a regeneratively amplified Ti:sapphire femtosecond laser to create optical birefringence in an isotropic glass medium. Between two crossed polarizers, regions modified by the femtosecond laser show bright transmission with respect to the dark background of the isotropic glass. This observation immediately suggests that these regions possess optical birefringence. The angular dependence of transmission through the laser-modified region is consistent with that of an optically birefringent material. Laser-induced birefringence is demonstrated in different glasses, including fused silica and borosilicate glass. Experimental results indicate that the optical axes of laser-induced birefringence can be controlled by the polarization direction of the femtosecond laser. The amount of laser-induced birefringence depends on the pulse energy level and number of accumulated pulses.

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The polarization reversal process in a rhombohedral ferroelectric ceramic material was investigated using field-induced strain measurements and texture development. Special attention was focused on the difference in the field-induced strains between the first quarter cycle and subsequent loading conditions. Results show that the initial field-induced strain is about twelve times greater than the subsequent strain, which immediately suggests that mechanisms involved in these conditions during the polarization reversal process are different. The difference in the magnitude of field-induced strain is discussed in terms of 180 degree and non-180 degree domain reorientation processes.

Meso-scale manufacturing processes are bridging the gap between silicon-based MEMS processes and conventional miniature machining. These processes can fabricate two and three-dimensional parts having micron size features in traditional materials such as stainless steels, rare earth magnets, ceramics, and glass. Meso-scale processes that are currently available include, focused ion beam sputtering, micro-milling, micro-turning, excimer laser ablation, femtosecond laser ablation, and micro electro discharge machining. These meso-scale processes employ subtractive machining technologies (i.e., material removal), unlike LIGA, which is an additive meso-scale process. Meso-scale processes have different material capabilities and machining performance specifications. Machining performance specifications of interest include minimum feature size, feature tolerance, feature location accuracy, surface finish, and material removal rate. Sandia National Laboratories is developing meso-scale mechanical components and actuators which require meso-scale parts fabricated in a variety of materials. Subtractive meso-scale manufacturing processes expand the functionality of meso-scale components and complement silicon based MEMS and LIGA technologies.

Chemically prepared Pb(Zr0.95Ti0.05)O3 (PZT 95/5) ceramics were fabricated with a range of different porosity levels, while grain size was held constant, by systematic additions of added organic pore former (Avicel). Use of Avicel in amounts ranging from 0 to 4.0 wt% resulted in fired ceramic densities that ranged from 97.3% to 82.3%. Hydrostatic-pressure-induced ferroelectric (FE) to antiferroelectric (AFE) phase transformations were substantially more diffuse and occurred at lower hydrostatic pressures with increasing porosity. An ∼12 MPa decrease in hydrostatic transformation pressure per volume percent added porosity was observed. The decrease in transformation pressure with decreasing density was quantitatively consistent with the calculated macroscopic stress required to achieve a specific volumetric macrostrain (0.40%). This strain was equivalent to experimentally measured macrostrain for FE-to-AFE transformation. The macroscopic stress levels were calculated using measured bulk modulus values that decreased from 84 to 46 GPa as density decreased from 97.3% to 82.3%. Good agreement between calculated and measured values of FE-to-AFE transformation stress was obtained for ceramics fired at 1275° and 1345°C.

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Meso-scale manufacturing processes are bridging the gap between silicon-based MEMS processes and conventional miniature machining. These processes can fabricate two and three-dimensional parts having micron size features in traditional materials such as stainless steels, rare earth magnets, ceramics, and glass. Meso-scale processes that are currently available include, focused ion beam sputtering, micro-milling, micro-turning, excimer laser ablation, femto-second laser ablation, and micro electro discharge machining. These meso-scale processes employ subtractive machining technologies (i.e., material removal), unlike LIGA, which is an additive meso-scale process. Meso-scale processes have different material capabilities and machining performance specifications. Machining performance specifications of interest include minimum feature size, feature tolerance, feature location accuracy, surface finish, and material removal rate. Sandia National Laboratories is developing meso-scale electro-mechanical components, which require meso-scale parts that move relative to one another. The meso-scale parts fabricated by subtractive meso-scale manufacturing processes have unique tribology issues because of the variety of materials and the surface conditions produced by the different meso-scale manufacturing processes.

This report summarizes materials issues associated with advanced micromachines development at Sandia. The intent of this report is to provide a perspective on the scope of the issues and suggest future technical directions, with a focus on computational materials science. Materials issues in surface micromachining (SMM), Lithographic-Galvanoformung-Abformung (LIGA: lithography, electrodeposition, and molding), and meso-machining technologies were identified. Each individual issue was assessed in four categories: degree of basic understanding; amount of existing experimental data capability of existing models; and, based on the perspective of component developers, the importance of the issue to be resolved. Three broad requirements for micromachines emerged from this process. They are: (1) tribological behavior, including stiction, friction, wear, and the use of surface treatments to control these, (2) mechanical behavior at microscale, including elasticity, plasticity, and the effect of microstructural features on mechanical strength, and (3) degradation of tribological and mechanical properties in normal (including aging), abnormal and hostile environments. Resolving all the identified critical issues requires a significant cooperative and complementary effort between computational and experimental programs. The breadth of this work is greater than any single program is likely to support. This report should serve as a guide to plan micromachines development at Sandia.

A substantial decrease in hydrostatic ferroelectric (FE) to antiferroelectric (AFE) transformation pressure was measured for Pb(Zr{sub 0.949}Ti{sub 0.051}){sub 0.989}Nb{sub 0.0182}O{sub 3} ceramics with decreasing grain size. The 150 MPa decrease in hydrostatic FE to AFE transformation pressure over the grain size range of 8.5 {micro}m to 0.7{micro}m was shown to be consistent with enhanced internal stress with decreasing grain size. Further, the Curie Point decreased and the dielectric constant measured at 25 C increased with decreasing grain size. All three properties: dielectric constant magnitude, Curie point shift and FE to AFE phase transformation pressure were shown to be semi-quantitatively consistent with internal stress differences on the order of 100 MPa. Calculations of Curie point shifts from the Clausius-Clapeyron equation, using internal stress levels derived from the hydrostatic depoling characteristics, were consistent with measured values.

Embedded resistor circuits have been generated with the use of a Micropen system Ag conductor paste (DuPont 6142D), a new experimental resistor ink from DuPont (E84005-140), and Low Temperature Co-fired Ceramic (LTCC) green tape (DuPont A951). Sample circuits were processed under varying peak temperature ranges (835 C-875 C) and peak soak times (10 min-720 min). Resistors were characterized by SEM, TEM, EDS, and high-temperature XRD. Results indicate that devitrification of resistor glass phase to Celcian, Hexacelcian, and a Zinc-silicate phase occurred in the firing ranges used (835-875 C) but kinetics of divitrification vary substantially over this temperature range. The resistor material appears structurally and chemically compatible with the LTCC. RuO{sub 2} grains do not significantly react with the devitrifying matrix material during processing. RuO{sub 2} grains coarsen significantly with extended time and temperature and the electrical properties appear to be strongly affected by the change in RuO{sub 2} grain size.

In October 1996, an interdisciplinary team began a three-year LDRD project to study the plasma processes of reactive ion etching and plasma-enhanced chemical vapor deposition on large-area silicon devices. The goal was to develop numerical models that could be used in a variety of applications for surface cleaning, selective etching, and thin-film deposition. Silicon solar cells were chosen as the experimental vehicle for this project because an innovative device design was identified that would benefit from immediate performance improvement using a combination of plasma etching and deposition processes. This report presents a summary of the technical accomplishments and conclusions of the team.

Chemically prepared Pb(Zr{sub 0.951}Ti{sub 0.949}){sub 0.982}Nb{sub 0.018}O{sub 3} ceramics were fabricated that were greater than 95% dense for sintering temperatures as low as 925 C. Achieving high density at low firing temperatures permitted isolation of the effects of grain size, from those due to porosity, on both dielectric and pressure induced transformation properties. Specifically, two samples of similar high density, but with grain sizes of 0.7 {micro}m and 8.5 {micro}m, respectively, were characterized. The hydrostatic ferroelectric (FE) to antiferroelectric (AFE) transformation pressure was substantially less (150 MPa) for the lower grain size material than for the larger grain size material. In addition, the dielectric constant increased and the Curie temperature decreased for the sample with lower grain size. All three properties: dielectric constant magnitude, Curie point shift, and FE to AFE phase transformation pressure were shown to be semi-quantitatively consistent with internal stress levels on the order of 100 MPa.

The electrical properties were investigated for ruthenium oxide based devitrifiable resistors embedded within low temperature co-fired ceramics. Special attention was given to the processing conditions and their affects on resistance and temperature coefficient of resistance (TCR). Results indicate that the conductance for these buried resistors is limited by tunneling of charge carriers through the thin glass layer between ruthenium oxide particles. A modified version of the tunneling barrier model is proposed to more accurately account for the microstructure ripening observed during thermal processing. The model parameters determined from curve fitting show that charging energy (i.e., the energy required for a charge carrier to tunnel through the glass barrier) is strongly dependent on particle size and particle-particle separation between ruthenium oxide grains. Initial coarsening of ruthenium oxide grains was found to reduce the charging energy and lower the resistance. However, when extended ripening occurs, the increase in particle-particle separation increases the charging energy, reduces the tunneling probability and gives rise to a higher resistance. The trade-off between these two effects results an optimum microstructure with a minimum resistance and TCR. Furthermore, the TCR of these resistors has been shown to be governed by the magnitude of the charging energy. Model parameters determined by our analysis appear to provide quantitative physical interpretations to the microstructural change in the resistor, which in turn, are controlled by the processing conditions.

High temperature XRD has been employed to monitor the devitrification of Dupont 951 low temperature co-fired ceramic (LTCC) and Dupont E84005 resistor ink. The LTCC underwent devitrification to an anorthite phase in the range of 835-875 C with activation energy of 180 kJ/mol as calculated from kinetic data. The resistor paste underwent devitrification in the 835-875 C range forming monoclinic and hexagonal celcian phases plus a phase believed to be a zinc-silicate. RuO{sub 2} appeared to be stable within this devitrified resistor matrix. X-ray radiography of a co-fired circuit indicated good structural/chemical compatibility between the resistor and LTCC.