Niobium doped lead-tin-zirconate-titanate ceramics near the PZT 95/5 orthorhombic AFE – rhombohedral FE morphotropic phase boundary Pb1-0.5y(Zr0.865-xTixSn0.135)1-yNbyO3 were prepared according to a 22+1 factorial design with x = 0.05, 0.07 and y = 0.0155, 0.0195. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1250°C for 6 hours. All compositions were ~98% dense with no detectable secondary phases by XRD. The ceramics exhibited equiaxed grains with intergranular porosity and grain size was ~5 μm, decreasing with niobium substitution. Compositions exhibited remnant polarization values of ~32 μC/cm2, increasing with Ti substitution. Depolarization by the hydrostatic pressure induced FE-AFE phase transition was drastically affected by variation of the Ti and Nb substitution, increasing at a rate of 113 MPa / 1% Ti and 21 MPa / 1% Nb. Total depolarization output was insensitive to the change in Ti and Nb substitution, ~32.8 μC/cm2 for the PSZT ceramics. The R3c-R3m and R3m-Pm3m phase transition temperatures on heating ranged from 90 to 105°C and 183 to 191°C, respectively. Ti substitution stabilized the R3c and R3m phases to higher temperatures, while Nb substitution stabilized the Pm3m phase to lower temperatures. Thermal hysteresis of the phase transitions was also observed in the ceramics, with transition temperature on cooling being as much as 10°C lower.
Niobium (Nb)-doped lead-tin-zirconate-titanate (PSZT) ceramics near the lead-zirconate-titanate 95/5 orthorhombic AFE-rhombohedral FE morphotropic phase boundary (PSZT 13.5/81/5.5 -1.6Nb) were prepared with up to 10 mol.% of hafnium (Hf) substituted for zirconium. The ceramics were prepared by a traditional solid-state synthesis route and sintered to near full density at 1150°C for 6 h in sealed alumina crucibles with self-same material as the lead vapor source. All compositions were ~98% dense with no detectable secondary phases by X-ray diffraction. The grain size was ~3 μm for all compositions, consisting of equiaxed grains with intergranular porosity. The compositions exhibited remnant polarization values of ~32 μC/cm2. Depolarization by the hydrostatic pressure-induced FE-AFE phase transition occurred at 310 MPa for all compositions, resulting in a total depolarization output of 32.4 μC/cm2 for the PSZT ceramics. Evaluation of the R3c-R3m and R3m-Pm $\bar{3}$ m phase transition temperatures by impedance spectroscopy showed temperatures on heating ranging from 86 to 92°C and 186 to 182°C, respectively, for increasing nominal Hf content. Thermal hysteresis of the phase transitions was also observed in the ceramics, with the transition temperature on cooling being 1–4°C lower. The study demonstrated that the PSZT ceramics are relatively insensitive to variations in Hf content in the range of 0 to 10 mol.%.
A preliminary finite-element model has been developed using the ALEGRA-FE code for explosive- driven depoling of a PZT 95/5 ferroelectric generator. The ferroelectric material is characterized using hysteresis-loop and hydrostatic depoling tests. These characteristics are incorporated into ALEGRA-FE simulations that model the explosive drive mechanism and shock environment in the material leading to depoling, as well as the ferroelectric response and the behavior of a coupled circuit. The ferroelectric-to-antiferroelectric phase transition is captured, producing an output voltage pulse that matches experimental data to within 10% in rise time, and to within about 15% for the final voltage. Both experimental and modeled pulse magnitudes are less than the theoretical maximum output of the material. Observations from materials characterization suggest that unmodeled effects such as trapped charge in the stored FEG material may have influenced the experimentally observed output. ACKNOWLEDGEMENTS The authors are thankful to Mr. Peter Bartkowski and Mr. Paul Berning at ARL for initiating this work and providing critical insight along the way. Also, we thank Dr. Thomas Hughes and Dr. James Carleton at Sandia for important technical discussions and guidance. Finally, we wish to thank Tom Chavez at Sandia, who was heavily involved in conducting the laboratory materials characterization.
This SAND report fulfills the final report requirement for the Born Qualified Grand Challenge LDRD. Born Qualified was funded from FY16-FY18 with a total budget of ~$13M over the 3 years of funding. Overall 70+ staff, Post Docs, and students supported this project over its lifetime. The driver for Born Qualified was using Additive Manufacturing (AM) to change the qualification paradigm for low volume, high value, high consequence, complex parts that are common in high-risk industries such as ND, defense, energy, aerospace, and medical. AM offers the opportunity to transform design, manufacturing, and qualification with its unique capabilities. AM is a disruptive technology, allowing the capability to simultaneously create part and material while tightly controlling and monitoring the manufacturing process at the voxel level, with the inherent flexibility and agility in printing layer-by-layer. AM enables the possibility of measuring critical material and part parameters during manufacturing, thus changing the way we collect data, assess performance, and accept or qualify parts. It provides an opportunity to shift from the current iterative design-build-test qualification paradigm using traditional manufacturing processes to design-by-predictivity where requirements are addressed concurrently and rapidly. The new qualification paradigm driven by AM provides the opportunity to predict performance probabilistically, to optimally control the manufacturing process, and to implement accelerated cycles of learning. Exploiting these capabilities to realize a new uncertainty quantification-driven qualification that is rapid, flexible, and practical is the focus of this effort.
This work represents a thorough investigation of the thermal conductivity (κ) in both thin film and bulk PbZr1-xTixO3 (PZT) across the compositional phase diagram. Given the technological importance of PZT as a superb piezoelectric and ferroelectric material in devices and systems impacting a wide array of industries, this research serves to fill the gap in knowledge regarding the thermal properties. The thermal conductivities of both thin film and bulk PZT are found to vary by a considerable margin as a function of composition x. Additionally, we observe a discontinuity in κ in the vicinity of the morphotropic phase boundary (MPB, x = 0.48) where there is a 20%-25% decrease in κ in our thin film data, similar to that found in literature data for bulk PZT. The comparison between bulk and thin film materials highlights the sensitivity of κ to size effects such as film thickness and grain size even in disordered alloy/solid-solution materials. A model for the thermal conductivity of PZT as a function of composition (κ (x)) is presented, which enables the application of the virtual crystal approximation for alloy-type material systems with very different crystals structures, resulting in differing temperature trends for κ. We show that in the case of crystalline solid-solutions where the thermal conductivity of one of the parent materials exhibits glass-like temperature trends the compositional dependence of thermal conductivity is relatively constant for most values of x. This is in stark contrast with the typical trends of thermal conductivity with x in alloys, where the thermal conductivity increases dramatically as the composition of the alloy or solid-solution approaches that of a pure parent materials (i.e., as x = 0 or 1).
The use of colloidal processing principles in the formation of ceramic materials is well appreciated for developing homogeneous material properties in sintered products, enabling novel forming techniques for porous ceramics or 3D printing, and controlling microstructure to enable optimized material properties. The solution processing of electronic ceramic materials often involves multiple cationic elements or dopants to affect microstructure and properties. Material stability must be considered through the steps of colloidal processing to optimize desired component properties. This review provides strategies for preventing material degradation in particle synthesis, milling processes, and dispersion, with case studies of consolidation using spark plasma sintering of these systems. The prevention of multication corrosion in colloidal dispersions can be achieved by utilizing conditions similar to the synthesis environment or by the development of surface passivation layers. The choice of dispersing surfactants can be related to these surface states, which are of special importance for nanoparticle systems. A survey of dispersant chemistries related to some commonsynthesis conditions is provided for perovskite systems as an example. These principles can be applied tomany colloidal systems related to electronic and optical applications.
It is well known that nanostructured metals can exhibit significantly improved properties compared to metals with conventional grain size. Unfortunately, nanocrystalline metals typically are not thermodynamically stable and exhibit rapid grain growth at moderate temperatures. This severely limits their processing and use, making them impractical for most engineering applications. Recent work has shown that a number of thermodynamically stable nanocrystalline metal alloys exist. These alloys have been prepared as powders using severe plastic deformation (e.g. ball milling) processes. Consolidation of these powders without compromise of their nanocrystalline microstructure is a critical step to enabling their use as engineering materials. We demonstrate solid-state consolidation of ball milled copper-tantalum nanocrystalline metal powder using cold spray. Unfortunately, the nanocrystalline copper-tantalum powder that was consolidated did not contain the thermodynamically stable copper-tantalum nanostructure. Nevertheless, this does this demonstrates a pathway to preparation of bulk thermodynamically stable nanocrystalline copper-tantalum. Furthermore, it demonstrates a pathway to additive manufacturing (3D printing) of nanocrystalline copper-tantalum. Additive manufacturing of thermodynamically stable nanocrystalline metals is attractive because it enables maximum flexibility and efficiency in the use of these unique materials.
Multilayer coextrusion is applied to produce a tape containing layers of alternating electrical properties to demonstrate the potential for using coextrusion to manufacture capacitors. To obtain the desired properties, we develop two filled polymer systems, one for conductive layers and one for dielectric layers. We describe numerical models used to help determine the material and processing parameters that impact processing and layer stability. These models help quantify the critical ratios of densities and viscosities of the two layers to maintain stable layers, as well as the effect of increasing the flow rate of one of the two materials. The conducting polymer is based on polystyrene filled with a blend of low-melting-point eutectic metal and nickel particulate filler, as described by Mrozek et al. (2010). The appropriate concentrations of fillers are determined by balancing measured conductivity with processability in a twin screw extruder. Based on results of the numerical models and estimates of the viscosity of emulsions and suspensions, a dielectric layer composed of polystyrene filled with barium titanate is formulated. Despite the fact that the density of the dielectric filler is less than the metallic filler of the conductive phase, as well as rheological measurements that later showed that the dielectric formulation is not an ideal match to the viscosity of the conductive material, the two materials can be successfully coextruded if the flow rates of the two materials are not identical. A measurable capacitance of the layered structure is obtained.