Niobium doped Lead Zirconate Titanate (PZT) with a Zr/Ti ratio of 95/5 (i.e., PZT 95/5-2Nb) is a ferroelectric with a rhombohedral structure at room temperature. A crystal (or a subdomain within a crystal) exhibits a spontaneous polarization in any one of eight crystallographically equivalent directions. Such a material becomes polarized when subjected to a large electric field. When the electric field is removed, a remanent polarization remains and a bound charge is stored. A displacive phase transition from a rhombohedral ferroelectric phase to an orthorhombic anti-ferroelectric phase can be induced with the application of a mechanical load. When this occurs, the material becomes depoled and the bound charge is released. The polycrystalline character of PZT 95/5-2Nb leads to highly non-uniform fields at the grain scale. These local fields lead to very complex material behavior during mechanical depoling that has important implications to device design and performance. This paper presents a microstructurally based numerical model that describes the 3D non-linear behavior of ferroelectric ceramics. The model resolves the structure of polycrystals directly in the topology of the problem domain and uses the extended finite element method (X-FEM) to solve the governing equations of electromechanics. The material response is computed from anisotropic single crystal constants and the volume fractions of the various polarization variants (i.e., three variants for rhombohedral anti-ferroelectric and eight for rhomobohedral ferroelectric ceramic). Evolution of the variant volume fractions is governed by the minimization of internally stored energy and accounts for ferroelectric and ferroelastic domain switching and phase transitions in response to the applied loads. The developed model is used to examine hydrostatic depoling in PZT 95/5-2Nb.
Piezoelectric polymers based on polyvinylidene fluoride (PVDF) are of interest for large aperture space-based telescopes as adaptive or smart materials. Dimensional adjustments of adaptive polymer films depend on controlled charge deposition. Predicting their long-term performance requires a detailed understanding of the piezoelectric material features, expected to suffer due to space environmental degradation. Hence, the degradation and performance of PVDF and its copolymers under various stress environments expected in low Earth orbit has been reviewed and investigated. Various experiments were conducted to expose these polymers to elevated temperature, vacuum UV, {gamma}-radiation and atomic oxygen. The resulting degradative processes were evaluated. The overall materials performance is governed by a combination of chemical and physical degradation processes. Molecular changes are primarily induced via radiative damage, and physical damage from temperature and atomic oxygen exposure is evident as depoling, loss of orientation and surface erosion. The effects of combined vacuum UV radiation and atomic oxygen resulted in expected surface erosion and pitting rates that determine the lifetime of thin films. Interestingly, the piezo responsiveness in the underlying bulk material remained largely unchanged. This study has delivered a comprehensive framework for material properties and degradation sensitivities with variations in individual polymer performances clearly apparent. The results provide guidance for material selection, qualification, optimization strategies, feedback for manufacturing and processing, or alternative materials. Further material qualification should be conducted via experiments under actual space conditions.
Smart polymeric materials, such as piezoelectric polymers which deform by application of an electric field, are of interest for use in controllable mirrors as large, lightweight space optics. An important consideration when using any organic material in a space application is their extreme vulnerability to the space environment. In LEO the presence of atomic oxygen, large thermal extremes, hard vacuum, short wavelength ultraviolet and particulate radiation can result in erosion, cracking and outgassing of most polymers. While much research has been performed examining the physical and chemical changes incurred by polymers exposed to actual and simulated LEO environments, little work has focused on the effects of the space environment on the performance of piezoelectric polymers. The most widely used piezoelectric polymers are those based on poly(vinylidene fluoride) (PVDF) and include copolymers synthesized from vinylidene fluoride and trifluoroethylene, hexafluoropropylene or chlorotrifluoroethylene. The presence of a comonomer group can greatly influence on the crystalline phase, melting point, Curie point, modulus and processing required for piezoelectricity. After a rigorous pre-selection process only two polymers, namely the PVDF homopolymer and a TrFE copolymer (80% comonomer content), satisfied most of the requirements for operation in the temperature/radiation environment of LEO. Based on this initial materials selection, we have now performed a detailed study of the effects of temperature, atomic oxygen and vacuum UV radiation simulating low Earth orbit conditions on these two polymers. Both polymers exhibited diminished but very stable piezoelectric performance up to 130 C despite the upper use temperatures suggested by industry of 80 C (PVDF) and 100 C (P(VDF-TrFE)). We believe that the loss of piezoelectric response in samples conditioned at 130 C compared with non-exposed samples is partly due to the depoling process which occurs when the highly stressed films undergo contraction via relaxation. The TrFE copolymer, which does not need to be stretched for the polar phase to be present, has better retention of piezoelectric properties at 130 C compared with the highly oriented homopolymer. AO/VUV exposure caused significant surface erosion and pattern development for both polymers. Erosion yields were 2.8 x 10{sup -24} cm{sup 3}/atom for PVDF and 2.5 x 10{sup -24} cm{sup 3}/atom for P(VDF-TrFE). The piezoelectric properties of the residual material for both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly crosslinked network was formed in the copolymer, presumably due to penetrating VUV radiation, while the homopolymer remained uncrosslinked. These differences were attributed to different levels of crystallinity and increased VUV absorption by P(VDF-TrFE) over PVDF. In this paper a summary of the performance limiting effects of temperature, radiation, atomic oxygen and VUV on the piezoelectric response of PVDF based polymers will be presented.
Smart polymeric materials, such as piezoelectric polymers which deform by application of an electric field, are of interest for use in controllable mirrors as large, lightweight space optics. An important consideration when using any organic material in a space application is their extreme vulnerability to the space environment. In LEO the presence of atomic oxygen, large thermal extremes, hard vacuum, short wavelength ultraviolet and particulate radiation can result in erosion, cracking and outgassing of most polymers. While much research has been performed examining the physical and chemical changes incurred by polymers exposed to actual and simulated LEO environments, little work has focused on the effects of the space environment on the performance of piezoelectric polymers. The most widely used piezoelectric polymers are those based on poly(vinylidene fluoride) (PVDF) and include copolymers synthesized from vinylidene fluoride and trifluoroethylene, hexafluoropropylene or chlorotrifluoroethylene. The presence of a comonomer group can greatly influence on the crystalline phase, melting point, Curie point, modulus and processing required for piezoelectricity. After a rigorous pre-selection process only two polymers, namely the PVDF homopolymer and a TrFE copolymer (80% comonomer content), satisfied most of the requirements for operation in the temperature/radiation environment of LEO. Based on this initial materials selection, we have now performed a detailed study of the effects of temperature, atomic oxygen and vacuum UV radiation simulating low Earth orbit conditions on these two polymers. Both polymers exhibited diminished but very stable piezoelectric performance up to 130 C despite the upper use temperatures suggested by industry of 80 C (PVDF) and 100 C (P(VDF-TrFE)). We believe that the loss of piezoelectric response in samples conditioned at 130 C compared with non-exposed samples is partly due to the depoling process which occurs when the highly stressed films undergo contraction via relaxation. The TrFE copolymer, which does not need to be stretched for the polar phase to be present, has better retention of piezoelectric properties at 130 C compared with the highly oriented homopolymer. AO/VUV exposure caused significant surface erosion and pattern development for both polymers. Erosion yields were 2.8 x 10{sup -24} cm{sup 3}/atom for PVDF and 2.5 x 10{sup -24} cm{sup 3}/atom for P(VDF-TrFE). The piezoelectric properties of the residual material for both polymers were largely unchanged after exposure, although a slight shift in the Curie transition of the P(VDF-TrFE) was observed. A lightly crosslinked network was formed in the copolymer, presumably due to penetrating VUV radiation, while the homopolymer remained uncrosslinked. These differences were attributed to different levels of crystallinity and increased VUV absorption by P(VDF-TrFE) over PVDF. In this paper a summary of the performance limiting effects of temperature, radiation, atomic oxygen and VUV on the piezoelectric response of PVDF based polymers will be presented.
Nuclear weapons and their storage facilities may benefit from in-situ structural health monitoring systems. Appending health-monitoring functionality to conventional materials and structures has been only marginally successful. The purpose of this project was to evaluate feasibility of a new smart material that includes self-sensing health monitoring functions similar to that of a nervous system of a living organism. Reviews of current efforts in the fields of heath-monitoring, nanotechnology, micro-electromechanical systems (MEMS), and wireless sensor networks were conducted. Limitations of the current nanotechnology methods were identified and new approaches were proposed to accelerate the development of self-sensing materials. Wireless networks of MEMS sensors have been researched as possible prototypes of self-sensing materials. Sensor networks were also examined as enabling technologies for dense data collection techniques to be used for validation of numerical methods and material parameter identification. Each grain of the envisioned material contains sensors that are connected in a dendritic manner similar to networks of neurons in a nervous system. Each sensor/neuron can communicate with the neighboring grains. Both the state of the sensor (on/off) and the quality of communication signal (speed/amplitude) should indicate not only a presence of a structural defect but the nature of the defect as well. For example, a failed sensor may represent a through-grain crack, while a lost or degraded communication link may represent an inter-granular crack. A technology to create such material does not exist. While recent progress in the fields of MEMS and nanotechnology allows to envision these new smart materials, it is unrealistic to expect creation of self-sensing materials in the near future. The current state of MEMS, nanotechnology, communication, sensor networks, and data processing technologies indicates that it will take more than ten years for the technologies to mature enough to make self-sensing materials a reality. Nevertheless, recent advances in the field of nanotechnology demonstrate that nanotubes, nanorods, and nanoparticles of carbon, boron and other materials have remarkable mechanical and electrical properties. This would provide. for a plethora of potential applications including self-sensing materials. Record strength-to-weight ratios, ballistic conductivity, and sensing capabilities (i.e., piezo- resistance and piezoelectricity) have been reported for carbon nanotubes. The first transistors, sensors, and actuators have been made from the carbon nanotubes and other nanomaterials. However, nanomaterials are notoriously difficult to manipulate into useful geometries. Nano-manufacturing processes often produce bundles or random networks of nanostructured materials. Samples of the material are then manipulated with advanced microscopy tools to measure properties or to create a single device. This is a laborious and time consuming process. An often overlooked property of the manufactured nanotube bundles is their similarity to the dendritic structure of neural networks with a great quantity of interconnects that may serve as initiation sites for artificial neurons in a self-sensing material nervous system. To accelerate the development of self-sensing materials, future research should concentrate on naturally occurring dendritic nano-structures. While self-sensing materials with subgrain size sensors (scale of micrometers) remain in the realm of basic research, meso-scale (millimeters to centimeters) sensors and their networks are in the state of mature research and have begun to find their way into commercial applications. Macro-scale (centimeters to decimeters) sensors and their networks are commercially available from various sources. The majority of applications that employ sensor networks are driven by the needs of the Department of Defense. Widespread adaptation of sensor networks has been limited by, on one hand, the sensor's high cost of design, development, and deployment, and on the other hand, a lack of reliable long-term power sources. Solutions to both of these drawbacks require significant investments driven by real-life applications. Possible applications for sensor networks at Sandia National Laboratories include dense data collection techniques for validation of numerical methods and material parameter identification. For example, an array of distributed wireless macro-scale sensors can record the structural response of soils and reinforced concrete during explosive loading. Another example is an array of surface mounted micro-sensors that can record the modal response of nuclear weapon components. The collected data would be used to validate existing numerical codes and to identify new physical mechanisms to improve Sandia's computational models.
This report summarizes research into effects of electron gun control on piezoelectric polyvinylidene fluoride (PVDF) structures. The experimental apparatus specific to the electron gun control of this structure is detailed, and the equipment developed for the remote examination of the bimorph surface profile is outlined. Experiments conducted to determine the optimum electron beam characteristics for control are summarized. Clearer boundaries on the bimorphs control output capabilities were determined, as was the closed loop response. Further controllability analysis of the bimorph is outlined, and the results are examined. In this research, the bimorph response was tested through a matrix of control inputs of varying current, frequency, and amplitude. Experiments also studied the response to electron gun actuation of piezoelectric bimorph thin film covered with multiple spatial regions of control. Parameter ranges that yielded predictable control under certain circumstances were determined. Research has shown that electron gun control can be used to make macrocontrol and nanocontrol adjustments for PVDF structures. The control response and hysteresis are more linear for a small range of energy levels. Current levels needed for optimum control are established, and the generalized controllability of a PVDF bimorph structure is shown.
Thin polymer films have been identified as one of the major enabling technologies for future space-based systems. Potential devices include those based on piezoelectric bimorph polymers that deform when a charge is deposited, for example, from an electron gun. The thin-film and lightweight nature of the polymeric devices will allow them to be launched more readily and deployed to operating conditions once in orbit. Until now little work has been done aimed at investigating the performance of piezoelectric properties of PVDF and its copolymers and the prediction of their long-term stability in low Earth orbit (LEO) environmental conditions. In this paper, the piezoelectric properties of PVDF and the copolymers formed from polymerization of vinylidene fluoride and trifluoroethylene (TrFE) or hexafluoropropylene (HFP) have been studied over a broad temperature range simulating that expected in LEO. The temperatures experienced by unprotected polymers on low altitude spacecraft have previously been reported as ranging from approximately -100 C to +130 C as the polymer/spacecraft passes in and out of the Earth's shadow. To examine the effects of temperature on the piezoelectric properties of poled PVDF, P(VDF-TrFE) and P(VDF-HFP) the d{sub 33} piezoelectric coefficients and electric displacement-electric field (D-E) hysteresis loops were measured up to 160 C for the d{sub 33} measurements and from -80 to +110 C for the D-E loops. The room temperature d{sub 33} coefficient of PVDF homopolymer films, annealed for extended periods at 50, 80 and 125 C, dropped rapidly within a few days of heating, then remained unchanged for periods of up to 300 days. In contrast, the TrFE copolymer exhibited greater thermal stability than the homopolymer, with the d{sub 33} remaining almost unchanged from the pre-annealing value after heating at 50, 80 and 125 C. The HFP copolymer exhibited poor retention of d33 at temperatures above 80 C. For all three polymers short term annealing at 160 C reduced the d{sub 33} to zero. The decrease in d{sub 33} for the TrFE copolymer was correlated with the change in Curie temperature upon annealing of the copolymer, as observed by differential scanning calorimetry (DSC). Unlike radiation damage, which may occur from vacuum UV and atomic oxygen in LEO, the depoling of the polymers on exposure to elevated temperatures was attributed to a physical randomization of the morphology rather than a chemical degradation process. In situ D-E loop measurements over the temperature range -80 to +110 C showed that the remnant polarization of the TrFE copolymer was more stable than the PVDF homopolymer. These results suggest that the TrFE copolymer appears to have a better overall performance in thermal extremes compared with PVDF or an HFP copolymer.
Mirrors made of PVDF film are being considered for lightweight transportation and deployment in space. An array of electrodes can be used to distribute charges over the PVDF film for active shaping of the mirrors. This paper presents the derivation of a matrix that enables calculation of the shape of the two-dimensional mirror for any given electron distribution. Finite element simulation shows good agreement with a theoretical example. Furthermore, if a desired shape is given, the required voltage distribution can be computed using the singular value decomposition. Experiments were done in a vacuum vessel, where an electron gun was used to actuate a PVDF bimorph to a desired shape. Dynamic shape control is attainable at low frequencies. At higher frequencies, still significantly below structural resonance, actuation lag and parasitic DC offset can be significant problems that require future research to solve.