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Increasing global energy demands continually heighten the need for novel, alternative energy conversion technologies, especially those that recover waste heat generated by traditional energy conversion processes. The so-called pyroelectric effect is one intrinsic material phenomenon that can be leveraged for waste heat energy scavenging. The pyroelectric effect is characterized by the pyroelectric coefficient (p), which describes the magnitude of the change in a material’s spontaneous polarization in response to a change in its temperature. The future of pyroelectric energy harvesting is dependent upon reliable experimental measurement technique, and an understanding of how to design harvesting systems to maximize their performance. In this thesis, we both describe measurement techniques for quantifying thin film pyroelectric materials and provide guidance for maximizing the power output of pyroelectric harvesting systems.We adapt an electrothermal technique commonly used for measuring thermal conductivity, the 3ω method, to measure p of mechanically clamped PZT thin films. Using the 3ω method combined with a 1D heat transport model, we simultaneously collect the thermally-generated pyroelectric current and measure the average temperature of the metallic heater line atop the thin film, allowing us to calculate p. Frequency sweeps across several decades allow us to identify the secondary (piezoelectric) contributions to the pyroelectric coefficient, which arise due to mismatched thermal expansion coefficients between the thin film and the bulk substrate. We develop and extend these techniques using the same physical system to directly measure the electrocaloric effect in thin films as a supplement to these pyroelectric measurements. Next, we experimentally quantify the performance of pyroelectric thin films as energy converters. Using the same experimental architecture as with the PZT measurements, we synchronize the temperature of PMN-0.32PT thin films with an externally-applied electric field to complete Ericsson cycles in the thermodynamic electric field-electric displacement space. The large pyroelectric coefficient of the PMN-0.32PT and fast cycle frequencies result in large energy and power densities. This combination of large energy and power density is a first in pyroelectric energy conversion, demonstrating the benefits of the thin film architecture and showing promise for pyroelectrics as a viable waste heat scavenging technology.We lastly analyze the heat transport in idealized, 1D pyroelectric energy harvesters to identify the physical constants (e.g. thermal conductivity and volumetric heat capacity) and system properties (e.g. length and heating frequency) that determine power harvesting performance. Modeling the pyroelectric as a current source and capacitor in parallel, we relate the spatially-averaged temperature amplitude of the pyroelectric material to the power delivered to a purely resistive external load. We consider both a temperature and a heat flux source as the driving thermal energy source for the pyroelectric harvester, and through dimensional analysis we isolate the effects of different system parameters on the power delivered to the external load. Finally, we identify figures of merit (FOM’s) for various operating regimes and provide general guidance for optimizing the power output of pyroelectric energy harvesters given freedom over different system variables.

Nanogenerator energy harvesting technologies that transform thermal energies into electricity may help address the growing need for green power. Therefore, this research aims to increase power generation by combining waste heat with pyroelectric nanogenerators as a sustainable energy source. Under optimal conditions, an external multi-pulse electric field can be utilized to generate power using thermoelectric cycle power generation. The greatest power may be gathered by applying various pulses of the external electric field at temperature changes on the surface of the pyroelectric materials. To generate pyroelectric power, a C9 BZT sample was used, and the lowest temperature difference for accomplishing this was 20 °C, with all measurements made on a sample with a lower limit of 120 °C. The maximum generation density was 0.104 mJ/cm2°CkV for a pulse width of 10 ms and 20 pulses of a low voltage (250 V/mm) input electric field. A multi-pulse electric field with low input voltage increases the power generation performance ratio (η) with the pulse count. At the largest number of pulses, the greatest η value for 250 V/mm was 7.834. Finally, it was determined that the developed pyroelectric power generation system may be more effective if a low-voltage, multi-pulse electric field is used.

Dielectrics are materials that can be polarized by an applied electric field. As the essential property for dielectrics, the relationship between electric field and dielectric polarization, has been widely studied and used in the area of electrical engineering. Representative applications are insulators and electrical energy storage capacitors. For some types of dielectrics, the dielectric polarization is not only decided by the applied electric field, but also is affected by mechanical and thermal properties. This work studies the electro-mechanical and electro-thermal energy inter-conversions and proposes the design of power converters for these materials. Piezoelectric effect is a cross-coupling between mechanical property and electrical property of dielectrics. It is a reversible process where external electric potential can generate internal mechanical force while external mechanical force can also generate internal electric potential. This effect is utilized to build a piezoelectric transformer (PT) by combining two sets of piezoelectric material together. One set is used as the input, to cause a geometric strain by applied electric field, while the other set is used as the output, to generate an electric charge by the coupled mechanical stress. Compared to traditional magnetic transformers, PTs store energy in mechanical inertia and compliance and therefore they do not generate electromagnetic noise. They are suitable for batch mass manufacturing since there is no winding requirement. Among many types of PTs, radial PT and Rosen-type PT are most widely used. To provide a guide for the design of PT-based converters, the electrical characteristics of PTs are first analyzed. The accuracy and applicability of different levels of models of PTs are compared and discussed. The detailed universal attributes of PTs, which include the gain characteristic, the input impedance characteristic and the efficiency characteristic, are also derived. In addition, with the assistance of additional compensation component(s), PTs can provide better performance. The impacts of the input and output inductors and capacitors on gain and efficiency characteristics of a PT are analyzed. Tunable PT is a recently developed raidal PT with three ports: input, output, and control ports. When connected with different impedance at the control port, tunable PT has different voltage gain characteristics. It is proposed to use this property for output voltage regulation while keeping constant switching frequency to ensure high efficiency operation of the PT in PT-based power converters. A closed-loop control scheme is proposed, where the regulation is done by a duty cycle controlled switched capacitor at the tunable PT control port. Two types of output filter are also analyzed and compared. Dc-dc converters with power rating ranging from 30 W to 100 W are built to verify the proposed design. Rosen-type PT features natural mechanisms for high transform ratio in a compact planar form, which provide an alternative solution for dc bus-fed high step-down voltage-ratio auxiliary power supplies in medium-/high-voltage systems without using bulky magnetic transformer with high turns numbers. The design procedure of the Rosen-type PT-based high step-down voltage-ratio dc-dc converter is presented. The proposed design is validated by a prototype with height of 1 cm, whose nominal output power is 5 W, input voltage ranges from 200 V to 1.5 kV, regulated output voltage is 5 V. Pyroelectric effect is a cross-coupling between thermal property and electrical property in some dielectrics. It is also reversible. The pyroelectric effect refers to the polarization change caused by temperature change, while the reversed pyroelectric effect refers to a temperature change generated by a electric field change. The reversed pyroelectric effect can be used for building a environmentally friendly thermodynamic system. Electrical characterization of the pyroelectric material is executed to facilitate the design of the power converter needed in the corresponding thermodynamic system. Specifically, this work proposes an energy recovery circuit to increase the coefficient of performance of the system since during the thermodynamic cycle, part of the electrical driving work does not pump heat and may therefore be recovered. Doctor of Philosophy When a dielectric material is placed in an electric field, electric charges slightly shift from their average equilibrium positions, causing dielectric polarization. In the area of electromagnetism, dielectric material is widely used as an electrical insulator and to build capacitors. For some types of dielectrics, dielectric polarization is not only affected by electric field. Strong couplings between electrical and mechanical characteristics, and between electrical and thermal characteristic also exist and can be utilized in practical applications. Piezoelectric effect is a coupling between electrical and mechanical characteristics. It is a reversible process where external electric potential can generate internal mechanical force and vice versa. It can be utilized to build transformers, which do not require coil winding nor generate electromagnetic interference compared to their magnetic counterparts. This work analyzed the electrical characteristics of piezoelectric transformers and proposed the design of dc-dc converters based on different types of piezoelectric transformers for different applications, which include tunable radial piezoelectric transformer-based power converters and Rosen-type piezoelectric transformer-based step-down converter with high voltage conversion ratio. (Reversed) pyroelectric effect is a coupling between electrical and thermal characteristics in some dielectrics. An adiabatically applied or removal electric field results in an increase or decrease in the temperature of the corresponding material. This effect can be used to build a environmentally friendly thermodynamic system instead of the most prevalent vapor compression method which involves the use of hydro-fluorocarbon gases leading to global warming and ozone depletion. Electrical characterization is executed first to facilitate the design of the power converter needed by the thermodynamic system. In addition, during the thermal cycle, part of the work done to drive representative cycles does not pump heat and may therefore be recovered. This work proposed circuit featuring energy recovery to provide the desired electric field for driving the thermodynamic system and charge recycling to improve the system efficiency.

Pyroelectric materials are important functional materials that can generate an electrical response upon a temperature change. Among the many different types of pyroelectric materials, lead-based materials are the most widely-used traditional pyroelectric material and they will soon be banned due to their high toxicity. Therefore, in the past decade, extensive studies have been conducted to search for high performance lead-free pyroelectric materials. Recent experimental efforts have led to significant advances in lead-free pyroelectrics in different forms. This has further motivated their application from a traditional sensing function to a future energy-related prospect. This article provides a comprehensive review on the up-to-date advances in lead-free pyroelectrics, including single crystals, ceramics, inorganic films, polymers and composites. Moreover, the recent rise in energy harvesting and the electrocaloric effect as well as the potential future development of pyroelectric applications will be presented.

X-rays are a type of electromagnetic energy which widely used in different areas. Since their discovery, x-rays have been used, especially for medical imaging applications. On the other hand, new efficient x-ray generation methods have still been under investigation. Although new imaging modalities arose, xrays have never lost their popularity in many applications like computed tomography and dental imaging. Among these new methods, x-ray generation using pyroelectric crystal materials is one of the promising technologies. Pyroelectric crystals generate an electric field when a temperature change occurs and are affected by various parameters like how many times (count) the crystal’s temperature changed in a second. Hence, this new technology needs more research. In this study, we investigated the relationship between the count number and x-rays’ energy level of pyroelectric materials using linear regression analysis. We used a commercial software package, which is called the Statistical Package for the Social Sciences (SPSS), for this purpose. As a result, we achieved a good fit value of R2 = 0.91.

cited By 2; International audience; We deal with the thermal energy which is one of the ambient energy sources surely exploitable, but it has not been much interest as the mechanical energy. In this paper, our aim is to use thermal energy and show that it's an important source for producing the electrical energy through pyroelectric effect which is the property of some dielectric materials to show a spontaneous electrical polarization versus temperature. In this context, we present a concept to harvest a thermal energy using infrared rays and pyroelectric effect. The pyroelectric material used in this work can generate an electrical voltage when it subjected to a temperature change which will be ensured by the use of infrared lamp. Our experimental results show that the electrical voltage, current and harvested power increased significantly when increasing the area of the pyroelectric element. The experimental results show also that with this simple concept we harvested a heavy amount value of power which will certainly be useful in an extensive range of applications, including sensors and infrared detection. These results shed light on the thermoelectric energy conversion by Ceramic lead zirconate titanate (PZT) buzzer having the pyroelectric property. © 2016 Elsevier B.V. All rights reserved.

Pyroelectricity is mainly affected by the structure of materials. To explore the influence of the structure on pyroelectricity, a new type of pyroelectric materials with structure of tourmaline consisting of Li9Mg3[PO4]4F3, Ba3Sr4(BO3)3F5 and tourmaline have been systematically studied in this work. Based on the comparison results of the pyroelectric coefficient of Li9Mg3[PO4]4F3 and Ba3Sr4(BO3)3F5 after heating and the variations of electric dipole moment, it suggests the tetrahedron is less stable than trigon, and is easily to cause the distortion and deformation of structure, which leads to the great enhancement of pyroelectricity. Additionally, it can find that the tetrahedron has the most contribution to the pyroelectricity by comparing the pyroelectric coefficient and total electric dipole moment of Li9Mg3[PO4]4F3, Ba3Sr4(BO3)3F5 and tourmaline which have different polyhedrons.

Icing on materials surface causes operational failures as well as technical and safety issues. Furthermore, it reduces the energy efficiency of the power supply and passenger/freight transportation systems. Conventional active deicing methods are widely used to remove ice, but are often associated with uneconomically high energy consumption and high maintenance costs, often not being aware of their environmental impact. Instead, passive anti-icing methods are being sought to prevent or delay ice formation by means of physico-chemical surface treatment. Pyroelectric materials can be used as possible anti-icing surfaces after their ability to inhibit ice nucleation has been experimentally demonstrated. This makes use of the effect of the pyroelectrically induced surface charge, which changes with the ambient temperature and thus, hypothetically, exerts an influence on the dipole orientation of the water molecules at the surface. This is expected to affect the hydrogen bonding network of the interfacial water in the supercooled liquid phase, depending on the sign of surface charge. However, the Classical Nucleation Theory predicts an increased nucleation rate with increasing electric field strength of the pyroelectric surface charge irrespective of its polarity, as confirmed by many experiments. This raises the question of what exactly influences the ice nucleation. The main purpose of this thesis is to find a relationship between the pyroelectricity and the ice nucleation rate. Various theoretical and experimental investigation methods have been used to examine which of the possible influencing factors related to the pyroelectric material surface plays a major role in promoting or inhibiting ice nucleation.:Contents Abstract i List of figures xi List of tables xv 1 Introduction 1 1.1 Motivation 1 1.2 Objective and Tasks 4 1.3 Structure of the thesis 6 2 Basics 7 2.1 Pyroelectric materials 7 2.1.1 Fundamental properties 7 2.1.2 Lithium niobate, LiNbO3 14 2.2 Ice nucleation and water freezing 21 2.2.1 Thermodynamics of ice nucleation 21 2.2.2 Factors influencing ice nucleation 26 3 Materials and Methods 29 3.1 Sample materials used for the investigation 29 3.2 Theoretical methods 31 3.2.1 Theoretical background of computational quantum mechanical modeling 31 3.2.2 LiNbO3 model system 38 3.2.3 DFT implementation in CP2K 41 3.3 Experimental methods 42 3.3.1 Optical and vibrational spectroscopy 43 3.3.2 X-ray spectroscopy 47 3.3.3 Atomic force microscopy 48 3.3.4 Environmental scanning electron spectroscopy 51 3.3.5 Pyroelectric measurement 52 3.3.6 Contact angle measurement 53 3.3.7 Icing temperature measurement 54 3.4 Tabular overview of the different methods 57 ix4 Results and Discussion 59 4.1 Results 59 4.1.1 Several results of DFT calculations 59 4.1.2 MD simulations of interfacial water 75 4.1.3 Results of optical and vibrational spectroscopy 80 4.1.4 X-ray spectroscopy on LiNbO3 surfaces 96 4.1.5 Extended treatment of the Classical Nucleation Theory 100 4.1.6 Results of atomic force microscopy 108 4.1.7 ESEM images of ice crystals grown on LiNbO3 116 4.1.8 Results of pyroelectric measurements 122 4.1.9 Results of contact angle measurements 124 4.1.10 Results of icing temperature measurements 126 4.2 Discussion 135 4.2.1 Surface charge 135 4.2.2 Surface structure 144 4.2.3 Surface reactivity 149 4.3 Conclusion of the findings and remarks 151 5 Summary and Outlook 157 5.1 Conclusion of the thesis 157 5.2 Recommendations for further investigations 161 5.3 Outlook 164 Appendix 167 A.1 Additional information to the DFT calculations 167 A.2 Background spectrum for ATR spectroscopy 175 A.3 Additional information to SFG/SHG spectroscopy 176 A.4 Additional information to the XPS results 181 A.5 Additional information to the AFM measurement 182 A.6 ESEM images of ice accretion in the sample system 187 A.7 FEM simulation of local temperature and flow velocity distribution 190 A.8 Additional information to the icing temperature measurement 203 A.9 Temperature-dependent pH variation of water at LiNbO3 surface 207 List of abbreviations and symbols 213 References 217 Publications 276 Acknowledgements 277 Erklärung 281 Vereisung auf Werkstoffoberflächen führt einerseits zu Betriebsausfällen und andererseits zur Reduzierung der Energieeffizienz von Energieversorgungs- sowie Personen- und Gütertransportsystemen. Sie stellt nicht selten ein sicherheitstechnisches und gesundheitliches Risiko dar. Da die konventionellen aktiven Enteisungsmethoden mit hohem Energieaufwand und hohen Wartungskosten verbunden sind, wird nach passiven Anti-icing-Methoden als vorbeugende Maßnahmen zur Vermeidung/Verzögerung von Eisbildung auf physikalisch-chemisch behandelten Oberflächen gesucht. Der Einsatz dieser Werkstoffoberflächen senkt nicht nur den Energieverbrauch, sondern soll auch die Umwelt schonen. Pyroelektrische Materialien kommen als passive Anti-icing-Oberflächen in Frage, nachdem ihre eiskeimbildungshemmende Fähigkeit experimentell nachgewiesen wurde. Dabei wird der Effekt der pyroelektrisch induzierten Oberflächenladung ausgenutzt, die sich mit der Umgebungstemperatur ändert und somit, hypothetisch gesehen, einen Einfluss auf die Dipolorientierung der Wassermoleküle an der Oberfläche ausübt. Das hat je nach Vorzeichen der Oberflächenladung Auswirkungen auf das Wassermolekülbindungsnetzwerk des Grenzflächenwassers in der unterkühlten flüssigen Phase. Da die klassische Keimbildungstheorie jedoch eine erhöhte Keimbildungswahrscheinlichkeit mit zunehmender Stärke des elektrischen Feldes der pyroelektrischen Oberflächenladung unabhängig von ihrem Vorzeichen voraussagt, wie es ebenfalls in vielen Experimenten nachgewiesen wurde, stellt sich die Frage, was genau die Eiskeimbildung beeinflusst. Das Hauptanliegen dieser Arbeit ist, einen Zusammenhang zwischen der Pyroelektrizität der Oberfläche und der Eiskeimbildungsrate zu finden. Mithilfe einer Vielzahl von verschiedenen theoretischen und experimentellen Methoden wird untersucht, welcher der möglichen Einflussfaktoren im Zusammenhang mit der pyroelektrischen Materialoberfläche eine große Rolle bei der Eiskeimbildung spielt.:Contents Abstract i List of figures xi List of tables xv 1 Introduction 1 1.1 Motivation 1 1.2 Objective and Tasks 4 1.3 Structure of the thesis 6 2 Basics 7 2.1 Pyroelectric materials 7 2.1.1 Fundamental properties 7 2.1.2 Lithium niobate, LiNbO3 14 2.2 Ice nucleation and water freezing 21 2.2.1 Thermodynamics of ice nucleation 21 2.2.2 Factors influencing ice nucleation 26 3 Materials and Methods 29 3.1 Sample materials used for the investigation 29 3.2 Theoretical methods 31 3.2.1 Theoretical background of computational quantum mechanical modeling 31 3.2.2 LiNbO3 model system 38 3.2.3 DFT implementation in CP2K 41 3.3 Experimental methods 42 3.3.1 Optical and vibrational spectroscopy 43 3.3.2 X-ray spectroscopy 47 3.3.3 Atomic force microscopy 48 3.3.4 Environmental scanning electron spectroscopy 51 3.3.5 Pyroelectric measurement 52 3.3.6 Contact angle measurement 53 3.3.7 Icing temperature measurement 54 3.4 Tabular overview of the different methods 57 ix4 Results and Discussion 59 4.1 Results 59 4.1.1 Several results of DFT calculations 59 4.1.2 MD simulations of interfacial water 75 4.1.3 Results of optical and vibrational spectroscopy 80 4.1.4 X-ray spectroscopy on LiNbO3 surfaces 96 4.1.5 Extended treatment of the Classical Nucleation Theory 100 4.1.6 Results of atomic force microscopy 108 4.1.7 ESEM images of ice crystals grown on LiNbO3 116 4.1.8 Results of pyroelectric measurements 122 4.1.9 Results of contact angle measurements 124 4.1.10 Results of icing temperature measurements 126 4.2 Discussion 135 4.2.1 Surface charge 135 4.2.2 Surface structure 144 4.2.3 Surface reactivity 149 4.3 Conclusion of the findings and remarks 151 5 Summary and Outlook 157 5.1 Conclusion of the thesis 157 5.2 Recommendations for further investigations 161 5.3 Outlook 164 Appendix 167 A.1 Additional information to the DFT calculations 167 A.2 Background spectrum for ATR spectroscopy 175 A.3 Additional information to SFG/SHG spectroscopy 176 A.4 Additional information to the XPS results 181 A.5 Additional information to the AFM measurement 182 A.6 ESEM images of ice accretion in the sample system 187 A.7 FEM simulation of local temperature and flow velocity distribution 190 A.8 Additional information to the icing temperature measurement 203 A.9 Temperature-dependent pH variation of water at LiNbO3 surface 207 List of abbreviations and symbols 213 References 217 Publications 276 Acknowledgements 277 Erklärung 281