Les matériaux ferroélectriques présentant une permittivité diélectrique élevée et de faibles pertes diélectriques présentent un grand intérêt pour la réalisation de condensateurs et le stockage de l'énergie électrique. Les propriétés structurales et diélectriques influencent les paramètres ferroélectriques tels que la polarisation maximale du matériau Pm et la polarisation rémanente Pr sous l'effet d'un champ électrique appliqué Em. Ce mémoire propose d'étudier les propriétés structurales, diélectriques et ferroélectriques des céramiques dérivées de BaTiO₃ (BT) et SrTiO₃ (ST) ainsi que des films épais PVDF pur et composites tels que PVDF/BT et PVDF/BZT. Les céramiques ont été synthétisées par la méthode de la réaction solide et le procédé sol-gel. La substitution dans les sites-A ou les sites-B du matériau BaTiO₃ avec des cations tels que Ca ²⁺, Sr²⁺ and Zr⁴⁺ réduit la densité d'énergie électrique stockée Wd et augmente l'efficacité de stockage énergétique η. La céramique BaZr₀.₅Ti₀.₅O₃ (BZT0.5) présente l'efficacité de stockage énergétique la plus élevée (η=75%). La substitution dans les sites-A du matériau SrTiO₃ avec 40% de cations Ca²⁺ diminue la permittivité diélectrique (ε'∽200), mais cette permittivité est cependant plus stable sur une large gamme de fréquence [100 Hz-1 GHz]. La céramique Sr₀.₆Ca₀.₄TiO₃ préparée par voie sol-gel présente la densité d'énergie électrique stockée la plus élevée (Wd=0.149 J/cm³) sous l'action d'un champ électrique maximal élevé (Em=105 kV/cm). Les films épais à base de polymère PVDF ont été synthétisés par Spin-Coating. La permittivité diélectrique des films épais PVDF pur augmente avec l'apaisseur du film. L'incorporation de particules BT et BZT0.15 dans la matrice polymère PVDF augmente la permittivité diélectrique des films composites PVDF/BT (ε'=32 pour 30% de particules BT) et PVDF/BZT0.15 (ε'=32 pour15% de particules BZT). / Ferroelectric materials with a high dielectric permittivity and low dielectric losses are very attractive for the realization of capacitors and for electrical energy storage. To improve the electrical energy density Wd, the structural and dielectric properties influence the ferroelectric parameters such as the maximum polarization Pm and the remanent polarization Pr under an applied electric field Em. This manuscript proposes to study the structural, dielectric and ferroelectric properties of ceramics derived from BaTiO₃ (BT) and SrTiO₃ (ST) as well as pure PVDF thick films and composites such as PVDF/BT and PVDF/BZT. The ceramics were synthesized by the solid state reaction reaction route and the sol-gel process. The subsitution in the A-sites or B-sites of the BaTiO₃ material with cations such Ca²⁺, Sr²⁺ and Zr⁴⁺ reduces the electrical energy density Wd and increases the energy storage efficiency η. The ceramic BaZr₀.₅Ti₀.₅O₃ (BZT0.5) has the highest energy storage efficiency (η=75%). The substitution in the A-sites of SrTiO₃ material with 40% of Ca²⁺ cations reduces the dielectric permittivity (ε'∽200), but is more stable over a wide frequency range [100 Hz -1 GHZ]. The Sr₀.₆Ca₀.₄TiO₃ ceramic prepared by sol-gel process has the highest electrical energy density (Wd = 0.149 J/cm³) under an electrical field Em = 105 kV/cm. The PVDF thick films were synthesized by Spin-Coating. The dielectric permittivity of pure PVDF thick films increases when increasing the thickness. The addition of BT and BTZ0.15 particles in the PVDF polymer matrix increases the dielectric permittivity of the composite PVDF/BT thick films (ε'=32 for 30% of BT particles) and PVDF/BZT0.15 ones (ε'=32 for 15% of BZT particles).

The beginning of this thesis contains an overview of properties of the insulators, and description of insulators that were used for in depth research of surface breakdown in vacuum. Furthermore, this work focuses on mechanisms of an electric breakdown initiation at the interface of the solid insulator and surrounding low pressure gas. Multiple methods for measurements of dielectric strength are examined. The experimental part describes the measurements performed in the vacuum chamber. The results of these measurements are then analysed. In conclusion, used insulators are compared and suggestions for further work are given.

Tato diplomová práce zkoumá flexibilní materiál k produkci elektřiny založený na piezoelektrickém polymeru Polyvinylidenfluorid (PVDF). Inkorporací piezoaktivní keramiky lze vlastnosti piezoelektrického polymeru PVDF významně zlepšit a převést na užitečnou elektrickou energii. PVDF byl vytvořen elektrostatickým zvlákňováním do vláken o tloušťce 1,5-0,3 µm a poté studován různými analytickými metodami. Tato práce nabízí popis elektrostatického zvlákňování, přípravu vzorků a teoretický úvod do analytických metod, kterým byly vzorky podrobeny. Morfologie a distribuce nanostrukturované keramiky do polymerní matrice PVDF byla pozorována použitím skenovací elektronové mikroskopie (SEM) a energiově disperzní spektroskopie (EDX). Pro tvorbu fáze a podrobné fázové složení byly vzorky charakterizovány infračervenou spektroskopií s Fourierovou transformací (FTIR). Práce také obsahuje analýzu s použitím Ramanovy spektroskopie, metody používané k identifikaci a porovnání chemických sloučenin. Elektrické vlastnosti byly studovány dielektrickou spektroskopií a je poskytnuta korelace se složením. Jednotlivé komponenty dotovaných vláken jsou charakterizovány a vyhodnocovány v souvislosti s jejich budoucím využitím v senzorech.

A flexible nanofibrous PVDF-BaTiO3 composite material is prepared for impact sensing and biomechanical energy harvesting applications. Dielectric polyvinylidene fluoride (PVDF) and barium titanate (BaTiO3)-PVDF nanofibrous composites were made using the electrospinning process based on a design of experiments approach. The ultrasonication process was optimized using a 2k factorial DoE approach to disperse BaTiO3 particles in PVDF solution in DMF. Scanning electron microscopy was used to characterize the microstructure of the fabricated mesh. The FT-IR and Raman analysis were carried out to investigate the crystal structure of the prepared mesh. Surface morphology contribution to the adhesive property of the composite was explained through contact angle measurements. The capacitance of the prepared PVDF- BaTiO3 nanofibrous mesh was a more than 40% increase over the pure PVDF nanofibers. A comparative study of dielectric relaxation, thermodynamics properties and impact analysis of electrospun polyvinylidene fluoride (PVDF) and 3% BaTiO3-PVDF nanofibrous composite are presented. The frequency dependent dielectric properties revealed micro structural features of the composite material. The dielectric relaxation behavior is further supported by complex impedance analysis and Nyquist plots. The temperature dependence of electric modulus shows Arrhenius type behavior. The observed non-Debye dielectric relaxation in electric loss modulus follows a thermally activated process which can be attributed to a small polaron hopping effect. The particle induced crystallization is supported with thermodynamic properties from differential scanning calorimetric (DSC) measurements. The observed increase in piezoelectric response by impact analysis was attributed to the interfacial interaction between PVDF and BaTiO3. The interfacial polarization between PVDF and BaTiO3 was studied using density functional theory calculations and atomic charge density analysis. The results obtained indicates that electrospinning offers a potential way to produce nanofibers with desired crystalline nature which was not observed in molded samples. In addition, BaTiO3 can be used to increase the capacitance, desired surface characteristics of the PVDF nanofibers which can find potential application as flexible piezoelectric sensor mimicking biological skin for use in impact sensing and energy harvesting applications.

Poly(vinylidene fluoride) PVDF is a semi-crystalline fluoropolymer that attracted researchers' attention more than a decade ago due to its remarkable properties, such as mechanical strength, thermal stability, chemical resistance, good processability, and excellent aging resistance. Due to these excellent properties, PVDF is applied in many applications such as membranes and filtration, biomedical applications, drug delivery, batteries, energy generation, energy storage, sensors, actuators, and energy harvesting applications. The dissertation was inspired by PVDF’s outstanding properties and applications. First of all, the effect of chain topology of on the crystallization and polymorphism between linear and star PVDF homopolymers were studied. Well-defined linear and stars PVDF homopolymers architectures were synthesized by reversible addition−fragmentation chain transfer (RAFT) polymerization. The non-isothermal crystallization study showed an increase in the amount of ferroelectric β-phase with respect to the paraelectric α-phase as the number of arms in the PVDF stars increases. This finding is explained by the increased topological complexity in the stars of several arms, which leads to the preferential formation of the less thermodynamically stable ferroelectric β-phase. Moreover, the isothermal crystallization kinetics of the PVDF stars was faster than the linear PVDF as a result of their speedier nucleation. Secondly, we report the synthesis of poly(n-isopropylacrylamide)-b-poly(vinylidene fluoride) (PNIPAM-b-PVDF), amphiphilic block copolymers with linear and star architectures by RAFT sequential living polymerization. Due to the presence of a lower critical solution temperature (LCST) for PNIPAM (coil-globule transition around 32 °C), the synthesized PNIPAM-b-PVDF block copolymers have thermo-responsive behavior, therefore, potential application in the fabrication of thermo-responsive membranes. All fabricated membranes by nonsolvent-induced phase separation (NIPS) method exhibited thermo-responsive behavior with water permeability and PEG rejection experiments. Moreover, the several heating-cooling cycles showed that the thermal-responsive behavior of these membranes are reversible and stable. Finally, a suggested potential future work is given to synthesize other PVDF-based block copolymers via sequential living polymerizations.

Polymer and composite polymer-ceramic nanofibers were prepared by electrospinning process. Solution of 20 wt.% polyvinylidene fluoride (PVDF) in a mixture of dimethyl sulfoxide (DMSO) and acetone in the ratio of 7:3 was chosen as the most suitable precursor. When preparing composite nanofibers, 20 wt.% of barium calcium zirconate titanate (BCZT) or barium titanate (BT) nanoparticles was added to this PVDF solution. Given parameters were defined as the most suitable for the process of electrospinning: voltage of 50 kV, feeding rate of 30 l/min, distance between emitter and collector of 20 cm and needle diameter of 17 G. The effect of polymer molecular weight and the rotation speed of collector was also studied. Various properties of prepared samples were studied: morphology and fiber diameter, phase composition with the use of x-ray diffraction and Fourier transform infrared spectroscopy and also chosen electrical properties. Lower fiber diameters appeared with lower polymer molecular weight and higher rotation speed of the collector. These parameters resulted in higher percentage of the piezoelectric phase as well. The smallest achieved fiber diameter was around 300 nm, the highest percentage of phase was 92 % and the highest piezoelectric constant had a value of 16 pC/N. Composite fibers filled with BT particles showed better properties that the ones filled with BCZT particles.

Zur Messung pyrelektrischer Koeffzienten wurde ein Messplatz nach einem erweiterten SHARP-GARN-Verfahren entwickelt und zur Untersuchung von Phasenumwandlungen in Pyroelektrika eingesetzt. Einerseits konnten pyroelektrische Messungen im elektrischen Feld die Pyroelektrizität einer neuen durch elektrisch angetriebene Defektmigration erzeugten Phase in Strontiumtitanat nachweisen. Andererseits gelang es, Ferroelektrizität in der Hochtemperaturphase von Poly(Vinylidenfluorid-Trifluorethylen), mittels phasenreiner Präparation der Hochtemperaturphase unterhalb der CURIEtemperatur und anschließender Polarisierung, nachzuweisen. Ferner ließen sich mittels thermisch angeregter Pyroelektrika Redoxprozesse antreiben, was durch Desinfektion von Escherichia coli Bakterien in wässriger Lösung mittels Lithiumniobat und -tantalat gezeigt wurde. Die Hypothese der Desinfektion durch reaktive Sauerstoffspezies konnte durch spektroskopisch nachgewiesene OH-Radikale - erzeugt mittels thermisch angeregter Bariumtitanatnanopartikel - belegt werden.

In this thesis, the results pertaining to various investigations carried out on Triglycine sulphate (TGS) single crystals, polyvinylidene fluoride (PVDF) films, lithium tantalate (LT)/PVDF nanocomposites and LT thin films are presented with emphasis on the characteristics that are crucial for their use in pyroelectric sensors. TGS single crystals (size 68 x 45 x 42 mm3), which have high pyroelectric coefficients, were grown by slow cooling method using newly designed platform technique based crystal growth work stations. The problem of slow growth rate along c-direction was overcome by placing (010) oriented seeds on the platform. The grown TGS crystals were used for the fabrication of the laser energy meter and temperature sensor. One drawback of TGS is its low Curie temperature (490C). As a consequence when the operating temperature approaches the Curie temperature, the crystals start depolarizing owing to the movement of domains. As a result the linearity of the devices gets affected and restricts the use of TGS. Therefore pyroelectric materials possessing higher Curie temperatures and larger pyroelectric coefficients than that of TGS are desirable. LT in single crystalline form having Curie temperature of ≈6000C has already been in use for pyroelectric device applications. However, growing stoichiometric LT single crystal is very difficult. On the other hand PVDF polymer films (Tc≈1800C) have low pyrolectric coefficients and difficult to pole electrically. Therefore efforts were made to prepare LT/PVDF nanocrystal composites to increase the pyroelectric coefficient of PVDF and to reduce the poling field. Nanoparticles of LT were prepared using sol-gel route. Spherical nanoparticles of size 20-40nm were prepared from sol by adding oleic acid to it. These nanoparticles were characterized using XRD, TEM, DSC and Raman spectroscopy. PVDF films with large percentage of β-phase (ferroelectric phase) were fabricated from solutions prepared using dimethylsulphoxide (DMSO) solvent. PVDF films (30µm thick), embedded with 20-40nm sized nanocrystallites of LT were fabricated to utilize them for pyroelectric sensor applications. The ferroelectric and pyrolectric properties of nano composite films were studied for sensor applications point of view. As a replacement for the single crystals of LT in pyroelectric sensors, investigations were carried out on oriented LT thin films. The studies on LT thin films yielded promising results which could be exploited for pyroelectric sensor applications.