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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.

<p>The overall time and cost for a drug to go from the drug discovery to the consumer market is  significant,  showing  a  need  for  improved  drug  testing  and  discovery  methods.    Work  on nonlinear  optical  methods  for  both  small  active  pharmaceutical  ingredient  drug  formulation analysis and large biological therapeutic stability testing has been shown to improve testing times for formulation, stability and dissolution testing.  Herein, we review the existing and conventional approaches to address stability testing that the pharmaceutical industry uses, and how leveraging nonlinear optical (NLO) methods can improve the current challenges.  The specificity, sensitivity and low limit of detection of second harmonic generation is discussed in application to crystal formation in small-molecule active pharmaceutical ingredients.  The nonlinear optical methods second harmonic generation and two-photon excited ultraviolet fluorescence are directly compared to  ‘gold  standard’  powder  X-ray  diffraction,  which  is  commonly  used  for  measuring  crystal formation and growth of active pharmaceutical ingredients in amorphous solid dispersions.  In addition, the existing FRAP method (with multiple limitations) is improved upon with the ability to  perform  recovered  diffusion  coefficient  data  analysis  in  the  spatial  Fourier  domain.    The collective results discussed in this thesis are just a small subset of the total breadth of investigations marrying the new challenges in the pharmaceutical industry with the new NLO tools tailored to meet them</p>

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Transition metal interface effects of on the crystallization of carbon and silicon were investigated. The graphitization of carbon was studied by ion beam sputter deposition of atomic carbon onto a nickel surface at temperatures ranging from room temperature to 550 °C. The resulting films were characterized by X-ray photoelectron spectroscopy, nuclear reaction analysis combined with Rutherford backscattering spectrometry, Raman spectroscopy and transmission electron microscopy. A temperature-induced and a nickel-induced effect on the graphitic ordering is demonstrated. The carbon films showed a two layered structure: directly on the nickel surface up to 8 monolayers of graphitic carbon, further deposited carbon formed less ordered structures, preferably perpendicular to the surface. The results are discussed on the basis of hyperthermal atom deposition, surface diffusion, metal-induced crystallization and dissolution-precipitation. The analysis points to a dominating role of surface diffusion-assisted crystallization in the carbon ordering process. The kinetics of silver-induced crystallization of amorphous silicon were studied in a series of isothermal annealing experiments at 350 °C, 400 °C, 450 °C and 500 °C. The annealing process was monitored in situ employing Raman spectroscopy and Rutherford backscattering spectrometry from which time resolved information on the phase transformation and hence the kinetics are obtained. The grain structure of the crystallized silicon film was investigated with optical and scanning electron microscopy which reveals grain diameters of 5 to 8 µm. The small scale crystallinity was measured with X-ray diffraction and crystal domain sizes from 20 to 50 nm were observed. The phase transformation kinetics are discussed based on the Johnson-Mehl-Avrami-Kolmogorov theory. The analysis points to a two-dimensional, diffusion limited process with fast Avrami-type nucleation and an activation energy of 0.8 eV/at.:Contents 1. Introduction 2. Metal-Induced Crystallization 2.1. Introduction and State of the Art of Metal-Induced Crystalliza-tion 2.2. Thermodynamics of Metal-Induced Crystallization 2.3. Kinetics of Metal-Induced Crystallization 3. Ion Beam Analysis 3.1. Rutherford Backscattering Spectrometry 3.2. Nuclear Reaction Analysis 4. Raman Spectroscopy 4.1. Light Scattering in Solids 4.2. Theory 4.2.1. The Raman Spectrum of Graphitic Carbon 4.2.2. The Silicon Raman Spectrum 5. The Cluster Tool at the Ion Beam Center 5.1. General Concept 5.2. Sputtering Chamber 5.3. The Environmental Chamber 5.4. The Analysis Chamber 5.5. The Ion Beam Analysis Chamber 5.5.1. The Experimental Setup 6. The Carbon Nickel System 6.1. Experimental Details 6.1.1. Film growth 6.1.2. Characterization 6.2. Results 6.3. Discussion 7. The Silicon Silver System 7.1. Experimental 7.1.1. Film Preparation 7.1.2. In Situ Raman Spectroscopy 7.1.3. In Situ Rutherford Backscattering Spectrometry 7.2. Results 7.2.1. Raman Spectroscopy 7.2.2. Rutherford Backscattering Spectrometry 7.2.3. X-ray Diffraction 7.2.4. Optical and Scanning Electron Microscopy 7.3. Discussion 8. Conclusion and Outlook A. Appendix A.1. Spectroscopic Lineshapes A.1.1. The Lorentzian Lineshape A.1.2. The Breit-Wigner-Fano Lineshape A.1.3. The Doniach-Sunjic Lineshape A.1.4. The Gaussian Lineshape A.1.5. The Voigt Lineshape A.2. Statistcial Distribution Functions A.2.1. The Gamma Distribution Bibliography / Der Einfluss von Übergangsmetallkontaktflächen auf die Kristallisation von Kohlenstoff und Silizium wurde untersucht. Dazu wurde Kohlenstoff bei Temperaturen von Raumtemperatur bis 550 °C auf Nickel mittels Ionenstrahl-Sputtern abgeschieden. Die so erzeugten Filme wurden mit Röntgenphotoelektronen Spektroskopie, Kernreaktionsanalyse kombiniert mit Rutherford Rückstreu Spektrometrie, Raman Spektroskopie und Transmissions-Elektronenmikroskopie charakterisiert. Ein Nickel- und ein Temperatureffekt auf den Graphitisierungsprozess wird nachgewiesen. Die Kohlenstofffilme zeigten einen zweilagigen Aufbau: Direkt auf der Nickeloberfläche bis zu 8 Monolagen graphitischen Kohlenstoffs, weiterer abgeschiedener Kohlenstoff bildet weniger geordnete Strukturen, die bevorzugt senkrecht zur Oberfläche ausgerichtet sind. Die Ergebnisse werden auf Basis von hyperthermischer, atomarer Abscheidung, Oberflächendiffusion, Metall-induzierte Kristallisation und Lösung-Ausfällung diskutiert. Die Analysen deuten auf eine dominante Rolle der Oberflächendiffusion im Graphitisierungsprozess hin. Die Kinetik der Silber-induzierten Kristallisation von amorphen Silizium wurde in einer Reihe von isothermalen Temperexperimenten bei 350 °C, 400 °C, 450 °C und 500 °C untersucht. Der Tempervorgang wurde mit in situ Raman Spektroskopie und in situ Rutherford Rückstreu Spektrometrie charakterisiert, wodurch zeitaufgelöste Information über den Phasenübergang und damit die Kinetik gewonnen wurden. Das Gefüge der entstandenen Siliziumschichten wurde mit optischer und Rasterelektronenmikroskopie untersucht, welche Korndurchmesser von 5 bis 8 µm zeigten. Die Kristallinität wurde mit Röntgendiffraktometrie analysiert. Hierdurch wurden Kristallitgrößen von 20 bis 50 nm bestimmt. Die Kinetik des Phasenüberganges wird anhand der Johnson-Mehl-Avrami-Kolmogorov Theorie diskutiert. Dies deutet auf einen zeidimensionalen, diffusionslimitierten Prozess mit schnell abklingender Avrami-Keimbildung hin. Die Aktivierungsenergie wurde zu 0.8 eV/At. bestimmt.:Contents 1. Introduction 2. Metal-Induced Crystallization 2.1. Introduction and State of the Art of Metal-Induced Crystalliza-tion 2.2. Thermodynamics of Metal-Induced Crystallization 2.3. Kinetics of Metal-Induced Crystallization 3. Ion Beam Analysis 3.1. Rutherford Backscattering Spectrometry 3.2. Nuclear Reaction Analysis 4. Raman Spectroscopy 4.1. Light Scattering in Solids 4.2. Theory 4.2.1. The Raman Spectrum of Graphitic Carbon 4.2.2. The Silicon Raman Spectrum 5. The Cluster Tool at the Ion Beam Center 5.1. General Concept 5.2. Sputtering Chamber 5.3. The Environmental Chamber 5.4. The Analysis Chamber 5.5. The Ion Beam Analysis Chamber 5.5.1. The Experimental Setup 6. The Carbon Nickel System 6.1. Experimental Details 6.1.1. Film growth 6.1.2. Characterization 6.2. Results 6.3. Discussion 7. The Silicon Silver System 7.1. Experimental 7.1.1. Film Preparation 7.1.2. In Situ Raman Spectroscopy 7.1.3. In Situ Rutherford Backscattering Spectrometry 7.2. Results 7.2.1. Raman Spectroscopy 7.2.2. Rutherford Backscattering Spectrometry 7.2.3. X-ray Diffraction 7.2.4. Optical and Scanning Electron Microscopy 7.3. Discussion 8. Conclusion and Outlook A. Appendix A.1. Spectroscopic Lineshapes A.1.1. The Lorentzian Lineshape A.1.2. The Breit-Wigner-Fano Lineshape A.1.3. The Doniach-Sunjic Lineshape A.1.4. The Gaussian Lineshape A.1.5. The Voigt Lineshape A.2. Statistcial Distribution Functions A.2.1. The Gamma Distribution Bibliography