Teses / dissertações sobre o tema "Bizmut"

This thesis deals with novel trends in solder paste technology. It focuses on nanoparticle applications used as a tool for improving a state of the art lead free solder alloys. The recently published results about the impact of different types of nanoparticles on properties of newly-emerged nanocomposite solders are discussed and summarized in the thesis. Preparation, practical application and testing of new solder paste based on low temperature SnBi alloy with an admixture of titanium dioxide are also discussed. Finally, properties of solder joints using these solder pastes are investigated and the results are evaluated.

Cilj ove doktorske disertacija  bio je razvoj  novih, osetljivih, selektivnih i ekonomskiisplativih  voltametrijskih  radnih  elektroda  za  praćenje  odabranih  analita  kako  ulaboratorijskim tako i pri terenskim uslovima.  Ispitivana je  mogućnost primene  ovih  radnih  elektroda  primenom  voltametrijskih  metoda  kako  u  model  rastvorima  tako  i  u  pojedinim realnim sistemima. SW-ASV  zasnovana  na  elektrodama  od  staklastog  ugljenika  površinski modifikovanim  Bi-MWCNT  i  BiOCl-MWCNT  je  primenjena  za  određivanje  jona  Pb(II)  i Cd(II)  pri  optimizovanim  uslovima  merenja.  Određivanje  ciljnih  jona  vršeno  je  pri  radnom potencijalu  od  -1,2  V  (izmeren  u  odnosu  na  zasićenu  kalomelovu  elektrodu)  i  vremenuelektrodepozicije jona  od 120 s. Sva merenja su izvršena u rastvoru acetatnog pufera čija je pH-vrednost iznosila  4,0. Primenjeni koncentracioni opseg ciljnih analita iznosio je  od 5 do 50  μg  dm ^-3 .  Primenom  ovog  tipa  elektrode  dobijene  su  vrednosti  granice  detekcije  za  jone Pb(II) i Cd(II) 0,57  μg dm ^-3 i 1,2 μg dm^-3 , redom. Dobijena RSD iznosila je manje od 10% za oba  jona.  Ova  metoda  je  primenjena  i  za  određivanje  ciljnih  jona  u  realnom  uzorku  porne vode  sedimenta  a  rezultati  dobijeni  optimizovanom  voltametrijskom  metodom  su  u  dobroj saglasnosti sa rezultatima koji su dobijeni primenom komparativne GFAAS metode. Bizmut oksihlorid-višezidne ugljenične nanocevi kompozitni materijal je primenjen za površinsko  modifikovanje  elektrode  od  staklastog  ugljenika  za  brzo  i  jednostavno voltametrijsko  određivanje  tragova  Zn(II)-jona  primenom  SW-ASV  metode.  BiOClMWCNT/GCE je pokazala linearan analitički odgovor u  osegu koncentracija od  2,50 do  80,0 μg  dm ^-3 sa dobijenom vrednošću GD 0,75 μg  dm^-3 pri akumulacionom vremenu od  120 s  i potencijalu  elektrodepozicije  -1,40  V  u  odnosu  na  ZKE.  Merenja  su  vršena  u  acetatnom puferu pH 4,5. Dobijena RSD iznosila je 4,8 %. Upoređene su performanse novodizajnirane BiOCl-MWCNT/GCE elektrode  i  tradicionalne elektrode na bazi bizmut filma (BiF/GCE), MWCNT/GCE,  BiF-MWCNT/GCE  i  nemodifikovane  GC  elektrode.  Novodizajnirana elektroda je primenjena za  detekciju  i određivanje  Zn(II)-jona  u realnim  uzorcima kao što sudijetetski  suplement  i  pekarski  kvasac.  Dobijeni  rezultati  su  uporedivi  sa  deklarisanom vrednošću  u  slučaju  dijetetskog  suplementa  a  u  slučaju  pekarskog  kvasca  sa  rezultatima dobijenih komparativnom FAAS .Elektroda od ugljenične paste je površinski modifikovana pripremljenim kompozitomkoji je  izgrađen od višezidnih ugljeničnih nanocevi i čestica  Sb₂O_3.  Kompozitni  materijal  je okarakterisan  primenom  TEM,  EDS  i  XRD  mernih  tehnika.  Sb₂O₃-MWCNT/CPE  je okarakterisana primenom ciklične voltametrije a merenja su vršena u rastvoru hlorovodonične kiseline  (pH  2,0).  Primenom  SW-ASV  metode  ova  radna  elektroda  je  upotrebljena  za određivanje  jona Pb(II) i Cd(II)  u  koncentracionom opsegu 2,0-40,0  μg  dm  ^-3 za  Pb(II)-jon  i 2,0-40,0  μg  dm ^-3 za  Cd(II)-jon  pri  čemu  su  dobijene  dobre  linearne  zavisnosti  za  oba  ciljna jona.  Optimalna  procedura  uključuje  primenu  Sb2O3-MWCNT/CPE  u  0,01  mol dm ^-3hlorovodoničnoj kiselini uz vreme elektrodepozicije jona iz rastvora od 120  s  na  potencijaluod  -1,2  V,  pri  čemu  su  dobijene  vrednosti  za  GD  1,1  μg  dm ^-3 Cd(II)  i  1,6  μg  dm ^-3 Pb(II). Optimizovana  metoda  zasnovana  na  ovom  tipu  voltametrijskog  senzora  je  uspešno primenjena  za  određivanje  jona  Cd(II)  u  obogaćenom  uzorku  česmenske  vode,  gde  su  se dobijene vrednosti u  saglasnosti sa očekivanom. Elektroda od ugljenične paste površinski je  modifikovana primenom  Sb₂O₃-MWCNT nanokompozitnog  materijala  i  primenjena  za  direktno  voltametrijsko  određivanje imidakloprida  u  model  rastvorima.  U  cilju  postizanja  što  boljih  analitičkih  performansi optimizovani su eksperimentalni uslovi merenja kao što su pH-vrednost rastvora pomoćnog elektrolita  i  kondicioniranje  površine  voltametrijskog  senzora.  Kao  optimalna  pH-vrednost pomoćnog elektolita (Britton-Robinsonovog pufera) odabrana je pH 7,0, a ponavljanje ciklusa cikliranja najmanje 4 puta povoljno utiče na stabilnost  voltametrijskih signala. Optimizovana metoda primenjena je za SW direktno katodno određivanje imidakloprida u koncentracionom intervalu od 1,41 do 32,77 μg cm ^-3 uz dobijeni korelacioni faktor od 0,9995. Na osnovu dobijenih rezultata može se zaključiti da su razvijene analitičke metode pre svega  osetljive,  selektivne,  reproduktivne  i   jednostavne  što  omogućava  njihovu  primenu  za veliki broj uzoraka.  Merenjima u model i realnim rastvorima dokazana je mogućnost njihove primene  u   komplikovanim  matriksima,  pri  različitim  pH  vredostima  pri  čemu  su  dobijenirezultati koji su u saglasnosti sa rezultatima primenjenih komparativnih metoda. Naravno, za dobijanje  reprezentativnih  rezultata  neohodno  je  izvršiti  optimizaciju  uslova  merenja  što podrazumeva sam odabir supstrat-elektrode, odabir površinskog modifikatora i optimizaciju eksperimentalnih uslova merenja.
The  aim of this  Ph.D. thesis  was the development of new, sensitive, selective and economically  viable  voltametric  working  electrode  for  continuous  monitoring  of  different target  analytes.  The  use  of  these  advantaged  working  electrodes  was  investigated  using voltametric methods both in model solutions and in certain real systems.SW-ASV  based on glassy carbon  electrode surface modified with  Bi- MWCNT and BiOCl-MWCNT  were  applied  for  determination  of  Pb(II)  and  Cd(II)  ions.  Voltametric determination  of  Pb(II)  and  Cd(II)  ions  was  performed  at  working  potential  of  -1.2  V (measured against the saturated calomel electrode) and time of electrodeposition of 120 s. All measurements were performed in acetate buffer solution pH 4.0. Concentration range of targetanalites were  5-50 μg  dm -3 . Using this type of electrode,  obtained  detection limits for  Pb(II) and Cd(II) ions  were  0.57  μg  dm -3 and 1.2  μg  dm -3 , respectively, with RSD lower than 10%.This  method  was  applied  for  target  ions  determination  in  sediment  pore  water  sample,  and obtained results are comparable with those who are obtained using GFAAS method. Bismuth oxychloride-multiwalled carbon nanotubes composite material was applied for  surface  modification  of  the  glass-carbon  electrode  for  quick  and  simple  voltametric determination  of  Zn(II)  ions  using  the  SW-ASV  method.  BiOCl-MWCNT/GCE  showed  a linear  analytical  response  in  a   concentration  from  2.50  to  80.0  μg  dm -3 with  a  value  of detection limit 0.75 μg dm -3 at a acumulation time of 120 s and an electrodeposition potential of  -1.40 V vs. saturated  calomel electrode.  Measurements were carried out in acetate buffer pH 4.5. The obtained  value of the RSD  was  4.8%. The performance of the newly designed BiOCl-MWCNT/GCE  electrode,  traditional  bismuth-based  electrode  (BiF/GCE), MWCNT/GCE,  BiF-MWCNT/GCE  and  unmodified  GC  electrodes  were  compared.  The applied electrode shows very good electroanalytic properties when determining this target ion. Obtained results are in good agreement with declared value in case of dietetic suplement, and in the brewer’s yeast sample results were comparable with FAAS results. Carbon  paste  electrode  surface  modified  with  new  composite  material  based  on multiwalled carbon nanotubes and  Sb2O3  particles. The composite is characterized by TEM, EDS and  XRD measurment. Sb2O3- MWCNT/CPE was characterized by cyclic voltammetry and measurements were carried out in a  hydrochloric acid  solution  (pH 2.0). Using the SWASV  method,  this  working  electrode  was  used  to  determine  Pb(II),  Cd(II)  ions  in  the concentration range  from  2.0  to 40.0  μg dm -3 for Pb(II) and 2.0-40.0  μg dm -3 for Cd(II) ions. Newly  designed  sensor  showed  good  linear  dependences  for  both  target  ions.  The  most optimal  procedure  involving  application  of  Sb2O3-MWCNT/CPE  in   .01  mol  dm -3 hydrochloric  acid,  with  electroposition  time  of  target  ions  120  s  at  a  electrodeposition potential  of  -1.2  V.  Obtained   values  of    LOD  1,1  μg  dm -3 for  Cd(II)  and  for  1,6  μg  dm -3 Pb(II)  ions.  An  optimized  method  based  on  this  type  of  voltametric  sensor  has  been successfully  applied  for  determination  of  Cd(II)  ion  in  a  spiked  tap  water  sample.  Results obtained during this measurment were in tune with expected results. CPE  was  surface  modified  using  Sb2O3-MWCNT  nanocomposite  material  and tested  for  direct  voltametric  determination  of  imidacloprid  in  model  solutions.  In  order  to achieve the best analytical performance, experimental conditions of measurement such as the pH value of the supporting electrolyte and conditioning of the voltametric sensor surface havebeen  optimized.  As  an  optimum  pH  value  of  the  supporting  electrolyte  (Britton-Robinson buffer), a pH 7.0 was selected, and the repeating cycles of the cycling process at least 4 times favorably  influenced  the  stability  of  the  voltametric  signals.  The  optimized  method  was applied for the SW direct cathodic determination  of  imidacloprid in the concentration range from 1.41 to 32.77 μg cm -3  with obtained correlation factor of 0.9995. Based on results it can be concluded that developed analytical methods are sensitive, selective, reproducibile and simple, which can enable their application for various number of samples. Measurements in the model and real solutions have demonstrated the possibility of their  application  in  complicated  matrices,  at  different  pH,  whereby  obtained  results  are  in accordance  with  the  results  of  the  applied  comparative  methods.  For  obtainig  of representative  results  it  is  necessary  to  optimize  conditions  of  measurment  which  include: selection of substrat electrode, surface modifier and optimization of experimental condition.

U disertaciji je izvršena voltametrijska karakterizacija i određivanje pet neonikotinoidnih insekticida (imidakloprida, tiametoksama, klotianidina, nitenpirama i acetamiprida) na različitim elektrodama na bazi ugljenika, kao što su elektroda od ugljenične paste, elektroda od staklastog ugljenika i bizmut-filmom modifikovani staklasti ugljenik. Pored ispitivanja u model-rastvorima, razvijene visokoosetljive diferencijalne pulsne voltametrijskemetode su primenjene za određivanje neonikotinoida u realnim uzorcima. Neonikotinoidi su određivani u uzorcima rečne vode i komercijalnim formulacijama, a praćena je i njihova fotolitička i fotokatalitička razgradnja. Radi potvrđivanja voltametrijskih rezultata, izvedena su komparativna merenja uz primenu tečne hromatografije sa detektorom od niza dioda i infracrvenespektrometrije. Detekcija pojedinih degradacionih proizvoda nastalih u toku ispitivanih fotodegradacionih procesa je praćena tečnohromatografskom metodom sa tandemskom masenospektrometrijskom detekcijom. Proučavana je površinska struktura CR 5 grafitnog praha, elektrode od ugljenične paste na bazi trikrezil-fosfata i elektrode od staklastog ugljenika pomoću skenirajuće elektronske mikroskopije.
This thesis is concerned with the voltammetric characterization and determination of five neonicotinoid insecticides (imidacloprid, thiamethoxam, clothianidin, nitenpyram and acetamiprid) at different carbon-based electrodes such as carbon paste, glassy carbon and bismuth-film modified glassycarbon. In addition to the investigations in model solutions, the developed highly sensitive differential pulse voltammetric methods were applied for the determination of neonicotinoids in real samples. Neonicotinoids were determined in river water samples, commercial formulations, and their photolytic and photocatalytic degradation was also monitored. To confirm the voltammetric results, comparative measurements were performed by liquid chromatography with diode-array detector and infrared spectrometry. Detection of some degradation products formed during the photodegradation processes was monitored using liquid chromatography with tandem mass-spectrometric detection. The surface structure of CR 5 graphite powder, tricresyl phosphate-based carbon paste electrode and glassy carbon electrode was investigated by scanning electron microscopy.

U ovom radu prikazani su rezultati ispitivanja termičkih, mehaničkih, električnih i optičkih karakteristika kvazibinarnih halkogenida iz sistema Bi-As2S3. Na osnovu termičkih merenja analizirana je kinetika kristalizacionih i predkristalizacionih procesa i utvrđen je mehanizam dekompozicije za različite sastave dobijenih stakala. Primenom impedansne spektroskopije kvantitativno su ocenjeni doprinosi relaksacionih procesa na pojedinim temperaturama u ukupnoj polaraziciji za stakla sa 5 i 7 at.% Bi. Na osnovu merenja Raman spektroskopije identifikovane su nastale strukturne jedinice i konstatovana pojava nanofazne separacije u staklima sa 1.5 i 3 at.% Bi. Mehanička merenja ispitivanih halkogenida različitog sastava ukazala su na povećanje Vickers-ove tvrdoće sa povećanjem udela primesnih atoma. Na osnovu procenjene vrednosti modula elastičnosti ustanovljeno je da uzorak sa 5 at.% Bi odlikuje najgušće atomsko pakovanje. Merenja električnih karakteristika u jednosmernom režimu (DC) pokazala su da je udeo lokalizovanih stanja u ukupnom mehanizmu provođenja značajan samo za manje koncentracije primesnih atoma, a da za veće koncentracije dominantan faktor postaju preskoci između delokalizovanih stanja. Skok u provodljivosti za nekoliko redova veličine kod sastava sa složenijom strukturom protumačen je kao posledica fazne separacije. Rezultati  ACmerenja dobijeni za sastav sa 5 at.% Bi ukazali su da je u mernom frekventnom intervalu i dalje dominantan mehanizam termičke aktivacije nosilaca naelektrisanja. Kod sastava sa maksimalnim sadržajem Bi uočena je promena provodljivosti u funkciji frekvencije na svim temperaturama, a dobijeni rezultati su u skladu sa postavkama modela korelisanih preskoka barijere (CHB model).
This paper presents the results of investigation ofthermal, mechanical, electrical and optical propertiesof quasibinar chalcogenides from the system Bi-As2S3. Kinetics analysis of softening and crystallizationprocesses was done on the basis of thermalmeasurements, as well the analysis of decompositionmechanism for different compositions of obtainedglasses. The application of impedance spectroscopy enabled quantitative description of relaxation process contributions at selected temperatures in the overallpolarization for the samples with 5 and 7 at.% Bi. Based on measurements of Raman spectroscopy identification of structural units in the investigated chalcogenides was made, as well as the appearance of nano-scale phase separation in the glasses with 1.5 and 3 at.% Bi. Mechanical measurements pointed to the increase of the Vickers hardness with increase of doping atoms content.  Based on the estimated value of the modulus of elasticity it was found that the sample  with 5 at.% Bi is characterized by the densest atomic arrangement. Measurements of the electrical properties in dc regime (DC) pointed out that the share of localized states in the whole mechanism of conduction is significant only for the smaller concentrations of doping atoms. For the samples with higher concentrations dominant  factor in conductivity are transitions between delocalized states. The jump in conductivity by few orders of magnitude, noticed for the compound with heterogeneous structure was interpreted as a consequence of micro-scale phase  separation. Results of  ACmeasurements for the  composition with 5 at.% Bi showed that the mechanism of thermal activation of charge carriers is still dominant in the measured frequency range. For   the composition with the maximum content of Bi changes in conductivity versus frequency were observed at all temperatures, and the results were interpreted in accordance with the model of correlated hopping over the barrier (CHB).

Doctoral Thesis show the electrical properties in relation to degree of structural heterogeneity, performed by using dielectric spectroscopy and scanning electron microscopy. The results obtained for the following materials are shown in Thesis: • bismuth manganite B-M-O and/or BM • lead zirconate titanate PZT • (1-x)PZT-xBM, where x = 0.00, 0.01, 0.02, 0.03, 0.04, 0.05, 0.055, 0.11, 0.15, 0.22 • (1-x)B-M-O-xPTO, where x = 0.04, 0.12, 0.24 • epoxy glue/B-M-O composite • epoxy glue/(1-x)PZT-xBM composite, where x = 0.00, 0.01, 0.11, 0.22. The Doctoral Thesis include motivation, literature review of the phenomena and models related to subject of studies, description of technology applied for production of the samples, and description of the apparatus set-up. Next part shows results and discussion. Properties of the reference bismuth manganite and the influence of the BM doping on dielectric permittivity, on relaxation properties, on induced relaxor state, on piezoelectric properties and on electrical conductivity of the PZT-BM ceramics. It was showed that BM increased crystal lattice disorder, induced one of the relaxation processes, modified piezoelectric features. The influence of PTO addition on B-MO properties was studied. It occurred that the PTO powders increased electrical conductivity of the B-M-O-PTO ceramics that covers the relaxation processes. It was shown that reduction of electrical conductivity was possible in new composite materials epoxy glue/B-M-O and epoxy glue/PZT-BM. The most important achievements of Doctoral Thesis were: (1) determination of the phase diagrams of PZT-BM for low and high concentrations of BM and (2) preparation of the composite epoxy glue/B-M-O and epoxy glue/PZT-BM materials, which exhibited reduced value of electrical conductivity in comparison to the reference ceramics. Moreover the Doctoral Thesis include results and references.

Three groups of materials were studied in this thesis. First studied group was Bi2WO6 (BWO). Two types of BWO single crystals were examined. BWO is an uniaxial ferroelectric material studied mainly due to its high spontaneous polarization, high Curie temperature as well as its ion conductivity, and excellent photocatalytic properties. BWO crystals were studied by X-ray diffraction, microscopic methods (SEM), dielectric and Raman experiments. Moreover, pyroelectric effect was examined. Dielectric studies confirmed existence of dielectric anisotropy. Raman experiments evidenced that symmetry distortion slowly decreases with increasing temperature. Moreover, the Raman spectra show no signs of phase transition in studied temperature range. At least five phonon modes show significant softening. Frequency of these modes does not decrease to zero in the vicinity of P21ab-B2cb transition. In higher temperatures, above P21ab-B2cb transition, the temperature dependence of frequency of 57 cm-1 mode is expected to change and decrease to zero in vicinity of ferroelectric phase transition. This mode is responsible for appearance of ferroelectric state in Bi2WO6. The second studied group of materials were nonstoichiometric AgxNbO2.5+x/2 ceramics. This research was performed to evaluate whether deficient of silver in crystal lattice is responsible for appearance of wide maximum of dielectric permittivity. Ceramics were obtained for silver concentrations x equal to 0.95, 0.98, 1.00, 1.02, and 1.05. Obtained samples were studied by scanning electron microscopy, X-ray diffraction, dielectric and thermal (DSC) experiments. SEM and XRD experiments showed that samples contained mainly perovskite phase of AgNbO3. Only for x=0.95 a small quantities of secondary phase were observed. For all compositions metallic silver precipitations appear and their quantity increase with the increase of x. Moreover, SEM and XRD studies show increase of homogeneity with increase of silver to niobium ratio. Finally, it was concluded that 2% excess of Ag2O in initial composition significantly increases the quality of ceramics. Dielectric and thermal measurements (DSC) were carried out in wide temperature range. They revealed that the phase transitions become less diffused and shifted towards higher temperatures with the increase of silver concentration. These temperature shifts are more significant for the low temperature phase transitions, which are connected with appearance of the polar ferroelectric and antiferroelectric states, than for high temperature transitions related to oxygen octahedra tilts. This happens because displacements of Ag ions create electric dipoles, which form polar phases in AgNbO3 with dipoles created by Nb ion displacements. Increase of silver concentration leads to increase of both quantity and value of interacting dipoles and thus increase temperatures of phase transitions. Last group of studied materials were silver lithium niobate ceramics Ag1-xLixNbO3 (ALN). ALN were studied in vicinity of morphotrophic phase transition (x≤0.1). These materials were studied mainly because of their high spontaneous polarization and their promising, as for lead-free materials, values of piezoelectric coefficients. Samples were examined by SEM method, XRD diffraction, mass spectroscopy SIMS, dielectric, thermal DSC and Raman experiments. Characterization of samples by SEM, XRD and SIMS point to their high quality. They consist mainly of perovskite phase and small amounts of secondary phase. Grains show high homogeneity. Only small amounts of secondary phase appear in spaces between grains as well in vicinity of holes. For concentration of lithium between 0.05 ÷ 0.06 morphotrophic phase transition from rhombic M1 phase and rhombohedral R phase occurs. Temperature evolution of dielectric permittivity for ceramics with x≤0.05 are very similar to those observed for pure AgNbO3. For x=0.06 maximum of ε’(T) related to M1-M2 transition vanish and for x>0.06 only two wide maxima of ε’(T) are observed. First maxima is related with transition from ferroelectric R phase to antiferroelectric M phase. Second is related with transition from M phase to paraelectric O phase. With increase of lithium concentration, character of all observed transition becomes more diffusive. This indicates increase of structural disorder. Thermal studies confirm these results. Basing on these studies phase diagram for Ag1-xLixNbO3 was proposed. Analysis of Raman spectra points to relationship between crystal lattice dynamics and appearance of antiferroelectric state and its transformation to ferrielectric state for x≤0.05, as well as appearance of ferroelectric order for solutions with lithium concentration higher than 0.06. Analysis of central peak shows that temperature evolution of relaxation time for Ag0.98Li0.02NbO3 and Ag0.96Li0.04NbO3, related with dynamics of displacements of Nb ions changes in partial freezing temperature Tf and in temperature of ferrielectric transition M1-M2. Moreover, maximum of intensity of central peak observed in vicinity of M2-M3 transition corresponds well with maximum of low frequency dielectric permittivity. This suggests that Nb relaxation is responsible for appearance of wide maximum of ε’(T). Analysis of low frequency Raman spectra for ferroelectric Ag0.9Li0.1NbO3 ceramic showed that strong central peak appears in the vicinity of R-M transition, while low frequency phonon mode shows significant softening. Therefore, this mode is responsible for appearance of ferroelectric state.

Pełne teksty dołączonych do pracy publikacji autora (s. 129-148), dostępne są lokalnie w sieci bibliotek Uniwersytetu Śląskiego: http://www.bc.us.edu.pl/publication/17374
Izolatory topologiczne (IT) są jednym z kluczowych materiałów do wykorzystania w nowej generacji urządzeń elektronicznych i spintronicznych. Takich jak na przykład układy do konwersji spin-ładunek lub nanometryczych diod Schottky'ego. Izolatory topologiczne po drastycznym zmniejszeniu ich wymiarów lub przy obecności domieszkowania, zaczynają wykazywać silne efekty, takie jak zmiana struktury elektronowej która w konsekwencji zmienia dynamiką nośników oraz fononów. W tej pracy chcieliśmy zaadresować kilka problemów dotyczących izolatorów topologicznych, a w szczególności tellurku bizmutu. Bi₂Te₃ ze względu na ogromny potencjał w zakresie przyszłej elektroniki wymaga od nas lepszego zrozumienia czynników które mogłyby ograniczyć jego zastosowania. Jednym z zjawisk, które do tej pory pomijano w literaturze, jest rola sprzężenia elektronon-fonon (sprzężenie z modem A₁g1 i silne sprzężenie elektronów powierzchniowych modem akustycznym), który ogranicza transport 2D elektronów powierzchniowych. Drugim zadaniem, które chcieliśmy w tej pracy poruszyć, było zwiększenie udziału stanów powierzchniowych w ogólnych właściwościach IT. W przypadku ultra cienkich warstw stosunek stanów powierzchniowych do stanów objętościowych zaczyna być istotny. Dla cienkich warstw, przy krytycznej grubości, stany powierzchniowe z przeciwległych powierzchni mogą się ze sobą łączyć i prowadzić do utworzenia zależnej od grubości przerwy energetycznej, co w rezultacie może generować kwantowo-spinowy efekt Halla, podobnie jak ma to miejsce w przypadku HgTe. Ostatnie wyzwanie, które chcieliśmy poruszyć w tej pracy, wiąże się z tworzeniem nowych urządzeń, które mogłyby efektywnie wykorzystać właściwości IT. A konkretnie reakcje tellurku bizmutu na obecność domieszkowania i obecności dodatkowych warstw. Ze względu na konieczność stosowania ferromagnetycznych lub metalicznych warstw o silnym sprzężeniu spinowo-orbitalnym (platyna/kobalt/żelazo), w celu stworzenia efektywnych układów służących do konwertowania prądu spinowego, musimy być w stanie wyhodować stabilne układy chemiczne, które nie będą zakłócać stanów powierzchniowych izolatora topologicznego i nadal będą pozwalały na przeniesienie wytworzonego spolaryzowanego prądu spinowego do innych warstw. W naszych badaniach skupiliśmy się na warstwie z y-Fe2O3. Aby być w stanie rozwiązać wymienione powyżej problemy w naszych badaniach wykorzystaliśmy zaawansowany klaster wysoko próżniowy wyposażony w komorę MBE. Urządzenie to umożliwiło nam hodowlę ultra-cienkich filmów Bi₂Te₃ o wysokiej jakości. Struktura krystalograficzna wyhodowanych warstw została przebadana za pomocą LEED’a, oraz RHEED’a, a struktura elektronowa za pomocą XPS’u. Nasze badania skupiły się na analizie przesunięć energetycznych poziomów rdzeniowych i pasma walencyjnego. Badania wzbudzania gorących nośników elektrycznych oraz generacji koherentnych fononów optycznych oraz akustycznych zostały przeprowadzone za pomocą spektroskopii femtosekundowej w Le Mans która dała nam unikatową możliwość bezpośredniej czasowo-rozdzielczej obserwacji tych zjawisk. W niniejszej pracy pokazaliśmy, że możliwe jest koherentne wzbudzenie fononu A₁g1 w cienkich filmach, bez wykrywalnego ograniczenia ich emisji, pokazaliśmy również że dynamika fononów optycznych nie jest w znacznym stopniu zależna od nanostruktury kryształu i opisaliśmy model ich generacji. Oprócz dynamiki fononów optycznych, zaobserwowaliśmy generacje koherentnych fononów akustycznych, których widmo drastycznie zależy od nanostruktury filmu, i według przedstawionego w naszej pracy modelu, ich generacja silnie zależy od modyfikacji potencjału deformacyjnego. W naszych badaniach pokazaliśmy również silną ewolucję dynamiki wzbudzonych nośników i fononów (czas relaksacji oraz częstotliwości) podobnych do tej obserwowanej w studniach kwantowych, dla warstw poniżej 5nm oraz w obecności dodatkowej warstwy tlenku żelaza. Wykonane przez nas eksperymenty optyczne dały nam bezpośredni wgląd w dynamikę nośników objętościowych jak i dynamikę nośników powierzchniowych. Przedstawione wyniki bezpośrednio pokazały że właściwości fizyczne izolatorów topologicznych ulegają silnej modyfikacji, po krytycznym zmniejszeniu ich wymiarów jak i w obecności interfejsu z metaliczną warstwą. Informacje zawarte w tej pracy mogą pomóc w projektowaniu potencjalnych urządzeń spintronicznych opartych na IT.

Thesis (D. Mus. Arts)--University of Washington, 1996.
Vita. Includes the program from the production of Carmen at the University of Puget Sound on August 12 and 13, 1995, in pocket. Includes bibliographical references (leaves [109]-111).

Darbe ištirtos ir palygintos dviejų elektrofotografinių mašinų „Xerox DC5000“ ir „Conica Minolta 6500“ spalvų reprodukavimo galimybės. Tyrimas buvo atliekamas dviem spaudos mašinomis po tam tikro spaudų skaičiaus atspausdinant kalibracinį testą (lapą su specialiai spektrofotometrui paruoštais vienodo dydžio įvairių atspalvių kvadratėliais, kuriuose yra skirtingas visų keturių CMYK spalvų rastrinių taškų skaičius), kurio spalvų intensyvumas buvo matuojamas spektrofotometru „Efi ES–1000“. Nustatyta, kad spaudos mašinos „Xerox“ reprodukuojamų spalvų sodris didesnis lyginant su „Minolta“, tai lemia spaudo padengimas laku, kuris sukelia veidrodinį efektą, eliminuojama patenkanti į matavimo prietaisą išsklaidyta šviesa. Nustatytas savikalibracinės sistemos netobulumas bei abiejų mašinų spaudų skaičius, po kurio mašina turi buti kalibruojama. Darbą sudaro 7 dalys: įvadas, literatūros apžvalga, tyrimų metodika, rezultatai ir jų aptarimas, išvados ir rekomendacijos, literatūros sąrašas, priedai. Darbo apimtis – 57 p. teksto be priedų, 3 lentelės, 33 paveikslai, 15 bibliografinių šaltinių. Darbo priedai pridedami darbo pabaigoje.
The research regarding colour reproduction possibilities of two electrographic machines “Xerox DocuColor 5000” and “Conica Minolta Bizhub pro C6500” was made. In it two stamped machines were used, which had to stamp fixed numbers of calibration test (a paper with specially made, same size and various colours quadrants for spectrofotometer, where is different number of all four CMYK bitmap colour dots), which colour intensity was measured with using spaectrofotometer “Efi ES-1000”. The results have shown that “Xerox” machine has larger colour reproduction depth comparing to “Minolta” . This condition is made because of varnish that covers stamp. It creates specular effect and eliminates resolved light that comes to measuring devices. Self calibrating system cracks were discovered as well. Also two machines have to be calibrated after fixed number of stamps. Thesis has 7 parts: Introduction, literature review, research methodology, results, results discussion, conclusion and recommendation, literature list, appendix. Thesis consist of: 57p. text without appendix, 3 tables, 33 pictures, 15 bibliographical.

Les pêcheurs de perles de Bizet, crées en 1863 au théâtre-lyrique, montrent par leur histoire et leurs caractéristiques les principaux aspects de l'opéra français du XIXe siècle. L’analyse génétique des sources offre l'occasion de reconstituer l'élaboration de l'œuvre et pose la question du sujet créateur. Le dépouillement de la presse et l'exploitation de divers documents permettent de brosser le tableau de la création, de comprendre la vie d'un théâtre lyrique, et font de cet ouvrage un opéra-mémoire. Reflétant les goûts et les débats esthétiques (wagnérisme, conservatisme etc. ) L'analyse littéraire et musicale met en avant les spécificités de la dramaturgie lyrique et de sa poétique, notamment l'écriture par stéréotypes, et montre l'invention de Bizet dans les domaines de la mélodie, de l'orchestration, et des motifs de rappel. L’exotisme de l'œuvre emprunte à un vaste courant artistique. Il puise aussi dans une typologie mise au point par Félicien David et devient ferment du style de Bizet. L’examen du cadre sociologique conduit à analyser le problème du genre et offre les premiers éléments nécessaires à la compréhension d'une esthétique prise entre tradition et renouveau
Bizet's pecheurs de perles was created in 1863 at the theatre-lyrique. Its history and caracteristics show the main aspect of the 19th century french opera. The genetic analysis of the sources gives the opportunity to reconstitute the building of the work and sets the question of the creating subject. Searching throughout the press and exploiting various documents gives an outline of the creation, allows us to understand life in a lyric theatre and makes this work a "memoryopera" reflecting the tastes and the aesthetic debates (wagnerism, conservatism etc. . . ). And musical analysis highlight the specificities of the lyrical dramaturgy of its poetics, especially the writing by orchestration and leitmotivs. The exoticism of the work was borrowed from a large artistic trend. It also takes from a typology elaborated by felicien david and becomes a ferment of Bizet's style. Examination of the sociological frame leads to the analysis of the genre and shows the first elements which are necessary for the understanding of the aesthetic caught between tradition and renewal

Quel est l’objet réel d’une transposition ? On le recherchera en explorant les différents niveaux du récit transposé et non pas seulement son « histoire ». En passant des structures narratives à l’organisation de la fiction jusqu’au niveau du discours, on peut voir que chaque palier narratif fait l’objet d’une transposition qui reconstruit pour l’opéra un conflit pathétique. La dramaturgie lyrique fait d’abord subir à l’histoire une triple opération de simplification, de stéréotypie et d’invraisemblance, qui repose cependant sur la logique stable d’un schéma narratif à partir duquel une relation de défi rhétorique s’instaure entre le discours du récit et celui de l’opéra. Sur ce dernier niveau, trois scènes de la passion sont analysées, au seul plan textuel, pour prouver que l’abolition du discours narratif n’entrave pas la transposition des émotions qu’il suscite – ce que montrent des correspondances entre les formes narratives (description, dialogue) et les formes lyriques (l’air, le duo). Pour l’opéra, le récit est donc un modèle pathétique complet et performant
What is the underlying objective when an artist creates an adaptation? To approach this, one has to explore the different levels of the transposed narrative, not merely the "story" or "storyline". Successive examinations of the narrative structures, the ayering of the fiction, and the finished discourse reveal that each level of narration involves transposing a pathetic conflict into the operatic form. The act of musical (lyrical) dramatization imposes upon the narrative a transformation in three ways: simplification, stereotyping and a final process which deconstructs verisimilitude. These processes are founded on a highly consistent narrative structure, which sets in motion a rhetorical tension between the narrative discourse and that of the opera itself. The present work takes this function as its starting point in order to conduct a purely textual analysis of three scenes of passion – the objective being to demonstrate that subsuming or even, abolishing, the narrative discourse, does not dilute or corrupt the emotions originally conveyed – this process is shown by structural correspondances between the narrative (description and dialog) and lyrical forms (aria and duet). Thus, when transposed into the operatic form, the narrative remains a complete and convincing model of pathos

Danas, u raznim analitičkim laboratorijama postoji veći broj analitičkih protokola,zasnovanih bilo na izuzetno sofisticiranim ili jednostavnijim tehnikama, koji služe zaodređivanje različitih ciljnih analita od farmakološkog značaja. Među tim grupama ciljnih analita pripadaju i antibiotici koji predstavljaju veliko otkriće u oblasti medicine i zahvaljujući njima spašeno je više od sedam miliona života, ali pored navedenih koristi, antibiotici mogu da izazovu  veliki broj neželjenih efekata i žučne kiseline zajedno sa svojim derivatima, koji su fiziološki deterdženti, mogu biti citotoksične za organizam ako se njihova koncentracija ne kontroliše. U ovoj doktorskoj disertaciji prikazan je razvoj analitičkih metoda pre svega voltametrijskihmetoda u kombinaciji sa jednostavnim i savremenim elektrodama/senzorima za određivanje  odabranih analita kao što je antraciklični antibiotik doksorubicin (DOX), makrolidni antibioticieritromicin-etilsukcinata (EES), azitromicina (AZI), klaritromicina (CLA) i roksitromicina  (ROX) i 3-dehidro-deoksiholne kiseline.Voltametrijska karakterizacija i određivanje gore navedenih antibiotika primenom obnovljive srebro-amalgam film elektrode (Hg(Ag)FE)rađena je direktnom katodnom  voltametrijom sa pravougaonim talasima (SWV) i visoko osetljivom adsorptivnom voltametrijom sa pravougaonim talasima (SW-AdSV) u Briton-Robinson puferu, kao pomoćnom elektrolitu, obuhvatajući širok opseg pH vrednosti. Odgovor DOX-a primenom  Hg(Ag)FE praćen je u intervalu potencijala od -0,20 do -0,80 V.  Za analizu tragova, optimizacija metode ukazuje da su optimalni parametri za analitički pik na potencijalu (Ep ) -0,57 V u odnosu na zasićenu kalomelovu elektrodu (ZKE): pH 6,0, potencijal  akumulacije -0,20 V i vreme  akumulacije 140 s. U model rastvoru, DOX je određivan u koncentracionom opsegu 4,99-59,64  ng mL^-1. Razvijena SW-AdSV metoda je primenjena za određivanje DOX-a u obogaćenom uzorku humanog urina. Niža koncentracija DOX-a 9,89ng mL^-1 u voltametrijskoj  ćeliji je određivana sa relativnom standardnom devijacijom (RSD) manjom od 6,0%. Što se ispitivanih makrolida tiče oni su pokazali redukcione signale u dalekoj negativnoj oblasti potencijala. Ispitivanja direktnom katodnom SWV rađena su u opsegu potencijala od -0,75 V do -2,00 V u odnosu na ZKE, pri čemu su dobijena jedan ili dva redukciona pika u opsegu potencijala od -1,5 V do -1,9 V. Oblik i intenzitet signala zavisi od primenjene pH vrednosti u širokoj pH oblasti. Za analitičke svrhe, radi razvoja direktne katodne SWV i adsorptivne inverzne/striping SWV metode, pogodnim su se pokazale neutralna i slabo alkalna sredina tj. pH 7,0 sa  E_p na -1,67 V u odnosu na ZKE za ROX i EES i pH 7,2 sa E_p na -1,85 V u odnosu na ZKE za AZI i pH 7,4 sa E_p na -1,64 V u odnosu na ZKE za CLA. Na osnovu snimljenih cikličnih voltamograma na  optimalnim pH vrednostima, može se predložiti adsorptivno-kontrolisan kinetički proces na elektrodi u slučaju sva  četiri ispitivana jedinjenja. Takođe,  ¹H NMR merenja uz potiskivanje  signala vode u pH oblasti između pH 6,0 i 10,5 ukazuju na to da su makrolidni molekuli pri optimalnim analitičkim uslovima predominantno u protonovanoj formi preko tercijerne amino grupe što potpomaže, u sva  četiri slučaja, njihovu adsorpciju na odgovarajuće polarizovanoj Hg(Ag)FE. Optimizovane direktne katodne SWV metode  pokazuju dobru linearnost u koncentracionom opsegu 4,81-23,3  µg mL^-1 , 4,53-29,8  µg mL^-1 , 1,96-28,6  µg mL^-1 i 1,48-25,9 µg mL^-1 za AZI, EES, CLA odnosno ROX. Razvijene SW-AdSV metode rezultiraju u linearnom odgovoru pri nižim koncentracionim intervalima 1,0-2,46 µg mL^-1 ,  0,69-2,44  µg mL^-1, 0,05-0,99 µg mL^-1 i 0,10-0,99  µg mL^-1 , za AZI, EES, CLA i ROX. RSD za sve razvijene metode nije veća od 1,5% izuzev SWV metode u slučaju AZI-a gde je 4,5%. Direktna katodna SWV metoda  je uspešno primenjena za određivanje EES-a u farmaceutskom proizvodu Eritromicin^® dok SW-AdSV metoda je primenjena u slučaju određivanja EES-a u obogaćenom uzorku humanog urina i za određivanje ROX-a u farmaceutskom proizvodu Runac^® . U svim pomenutim slučajevima, primenjena je metoda standardnog dodatka. Pouzdanost i tačnost elaboriranih procedura u slučaju određivanja EES-a u model sistemu i  farmaceutskom proizvodu Eritromicin^® su potvrđena poređenjem sa rezultatima dobijenim primenom HPLC-DAD metode.Nakon preliminarnih studija 3-dehidro-deoksiholne  kiseline/3-dehidro-deoksiholata primenom elektrode od staklastog ugljenika (GCE), gde je uočeno da ne dolazi do formiranja redukcionog signala u Briton-Robinson puferu između pH 5,0 i 11,8 primenom direktne katodne SWV, bizmut-film je izdvojen  ex situ na površini iste elektrode od staklastog ugljenika (BiF-GCE) iz uobičajeno korišćenog rastvora za elektrodepoziciju (0,02 mol L^-1 Bi(NO₃)₃, 1,0 mol L^-1 HCl i 0,5 mol L^-1 KBr) i tako pripremljena elektroda je primenjena za karakterizaciju i određivanje pomenutog jedinjenja u alkalnoj sredini. Redukcioni signal ispitivanog analita od analitičkog značaja je uočen jedino primenom BiF-GCE u Briton-Robinson puferusa pH vrednostima između 9,5 i 11,8 u režimu adsorptivne inverzne/stripingvoltametrije sa pravougaonim talasima, dok u slučaju direktnih katodnih SWV eksperimentalnih uslova uočen je slab redukcioni pik sa niskom strujom maksimuma pika. Optimizovani eksperimentalni uslovi za određivanje 3-dehidro-deoksiholata obuhvataju odgovarajuće kondicioniranje elektrode uključujući kondicioniranje  ex situ pripremljene BiF-GCE u Briton-Robinson pomoćnom elektrolitu pH 11,8 do stabilizacije struje bazne linije elektrohemijskim cikliranjem potencijala radne elektrode u potencijalskom opsegu između -1,00 i -2,00 V u odnosu na ZKE (blizu 15 puta) i primenu dva ključna parametara adsorptivne voltametrije sa pravougaonim talasima: vreme akumulacije od 30 s i potencijal akumulacije  -1,00 V u odnosu na ZKE. Zbog relativne asimetričnosti dobijenih redukcionih signala ispitivanog analita sa  E_p na -1,35 V u odnosu na ZKE, što je takođe prisutno i u slučaju primene SW-AdSV, određivanje ispitivanog analita je zasnovano na linearnoj zavisnosti između površine pika redukcionog signala  spitivanog analita i njegove odgovarajuće koncentracije i postignuta granica detekcije je 1,43 µg mL^-1 sa dva linearna opsega kalibracione krive od 4,76 µg mL^-1 do 13,0 µg mL^-1 i od 13,0 µg mL^-1 do 23,1 µg mL^-1 za razvoj analitičke metode. RSD metode je 3,22%. Dodatni eksperimenti, elektroliza ispitivanog analita na potencijalu -1,55 V (blizu maksimuma pika ciljnog analita) u odnosu na ZKE su rađeni primenom GCE u obliku ploče (površina 33,52 cm 2 ) modifikovane sa  ex situ pripremljenim bizmut-filmom. Rastvor od interesa uzorkovan je na početku eksperimenta, nakon 2,5 h i nakon 4,5 h tretmana. Ovakvi uzorci su analizirani primenom ¹H NMR merenja uz potiskivanje signala vode u puferskom rastvoru pH 11,8. Može se pretpostaviti da tokom elektrolize 3-dehidro-deoksiholata dolazi do redukcije keto grupe prisutne u strukturi ispitivanog analita.Na osnovu literaturnih podataka da neki od ciljnihmakrolidnih antibiotika kao što je npr. azitromicin pokazuju oksidativno ponašanje na elektrodi od ugljenične paste i elektrodi od zlata deteljna karakterizacija i određivanje  četiri makrolidna antibiotika rađena je primenom  asične elektrode od ugljenične paste (CPE) koja se sastoji samo od grafitnog praha i parafinskog ulja sa optimizovanih direktnih anodnih SWV metoda. U slučaju EES-a i AZI-a diferencijalna pulsna voltametrija (DPV) je testirana za iste svrhe. Ključni  parametar u slučaju razvoja analitičkih voltametrijskih metoda je odabir pH vrednosti pomoćnog elektrolita gde je oblik/simetričnost i intenzitet oskidacionog pika glavni kriterijum prilikom odabira. Kao odgovarajuće pH vrednosti za voltametrijsko određivanje EES-a primenom SWV metode odabrana je pH 8,0 sa E_p na 0,83V u odnosu na ZKE, dok u slučaju DPV metode pH 12,0 sa  E_p na 0,55 V u odnosu na ZKE je bila najpogodnija za analitičke svrhe. Za određivanje AZI-a, u slučaju obe SWV i DPV metode pH 7,0 se pokazala najpogodnijom sa E_p analitičkog signala na 0,85 V odnosno 0,80 V u odnosu na ZKE, dok u slučaju CLA i ROX koji su ispitivani samo primenom SWV metode za analitičke svrhe pH 12,0 je bila najpogodnija sredina sa E_p analitičkog signala na 0,65 V odnosno na 0,63 V u odnosu na ZKE. Postignute granice detkcije primenom nemodifikovane CPE i direktne anodne SWV su uglavnom u submikrogramskom koncentracionom opsegu 0,17 µg mL^-1 , 0,32  µg mL^-1 i 0,30  µg mL^-1, u slučaju EES-a, AZI-a i ROX-a i u niskom mikrogramskom koncentracionom opsegu 1,43  µg mL^-1 za CLA. Razvijena SWV metoda sa jednostavnom CPE pokazala se pogodnom za određivanje ROX-a u komercijalnom proizvodu Runac^® tableti. U slučaju optimizovanih DPV metoda postignute granice detekcije za EES i AZI su u niskom mikrogramskom  koncentracionom opsegu 1,03  µg mL^-1 odnosno 1,53  µg  mL^-1 . U želji da se postigne niža granica detekcije za AZI, DPV metoda  je testirana u kombinaciji sa  CPE radnom elektrodom površinski modifikovanom sa zlatnim nanočesticama  prečnika 10 nm (Au-CPE) i  postignuta granica detekcije je 0,95  µg mL^-1 sa  E_p analitičkog signala na 0,80 V u odnosu na  ZKE. RSD metode u slučaju Au-CPE je 3,5%, dok je u slučaju nemodifikovane CPE 6,0%.  Linearnost analitičke metode zasnovane na primeni Au-CPE je dva puta šira nego u slučaju  primene nemodifikovane CPE.Na osnovu dobijenih rezultata može se zaključiti da  odgovarajuće kombinacije  optimizovanih voltametrijskih tehnika sa ekološki prihvatljivim i lako primenljivim radnim  elektrodama, kao što su Hg(Ag)FE, BiF-GCE i CPE zajedno sa Au-CPE, rezultuju razvojem  pouzdanih analitičkih metoda, kako u oksidacionim tako i u redukcionim proučavanjima, koje  često omogućuju  određivanje tragova analita od farmakološkog značaja u jednostavnim, a u nekim slučajevima i u složenim sistemima. 
Nowadays in different analytical laboratories there is the increasing number of analytical protocols, either based on highly sophisticated or simpler measurements techniques, which serving for determination of different target analytes of pharmacological importance. Among such target groups of the analyte belongs the antibiotics which present a great discovery in the field of medicine and thanks to them were saved more than seven million people but beside to the mentioned great benefits, antibiotics can cause a large number of side effects and bile acids together with their derivatives which are physiological detergents but if their concentration is notcontrolled they can be cytotoxic to the body. In the present doctoral dissertation the development of analytical methods, primarily analytical voltammetric methods in combination with simple and contemporary electrodes/sensors, for the determination of selected analytes as antracycline antibiotic doxorubicin (DOX), macrolide antibiotics erythromycin ethylsuccinate (EES), azithromycin (AZI), clarithromycin (CLA) and roxithromycin (ROX) and 3-dehydrodeoxycholic acid were performed.Voltammetric characterization and determination of the above mentioned antibiotics using a renewable silver-amalgam film electrode (Hg(Ag)FE) was performed by direct cathodic square-wave voltammetry (SWV) and by highly sensitive adsorptive square-wave voltammetry (SW-AdSV) in aqueous Britton-Robinson buffer solutions as supporting electrolyte covering the wider pH range. The Hg(Ag)FE response of DOX was monitored in the potential range between -0.20 and -0.80 V. For the trace level analysis the method optimization showed that the optimal conditions for the analytical peak with peak potential (E_p) at -0.57 V vs. SCE were: the pH 6.0, the accumulation potential -0.20 V, and the accumulation time 140 s. In the model solutions, DOX was determined in the concentration range of 4.99-59.64 ng mL^-1. The developed SWAdSV method was applied for the determination of DOX in spiked human urine sample. The lowest concentration of DOX of 9.89 ng mL^-1 in voltammetric vessel was determined with the relative standard deviation (RSD) less than 6%. As for the investigated macrolides, they showed reduction signals in fairly negative potential range. During direct cathodic SWV investigations conducted over the potential range from -0.75 V to -2.00 V vs. SCE, either one or two reduction peaks were obtained in the  potential range from -1.5 to -1.9 V. For analytical purposes concerning the development of direct cathodic SWV and adsorptive stripping SWV methods the neutral  and slightly alkaline media were suitable as pH 7.0 with E_p at -1.67 V vs.  SCE for ROX and EES and pH 7.2 and pH 7.4 with E_p at -1.85 V and -1.64 V vs. SCE for AZI and CLA, respectively. Based on the cyclic voltammograms recorded at these pH values, adsorptioncontrolled electrode kinetics process can be proposed for all four investigated compounds. The water suppressed ¹H NMR measurements in the pH range between 6.0 and 10.5 indicated that the macrolide molecules at the optimal analytical conditions are predominantly in protonated form via their tertiary amino groups which supported in all four cases their adsorption on the appropriately polarized Hg(Ag)FE electrode. The optimized direct cathodic SWV methods showed good linearity in concentration ranges 4.81-23.3 μg mL^-1, 4.53-29.8 μg mL^-1, 1.96-28.6  μg mL^-1, and 1.48-25.9 μg mL^-1 for AZI, EES, CLA and ROX, respectively. The SW-AdSV methods resulted in the linear responses at lower concentration ranges as 1.0-2.46 μg mL^-1, 0.69- 2.44 μg mL^-1, 0.05-0.99 μg mL^-1 and 0.10-0.99 μg mL^-1, for AZI, EES, CLA and ROX, respectively. The RSD for all developed methods was not higher than 1.5% except the SWV method for AZI with 4.7%. The direct cathodic SWV method was successfully applied for the determination of EES in the pharmaceutical preparation Eritromicin^®, while SW-AdSV was tested in the case of the spiked urine sample and for determination of ROX in pharmaceutical preparation Runac^®. In all above cases, the standard addition method was used. The reliability and accuracy of the above procedures in the case of EES determination in model system and pharmaceutical preparation Eritromicin^® were validated by comparing them with those obtained by means of HPLC-DAD measurements.After initial study of 3-dehydro-deoxycholic acid/3-dehydro-deoxycholate by glassy carbon electrode, where the absence of any reduction peak was observed in the Britton-Robinson buffer solutions between pH 5.0 and 11.8 by direct cathodic SWV, a bismuth-film was electrodeposited ex situ on the same glassy carbon electrode surface (BiF-GCE) from the usually used plating solution (0.02 mol L^-1 Bi(NO₃)₃, 1.0 mol L^-1 HCl and 0.5 mol L^-1 KBr) and such prepared film-electrode was applied for the characterization and determination of the the target analyte in alkaline media. The reduction signal of analytical importance was observed only by BiF-GCE in Britton-Robinson buffer solutions with pH values between 9.5 and 11.8 in adsorptive stripping square-wave voltammetry working regime, while in the case of the direct cathodic SWV experimental protocol only a very poor reduction peak was obtained. The optimized experimental conditions for the 3-dehydro-deoxycholate determination consist of the optimized electrode conditioning including the electrochemical cycling of the ex situ prepared BiF-GCE potentials in the potential span between -1.0 and -2.0 V vs. SCE (nearly 15 times) in the Britton-Robinson supporting electrolyte pH 11.8 till the stabilization of the baseline current, and the application of two key parameters of the adsorptive square-wave voltammetric protocol: the accumulation time as 30 s and accumulation potential as -1.0 V vs. SCE. Because of the relative asymmetry of the obtained reduction signals of the target analyte with peak E_p at -1.35 V vs. SCE, which is still present in the case of the SW-AdSV, the quantification of the target analyte was based on the linear correlation between peak area of the reduction signal and its appropriate concentrations, and reached limit of detection is 1.43 μg mL^-1 and with two linear ranges of calibration curve from 4,76 μg mL^-1 to 13.0 μg mL^-1 and from 13,0 μg mL^-1 to 23,1 μg mL^-1 for the development of analytical method. The RSD of the method  was 3.22%. Additional experiments were performed applying GCE with rectangular form (area 35.32 cm²) modified with ex situ prepared bismuth-film for the electrolysis of the target analyte which was performed at the potential -1.55 V (nearly the peak maxima of the target analyte) vs. SCE. The solution of interest was sampled at the beginning of the experiment, after 2.5 h and after 4.5 h of treatment. Such samples were analysed by simply water suppressing ¹H NMR measurements in the buffered solution at pH 11.8. It can be assumed that during electrolysis of 3-dehydrodeoxycholate the reduction of the keto group present in the structure of the target analyte can be occurred.Driven by earlier literature data about the fact that some of the target macrolide antibiotics as e.g. azithromycin showed oxidation behavior at a carbon paste and gold working electrodes detailed characterization and determination of four target macrolide antibiotics were performed on classical carbon paste electrode (CPE) constituted only from graphite powder and paraffin oil with optimized direct anodic SWV methods. In the cases of EES and AZI differential pulse voltammetric (DPV) methods were tested for the same purpose as well. The key parameter in the case of the development of the analytical voltammetric methods is the selection of the pH value of the supporting electrolyte where the shape/simmetry and intensity of the oxidation peak were the criteria. As the appropriate pH value for determination of EES by SWV method the pH 8.0 was selected with E_p at 0.83 V vs. SCE while in the case of the DPV method the pH 12.0 with E_p at 0.55 V vs. SCE was the most suitable for analytical  purpose. As for AZI determination, in the case of both SWV and DPV methods the pH 7.0 was the most appropriate supporting electrolyte with the Ep of analytical signal at 0.85 V and 0.80 V vs. SCE, respectively, while in the case of CLA and ROX which were investigated only with SWV method for the analytical purposes the pH 12.0 was the most suitable with E_p at 0.65 V and at 0.63 V vs. SCE. The obtained detection limits applying the bare CPE and the direct anodic SWV are mainly  in submicrogram concentration range as 0.17 μg mL^-1; 0.32 μg mL^-1 and 0.30 μg mL^-1 for EES, AZI, and ROX and in the low microgram concentration range as 1.43 μg mL^-1 for the CLA, respectively. The developed method succesfully tested for the determination of ROX in the commercial formulation, Runac^® tablet. In the case of the optimized DPV methods the obtained detection limits for EES and AZI are in the low microgram concentration range 1.03 μg mL^-1 and 1.53 μg mL^-1, respectively. For the improvement of the sensitivity for AZI the DPV method was tested in combination with a  CPE working electrode surface modified with gold nanoparticles with diameter of 10 nm (Au-CPE) and reached the limit of detection was 0.95 μg mL^-1 at E_p of 0.80 V vs. SCE. The RSD of the method in the case of the Au-CPE is 3.5% while in the case of the native CPE 6.0%. The linearity of the Au-CPE based analytical method is twice wider then it is case with the bare CPE applying protocol.Based on the obtained results it can be conclude that the appropriate combination of the optimized voltammetric pulse techniques and the environmentally friendly and easy to use working electrodes as Hg(Ag)FE, BiF-GCE and CPE together with Au-CPE resulted in the development of reliable analytical method either in the oxidation or reduction studies, often allowing trace level determination of pharmacological importance target analytes in simpler and in some case complexes systems.

Mezzo-soprano roles in French opera at the end of the nineteenth century were fatalistic; that is, the y inevitably bring about min or death. This thesis studies three mezzo-soprano roles in French Romantic opera from a performer's perspective: Carmen in Georges Bizet's Carmen, Dalila in Camille Saint-Sans' Samson et Dalila and Charlotte in Jules Massenet's Werther. These three characters cause the min of three romantic heroes all performed by tenors. What are the new narrative and dramatic functions of mezzo-sopranos in French opera at the end of the nineteenth century? As a performer, it is important to understand one's voice-type, the roles that are generally attributed to it, and the impact they have on dramatic and musical representation. This short analysis will help young performers in their approach to a character in order to have a better comprehension of aIl the dimensions and subtleties that are related to it.
Les rles des mezzo-sopranos dans l'opra franais de la fin du 19ime sicle sont trs fatalistes, c'est--dire qu'ils entranent invitablement la ruine, la mort. Ainsi, dans une perspective d'interprte, cette thse se penche sur trois rles fminins de mezzosoprano de l'opra franais romantique la fin du 19ime sicle : Carmen dans l'opra du mme titre de Georges Bizet, Dalila dans Samson et DWa de Camille Saint-Sans ainsi que Charlotte dans Werther de Jules Massenet. Ces trois personnages occasionnent la perte de trois hros romantiques tous interprts par des tnors. En ce sens, quelles sont les nouvelles fonctions narratives et dramatiques des mezzo-sopranos dans l'opra franais du 19ime sicle? En tant qu'interprte, il est important de bien comprendre notre type de voix, les rles qui lui sont gnralement attribus, l'impact de ceux-ci dans les histoires opratiques et dans leur reprsentation musicale. Cette courte analyse permettra de jeunes interprtes de les guider, de les aider dans leur approche d'un personnage et de mieux comprendre toutes les dimensions et les subtilits qui s'y rattachent.

L'étude de "Carmen : l'adaptation" se répartit en 3 volumes. La 1e partie étudie le passage de la nouvelle à l'opéra et au cinéma. Elle observe des solutions précises, en particulier dans les films de 1983, aux différentes étatpes suivantes : adaptation littéraire, visuelle musicale, et adaptation mise en scène. La 2e partie propose une réflexion didactique et des séquences précises sur l'enseignement de l'image, de la nouvelle et du groupement de textes. Quelle serait la place de Carmen dans les instructions et les recherches actuelles du cours de français, comme la lecture méthodique ? Comment construire une démarche progressive ? Comment intégrer l'étude de l'adaptation dans une théorie de l'acte de lire et quel rapport établir avec la construction de sens ? La 3e partie est une approche historique et comparatiste de la notion d'adaptation d'après "Carmen". Elle donne tous les résultats de l'enquête menée dans les cinémathèques sur tous les films, les réalisateurs, les actrices et les acteurs de "Carmen" du muet à aujourd'hui. Elle analyse l'intertextualité dans "La femme et le pantin" ainsi que l'exposition "Seita, photo gitanes". Conclusion sur le personnage de Carmen, l'évolution de la notion d'adaptation et les rapports de la littérature et du cinéma
The study is divided into 3 parts. The first part focuses on the adaptation of thee short story for the opera and the screen. Based more secularly on the four films shot in 1983, it shows several possible solutions to the different stages of the development of a film: literary adaptation, visual adaptation, musical adaptation and adaptation to the screen. The second part is a didactic approach structured around sequences on the teaching of image, short story and their study of French. A far as official instructions and research on the teaching of language are concerned, what place could be given to "Carmen"? How to build a progressive learning process? How to integrate a study of the adaptation into a reading and what link could be established with the construction of the meaning? The third part is an historical and comparative approach. It gives the results of a survey conducted in the film libraries, on all the films (from the silent ones) on the film-directors, the actors and the actresses involved in a Carmen adaptation. It analyses an example of intertextuality ("The woman and the puppet") and the exhibition "Seita, photo gitanes". Conclusion on the character of Carmen, the changes in the adaptation, literature and cinema

Georges Bizet (1838-1875) is best known for his operatic masterpiece, Carmen, but his other works have received much criticism. Much of this criticism stems from the belief that his work was simply derivative of other composers, including the father of French musical exoticism, Felicien David (1810-1876). However, there has never been any formal study comparing the two composers' compositional techniques.The purpose of this study is to compare the approaches that both Bizet and David took to portray the exotic in their operatic works, and to categorize any differences or similarities between the two composers' styles. The operas chosen for this study include Bizet's Les Pecheurs de perles (1863) and Djamileh (1872), as well as David's La Perle du Bresil (1851) and Lalla-Roukh (1862). Detailed historical background and musical analysis will be provided for each opera.
School of Music

La première partie de cette thèse traite des analyses littéraire et musicale de la Carmen de Prosper Mérimée et de la Carmen de Georges Bizet. Notre intérêt se concentre sur la qualité mythique de Carmen telle que Mérimée la créa et son expression musicale transposée par Bizet. Dans la deuxième partie de cette étude, sept représentations, au vingtième siècle, du personnage de Carmen, sous une forme théâtrale, sont présentées et analysées par rapport à la multiplicité des points de vue sur le personnage principal comme phénomène culturel et social. Quatre adaptations de Carmen ont été choisies pour cette étude : la Carmen Jones d'Oscar Hammerstein, la Carmen de Roland Petit, la Carmen de Peter Brook, et celle de Carlos Saura; et trois interprétations de la Carmen de Bizet et nos jours sont étudiées : celles de Bodo Igesz, de Francesco Rosi, et de Peter Hall
The first part of this thesis focuses on literary and musical analyses of prosper Merimee’s and of Georges Bizet’s Carmen. We are concentrating on the mythical quality with which Merimee imbued Carmen and for which Bizet created an expression in purely musical terms. In the second part; seven twentieth-century representations of the character of Carmen in theatrical form are presented and analyzed in regard to the multiplicity of viewpoints on the main character as a cultural and social phenomenon. Four adaptations of Carmen have been chosen for this study: Oscar Hammerstein’s Carmen Jones, Roland Petit's Carmen, Peter Brook's and Carlos Saura's Carmen; and three contemporary interpretations of Bizet’s Carmen are examined : the Carmens by Bodo Igesz, Francesco Rosi, and Peter Hall

An analysis of re-orchestrations of Robert Schumann's four symphonies employed by conductor Felix Weingartner (1863-1942). The text includes a brief history of Schumann's orchestral writing career and an overview of Weingartner's life as a conductor. The bulk of the dissertation discusses actual changes suggested by Weingartner (with score examples). Patterns of modifications are identified and discussed as they relate to historically entrenched problems perceived with Schumann's originally employed practices of orchestration. The analysis focuses on overall patterns of alteration imposed by Weingartner and their perceived effectiveness in achieving a noticeably improved aural outcome.

El primer capítulo trata de la dificultad que supone encuadrar un tema de estudio por lo que comporta de excluir y se justifican múltiples opciones que no se siguen. Del capítulo dos, dedicado a la novela, se recoge el carácter iniciático que para el autor supuso este viaje al Sur, visto como un lugar anárquico, en busca del orden interno que lo sustenta. Y la identificación de Carmen con este Sur en el que el espíritu/intelecto del autor se aproxima a la materia/naturaleza, a la madre tierra que le atrae pero a la que no sabe dominar, y porque le da miedo, la destruye. Carmen representa el eterno enfrentamiento entre los pares de opuestos irreconciliables: Norte/Sur, Vasco/Gitana, Hombre/Mujer, Orden/Anarquía, y la constante búsqueda del individuo para encontrar su conciliación. En la base de la investigación está la elección de la pasión, la muerte, la libertad y el destino que, simbolizados por la flor, el cuchillo, el anillo y las cartas, recorren la mayoría de las reinterpretaciones. En el tercer capítulo, dedicado a la ópera, se recoge el efecto amplificador que la música y el libreto han proporcionado a la novela. En la traslación de códigos que supone el paso de la novela a la escena el elemento decisivo es el hecho de que se convierte en espectáculo: cada Carmen que canta está representando el rito y reviviendo el sacrificio, sacralizándolo. Los tres personajes alrededor de los cuales gira la novela: el viajero, Carmen y Don José se convierten en cuatro. Micaela y Escamillo aportan la dimensión espacio temporal en tanto que parejas ideales para D. José y Carmen respectivamente; si no hubiera aparecido la FATALIDAD alterando el orden del espacio social y provocando la tragedia. El elemento trágico equilibrado por otros cuatro secundarios, Frasquita, Mercedes, Remendado y Dancaire, aportando el elemento ligero y cómico, mientras que los coros confirman el carácter mítico y la dimensión social: Don José puede matar a Carmen pero no a las cigarreras que cantan al placer que sienten al fumar, ni a los bandoleros que exaltan su libertad en las montañas, ni a los niños que parodian a los soldados. La música de Bizet es un ingrediente importante en la popularización de la anécdota y en su devenir mítico. El capítulo cuarto está dedicado principalmente al cine. La colocación de la cámara, la ausencia/presencia de sonido y cromatismo, la utilización de una u otra música, son, junto con la estructura narrativa que se elija en cada caso, así como las respectivas presencias físicas de los protagonistas, elementos que tienden a diversificar la obra. Se demuestra que las inferencias sociales que se traducen en ciertas aportaciones anecdóticas traslucen mucho más de lo que en apariencia representan. La pasión amorosa para Carmen es su forma de vida, el Amor para Carmen no puede ser sino búsqueda y juego. Y como en todo juego, el riesgo forma parte de lo inevitable. La "infidelidad" de Carmen es libertad en el hecho de amar y por tanto fidelidad hacia su propia concepción del amor. Don José no entiende estos códigos y se siente víctima de un sortilegio, del que sólo podrá librarle el "sacrificio" de la culpable. El aire de libertad que respira Carmen, la mujer que no obedece, que no está sometida, es la destilación del aire de libertad colectiva de los pueblos que han aprendido a rebelarse contra la Monarquía en la Revolución Francesa y siguen haciéndolo contra Napoleón, la República, o la Comuna. Al ser esta tesis pluridisciplinar, ha sido acompañada por un trabajo videográfico que la ilustra y la completa.
A study of the novel Carmen by Prosper Mérimée and, more especially, of its protagonist and the subsequent transmutations she has inspired in other creative artists in various media. The thesis is divided into five chapters and also includes a bibliography and six appendices. The first chapter explains the concept and methodology employed. The second deals with the genesis of Mérimée's novel. It starts with a view on life and politics in Spain, from 1830 to 1870 and continues with an approach on Mérimée's life and interests and a description of the novel and its literary precedents. The third chapter refers to Bizet's opera. It starts with a view on the impressions left by travelers visiting Spain in the 1850's, presents Bizet and the librettists Meilhac and Halévy, a functional analysis of the opera and concludes with opinions and commentaries about the work by some of the artists who have interpreted it. The fourth chapter provides a panoramic view on the 50 films on the subject for which there are entries in the filmogra¬phy, and analyses 15 of them. There is a view on the productions by Peter Brook in Theatre and T.V., and on some of the known choreography in ballet, and the work in theatre of Antonio Gala in Carmen, Carmen. The fifth chapter is devoted to the conclusions. The appendices are: 1. The technical script and literary commentary on the videocassette which accompany and complete the thesis. 2. A discography of recordings of the opera from 1908 to 1984. 3. A filmography of over 50 films on the theme from 1904 to 1990. 4. Ephemera: a collection of articles from newspapers and magazines in French, English and Spanish from 1980 to 1990. 5. The text of Les Bohémiens by Pushkin in its translation into French by Mérimée, which is used in the thesis 6. The catalogue of two books illustrated by Picasso which relate to two editions of Carmen.

Master’s thesis deals with problematic of operating aspects and competitiveness of VLJ aircraft in Czech and Europe market. The Thesis contain information about different types of VLJ, their operational costs and comparisons with competitors, some information about aircraft fractional ownership and their operation. There is written a market analysis for this aircraft and air taxi service in analyzed.

Lorsque l’on évoque la symphonie en France au milieu du XIXe siècle, on ne retient généralement que le nom de Berlioz et l’on insiste sur une désaffection du genre tant de la part des compositeurs que du public. Pourtant, malgré un recul des créations, malgré le défi posé par l’héritage beethovénien et alors même que le contexte musical favorise principalement la scène lyrique, une soixantaine de compositeurs continuent à s’intéresser au domaine exclusivement instrumental de la symphonie et assurent le maintien d’un genre entre 1830 et la génération franckiste. Au-delà de son aspect historique, cette thèse vise à cerner les caractéristiques stylistiques de tout un ensemble d’œuvres, à les situer dans l’évolution d’un genre en les analysant à la fois par rapport aux normes viennoises, aux productions contemporaines germaniques et aux avancées plus générales du langage. Après une première partie centrée sur le contexte musical qui a vu naître ces symphonies, les enjeux pédagogiques qu’elles suscitent et le rôle décisif des sociétés orchestrales, l’analyse entre au cœur des partitions dans une démarche comparative à la fois quantitative et qualitative, depuis l’agencement interne des plus petits éléments musicaux jusqu’à la réalisation de la grande forme. À travers l’observation des pratiques globales et individuelles qui concourent à une réévaluation des normes, à la refonte ponctuelle mais progressive des cadres, se dégagent l’autonomie d’un genre par rapport à son modèle germanique et la permanence d’une école symphonique française tout au long du XIXe siècle
When one deals with the symphony in mid-19th century France only the name of Berlioz comes to mind and one emphasizes a disaffection for the genre among composers as well as audiences. However, despite fewer creations, despite the awe-inspiring Beethovenian legacy and despite the overwhelming place held by the operatic scene during those decades, some sixty composers around Hector Berlioz still devoted themselves to the purely instrumental genre and achieved the development of the symphony between 1830 and the Franckist generation. Beyond its historical relevance, this doctoral dissertation aims at defining the stylistic features of a corpus of symphonic works and at placing them in the evolution of the genre by analyzing them in relation to Viennese standards, to contemporary Germanic productions and to the more general innovations in the musical language. After first focusing on the musical context in which these symphonies were composed, on the pedagogic stakes entailed and on the decisive role of orchestral societies, the analysis will then closely examine the scores in a quantitative and qualitative comparative approach moving from the internal construction of the smallest musical elements to the completion of the large form. The autonomy of a genre distinct from its Germanic model and the permanence of a French symphonic school throughout the 19th century will emerge thanks to the observation of collective and individual practices which contributed to a reassessment of norms, to a selective but gradual revision of musical forms

碩士
國立臺北教育大學
音樂學系碩士班
100
Abstract Georges Bizet (1838~1875) is an important musician of Romanticism in 19th Century, and Victor Marie Hugo (1802~1885) a great writer. Hugo’s poetry is often the source of inspiration for the composers of Mélodie (French Art Songs.) The theme of this thesis is based on five mélodies from Hugo composed by Bizet. Through melody and musical form of music and poetic rhythm, the excellence of the combination of Bizet’s music and Hugo’s poetry is unveiled and studied. The thesis is composed of five chapters. Chapter 1 states the purposes and structures of this study. Chapter 2 is an introduction to the life of Bizet and the feature of his music. Chapter 3 is an introduction to the life of Hugo and the feature of his masterpiece. Chapter 4 analyzes and studies the lyrics of five mélodies by G. Bizet inspired from V. M. Hugo's poetry, their respective translations and explanations, compositional styles and frameworks, and vocal performances. The mélodies include Adieux de l’hotesse arabe, Guitare, Après l’hiver, La chanson du fou, and La coccinelle. A concluding remarks of this study is set forth in Chapter 5. Hopefully, through my analysis and performance of the five melodies, the study can allow the readers to gain a better understanding of Bizet’s melodies on the one hand, and, on the other, serve as a source of reference materials for those who will perform the songs in the future.

The global energy demand increases with the development of civilisation. Widely used energy sources are mostly based on fossil fuels (e.g. coal, oil, natural gas), and technologies used for production of energy strongly affect the degradation of the environment. Increasing environmental pollution and temperature rise due to greenhouse gas emissions may lead to an ecological disaster. Therefore, research aimed at, on the one hand, the development of an efficient energy production process but not related to CO2 emissions and, on the other hand, the reduction of environmental pollution has been of great interest in recent years. One of the most widely reported topics is the use of solar energy, the resources of which significantly exceed the global energy consumption and at the same time it is widely available in large parts of the world. In addition to energy production, its efficient storage is crucial. In this respect, hydrogen can play an important role, as it is considered to be the main vector for future energy storage and processing. Chemical energy stored in the form of H2 can be converted into electricity through appropriately designed fuel cells that produce water as the only by-product. Therefore, the production of H2 in the photoelectrochemical water splitting process seems to be a good solution. Furthermore, photocatalysis can be successfully used to remove harmful gases and greenhouse gases such as CO2 or NOx. Over the past decades, photocatalytic processes have been widely used to treat water from organic pollutants. Important advantages of this process are: i) the possibility of complete decomposition of pollutants and ii) the relatively low temperature required for this process. This dissertation presents experimental results, together with their detailed analysis, concerning both above mentioned processes, photoelectrochemical water splitting and decomposition of organic pollutants in water. Both the simple method of preparation of photoanodes based on earth-abundant elements, as well as actions taken to increase their efficiency are presented. This work also deals with the problem of explaining the mechanism of photoelectrocatalytic processes taking place at the boundary formed between photoabsorbers, i.e. the semiconductor light-absorbing material, and catalysts at the moment when the created system contains both elements. In the first part of the thesis the influence of the photoabsorber/electrocatalyst interface on the photoelectrochemical decomposition of organic pollutants was evaluated. In this part, photo- anodes made of TiO2 and modified with plasmonic nanostructures of Au or Ag were used. For both types of the electrodes studied it was shown that the modification initially enhanced the photoelectrocatalytic activity towards acetic acid and 2-propanol decomposition (used as model organic pollutant) using radiation in the visible light range. However, repeated measurements of the incident photon-to-current conversion efficiency (IPCE) for the generated photocurrent showed a rapid decrease in the spectral range, where an increase in intensity was originally observed as a result of the presence of plasmonic nanostructures. This has been shown to be caused by irreversible surface oxidation of plasmonic nanostructures, which strongly suggests that deactivation of photocatalysts is of general importance and should always be considered in the context of designing new efficient photoelectrocatalytic and photocatalytic systems. Then, as part of this work, an efficient oxygen evolution reaction catalyst consisting of three metal oxides was developed together with an activation method that improves its photoelectrochemical activity. It has also been shown that the successful combination of this electrocatalyst with the TiO2 photoanode cannot be easily transferred to other photoanodes. The application of this strategy revealed that even the combination of the same photoabsorber and catalyst but only using a different photoanode architecture may lead to completely different results. A thorough examination of a carefully chosen set of oxygen evolution catalysts in combination with the same photoabsorber (Mo-doped BiVO4) showed that the initial theory of the special behaviour of certain materials as catalysts is quite general and can be applied to a wide range of catalysts. In a further step, selected oxygen evolution catalysts were combined with another photoabsorber (WO3) in two of the previously tested configurations. This work has shown that the conscious design of the interface between the photoabsorber and the catalyst drastically changes the performance of the resulting hybrid system. The results obtained once again have shown that the nature of the catalyst is not a dominant factor in improving the performance of the photoanode, but the interface formed between the photoabsorber and the catalyst should always be taken into consideration as well. Finally, the influence of the combination of the photoabsorber with the catalyst on the stability of the photoanode was evaluated. Experiments on photocorrosion of the photoanode material were carried out. It was shown that the addition of a catalyst can also be used to protect the photoanode against photocorrosion as well as to modify the dissolution profile of its components. The methods and results described in this work allowed to deepen the knowledge of environmentally friendly photoelectrocatalysis and to produce materials with increased activity, which can be used in light-assisted water electrolysis or decomposition of organic pollutants. The obtained results clearly indicate the important role of the interface formed between photoabsorbers and electrocatalysts in photoelectrochemical processes and provided valuable information on this phenomenon. The knowledge gained in this work on the nature of the interface formed between a photoabsorber and a catalyst can be potentially used in other important photoelectrochemical processes, such as light-assisted CO2 electroreduction.
Światowe zapotrzebowanie na energię wzrasta wraz z rozwojem cywilizacji. Powszechnie wykorzystywane źródła energii są w większości oparte na paliwach kopalnych (węgiel, ropa naftowa, gaz ziemny), a technologie służące produkcji energii silnie wpływają na degradację środowiska naturalnego. Wzrastające zanieczyszczenie środowiska oraz wzrost temperatury spowodowany emisją gazów cieplarnianych może doprowadzić do katastrofy ekologicznej. W związku z tym, badania mające na celu, z jednej strony opracowanie wydajnego procesu wytwarzania energii, ale nie związanego z emisją CO2, a z drugiej ograniczenie zanieczyszczenia środowiska cieszą się w ostatnich latach dużym zainteresowaniem. Jednym z szeroko badanych zagadnień jest wykorzystanie energii światła słonecznego, której zasoby znacznie przewyższają globalne zużycie energii i jednocześnie jest ona powszechnie dostępna w dużej części naszego globu. Oprócz wytwarzania energii kluczowe jest jej efektywne magazynowanie. W tym zakresie ważną rolę może odegrać wodór, który jest uważany za substancję podstawową dla przyszłego magazynowania i przetwarzania energii. Energia chemiczna przechowywana w postaci H2 może być przetwarzana w energię elektryczną poprzez odpowiednio zaprojektowane ogniwa paliwowe wytwarzające wodę jako jedyny produkt uboczny. Dlatego też produkcja H2 w procesie fotoelektrochemicznego rozkładu wody (ang. photoelectrochemical water splitting, PEC water splitting) wydaje się być dobrym rozwiązaniem. Ponadto, fotokataliza może być z powodzeniem wykorzystana do usuwania szkodliwych gazów i gazów cieplarnianych, takich jak CO2 czy NOx. W ciągu ostatnich dziesięcioleci procesy fotokatalityczne były szeroko stosowane do oczyszczania wód z zanieczyszczeń organicznych. Istotnymi zaletami tego procesu są: i) możliwość całkowitego rozkładu zanieczyszczeń i ii) stosunkowo niska temperatura wymagana dla tego procesu. W niniejszej rozprawie doktorskiej przedstawiono wyniki eksperymentów, wraz z ich szczegółową analizą, dotyczące obu wspomnianych wyżej procesów, fotoelektrochemicznego rozkładu wody oraz oczyszczania wód z zanieczyszczeń organicznych. Przedstawione zostały, zarówno prosta metoda syntezy fotoanod opartych na pierwiastkach powszechnie występujących na ziemi, jak i działania podjęte w celu zwiększenia ich wydajności. Praca ta dotyczy również problemu wyjaśnienia mechanizmu procesów fotoelektrokatalitycznych zachodzących na granicy formującej się między fotoabsorberami (półprzewodnikowy materiał absorbujący światło) a katalizatorami w momencie tworzenia układów zawierających oba elementy. W pierwszej części pracy oceniono wpływ granicy fotoabsorber-elektrokatalizator na fotoelektrochemiczny rozkład zanieczyszczeń organicznych. W tej części pracy wykorzystywane były fotoanody z TiO2 modyfikowane plasmonicznymi nanostrukturamii Au lub Ag. W przypadku obu typów badanych elektrod wykazano, że modyfikacja początkowo wzmocniła aktywność fotoelektrokatalityczną w kierunku rozkładu kwasu octowego i 2- propanolu (stosowanych jako modelowe zanieczyszczenie organiczne) z wykorzystaniem promieniowania w zakresie światła widzialnego. Wielokrotnie powtarzane pomiary generowanego fotoprądu w zależności od energii światła padającego na elektrodę (ang. incident photon-to-current conversion efficiency, IPCE) wykazały jednak szybki spadek wartości IPCE w zakresie spektralnym, w którym pierwotnie obserwowano wzrost intensywności w wyniku obecności nanostruktur plazmonicznych. Przyczyną tego stanu rzeczy było nieodwracalne utlenianie powierzchniowe nanostruktur plazmonowych, co silnie wskazuje, że dezaktywacja fotokatalizatorów ma znaczenie ogólne i powinna być zawsze brana pod uwagę w kontekście projektowania nowych, wydajnych układów fotoelektrokatalitycznych oraz fotokatalitycznych. Następnie, w ramach niniejszej pracy, opracowano wydajny katalizator wydzielania tlenu (ang. oxygen evolution reaction catalyst, OER catalyst) składający się z trzech tlenków metali wraz z metodą aktywacji, która poprawia jego aktywność fotoelektrochemiczną. Wykazano również, że udane połączenie tego elektrokatalizatora z fotoanodą TiO2 nie może być łatwo przeniesione do innych fotoanod. Zastosowanie tej strategii ujawniło, że nawet zastosowanie tego samego fotoabsorbera i tego samego katalizatora oraz modyfikacja jedynie architektury fotoanody prowadzi do kompletnie różnych wyników. Dokładne zbadanie starannie dobranego zestawu katalizatorów wydzielania tlenu w połączeniu z tym samym fotoabsorberem (Mo:BiVO4) wykazało, że wstępna teoria o szczególnym zachowaniu niektórych materiałów jako katalizatorów jest dość ogólną cechą i może być stosowana do szerokiej gamy katalizatorów. W kolejnym etapie wybrane katalizatory wydzielania tlenu zostały połączone z innym fotoabsorberem (WO3) w dwóch wcześniej przebadanych konfiguracjach. Praca ta pokazała, że świadome projektowanie granicy pomiędzy fotoabsorberem a katalizatorem, drastycznie zmienia wydajność otrzymanego układu hybrydowego. Uzyskane wyniki po raz kolejny pokazały, że charakter katalizatora nie jest czynnikiem dominującym dla poprawy działania fotoanody, natomiast zawsze należy wziąć pod uwagę również granicę utworzoną pomiędzy fotoabsorberem a katalizatorem. Na końcu oceniono wpływ połączenia fotoabsorbera z katalizatorem na stabilność fotoanody. Przeprowadzone zostały eksperymenty fotokorozji materiału fotoanody. Wykazano, że dodatek katalizatora może być stosowany również w celu ochrony fotoanody przed fotokorozją, a także w celu modyfikacji profilu rozpuszczania jej składników. Opisane w niniejszej pracy metody i wyniki pozwoliły na pogłębienie wiedzy na temat przyjaznej dla środowiska fotoelektrokatalizy oraz na wytworzenie materiałów o zwiększonej aktywności, które mogą być wykorzystywane w procesie wspomaganej światłem elektrolizy wody lub rozkładu zanieczyszczeń organicznych. Uzyskane wyniki wyraźnie wskazują na ważną rolę granicy utworzonej pomiędzy fotoabsorberami a elektrokatalizatorami w procesach fotoelektrochemicznych i dostarczyły cennych informacji na temat tego zjawiska. Jestem przekonana, że uzyskana w ramach niniejszej pracy wiedza na temat charakteru granicy powstającej pomiędzy fotoabsorberem a katalizatorem może być z powodzeniem wykorzystana w innych ważnych procesach fotoelektrochemicznych, takich jak np. wspomagana światłem elektroredukcja CO2.

碩士
國立臺北藝術大學
音樂學系碩士在職專班
105
Georges Bizet (1838-1875) is a famous French composer in the nineteenth century. He is one of the most representative composers of the Romantic Era. Bizet is most known for his operatic works. However, in his short life, Bizet compsed other forms in music, such as orchestral works, theatrical works, piano works, art songs, etc. Although other genres of his composition are not as famous as his operatic works, they all share the characteristics of having creatic and unique thoughts. These works are very moving and well-loved. This thesis will focused on discussing Bizet’s art songs. Bizet wrote forty-eight art songs in his lifetime. Although the number of Bizet’s art songs is not high, his art songs are excellent works with rhythmic sensitivity and exotic colors. I will discuss are Pastorale, Vieille Chanson, Adieux de l'hôtesse arabe, and Ouvre ton coeur the four mélodies. I will study the life and the musical characteristics of Bizet, and to discuss each work by analyzing its musical structure. I expect to have a deeper understanding of the connotation of the song and encourage more performance in the furture.

碩士
國立臺灣師範大學
音樂學系
105
Mélodie originated from the 18th Century Romance. The themes of the lyrics in Romance are mostly related to history, pastures, or sorrowful emotions. Because of the Parnassism influence in the 19th century, the poets eschewed the influences of the subjective perspectives of the Romantics, and daringly undertook the objective narrative and the narrative of exotic countries. One discovers that when selecting poems, the composers usually use Parnassism poems that are easy to orchestrate and evoke the characteristics of the animals. This thesis looked into the nine animal-related titled French art songs of four composers between 1865 to 1890, which include: La coccinelle and Le rossignol composed by Camille Saint-Saëns (1835-1921), La coccinelle composed by Georges Bizet (1838-1875), Ballade des gros dindons, Les cigales, Pastorale des cochons roses and Villanelle des petits canards composed by Emmanuel Chabrier (1841-1894), and finally, Les papillons and Le colibri composed by Ernest Chausson (1885-1899). These works of the famous French poets of the 19th century. They are Victor Hugo (1802-1885), Théodore de Banville (1823-1891), Edmund Rostand, (1868-1918), Rosemonde Gérard (1866-1953), Théophile Gautier (1811-1872) and Charles Leconte de Lisle (1818-1894). From these nine songs, the poems are generally with regular rhyme schemes, fluid rhythms and musical phrases. The topics generally express the realistic characters with a metaphorical manner or a parody instead of simply portrays the scenery or animals. The structures of the pieces are either through-composed or strophic, the composers liked to utilize motifs or themes to present the movements, sounds, or characters of the animals, and to unite the musical ideas. The composers used similar figure for the animals’ movements, used notes on the same pitch in voice melody or the piano part to represent a speech mannerism or inner thoughts of a person, used melismatic passages to paint the different character of the animals. The composers used sequences to heighten the ambience or build up to a climax, and sometimes quote phrases from predecessors as a way of allusion. The accompaniment usually relays the ends of the singer’s phrases or creates different settings in the song. These works are with repetitive musical figures or phrases. The overtly repetition create a comical effect, leaving a strong impression on the way it was utilized, making these mélodies different from the elegant ones. All these characteristics were prominent features of the French mélodie during this period. These works focus upon animal-related titles, therefore the interpretation of the humorous songs should be more animated than others, and also increase the conversion of tone. The singer must quickly immerse oneself in the narrative, using facial expressions and appropriate body movements to express the humor in the lyrics, in order to fully express the atmosphere that the composer had intended.