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Karakterisering av høytemperaturegenskaper i Ca12Al14O33
No full textSammendrag
Denne oppgaven beskriver arbeidet med å karakterisere høytemperaturegenskapene til Ca12Al14O33, også kalt Mayenitt, 12CaO•7Al2O3 eller bare C12A7. Det er rapportert at Mayenitt inneholder hydridioner etter reduksjon i høy temperatur, og at disse kan fungere som elektrondonorer ved fotoeksitasjon under UV-bestråling. Ca12Al14O33 har en mikroporøsporøs kubisk struktur, hvor Ca12Al14O322+ danner et gitter med seks sub-nanometer bur inneholdende ett O2-ion. Dette oksygenionet er løst bundet sammenlignet med oksygenionene i gitteret, og dette gjør det enkelt å redusere stoffet, slik at oksygen kan erstattes av lokaliserte elektroner på oksygenplass. Ca12Al14O33 har høy oksygenioneledningsevne i oksiderende, tørr atmosfære, og er rapportert som en blanding av elektronisk leder og protonleder i reduserende atmosfære. Imidlertid dekomponerer stoffet i reduserende, tørr atmosfære ved T > 1100 °C.
Mayenitt ble syntetisert ved bruk av sitratmetoden, og det ble preparert porøse og tette prøver til bruk ved henholdsvis termogravimetriske målinger og ledningsevnemålinger. Prøvene ble karakterisert både før og etter målingene ved røntgendiffraksjon og scanning elektronmikroskopi.
Det ble gjort termogravimetriske målinger av vannopptak som funksjon av temperatur, pO2 og pH2O, og termodynamiske data for hydratiseringsreaksjonen ble utledet. Termogravimetriske målinger ble også benyttet for å teste stabilitet over lengre tid i reduserende, tørr atmosfære.
Det ble videre gjort ledningsevnemålinger som funksjon av pO2, temperatur og pH2O. Ledningsevnen ble i tillegg målt over lengre tid i reduserende, tørr atmosfære for å teste effekten av en eventuell dekomponering. Det ble også gjennomført impedansspektroskopi i oksiderende og reduserende atmosfære.
Resultatene viste at Ca12Al14O33 i hovedsak har elektronisk ledningsevne i reduserende atmosfære og ionisk ledningsevne i oksiderende atmosfære ved T > 900 °C. Termodynamiske data for hydratiseringsreaksjonen ble beregnet til -223 kJ•K-1 for ∆H og -120 J•K-1•mol-1 for ∆S. Aktiveringsenergi for elektronisk ledningsevne ble beregnet til 2,6 eV på bakgrunn av målte data.
Det ble bekreftet ved røntgendiffraksjon og scanning elektronmikroskopi at prøven hadde gjennomgått en faseovergang i løpet av målingene
Oxygen electrodes for ceramic fuel cells with proton and oxide ion conducting electrolytes
No full textThe overall aim of this work is to contribute to a better understanding of the reactions taking place at the oxygen electrode in proton ceramic fuel cells (PCFCs) and, moreover, to develop new materials with improved performance for this electrode. PCFCs and their cathode reactions are the main focus of the study, but these reactions are often running in parallel with reactions associated with other charge carriers that also need to be addressed. Most proton conducting ceramics exhibit also transport of oxide ions, and although small at intermediate temperatures, the relative contribution from partial oxide ion conductivity increases with temperature and eventually dominates at higher temperatures. Hence, characterization of the performance of a PCFC cathode may at higher temperatures in reality be affected by or even directly reflect the cathode reactions of an oxide ion conducting solid oxide fuel cell (SOFC) rather than that of a PCFC. The crossover between SOFCs and PCFCs with respect to the oxygen electrode reactions is emphasized in this work.
The first manuscript presents status and challenges of PCFC research undertaken in Norway by the start of 2010. The work comprises manufacturing of single cells and cell stacking, focusing on the performance, the mechanical and thermal properties, as well as, the chemical stability of the different PCFC component materials. State-of-the-art cathode material at that time, La0.8Sr0.2MnO3 (LSM), showed a polarization resistance (Rp) of 30 Ωcm2 800°C on proton conducting Ca doped LaNbO4 electrolyte, revealing the necessity for a significant improvement in the cathode performance. New materials had to be found and their microstructural design optimized, based on the requirements specific for the proton conductor oxygen reaction.
Reaction kinetics, with particular emphasis on the features specific for the PCFC oxygen electrode is investigated in manuscripts II, III and V. In manuscript IV, the experimental conditions are such that the SOFC reactions dominate the electrode process. The electrolyte/electrode interfacial exchange of protons instead of oxide ions distinguishes PCFCs from oxide ion conducting SOFCs and entails that water is formed on the oxygen side of the electrolyte. A major challenge with the PCFC cathode candidate materials studied so far is the confinement of the electrochemical process to pass the electrolyte / electrode / gas triple phase boundary (tpb), instead of utilizing the whole electrode area as for the best mixed conducting SOFC electrodes. The challenges related to tpbs as a bottleneck are addressed by microstructural improvements. Moreover, a novel material with simultaneous transport of electrons and protons is introduced that will enable also the PCFC cathode reactions to occur over the electrode surface, thereby extending the tpb reaction zone.
The effect of water formation on the cathode reaction is studied in detail on a Pt model electrode. The results show higher reaction rates upon increased water vapor partial pressure, pH2O. Since the Pt electrode is rate limited by surface diffusion both under dry and wet conditions, the pH2O effect is explained by the formation of surface hydroxyls with high surface mobility relative to the adsorbed oxide ions which dominate under drier conditions. The presence of surface hydroxyls is confirmed by X-ray photoelectron spectroscopy. Water is looped in the oxygen reaction series, acting both as reactant and product. In manuscript V and in the results part of the thesis it is shown that ambient water vapor gives the same positive effect for the mixed conducting electrodes BaGd0.8La0.2Co2O6-δ (BGLC) and BaPrCo2O6- (BPC) when operated on a BaZr0.7Ce0.2Y0.1O3 (BZCY72) proton conducting electrolyte. At higher temperatures where BZCY72 is mainly oxide ion conducting, water vapor on the other has an adverse effect on the electrode reaction rate for the same mixed conducting electrodes. With the mixed oxide ion-p-type electron conductor La2NiO4+δ (LNiO) as electrode and La27.16W4.85O55.27, (La/W ≈ 5.6; LWO56) as electrolyte (manuscript IV), the electrode performance was independent of pH2O under conditions where oxide ion conductivity dominates in the electrolyte (above 700°C).
Three well-established routes to improve the electrode microstructure were followed in this work; (i) addition of nano-sized catalysts by infiltration, (ii) improvement of the functional layer close to the electrolyte and (iii) manufacturing of composite electrodes by mixing electrode and electrolyte materials. The two first methods showed promising results: Addition of Pt nanoparticles in the LSM electrode lowered significantly the polarization resistance; from 260 to 40 Ωcm2 at 650°C. Characterization of the microstructure of BGLC and BPC electrodes showed that a fine-grained functional layer was successfully manufactured. The composite electrode approach did, however, not prove to enhance the performance of an electrode rate limited by surface reactions.
The materials investigated in this work range from well-known pure electron conductors such as Pt and LSM, used first and formerly for the detailed characterization of the electrode reactions, via the promising mixed conducting candidate LNiO, to the novel mixed conducting double perovskites BGLC, BPC and their B-site iron-substituted variants BaGdCo1.8Fe0.2O6-δ (BGCF) and BaPrCo1.4Fe0.6O6-δ (BPCF). For Pt and LSM, high capacitance processes like surface diffusion is limiting the overall electrode reaction rate. For the mixed conducting electrodes LNiO and BGLC, the oxide ion transfer is shown to happen through the electrode interior. The latter also shows indications of partial bulk proton conductivity concluded based on the pH2O dependencies encountered for Rp and supported by hydration of the material at low temperatures with a hydration enthalpy of -50 kJ/mol. Bulk proton transport would facilitate the low temperature PCFC cathode reaction and widen the triple phase reaction zone improving the electrode performance. The behavior of these mixed conducting double perovskites, especially BGLC but possibly also BPC, with polarization resistances measured to 0.05 and 0.09 Ωcm2 at 650°C for BGLC and BPC, consequently gives indications of the first established mixed proton / electron conducting materials with sufficient electrochemical performance on a proton conducting electrolyte.
To account correctly for mixed conductivity in the electrolyte is challenging when studying electrode reactions. In manuscript III and V, a model for the separation of the measured polarization resistance into the contributions from more than one charge carrier is developed. The model accounts also for the effect of parallel non-faradaic current during high temperature measurements under oxidizing conditions. The results of the modelling show that the measured polarization resistance for the system investigated here and reported above for 650°C is underestimated by approximately one order of magnitude. The same underestimation would apply to any other oxygen electrode measured on BZCY72 if the effect of electrolyte p-type partial conductivity was not properly addressed. In a running fuel cell or electrolyzer cell, the fuel-side reducing conditions are expected to induce a blocking layer for electronic conductivity in the electrolyte. The "true" polarization resistance will therefore be higher when the partial short circuit is absent. At lower temperatures, this effect of parallel non-faradaic current is less pronounced during half-cell electrode characterization.
BGLC exhibits a total polarisation resistance for proton transport of only 10 Ωcm2 at 350°C, with an activation energy of 50 kJmol-1 ascribed mainly to the surface electrode reaction. Based on this, there is reason to believe that further improvements of the cathode performance can be achieved by enhanced microstructural processing, such as infiltration of BGLC in a BZCY backbone
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation
counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings
are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that
only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into
account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed
Variations on the Author
Get PDF“Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship
Appropriate Similarity Measures for Author Cocitation Analysis
Get PDFWe provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis
Dispelling the Myths Behind First-author Citation Counts
Get PDFWe conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued
use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation
counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more
sophisticated methods
koamabayili/VECTRON-author-checklist: VECTRON author checklist
No full textWe have done our best to complete the author checklist relating to the use of animals in the hut study. Note that the objective for the hut study was to evaluate the IRS treatment applications for residual efficacy against Anopheles mosquitoes, including the local An. coluzzii mosquito population. Cows were only used to attract mosquitoes into the huts and no tests were carried out directly on the cows. The author checklist is intended for use with studies where experiments are carried out on animals, which is why we have had such difficulty in completing this for the hut study, as many of the questions do not relate to how the cows were used
Author-wise bibliometric analysis based on entropy.
No full textAuthor-wise bibliometric analysis based on entropy.</p
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