Increased equipment failures and the resultant increase in unplanned downtime as the result of process optimization programs continue to plague pulp mills. The failures are a result of a lack of understanding of corrosion in the different pulping liquors, specifically the parameters responsible for its adjustment such as the role and identification of inorganic and organic species. The current work investigates the role of inorganic species, namely sodium hydroxide and sodium sulfide, on liquor corrosivity at a range of process conditions beyond those currently experienced in literature. The role of sulfur species, in the activation of corrosion and the ability of hydroxide to passivate carbon steel A516-Gr70, is evaluated with gravimetric and electrochemical methods. The impact of wood chip weathering on process corrosion was also evaluated. Results were used to identify black liquor components, depending on the wood species, which play a significant role in the activation and inhibition of corrosion for carbon steel A516-Gr70 process equipment. Further, the effect of black liquor oxidation on liquor corrosivity was evaluated. Corrosion and stress corrosion cracking performance of selected materials provided information on classes of materials that may be reliably used in aggressive pulping environments.

This thesis studies State-of-Charge (SOC) method for widely used lead-acid batteries and the most prospective lithium-ion batteries. First, the relationship between the battery capacity and the open-circuit-voltage under different charging/discharging currents is investigated based on the equivalent circuit. Experimental results indicate that the open-circuit-voltage of the lead-acid battery varies regularly with the charging/discharging current and the duration of time for the battery disconnected from the load. Accordingly, a dynamic open-circuit-voltage method in considerations the open-circuit-time and the previous operating current is capable of precisely estimating the battery capacity in a shorter time. As for the lithium-ion batteries, their charging/discharging characteristics reveal that the Coulomb/Ampere-Hour Counting method is capable of yielding accurate estimations. Finally, through the experiments that emulate practical operations, the SOC estimations of batteries are verified to demonstrate the effectiveness and accuracy of the proposed methods.

Organic solar cells have the potential to be portable power sources that are light-weight, flexible, and inexpensive. However, the highest power conversion efficiency for organic solar cells to date is ~8%, and most high-efficiency solar cells have an area of less than 1 cm². This thesis advances the field of organic solar cells by studying the physics and engineering of the devices to understand the reverse saturation current, which is related to efficiency, and the effects of area scaling. The most commonly accepted models to describe the physics of organic photovoltaic devices are reviewed and applied to planar heterojunction solar cells based on pentacene / C60 as a model system. The equivalent circuit model developed for inorganic solar cells is shown to work well to describe the behavior of organic devices and parameterize their current-voltage characteristics with five parameters. Changes in the parameters with different material combinations or device structures are analyzed to better understand the operation of the presented organic solar cells. A one-dimensional diffusion model for the behavior of excitons and treatment of the organic layers as planes is demonstrated to adequately model the external quantum efficiency and photocurrent in pentacene / C60 solar cells. The origin of the open-circuit voltage is studied using cells with different electrodes and different donor materials. While changing the electrodes does not affect open-circuit voltage, it is greatly modified by changes in the donor. Tests with additional semiconductors show the change in open-circuit voltage is not consistent from donor to donor as the acceptor is varied, suggesting a more complex relation than just the difference in energy levels. Study of the temperature dependence of the equivalent circuit parameters shows that the reverse saturation current, which has a significant role in determining the open-circuit voltage, has a thermally activated behavior. From this behavior, the reverse saturation current is related back to charge transfer at the donor / acceptor heterojunction to suggest that both the effective energy barrier presented by the energy levels and the electronic coupling are important in determining the reverse saturation current and open-circuit voltage. This marks a shift from just considering a built-in voltage or the energy levels to also considering the electronic coupling of the donor and acceptor materials. Temperature-dependent performance characteristics are also used to show key differences between organic and inorganic devices. Finally, the effect of area scaling is explored with pentacene / C60 solar cells having areas of 0.11, 7, and 36.4 cm². Analysis with the equivalent circuit model shows that performance decreases as area increases because of an increasing series resistance presented by the transparent electrode. A metal grid, to provide low resistance pathways for current, fabricated on top of the transparent electrode is proposed to reduce the effective resistance. The grid is unique in that it is placed between the electrode and the semiconductor layer and must be passivated to prevent shorts through the thin semiconductor to the back metal electrode. Analysis of the grid predicts greatly reduced series resistance, and experimental results show reduced resistance and improved performance for the 7 cm² and 36.4 cm² devices when including the grid.

Foi construída uma nova versão de um sistema para medidas de correntes termo-estimuladas em circuito aberto (DTE). Mostrou-se que no Teflon FEP, carregado com corona negativa, os ruídos que aparecem nas curvas de DTE , que são devidos a micro rupturas elétricas na amostra, causam uma variação de potencial considerável na mesma. Verificou-se também que a corrente anômala originada pelo deslocamento de cargas na camada de ar entre a amostra e a placa sensora pode perturbar as medidas de DTE com amostras virgens carregadas positivamente. A inversão de polaridade da corrente nas medidas de DTE na região próxima a temperatura ambiente, foi explicado como sendo devido a variação da capacitância da amostra em função da temperatura. Medidas de DTE, realizadas com o polímero PETP (Mylar), mostraram que o processo de transporte que dá origem ao pico de corrente acima de 100 C é devido a uma condutividade intrínseca originária da geração de portadores em centros neutros de ionização. Essa geração possui uma dependência com o campo elétrico do tipo Poole-Frenkel e a mobilidade dos portadores livres, depende do volume livre o qual tem valor maior que o de equilíbrio abaixo da temperatura da transição vítrea / A new version of thermo stimulated current setup (DTE) in open circuit was built. It was shown in measurements electric noise is present in the DTE curve in Tefon FEP negatively charged which is due to micro electric breakdown in the sample. It was also found that the electric current in air gap between the sample surface and the sensor plate can disturb DTE measurements performed in positively charged samples. The polarity inversion on the DTE curves at room temperature range is due to the capacitance variation with the temperature. DTE measurements on PETP (Mylar) showed that the charge transport gives a current peak at 100 C due to an intrinsic conductivity generated by carriers from ionization centers. This process is described by a Poole-Frenkel

Apesar de toda a atenção dada à eletro-oxidação do íon boroidreto, pela possibilidade de seu uso em células a combustível, pouco se tem discutido a respeito das instabilidades cinéticas associadas a esse processo. A maioria das pesquisas tem como foco o estudo da cinética dos processos na região de baixos sobrepotenciais, numa região relativamente próxima ao estado de equilíbrio termodinâmico. Em uma região afastada do equilíbrio, diferentes mecanismos regem o sistema e desta forma diferentes informações podem ser obtidas. O objetivo da presente dissertação consiste na investigação sistemática da cinética complexa associada aos processos de adsorção, oxidação e interação do íon boroidreto em superfícies policristalinas de platina. As investigações foram realizadas em condições afastadas do equilíbrio utilizando-se técnicas eletroquímicas convencionais, incluindo: voltametria cíclica, cronoamperometria, experimentos quase estacionários sob controle potenciostático utilizando diferentes valores de resistência total e transientes de circuito aberto. Dentre os resultados obtidos pode-se destacar: a alta velocidade na redução dos óxidos de platina em transientes de circuito aberto (i.e. 0,5 s), sendo esta mais alta do que para álcoois ou hidrogênio; dois processos auto-catalíticos no perfil de potencial de circuito aberto, que podem ser relacionadas com uma biestabilidade do sistema; as oscilações de corrente obtidas em experimentos quase estacionários utilizando diferentes valores de resistência externa; e as oscilações de baixa frequência obtidas na ausência de resistência externa presentes em uma ampla faixa de potencial. Estes resultados apresentam aspectos tecnológicos, como a relação direta entre o baixo tempo de redução de óxido e a perda de desempenho de células a combustível por conta de difusão de combustível, e fundamentais, como a emergência de oscilações e a caracterização do sistema como N-NDR, que podem contribuir para um maior entendimento sobre o uso deste combustível. Esses são resultados ainda não explorados na literatura e o presente trabalho propõe o preenchimento desta lacuna. / Despite all attention given to the electro-oxidation of the ion borohydride, for its applicability in fuel cells, few discussions have been made on the kinetical instabilities possibly present on this process. Most researches focuses on the kinetical study of these processes at a low overpotential range, relatively close to the thermodynamic equilibrium. Under far from thermodynamic condition, different mechanisms rule the system and different information can be obtained. The present dissertation aims at a systematic investigation of the complex kinetic associated to the adsorption, oxidation and interaction processes of the borohydride ion over polycrystalline platinum surface. The investigations were realized under far from thermodynamic equilibrium conditions using conventional electrochemical techniques, including: cyclic voltammetry, chronoamperometry, quasi-steady experiments under potentiostac control using different values of external resistance and open circuit transients. Among the results it is possible to highlight: the fast reduction of platinum oxides in open circuit transients (i.e. 0.5s), which is faster than when alcohol or hydrogen is used; two auto-catalytic processes in the open-circuit profile, which can be related to a bistability of the system; current oscillations in quasi-steady experiments using different values of external resistances; and the low frequency oscillations obtained without external resistance under a large potential range. These results show technological aspects, such as the direct relationship of the short time for oxide reduction and the performance loss of a fuel cell by crossover, and fundamental, such as the emergency of oscillations and the characterization of the system as a N-NDR, which can contribute to a better understanding of this fuel. These are yet not explored results in literature and the present research propose filling the gap.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20405号 / 工博第4342号 / 新制||工||1673(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大北 英生, 教授 赤木 和夫, 教授 木村 俊作 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The paper presents the development methodology of a hydrostatic pump/motor for use in Parker Hannifin’s advanced series hydraulic hybrid transmissions for medium and heavy duty commercial vehicles. With Parker’s established bent-axis pump/motor technology for heavy duty mobile applications as a basis, it describes the main stages of further development and qualification for demanding automotive main drive transmissions. Parker’s APQP based, customer focused product development model was employed for this development which resulted in the variable bent-axis pump/motor C24 for open circuit hydrostatic transmissions. Positive customer results from a large fleet of in-service refuse collection trucks and parcel delivery vans with Parker advanced hydraulic hybrid drive systems using C24 pumps/motors serve as evidence of Parker’s product development model effectiveness. High reliability, good fuel economy, increased productivity and long brake life of the vehicles can directly be traced back to the streamlined, front-loaded and iterative development model.

π-Conjugated polymers have attracted considerable attention since they are potential candidates for various opto-electronic devices such as solar cells, light emitting iodes, photodiodes, and transistors. Electronic de vices based on conjugated polymers can be easily processed at low temperature using inexpensive technologies. This leads to cost reduction, a key-deriving factor for choosing conjugated polymers for various types of applications. In particular, polymer based solar cells are of special interest due to the fact that they can play a major role in generating clean and cheap energy in the future. The investigations described in thesis are aimed mainly at understanding charge transport and the role of energy le vels in solar cells based on polymer/acceptor bulk heterojunction (BHJ) active films. Best polymer based solar cells, with efficiency 4 to 5%, rely on polymer/fullerene BHJ active films. These solar cells are in an immature state to be used for energy conversion purposes. In order to enhance their performance, it is quite important to understand the efficiency-limiting factors. Solid films of conjugated polymers compose conjugation segments that are randomly distributed in space and energy. Such distributio n gives rise to the localization of charge carriers and hence broadening of electron density of states. Consequently, electronic wave functions have quite poor overlap resulting into absence of continuous band transport. Charge transport in polymers and organic materials, in general, takes place by hopping among the localized states. This makes a bottleneck to the performance of polymer-based solar cells. In this context, the knowledge of charge transport in the solar cell materials is quite important to develop materials and device architectures that boost the efficiency of such solar cells. Most of the transport studies are based on polyfluorene copolymers and fullerene electron acceptor molecules. Fullerenes are blended with polymers to enhance the dissociation of excited state into free carriers and transport free electrons to the respective electrode. The interaction within the polymer-fullerene complex, therefore, plays a major role in the generation and transport of both electrons and holes. In this thesis, we present and discuss the effect of various polymer/fullerene compositions on hole percolation paths. We mainly focus on hole transport since its mobility is quite small as compared to electron mobility in the fullerenes, leading to creation of spa ce charges within the bulk of the solar cell composite. Changing a polymer band gap may necessitate an appropriate acceptor type in order to fulfill the need for sufficient driving force for dissociation of photogenerated electron-hole pairs. We have observed that different acceptor types give rise to completely different hole mobility in BHJ films. The change of hole transport as a function of acceptor type and concentration is mainly attributed to morphological changes. The effect of the acceptors in connection to hole transport is also discussed. The later is supported by studies of bipolar transport in pure electron acceptor layers. Moreover, the link between charge carrier mobility and photovoltaic parameters has also been studied and presented in this thesis. The efficiency of polymer/fullerene-based solar cells is also significantly limited by its open-circuit voltage (Voc), a parameter that does not obey the metal-insulator-metal principle due to its complicated characteristics. In this thesis, we address the effect of varying polymer oxidation potential on Voc of the polymer/fullerene BHJ based solar cells. Systematic investigations have been performed on solar cells that comprise several polythiophene polymers blended with a fullerene derivative electron acceptor molecule. The Voc of such solar cells was found to have a strong correlation with the oxidation potential of the polymers. The upper limit to Voc of the aforementioned solar cells is thermodynamically limited by the net internal electric filed generated by the difference in energy levels of the two materials in the blend. The cost of polymer-based solar cells can be reduced to a great extent through realization of all-plastic and flexible solar cells. This demands the replacement of the metallic components (electrodes) by highly conducting polymer films. While hole conductor polymers are available, low work function polymer electron conductors are rare. In this thesis, prototype solar cells that utilizes a highly conducting polymer, which has a work function of ~ 4.3 eV, as a cathode are demonstrated. Development of this material may eventually lead to fabrication of large area, flexible and cheap solar cells. The transparent nature of the polymer cathode may also facilitate fabrication of multi-layer and tandem solar cells. In the last chapter of this thesis, we demonstrate generation of red and near infrared polarized light by employing thermally converted thin films of polyfluorene copolymers in light emitting diodes. This study, in particular, aims at fabricating polarized infrared light emitting devices. / On the day of the defence day the status of article III was In press and article VI was Manuscript.

P3HT single layer, P3HT/PCBM bilayer and P3HT/PCBM inverted bilayer devices were produced by spin coating organic layers onto ITO patterned glass in air, and clamping it with an Au coated silicon wafer, as top electrode, at the end (Figure13). Normal and inverted bilayer devices were also fabricated with and without PEDOT:PSS. All devices were divided into two groups by changing concentration of P3HT solution. The first group of devices contained 1.0 wt. % P3HT solution (P3HT in dichlorobenzene); the second group 0.56wt %. Power conversion efficiency, short circuit current, open circuit voltage, fill factor and maximum extracted power were measured on all produced devices. In contrast, all devices with 1.0wt % P3HT concentration showed better result than the devices with 0.56wt %. The highest result was obtained for P3HT single layer devices in both cases with short circuit current 56uA/cm2, open circuit voltage 0.94mV, maximum power 11.4uW/cm2 and power conversion efficiency of 0.11%. Inverted bilayer devices performed better than the non-inverted one. The devices with PEDOT:PSS got slightly better performance than the non-PEDOT:PSS used one. Charge carrier mobility measurement was done for all fabricated devices with charge extraction by linearly increasing voltage (CELIV) and dark injected space charge limited current (DI-SCLC) methods. All devices showed same magnitude of charge carrier mobility 10-5 cm2/V.s, the highest value still belongs to P3HT single layer device. The charge carrier mobility in all devices observed by DI-SCLC technique is one order of magnitude higher than by CELIV technique. This may be due to DI-SCLC method`s restriction on ohmic contacts between material and electrode. / بۇ تەتقىقاتتا ئورگانىك ماتېرىيالدىن پايدىلنىپ ئۈچ خىل قۇياش ئىنىرگىيەلىك باتارىيە ئادەتتىكى ئۆي مۇھىتىدا ياساپ چىقىلدى. ئەڭ چوڭ توك كۈچى، ئەڭ                                                    يۇقىرى بېسىم، ئەڭ يۇقىرى قۇۋەت ۋە زەرەت يۆتكۈلۈش تېزلىكى ئۆلچەپ چىقىلدى ئۇيغۇر

Battery Management System (BMS) is an essential part in battery powered applications where large battery packs are in use. BMS ensures protection, controlling, supervision and accurate state estimation of battery pack to provide efficient energy management. However the particular application determines the accuracy and requirements of BMS where it has to implement; in electric vehicles (EVs) accuracy cannot be compromised. The software part of BMS estimates the states of the battery pack and takes the best possible decision. In EVs one of the key tasks of BMS’s software part is to provide the actual state of charge (SOC), which represents a crucial parameter to be determined, especially in lithium iron phosphate (LiFePO4) batteries, due to the presence of the high hysteresis behavior in the open circuit voltage than other kind of lithium batteries. This hysteresis phenomena appears with two different voltage curves during the charging and discharging process. The value of the voltage that the battery is going to assume during the off-loading operation depends on several factors, such as temperature, loop direction and ageing. In this research work, hybrid method is implemented in which advantages of several methods are achieved by implementing one technique combined with another. In this work SOC is calculated from coulomb counting method and in order to correct the error of SOC, an hysteresis model is developed and used due to presence of hysteresis effect in LiFePO4 batteries. An hysteresis model of the open circuit voltage (OCV) for a LiFePO4 cell is developed and implemented in MATLAB/Simulink© in order to reproduce the voltage response of the battery when no current from the cell is required (no load condition). Then the difference of estimated voltage and measured voltage is taken in order to correct the error of SOC calculated from coulomb counting or current integration method. To develop the hysteresis model which can reproduce the same voltage behavior, lot of experiments have been carried out practically in order to see the hysteresis voltage response and to see that how voltage curve change with the variation of temperature, ageing and loop direction. At the end model is validated with different driving profiles at different ambient temperatures.