Smart building's benefits range from improving comfort of occupant, increased productivity, reduction in energy consumption and operating costs, lower CO2 emission, to improved life cycle of utilities, efficient operation of building systems, etc. [65]. Hence, modern building owners are turning towards smart buildings. However, the current smart buildings mostly are not capable of achieving the objectives they are designed for and they can improve a lot better [22]. Therefore, a new technology called, Internet of Things, or IoT, is combined with the smart buildings to improve their performance [23]. IoT is the inter-networking of things embedded with electronics, software, sensors, actuators, and network connectivity to collect and exchange data, and things in this definition is anything and everything around us and even ourselves. Using this technology, e.g. a door can be a thing and can sense how many people have passed it's sensor to enter a space and let the lighting system know to prepare appropriate amount of light, or the HVAC (Heating Ventilation Air Conditioning) system to provide desirable temperature. IoT will provide a lot of useful information that before that accessibility to it was impossible, e.g., condition of water pipes in winter, which helps avoiding damages like frozen or broken pipes. However, despite all the benefits, IoT suffers from being vulnerable to cyber attacks. Examples have been provided later in Chapter 1. In this project among building systems, HVAC system is chosen to be automated with a new control method called MPC (Model Predictive Control). This method is fast, very energy efficient and has a lower than 0.001 rate of error for regulating the space temperature to any temperature that the occupants desire according to the results of this project. Furthermore, a PID (Proportional–Integral–Derivative) controller has been designed for the HVAC system that in the exact same cases MPC shows a much better performance. To design controllers for HVAC system and set the temperature to the desired value a method to automate balancing the heat flow should be found, therefore a thermal model of building should be available that using this model, the amount of heat, flowing in and out of a space in the building disregarding the external weather would be known to estimate. To automate the HVAC system using the programming languages like MATLAB, there is a need to convert the thermal model of the building to a mathematical model. This mathematical model is unique for each building depending on how many floors it has, how wide it is, and what materials have been used to construct the building. This process is needs a lot of effort and time even for buildings with 2 floors and 2 rooms on each floor and at the end the engineer might have done it with error. In this project you will see a software that will do the conversion of thermal model of buildings in any size to their mathematical model automatically, which helps improving the HVAC controllers to set temperature to the value occupants desire and avoid errors and time loss which is put both into calculations and troubleshooting. In addition, a test environment has been designed and constructed as a cyber physical system that allows us to test the IoT- enabled control systems before implementing them on real buildings, observe the performance, and decide if the system is satisfying or not. Also, all cyber threats can be explored and the solutions to those attacks can be evaluated. Even for the systems that are already out there, there is an opportunity to be assessed on this testbed and if there is any vulnerability in case of cyber security, solutions would be evaluated and help the existing systems improve. / Master of Science / Buildings function as shelters more than any thing else, and this has allowed humans to use it as a space to store important things like private and important information. Therefore, this space should be safe and secure from any vulnerabilities for occupants and their information. Smart buildings, have made a great difference in increasing the comfort level of occupants, but they haven’t been greatly successful achieving their objectives [50]. Therefore, a new technology called, Internet of Things, or IoT, is combined with the smart buildings to improve their performance [23]. IoT is the inter-networking of things embedded with electronics, software, sensors, actuators, and network connectivity to collect and exchange data, and things in this definition is anything and everything around us and even ourselves. Internet of Things (IoT) has helped improving the smart buildings and getting a considerable amount of energy efficiency [27]. But adding Internet of Things has added a network of things connected to internet, which gives the cyber hackers an opportunity to hack the buildings, and get access to the information stored inside the building or put even occupants lives in danger. Therefore, in this thesis the following items have been contributed: • Designing and programming a novel control system for HVAC system of the buildings (Model Predictive Control): This is a new method to control HVAC system of buildings and in comparison with the methods available in the market, it is the most energy efficient, it is faster, and it has a lower error rate in following the desired temperature of the occupants. • Design and construction of IoT- enabled smart building testbed: Since cyber attacks make buildings vulnerable, the author believes it is better to build a test environment to simulate the buildings and the control methods that are used inside the buildings, and try to evaluate performance of the control methods before implementing them on real buildings. Also, by installing IoT sensors inside the test environment, the engineers can perform some cyber attack tests, and also evaluate the solutions for each attack on the testbed. • Design and program a software to convert thermal model of buildings to mathematical model : In designing a new control method for HVAC system of buildings, the first required information is the thermal model of the buildings. Eventually, there is a need to program. Thus, the thermal model should be converted to a mathematical model. However, there is a heavy manual calculation behind it that is really overwhelming, tiring, with a high possibility of error, and time-consuming even for a very small sized building. Therefore, automating this process in terms of a software that takes the information of thermal model of buildings as an input and giving the output of the mathematical model of building is a considerable achievement.

Submitted by Charles Yukihiro Watanabe (cyukwat@hotmail.com) on 2018-09-26T11:43:17Z No. of bitstreams: 1 Dissertacao_Charles__Yukihiro_Watanabe_2509_VersãoFinal.pdf: 1687798 bytes, checksum: c719bf7dc9a13db773f981999e12f851 (MD5) / Approved for entry into archive by Maria Lucia Martins Frederico null (mlucia@fca.unesp.br) on 2018-09-26T12:46:36Z (GMT) No. of bitstreams: 1 watanabe_ cy-me_botfca.pdf: 1316993 bytes, checksum: 86e71f789ca976b134a2e7ace9ba7e81 (MD5) / Made available in DSpace on 2018-09-26T12:46:36Z (GMT). No. of bitstreams: 1 watanabe_ cy-me_botfca.pdf: 1316993 bytes, checksum: 86e71f789ca976b134a2e7ace9ba7e81 (MD5) Previous issue date: 2018-07-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Objetivou-se avaliar a influência de porta-enxertos, fontes e doses de potássio na duração dos estádios fenológicos, na produção e nas características físicas e químicas dos cachos e bagas da uva ‘Niagara Rosada’. O experimento foi realizado nos ciclos produtivos de 2016 e 2017 na Faculdade de Ciências Agronômicas - UNESP, no município de Botucatu-SP, situado a 22º 51’ 55” S e 48º 27’ 22” O e a 810 m. O sistema de condução utilizado nas videiras foi a espaldeira baixa no espaçamento de 2,0 x 0,8 m. O delineamento experimental foi de blocos casualizados em esquema fatorial 4 x 2 x 2, sendo quatro doses (0, 75, 150, 300 kg K2O ha1), duas fontes de potássio (cloreto de potássio e sulfato de potássio) e dois porta-enxertos (‘IAC 572’ e ‘IAC 766’). Em cada ciclo de produção, a aplicação dos tratamentos foi parcelada em duas vezes durante o ciclo, sendo a metade da dose aplicada na época da poda e outra no início da maturação dos frutos. As variáveis analisadas durante os ciclos foram a avaliação dos estádios fenológicos, análise de K disponível no solo e diagnose foliar. Na colheita foram avaliadas: produção, produtividade, massa fresca, comprimento e largura dos cachos, massa fresca de bagas e engaços. No mosto da uva foram avaliados o teor de sólidos solúveis (SS), Acidez titulável (AT), relação (SS/AT) e pH. Concluiu-se que, a adubação potássica incrementou os teores de potássio no solo nas camadas de 0-20 e 20-40 cm, e os teores de potássio e cálcio nas folhas na época da floração. A adubação potássica não influenciou a produção, produtividade e as características físicas e químicas dos frutos. / The aim of this study was to evaluate the influence of rootstocks, sources and rates of potassium in the production and physicochemical characteristics of bunches and berries of grape ‘Niagara Rosada’. The experiment was conducted in the productive cycles of 2016 and 2017 at the Experimental Farm of the Faculty of Agricultural Sciences- UNESP, located in Botucatu, SP (22º 51’ 55” S and 48º 27’ 22” O and 810 m). The plants were spaced 2,0 x 0,80 m, in espalier support system low. The experimental design was a randomized complete block design in a 4 x 2 x 2 factorial scheme, with four rates (0, 75, 150, 300 kg K20 ha-1), two potassium sources (potassium chloride and potassium sulfate) and two rootstocks ('IAC 572' and 'IAC 766'). The application of the treatments were divided in two times in the cycle, half of the rate in the season of pruning and another half in the beginning of the maturation of the fruits. During the cycle were evaluated the phenological stages, potassium contents in the soil and nutritional leaf samples. At harvest, were evaluated: production; productivity; fresh weight, length and width of bunches, weight of berries and stems. The must grape was evaluated for soluble solids (SS), titratable acidity (TA), relationship SS/TA and pH. It was concluded that, potassium fertilization increased the potassium contents in the layers of 0-20 and 20-40 cm, and in the potassium contents and leaf compensation at the time of flowering. Potassium fertilization is not influential in production, productivity and physical and chemical characteristics of fruits.

No description available.

<p>Samples of SCR catalysts were impregnated with the following alkali salts; KCl, K2SO4 and ZnCl2 at two different concentrations in a wet impregnation method. The activities of the six samples were measured in a test reactor and at different temperatures between 250-350 ºC. Compared to fresh catalyst, the impregnated samples all had lower activity. It seems like KCl is the most poisoning salt, depending on the lowest value of the activity. The experimental results are expected as compared to earlier articles, which reports that all alkali salts has deactivating effects on a catalyst and that KCl is among the most poisoning ones. By making a cross-section SEM analysis, the penetration of the metals at different depths in to the catalyst material wall was evaluated. An ICP-AES analysis was carried out in order to see the concentration of K and Zn of the test samples. Finally, the pore diameter and active surface was measured by BET method. Since the values of the active surface didn’t change compared to a fresh catalyst and the pore diameter was only slightly decreased we can suppose that the alkali salts deactivates the catalyst by coating of the catalyst pore structure and not as a pore blocking.</p>

Understanding the characteristics of special nuclear materials in LiCl-KCl eutectic salt is extremely important in terms of effective system operation and material accountability for safeguarding pyroprocessing technology. By considering that uranium (U) is the most abundant and important element in the used nuclear fuel, measurements and analyses of U properties were performed in LiCl-KCl eutectic salt. Therefore, the electrochemical techniques such as cyclic voltammetry (CV), open circuit potential (OCP), Tafel, linear polarization (LP), and electrochemical impedance spectroscopy (EIS) were conducted under different experimental conditions to explore the electrochemical, thermodynamic, and kinetic properties of U in LiCl-KCl eutectic. The ultimate goal of this study was to develop proper methodologies for measuring and analyzing the exchange current density (i0) of U3+/U reaction, which has not been fully studied and understood in literature. In the preliminary study, cerium (Ce) was selected as a surrogate material for uranium and its behavior was being explored with the developments of experimental methods. CV was performed to evaluate Ce properties such as the diffusion coefficients (D), apparent standard reduction potential (E0*), Gibbs free energy (DG), and activity coefficient (g). In addition, EIS methods were adapted and specific experimental procedures were established for the proper i0 measurements providing repeatable and reproducible data sets. The i0 values for Ce3+/Ce pair were ranging from 0.0076 A cm-2 to 0.016 A cm-2, depending on the experimental conditions. These preliminary results give insight in developing the experimental setups and methods to evaluate the properties of U in LiCl-KCl. Plus, Ce is one of the lanthanide (Ln) fission products in electrorefiner (ER) system; therefore, the resulting data values yield useful information of the fundamental behaviors of Ln elements in the system. Based on these developed methodologies, the experimental designs and routines were established to explore the main properties (e.g., D, E0*, etc.) of UCl3 in LiCl-KCl eutectic salt under different concentrations (0.5 wt% to 4 wt% UCl3) and temperatures (723 K to 798 K). Specially, the i0 values of U3+/U were evaluated via EIS, LP, Tafel, and CV methods. All i0 values had linear trends with the change of concentration and temperature; however, these values measured by LP, Tafel, and CV methods were greatly influenced by the change in electrode surface area. Overall, the i0 values agreed within 33% relative error range with the EIS method being the most consistent and accurate in comparison to reported literature values. The measured values of i0 were ranging from 0.0054 A cm-2 to 0.102 A cm-2. Therefore, an extremely reliable database for i0 was provided and it is feasible to anticipate the i0 kinetics in other experimental conditions by using the provided equation models. Furthermore, GdCl3 was added to the LiCl-KCl-UCl3 system to explore the effects of other elements on the U properties such as the diffusion coefficients, thermodynamic properties, and i0 kinetics. The diffusion coefficient was generally decreased by 12 ~ 35% with addition of GdCl3 in LiCl-KCl-UCl3; however, the apparent standard potentials and exchange current density follow the same trends with data obtained without GdCl3 additions. Hence, the results indicate that the thermodynamic and kinetic values for U3+/U reaction in LiCl-KCl eutectic salt are not greatly influenced by the presence of GdCl3.

Field trials were conducted in 2016, 2017 and 2018 with dark fire-cured, dark air-cured, and burley tobacco at Princeton, Murray and Lexington Kentucky. Tobacco variety used in 2016 was a low converter (LC) variety, varieties used in 2017 and 2018 were LC and higher converter (HC) varieties. Potassium sources used at all locations and in all years were potassium sulfate (K2SO4) and potassium chloride (KCl). Application rates used at all locations and in all years were 93, 186, 279 kg K ha-1along with an untreated control that received no potassium. In all trials, tobacco that was treated with either potassium source yielded numerically higher than the untreated control. In seven out of 10 trials, LC varieties had a higher moisture content than HC varieties. Tobacco treated with KCl had higher chloride levels than tobacco treated with K2­SO4.Quality grade index was similar for tobacco treated with KCl compared to tobacco treated with K2SO4. In all trials, tobacco treated with KCl had numerically lower Tobacco Specific Nitrosamines (TSNA) levels than tobacco treated with K2SO4. Reductions in TSNA levels were 30% lower in tobacco treated with KCl compared to tobacco treated with K2SO­4.

L'altération des pierres par les sels est un phénomène connu depuis l'antiquité. En revanche, le ou les mécanismes mis en jeu. Ce type d'altération est aujourd'hui considéré comme la principale cause de dégradation des monuments historiques. Actuellement, on attribue la dégradation à la capacité de ces phases minérales à développer une pression de cristallisation. Cette pression pourrait atteindre plusieurs mégapascals et dépasser la résistance mécanique des pierres. Ce concept de pression de cristallisation est né d'études expérimentales réalisées entre la fin de XIXème et le milieu du XXème siècle mais ces notions se concilient difficilement avec les principes de la croissance cristalline tels qu'ils sont connus actuellement. Cette étude a pour but de reproduire les expériences anciennes avec des monocristaux de KCl en contrôlant rigoureusement les paramètres environnementaux. Ce travail montre que, dans les conditions de sursaturation et de croissance, quelque soit la charge imposée, le cristal croit dans les directions non contraintes et adopte à la fin des expériences un faciès trapézoïdal à base tronquée. Ceci est dû à un gradient vertical de concentration et à une répartition non homogène de la contrainte au sein du cristal. Dans la direction de la contrainte le cristal se dissout plus ou moins selon la charge imposée. Cette dissolution n'est pas linéaire et présente deux régimes ; le premier, rapide et non linéaire est fonction de la surface de contact cristal/charge, le second plus lent et quasiment linéaire est fonction de la sursaturation de la solution. En aucun cas, le monocristal de KCl ne développe de pression de cristallisation. Il semble improbable qu'un cristal du type KCl puisse dégrader une pierre en exerçant par pression de cristallisation.

Aquest treball tracta dels diferents comportaments que ha tingut l'aigua subterrània a la vall Salada de Cardona i en el seu aiguabarreig amb el riu Cardener. Aquest riu, ha arribat a ser problemàtic per les seves conseqüències ambientals i de potabilitat en les xarxes públiques de Barcelona i l'àrea metropolitana.La vall Salada és un impressionant aflorament de materials salins en forma de diapir, en el qual hi ha diferents aportacions d'aigua superficial i subterrània. La dissolució dels materials salins per l'aigua dolça és el primer motor que altera la fisonomia de la Muntanya de Sal i també la morfologia de la vall. Tant l'aigua superficial com la interna han provocat esfondraments dels materials superiors a manera de bòfies. En tota aquesta dinàmica de dissolució dels materials salins, hi ha un procés de protecció natural amb la salmorra resultant, que actua sempre que no hi ha un flux exterior prou important per retirar-la. D'aquesta manera, en les zones amb materials salins, propenses a la dissolució per l'aigua, es forma una capa de salmorra a les parts baixes, a manera de cubeta autoprotegida en la base. Els fets més importants pel que fa al comportament de l'aigua subterrània a la vall Salada han estat les entrades d'aigua a la mina. En la darrera i més greu entrada d'aigua a la mina Las Salinas (14 de març de 1998), l'alteració dels materials salins situats sobre la mina es va anar estenent i aprofundint fins a interceptar el sostre de la cavitat subterrània a uns 50 metres de la superfície. Però hi havia un lleuger llindar entre les cubetes d'alteració i la del riu Cardener. Una vegada desprotegit aquest llindar per l'escolament de les salmorres residuals, les aigües dolces dissolen aquesta barrera natural i arriba un moment (a principis de gener del 1999) que les aigües del riu Cardener es desplacen cap a l'interior de la mina seguint el gradient més favorable. Afortunadament, durant els darrers mesos l'Administració s'afanyà a construir un túnel pel riu, de manera que s'anul·là el meandre del Cardener al seu pas pels materials salins de la vall Salada.Posteriorment a la construcció del túnel de derivació del Cardener, i amb el consegüent bombeig cap al col·lector, sembla que s'hagi trobat la solució gairebé definitiva a la salinització de l'aigua del riu. Però el cabal que recull la bomba al fons de la mina, més aviat sembla que augmenta. Es fan hipòtesis d'altres possibilitats de recàrrega a l'aqüífer pels laterals del diapir. S'han fet mesures de georesistivitat elèctrica i es poden obtenir dades de pous als laterals del diapir i dins la llera antiga del riu;això permet demostrar que encara entren cabals similars als que es bombegen a l'interior de la mina. A partir d'aquestes dades es reconstrueix el futur hidrogeològic de la vall Salada. Així doncs, es creuque aquest cabal residual que entra a la vall serà cada vegada més gran, pel fet que l'aigua dolça dissoldrà cada vegada més el llindar dels laterals. Llavors s'esdevindrà un gradient més accentuat, cosa que produirà esfondraments per falta de material als laterals. D'altra banda, si algun dia deixa de funcionar la bomba, el nivell de salmorra de l'interior de la mina pujarà fins al nivell natural de la antiga llera del riu. En aquesta zona es podrà formar per dissolució un llac d'aigua salada. Segurament, a més llarg termini, a escala geològica, la pujadadiapírica dels materials salins més el sobrepès de la salmorra frenaran progressivament l'avenç d'aquest procés i es podrà tornar a tenir unes condicions similars a les que la vall Salada havia tingut.

Samples of SCR catalysts were impregnated with the following alkali salts; KCl, K2SO4 and ZnCl2 at two different concentrations in a wet impregnation method. The activities of the six samples were measured in a test reactor and at different temperatures between 250-350 ºC. Compared to fresh catalyst, the impregnated samples all had lower activity. It seems like KCl is the most poisoning salt, depending on the lowest value of the activity. The experimental results are expected as compared to earlier articles, which reports that all alkali salts has deactivating effects on a catalyst and that KCl is among the most poisoning ones. By making a cross-section SEM analysis, the penetration of the metals at different depths in to the catalyst material wall was evaluated. An ICP-AES analysis was carried out in order to see the concentration of K and Zn of the test samples. Finally, the pore diameter and active surface was measured by BET method. Since the values of the active surface didn’t change compared to a fresh catalyst and the pore diameter was only slightly decreased we can suppose that the alkali salts deactivates the catalyst by coating of the catalyst pore structure and not as a pore blocking.

The aim of this experimental study is to investigate the inhibitive properties of polyglycol and polyglycol+KCl aqueous solutions on hydrate formation, which causes serious fluid flow problems, especially during deepwater drilling operations. As the petroleum industry continues to search oil in deeper and deeper seas, the possibility of facing hydrate problems during drilling operations increases because of the suitable conditions for hydrate formation. The main goal of this study is to investigate the hydrate inhibition capacity (thermodynamic and/or kinetic inhibition) of polyglycol and KCl which are mainly used in drilling fluids for shale inhibition and wellbore stability. A high pressure hydrate forming reactor is used to form and dissociate methane hydrate from aqueous solutions of polyglycol and polyglycol+KCl. In total 10 experiments were carried out, 5 of them with 0%, 1%, 3%, 5% and 7 % by volume of polyglycol solutions (Group-A experiments). The remaining 5 experiments (Group-B) had 8% by weight of KCl in solution in addition to the same polyglycol concentrations of Group-A experiments. Among the two chemicals tested for their hydrate inhibiting potentials, polyglycol did not exhibit any thermodynamic inhibition capacity while KCl was observed to have the ability of hydrate inhibition thermodynamically. On the other hand, increase in polyglycol concentration at constant KCl concentration (Group-B) increases the hydrate formation depression capacity of KCl. Polyglycol inhibits methane hydrate formation kinetically. The higher the polyglycol concentration in aqueous solution, the lower is the initial rate of methane hydrate formation (corresponding to first 15 minutes of hydrate formation). On the other hand, there exists a slower change of methane hydrate formation rate as polyglycol concentration increases.