This master's thesis deals with proposals for solutions to increase the stiffness of the slide for CNC horizontal boring standing in order to optimize the design of the slide. Selected problem was solved by sensitivity analysis using desegin of experiment in conditions of linear regression analysis. Data for the sensitivity analysis were obtained by using computational modeling using finite element method. The solution provides a view of the degree of influence on the deformation of the examined elements of the slide. Based on these results were selected elements with the greatest influence and created three ideological designs for improvement. Of these designs, was chose an optimal variant by PATTERN method acoording on the technical, economic and technical-economic aspect. This work offers a new look for the innovating the design to increase rigidity.

Augmenting/reducing of the evoked potential has been shown to be related to sensation seeking (SS) and specific clinical disorders. Buchsbaum demonstrated that patients with bipolar affective disorders (BAD) tend to be augmenters, as is the case with sensation seekers, and patients with unipolar affective disorders (UPD) tend to be reducers. In addition, he reported that prophylactic medication reduced the tendency to augment in bipolar patients. However, evidence for these relations is restricted to a few studies. This study explores whether Buchsbaum’s initial findings can be found in a naturalistic clinical setting. Acoustic evoked potentials were recorded for six levels of intensity (59, 71, 79, 88, 92, 96 dB SPL) from 24 healthy adults, 21 unipolar depressed patients, and 21 patients with BAD. Participants also completed personality questionnaires, especially the Sensation Seeking Scales Form V. Results revealed a positive correlation between SS and augmenting/reducing in healthy controls, thereby replicating earlier findings. Bipolar depressed patients showed larger P1/N1 slopes than healthy controls, when medication was statistically controlled. Unipolar depressed patients showed smaller P2 slopes, but only when medication was not controlled. Implications of these results for further research on augmenting/reducing and affective disorders and their relationship to SS are discussed. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

South Africa is a water scarce country. The expansion of the industrial, mining, and agricultural sectors to meet the needs of South Africa’s growing population requires more water. There is therefore an urgent need to develop effective wastewater treatment processes in order to recover and reuse water. This dissertation presents the treatment of an acidic wastewater stream from a platinum refinery which at present is being disposed of by contract with a waste disposal company. The major concern in treating the acid effluent stream is the high concentration of sodium ions (18 200 mg/l) and chloride ions (104 900 mg/l). The precipitation process is used to treat wastewater, but ultimately it generates more secondary waste as a sludge. The other process that is used to treat wastewater is reverse osmosis (RO). RO is usually preferred in the last stage of the treatment because the process is more expensive as membranes need to be replaced regularly. The approach used in this research focuses on evaporating liquid, consequently concentrating the remaining solution until the ions in the solution crystallize. The liquid produced is recycled back into the platinum plant for reuse, and the remaining salt crystals are collected as the useful product. The proposed water treatment process produces dilute hydrochloric acid as the condensate and a crystallized sodium chloride rich residue. The refinery is currently disposing of around 20 000 l/day of wastewater to landfills. The proposed treatment process can recover half of the volume of the wastewater stream to the refinery, helping reduce the fresh water consumption of the process by 10 000 l/day. Furthermore, this will reduce the volume of wastewater going to disposal by a half, namely only 10 000 l/day will need to be disposed of. The amount of Cl that can be recovered is variable and depends on the quantity of chloride in the wastewater. In the two samples processed the recovery was between a 2,5 w% and 10,7 wt% aqueous HCl solution. This corresponds to a saving of between 250 to 1000 kg/day of HCl. As the concentration of the recovered solution is variable, the recycling process would need to monitor the composition of the recycled stream and make up the acid concentration to some fixed value for reuse in the prices. The production of a dilute hydrochloric acid stream should be particularly attractive to the platinum refinery as the operation of the refinery requires hydrochloric acid as a feed. Thus, by recycling the wastewater, the refinery would reduce the volume of wastewater to be disposed of thereby reducing the cost of disposal of the waste while simultaneously reducing the cost of buying fresh hydrochloric acid. The proposed recovery of liquid and recycling it back to the refinery, will also reduce the environmental impact of the refinery, and very importantly in a water scarce country, reduce the freshwater consumption of the process. / Physics / M. Sc. (Physics)

Volume changes are one of the priority characteristics of concrete that plays an important role place mainly in the durability of structures as such. These low volume changes are required especially for structures as: industrial concrete floors, massive structures and waterproof structures. One of the possibilities in reducing these changes is the use of mineral admixtures with suitable grain curve of aggregate. Another possibility is the use of shrinkage reducing admixtures. There can occur problem with efficiency (long term age) with other components of the mixture. Therefore, the effort of this work is to use the avaible processes for maximum reduction of shrinkage and hydration temperatures.

V současné době se problematika energetických úspor dostává do popředí zájmu jak na úrovni jednotlivých podniků, tak i na úrovni celého státu. Často bývá příčinou sporů ve vědeckých kruzích i mezi odborníky z praxe. Lidstvo tradičně začalo využívat energii z minerálních přírodních zdrojů, které však ve srovnání s obnovitelnými zdroji energie mají omezení. Výzkum a implementace moderních technologií jsou ztíženy otázkou investic a časově omezeny. Proto se evropská strategie energetické bezpečnosti zaměřuje na energetickou účinnost, která je jedním z nejefektivnějších způsobů zlepšení bezpečnosti spotřeby energie. Velké společnosti a podniky jsou jedním z hlavních spotřebitelů energie. Proto je tato vědecká práce zaměřena na problematiku úspor energie a zlepšování energetické účinnosti podniku. Těžiště práce spočívá ve vytvoření a zavedení metodiky pro úsporu energie a managementu hospodaření s energií ve výrobním procesu automobilového podniku. Dále je pro účely této práce vytvořen a popsán způsob vizualizace spotřeby energie v prostředí virtuální reality

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Les dérivés cyclopropanoïques sont des composés importants dans plusieurs domaines tels que la synthèse organique, la chimie médicinale et la science des matériaux. La synthèse asymétrique des dérivés cyclopropanoïques s'est de plus en plus concentrée sur la synthèse stéréocontrolée de cyclopropanes polysubstitutés qui arborent toute une gamme de substituants distincts. Ces méthodes permettent d’accéder à des synthèses divergentes pour préparer des composés pharmaceutiques comportant cette sous-unité. De plus, l'ouverture facile de ce cycle très tendu en fait une bonne cible pour étudier l'activation de la liaison C‒C. C’est pourquoi les cyclopropanes sont parmi les composés les plus attrayants et les plus diversifiés en synthèse organique. La synthèse divergente de dérivés cyclopropanoïques repose sur l'utilisation de précurseurs stables mais réactifs. L'une des réactions pour former des liaisons C‒C les plus couramment utilisées dans la fonctionnalisation à un stade avancé, est la réaction de couplage croisé de Suzuki-Miyaura. C'est l'une des raisons pour lesquelles les borocyclopropanes sont devenus des précurseurs synthétiques attrayants pour la fonctionnalisation et diversification des molécules complexes. L’accès à de telles molécules faciliterait la préparation de molécules cyclopropanoïques de structures diversifiées. Il est difficile de préparer des borocyclopropanes de manière énantiosélective. Dans cette thèse, une cyclopropanation énantiosélective d'acides boroniques protégés dérivés d'alcools allyliques a été réalisée via la réaction de cyclopropanation asymétrique en présence du ligand chiral de type dioxaborolane. Le développement de cette méthodologie a nécessité une modification de la décomplexation oxydative existante du dioxaborolane via son complexe dérivé de la diéthanolamine. Le protocole est maintenant applicable aux dérivés boronates qui incluent des groupements fonctionnels qui sont incompatibles avec les bases. Les borocyclopropanes tétracoordonnés obtenus permettent également la formation de liaisons C‒C et ont démontré une stabilité améliorée par rapport à leurs dérivés tricoordonnés. Une étude plus approfondie sur des complexes cyclopropylméthylamine-boranes (CAB) a démontré que ces derniers pouvaient conduire aux amine-boranes spirocycliques (SCAB). Ces SCAB ont été obtenus grâce à une cascade d'activation des CABs en utilisant le bis(trifluorométhanesulfonimide) (Tf2NH) comme initiateur. L'ouverture du cycle des CAB représente la première conversion des cyclopropanes en spirocycles contenant à la fois un N-spirocentre et un spiro amine-borane. Les amine-boranes ont démontré une activité pharmacologique telle que des propriétés anticancéreuses, anti-inflammatoires et anti-ostéoporotiques. L'incorporation de spirocycles dans un motif augmente le caractère sp3 et la chiralité inhérente. Les SCAB rendent alors des candidats attrayants pour la conception de médicaments. La réaction de SCAB avec de Tf2NH en quantités stoechiométriques a donné un complexe SCAB•NTf2 qui est capable de réduire les fonctions cétone, aldéhyde, imine, nitrobenzène, nitrosobenzène, anthracène, indole et aryl méthyl éther. Le complexe SCAB•NTf2 est également capable de réduire le diphénylacétylène de manière Z-sélective en cis-stilbène. Des études spectroscopiques approfondies ont donné plus d'informations sur la structure de SCAB•NTf2 et nous ont permis de proposer un mécanisme de réduction des groupements fonctionnels ci-dessus. Les études spectroscopiques (RMN, IR et Raman) ont également révélé l'implication d'une liaison α-C‒H au bore dans une liaison hydrogène hypsochromique « improper hydrogen bond » avec [Tf2N]-. L'hyperconjugaison avec l’atome de bore, un acide de Lewis, est proposée, ce qui rend la liaison C‒H acide et donc suffisamment polarisée pour agir comme un donneur de pont hydrogène. / Cyclopropane derivatives are incredibly versatile building blocks used in organic synthesis, medicinal chemistry, and materials science. The asymmetric synthesis of cyclopropane derivatives has increasingly focused on achieving polysubstituted cyclopropanes with a range of distinct substituents and their use in divergent syntheses to access pharmaceutical compounds. Moreover, the ring-opening potential of the cyclopropane ring, due to its inherent strain, makes it a facile target for C‒C bond activation and one of the most attractive and diverse cycloalkanes in organic synthesis. Divergent synthesis of cyclopropanes relies on stable pre-installed handles on cyclopropanes that can be activated readily. One of the most common C‒C bond formation approaches used in late-stage functionalization is the Suzuki-Miyaura cross-coupling reaction. As a result, borocyclopropanes have become attractive synthetic building blocks for their use in late-stage functionalization. Methods for the enantioselective synthesis of borocyclopropanes are scarce. In this thesis, the first enantioselective cyclopropanation of an allylic alcohol bearing a tetracoordinate boronate has been achieved via the Charette dioxaborolane-mediated enantioselective cyclopropanation reaction. The development of our method required modification of the existing oxidative decomplexation of dioxaborolane via diethanolamine. The protocol has now been expanded to include boronates and base-sensitive functionalities. The tetracoordinate borocyclopropane obtained was also shown to undergo C‒C bond formation and demonstrated enhanced stability compared to its tricoordinate boronate derivative. Further investigation of boron tethered cyclopropanes led to the discovery of the unique transformation of cyclopropane amine-boranes (CABs) to spirocyclic amine-boranes (SCABs). SCABs were obtained through a cascade activation of CAB via bis(trifluoromethane)sulfonimide (Tf2NH). The ring-opening of CABs represents the first conversion of cyclopropanes to spirocycles containing an N-spirocenter and furthermore an amine-borane spirocore. Amine-boranes have shown pharmacological activity such as anti-cancer, anti-inflammatory, and anti-osteoporotic properties. Incorporating spirocycles into a motif increases sp3 character and inherent chirality, rendering SCABs as attractive candidates for drug design. The reaction of SCAB with stoichiometric amounts of Tf2NH resulted in a SCAB•NTf2 complex that was found to be able to reduce ketone, aldehyde, imine, nitrobenzene, nitrosobenzene, anthracene, and indole functionalities as well as demethylate aryl methyl ethers. The SCAB•NTf2 complex was also capable of reducing diphenylacetylene in a Z-selective manner to cis-stilbene. In-depth spectroscopic studies revealed the structure of SCAB•NTf2 and a mechanism for the reduction of the above functionalities is proposed. The spectroscopic studies (NMR, IR and Raman) revealed the involvement of an α-C‒H bond to boron in improper hydrogen bonding with [Tf2N]-. Hyperconjugation to the Lewis acidic boron is proposed to make the C‒H bond acidic and therefore polarized enough to act as a hydrogen bond donor.

The use of waste (or recycled) wood as a fuel in heat and power stations is becoming more widespread in Sweden (and Europe), because it is CO2 neutral with a lower cost than forest fuel. However, it is a heterogeneous fuel with a high amount of chlorine, alkali and heavy metals which causes more corrosion than fossil fuels or forest fuel. A part of the boiler which is subjected to a high corrosion risk is the furnace wall (or waterwall) which is formed of tubes welded together. Waterwalls are made of ferritic low-alloyed steels, due to their low price, low stress corrosion cracking risk, high heat transfer properties and low thermal expansion. However, ferritic low alloy steels corrode quickly when burning waste wood in a low NOx environment (i.e. an environment with low oxygen levels to limit the formation of NOx). Apart from pure oxidation two important forms of corrosion mechanisms are thought to occur in waste environments: chlorine corrosion and alkali corrosion. Although there is a great interest from plant owners to reduce the costs associated with furnace wall corrosion very little has been reported on wall corrosion in biomass boilers. Also corrosion mechanisms on furnace walls are usually investigated in laboratories, where interpretation of the results is easier. In power plants the interpretation is more complicated. Difficulties in the study of corrosion mechanisms are caused by several factors such as deposit composition, flue gas flow, boiler design, combustion characteristics and flue gas composition. Therefore, the corrosion varies from plant to plant and the laboratory experiments should be complemented with field tests. The present project may thus contribute to fill the power plant corrosion research gap. In this work, different kinds of samples (wall deposits, test panel tubes and corrosion probes) from Vattenfall’s Heat and Power plant in Nyköping were analysed. Coated and uncoated samples with different alloys and different times of exposure were studied by scanning electron microscopy (SEM), energy dispersive x-ray analysis (EDX), X-ray diffraction (XRD) and light optical microscopy (LOM). The corrosive environment was also simulated by Thermo-Calc software. The results showed that a nickel alloy coating can dramatically reduce the corrosion rate. The corrosion rate of the low alloy steel tubes, steel 16Mo3, was linear and the oxide scale non-protective, but the corrosion rate of the nickel-based alloy was probably parabolic and the oxide much more protective. The nickel alloy and stainless steels showed good corrosion protection behavior in the boiler. This indicates that stainless steels could be a good (and less expensive) alternative to nickel-based alloys for protecting furnace walls. The nickel alloy coated tubes (and probe samples) were attacked by a potassium-lead combination leading to the formation of non-protective potassium lead chromate. The low alloy steel tubes corroded by chloride attack. Stainless steels were attacked by a combination of chlorides and potassium-lead. The Thermo-Calc modelling showed chlorine gas exists at extremely low levels (less than 0.1 ppm) at the tube surface; instead the hydrated form is thermodynamically favoured, i.e. gaseous hydrogen chloride. Consequently chlorine can attack low alloy steels by gaseous hydrogen chloride rather than chlorine gas as previously proposed. This is a smaller molecule than chlorine which could easily diffuse through a defect oxide of the type formed on the steel. / <p>QC 20130423</p>

Объектами исследования являются 2-замещеные хиноксалины. Целью данной работы является изучение химических свойств хиноксалина и его производных. В работе рассматривалось восстановление производных хиноксалина (окислительно-восстановительные свойства, потенциал восстановления, ЭПР спектр, квантово-химический расчеты). Сравнение восстановительных свойств синтезированного ряда производных хиноксалина. Определено количество электронов, участвующих в процессе восстановления производных хиноксалина. Смоделирован процесс восстановления. Доказан одноэлектронный переход хиноксалина. Далее приводится количественное определение производных хиноксалина вольтамперометрическим способом. Изучение свойств хиноксалина является важной задачей, так как вновь синтезированные производные хиноксалинов проявляют химическую и биологическую активность. Из-за значительного увеличения вирусов и необходимости поиска новых лекарственных препаратов, исследование производных хиноксалинов и их химической активности, а также количественное определение новых синтезированных хиноксалинов является нужной и важной задачей. В работе доказан одноэлектронный переход хиноксалина экспериментальными и расчетными методами (ЭПР спектр, квантово-химический расчеты, хроноамперометрия). Также был построен ряд восстановительной активности хиноксалина и его производных. После чего были выбраны производные для количественного определения вольтамперометрическим методом. Результаты показали, что одноэлектронный переход хиноксалина свойственен и для его производныхРазработаны методики количественного определения формальдегида в объектах фармации на примере ЛП «Эндофальк» и товарного уротропина от ПАО «Метафракс». Правильность полученных результатов подтверждена сравнением с результатами независимых методов анализа, прописанных в ФС РФ XIV издания на субстанции уротропина и «Макрогола 3350». / The object of research is 2-substituted quinoxalines. The goal of this work is to study the chemical properties of quinoxaline and its derivatives. This goal is divided into the following tasks: 1) Study of literature sources on the use of quinoxaline derivatives, chemical and electrochemical properties of these compounds, possible published methods for quantitative determination of quinoxaline derivatives by voltammetric method. 2) Study of reducing properties of compounds of quinoxalin derivatives (redox properties, reduction potential, EPR spectrum, quantum chemical calculations). Comparison of reducing properties of a synthesized series of quinoxaline derivatives. 3) Determination of the number of electrons involved in the reduction of quinoxaline derivatives. Modeling the reduction process. Proof of a single-electron quinoxalin transition. 4) Quantitative determination of quinoxalin derivatives by voltammetric methods.

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