A INFLUÊNCIA DA LIGAÇÃO DE HIDROGÊNIO EM REAÇÕES QUÍMICAS: REAÇÃO DE PRILESCHAJEW

Theoretical analysis at the BHandHLYP/6-311++G(d,p) level of theory with the support of QTAIM calculations was used to reinvestigate the structure of an intermolecular system formed between ethylene oxide (C2H4O) and formic acid (HCO2H) after the epoxidation known as the Prileschajew reaction. Geometric and infrared vibration results revealed that HO2CH forms a strong hydrogen bond with C2H4O followed by a larger red-shift of the H−O bond. NBO analysis was applied to justify this frequency shift. Finally, QTAIM calculations identified the formation of two hydrogen bonds, namely O···H−O and H···O=C.

AVALIAÇÃO DE PROPRIEDADES FÍSICAS E QUÍMICAS DE ELETRODEPÓSITOS DE Ni-W-P OBTIDOS EM CÉLULA DE HULL

Ni–W–P electrodeposits were synthesized in a Hull cell in order to simulate the obtainment under industrial conditions. Complete coverage of panels was accomplished by applying total currents of 1.0 and 2.0 A. Panels obtained with a current of 1.0 A appeared brighter. The best compositional uniformities, as determined by Energy Dispersive Spectrometer (EDS) occurred in the current density ranges of 0.6 to 3.0 A dm−2 and 1.6 to 6.0 A dm−2 obtained with 1.0 and 2.0 A, respectively. However, the best morphological characteristics, as determined by Scanning Electro Microscope (SEM), were observed in those obtained with a total current of 1.0 A. Analysis of corrosion resistance by Electrochemical Impedance Spectroscopy (EIS) and Potentiodynamic Linear Polarization (PLP) in NaCl have shown significant variations in the amount of corrosion potential, polarization resistance, and even total impedance. The alloys exhibited amorphous character (XRD) and crystallized above 400 °C to Ni and Ni3P phases, and possibly Ni–W, with a subsequent increase in hardness. The results suggest that under industrial conditions, current density variations due to the large and complex geometric shapes of substrates lead to formation of distinct alloys. Furthermore, these materials are potential substitutes for chromium deposits in many applications.

COMPARAÇÃO ENTRE FUNCIONAIS DE DENSIDADE NO ESTUDO DE PROPRIEDADES ELETRÔNICAS DE DERIVADOS DA ARTEMISININA

The present paper demonstrates the application of functional GGA hybrids, with long-range corrections, for the calculation of the electronic properties of artemisinin and two of its derivatives - artemether e artesunate. Due to the relatively large amount of data obtained, the statistical method of Principal Component Analysis was employed. The functionals of the WB97 family are observed to be the most appropriate for the determining of reactivity indexes, which are the principal descriptors that, probably, are associated with the antimalarial and anticancer properties of this group of molecules. In addition, it was also observed that all the functionals obtained satisfactorily describe the geometric properties of the studied.

Ultrakevyen rahtialuksen kansiluukkujen sekä luukkujen siirto- ja varastointijärjestelmän suunnittelu hyödyntäen kevytrakennekonsepteja

Tämän työn tarkoituksena oli tutkia miten rahtialuksen kansiluukut voitaisiin valmistaa mahdollisimman kevyiksi. Katettavan ruuman pinta-ala on n. 10 m x 40 m. Luukkujen suuresta jännevälistä johtuen, rakenteelta vaaditaan suurta jäykkyyttä. Erilaisina vaihtoehtoina tutkittiin vaahtomaista alumiinia, alumiinisia kennorakenteita ja polyuretaanisia sandwich-rakenteita. Työssä vertailtiin myös erilaisia geometrisia ratkaisuja, joilla kansiluukkujen jäykkyyttä pyrittiin lisäämään ja sitä kautta pääsemään pienempään materiaalin tarpeeseen. Geometriaa suunniteltaessa huomioitiin myös vaikutukset ruuman tilavuuteen ja lainsäädännön asettamat reunaehdot. Lainsäädännöstä saatiin esimerkiksi turvakaiteiden minimikorkeus, joka vaikuttaa suoraan ruuman tilavuuteen, kun aluksen korkeimmaksi kohdaksi on valittu laivan keskilinja ja tämä korkeus on annettu suunnittelun lähtötietona. Tietokoneavusteisen lujuuslaskennan avulla eri vaihtoehdoista muodostettiin elementtimallit. Malleja varioimalla ja tuloksia vertailemalla saatiin selville kevyin mahdollinen rakenne ja geometria. Malleista saatiin selville myös luukkujen tukireaktiovoimat, eli voimat, jotka luukut kohdistavat aluksen muihin rakenteisiin. Lisäksi työssä mietittiin erilaisia tapoja ruuman avaamiseen ja avaamistavan vaikutusta kansiluukkujen painoon, geometriaan ja ruuman tilavuuteen.

Harustetun 110 kV kannatuspylvään konseptin kehittäminen

Diplomityössä kehitettiin harustetun 110 kV kannatuspylvään konsepti tuotteeksi. Pylväs on säänkestävästä teräksestä valmistettu putkipalkkirakenteinen I-pylväs. Tavoitteena oli suunnitella rakenteesta kokonaistaloudellisesti edullinen. Rakenteen suunnittelussa otettiin huomioon valmistus-, kuljetus- ja varastointi- sekä rakentamisnäkökohtia. Työssä perehdyttiin pylväsrakenteiden yksityiskohtiin, putkipalkkien liitosmenetelmiin ja pylvään jalan nivelöintiratkaisuihin. Säänkestävä rakennemateriaali otettiin huomioon rakennesuunnittelussa. Rakenteen lujuusteknisen suunnittelun apuna käytettiin epälineaarista elementtimenetelmää. Pylväsrakenteen käyttäytyminen mallinnettiin geometrisesti epälineaariseksi, ja liitosdetaljien analysointia varten kehitettiin epälineaarisia materiaalimalleja. Rakenteen värähtelykäyttäytyminen analysoitiin myös elementtimenetelmällä. Lopputuloksena saatiin aikaan pylväs, joka täyttää sille asetetut vaatimukset. Pylväs on helposti valmistettava, kuljetettava ja pystytettävä.

Numerics of Spacecraft Dynamics

Whenever a spacecraft is launched it is essential that the algorithms in the on-board software systems and at ground control are efficient and reliable over extended periods of time. Geometric numerical integrators, and in particular variational integrators, have both these characteristics. In "Numerics of Spacecraft Dynamics" new numerical integrators are presented and analysed in depth. These algorithms have been designed specifically for the dynamics of spacecraft and artificial satellites in Earth orbits. Full analytical solutions to a class of integrable deformations of the two-body problem in classical mechanics are derived, and a systematic method to compute variational integrators to arbitrary order with a computer algebra system is introduced.

Försök til en historisk, geometrisk och physico-oeconomisk beskrifning öfwer Pedersöre sokn i Österbotn : Första delen : Öfwer sjö-staden Jacobsstad : ... under ... Pehr Kalms inseende ... förswarad af Hans Henric Aspegren, österbotninge. Den 1 Julii 1763, för midd. i Åbo Acad. öfre lärosal.

Dedicated to: Pontus de la Gardie, Ephraim Otto Runeberg, Johan Billmark, Carl Joh. Bäckman, Lars Blom, Nathanael Häggström, Matths Nyman, Anders Biring, Anders Winstefn, Petter Teliin, Carl Malm.

Försök til en historisk, geometrisk och physico-oeconomisk beskrifning öfwer Pedersöre sokn i Österbotn : Andra eller Historiska delen ... : Til allmän granskning utgifwen af Hans Henric Aspegren ... förswarad af Gabriel G. Aspegren, österbotninge. Den 19 Martii 1766. på wanlig tid förmidd.

Dedicated to: Pedersöre sokns innebyggare.

Quasiconformal mappings and inequalities involving special functions

This PhD thesis in Mathematics belongs to the field of Geometric Function Theory. The thesis consists of four original papers. The topic studied deals with quasiconformal mappings and their distortion theory in Euclidean n-dimensional spaces. This theory has its roots in the pioneering papers of F. W. Gehring and J. Väisälä published in the early 1960’s and it has been studied by many mathematicians thereafter. In the first paper we refine the known bounds for the so-called Mori constant and also estimate the distortion in the hyperbolic metric. The second paper deals with radial functions which are simple examples of quasiconformal mappings. These radial functions lead us to the study of the so-called p-angular distance which has been studied recently e.g. by L. Maligranda and S. Dragomir. In the third paper we study a class of functions of a real variable studied by P. Lindqvist in an influential paper. This leads one to study parametrized analogues of classical trigonometric and hyperbolic functions which for the parameter value p = 2 coincide with the classical functions. Gaussian hypergeometric functions have an important role in the study of these special functions. Several new inequalities and identities involving p-analogues of these functions are also given. In the fourth paper we study the generalized complete elliptic integrals, modular functions and some related functions. We find the upper and lower bounds of these functions, and those bounds are given in a simple form. This theory has a long history which goes back two centuries and includes names such as A. M. Legendre, C. Jacobi, C. F. Gauss. Modular functions also occur in the study of quasiconformal mappings. Conformal invariants, such as the modulus of a curve family, are often applied in quasiconformal mapping theory. The invariants can be sometimes expressed in terms of special conformal mappings. This fact explains why special functions often occur in this theory.

Algorithmic Solutions for Combinatorial Problems in Resource Management of Manufacturing Environments

This thesis studies the use of heuristic algorithms in a number of combinatorial problems that occur in various resource constrained environments. Such problems occur, for example, in manufacturing, where a restricted number of resources (tools, machines, feeder slots) are needed to perform some operations. Many of these problems turn out to be computationally intractable, and heuristic algorithms are used to provide efficient, yet sub-optimal solutions. The main goal of the present study is to build upon existing methods to create new heuristics that provide improved solutions for some of these problems. All of these problems occur in practice, and one of the motivations of our study was the request for improvements from industrial sources. We approach three different resource constrained problems. The first is the tool switching and loading problem, and occurs especially in the assembly of printed circuit boards. This problem has to be solved when an efficient, yet small primary storage is used to access resources (tools) from a less efficient (but unlimited) secondary storage area. We study various forms of the problem and provide improved heuristics for its solution. Second, the nozzle assignment problem is concerned with selecting a suitable set of vacuum nozzles for the arms of a robotic assembly machine. It turns out that this is a specialized formulation of the MINMAX resource allocation formulation of the apportionment problem and it can be solved efficiently and optimally. We construct an exact algorithm specialized for the nozzle selection and provide a proof of its optimality. Third, the problem of feeder assignment and component tape construction occurs when electronic components are inserted and certain component types cause tape movement delays that can significantly impact the efficiency of printed circuit board assembly. Here, careful selection of component slots in the feeder improves the tape movement speed. We provide a formal proof that this problem is of the same complexity as the turnpike problem (a well studied geometric optimization problem), and provide a heuristic algorithm for this problem.

Optimization of the refining and shoe press in board production

Optimointi on tavallinen toimenpide esimerkiksi prosessin muuttamisen tai uusimisen jälkeen. Optimoinnilla pyritään etsimään vaikkapa tiettyjen laatuominaisuuksien kannalta paras tapa ajaa prosessia tai erinäisiä prosessin osia. Tämän työn tarkoituksena oli investoinnin jälkeen optimoida neljä muuttujaa, erään runkoon menevän massan jauhatus ja määrä, märkäpuristus sekä spray –tärkin määrä, kolmen laatuominaisuuden, palstautumislujuuden, geometrisen taivutusjäykkyyden ja sileyden, suhteen. Työtä varten tehtiin viisi tehdasmittakaavaista koeajoa. Ensimmäisessä koeajossa oli tarkoitus lisätä vettä tai spray –tärkkiä kolmikerroskartongin toiseen kerrosten rajapintaan, toisessa koeajossa muutettiin, jo aiemmin mainitun runkoon menevän massan jauhatusta ja jauhinkombinaatioita. Ensimmäisessä koeajossa tutkittiin palstautumislujuuden, toisessa koeajossa muiden lujuusominaisuuksien kehittymistä. Kolmannessa koeajossa tutkittiin erään runkoon menevän massan jauhatuksen ja määrän sekä kenkäpuristimen viivapaineen muutoksen vaikutusta palstautumislujuuteen, geometriseen taivutusjäykkyyteen sekä sileyteen. Neljännessä koeajossa yritettiin toistaa edellisen koeajon paras piste ja parametreja hieman muuttamalla saada aikaan vieläkin paremmat laatuominaisuudet. Myös tässä kokeessa tutkittiin muuttujien vaikutusta palstautumislujuuteen, geometriseen taivutusjäykkyyteen ja sileyteen. Viimeisen kokeen tarkoituksena oli tutkia samaisen runkoon menevän massan vähentämisen vaikutusta palstautumislujuuteen. Erinäisistä vastoinkäymisistä johtuen, koeajoista saadut tulokset jäivät melko laihoiksi. Kokeista kävi kuitenkin ilmi, että lujuusominaisuudet eivät parantuneet, vaikka jauhatusta jatkettiin. Lujuusominaisuuksien kehittymisen kannalta turha jauhatus pystyttiin siis jättämään pois ja näin säästämään energiaa sekä säästymään pitkälle viedyn jauhatuksen mahdollisesti aiheuttamilta muilta ongelmilta. Vähemmällä jauhatuksella ominaissärmäkuorma saatiin myös pidettyä alle tehtaalla halutun tason. Puuttuvat lujuusominaisuudet täytyy saavuttaa muilla keinoin.

Structural and operational optimisation : applications in energy systems

In this work mathematical programming models for structural and operational optimisation of energy systems are developed and applied to a selection of energy technology problems. The studied cases are taken from industrial processes and from large regional energy distribution systems. The models are based on Mixed Integer Linear Programming (MILP), Mixed Integer Non-Linear Programming (MINLP) and on a hybrid approach of a combination of Non-Linear Programming (NLP) and Genetic Algorithms (GA). The optimisation of the structure and operation of energy systems in urban regions is treated in the work. Firstly, distributed energy systems (DES) with different energy conversion units and annual variations of consumer heating and electricity demands are considered. Secondly, district cooling systems (DCS) with cooling demands for a large number of consumers are studied, with respect to a long term planning perspective regarding to given predictions of the consumer cooling demand development in a region. The work comprises also the development of applications for heat recovery systems (HRS), where paper machine dryer section HRS is taken as an illustrative example. The heat sources in these systems are moist air streams. Models are developed for different types of equipment price functions. The approach is based on partitioning of the overall temperature range of the system into a number of temperature intervals in order to take into account the strong nonlinearities due to condensation in the heat recovery exchangers. The influence of parameter variations on the solutions of heat recovery systems is analysed firstly by varying cost factors and secondly by varying process parameters. Point-optimal solutions by a fixed parameter approach are compared to robust solutions with given parameter variation ranges. In the work enhanced utilisation of excess heat in heat recovery systems with impingement drying, electricity generation with low grade excess heat and the use of absorption heat transformers to elevate a stream temperature above the excess heat temperature are also studied.

Hyperbolic type metrics and distortion of quasiconformal map pings

This Ph.D. thesis consists of four original papers. The papers cover several topics from geometric function theory, more specifically, hyperbolic type metrics, conformal invariants, and the distortion properties of quasiconformal mappings. The first paper deals mostly with the quasihyperbolic metric. The main result gives the optimal bilipschitz constant with respect to the quasihyperbolic metric for the M¨obius self-mappings of the unit ball. A quasiinvariance property, sharp in a local sense, of the quasihyperbolic metric under quasiconformal mappings is also proved. The second paper studies some distortion estimates for the class of quasiconformal self-mappings fixing the boundary values of the unit ball or convex domains. The distortion is measured by the hyperbolic metric or hyperbolic type metrics. The results provide explicit, asymptotically sharp inequalities when the maximal dilatation of quasiconformal mappings tends to 1. These explicit estimates involve special functions which have a crucial role in this study. In the third paper, we investigate the notion of the quasihyperbolic volume and find the growth estimates for the quasihyperbolic volume of balls in a domain in terms of the radius. It turns out that in the case of domains with Ahlfors regular boundaries, the rate of growth depends not merely on the radius but also on the metric structure of the boundary. The topic of the fourth paper is complete elliptic integrals and inequalities. We derive some functional inequalities and elementary estimates for these special functions. As applications, some functional inequalities and the growth of the exterior modulus of a rectangle are studied.

Dynamic optimization for the trajectory planning of robot manipulators in the presence of obstacles

This paper presents an approach to the solution of moving a robot manipulator with minimum cost along a specified geometric path in the presence of obstacles. The main idea is to express obstacle avoidance in terms of the distances between potentially colliding parts. The optimal traveling time and the minimum mechanical energy of the actuators are considered together to build a multiobjective function. A simple numerical example involving a Cartesian manipulator arm with two-degree-of-freedom is described.

Modeling, optimizing and simulating robot calibration with accuracy improvement

This work describes techniques for modeling, optimizing and simulating calibration processes of robots using off-line programming. The identification of geometric parameters of the nominal kinematic model is optimized using techniques of numerical optimization of the mathematical model. The simulation of the actual robot and the measurement system is achieved by introducing random errors representing their physical behavior and its statistical repeatability. An evaluation of the corrected nominal kinematic model brings about a clear perception of the influence of distinct variables involved in the process for a suitable planning, and indicates a considerable accuracy improvement when the optimized model is compared to the non-optimized one.