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No. of bitstreams: 1 lima_jj_dr_bauru.pdf: 2168304 bytes, checksum: 65aa625d79b7b8de002c02599c5f3983 (MD5) Previous issue date: 2017-09-29 / Manipuladores robóticos leves trazem diversas vantagens quanto ao custo de produção e eficiência na relação carga útil e peso do robô. No entanto a utilização de materiais leves tende a aumentar a flexibilidade estrutural, principalmente na transmissão do torque e nos elos. As propostas de manipuladores apresentadas neste trabalho possuem requisitos conflitantes, pois deseja-se a redução do peso dos mecanismos e aumentar o desempenho, surgem então alguns desafios de engenharia. Desta forma, esta tese trata da modelagem mecânica, análise dinâ- mica e controle híbridos, utilizando atuadores inteligentes, para manipuladores robóticos com características flexíveis. Dois principais modelos de manipuladores robóticos com características flexíveis serão considerados neste trabalho: um para carregamento de carga conectadas a um cabo e outro para manuseio de ferramenta rotativa, ambos com interação não-ideal do elemento manipulado. É possível verificar comportamento caótico ao adicionar a carga aos manipuladores, trazendo assim, maiores desafios a proposta de controle. Na estratégia de controle são considerados como atuadores os motores CC (Corrente Contínua) e atuadores classificados como materiais inteligentes como a Liga de Memória de Forma (LMF), atuando nos elos flexí- veis, e freio Magneto-Reológico (MR-Brake), atuando nas juntas flexíveis. Utilizou-se da rede neural RBFNN para estimativa das variáveis de controle dos atuadores LMF e MR-Brake. O controle DSDRE (Discrete State Dependent Ricatti Equation) é utilizado como a lei de controle. Os resultados numéricos mostram que a adição de atuadores híbridos trazem um ganho considerável no controle de vibração e posicionamento dos manipuladores. / Light-weight robotic manipulators have advantages over the cost of production and efficiency in relation to payload and weight of the robot. However, the use of light-weight materials tends to increase structural flexibility in torque transmission and in the links of the robot. The manipulator proposals presented in this work have conflicting requirements since it is desired to reduce the weight of the mechanisms and increase the performance, it makes some engineering challenges. Thus, this thesis deals with mechanical modeling, dynamic analysis and hybrid control, using intelligent actuators, for robotic manipulators with flexible characteristics. Two models of robotic manipulators with flexible characteristics will be considered in this work: one for payload connected to a cable and another one for rotary tool, both with non-ideal interaction of the manipulated element. It is possible to verify chaotic behavior by adding the load to the manipulators, becoming a great challenger to the proposal control. DC motors and actuators classified as intelligent materials such as the shape memory alloy (SMA), acting on the flexible links, and Magneto-Rheological Brake (MR-Brake), acting on the flexible joints, are used in the strategy control. The neural network RBF was used to estimate the control variables of the SMA and MR-Brake actuators. The DSDRE (Discrete State Dependent Ricatti Equation) control is used as the control law. The numerical results show that the addition of hybrid actuators possibly have a considerable gain in the control of vibration and positioning of the manipulators.

Ziel der vorliegenden Arbeit ist es, das Verhalten polyelektrolytischer Gele und Hydrogelschichtsysteme auf Basis der Kontinuumsmechanik zu modellieren. Die Untersuchung des Materialverhaltens gegenüber externer Stimulation erfolgt anhand numerischer Simulationen, wodurch Einblicke in den komplexen Quellprozess und darin auftretende Phänomene gewährt werden. Die vorgenommene Modellierung und Simulation gestattet dabei eine Optimierung der Systemeigenschaften für den Anwendungsfall. Anwendungsfehler und die Anzahl nötiger Versionen zur Systemgestaltung können hierdurch effektiv verringert werden. Hydrogele stellen wichtige Vertreter aus der Klasse intelligenter Materialien dar, d.h. sie sind in der Lage auf Umwelteinflüsse durch eine reversible Änderung ihrer Materialeigenschaften zu reagieren. Sie bestehen aus einer mit Wasser gefüllten Polymermatrix, in welcher ionische Ladungsträger vorliegen. Dabei sind mobile Ladungsträger im Wasser enthalten. Die Materialeigenschaften von Hydrogelen beruhen auf ihrer chemischen Zusammensetzung und können jeweils spezifisch für ihren Anwendungsfall angepasst werden. So reagieren polyelektrolytische Hydrogele mit einem reversiblen Quell- bzw. Schrumpfungsprozess auf externe elektrische Felder und die Änderung der chemischen Zusammensetzung im umgebenden Lösungsmittelbad. Die reversible Volumenänderung gegenüber externer Stimuli eröffnet Hydrogelen ein breites Anwendungsfeld. Insbesondere sind sie für die Entwicklung neuer Messsysteme relevant, da über klassische Messgrößen hinaus auch sehr spezifische chemische Größen untersucht werden können. Auch eignen sich Hydrogele als aktive Komponenten mikrofluidischer Ventile, welche auf die Zusammensetzung des Fluides reagieren. Da sie keine externe Ansteuerung bzw. Energieversorgung benötigen, sind sie leichter miniaturisierbar als klassische Ventile. Aufgrund ihrer hohen Leistungsdichte sind Hydrogele prinzipiell auch für die Entwicklung leichter und energieeffizienter Aktoren geeignet. Hierbei stellt die von der Größe des Hydrogels abhängige Reaktionszeit bislang jedoch eine Hürde dar, wodurch ihr Einsatz in kleinskaligen Anwendungen wahrscheinlicher ist. Die Kombination mehrerer Schichten aus Hydrogelen ermöglicht hierbei die Anwendung als Biegeaktoren bzw. Messsysteme mit erhöhter Genauigkeit. Da ein fundiertes Wissen über die komplexen Vorgänge im Hydrogel eine große Rolle bei der Weiterentwicklung neuartiger Anwendungen spielt, wird in dieser Arbeit das komplexe Materialverhalten numerisch abgebildet. Hierbei wird insbesondere Wert auf die Interaktion der chemischen, elektrischen sowie der mechanischen Domäne gelegt. Dabei wird a priori angenommen, dass die komplizierte Mikrostruktur des porösen Hydrogels als Kontinuum darstellbar ist und die relevanten Phänomene über Feldgleichungen abgebildet werden können. Es wird eine Einführung über polyelektrolytische Hydrogele und Hydrogelschichtsysteme gegeben, wobei insbesondere auf deren mikrostrukturellen Aufbau und daraus ableitbare Einsatzgebiete eingegangen wird. Mittels eines Überblicks über Modellierungsansätze in der publizierten Literatur werden die hier verwendeten Modellierungsansätze motiviert und in das Umfeld bestehender Vorarbeiten eingeordnet. Nach der Einführung notwendiger Grundlagen der physikalischen Chemie wird die Modellbildung mit der gewählten Kinematik, den Bilanzgleichungen und den Materialgleichungen zur Beschreibung von Hydrogelen und Hydrogelschichtsystemen vorgestellt. Die Bilanzgleichungen umfassen hierbei die Massenerhaltung des Polymers und der ionischen Spezies, die Impuls- und Drehimpulsbilanz sowie die Maxwell-Gleichungen. Nach der Beschreibung geeigneter Materialgleichungen folgt eine Zusammenstellung des gekoppelten chemo-elektro-mechanischen Feldproblems. Zur Lösung des gekoppelten Feldproblems wird die Finite-Elemente-Methode (FEM) genutzt. Die Validierung des erstellten Modells wird anhand eines Quellexperiments von Frijns et al. durchgeführt. Durch den Vergleich mit einem auf der Theorie Poröser Medien (TPM) basierenden Modells kann das hier verwendete Modell abgeglichen werden, wobei eine gute Übereinstimmung zwischen den Ergebnissen beider Modelle herrscht. Basierend auf den Vorarbeiten von Wallmersperger et al. und Attaran et al. wurde das hier genutzte Modell um einen zeitlichen Term in der Beschreibung der Referenzkonzentration erweitert. Hieraus resultiert eine qualitative Verbesserung in der Darstellung des zeitlichen Quellverlaufes bei chemischer Stimulation. In Anlehnung an vorhergehende Arbeiten auf dem Gebiet erfolgt die Kopplung von der mechanischen Domäne zur chemischen Domäne über eine vom Verzerrungszustand abhängige Konzentration gebundener Ladungsträger. Hier durchgeführte Untersuchungen zeigen, dass diese Rückkopplung auch unter der Annahme kleiner Deformationen Relevanz besitzt und nicht vernachlässigt werden sollte. Anders als z.B. mit der TPM oder mit dem Flory-Rehner Modell ist es unter Verwendung des hier entwickelten Modells möglich, Grenzschichtphänomene zwischen Gel und Lösungsmittelbad aufzulösen. Durch die Untersuchung der Grenzschicht zeigt sich eine annähernd lineare Abhängigkeit der Grenzschichtdicke von der relativen Permittivität des Hydrogels. Auch lässt sich ein Zusammenhang zwischen der Konzentration gebundener Ladungsträger und der Grenzschichtdicke identifizieren. Um das Potential der gewählten Methode zu demonstrieren, wird anhand des Beispiels eines einfachen zweischichtigen Hydrogel-Biegebalkens eine Untersuchung über die inneren Vorgänge im Schichtsystem durchgeführt. Die Untersuchung gewährt hierbei Einblicke z.B. in den zeitlichen Verlauf des elektrischen Potentials, der Konzentration mobiler Ionen sowie der resultierenden Verzerrungen. In einem abschließenden numerischen Beispiel wird die Kontaktkraft sowie die auftretenden mechanischen Spannungen in einem Greifersystem, bestehend aus zwei hydrogelbasierten Biegeaktoren, ausgewertet. / Aim of this work is to model the behavior of polyelectrolyte gels and hydrogel-layer systems based on continuum mechanics. For this, numerical simulations are conducted to gain an insight into the complex phenomena occurring during the swelling process of hydrogels. The process of modeling and simulation is important to enhance the understanding of these systems and to improve the properties of hydrogel-based applications. Also, errors resulting from a lack of knowledge as well as from the number of required experimental works can be reduced significantly. Hydrogels belong to the class of smart materials. Therefore, they show a response to changes in their environment by a reversible change of material properties. Polyelectrolyte hydrogels consist of a polymer network with fixed ionic groups. Within the void of the polymer matrix, interstitial water containing mobile ions is present. The properties of hydrogels depend on their chemical composition and can be adjusted for the specified application. They exhibit a reversible swelling or deswelling process when subjected to electric fields or changes of the chemical composition of the surrounding solution bath. This reversible volume change opens a wide field of potential applications. The most promising field of application seems to be in the realms of measurement systems, since hydrogels can be used for the investigation of very specific chemical or biochemical measures. In addition, hydrogels can be used as active components in microfluidic devices, which open and close depending on the chemical composition of the bypassing fluid. Without a need for external control and energy supply, they are suitable for miniaturisation. As a consequence of their high energy density, hydrogels are also relevant candidates for the development of lightweight and energy efficient actuator systems. Due to their size-dependent reaction time, their use in small-scale actuatoric devices is the most promising in this field. the combination of multiple hydrogel layers can be used to increase the sensitivity of hydrogel-based measurement devices. Hydrogel-layer systems can also be used for actuatoric devices, such as gripper devices or microfluidic valves. In the presented model, the interaction between the electrical, chemical and the mechanical fields are respected. It is assumed, that the complex microstructure of hydrogels may be treated as a continuum and that the relevant phenomena can be described using field equations. A brief introduction on polyelectrolyte gels and hydrogel-layer systems is given. Here, their microstructure is described and relevant applications are summarized. By giving a brief literature review, the modeling approaches of this thesis are motivated and arranged within the field of existing models. After an introduction of relevant basics of physical chemistry, the model formulation is presented. Here, the chosen kinematics as well as the used balance equations and material laws are given. They include the conservation of mass for the polymer and the ionic species, the conservation of linear momentum and angular momentum as well as the Maxwell equations. After presenting suitable material laws, the field equations of the fully coupled chemo-electro-mechanical field problem are summarized. The numerical solution of the field problem is obtained by applying the Finite-Element-Method (FEM). The validation of the presented model is conducted by a comparison with experimental results of Frijns et al. After this, the used model is compared with the Theory of Porous Media (TPM), which results in a good agreement of both approaches. Since the used model represents an extension of the preliminary work of Wallmersperger et al. and Attaran et al., differences in the models are discussed. By extending the previous models by an additional temporal term in the description of the reference concentration, a qualitative improvement of the prediction of the time behavior under chemical stimulation is achieved. As done in preliminary works, the mechanical and the chemical domains are coupled by a strain dependent concentration of fixed charges. It can be shown, that this backcoupling is of significance also for small deformations. In contrast to the TPM and the Flory-Rehner model, phenomena occurring in the interface layer between adjacent domains can be investigated using the presented model. An almost linear dependence between the relative permittivity of the hydrogel and the thickness of the boundary layer is observed. It also depends on the concentration of fixed charges in the polymer network. To demonstrate the potential of the applied method, a numerical investigation of a two-layered hydrogel bending actuator is investigated. The results give an insight for example into the time-dependent distribution of the electric potential, the concentration of mobile ions as well as the resulting strains. In another numerical example, the contact force in a gripper consisting of two hydrogel-based bending actuators is evaluated.

The framework of this thesis aims to fabricate materials, which change surface characteristics in response to environmental conditions. This response may be employed to improve material characteristics as adhesion, wettability, interaction with cells etc. The mixed brushes introduce adaptive and switching behavior in different surrounding media. Two main approaches were employed to fabricate mixed polymer brushes: "grafting to" and "grafting from". Mixed PS/PVP polymer brushes were synthesized via step-by-step grafting of these two polymers from polyamide (PA) surfaces. NH3 plasma was used for the introduction of amino and OH functionalities on PA surfaces with following attachment of azo initiator of radical polymerizaton. The mixed brushes prepared on the surface of PA textiles combine both the switching effect and effect of composite surface (i.e. micrometer scale roughness) which substantially amplifies the switching range. Mixed polymer brushes prepared from P(S-b-2VP-b-EO) and P(S-b-4VP) block copolymers were grafted to both the flat surface of Si wafers and to the surface of silica nanoparticles via quaternization reaction of the pyridine nitrogen. This one step grafting technique has a substantial advantage over the multistep grafting of mixed polymer brushes. We have demonstrated that combination of the two level hierarchical organization of polymer films at macroscopic and nanoscopic levels resulted in the formation of self adaptive surfaces switchable in controlled environment from ultra-hydrophobic to hydrophilic energetic states. The PFS/PVP mixed brush was grafted onto the pre-treated PTFE surface (plasma etching) with the needle like topography. The size of vertical needles was at micron scale. If the brush is switched to the hydrophobic state the layer has shown a unique ultra-hydrophobic behavior (complete non-wetting) with the contact angle approaching value of 160o. If the mixed brush was switched into the hydrophilic state the surface became completely wetted due to the capillary forces in the pores formed by the needle like structure. Thus, the surface can be either highly wettable or completely non-wettable with the self cleaning properties.

The framework of this thesis aims to fabricate materials, which change surface characteristics in response to environmental conditions. This response may be employed to improve material characteristics as adhesion, wettability, interaction with cells etc. The mixed brushes introduce adaptive and switching behavior in different surrounding media. Two main approaches were employed to fabricate mixed polymer brushes: "grafting to" and "grafting from". Mixed PS/PVP polymer brushes were synthesized via step-by-step grafting of these two polymers from polyamide (PA) surfaces. NH3 plasma was used for the introduction of amino and OH functionalities on PA surfaces with following attachment of azo initiator of radical polymerizaton. The mixed brushes prepared on the surface of PA textiles combine both the switching effect and effect of composite surface (i.e. micrometer scale roughness) which substantially amplifies the switching range. Mixed polymer brushes prepared from P(S-b-2VP-b-EO) and P(S-b-4VP) block copolymers were grafted to both the flat surface of Si wafers and to the surface of silica nanoparticles via quaternization reaction of the pyridine nitrogen. This one step grafting technique has a substantial advantage over the multistep grafting of mixed polymer brushes. We have demonstrated that combination of the two level hierarchical organization of polymer films at macroscopic and nanoscopic levels resulted in the formation of self adaptive surfaces switchable in controlled environment from ultra-hydrophobic to hydrophilic energetic states. The PFS/PVP mixed brush was grafted onto the pre-treated PTFE surface (plasma etching) with the needle like topography. The size of vertical needles was at micron scale. If the brush is switched to the hydrophobic state the layer has shown a unique ultra-hydrophobic behavior (complete non-wetting) with the contact angle approaching value of 160o. If the mixed brush was switched into the hydrophilic state the surface became completely wetted due to the capillary forces in the pores formed by the needle like structure. Thus, the surface can be either highly wettable or completely non-wettable with the self cleaning properties.

An environment is defined by a set of field values, such as temperature, electro-magnetic field, light intensity, air humidity and air composition. Smart materials, such as hydrogels, are able to react to these kinds of stimuli. The spatial and time development of environmental values is governed by transport equations. Hence the reaction, i.e. actuation or sensing, of the smart material can be described based on the same assumptions. The displacement, here swelling and deswelling, of the material depends on the combination of the environmental parameters. Smart materials are called multi-sensitive, when more than one parameter is purposely used (i) to manipulate the material, i.e. as an actuator or (ii) to measure the quantities, i.e. as a (multi-)sensor. However, the material can also perform (iii) the objective of a logic processing unit in addition to (i) and (ii). In the current work, we present a device that realizes this concept: An automatic window opener that senses environmental parameters (light-level and air temperature) and reacts accordingly. The hydrogel material that is included in the simplistic device simultaneously acts as sensor, logic processing unit and actuator.

<p style="text-align: justify;">U ovom radu sintetisani su hidrogelovi na osnovu akrilamida i akrilne kiseline, radikalnom polimerizacijom, primenom konvencionalne i mikrotalasne metode sinteze. Varirani su početni odnosi monomera i udeo umreživača, u cilju ispitivanja uticaja sastava reakcione sme&scaron;e na svojstva dobijenih hidrogelova. Optimizovani su uslovi sinteze u mikrotalasnom polju kao brže, jednostavnije i ekonomičnije metode. U cilju uspostavljanja korelacije između mehanizma sinteze, strukture i svojstava dobijenih hidrogelova, primenom relevantnih metoda karakterizacije, upoređena su apsorpciona, reolo&scaron;ka, toplotna i strukturna svojstva hidrogelova dobijenih dvema metodama.&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp;&nbsp; Ustanovljeno je da se mikrotalasnom metodom sinteze na brži i jednostavniji način uz smanjen utro&scaron;ak vremena i energije dobijaju hidrogelovi konkurentni onima koji se dobijaju konvencionalnim zagrevanjem u vodenom rastvoru. Drugi deo doktorata obuhvata sintezu hidrofilnih polimernih mreža na osnovu natrijum karboksimetilceluloze (NaCMC) i karboksilnih kiselina, od kojih je jedna serija sintetisana prožimanjem linearnim kopolimerima akrilamida i akrilne kiseline u cilju povećanja potencijala primene u floku-lacione svrhe. Rezultati ispitivanja svojstava bubrenja, strukturnih toplotnih i flokulacionih svojstava pokazali su međusobno slaganje. Dobijeni rezultati pokazali su da od primenjenih karboksilnih kiselina, linunska kiselina u udelu od 15% u odnosu na masu NaCMC daje hidrogelove najboljih svojstava. Kombinacijom ove mreže sa kopolimerom akrilamida i akrilne kiseline u masenom odnosu 10/90, stvara se teorijska platforma za dobijanja flokulanta koji bi mogao da pokaže visoku efikasnost u preči&scaron;ćavanju vode u kojoj dominiraju pozitivno naelektrisane čestice, pravilnim izborom parametara flokulacije.</p> / <p>In this paper, hydrogels based on acrylamide and acrylic acid were synthesized using conventional and microwave synthetic methods via free-radical polymerization. The initial monomers ratio and amount of crosslinking agent were varied in order to investigate the effect of the composition of the reaction mixture on the properties of the obtained hydrogels. The conditions of synthesis in the microwave field as faster simpler and more economical method have been optimized. In order to establish a correlation between the mechanism of synthesis, structure and properties of the obtained hydrogels using the relevant methods of characterization, the absorption, rheological, thermal and structural properties of the hydrogels obtained by the two methods were compared. It has been found that the microwave synthesis is a faster and simpler method, which enables reduced consumption of time and energy and produces hydrogels competitive to those ones obtained by conventional heating in aqueous solution. The second part of the thesis includes the synthesis of hydrophilic polymer networks based on sodium carboxymethylcellulose (NaCMC) and carboxylic acids, whereby one series is synthesized by interpenetration of the network using the linear acrylamide and acrylic acid copolymers in order to increase the potential application of hydrogels for flocculation purposes. The results of measurements of swelling, structural, thermal and flocculation properites have shown mutual agreement. The obtained results have shown that among applied carboxylic acids, citric acid in the amount of 15% per mass of NaCMC, has given the hydrogels with the best properties. The Combination of this network with a copolymer of acrylamide and acrylic acid in a mass ratio of 10/90 has created a theoretical platform for the production of flocculant which could show high efficacy in purifying of water dominated by positively charged particles.</p>