Gegenstand der Arbeit ist die Erarbeitung und Umsetzung eines reaktiven Aufbereitungsverfahrens im Doppelschneckenextruder zur kontinuierlichen Herstellung von gummimehlbasierten Elastomerlegierungen mit Polypropylenmatrix. Es wird eine Übersicht über den technischen Stand der Polymeraufbereitung in Doppelschneckenmaschinen sowie den Einsatz von Gummimehlen als funktionellem Füllstoff in Thermoplastmatrices gegeben, wobei neben verfahrenstechnischen Aspekten besonders auf die Möglichkeiten der Phasenkompatibilisierung in gummimehlhaltigen Polyolefincompounds zur Herstellung Thermoplastischer Elastomere eingegangen wird. Den Ausgangspunkt für die Verfahrensentwicklung bildet ein reaktiver Schmelzemischprozess in einem Innenmischer, auf dessen Basis die Auswahl der Rezepturkomponenten erfolgte. Gestützt auf eine Modellrezeptur erfolgte in diskontinuierlichen Voruntersuchungen im Labormesskneter eine Anpassung des Werkstoffsystems sowie die experimentelle Verifizierung möglicher Verfahrenskonzepte für die kontinuierliche reaktive Aufbereitung im Doppelschneckenextruder. Für die ausgewählten Verfahrenskonzepte wurden konkrete Extruderaufbauten konzipiert, deren stoff- und prozessgrößenabhängiges Betriebsverhalten auf Basis eines analytischen Prozessmodells abgeschätzt wurde. Nach vergleichenden experimentellen Untersuchungen der kontinuierlichen Verfahrensaufbauten, die auch Verweilzeitmessungen und Rezepturanpassungen einschlossen, wurde eine praxistaugliche Extruderkonfiguration ausgewählt und der Einfluss der technologischen Prozessgrößen auf die Werkstoffeigenschaften der Elastomerlegierungen untersucht. Mit optimierten Prozessparametern erfolgte die kontinuierliche reaktive Aufbereitung von Elastomerlegierungen mit variablen Gummimehlgehalten, deren Werkstoffverhalten umfassend charakterisiert wird / The present thesis deals with the development and implementation of a reactive compounding procedure in a co-rotating twin-screw extruder for the continuous preparation of ground rubber based Elastomeric Alloys with a polypropylene matrix. An overview about the state of the art of polymer compounding in twin-screw devices as well as of the utilisation of rubber powders as functional fillers in thermoplastic matrices is given. Beside process related aspects especially the methods of phase compatibilisation in ground rubber containing polyolefinic compounds for the preparation of Thermoplastic Elastomers are addressed. A reactive melt-mixing procedure in an internal mixer served as the base for the development of the continuous process as well as for the materials and formulations used. Preliminary experiments with a model formulation were carried out in a laboratory batch kneader to adapt the material system onto the requirements of the continuous process as well as to verify and select promising process concepts for the continuous reactive compounding in the twin-screw extruder. The selected concepts were transformed into extruder configurations followed by a simulation of their operating characteristics based on an analytical process model. The performance of the extruder configurations was verified by experiments that included also residence time investigations and further adaption of the formulation. The most suitable extruder setup was chosen for the investigation of the influence of the technological process parameters on the material properties of the Elastomeric Alloy model formulation. Using optimised technological parameters a familiy of Elastomeric Alloys with variable rubber powder content was prepared by continuous reactive compounding in the twin-screw extruder and followed by a comprehensive characterisation of their material performance and properties.

La présente étude a démontré l'effet de certains additifs sur les propriétés de vieillissement des composites élastomères. Dans les travaux actuels des colorants, des pigments à hautes performances et des liquides ioniques conducteurs ont été utilisés comme additifs pour obtenir des composites à base d'élastomère, caractérisés par une meilleure résistance aux intempéries et au vieillissement et avec de bonnes propriétés mécaniques. Les propriétés mécaniques des composites d'éthylène – norbornène, ont confirmé que les colorants avec des substituants fortement donneurs d'électrons, apportent une meilleure et plus efficace protection contre le vieillissement dans le spectre solaire, que la plupart des stabilisants commerciaux utilisés dans la technologie des polymères. La partie suivante de la thèse a porté sur l'impact des liquides ioniques hydrophile et hydrophobe à base d'imidazolium dans les caoutchoucs butadiène-acrylonitrile. L'influence de la nature de l'anion (thiocyanate SCN, bis (trifluorométhylsulfonyl)imide TFSI) et de la longueur de la chaîne alkyle du cation (éthyl, hexyl) des liquides ioniques à base d'imidazolium sur la cinétique de durcissement, sur les propriétés mécanique et morphologique, sur la conductivité ionique et sur la tenue aux intempéries des composites en caoutchouc nitrile a été étudiée. Il a été constaté que l'addition de liquides ioniques hydrophobes à base d'imidazolium – TFSI – en quantité de 2,5 à 5 phr, améliore le plus efficacement les propriétés mécaniques ainsi que la conductivité ionique des matériaux composites NBR et présente un effet positif sur la matrice de caoutchouc pendant l'exposition à l'extérieur / The present study demonstrated the effect of some additives on aging properties of elastomer composites. In the current work solvent dyes, high performance pigments and conductive ionic liquids were employed as additives to obtain elastomer composites, characterized by enhanced weathering aging resistance and good mechanical properties. In the first part of the investigation, selected solvent dyes mainly with anthraquinone chromophores and high performance pigments, which exhibited high light and temperature resistance, were applied in ethylene-norbornene cyclic olefin and acrylonitrile butadiene rubber and then subjected to aging process. The mechanical properties as well as surface analysis of ethylene-norbornene composites, confirmed that solvent dyes, provided better efficient protection against aging in full sun spectrum, than most investigated commercial stabilizers used in polymer technology. Next part of thesis was focused on impact of hydrophilic and hydrophobic imidazolium ionic liquids on acrylonitrile-butadiene rubber. The influence of (thiocyanate, SCN;bis(trifluoromethylsulfonyl)imide, TFSI) anion type and the length of alkyl chain (from ethyl to hexyl) for the cations of imidazolium ionic liquids on the curing kinetic, mechanical, morphological, ionic conductivity and weathering properties of nitrile rubber composites was investigated. It was found, that the addition of hydrophobic TFSI-based imidazolium ILs in quantity 2.5-5 phr, the most effectively improved, mechanical properties and ionic conductivity of the NBR composites and exhibit some positive effect on rubber matrix during outdoor exposure

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Various silicone elastomers have been evaluated for use in the prosthetic reconstruction of facial defects. Their strength, texture, flexibility, hardness, ease of preparation, pigment receptivity and retention, and their resistance to cleaning were compared and the data consulted when an elastomer was chosen to restore defects, improve aesthetics and reestablish the confidence of a selection of patients. Detailed case reports are provided, together with information on the adhesives or mechanical methods available for retaining the facial prosetheses. Cyanoacrylate adhesives for use on skin surfaces and as tissue adhesives have been studied in detail. A novel n-butyl 413 cyanoacrylate has been developed with a viscosity, haemostatic property and stability to make it particularly suitable for use in skin grafting and tissue repair. It has already been used with good results on patients with severe burns. An improved formulation, containing a fluorescent dye, can be precisely applied through a specially constructed foot-controlled dispenser illuminated by a fibre-optic supplying UV-light. Cyanoacrylates are already being used as tissue adhesives in place of the conventional but potentially disfiguring suture. The availability of improved, imperceptible adhesives and a precision applicator, which can be used in a modern operating theatre, will extend their effectiveness and satisfy some of the needs of Plastic, and Oral and Maxillo-Facial Surgeons. Portable applicators have potential use in battlefield and in veterinary surgery and overcome the imprecision characteristic of earlier methods. / Loctite UK

Silicone polymers and network-materials have proven extremely useful in a variety of applications owing to their superb properties when compared to carbon-based polymers. Polysiloxanes containing functional groups other than simple alkyl moieties have allowed for further manipulations of pendant groups along the polymer backbone leading to a greater range of possible chemical transformations, as well as changes in physical/interfacial properties. One aspect of functional polymers that has yet to be explored with respect to primarily silicone-based systems is that of stimuli-responsive materials. In order for this unique application to work, silicones must be functionalized with a group or groups that can influence the polymer’s properties based on that group’s response to specific external stimuli. Boronic acids represent one such group, wherein the most common stimuli used to affect changes in ionization state and solubility are pH and diol-binding. Boronic acids are also capable of forming weak hydrogen-bonded dimers with other boronic acids, and dynamic covalent bonds with Lewis bases. It is proposed that the covalent attachment of boronic acids and their derivatives onto silicones could lead to stimuli-responsive silicone materials. Herein, the synthesis of silicone-boronic acids and their protected boronic esters is described. The simple two-step method involving boronic acid protection followed by hydrosilylation has led to a variety of molecules differing in molecular weight and three-dimensional geometry through the use of commercially available hydride-functional silicones. Initial results regarding saccharide binding selectivity and the impacts on silicone solubility are provided. The unique interfacial behaviour of silicone-boronic esters and their propensity to form self-assembled, crosslinked films at an air/water interface are also reported. Using several different diol protecting groups and a variety of aqueous sub-phases, the mechanism for changes in physical properties as well as crosslinking were revealed. Finally, the production of new thermoplastic silicone elastomers from silicone-boronic esters and amine-containing molecules is discussed. The Lewis acid/Lewis base complexation that occurs between nitrogen and boron can provide enough strength to produce robust, yet recyclable, silicone elastomers without the use of catalyst or solvent. Elastomers can be easily dissolved and reformed through the introduction and removal of a mono-functional Lewis base. The impact of crosslink density, controlled by the quantities and molecular weights of each polymer component used, on physical characteristics is reported. / Thesis / Doctor of Philosophy (PhD)

3D printing technology, which has its origins in rapid prototyping, is increasingly used to build functional devices. Although 3D printing technology has been well developed for thermoplastic polymers and metals, it is still in the research phase for soft polymeric materials such as silicones. Silicones are an industrially vital polymer characterized by a broad spectrum of chemical and physical properties for several smart applications, including on skin printing, smart sensors, multigradient material, and soft actuators. Extrusion-based multimaterial printing is one of the 3D printing techniques that have been adapted due to its compatibility to process silicone-based materials for constructing various functional devices. However, there are several challenges such as achieving on the fly mixing at low Reynolds numbers regime, achieving fast switching while using Newtonian/non-Newtonian inks, and achieving multimaterial printing on nonplanar surfaces. The development of suitable and robust printheads that are able to tackle those challenges can expand the application of this technology to a wide range of fields. In this thesis, several deposition-controlled printhead designs have been created for 3D printing multifunctional devices using an understanding of microfluidics. The established printhead can be controlled to formulate different multigradient structures through on the fly mixing during the material printing. Moreover, the developed printhead can be adapted to print multi viscous inks with high switching rates up to 50 Hz. Through the developed system, the printhead was able to track topologies in real-time, allowing objects to be printed over complex substrates. These new capabilities were applied to fabricate functional structures in order to demonstrate the potential of the developed printhead approaches that can be used in various applications, including smart sensors, soft robotics and multigradient objects. / Thesis / Doctor of Philosophy (PhD) / 3D printing techniques, such as extrusion-based multimaterial printing, have recently been utilized to process silicones due to their versatility in different smart applications, including multigradient material and soft actuators. Although it represents significant progress, there are still several challenges, including the proper mixing during printing with a laminar flow regime, the fast switching between different inks, and the printing over complex topographies. Therefore, various printhead designs have been developed in this thesis to tackle these challenges. In particular, a mixer printhead has been designed to allow mixing during printing for building multigradient objects. Also, a scalable printhead has been developed to allow fast switching for creating pixelated structures. Finally, a simple mechanical system has achieved multimaterial printing over various nonplanar surfaces. To the best of the author's knowledge, the developed printheads can be used in many fields, such as soft robotics and smart devices.

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The paper reports on a composite based on a polydimethylsiloxane matrix filled with liquid metal and magnetic hard microparticles. The effect of the concentration of such a complex filler on the elasticity and relative permittivity of the composite has been investigated. Inclusions of liquid metal provide improved permittivity compared to the unfilled matrix, while the stiffening effect is not as high as when the matrix is filled with solid particles alone. On the other hand, magnetic hard fillers allow the functionalisation of the composite in terms of its magnetic properties. It is also shown that changing the residual magnetisation of the composite has no significant effect on the elasticity and relative permittivity.