This PhD project investigated the ramifications of air-cured and nitrogen-cured manufacturing processes during silicone hydrogel contact lens manufacture in terms of lens surface characterisation and clinical performance. A one-hour contralateral clinical study was conducted for ten subjects to compare the clinical performance of the two study lenses. The main clinical findings were reduced levels of subjective performance, reduced surface wettability and increased deposition. Contact angle analysis showed the air-cured lenses had consistently higher advancing and receding contact angle measurements, in comparison with the nitrogen-cured lens. Chemical analysis of the study lens surfaces in the dehydrated state, by x-ray photoelectron spectroscopy (XPS) and time-of-flight mass spectrometry (ToF-SIMS), showed no difference due to surface segregation of the silicone components. Analysis of frozen lenses limited surface segregation and showed a higher concentration of silicone polymer components and lower concentration of hydrophilic polymer components at the surface of the air-cured lens, in comparison with the nitrogen-cured lens. Scanning electron microscope (SEM) imaging showed the nitrogen-cured lens to have a surface typical of a hydrogel material, whereas the air-cured lens had regions of apparent phase separation. In addition, atomic force microscopy (AFM) showed the air-cured lens to have a rougher surface associated with greater adherence of contaminants (often observed in materials with reduced polymer cross-linking). In conclusion, clinical assessment of the study lenses confirmed the inferior performance of the air-cured lens. Surface analysis suggested that the non-wetting regions on the air-cured lenses were associated with elevated level of silicone components, reduced polymer cross-linking and polymer phase separation.

The aim of this thesis is to design crankshaft for in-line six-cylinder diesel engine and to design viscous torsional vibration damper for the cranktrain of specified parameters. The thesis includes the creation of a dynamic torsional model of cranktrain and calculation of forced vibrations of mechanism with and without damper. Part of this thesis is also strength analysis of the designed crankshaft with damper using the Finite Element Method (FEM).

The main idea of this thesis is measurements of dielectric materials by using a device Tettex. The thesis is about basic physic properties of dielectric materials. The determination of a dielectric material is considered. The behavior of these materials in electrical fields and reasons, those can have an influence on it, are considered as well. In the text are described measuring methods of chosen parameters of dielectric materials by device Tettex and its functional principles. There are an evaluation of measurements, which were done, and a discussion about achieved results.

This work deals with the classification and diagnosis of electrical insulating liquids. Furthermore, the theoretical part describes the mathematical and physical principles of these liquids. The automated workplace was compiled with development environment VEE Pro for measurement of viskosity and control thermostat medingen and modifiable components for measuring complex permittivity in the frequency range. In the experimental part was carried out measurements of selected material parameters, investigated the effect of difficult conditions and made the mathematical evaluation of physical phenomena.

This thesis "Silicone damper of a six-cylinder in-line diesel engine " is focused on the proposal of alternative using of silicone damper for the a six-cylinder in-line diesel engine, which is made for tractors and other industrial aplications. The aim of this thesis is to count the oscilation of crankshaft by the help of appropriate dynamic model, then to propose such a basic parameters of silicone damper, which absorbes torsion blip crankshaft to acceptable value. The next part of my thesis is proposal of the constructive implementation of fixation the silicone damper on the free part of crankshaft. The last part of my thesis is comparing and evaluating the oscilation of crankshaft without a dumper and with a new propsal of the silicone damper.

Corrosion protection is very significant for metals in modern society from the view of industrial development. This thesis work project involves a research study that is aimed to investigate the effect of corrosion on the mechanical strength and magnetic properties of four no treated or treated Somaloy® component samples (Somaloy®700 1P,  Somaloy®700 3P, Somaloy®700HR 5P and Somaloy®110i 5P) provided by Höganäs AB and laminated steel sheets by salt spray test. The coatings for protection are phosphoric acid coating, sodium silicate coating, DCA-Modified silicone conformal coating and water-borne single coat paint respectively. Then the protective properties are evaluated by Electrochemical Impedance Spectroscopy (EIS) in 0.1 mol/L NaCl solution after 7 days exposure.   From transverse rupture strength (TRS) and hysteresis loop measurements by salt spray test, although the bar samples are treated coating, the corrosion decreases the mechanical strength to a certain extent more or less over time. For the magnetic properties, the corrosive environments hardly influence the magnetic parameters of the no treated or four types of coatings treated Somaloy® components. But the all kinds of magnetic parameters for laminated ring samples have a great variation after salt spray test.   In the EIS measurements, for the no treated samples, the initial corrosion resistance is only several hundred ohms and decreases after 1 hour, 8 hours and 1day exposure, then increases to a certain extent with time due to the corrosion products formed on the surface. For the sodium silicate coating, the initial corrosion resistance is approximately several ten thousands ohms and decreases rapidly only after 1 day exposure to several hundred ohms due to the sodium silicate film dissolves in the electrolyte solution and has no effective protective property. Then the following corrosion process is almost same as the no treated samples. For the water-borne single coat paint, the initial corrosion resistance can reach to several Giga-ohms and decreases over time, but can still stay at  level, indicating that this coating has a very good and effective protective properties.   EIS experiments indicate that water-borne single coat paint has a more effective protection than sodium silicate coating and can apply a better corrosion protection for the Somaloy® components   Key words: corrosion protection, soft magnetic composites, phosphoric acid coating, sodium silicate coating, DCA-Modified silicone conformal coating , water-borne single coat paint, salt spray test, TRS, hysteresis loop, EIS

The increasing awareness of sustainability motivates the development of building materials from renewable resources. The requirements of wood-based products with improved durability, for example, an enhanced liquid repellence, is still a challenge. The aim of this thesis is to develop and study concepts to functionalize wood surfaces to obtain superhydrophobicity or superamphiphobicity, i.e. extreme liquid repellence of both water and oils. Birch and acetylated birch veneer samples were surface-modified by hydrophobized silicone nanofilaments. Specifically, birch samples surface-modified by fluorinated silicone nanofilaments (F-SMB) showed superamphiphobicity, which repelled water, ethylene glycol and hexadecane with static contact angles greater than 150° and roll-off angles lower than 10°. Birch and acetylated birch samples surface-modified by non-fluorinated silicone nanofilaments (SMB and SMAB) showed superhydrophobicity with static contact angles greater than 160° towards water, even for samples prepared using the shortest silicone nanofilaments reaction time of 1 h. In liquid uptake measurements submerging the F-SMB in water, ethylene glycol and hexadecane, a superamphiphobic plastron effect was observed which indicates that the wood surface was in Cassie-Baxter state. The plastron reduced the liquid uptake rate and extent depending on the interactions (diffusion and solubility) between the liquid and the silicone nanofilaments. The F-SMB showed good self-cleaning properties towards water and hexadecane. In multicycle Wilhelmy plate measurements, the SMB showed a lower water uptake than that of the acetylated samples, while the SMAB showed the lowest water uptake, i.e. a pronounced increased water resistance, due to a combined effect of acetylation and surface modification. In addition, the SMB exhibited more color change than the SMAB, which was caused by the release of hydrochloric acid during the surface modification process. / Den ökande medvetenheten kring hållbarsamhällsutvecklingmotiverarutveckling avbyggmaterial från förnybara resurser. Kraven på träbaserade produkter med förbättrad beständighet, exempelvisennödvändig vätskeavvisandeförmåga, är fortfarande en utmaning.Syftet med dennaavhandling äratt utveckla och studera koncept för attfunktionalisera träytorför att uppnåsuperhydrofobicitet ochsuperamfifobicitet, dvs en extrem vätskerepellerande egenskap för både vatten och oljor.Björk-och acetyleradebjörkfanérproverytmodifierades med hydrofobiserad silikon-nanofilament. Specifikt visade björk ytmodifierademedfluorerade silikon-nanofilament (F-SMB) superamfifobicitet, som repelleradevatten, etylenglykol och hexadekan med kontaktvinklar större än 150° och avrullningsvinklar lägre än 10°. Björk-och acetyleradebjörkproverytmodifierademedicke-fluorerade silikon-nanofilament (SMB och SMAB) visade superhydrofobicitet med kontaktvinklar större än 160° förvatten, även förprover framställda medkortast reaktionstid på 1 timme.Vid vätskeupptagningsmätningargenom att sänka F-SMB i vatten, etylenglykol och hexadekanobserverades en plastroneffekt som indikerade att träytan var i Cassie-Baxter-tillstånd. Plastronen minskade F-SMB vätskeupptagningshastighet och -nivåberoende på växelverkan(diffusion och löslighet) mellan vätskan och silikon-nanofilament. F-SMB uppvisadegoda självrengörande egenskaper förvatten och hexadekan.Vidmulticykel Wilhelmy-mätningarvisade SMB ett lägre vattenupptag än det acetylerade träet, medan SMAB visade denlägsta vattenupptagningen,det vill säga en mycketmärkbar ökad vattenavvisning, tack vareav en kombinerad effekt av acetylering och ytmodifiering. Dessutom uppvisade SMB en störrefärgförändring än SMAB, orsakad av frisättningen av saltsyra under ytmodifieringsprocessen. / <p>QC 20201113</p>

Les poly(silméthylènesiloxane)s, aussi dénommés silicones hybrides, sont constitués d’un squelette portant un groupement méthylène entre 2 unités SiOSi. La synthèse de ces polymères par polycondensation ne permet pas d’atteindre des masses molaires très élevées, contrairement aux produits issus de la polymérisation par ouverture de cycle. Ce manuscrit décrit la procédure choisie pour aboutir à une synthèse contrôlée de poly(silméthylènesiloxane)s, des précurseurs (monomères, amorceurs) aux polymères. Le monomère cyclique silméthylène a été préparé par cyclisation de le 1,3-dichlorotetraméthylsilméthylène. Ce dernier peut être généré par redistribution de sous-produits de l’industrie de type halogénures d’alkylsilanes. Deux voies de redistribution ont été étudiées, la méthylation par le méthyllithium, et la dismutation des chlorosilanes en présence d’AlCl3 et de tétraméthylsilane. Cette dernière méthode conduit à une nouvelle distribution de chlorosilanes et chlorosilméthylènes jamais obtenue auparavant. La polymérisation par ouverture de cycle en présence d’acide triflique du 1,1,3,3,5,5,7,7-octamethyl-2,6-dioxa-1,3,5,7-tetrasilacyclooctane conduit à des poly(silméthylènesiloxane)s terminés silanol. Suivant la pureté du monomère, différentes masses molaires peuvent être atteintes. La température réactionnelle joue un rôle crucial afin d’éviter toute cyclisation des chaînes. Par comparaison avec des monomères organiques conventionnels (ether, oxiranes, etc...), le mécanisme de polymérisation implique deux espèces en équilibre, un ion silyl-oxonium et un ester silyl-triflate. Une augmentation de la température de réaction déplace cet équilibre vers les espèces ioniques, responsables des réactions de rétroscission. Ainsi la température optimale de réaction a été localisée à 25°C. La polymérisation par ouverture de cycle a été également testée en présence de catalyseur (acide triflique) et d’un amorceur (molécule portant une (des) fonction(s) silanol). Dans les conditions de température données, des polymères de masses molaires et de fonctionnalités contrôlées sont obtenus. Ces expériences ouvrent la porte à de nouvelles voies de polymérisation des cyclosiloxanes, mettant en lumière la compétition entre deux mécanismes de polymérisation, la propagation par bouts de chaînes activés (ACE) et par monomères activés (AM). / Polysilmethylenesiloxanes are belonging to the “hybrid” silicone family. The presence of a methylene group into the polymer backbone enhances their thermal stability, which is particularly interesting in high-tech applications. The synthesis of such polymers by polycondensation did not so far lead to high molar mass polymers, contrary to those prepared by ring-opening polymerization. The synthesis of such polymers is described in this manuscript, from the monomer to the macromolecule. The silmethylene cyclic dimer, the monomer of interest, is synthesized by cyclization of 1,3-dichlorotetramethylsilmethylene. This latter can be generated from the disproportionation of the direct process residue, a by-product of the silicone industry. The disproportionation proceeds either by methylation with methyl lithium, or by Me/Cl interchange reaction catalyzed by AlCl3 in presence of tetramethylsilane. This latter led to a selective dechlorination of chlorosilanes and chlorosilmethylenes in mild conditions, which has not been yet observed with the DPR. Cationic ring-opening polymerization in presence of triflic acid of such silmethylene cyclic dimer led to bis-silanol polysilmethylenesiloxanes. Depending on the purity of monomer, high molar masses can be targeted. The reaction temperature also plays a critical role in order to avoid any cyclization of the growing chains. While triflic acid plays a role of catalyst, it does not allow controlling molar masses. Comparisons with conventional organic monomers were made to identify the polymerization mechanism which involves two propagating species in equilibrium, a silyl-oxonium ion and a silyltriflate ester. An increase of the reaction temperature shifts this equilibrium towards ionic species, responsible of back- and end-biting reactions. Thus the optimal reaction temperature of ROP of the silmethylene cyclic dimer has been set at 25°C previously and confirmed here. The ROP reaction of the silmethylene cyclic dimer in presence of triflic acid and silanol molecule allows designing the obtained molar masses, while keeping a certain control of end-groups. Variations of molar masses with the silanol content speaks for a polymerization occurring through an activated monomer mechanism. Experiments done to confirm this mechanism open routes to the polymerization of other cyclosiloxanes where the competition between the activated chain end (ACE) and the activated monomer (AM) mechanisms could be controlled.

Die Einbrennsilikonisierung wird schon lange verwendet, um spezielle Eigenschaften bei pharmazeutischen Glasbehältnissen zu erzielen. Üblicherweise werden Silikonöle verwendet um Gleitfilme auf den Oberflächen vorgefüllter Glasspritzen zu erzeugen oder die Glaswand zu hydrophobieren damit wäßrige Inhalte sauber ablaufen können. Weiterhin kann durch die hydrophobe Deaktivierung der Glaswände eine Reduktion der Adsorption von Wirk- und Hilfsstoffen sowie eine Erhöhung der hydrolytischen Resistenz erreicht werden. Wegen des parenteralen Verwendungszweckes werden meistens Gläser der Glasart 1 entsprechend dem europäischen Arzneibuch eingesetzt. Die Silikonölfilme (Trimethylsiloxy-endgeblockte Polydimethylsiloxane, PDMS) werden aus verdünnter wäßriger Emulsion auf der inneren Behältnisoberfläche gespreitet und anschließend bei Temperaturen oberhalb von 300°C für ca. 10-30 min hitzebehandelt. Neben der Sterilisation und Entpyrogenisierung wird der Silikonfilm durch das Einbrennen verändert. In der Literatur wurde dieser Prozeß bisher als Hitzefixierung oder -härtung bezeichnet in der Annahme, daß das Silikonöl durch Glasbindung oder Quervernetzung immobilisiert wird. Es wurden weitere Effekte wie Verdampfung oder Zersetzungsreaktionen als Folge der Hitzebehandlung angenommen. Die Dissertation hatte daher zum Ziel diese Vorstellungen analytisch zu belegen. Die Eigenschaften einbrennsilikonisierter Gläser lassen sich durch einfache Experimente beschreiben. Durch organische Extraktion der Gläser (z.B. Toluol, Dichlormethan) läßt sich der überwiegende Silikonanteil (ca. 80%) wiederfinden. Nach erschöpfender Extraktion zeigt sich eine beständige Hydrophobie z.B. durch die Ausbildung hoher Randwinkel von Wasser oder das veränderte Ablaufverhalten von Flüssigkeiten in diesen Behältnissen festgestellt werden. Basierend auf diesen Beobachtungen wurde die Anwesenheit einer gebundenen neben einer löslichen Silikonölfraktion nach dem Einbrennen angenommen. Alle analytischen Studien wurden an dieser zwei Lagen Theorie orientiert und durchgeführt. Dazu wurden einige oberflächensensitive Techniken wie z.B. die kombinierte Röntgenphotoelektronen- und Augerelektronenspektroskopie (XPS/AES) und die Flugzeit-Sekundärionenmassenspektroskopie (TOF-SIMS) eingesetzt. Durch chemische Zustandsdiagramme und massenspektroskopische Strukturanalyse konnte die Ausbildung von Bindungen zwischen Glas und Silikon detektiert werden. Kontaktwinkelmessungen zeigten, daß das gebundene Silikon bis ca. 400°C thermostabil ist und oberhalb von 450°C pyrolysiert wird. Die extrahierbare Silikonfraktion wurde ebenfalls mit einigen analytischen Techniken im Vergleich mit den jeweiligen unbehandelten Ausgangsmaterialien untersucht. Chromatographische Studien mittels Größenausschluß- und Hochtemperatur-Gaschromatographie (SEC,GC) zeigten signifikante Unterschiede in der polymeren Zusammensetzung des PDMS. Die Molekulargewichtsmittel stiegen als Folge von Verlusten von niedermolekularen Siloxanen einer Größe zwischen 0-100 Siloxaneinheiten (SU) an. Diese Defizite können auf Verdampfungs- (0-50 SU) und Zersetzungsreaktionen (50-100 SU) zurückgeführt werden. Die Untersuchung des extrahierbaren eingebrannten Silikonöls mit der Fourier Transform Infrarot Spektroskopie (FTIR) zeigte keine strukturelle Veränderung der PDMS Moleküle, z.B. durch Hydrolyse, Oxidation oder Verzweigung an. Die Emulgatoren werden durch das Einbrennen zerstört. Dies wurde durch die 1H-Kernresonanz Spektroskopie (1H-NMR) nachgewiesen. Die Thermostabilität des PDMS wird durch katalytische Effekte der Emulsionshilfsstoffe und durch die Anwesenheit von Sauerstoff erniedrigt, wie aus thermogravimetrische Analysen (TGA) mit kommerziellen Silikonölen und Ölemulsionen modellhaft abgeleitet wurde. Um die Migration von Silikonölspuren in Arzneimittel in silikonisierten Glasbehältnissen zu bewerten wurde eine Atom Absorptions spektroskopische (AAS) Methode entwickelt und entsprechend den ICH-Richtlinien validiert (Bestimmungsgrenze in Liquida 10 mg/L). Die Schlußfolgerung aus den Analysen ist, daß nach der Einbrennsilikonisierung zwei differenzierbare Silikonfraktionen an der Glasoberfläche anwesend sind. Die kovalent gebundene Dünnschicht ist unlöslich und verliert ihren Ölcharakter, ist aber für die Hydrophobisierung ausreichend. In der löslichen Fraktion, werden die mittleren Molekulargewichte durch den Verlust von niedermolekularen Anteilen erhöht. Der Anteil dieser Schicht hängt von der eingesetzten Ausgangsmenge an Silikonöl ab. Durch die Entfernung der niedermolekularen Anteile und die Zerstörung der Emulgatoren können toxikologische Bedenken zurückgestellt werden. / Heat Curing Siliconization of Pharmaceutical Glass Containers The heat curing siliconization has long since been used to introduce special properties to pharmaceutical glass containers. Silicone oils are usually applied to the containers to form lubricating films on the inner surface of prefilled syringes or to gain hydrophobic container walls for clear draining aqueous solutions, e.g. in injection vials. Furthermore the deactivation of the glass wall reduces adsorption of hydrophilic drug compounds and increases the hydrolytic stability of the glass surface. Due to the parenteral targeting the glass containers are made from glass type 1 according to the European Pharmacopoeia. The silicone oil films (= trimethylsiloxy endcapped polydimethylsiloxane, PDMS) are spread from diluted aqueous silicone oil emulsions on the inner surface and successively heat treated above 300°C for 10-30 minutes. Apart from sterilization and depyrogenation, the silicone layer is changed by the burning-in treatment. In literature the process has previously been designated as heat fixing or heat curing assuming that silicone oil is immobilized by bonding to the glass or branching. Further effects such as vaporization or degradation were suggested along with the heating. Proving these suggestions analytically was therefore the aim of the dissertation. The properties of siliconized glass containers can be characterized by simple experiments. Extraction of the glasses with suitable organic solvents (e.g. toluene, dichloromethane) recovers most of the silicone (approximately 80%) after a typical heat curing process. Still, after exhaustive solvent extraction there are persisting hydrophobic properties of the glasses evidenced by high contact angles of water and changed draining behaviour of fluids in the containers. From this observations it was assumed that a bound and a soluble silicone species is present after the heat curing siliconization. All analytical studies were based on the two-layer hypothesis and thus divided in two parts. Several surface analysis techniques were employed to detect and characterize the fixed silicone layer among them the combined X-ray photoelectron and augerelectron spectroscopy (XPS/AES) and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). The formation of new bonds between silicone and glass was evidenced by chemical state plots and mass spectroscopic structural analysis. Contact angle measurements showed that the bound silicone was thermostable up to 400°C and pyrolyzed at temperatures above 450°C. The extractable silicone was also studied with several analytical techniques in comparison with the respective uncured starting materials. Chromatographic studies using size exclusion (SEC) and high temperature gas chromatography (GC) revealed significant changes in the composition of the silicone polymer. The molecular weight averages increase because low molecular weight siloxanes (LMWS) with 0-100 dimethylsiloxane units are removed through the heat curing process. These deficits can be related to vaporization (molecules from 0-50 units) and degradation (molecules from 0-100 units) effects. A Fourier transform infrared spectroscopic (FTIR) investigation of the molecular structure of the extractable PDMS after heat treatment showed no chemical changes e.g. by hydrolysis, branching or oxidation. The emulsifiers are destroyed in the heating process which was proved by a proton nuclear magnetic resonance (1H-NMR) study. The thermostability of the silicones is decreased by katalytic effects of auxiliary substances in the emulsions and the presence of oxygen. This was concluded from model thermogravimetric studies (TGA) with commercial medical grade silicone oils and emulsions. To evaluate migration of silicone traces to drug formulations in siliconized glass containers a trace analytical method by graphite furnace atomic absorption spectrometry (GF-AAS) was developed and validated according to the ICH guidelines. In liquid formulations levels of 10µg/L can be properly quantified. It was concluded that two main species of silicone can be differentiated on the glass surface after heat curing siliconization. The bonded thin layer is insoluble and sufficient for hydrophobic deactivation. The oil properties are lost. The extractable fraction is altered by removal of LMWS which increases molecular weight and viscosity and determines the lubricating properties. Its amount depends on the used silicone mass. No toxicological concern has to be made about LMWS and emulsifiers in the drug product due to their removal in the curing step.

A spin-cast silicone membrane has been successfully bonded between two injection-molded microstructured plastic discs. This sandwich structure creates a useful platform for mass production of microfluidic systems, provided that the bonds are leakproof. The bonds were achieved by a silicon dioxide coating deposited on the plastic discs by evaporation. This investigation is concerned with the process and the result only, no theory is discussed.