Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with twomonoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LBmethod may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.

Photocatalytic activity of nanostructured anatase coatings obtained by cold gas spray

[EN] This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS) supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Process for reinforcing SLS parts by epoxy resin

[ES]The purpose of this paper is to report on the use of a combination of selective laser sintering (SLS) and vacuum casting to create plastic composites made by additive manufacturing.

Functional polymer coatings — My-Patterning and My-Analysis

In dieser Arbeit werden Strukturen beschrieben, die mit Polymeren auf Oberflächen erzeugt wurden. Die Anwendungen reichen von PMMA und PNIPAM Polymerbürsten, über die Restrukturierung von Polystyrol durch Lösemittel bis zu 3D-Strukturen, die aus PAH/ PSS Polyelektrolytmultischichten bestehen. Im ersten Teil werden Polymethylmethacrylat (PMMA) Bürsten in der ionischen Flüssigkeit 1-Butyl-3-Methylimidazolium Hexafluorophospat ([Bmim][PF6]) durch kontrollierte radikalische Polymerisation (ATRP) hergestellt. Kinetische Untersuchungen zeigten ein lineares und dichtes Bürstenwachstum mit einer Wachstumsrate von 4600 g/mol pro nm. Die durchschnittliche Pfropfdichte betrug 0.36 µmol/m2. Als Anwendung wurden Mikrotropfen bestehend aus der ionischen Flüssigkeit, Dimethylformamid und dem ATRP-Katalysator benutzt, um in einer definierten Geometrie Polymerbürsten auf Silizium aufzubringen. Auf diese Weise lässt sich eine bis zu 13 nm dicke Beschichtung erzeugen. Dieses Konzept ist durch die Verdampfung des Monomers Methylmethacrylat (MMA) limitiert. Aus einem 1 µl großen Tropfen aus ionischer Flüssigkeit und MMA (1:1) verdampft MMA innerhalb von 100 s. Daher wurde das Monomer sequentiell zugegeben. Der zweite Teil konzentriert sich auf die Strukturierung von Oberflächen mit Hilfe einer neuen Methode: Tintendruck. Ein piezoelektrisch betriebenes „Drop-on-Demand“ Drucksystem wurde verwendet, um Polystyrol mit 0,4 nl Tropfen aus Toluol zu strukturieren. Die auf diese Art und Weise gebildeten Mikrokrater können Anwendung als Mikrolinsen finden. Die Brennweite der Mikrolinsen kann über die Anzahl an Tropfen, die für die Strukturierung verwendet werden, eingestellt werden. Theoretisch und experimentell wurde die Brennweite im Bereich von 4,5 mm bis 0,21 mm ermittelt. Der zweite Strukturierungsprozess nutzt die Polyelektrolyte Polyvinylamin-Hydrochlorid (PAH) und Polystyrolsulfonat (PSS), um 3D-Strukturen wie z.B. Linien, Schachbretter, Ringe, Stapel mit einer Schicht für Schicht Methode herzustellen. Die Schichtdicke für eine Doppelschicht (DS) liegt im Bereich von 0.6 bis 1.1 nm, wenn NaCl als Elektrolyt mit einer Konzentration von 0,5 mol/l eingesetzt wird. Die Breite der Strukturen beträgt im Mittel 230 µm. Der Prozess wurde erweitert, um Nanomechanische Cantilever Sensoren (NCS) zu beschichten. Auf einem Array bestehend aus acht Cantilevern wurden je zwei Cantilever mit fünf Doppelschichten PAH/ PSS und je zwei Cantilever mit zehn Doppelschichten PAH/ PSS schnell und reproduzierbar beschichtet. Die Massenänderung für die individuellen Cantilever war 0,55 ng für fünf Doppelschichten und 1,08 ng für zehn Doppelschichten. Der daraus resultierende Sensor wurde einer Umgebung mit definierter Luftfeuchtigkeit ausgesetzt. Die Cantilever verbiegen sich durch die Ausdehnung der Beschichtung, da Wasser in das Polymer diffundiert. Eine maximale Verbiegung von 442 nm bei 80% Luftfeuchtigkeit wurde für die mit zehn Doppelschichten beschichteten Cantilever gefunden. Dies entspricht einer Wasseraufnahme von 35%. Zusätzlich konnte aus den Verbiegungsdaten geschlossen werden, dass die Elastizität der Polyelektrolytmultischichten zunimmt, wenn das Polymer gequollen ist. Das thermische Verhalten in Wasser wurde im nächsten Teil an nanomechanischen Cantilever Sensoren, die mit Poly(N-isopropylacrylamid)bürsten (PNIPAM) und plasmapolymerisiertem N,N-Diethylacrylamid beschichtet waren, untersucht. Die Verbiegung des Cantilevers zeigte zwei Bereiche: Bei Temperaturen kleiner der niedrigsten kritischen Temperatur (LCST) ist die Verbiegung durch die Dehydration der Polymerschicht dominiert und bei Temperaturen größer der niedrigsten kritischen Temperatur (LCST) reagiert der Cantilever Sensor überwiegend auf Relaxationsprozesse innerhalb der kollabierten Polymerschicht. Es wurde gefunden, dass das Minimum in der differentiellen Verbiegung mit der niedrigsten kritischen Temperatur von 32°C und 44°C der ausgewählten Polymeren übereinstimmt. Im letzten Teil der Arbeit wurden µ-Reflektivitäts- und µ-GISAXS Experimente eingeführt als neue Methoden, um mikrostrukturierte Proben wie NCS oder PEM Linien mit Röntgenstreuung zu untersuchen. Die Dicke von jedem individuell mit PMMA Bürsten beschichtetem NCS ist im Bereich von 32,9 bis 35,2 nm, was mit Hilfe von µ-Reflektivitätsmessungen bestimmt wurde. Dieses Ergebnis kann mit abbildender Ellipsometrie als komplementäre Methode mit einer maximalen Abweichung von 7% bestätigt werden. Als zweites Beispiel wurde eine gedruckte Polyelektrolytmultischicht aus PAH/PSS untersucht. Die Herstellungsprozedur wurde so modifiziert, dass Goldnanopartikel in die Schichtstruktur eingebracht wurden. Durch Auswertung eines µ-GISAXS Experiments konnte der Einbau der Partikel identifiziert werden. Durch eine Anpassung mit einem Unified Fit Modell wurde herausgefunden, dass die Partikel nicht agglomeriert sind und von einer Polymermatrix umgeben sind.

Characterization of mode I disbonding behaviour of carbon/epoxy composites bonded with two adhesion qualities

La mancanza di procedure standard per la verifica delle strutture in compositi, al contrario dei materiali metallici, porta all’esigenza di una continua ricerca nel settore, al fine di ottenere risultati significativi che culminino in una standardizzazione delle procedure. In tale contesto si colloca la ricerca svolta per la stesura del presente elaborato, condotta presso il laboratorio DASML del TU Delft, nei Paesi Bassi. Il materiale studiato è un prepreg (preimpregnated) costituito da fibre di carbonio (M30SC) e matrice epossidica (DT120) con la particolare configurazione [0°/90°/±45°/±45°/90°/0°]. L’adesivo utilizzato per l’incollaggio è di tipo epossidico (FM94K). Il materiale è stato assemblato in laboratorio in modo da ottenere i provini da testare, di tipo DCB, ENF e CCP. Due differenti qualità dello stesso materiale sono state ottenute, una buona ottenuta seguendo le istruzione del produttore, ed una povera ottenuta modificando il processo produttivo suggerito, che risulta in un incollaggio di qualità nettamente inferiore rispetto al primo tipo di materiale. Lo scopo era quello di studiare i comportamenti di entrambe le qualità sotto due diversi modi di carico, modo I o opening mode e modo II o shear mode, entrambi attraverso test quasi-statici e a fatica, così da ottenere risultati comparabili tra di essi che permettano in futuro di identificare se si dispone di un materiale di buona qualità prima di procedere con il progetto dell’intera struttura. L’approccio scelto per lo studio dello sviluppo della delaminazione è un adattamento della teoria della Meccanica della Frattura Lineare Elastica (LEFM)

Fully bio-based epoxy resins

Epoxy resins are mainly produced by reacting bisphenol A with epichlorohydrin. Growing concerns about the negative health effects of bisphenol A are urging researchers to find alternatives. In this work diphenolic acid is suggested, as it derives from levulinic acid, obtained from renewable resources. Nevertheless, it is also synthesized from phenol, from fossil resources, which, in the current paper has been substituted by plant-based phenols. Two interesting derivatives were identified: diphenolic acid from catechol and from resorcinol. Epichlorohydrin on the other hand, is highly carcinogenic and volatile, leading to a tremendous risk of exposure. Thus, two approaches have been investigated and compared with epichlorohydrin. The resulting resins have been characterized to find an appropriate application, as epoxy are commonly used for a wide range of products, ranging from composite materials for boats to films for food cans. Self-curing capacity was observed for the resin deriving from diphenolic acid from catechol. The glycidyl ether of the diphenolic acid from resorcinol, a fully renewable compound, was cured in isothermal and non-isothermal tests tracked by DSC. Two aliphatic amines were used, namely 1,4-butanediamine and 1,6-hexamethylendiamine, in order to determine the effect of chain length on the curing of an epoxy-amine system and determine the kinetic parameters. The latter are crucial to plan any industrial application. Both diamines demonstrated superior properties compared to traditional bisphenol A-amine systems.

Preparazione di una resina epossidica bio-based e studio delle relative proprietà

Epoxy resins are very diffused materials due to their high added value deriving from high mechanical proprieties and thermal resistance; for this reason they are widely used both as metallic coatings in aerospace and in food packaging. However, their preparation uses dangerous reagents like bisphenol A and epichlorohydrin respectively classified as suspected of causing damage to fertility and to be carcinogen. Therefore, to satisfy the ever-growing attention to environmental problems and human safeness, we are considering alternative “green” processes through the use of reagents obtained as by-products from other processes and mild experimental conditions, and also economically sustainable and attractive for industries. Following previous results, we carried out the reaction leading to the formation of diphenolic acid (DPA), its allylation and the following epoxidation of the double bonds, all in aqueous solvent. In a second step the obtained product were cross-linked at high temperature with and without the use of hardeners. Then, on the obtained resin, some tests were performed like release in aqueous solution, scratch test and DSC analysis.

Coatings ibridi organici-inorganici ottenuti mediante processo sol-gel e contenenti assorbitori di radiazioni uv

In questo progetto di tesi si è cercato il modo di rendere più efficace la resistenza dei materiali plastici alla fotodegradazione indotta dai raggi ultravioletti, attraverso l’utilizzo di coatings ibridi organici-inorganici preparati utilizzando il processo sol-gel. Tali rivestimenti in grado di migliorare la resistenza superficiale potrebbero essere applicati a diversi materiali ed in particolare ai policarbonati che per le loro eccellenti proprietà di trasparenza vengono molto utilizzati in illuminotecnica ed altre applicazioni per l’esterno. In particolare il lavoro ha riguardato lo studio e l’utilizzo di due assorbitori UV di tipo fenolico, il 2,2’-diidrossi-4-metossibenzofenone e il 2,2’,4,4’-tetraidrossibenzofenone. Si è provato a non collocare semplicemente tali assorbitori all’interno del coating sol-gel ma a legarli covalentemente al network tridimensionale di silani auspicando una migliore resistenza alla fotodegradazione UV-indotta. Il nostro interesse si è concentrato soprattutto sul 2,2’,4,4’-tetraidrossibenzofenone, in quanto abbiamo visto che una sua funzionalizzazione rispetto all’altro assorbitore UV risulta più semplice ed efficace.

Mechanical insertion properties of calcium-phosphate implant coatings

Abstract Objectives: To investigate the influence of protein incorporation on the resistance of biomimetic calcium-phosphate coatings to the shear forces that are generated during implant insertion. Materials and Methods: Thirty-eight standard (5 x 13 mm) Osseotite((R)) implants were coated biomimetically with a layer of calcium phosphate, which either lacked or bore a co-precipitated (incorporated) depot of the model protein bovine serum albumin (BSA). The coated implants were inserted into either artificial bone (n=18) or the explanted mandibles of adult pigs (n=12). The former set-up was established for the measurement of torque and of coating losses during the insertion process. The latter set-up was established for the histological and histomorphometric analysis of the fate of the coatings after implantation. Results: BSA-bearing coatings had higher mean torque values than did those that bore no protein depot. During the insertion process, less material was lost from the former than from the latter type of coating. The histological and histomorphometric analysis revealed fragments of material to be sheared off from both types of coating at vulnerable points, namely, at the tips of the threads. The sheared-off fragments were retained within the peri-implant space. Conclusion: The incorporation of a protein into a biomimetically prepared calcium-phosphate coating increases its resistance to the shear forces that are generated during implant insertion. In a clinical setting, the incorporated protein would be an osteogenic agent, whose osteoinductive potential would not be compromised by the shearing off of coating material, and the osteoconductivity of an exposed implant surface would not be less than that of a coated one. To cite this article: Hägi TT, Enggist L, Michel D, Ferguson SJ, Liu Y, Hunziker EB. Mechanical insertion properties of calcium-phosphate implant coatings. Clin. Oral Impl. Res. xx, 2010; 000-000. doi: 10.1111/j.1600-0501.2010.01916.x.

Characterization of vascular cavity coatings and microscopic tube-shaped structures from Upper Cretaceous dinosaur bone: evidence of a bacterial origin for dinosaur blood vessels""

Recent claims of blood vessels extracted from dinosaur fossils challenge classical views of soft-tissue preservation. Alternatively, these structures may represent postdepositional,diagenetic biofilms that grew on vascular cavity surfaces within the fossil. Similar red, hollow, tube-shaped structures were recovered from well-preserved and poorly-preserved (abraded, desiccated, exposed) Upper Cretaceous dinosaur fossils in this study. Integration of light microscopy, scanning electron microscopy, and energy dispersive x-ray spectroscopy was used to compare these vessel structures to the fossils from which they are derived. Vessel structures are typically 100-400 μm long, 0.5-1.5 μm thick, 10-40 μm in diameter and take on a wide range of straight, curved, andbranching morphologies. Interior surfaces vary from smooth to globular and typically contain spheres, rods, and fibrous structures (< 2 μm in diameter) incorporated into the surface. Exterior surfaces exhibit 2-μm-tall converging ridges, spaced 1-3 μm apart, that are sub-parallel to the long axis of the vessel structure. Fossil vascular cavities are typically coated with a smooth or grainy orange layer that shows a wide range of textures including smooth, globular, rough, ropy, and combinations thereof. Coatings tend to overlay secondary mineral crystals and framboids, confirming they are not primary structures of the fossil. For some cavity coatings, the surface that had been in contact with the bone exhibits a ridged texture, similar to that of vessel structures, having formed as a mold of the intravascular bone surface. Thus, vessel structures are interpreted as intact cavity coatings isolated after the fossil is demineralized. The presence of framboids and structures consistent in size and shape with bacteria cells, the abundance of iron in cavity coatings, and the growth of biofilms directly from the fossil that resemble respective cavity coatings support the hypothesis that vessel structures result from ironconsuming bacteria that form biofilms on the intravascular bone surfaces of fossil dinosaur bone. This also accounts for microstructures resembling osteocytes as some fossil lacunae are filled with the same iron oxide that comprises vessel structures andcoatings. Results of this study show that systematic, high-resolution SEM analyses of vertebrate fossils can provide improved insight on microtaphonomic processes, including the role of bacteria in diagenesis. These results conflict with earlier claims of dinosaurblood vessels and osteocytes.

The influence of toothbrushing and coffee staining on different composite surface coatings

The aim of our study is to evaluate the performance of surface sealants and conventional polishing after ageing procedures. Eighty circular composite restorations were performed on extracted human molars. After standardised roughening, the restorations were either sealed with one of three surface sealants (Lasting Touch (LT), BisCover LV (BC), G-Coat Plus (GP) or a dentin adhesive Heliobond (HB)) or were manually polished with silicon polishers (MP) (n = 16). The average roughness (Ra) and colourimetric parameters (CP) (L*a*b*) were evaluated. The specimens underwent an artificial ageing process by thermocycling, staining (coffee) and abrasive (toothbrushing) procedures. After each ageing step, Ra and CP measurements were repeated. A qualitative surface analysis was performed with SEM. The differences between the test groups regarding Ra and CP values were analysed with nonparametric ANOVA analysis (α = 0.05). The lowest Ra values were achieved with HB. BC and GP resulted in Ra values below 0.2 μm (clinically relevant threshold), whereas LT and MP sometimes led to higher Ra values. LT showed a significantly higher discolouration after the first coffee staining, but this was normalised to the other groups after toothbrushing. The differences between the measurements and test groups for Ra and CP were statistically significant. However, the final colour difference showed no statistical difference among the five groups. SEM evaluation showed clear alterations after ageing in all coating groups. Surface sealants and dentin adhesives have the potential to reduce surface roughness but tend to debond over time. Surface sealants can only be recommended for polishing provisional restorations.

Comparative stability studies of poly(2-methyl-2-oxazoline) and poly(ethylene glycol) brush coatings

Non-fouling surfaces that resist non-specific adsorption of proteins, bacteria, and higher organisms are of particular interest in diverse applications ranging from marine coatings to diagnostic devices and biomedical implants. Poly(ethylene glycol) (PEG) is the most frequently used polymer to impart surfaces with such non-fouling properties. Nevertheless, limitations in PEG stability have stimulated research on alternative polymers that are potentially more stable than PEG. Among them, we previously investigated poly(2-methyl-2-oxazoline) (PMOXA), a peptidomimetic polymer, and found that PMOXA shows excellent anti-fouling properties. Here, we compare the stability of films self-assembled from graft copolymers exposing a dense brush layer of PEG and PMOXA side chains, respectively, in physiological and oxidative media. Before media exposure both film types prevented the adsorption of full serum proteins to below the detection limit of optical waveguide in situ measurements. Before and after media exposure for up to 2 weeks, the total film thickness, chemical composition, and total adsorbed mass of the films were quantified using variable angle spectroscopic ellipsometry (VASE), X-ray photoelectron spectroscopy (XPS), and optical waveguide lightmode spectroscopy (OWLS), respectively. We found (i) that PMOXA graft copolymer films were significantly more stable than PEG graft copolymer films and kept their protein-repellent properties under all investigated conditions and (ii) that film degradation was due to side chain degradation rather than due to copolymer desorption.

Corrosion Characteristics And Mechanical Properties Of Aluminum Coatings Applied By The Cold Spray Process

Aluminum coatings were applied to 2024-T3 and 7075-T6 aluminum alloys via the Cold Spray process. The coatings were applied to substrateswith various surface preparation and Cold Spray carrier gas combinations. Some samples were coated with an additional sealant with and without a chromate conversion layer. An exhaustive corrosion analysis was then performed which utilized a number of long termand accelerated tests in order to characterize the corrosion protection of the coatings.