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Eingeladener Vortrag
- nein (29)
It has been shown that selected types of substituents are able to vary the oxidative behavior of multi-walled carbon nanotubes. Such substituents investigated were sterically hindered secondary amino groups bonded in grafted piperidine units and covalently bonded bromine groups. Their interference and activity was preliminary determined in the model cumene and then in oil diesel fraction and low density polyethylene oxidation reactions. Results obtained indicate that chemical linking of amine moieties containing –NH groups directly to the carbon nanotubes core significantly increases their intrinsic anti-oxidative capacity while the grafting of Br-groups provokes the opposite functioning of the pristine samples. This inference was proved by thermogravimetric and differential thermal analysis of the polyethylene composites and experiments on profound aerobic oxidation of petroleum naphthenic fraction derived from the commercial Baku oils blend diesel cut.
A facile and versatile synthetic route for controlling the size and surface potential of organic–inorganic hybrid silica nanoparticles (NPs) is introduced in this paper. For polymer-grafted NPs, the density of polymer chains on the surface is strongly affected by the concentration of precursor. Nevertheless, for condensed NPs, the precursor concentration determines the particle size but not the density of polymer chains on the surface or the adsorption of bovine serum albumin (BSA). Results presented here may have Major implications in biomedical and colloidal chemistry since interfacial and colloidal properties are known to drive several processes associated with nanoparticles in biological media.
The study of protein corona formation on nanoparticles (NPs) represents an actual main issue in colloidal, biomedical and toxicological sciences. However, little is known about the influence of polymer shells on the formation and time evolution of protein corona onto functionalized NPs. Therefore, silicapoly(ethylene glycol) core–shell nanohybrids (SNPs@PEG) with different polymer molecular weights (MW) were synthesized and exhaustively characterized. Bovine serum albumin (BSA) at different concentrations (0.1–6 wt%) was used as model protein to study protein corona formation and time evolution. For pristine SNPs and SNPs@PEG (MW = 350 g/mol), zeta potential at different incubation times show a dynamical evolution of the nanoparticle–protein corona. Oppositely, for SNPs@PEG with MW ≥2000 g/mol a significant suppression of corona formation and time evolution was observed.
Furthermore, AFM investigations suggest a different orientation (side-chain or perpendicular) and Penetration depth of BSA toward PEGylated surfaces depending on the polymer length which may explain differences in protein corona evolution.
The adhesion of thick poly(allylamine)-polyphosphate layers (1 µm) deposited by the wet-chemical layer-by-layer technique (LbL) onto polyethylene or polystyrene (each 100 µm) was very low. To promote the adhesion of these LbL layers the polyolefin substrates were oxidized at the surface by short exposure to the oxygen plasma (2 or 5 s) and subsequently coated with an interlayer of plasma-deposited poly(allylamine) or poly(allyl alcohol) (100 nm). The plasma polymer interlayers have improved strongly the adhesion between polyolefin substrates and polyphosphate coatings. Such phosphate coatings are interesting for life sciences (nucleotide formation) but also for fire retardancy in combination with N-rich compounds such as melamine.
The intention was to prefer chemical and hydrogen bonds for adhesion promoting because of their high binding energy. Therefore, the introduced oxygen-containing groups at the polyolefin surface could interact with the OH or NH2 groups of the adhesion-promoting plasma polymer interlayer. These groups were also able to interact strongly with the poly(allylamine)-polyphosphate topcoating.
The coated polyolefins were investigated using Fourier Transform Infrared Spectroscopy in Attenuated Total Reflectance mode (FTIR-ATR), X-ray Photoelectron Spectroscopy (XPS), Thermo-Gravimetric Analyses (TGA) and Atomic Force Spectroscopy (AFM) and 90° peel test.
Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiberepoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (electrophoretic effect'). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions.
Melamine resins were used as 50-µm-thick fire retardant coatings for polypropylene (PP). Preceding deposition, low-pressure plasma polymer films of allyl alcohol were coated onto PP to improve the adhesion between PP and melamine resin coatings. The efficiency of such fire retardant coatings was confirmed by flame tests. The plasma-deposited polymer and the dip-coated melamine resin films were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesion of coatings was measured using a 90° peel test with a doubled-faced adhesive tape. To detect the locus of failure, the peeled layer surfaces were inspected using optical microscopy and XPS. Thermal properties of PP thick melamine resin-coated films were analyzed by thermogravimetric analysis.
Melamine and melamine resins are widely used as fire-retardants for polymer building materials. Cured melamine systems are used in heat-sensitive items, such as furniture and window frames and sills. In this work, differently cured methylated poly(melamine-co-formaldehyde) (cmPMF) resins were used as fire-retardant coverage for poly(styrene) (PS) and poly(ethylene) (PE) building materials. Such polymer layers should have several tenths of micrometers thickness to produce sufficient fire retardancy. These thick layers were produced by dip-coating. To promote sufficient adhesion of such thick coating to the polyolefin substrates, also in the case of high temperatures occurring at fire exposure, the polymer substrates were firstly coated with a few hundred nanometer thick adhesion-promoting plasma polymer layer. Such thin plasma polymer layers were deposited by low-pressure plasma polymerization of allyl alcohol (ppAAl). It was assumed that the hydroxyl groups of ppAAl interact with the melamine resin; therefore, ppAAl was well suited as adhesion promoter for thick melamine resin coatings. Chemical structure and composition of polymer films were investigated using infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). Peel strengths of coatings were measured. After peeling, the peeled polymer surfaces were also investigated using optical microscopy and XPS the layers for identification of the locus of peel front propagation. Thermal properties were analyzed using TGA (thermo-gravimetric analyses). Finally, the fire-retardant properties of such thick coated polymers were evaluated by exposure to flames.
Polyglycerol (PG) coated polypropylene (PP) films were synthesized in a two-step approach that involved plasma bromination and subsequently grafting hyperbranched polyglycerols with very few amino functionalities. The influence of different molecular weights and density of reactive linkers were investigated for the grafted PGs. Longer bromination times and higher amounts of linkers on the surface afforded long-term stability. The protein adsorption and bacteria attachment of the PP-PG films were studied. Their extremely low amine content proved to be beneficial for preventing bacteria attachment.
Melamine and melamine resins are widely used as fire retardants for polymer materials used in pharmaceutical, plastic, textile, rubber, and construction industry. Melamine-based flame retardants act by blowing off intumescent layers, char formation, and emission of quenching ammonia gas and diluent molecular nitrogen. Special advantages are: low cost, low smoke density and toxicity, low corrosive activity, safe handling, and environmental friendliness. Methylated poly(melamine-co-formaldehyde) (mPMF) was used as thick (≥40 µm) fire-retardant coating for plasma pretreated polymers. A combined low-pressure plasma pretreatment consisting of oxygen plasma exposure followed by deposition of thin poly(allylamine) (ppAAm) and poly(allyl alcohol) (ppAAl) plasma polymers as adhesion promoters have improved the adhesion of thick mPMF coatings strongly. Chemical structure and composition of deposited polymer films were characterized by infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). After peeling, the peeled layer surfaces were also investigated for identification of the locus of failure and their topography using optical microscopy and XPS. Often the adhesion promotion was so efficient that the peeling of coating was not possible. Thermal properties of plasma polymers and dip-coating films were analyzed by thermogravimetric analysis. Significant improvement of fire-retardant properties of coated polymers was confirmed by flame tests.
Polymer deposition morphology by electrospray deposition - Modifications through distance variation
(2014)
Electrospray deposition (ESD) of highly diluted polymers was examined with regard to the deposited surface structure. Only the flight distance (flight time) onto the resulting deposited surface was varied from 20 to 200 mm.
An apparatus without any additional heating or gas flows was used. Polyacrylic acid (PAA) and polyallylamine (PAAm) in methanol were deposited on Si wafers. The polymer layers were characterized by scanning electron microscopy, X-ray photoelectron spectroscopy, derivatization reactions and Fourier transform infrared spectroscopy using a grazing incidence unit.
SEM images illustrated the changing structures of PAA and PAAm. For PAA the deposited structure changed from a smooth film (20 mm) to a film with individual droplets on the coated surface (100 mm and 200 mm), while for PAAm individual droplets can be seen at all distances. The ESD process with cascades of splitting droplets slows down for PAA after distances greater than 40 mm. In contrast, the ESD process for PAAm is nearly stopped within the first flight distance of 20 mm. Residual solvent analysis showed that most of the solvent evaporated within the first 20 mm capillary-sample distance.