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Organisationseinheit der BAM
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.
Brominated single-walled carbon nanotubes [(Br)n-SWCNT) produced by the plasma-chemical technique were involved in the liquid-phase process of hydrocarbons aerobic oxidation. The significant catalytic effect of the (Br)n-SWCNT was revealed at first by the cumene initiated model oxidation and then in experiments on profound aerobic oxidation of petroleum naphthenic fraction derived from the commercial Azerbaijan (Baku) oils blend diesel cut. The ability of (Br)n-SWCNT to accelerate the aerobic oxidation of the hydrocarbons was found out for the first time. Obviously this phenomenon originates from the peculiarities of electronic configuration of the (Br)n-CNT patterns. The plausible mechanism of (Br)n-SWCNT catalytic action is inclined to the formation of reactive oxygen species. The catalytic activity of (Br)n-SWCNT markedly exceeds the activity of the industrial catalysts, manganese salt of indigenous petroleum acids, used for the liquid phase petroleum hydrocarbons oxidation process.
1Brominated carbon nanotubes as effective catalysts for petroleum hydrocarbons aerobic oxidation
(2012)
The initial attachment and subsequent biofilm formation of electroactive bac-teriaShewanella putrefaciensCN32 was investigated to clarify the influence oforganic conditioning layers. A selection of macromolecules and self-assembledmonolayers (SAMs) of different chain lengths and functional groups were pre-pared and characterized by means of infrared spectroscopy in terms of theirchemistry. Surface energy and Zeta (ζ-) potential of the conditioning layers wasdetermined with contact angle and streaming current measurements. Amongthe studied surface parameters, a high polar component and a high ratio ofpolar-to-disperse components of the surface energy has emerged as a successfulindicator for the inhibition of the initial settlement ofS. putrefacienson stainlesssteel AISI 304 surfaces. Considering the negative surface charge of planktonicS. putrefacienscells, and the strong inhibition of cell attachment by positivelycharged polyethylenimine (PEI) conditioning layers, our results indicate thatelectrostatic interactions do play a subordinate role in controlling the attach-ment of this microorganism on stainless steel AISI 304 surfaces. For the biofilmformation, the organization of the SAMs affected the local distribution of thebiofilms. The formation of three-dimensional and patchy biofilm networks waspromoted with increasing disorder of the SAMs.
Since more than 40 years ammonia plasma exposure of polyolefins is used for introduction of primary amino groups. The selectivity of this reaction and the yield in primary amino groups was found to be low. Here, a prominent side-reactions of this process was investigated, the hydrogenation by NH3 plasma. For identification of hydrogenation ammonia (NH3) and deuterated ammonia (ND3) were exposed to Polyethylene (h-PE) and fully deuterated polyethylene (d-PE) as well as hexatriacontane (h-HTC) and fully deuterated hexatriacontane (d-HTC) as low-molecular weight model for PE. HD exchange was assumed and detected by Time-of-Flight Secondary Ion Mass Spectrometry (ToFSIMS), X-ray Photoelectron Spectroscopy (XPS), Attenuated Total Reflectance (ATR-FTIR) and 1H and 2H Nuclear magnetic Resonance. Results show a significant HD exchange within the sampling depth of ATR (2.5 µm). However, N- and NH2 introduction was limited to the topmost surface as shown by SIMS and XPS (a few nanometers).
In contrast to other plasma modification processes of polymer surfaces, the bromination is very selective and shows a high yield in C—Br groups. The most convenient bromination process was found using bromoform, which was thus preferred to elemental bromine, allyl bromide, vinyl bromide or tert-butylbromide. The bromoform process give yields in C—Br up to 40 C—Br or more, with only 2-3% co-introduction of O-functionalities whereas allyl bromide results in yields of about 20 C—Br and more, but in more than 10% oxygen-containing by-products. C—Br groups serve as anchoring points for grafting of molecules, oligomers and pre-polymers of diole or diamine character.
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.
Biofuels, particularly biodiesel, have gained significant attention as an alternative to traditional fossil fuels in recent years. Unlike diesel, which contains hundreds of compounds, biodiesel only contains a few compounds in the C16-C18 carbon chain. However, the use of biodiesel in automobile and transportation applications can result in problems of degradation or even damage in materials. Among the commonly used polymer materials, fluorocarbon (FKM) shows excellent performance and high stability and compatibility towards oil, diesel, ethanol, and other chemicals. FKM is a family of fluorocarbon-based fluoroelastomer materials, which provide excellent high-temperature and chemical stability compared to other elastomers. As a result, FKM is widely used in chemical processes such as petroleum refining, where it is used for sealings, pumps, and other components.
Mixtures of hexamethyldisiloxane (HMDSO) and oxygen have been used for deposition of SiO2-like layers by plasma polymerization under low-pressure conditions onto polyethylene and polystyrene used as basecoat. Water glass was cast onto these 0.5 µm plasma thick siloxane-like layers with a thickness of 5 to 40 µm. The adhesion of these bilayer systems and their flame resistance were tested.
The effect of different plasma parameters such as monomer/gas ratio, pressure and power input into the discharge on the deposition rate and the composition of the formed layers was studied. Characterization and chemical composition of the formed films were performed using infrared, X-ray photoelectron and solid state nuclear magnetic resonance spectroscopy.
Peel strengths of composites were measured and the locus of peel front propagation was detected. Thermal properties of composites were analyzed by thermo-gravimetric analysis. Finally, the fire-retardant properties of thick coated polymers were determined by exposure to flames and the behavior of coatings on the polymers during flaming was observed visually.
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.