Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (132)
- Beitrag zu einem Tagungsband (44)
- Beitrag zu einem Sammelband (35)
- Vortrag (29)
- Posterpräsentation (10)
- Buchkapitel (5)
- Monografie (2)
- Sonstiges (1)
Schlagworte
- Plasma polymerization (22)
- Plasma (15)
- NEXAFS (13)
- Plasma modification (9)
- Adhesion (8)
- Surface modification (8)
- Allyl alcohol (7)
- Polymer (7)
- Surface functionalization (7)
- Polystyrene (6)
Eingeladener Vortrag
- nein (29)
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.
Die Elektrospray-Ionisations (ESI)-Vernebelung von Polymerlösungen wird analytisch zur massenspektrometrischen Bestimmung der Molmassen von Makromolekülen genutzt. Dabei werden die Polymermoleküle nach einem speziellen Mechanismus im Hochspannungsfeld unter Normaldruckbedingungen vereinzelt und in das Massenspektrometer überführt. Dieser Prozeß kann auch zur flächigen Abscheidung einzelner Polymermoleküle genutzt werden. Die Struktur und Zusammensetzung sowie die Molmassenverteilung der Polymere bleiben dabei erhalten. Schichten polarer oder ionischer Polymere der Dicke einer Quasi-Monolage bis hin zu mehreren 100 Nanometern können abgeschieden werden. Erwähnenswert ist, daß der ESI-Prozeß zu den elektrophoretischen Verfahren gehört, was die Ausbildung lochfreier Schichten auf elektrisch leitenden Substraten nicht nur auf der der Spraydüse zugewandten Seite ermöglicht, sondern auch auf der abgeschatteten Rückseite. Dieses Verhalten wurde zur vollständigen ESI-Umhüllung von dichtgepackten Kohlenstoff-Faser-Bündeln mit haftvermittelnden Polymerschichten ausgenutzt.
Nebulizing of polymer solutions, in a high-voltage field under atmospheric conditions by electrospray ionization (ESI), is a comfortable way to deposit ultra-thin layers of polar or ionic polymers onto any conductive substrate materials. The substrate is grounded and the polymer solution is sprayed through a powered capillary. The formed charged droplets shrink by solvent evaporation during their way to the grounded substrate, the charges close ranks and the droplets collapse consecutively by charge repulsion, thus forming finally charged single macromolecules. After their discharging at the grounded substrate, an ultrathin ‘quasi-monomolecular’ polymer layer is formed. It could be shown by imaging of scratches through the polymer layer by atomic force microscopy that the deposited polymer layers are dense at a thickness of about 10 nm. Carbon fibre bundles were coated with poly (allylamine) (PAAm) or poly(acrylic acid) (PAA) as potential adhesion-promoting layers in fibre–polymer composites. The polymer deposition is self-inhibiting after formation of a continuous coverage of about 200 nm for PAAm and 30 nm for PAA as result of surface charging. Continuous deposition onto such isolating layers or polymers without charging can be achieved by using current of alternating polarity. The film formation is self-healing because of the electrophoretic effect, i.e. the ion discharging occurs preferentially at noncoated areas. This electrophoretic effect of ESI was demonstrated by completely enwrapping all the carbon fibres of the roving within a distance of about 100 μm far from its outside and also at the backside of the fibre bundle with about 80% of the topside coverage, as measured by X-ray photoelectron spectroscopy and visualized using scanning electron microscopy.
Substrate-induced self-assembly of donor-acceptor type compounds with terminal thiocarbonyl groups
(2013)
Two types of conjugated thiocarbonyl-terminated compounds have been synthesized and their ability to be adsorbed on surfaces of the different nature, namely, glass, polytetrafluoroethylene (PTFE), and gold has been studied. Different morphology of the films prepared by thermal vacuum evaporation and drop-casting from solutions has been observed depending on the surface used. It has been found that gold surface has a unique property to influence self-assembly of both monolayer and larger aggregates or crystals of the compounds, in contrast to glass and PTFE substrates. It was found that thiocarbonyl group is able to be chemisorbed to the gold surface. However, it was concluded that in spite of the fact that the thiocarbonyl groups are important for the chemical interaction with the gold surface, physical adsorption on the substrate surface, compoundcompound and compound–solvent (when using solution) interactions are of great significance to drive self-assembly of the final film.
Degradation behavior of thin polystyrene films on exposure to Ar plasma and its emitted radiation
(2013)
Spin-coated films of amorphous polystyrene (PS) were exposed to argon plasma for a few seconds to several minutes. The PS film was either in direct contact with the plasma or was shielded from the direct plasma contact by filters with different cutoff wavelengths in the vacuum UV region or by a Faraday cage (FC) made from metal mesh to prevent the impinging of charged species. Only energy-rich neutrals and plasma radiation may be operative in presence of the FC. lithium fluoride (LiF) filter protects the sample from direct contact with the plasma. Wavelengths of plasma radiation shorter than c. 105 nm (≈ 11.8 eV) were cut off. Glass filters made of fused SiO2 have a cutoff at λ ≈175?nm completely the vacuum UV radiation of plasma (ca. 175 nm ≈ 7.0 eV). These energies are sufficient to produce C–C, C–H bond scissions in case of direct Ar plasma exposure and Ar plasma exposure with use of the LiF filter. Only quartz glass shielding did not produce significant effects on the polymer surface in comparison to the reference PS, either in surface energy or O/C ratio or in IR spectra. Oxygen plasma has worked most aggressive and had etched the PS film, thus establishing a steady state between introduction of new oxygen functionalities and polymer etching. Ar plasma exposure produces also oxidation and etching of the polymer films as the oxygen plasma. Using of a FC during Ar plasma exposure or the LiF filter a slightly weaker oxidation was observed.
Poly(allyl alcohol) films with a thickness of about 150 nm were deposited by pulse plasma polymerization onto different substrates (inorganic and organic). The structure/property relationships of these samples were studied in dependence on the duty cycle (DC) of the plasma by a broad combination of different techniques and probes. For the first time volume sensitive methods (FTIR and dielectric spectroscopy) are combined with surface analytics by employing XPS for that system. FTIR spectroscopy gives qualitatively the same dependence of the concentration of the OH groups on DC like XPS.
The observed differences are discussed considering the different analytical depths of both the methods. The dielectric measurements show that the plasma deposited films are not thermally stable but undergo a post plasma chemical reaction during heating. The results obtained by dielectric spectroscopy are discussed in detail with the data from FTIR and XPS measurements.
Polystyrene (PS) spin coated thin films were modified by O2 and Ar plasma as
well as by UV irradiation treatments. The modified PS samples were compared with
plasma polymerized and commercial polystyrene. The effects of plasma (O2 and Ar) and
UV irradiation treatments on the surface and the bulk properties of the polymer layers were
discussed. The surface properties were evaluated by X-ray Photoelectron Spectroscopy and
Contact angle measurements and the bulk properties were investigated by FTIR and
dielectric relaxation spectroscopy. As a result only one second treatment time was sufficient
to modify the surface. However, this study was also dedicated to understand the effect
of plasma and plasma irradiation on the deposited layers of plasma polymers. The
dielectric measurements showed that the plasma deposited films were not thermally stable
and underwent an undesired post-plasma chemical oxidation.
Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition and their structures were studied in dependence on the duty cycle (DC) for a fixed composition of 1:1. As a result, low values of DC doses preserve the structure of monomers in the plasma deposited polymers while high DC leads to a higher degree of fragmentation and a loss in regular structure. Regarding plasma copolymerisation as a feasible method to finish surfaces with a definite number of functional groups it is necessary to characterize both, the chemical nature and the physical properties of the deposited layer. Therefore, a combination of different methods was employed for the characterization of thin plasma copolymer films (FTIR, dielectric spectroscopy, differential scanning calorimetry, X-ray photoelectron spectroscopy (XPS)). Special attention was paid on the unambiguous identification of COOH groups at the surface after derivatization with trifluoroethanol by XPS and in the volume by FTIR. The glass transition temperature of the copolymer system is lower than that for the both plasma deposited homopolymers and increases with the DC in difference to plasma deposited poly(acrylic acid). The dielectric measurements showed that the plasma deposited films were not thermally stable and underwent an undesired post-plasma chemical reaction. The results obtained by dielectric spectroscopy are discussed in detail in comparison with the data from FTIR and XPS measurements.
Copolymers of acrylic acid and styrene (AA/S) were prepared by pulsed plasma deposition technique. Their structure–property relationships were studied in dependence on the comonomer ratio. Both, the regularity of the structure and the composition of the thin copolymer films were investigated by bulk-sensitive (dielectric spectroscopy, FTIR, and differential scanning calorimetry) as well as surface-sensitive methods such as X-ray photoelectron spectroscopy (XPS). For an unambiguous identification of the functionality of the deposited films the COOH groups were estimated by derivatization with trifluoroethanol and subsequent XPS measurement as well as by the quantitative analysis of the FTIR data. As a result, the concentration of COOH groups on the surface and in the bulk is increasing with the fraction of AA in precursor mixture in a non-monotonous way but similar to the dependence obtained by conventional free radical polymerization.