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Validierte Messverfahren für die nichtgeometrische Größe Hydrophilie - Anwendung in der Mikrofluidik
(2011)
Plasma deposited ethylene/allylamine and styrene/allylamine copolymer films were prepared and analyzed using XPS, NEXAFS and ToF-SIMS. The relative partial flow rate of the each monomer was used as the variable deposition parameter, while the other deposition parameters were kept constant at optimized values for the retention of functional groups. The effect of the variation in the relative partial flow rates of co-monomers on various chemical aspects of the films like unsaturation, nitrogen retention and branching was investigated revealing several non-linear correlations. This observation is taken as an indication for chemical copolymerization processes during film deposition. An attempt is made to compare these non-linear correlations with approaches which have been developed for classic radical copolymerization processes. The aging behavior of these plasma copolymer films was also studied; the results indicated a stabilization against oxidation in comparison to the aging of allylamine plasma homopolymers.
Plasma deposited styrene/allyl alcohol and ethylene/allyl alcohol copolymer films were prepared and characterized using XPS, NEXAFS and ToF-SIMS. The relative partial flow rates of the co-monomers are used as deposition process parameters to vary and all other process parameters were constrained to conditions optimized for retention of functional groups. By doing this it is possible to control certain chemical properties of the copolymer films such as unsaturation, oxygen and hydroxyl group relative surface contents. The aging behavior of the plasma copolymer films on air was studied, too. Non-linear variations of relative oxygen contents, contents of C—OR species and contents of carbonyl species are obtained vs. variation of feed gas composition for both monomer combinations. The chemical character of the plasma copolymer films varies between the limits given by the respective plasma homopolymers. The observed non-linear correlations are discussed in terms of approaches developed for classic radical copolymerization. The aging behavior of the different plasma copolymers films depends on the feed gas composition. Principally these aging phenomena known from plasma polymer aging studies of that respective monomer which dominates the character of the plasma copolymer are observed.
XPS and NEXAFS spectroscopy were used for the chemical characterization of pulsed plasma-deposited ethylene films before and after exposure to ambient air. The influence of external plasma parameters on the spectroscopic results was investigated. Information on the chemical character of the plasma-polymerized films, such as the regularity of the primary structure, the amount of long-living radicals, and branching or cross-linking or both was derived from this data. Irregularity and radical concentration for post-plasma reactions of the plasma-deposited films increased with the duty cycle or power. A decreased level of monomer fragmentation and, consequently, an increase in regularity is partially concluded from the experimental data when the monomer pressure is increased. The concentration of surface radicals available for post-plasma reactions also increased with monomer pressure. The correlation found between the degree of the post-plasma oxygen incorporation and the variation of the various external parameters agreed with earlier ToF-SSIMS findings.
Pulsed-plasma-deposited ethylene films were studied by time-of-flight static secondary ion mass spectrometry (ToF-SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma-deposited ethylene films was investigated. From these data, information on the chemical character of the plasma-deposited ethylene films was derived. The investigation of the effect of external plasma parameters on the chemical character of the plasma-deposited ethylene films revealed that there were some drastic changes in the secondary ion mass spectra of the films. It was found that fragmentation and re-arrangement of the monomer molecules in the plasma, which affects the chemical character of the deposited films, vary according to the external plasma parameters. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of. Some indications for the formation and decay of peroxy radicals (COO) and, subsequently, hydroperoxides (COOH) are found. It was observed that the oxygen uptake of the plasma deposited ethylene films increase when the plasma conditions become harder.
Chemical properties of plasma-polymerized styrene films can be effectively controlled by the appropriate choice of external plasma parameters, such as duty cycle, power and monomer pressure. Chemical properties here are the regularity of the primary structure, the amount of long living radicals and branching or cross-linking or both in plasma polymerized styrene films, which can be indirectly monitored by X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. Principally, XPS and NEXAFS spectra of plasma-polymerized styrene show all the spectroscopic fingerprints characteristic of atactic polystyrene indicating an inherent similarity of the respective primary chemical structures. There is an increase in irregularity and radical concentration for the plasma deposited films with increasing duty cycle or power. With an increase in monomer pressure, a decreased level of monomer fragmentation and, consequently, an increase in regularity must be concluded from the experimental data. The applied power regulates the fragmentation of the monomers as monitored by spectroscopic signals correlated to the aromatic rings. A trend in the extent of the post-plasma oxygen incorporation according to the variation of the various external plasma parameters was deduced, which agrees with earlier ToF-SIMS findings
Pulsed plasma-deposited polystyrene films were studied by time-of-flight static secondary ion mass spectrometry (ToF-SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma-deposited polystyrene films was investigated. From these data, information on the chemical character of the plasma polystyrene films was derived. In the range of deposition conditions applied in this study, the fragmentation of styrene is a minor process. The main process is probably the radical chain propagation to polymers. All the polystyrene plasma polymers, relying on ToF-SIMS, seem to be rather similar to a reference polystyrene oligomer sample. When the plasma polymers are exposed to air, extensive oxygen incorporation occurs. Oxygen uptake was found to alter the emission probabilities of secondary ions. A relation between the regularity of the plasma polymers and the amount of oxygen incorporation was found. The result was that the chemical regularity of the plasma polystyrene decreases when the effective power in the plasma is increased.
Pulsed plasma deposited styrene and ethylene films were studied by Time of Flight Static Secondary Ion Mass Spectrometry (ToF-SSIMS) before and after exposure to ambient air. The influence of the external plasma parameters on the secondary ion mass spectra of plasma deposited films was investigated. Approaches for the interpretation of SSIMS spectra of organic materials were reviewed and applied to the evaluation of SSIMS data of plasma deposited films. From these data, information on the chemical character of the plasma deposited films was derived.
When the plasma polymers are exposed to air oxygen incorporation occurs. The oxygen uptake is high at the beginning and then it levels of.
A relation that higher the regularity of the film lower is the oxygen uptake was found. Harder plasma conditions, which could be obtained by applying higher plasma power or lower monomer flow rate, result in higher oxygen uptake and vice versa.