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  • 1
    ISSN: 1572-8978
    Keywords: Plasma polymers ; oxidation ; XPS ; photoelectron binding energy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Technology
    Notes: Abstract The incorporation of oxygen into nitrogen-containing plasma deposited polymers was studied by X-ray Photoelectron Spectroscopy (XPS). As the oxygen content of the plasma polymer increased, the binding energy of the N 1s photoelectrons increased. Conversely, the binding energy of the O 1s photoelectrons was inversely proportional to the nitrogen content of the plasma polymer. The data from a large number of samples all obeyed the same “universal” correlations of photoelectron binding energy versus chemical composition. The data were described by the same curve regardless of whether the oxygen was incorporated rapidly into the thin film during plasma deposition or whether the oxygen was added slowly during spontaneous oxidation of the film in air. This implies that the same thermodynamic principles of radical reactions governed the addition of oxygen to the plasma polymer. The shift in the O 1s and N 1s photoelectron binding energies as a function of chemical composition was used to monitor the proximity of nitrogen and oxygen. By contrasting the experimental data with a simple binomial model which described the random addition of oxygen to a lattice containing carbon and nitrogen, we were able to show that oxygen was preferentially added near nitrogen-containing groups in plasma polymers.
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  • 2
    Electronic Resource
    Electronic Resource
    Chichester [u.a.] : Wiley-Blackwell
    Surface and Interface Analysis 26 (1998), S. 498-511 
    ISSN: 0142-2421
    Keywords: plasma polymers ; fluorocarbons ; oxidation ; ageing ; surface restructuring ; XPS ; FTIR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Plasma polymer coatings were deposited from perfluoro-1,3-dimethylcyclohexane (PFDMCH) and their composition and surface properties studied by XPS, grazing-angle Fourier transform infrared spectroscopy and contact angle measurements as a function of time after fabrication as they were stored under ambient conditions for more than 2 years. The spontaneous ambient oxidation of PFDMCH plasma polymers was found to be a multi-step process. The rapid initial oxygen uptake, assigned to reaction between carbon-centred radicals incorporated into the coating during deposition and in-diffusing atmospheric O2, was similar to that of plasma polymers deposited from hydrocarbon-based monomers (alkanes, alkylamines, alcohols), suggesting that the density of radicals incorporated during deposition was similar. Subsequently, however, the extent of oxidation was much lower for PFDMCH coatings. This can be attributed to the lack of availability of hydrogen abstraction reactions, which are important for radical propagation in hydrocarbon-based plasma polymers. While XPS recorded a continuous incorporation of oxygen for more than 2 years, the air/water contact angles decreased only during the first 2 months and on further storage remained stable. There appeared to be only a small extent of surface restructuring as assessed from the small depth variations of compositions. The surface was enriched in CF3 groups at all times. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 9 Ill.
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  • 3
    ISSN: 0142-2421
    Keywords: XPS ; coating thickness ; global analysis ; multilayers ; curvature ; roughness ; atomic force microscopy ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Physics
    Notes: Approaches are described for the analysis of XPS signals from samples comprising thin conformal coatings on substrates with non-ideal surface topography. In particular, attention is focused on arbitrarily shaped rough or curved substrates. Relations are derived for the relative x-ray photoelectron intensities emitted from various elements in such non-ideal samples. The surface topography of arbitrarily rough samples is analysed by atomic force microscopy to provide a frequency histogram of the local slopes, which is incorporated into a global, multi-element analysis method for interpretation of the observed XPS elemental intensities. An analogous approach is used for the analysis of curved samples. Our algorithms also enable simultaneous analysis of successively coated multilayer structures. When the elemental composition of the individual layers is known, the fit procedure enables determination of the thickness values of single-layer and multilayer coatings. The range of validity of the theory is discussed. © 1997 by John Wiley & Sons, Ltd.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 32 (1994), S. 1399-1414 
    ISSN: 0887-624X
    Keywords: plasma polymers ; oxidation ; XPS ; FTIR ; SEM ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Long-term compositional changes were observed when n-hexane plasma polymers were stored in air at ambient temperature. These post-deposition changes were monitored over periods exceeding one year using XPS, grazing angle FTIR, and SEM. A rapid initial increase in the oxygen content was followed by a slower oxygen uptake, which continued for many months. In contrast to the reported autocatalytic acceleration of the oxidation of polyolefins, the rate of oxidation of n-hexane plasma polymers was found to decrease continuously, and it did not proceed to the same extent toward higher oxidation states. The plasma polymer coatings did not show physical manifestations of oxidative degradation such as cracking, reduction in thickness, or loss of physical integrity. Comparison of the XPS and FTIR data suggested that the top few nanometers of the plasma polymer coatings oxidized at a faster rate than the “bulk.” The experimental data were interpreted using a model comprising reactions known from the oxidative degradation of polyolefins: carbon-centered radicals, trapped in the course of the plasma deposition, combine with atmospheric oxygen to form metastable peroxy radicals and hydroperoxides, which decompose to generate a variety of stable product groups such as hydroxyl, carbonyl, and carboxylic groups. There was broad agreement between the XPS data and the time dependence of particular species in model calculations. © 1994 John Wiley & Sons, Inc.
    Additional Material: 10 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 36 (1998), S. 985-1000 
    ISSN: 0887-624X
    Keywords: plasma polymers ; methyl methacrylate ; oxidation ; long-term stability ; XPS ; FTIR ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Plasma polymer films were deposited from methyl methacrylate (MMA) vapor under various plasma conditions and XPS and FTIR used to study the changes to the compositions of the films as they were stored in air for longer than 1 year. The plasma power input per monomer mass unit (W/FM) markedly affected the composition of the freshly deposited MMA plasma polymers. A low value of W/FM led to a high degree of retention of the original monomer structure, whereas a high value of W/FM resulted in substantial monomer fragmentation and the formation of a partially unsaturated material considerably different to conventional PMMA. As the MMA plasma coatings were stored in ambient air after fabrication, all showed spontaneous oxidative changes to their composition, but the extents and reaction products differed substantially. Deposition at low W/FM led to moderate oxidative changes, whereas high power led to a pronounced increase in the oxygen content over time and resulted in a wide range of carbon-oxygen functionalities in the aged material. As the initial compositions/plasma deposition conditions thus influenced the oxidative postdeposition reactions, MMA plasma polymers deposited under different conditions not only varied in their initial composition but then became even more diverse as they aged. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 985-1000, 1998
    Additional Material: 11 Ill.
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