There is a growing awareness of the risks of pollution in biological systems and one potential problem is the synthetic antioxidants, used for e.g. the stabilisation of polymeric materials. Natural antioxidants are an interesting alternative, if the high efficiency and thermal stability of the synthetic compounds can be reached. In the work described in this thesis, vitamin E (alfa-tocopherol) was studied as a natural antioxidant for the stabilisation of one of the major plastics, polyethylene (PE). The dependence of the surrounding environment for the efficiency of alfa-tocopherol in polyethylene (PE), throughout thermal aging, was characterised by sensitive techniques. Two techniques which have shown a high sensitivity in oxidation detection of polymers; chemiluminescence (CL) and gas chromatographic analysis, were compared with the commonly used methods, infrared spectroscopy (FT-IR) and thermal analysis. Three different additive systems were selected as active domains for -tocopherol in PE. Two of these contained carboxylic acid groups, poly (ethylene-co-acrylic acid) (EAA) and polyTRIM/PAA core-shell particles (Core), and the third, oat starch, had no such groups. The additives containing carboxylic groups improved the long-term efficiency of alfa-tocopherol in PE, according to carbonyl index measurements made by FT-IR, while the additive without carboxylic acid groups gave no improvement. The amount of carboxylic acids emitted from the materials after thermal aging, assessed by head-space solid-phase microextraction (HS-SPME) and gas chromatography-mass spectroscopy (GC-MS), also showed that EAA increased the antioxidant efficiency of alfa-tocopherol, whereas the Core system showed lower antioxidant efficiency. Reference systems containing the synthetic antioxidant Irganox 1076 and EAA or oat starch had the same performance as the materials stabilised with only the antioxidants. CL measurements in an inert atmosphere (TLI) have earlier been shown to give earlier oxidation detection than carbonyl index measurements in unstabilised PE. In this work, the TLI analysis and the carbonyl index measurements had the same sensitivity in the detection of oxidation in the stabilised materials. Assessment of low-molecular weight carboxylic acids in PE during the aging was made by gas chromatographic analysis together with solid-phase extraction. Propanoic acid showed the best correlation with the carbonyl index measurements, even if the carbonyl index showed earlier detection of oxidation. It was also found that TLI and CL in an oxidative atmosphere (CL-OIT) had the same sensitivity and were in accordance for all of the materials, with exception of the materials containing EAA and alfa-tocopherol or Irganox 1076. CL-OIT was also compared to the oxygen induction time determined by thermal analysis. / QC 20100921

Im Rahmen der Arbeit wurde ein semi-analytisches Berechnungsmodell für den Reibwert einzelner kugelförmiger Erhebungen erarbeitet, das die Berechnung der deformativen (μ_def) und adhäsiven (μ_adh) Reibanteile ermöglicht. Die Integration eines plastischen (Radius der Laufspur R_Spur) und eines viskosen (Rückstellwinkel ω) Verformungsanteils gestattet die Berechnung der realen Kontaktfläche während des Reibvorgangs. In Abhängigkeit des mittleren Kontaktdrucks kann damit der adhäsive Reibanteil μ_adh bestimmt werden. Die experimentelle Untersuchungen umfassten neben ungeschmierten Reibversuchen, die zur Ermittlung des gesamten Reibwertes (μ_ges) dienten, auch mit Silikonöl geschmierte Versuche aus denen sich μ_def ergibt. Anhand der Verifikationsversuche konnte einerseits gezeigt werden, dass beide Schmierungszustände zu gleichen Verformungen führen und andererseits wurde der Nachweis erbracht, dass der im Berechnungsmodell postulierte Zusammenhang zwischen dem Rückstellwinkel ω und μ_def Gültigkeit besitzt. Hierzu wurden Reibversuche mit segmentierten Kugeln durchgeführt, die eine gezielte Variation des Rückstellwinkels ω erlauben. Für beide untersuchten Reibpaarungen (Stahl | PE-UHMW und POM-C | PE-UHMW) kann abgeleitet werden, dass der deformative Reibanteil μ_def generell von untergeordneter Rolle ist (ca. 1/3 μ_ges) und der Einfluss des adhäsiven Reibanteils μ_adh überwiegt (ca. 2/3 μ_ges). Dabei sinkt μ_adh und folglich auch μ_ges mit zunehmendem Kontaktdruck p_(max,Ebene). Dieser wurde als verallgemeinerte Bezugsgröße eingeführt und beschreibt den maximalen Hertz´schen Kontaktdruck eines äquivalenten Kugel-Ebene-Kontaktes, der sich unter Eingabe des Kugelradius r_Kugel, der Normalkraft und der Verwendung der statischen E-Moduln beider Werkstoffe ergibt. Weiterhin zeigten die Untersuchungen, dass die oszillierende Bewegungsform im Vergleich zur rotierenden Bewegung immer einen erhöhten Reibwert μ_ges auszeichnet. Abschließend wurden noch Reibexperimente zu Mehrfachstrukturen aus POM-C mit je 6 Einzelerhebungen im Kontakt durchgeführt. Auch hier lag eine hohe Übereinstimmung zwischen Experiment und Modell vor. Es konnte gezeigt werden, dass Reibwerte für beide Bewegungsformen auf μ_ges ~ 0,13 gesenkt werden können. Bezogen auf den jeweiligen höchsten Reibwert (μ_(ges,rotierend) ~ 0,24, μ_(ges,oszillierend) ~ 0,34), welcher mit glatten Probekörpern ermittelt wurde, stellt dies eine erhebliche Reduktion dar. / In this thesis, a semi-analytical calculation model for the coefficient of friction (COF) of single spherical protrusions which allows the calculation of the deformative (μ_def) and adhesive (μ_adh) friction parts was developed. The integration of a plastic (radius of the running track R_Spur) and a viscous (rear angle ω) component of deformation allows the calculation of the real area of contact during the friction process. Depending on the mean contact pressure, the adhesive friction part μ_adh can be determined. The experimental studies included unlubricated friction tests, which served to determine the total COF (μ_ges), as well as tests being lubricated with silicone oil, from which μ_def is obtained. Based on the verification tests, it could be shown that both states of lubrication result in the same deformation and that the relationship between the rear angle ω and μ_def postulated in the calculation model is valid. Therefore, friction tests were carried out with segmented spheres, which allow a specific variation of the rear angle ω. For both friction pairings investigated (steel | PE-UHMW and POM-C | PE-UHMW), it can be concluded that the deformative friction part μ_def is generally of minor significance (approx. 1/3 μ_ges) and the influence of the adhesive friction part μ_adh predominates (approx. 2/3 μ_ges). Thereby μ_adh and consequently also μ_ges decreases with increasing contact pressure p_(max,Ebene). The latter was introduced as a generalised reference value and describes the maximum Hertzian contact pressure of an equivalent sphere-plane contact, which is obtained by entering the radius of the sphere r_Kugel, the normal force and using the static E-moduli of both materials. Furthermore, the investigations revealed that the oscillating form of motion always has an increased COF μ_ges compared to the rotating motion. Finally, friction experiments on multiple structures made of POM-C were carried out, each with 6 individual protrusions in contact. Also here, there was good agreement between the experiment and the model. It could be demonstrated that COF for both forms of motion can be reduced to μ_ges ~ 0.13. In comparison to the highest COF (μ_(ges,rotating) ~ 0.24, μ_(ges,oscillating) ~ 0.34), which were obtained with flat specimens, this is a significant reduction.