TY - JOUR A1 - Müller, Werner A1 - Büttgenbach, Beate A1 - Jakob, Ines A1 - Mann, Heidemarie T1 - Comparison of the oxidative resistance of various polyolefin geotextiles N2 - Data are reported from oven aging in circulating air and water immersion tests at 80°C on various polyolefin (polyethylene (PE) and polypropylene (PP)) needle-punched nonwoven geotextiles (GTnws) and the results of these long-term tests are compared with the oxidative resistance of high-density PE geomembranes (HDPE GMs) described in a preceding paper (Polym. Degr. Stability 79(1) (2003) 161). Polyolefin fibers used in geotextiles are typically less stabilized, have a very high surface-to-volume ratio and an oriented morphology compared with HDPE GMs. Therefore, significant differences in the oxidation behavior of these products are expected which may affect their durability. Two general results can be obtained from our measurements: Firstly, while the lifetime of the HDPE GM is essentially determined by the slow loss of stabilizers, for all GTnws a rapid reduction in the oxidative induction time (OIT) and, as we conclude, in the amount of stabilizer was observed during water immersion and air aging. Secondly, the mechanical property degradation of the GTnws depended strongly on the oxidation conditions: the induction period prior to the degradation was much longer for immersion in water than for oven aging in circulating air. After antioxidant depletion, an induction time of the oxidation reaction, which depends on the draw ratio of the stretched fibers and the oxygen supply, might substantially contribute to the induction period of the mechanical property degradation of GTnws. For one PP GTnw product, a sudden reduction in the mechanical strength occurred after onset of degradation which continued rapidly until complete deterioration. For other PP samples as well as for all PE GTnws the reduction in mechanical strength proceeded slowly. Best fits were obtained by modeling the degradation process of the PE GTnws by a second-order kinetic. Using an activation energy of 60 kJ/mol (Geotextiles, Geomembranes and Related Products, Balkema, Rotterdam, 1990; Conference Proceedings of the Sixth International Conference on Geosynthetics, Industrial Fabrics Association International (IFAI), Atlanta, USA, 1998, pp. 683–690; Clay Geosynthetic Barriers, Balkema, Lisse, The Netherlands, 2002, pp. 87–96), lower limits of the half-live of the degradation at worst case field conditions were obtained in the range 30–83 years. Some decades have to be added for the overall induction time. However, under field conditions with limited oxygen supply, the expected service lifetime might be at least half an order of magnitude longer. KW - Durability KW - Geotextile KW - Oxidative resistance KW - Test methods KW - Long-term testing PY - 2003 DO - https://doi.org/10.1016/S0266-1144(03)00032-3 SN - 0266-1144 VL - 21 SP - 289 EP - 315 PB - Elsevier CY - Amsterdam AN - OPUS4-2632 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, Werner A1 - Jakob, Ines T1 - Oxidative resistance of high-density polyethylene geomembranes N2 - Data are reported from oven aging in air for more than 13 years (!) and from water immersion tests for 6 years at 80 °C on various high-density polyethylene geomembranes (GM) used in landfill lining. The mechanical properties and oxidative induction times (OIT) of the samples were monitored during the long-term testing. Aging behavior in hot air is different from that in hot water. During oven aging a slow, exponential decrease of OIT is observed. Even after 13.6 years there is no indication of an oxidative degradation of the mechanical properties. During immersion in water a strong reduction in OIT occurs within the first year, after which time the curve levels off. Oxidation starts when very low OIT-values are reached after about 5 years at which time the mechanical strength rapidly falls to values below the yield point. We conclude from these data that the service life of HDPE GM's is essentially determined by the slow loss of stabilizers due to migration. The oxidation starts only after the depletion of antioxidants and then quickly leads to brittleness of the sample. However, no complete oxidative deterioration has been observed to date. We estimate by the van't Hoff rule that under normal ambient conditions many centuries will have to pass before the functional mechanical properties of state-of-the-art stabilized HDPE bulk material will be reduced below acceptable limits by oxidative degradation. KW - Durability KW - HDPE geomembrane KW - Oxidation KW - Oxidative resistance testing PY - 2003 DO - https://doi.org/10.1016/S0141-3910(02)00269-0 SN - 0141-3910 SN - 1873-2321 VL - 79 IS - 1 SP - 161 EP - 172 PB - Applied Science Publ. CY - London AN - OPUS4-2134 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Müller, Werner A1 - Jakob, Ines A1 - Robertson, Daniela A1 - Tatzky-Gerth, Renate A1 - Wöhlecke, Andreas T1 - Die oxidative Alterung von Geokunststoffen aus Polyethylen und Polypropylen N2 - Geokunststoffe aus Polyethylen (PE) oder Polypropylen (PP) müssen mit Antioxidantien (AO) stabilisiert werden, damit sie die für die Anwendung in der Geotechnik erforderliche Lebensdauer erreichen. Die Lebensdauer ist dann aber nicht durch die Empfindlichkeit des Polymers gegen Oxidation, sondern durch den Verlust der AO im Laufe der Zeit bedingt. AO können durch den Verbrauch bei Oxidationsreaktionen, durch den Abbau im Polymer, durch die Wanderung an dessen Oberfläche, durch den Abbau auf der Oberfläche, schließlich durch Abdampfen von der Oberfläche oder durch sich Lösen in einem umgebenden flüssigen Medium verloren gehen. Bei den Geokunststoffen aus PP und PE wie auch bei anderen polyolefinen Kunststoffprodukten findet man häufig zwei bestimmte „Pakete“ aus Antioxidantien: (1) eine Kombination von Substanzen aus bestimmten Klassen von sterisch gehinderten Phenolen und Phosphiten und (2) eine Substanz aus der Klasse der sterisch gehinderten Amine (HAS) in Verbindung mit einer geringfügigen phenolischen und phosphitischen Verarbeitungsstabilisierung der Formmasse. Der Verlust der AO wie auch der oxidative Abbau der mechanischen Eigenschaften des Geokunststoffs verläuft ganz unterschiedlich, je nachdem mit welchem Paket stabilisiert wurde. Diese Unterschiede werden im Rahmen eines „3-Stadien-Modells“ diskutiert. Stadium A: die Antioxidantien gehen verloren. Stadium B: die Oxidation läuft langsam an. Stadium C: die Oxidation wirkt sich mehr oder weniger drastisch auf die Produkteigenschaften aus. Dabei zeigt sich, dass das Modell nur auf das Paket 1 anwendbar ist. Im Falle des Pakets 2 findet in gewissem Umfang schon im Stadium A ein oxidativer Abbau statt, ln beiden Fällen ist es aber die AO-Verlustzeit die eigentlich die Lebensdauer bestimmt. Es werden dann Abschätzungen der Lebensdauer von PEHDDichtungsbahnen und von PP-Vliesstoffen gegeben. Die Prüfung und Bewertung der oxidativen Beständigkeit muss die Eigenart der Wirkung und des Verlusts unterschiedlicher Stabilisierungen berücksichtigen. Vor diesem Hintergrund wird die Hochdruck-Autoklav-Prüfung beurteilt. Es werden die Besonderheiten dieser Prüfmethode aufgezeigt, die sich jeweils bei der Anwendung auf Produkte ergeben, die entweder mit dem Paket 1 oder dem Paket 2 stabilisiert wurden. Eine Vorhersage der Lebensdauer unter Anwendungsbedingungen aus den Ergebnissen der Autoklav-Prüfung ist sehr schwierig und vermutlich nur in bestimmten Fällen überhaupt möglich. Ähnliches gilt auch für die vergleichende Bewertung der oxidativen Beständigkeit von Produkten. T2 - Fachtagung Nutzungsdauer von Rohren und Geokunststoffen aus Polyolefinen CY - Würzburg, Germany DA - 14.11.2013 KW - Geokunststoffe KW - PE KW - PP KW - Oxidative Alterung PY - 2013 SP - 1 EP - 48 PB - SKZ - Das Kunststoff-Zentrum CY - Würzburg AN - OPUS4-29606 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müller, Werner A1 - Jakob, Ines A1 - Tatzky-Gerth, Renate A1 - Wöhlecke, Andreas T1 - A Study on antioxidant depletion and degradation in polyolefin based geosynthetics: sacrificial versus regenerative stabilization N2 - Plastic products used in geotechnical engineering, so-called geosynthetics, are often made of polyolefins (polyethylene or polypropylene) and stabilized against oxidative degradation by antioxidants (AO). Three types of AO “packages” are used: (P1) phenols and phosphites/sulfides, (P2) hindered amines (HAS) with a marginal stabilization P1 of the basic resin, (P3) a combination of packages P1 and P2 with comparable amounts of phenol and HAS. We report about long-lasting oven aging and water immersion tests at 80 °C of 29 different polyolefin based products (geomembranes, geonets and geotextiles). Pronounced differences in the degradation behavior were found depending solely on the type of AO package. In case of P1, the oxidative degradation is prevented by the AO. Autocatalytic oxidation only begins after depletion of AO and may lead to catastrophic failure depending on the environmental conditions. In case of P2, degradation starts right from the beginning. However, it is decelerated and proceeds gradually. In case of P3, the degradation behavior seems to be a superposition of the characteristics obtained for P1 and P2. Plotting the fractional loss of the AO in P1 and P2 as function of the square root of aging time, we identified two regimes of AO depletion. We suggest to attribute this observation to the different mechanisms of AO depletion. KW - Geosynthetics KW - Oxidation KW - Antioxidant KW - Stabilization PY - 2016 DO - https://doi.org/10.1002/pen.24199 SN - 0032-3888 VL - 56 IS - 2 SP - 129 EP - 142 PB - John Wiley & Sons CY - New York AN - OPUS4-35630 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -