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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.
The German Federal Institute for Materials Research and Testing (BAM) has established a testing guideline to assess the suitability of geosynthetic or geocomposite drain (GCD) elements for final landfill cover systems. In an earlier paper the uniform procedure according to the BAM guideline for determining long-term water flow capacity was described, and the structural stability of drain cores under creep was investigated. The extrapolation of creep curves is permissible only when it can be shown, over the extrapolated period (at least 100 years), that oxidative aging does not invoke any relevant changes in the polyolefin material. This can be shown by measuring antioxidant depletion and mechanical degradation of the drain cores and filter/protection geotextiles in oven aging and water immersion tests. In this paper the results of such aging studies on three different GCD products are reported. Degradation of the tensile strength of HALS-stabilized polypropylene needle-punched nonwoven geotextiles (PP NWGTs) starts right from the beginning of the oven aging. This has to be taken into account for lifetime predictions based on residual tensile strength. The rate of oxidative degradation of NWGTs decreases significantly with increasing mass per area. Therefore the expected service life sets a limit on acceptable geotextile grammage. Antioxidant depletion in the drain cores, which are made of relatively thick PP strands or HDPE ribs, is about an order of magnitude slower than in filter and protection NWGTs, which are made of thin fibers. Service life values in excess of 100 years may be obtained for the products when the geotextiles and drain cores are properly stabilized and designed.
Hydrolytic degradation and functional stability of a segmented shape memory poly(ester urethane)
(2009)
In order to understand the effects of water and hydrolytic ageing on semi-crystalline poly(ester urethane) and its shape memory functionality, water immersion experiments at elevated temperature have been performed on a model substance and various parameters were monitored: change of the melting/crystallisation temperatures, substantial increase in crystallinity, temperature dependence of the water diffusion coefficient and solubility, hydrogen-bonding index and phase mixing by peak deconvolution of the FT-IR carbonyl region and day-to-day tensile and thermo-mechanical cyclic tensile tests. A rising fraction of freezable water agglomerates in the polymer was found for specimens cooled from the immersion temperature. The degradation process could be divided into three phases: an induction phase, a phase of continuous degradation and a phase of accelerated degradation. Shape recovery remains fairly constant during phase one and decreases slowly during phase two. The increase in crystallinity in phase two is accompanied by an increase in shape fixing ability.
Long-term water flow capacity of geosynthetic drains and structural stability of their drain cores
(2008)
Geosynthetic clay liners (GCLs) often have a sandwich-like multilayer structure, e.g. bentonite encased between two geotextile layers connected by fibers or yarns, either by needle-punching or stitch-bonding. Therefore, the internal shear strength of the GCL depends on the strength of reinforcing fiber bundles or yarns and their anchoring strength in the cover and carrier geotextiles. When used on long and steep slopes and covered with thick soil layers, the GCL is permanently exposed to a combined action of compressive and shear stress. Such load conditions are characteristic for landfill covers and the slope stability of the overall cover system in the long run strongly depends on the long-term internal shear strength of the GCL. A new test method was developed to study this long-term shear behavior. The focus was not only on creep, as it is normally done, but on aging effects. The shear test devices allow the measurement of creep curves and times-to-failure at elevated temperatures in different media (tap water and de-ionized water). In this publication, the main findings of the experiments on needle-punched GCLs with and without thermal treatment are summarized. Tap water as a test medium was essential to ensure sodium to calcium ion exchange in the bentonite layer. Under this condition extremely long test durations without failure were achieved. Sliding failure occurred when de-ionized water was used. Two failure modes were observed: brittle failure of the GCLs with thermal treatment and slow disentanglement of fiber bundles for untreated GCLs. Short-term shear strength (e.g. peel strength) is unrelated to the actual long-term shear strength, i.e. to the times-to-failure achieved in long-term shear strength test. Hence, short-term shear strength alone will not provide reliable dimensioning data for product design and choice of resins. Therefore, the often suggested approach, namely, restriction to short-term tests only and application of factors of safety, is challenged by these results.
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. 683690; Clay Geosynthetic Barriers, Balkema, Lisse, The Netherlands, 2002, pp. 8796), lower limits of the half-live of the degradation at worst case field conditions were obtained in the range 3083 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.
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.