TY - JOUR A1 - Ramanujam, Maalolan A1 - Wachtendorf, Volker A1 - Purohit, Purv A1 - Mix, Renate A1 - Schönhals, Andreas A1 - Friedrich, Jörg Florian T1 - A detailed dielectric relaxation spectroscopy study of artificial UV weathered low density polyethylene N2 - Artificial weathering of LDPE under dry conditions (<10% of relative humidity) by UV radiation was monitored by dielectric spectroscopy. For an apolar polymer like LDPE, dielectric study yields Information about the change in structure and dynamics of the system. The fluctuations of the polar groups which are generated as a result of photooxidation such as carbonyl groups can be monitored as characteristic relaxation processes like the αc or β mode. The dielectric loss characterized by typical dielectric parameters like the activation energy and dielectric strength are strongly dependent upon changes induced by photooxidation in the amorphous and crystalline domains. This paper discusses in detail how the foil reached its mechanical disintegration. It was found that initial stages of weathering induce chain scission and/or crosslinking in the amorphous domains of the polymer and the motional processes in the crystalline regions are not affected. After this induction period, an increase in the degree of crystallization was observed by employing differential calorimetry. The increasing crystallinity is considered as one of the reasons for embrittlement which finally leads to the complete loss of the structural integrity. KW - Artificial weathering KW - UV radiation KW - Dielectric relaxation KW - LDPE PY - 2012 DO - https://doi.org/10.1016/j.tca.2011.12.003 SN - 0040-6031 SN - 1872-762X VL - 530 SP - 73 EP - 78 PB - Elsevier CY - Amsterdam AN - OPUS4-25547 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ciornii, Dmitri A1 - Hodoroaba, Vasile-Dan A1 - Wachtendorf, Volker A1 - Fengler, Petra A1 - Altmann, Korinna T1 - Interlaboratory Comparison Reveals State of the Art in Microplastic Detection and Quantification Methods N2 - In this study, we investigate the current accuracy of widely used microplastic (MP) detection methods through an interlaboratory comparison (ILC) involving ISO-approved techniques. The ILC was organized under the prestandardization platform of VAMAS (Versailles Project on Advanced Materials and Standards) and gathered a large number (84) of analytical laboratories across the globe. The aim of this ILC was (i) to test and to compare two thermo-analytical and three spectroscopical methods with respect to their suitability to identify and quantify microplastics in a water-soluble matrix and (ii) to test the suitability of the microplastic test materials to be used in ILCs. Two reference materials (RMs), polyethylene terephthalate (PET) and polyethylene (PE) as powders with rough size ranges between 10 and 200 μm, were used to press tablets for the ILC. The following parameters had to be assessed: polymer identity, mass fraction, particle number concentration, and particle size distribution. The reproducibility, SR, in thermo-analytical experiments ranged from 62%−117% (for PE) and 45.9%−62% (for PET). In spectroscopical experiments, the SR varied between 121% and 129% (for PE) and 64% and 70% (for PET). Tablet dissolution turned out to be a very challenging step and should be optimized. Based on the knowledge gained, development of guidance for improved tablet filtration is in progress. Further, in this study, we discuss the main sources of uncertainties that need to be considered and minimized for preparation of standardized protocols for future measurements with higher accuracy. KW - Microplastics KW - Interlaboratory comparison KW - PlasticsFatE KW - PET KW - PE KW - Reference materials KW - VAMAS KW - Thermo-analytical methods KW - Spectroscopical methods PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630462 DO - https://doi.org/10.1021/acs.analchem.4c05403 SN - 1520-6882 VL - 97 SP - 8719 EP - 8728 PB - ACS Publications AN - OPUS4-63046 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Altmann, Korinna A1 - Wimmer, Lukas A1 - Alcolea-Rodriguez, Victor A1 - Waniek, Tassilo A1 - Wachtendorf, Volker A1 - Matzdorf, Kay A1 - Ciornii, Dmitri A1 - Fengler, Petra A1 - Milczewski, Frank A1 - Otazo-Aseguinolaza, Itziar A1 - Ferrer, Manuel A1 - Bañares, Miguel A. A1 - Portela, Raquel A1 - Dailey, Lea Ann T1 - Quality-by-design and current good practices for the production of test and reference materials for micro- and nano-plastic research N2 - Understanding the environmental and human health impacts of micro- and nanoplastic pollutants is currently a high priority, stimulating intensive methodological research work in the areas of sampling, sample preparation and detection as well as intensive monitoring and testing. It is challenging to identify and quantify microplastics in complex organic matrices and concepts for nanoplastic detection are still in their infancy. All analytical techniques employed in studying micro- and nanoplastics require suitable reference materials for validation measurements, with requirements as diverse as the analytical tools used, ranging from different polymer types, size distributions and shapes of the material to the concentrations employed in different experimental set ups (ng to g amounts). The aim of this manuscript is to outline current good practices for small-scale laboratory production and characterization of suitable test and reference materials. The focus is placed on top-downfragmentation methods as well as bottom-up precipitation methods. Examples using polyethylene, polypropylene, polystyrene and polyethylene terephthalate with size distribution classes of mainly 10–1000, 1–10 and <1 μm particles will be provided. Experiences and suggestions on how to produce well-characterized micro- and nano-plastics for internal research needs will ensure that studies using the materials have robust and informative outcomes. KW - Mmicroplastics KW - Nanoplastics KW - Reference materials KW - Standard validation method PY - 2025 DO - https://doi.org/10.1016/j.jhazmat.2025.139595 SN - 0304-3894 VL - 497 SP - 1 EP - 20 PB - Elsevier B.V. AN - OPUS4-63958 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Theiler, Geraldine A1 - Wachtendorf, Volker A1 - Elert, Anna Maria A1 - Weidner, Steffen T1 - Effects of UV radiation on the friction behavior of thermoplastic polyurethanes N2 - The effects of weathering exposure on unfilled and filled thermoplastic polyurethanes (TPU) materials are described as performed under different humidity conditions. For this purpose, a weathering device was used with UV-A 340 nm lamps at a constant temperature of 40 °C. The effects of environmental (UV and humidity condition) degradation on the frictional properties of TPU materials are presented along with surface analyses to characterize the chemistry of the degradative process. Photooxidative degradation of unfilled polymer leads to deterioration of physical and mechanical properties, which affects its tribological behavior significantly. Due to crosslinking, the stiffness of the material increases, reducing drastically the friction coefficient of unfilled TPUs. The frictional behavior of glass fiber reinforced TPU is less affected by radiation. KW - Photooxidation KW - UV radiation KW - Friction KW - TPU KW - Humidity PY - 2018 DO - https://doi.org/10.1016/j.polymertesting.2018.08.006 SN - 0142-9418 SN - 1873-2348 VL - 70 SP - 467 EP - 473 PB - Elsevier Ltd. CY - Amsterdam AN - OPUS4-45709 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholz, Philipp A1 - Wachtendorf, Volker A1 - Panne, Ulrich A1 - Weidner, Steffen ED - Scholz, Philipp T1 - Degradation of MDI-based polyether and polyester-polyurethanes in various environments - Effects on molecular mass and crosslinking N2 - Size-exclusion chromatography (SEC) was used to monitor changes of the molecular masses of thermoplastic polyether – and polyester urethane (TPU) exposed to thermal, hydrolytic, and photo-oxidative (UV) Degradation conditions for several days. The thermal treatment was performed at elevated temperatures (100–200 °C) under oxidative (air) as well as non-oxidative (nitrogen) conditions to evaluate the specific influence of oxygen on the degradation. At higher temperatures (≥175 °C) a fast decrease of the molecular masses of both PU accompanied by a high degree of crosslinking was found. At lower temperatures (≤150 °C) the polymers remained widely unaffected by thermal degradation within the investigated degradation interval of up to two weeks. Surprisingly, the influence of oxygen (air) was found to be less distinct. In contrast to that, UV treatment at 25 °C at less than 10% rel. humidity (RH) resulted in a fast crosslinking, whereas the molecular masses of both PU decreased slower than for thermal treatments. The depth of penetration of the UV radiation was estimated using 3D printed PU samples with different thicknesses. Hydrolysis based degradation effects were less significant. Only slight molecular mass changes were detected at temperatures ≤80 °C within a time span of 14 days, while no crosslinking could be measured. Considering the degradation results at the investigated exposure parameters, it could be shown that esterbased PU in general exhibits a significant higher stability compared to ether-based materials. KW - Polyurethane KW - Thermal degradation KW - UV degradation KW - Molecular masses KW - Crosslinking PY - 2019 UR - https://www.sciencedirect.com/science/article/pii/S0142941819302363 DO - https://doi.org/10.1016/j.polymertesting.2019.04.028 SN - 0142-9418 VL - 77 SP - 105881, 1 EP - 12 PB - Elsevier CY - Amsterdam AN - OPUS4-48619 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scholz, Philipp A1 - Wachtendorf, Volker A1 - Elert, Anna Maria A1 - Falkenhagen, Jana A1 - Becker, Roland A1 - Hoffmann, Katrin A1 - Resch-Genger, Ute A1 - Tschiche, Harald A1 - Reinsch, Stefan A1 - Weidner, Steffen ED - Scholz, Philipp T1 - Analytical toolset to characterize polyurethanes after exposure to artificial weathering under systematically varied moisture conditions N2 - Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography (SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands. KW - Polyurethane KW - Artificial weathering KW - Moisture KW - Crosslinking KW - Degradation PY - 2019 UR - https://www.sciencedirect.com/science/article/pii/S0142941819303708 DO - https://doi.org/10.1016/j.polymertesting.2019.105996 SN - 0142-9418 VL - 78 SP - 105996, 1 EP - 9 PB - Elsevier CY - Amsterdam AN - OPUS4-48625 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wachtendorf, Volker A1 - Geburtig, Anja T1 - Alterungseffekte bei Polymerwerkstoffen messen N2 - Bei der Auswahl von Werkstoffen spielt deren Alterung oft eine untergeordnete Rolle, stattdessen wird häufig der ungealterte Ausgangszustand optimiert. Materialien altern aber unterschiedlich. Der Effekt der molekularen Alterung spiegelt sich in den Eigenschaften mehr oder weniger stark und in unterschiedlichem zeitlichen Verlauf wider. Da es kein physikalisch-chemisches Modell dafür gibt, sind Alterungseffekte empirisch zu bestimmen. KW - Alterung KW - Polymerwerkstoff KW - Eigenschaftsänderung PY - 2012 DO - https://doi.org/10.1002/nadc.201290356 SN - 1439-9598 SN - 1521-3854 VL - 60 IS - 10 SP - 1018 EP - 1022 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-26666 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wachtendorf, Volker A1 - Schulz, Ulrich A1 - Geburtig, Anja A1 - Stephan, Ina T1 - Mildew growth on automotive coatings influencing the results of outdoor weathering N2 - As the results of a 14 weeks outdoor exposure of a series of automotive coatings in South Florida, the panels were found to be overgrown with an almost closed layer of mildew. Pinholes remained as permanent surface damage after removing the mildew mycelium. The extent of the damage differed in dependence of the kind of the coating. By tracing the images and profiles of the coating surfaces systematically over all phases of weathering and the subsequent cleaning procedure, a connection between formation of pinholes and mildew growth could be found. Outdoor weathering tests in other regions of Florida as well as in Europe and Australia showed that pinholes caused by mildew attack could also be found in all other locations, but always to a lower extent than in South Florida. The standardised mildew tests EN ISO 846 and MIL-STD 810F for laboratory exposure failed to reproduce the formation of pinholes. KW - Coatings KW - Mildew KW - Weathering KW - South Florida PY - 2012 DO - https://doi.org/10.1002/maco.201005784 SN - 0947-5117 SN - 1521-4176 VL - 63 IS - 2 SP - 140 EP - 147 PB - Wiley-VCH Verl. CY - Weinheim AN - OPUS4-25467 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schulz, Ulrich A1 - Wachtendorf, Volker A1 - Geburtig, Anja T1 - Pinholes - the negative impact of mildew growth PY - 2004 SN - 0930-3847 VL - 5 SP - 26 EP - 30 PB - Vincentz CY - Hannover AN - OPUS4-21350 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geburtig, Anja A1 - Wachtendorf, Volker A1 - Schmidt, Anita A1 - Goedecke, Thomas T1 - Combined impact of UV radiation and nitric acid on HDPE containers during outdoor exposure T1 - Kombinierte Einwirkung von UV-Strahlung und Salpetersäure auf HDPE-Behälter bei der Freibewitterung N2 - Unpigmented HDPE jerrycans filled with nitric acid (55%) and water respectively had been exposed to outdoor conditions for one Berlin summer season. As both liquids underwent equal temperature progression, exposure effects of UV radiation and nitric acid as well as of their combination can be separated and compared. On the basis of various property changes after these exposures, synergistic action is evaluated and compared to a damaged Intermediate Bulk Container (IBC) from a transport accident. It is found that carbonyl formation goes along with lightness increase in color measurement due to microcracking and with a worsening in mechanical behavior, all of them showing synergistic effects of UV and nitric acid exposure. In contrast, embedding nitrogen compounds goes along with yellowing of the material but cannot be correlated to oxidation. The reason for intensified damaging is the decomposition of the 55-percent nitric acid and formation of nitrogen oxides even at ambient temperatures, caused by UV radiation. Thus, damaging effects become similar to those caused by fuming nitric acid exposure at temperatures above 60 °C, with the result of strong oxidative degradation of the polyethylene. In contrast, exclusive exposure to the 55-percent nitric acid at 40 °C does not cause any failure. It can therefore be assumed that also the damaged IBC had been exposed to both UV radiation and nitric acid, probably outdoors. KW - Polyethylene KW - Nitric acid KW - UV radiation KW - Outdoor weathering KW - Resistance PY - 2018 DO - https://doi.org/10.3139/120.111148 SN - 0025-5300 VL - 60 IS - 3 SP - 257 EP - 264 PB - Carl Hanser Verlag CY - München AN - OPUS4-44567 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geburtig, Anja A1 - Wachtendorf, Volker A1 - Falkenhagen, Jana T1 - Combined impact of UV radiation and nitric acid on high‐density polyethylene containers as a laboratory test N2 - In a laboratory test, transparent high‐density polyethylene (HDPE) jerrycans have been exposed to both UV radiation and 55 wt‐% nitric acid solution at (41 ± 2)°C, for up to 20 days. For comparison, UV radiant exposure (21 days) and nitric acid exposure (up to 6 weeks) were performed separately, at nearly equal temperatures. The damages are compared with FTIR spectroscopy in ATR and HT‐gel permeation chromatography(GPC) on a molecular level and with hydraulic internal pressure testing as a component test. For the used jerrycans, relevant oxidation can only be found after the combined exposure. This is caused by the decomposition of nitric acid into nitrous gases by UV radiation, which is also observed at lower concentrations (28 wt‐%). After 6 days of laboratory exposure, this is rated as critical, which corresponds to about 1/10 year in Central Europe, according to the UV radiant exposure. The gradual increase in oxidative damage shows the reproducibility of the test. KW - Molecular mass distribution KW - High-density polyethylene KW - Nitric acid KW - UV radiation PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-550141 DO - https://doi.org/10.1002/pts.2673 SN - 0894-3214 VL - 35 IS - 10 SP - 729 EP - 735 PB - Wiley CY - New York, NY AN - OPUS4-55014 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Trubiroha, Peter A1 - Geburtig, Anja A1 - Wachtendorf, Volker T1 - Referenzmaterialien für Bewitterungsprüfungen von polymeren Werkstoffen KW - Referenzmaterial KW - Bestrahlen KW - Bewitterern KW - Polymer PY - 2003 SN - 0341-230X SN - 1431-827X VL - 36 IS - 3 SP - 35 EP - 39 PB - Baltz CY - München AN - OPUS4-2864 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Geburtig, Anja A1 - Wachtendorf, Volker A1 - Trubiroha, P. T1 - Exposure response function for a quantitative prediction of weathering caused aging of polyethylene N2 - The exposure response function of the carbonyl formation over the bulk has been determined for a high-density polyethylene of a thickness of 200 μm, which was used as a weathering reference material according to ISO TR 19032. To this end, spectral sensitivity was studied by local measurement of the effect of spectrally dispersed irradiation. Both the exposure device and the methodology of determination are described. The temperature dependency of photooxidation was determined by UV exposure at various temperatures between 23 and 80 °C. Deviations from linearity and thus reciprocity below 40 °C are discussed and assumed to be related to diffusion limitations. An Arrhenius approach –based on data of linear carbonyl formation – has been incorporated into the exposure response function. Using this exposure response function, aging in terms of the distribution of a quantitative property change over a plastic component can be predicted for a specific outdoor location with real chronologic weather data as input for the exposure. Thus, artificial and natural weathering can be linked and compared. The established exposure response function has been validated by outdoor exposure results from the literature. If an estimated diffusion limitation is taken into consideration, calculations and published data are in good agreement. KW - Irradiation KW - Weathering KW - Spectral sensitivity KW - Temperature dependency KW - Spectral irradiation PY - 2019 DO - https://doi.org/10.3139/120.111348 SN - 0025-5300 VL - 61 IS - 6 SP - 517 EP - 526 PB - Carl Hanser Verlag GmbH & Co. KG AN - OPUS4-48295 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -