Filtern
Dokumenttyp
- Zeitschriftenartikel (13)
- Beitrag zu einem Sammelband (1)
- Beitrag zu einem Tagungsband (1)
- Vortrag (1)
- Forschungsbericht (1)
- Forschungsdatensatz (1)
Schlagworte
- Crosslinking (3)
- Incineration bottom ash (3)
- Polyurethane (3)
- Rostasche (3)
- Thermal degradation (3)
- Degradation (2)
- Ecotoxicity (2)
- Geosynthetics (2)
- Geotextiles (2)
- Microplastic (2)
Organisationseinheit der BAM
- 4 Material und Umwelt (13)
- 4.3 Schadstofftransfer und Umwelttechnologien (13)
- 6 Materialchemie (5)
- 6.3 Strukturanalytik (5)
- 1 Analytische Chemie; Referenzmaterialien (2)
- 1.7 Organische Spuren- und Lebensmittelanalytik (2)
- 4.4 Thermochemische Reststoffbehandlung und Wertstoffrückgewinnung (2)
- 1.2 Biophotonik (1)
- 5 Werkstofftechnik (1)
- 5.6 Glas (1)
- 6.6 Physik und chemische Analytik der Polymere (1)
- 7 Bauwerkssicherheit (1)
- 7.5 Technische Eigenschaften von Polymerwerkstoffen (1)
- 8 Zerstörungsfreie Prüfung (1)
- 8.5 Röntgenbildgebung (1)
Eingeladener Vortrag
- nein (1)
With the aim of improving limits of detection (LOD) of trace elements in a matrix with adjacent fluorescence energies, a simple double dispersive X-ray fluorescence detection system (D2XRF) was constructed to operate at the beamlines BAMline and the mySpot @ BESSY II. This system is based on the combination of a crystal analyzer with an energy resolving single photon counting pnCCD. Without further collimators, the efficient suppression of the background by the pnCCD and the good energy resolution of the crystal results in improved LOD. In first order reflections, an energy resolution of 13 eV for Cu Kα was reached, and an energy range of 1 keV was covered in one shot.
This new system was applied to the detection of platinum (Pt) in gold leaves with a LOD of 0.9 mg/kg, which is the lowest attained by totally non-destructive methods nowadays. The presence of Pt in gilded objects from Abydos and Byzantine mosaics provides vital information, as it indicates the alluvial origin of the gold for these examples.
Degradation of polyurethanes in various environments – Effects on molecular mass and crosslinking
(2019)
The increasing application of polyurethanes (PU) in safety relevant sectors (fire protection, insulation, medicine technique) requires detailed knowledge of the stability and reliability of these materials. Different climate factors are supposed to induce diverse and overlapping degradation reactions. The knowledge of these degradation mechanisms is necessary for an estimation of the period of application depending on usage of the material. An essential property of a polymeric system is represented by the molecular weight. Since a change of the molecular weight is a measure for the chemical stability of a polymer, size-exclusion chromatography (SEC) was used to monitor changes of the molecular weight of thermoplastic polyether- and polyester urethane (TPU) exposed to thermal, hydrolytic and photo-oxidative (UV) degradation conditions for several days. Thermal treatments were 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, which was already known from FTIR spectroscopy[1]. 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 during the thermal treatments. The depth of penetration of the UV radiation was determined 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 ester-based PU in general exhibits a significant higher stability compared to ether-based materials.
Mechanochemically synthesized metal–organic Framework material HKUST-1 in combination with acrylonitrile butadiene styrene polymer was used to form a polymer metal–organic framework composite material by a simple extruder.
This composite filament was used for 3D printing. Xray diffraction measurements were used to prove the homogeneous distribution of the metal–organic framework in the polymer on a centimeter scale, whereas X-ray Absorption Edge Tomography using a synchrotron radiation source was able to evaluate the 3D distribution of the metal–organic framework material both in the filament and the resultant printed sample with a resolution of a few lm. Our very first data indicate that, apart from a few clusters having significantly higher Cu concentration, HKUST-1 is distributed homogeneously down to the 100 lm length scale in both polymer bulk materials in the form of clusters with a size of a few lm. Absorption Edge Tomography in combination with data fusion also allows for the calculation of the metal–organic framework amount located on the external polymer surface.
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.
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.
Geosynthetic materials are applied in measures for coastal protection. Weathering or any damage of constructions, as shown by a field study in Kaliningrad Oblast (Russia), could lead to the littering of the beach or the sea (marine littering) and the discharge of possibly harmful additives into the marine environment. The ageing behavior of a widely used geotextile made of polypropylene was studied by artificial accelerated ageing in water-filled autoclaves at temperatures of 30 to 80 °C and pressures of 10 to 50 bar. Tensile strength tests were used to evaluate the progress of ageing, concluding that temperature rather than pressure was the main factor influencing the ageing of geotextiles. Using a modified Arrhenius equation, it was possible to calculate the half-life for the loss of 50% of the strain, which corresponds to approximately 330 years. Dynamic surface leaching and ecotoxicological tests were performed to determine the possible release of contaminants. No harmful effects on the test organisms were observed.
Im Rahmen des Projekts konnte gezeigt werden, dass Geokunststoffe bei ausreichender Stabilisierung Einsatzdauern von über 100 Jahren besitzen. Es werden keine Stoffe freigesetzt, die für Wasserorganismen schädlich sind. An den Ostseestränden im Gebiet Kaliningrad werden nennenswerte Mengen von Kunststoffresten gefunden, die zum Teil aus Küstenschutzbauwerken stammen. Ursache ist hier jedoch eine verfehlte Materialauswahl. Hauptsächlich stammen die Kunststoffreste am Strand jedoch aus unsachgemäße Abfallbehandlung.
The most massive design on the Baltic shore used geosynthetic materials, the landslide protection construction in Svetlogorsk (1300 m long, 90,000 m2 area, South-Eastern Baltic, Kaliningrad Oblast, Russian Federation) comprises the geotextile and the erosion control geomat coating the open-air cliff slopes. Due to changes in elastic properties during long-term use in the open air, as well as due to its huge size, this structure can become a non-negligible source of microplastic pollution in the Baltic Sea. Weather conditions affected the functioning of the structure, so it was assessed that geosynthetic materials used in this outdoor (open-air) operation in coastal protection structures degraded over time. Samples taken at points with different ambient conditions (groundwater outlet; arid places; exposure to the direct sun; grass cover; under landslide) were tested on crystallinity and strain at break. Tests showed a 39–85% loss of elasticity of the polymer filaments after 3 years of use under natural conditions. Specimens exposed to sunlight are less elastic and more prone to fail, but not as much as samples taken from shaded areas in the grass and under the landslide, which were the most brittle.
The chemical state of antimony and vanadium species in municipal solid waste incineration bottom ash
(2023)
Due to the large quantity as residual mineral waste, municipal solid waste incineration - bottom ash (MSWI-BA) is an interesting secondary raw material that can be utilized for road construction. However, leaching of chloride, sulfate and potentially hazardous heavy metals from MSWSI-BA into the environment may cause problems in utilization of it in civil engineering. In a previous study, we performed a long-term leaching test of MSWI-BA in a lysimeter for almost six years to investigate the efficiency of the treatment process on the release of hazardous substances. While concentrations of chloride, sulfate and the majority of the heavy metals started to decrease rapidly with progressive liquid-to-solid ratio (L/S), the ecotoxic hazardous elements antimony (Sb) and vanadium (V) behaved differently. To unravel these unusual release behaviors and the oxyanion-formation of Sb and V we will apply HERFD-XANES spectroscopy to analyze their chemical state.
Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.