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- Artificial weathering (1)
- BODIPY (1)
- Bewitterung (1)
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- Degradation (1)
- Dye (1)
- Fluorescence (1)
- Functional group detection (1)
- Imaging (1)
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Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (2)
- 1.2 Biophotonik (2)
- 1.7 Organische Spuren- und Lebensmittelanalytik (1)
- 5 Werkstofftechnik (1)
- 5.6 Glas (1)
- 6 Materialchemie (1)
- 6.3 Strukturanalytik (1)
- 6.6 Physik und chemische Analytik der Polymere (1)
- 7 Bauwerkssicherheit (1)
- 7.5 Technische Eigenschaften von Polymerwerkstoffen (1)
One of today’s major problems in many technical plants as well as fuel tanks is Microbial induced corrosion (MIC), leading to considerable damage and huge financial losses. Successful prevention of MIC requires the localization of first signs of corrosion as well as the identification of factors influencing the corrosion process. Hence, there is a growing need for sensitive and preferably inexpensive tools that enable the early detection of MIC. Of utmost importance are methods, which provide spatially and time-resolved information and allow the determination of corrosion rates at sites of interest for possible prevention of MIC.
Polyurethanes (PU) are formed by polyaddition reaction between diols and diisocyantes. They can be formed utilizing three building blocks, namely a polyol or long-chain diol, a chain extender or short-chain diol, and a diisocyanate. The derived multi-phase block copolymer has thermoplastic properties and is called thermoplastic PU (TPU). This modular approach allows for a variety of alternations yielding a broad range of structural properties and applications. TPUs are based on three main classes of polyols, i.e. polyethers, polyesters, and polycaprolactones. With these different polyols and the ability of changing the ratio of building blocks a variety of material properties can be obtained thus TPUs find numerous applications in e.g. lightweight construction1, insulation, flame retardants, lacquer and glue, as well as medicine.
Linear, isocyanate terminated, polyurethane prepolymers prepared from non-equivalent amounts of diisocyanate such as methylene diphenyl diisocyanate (MDI) attached to a polyol are widely used as precursors of the correspondent polymers. Chain-extending reactions with low molecular weight compounds bearing different amounts of active hydrogens enable both linear and crosslinked polyurethane to be formed.
Due to TPUs being used in a broad range of applications facing a variety of stress (e.g. mechanical, hydrolytic, thermal, radiative/UV, as well as its combinations) the complexity of possible degradation mechanism is high. A functional group derived from degradation of the bulk matrix can be detected utilizing a suited fluorogenic sensor molecule. There are several fluorogenic dyes known for the application as sensor for amine groups e.g. fluorescamine, pyrylium dyes, deriving a fluorescent signal upon reaction.
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.
We report on the temperature- and structural-dependent optical properties and photophysics of a set of boron dipyrromethene (BODIPY) dyes with different substitution patterns of their meso-aryl subunit. Single-crystal Xray diffraction analysis of the compounds enabled a classification of the dyes into a sterically hindered and a unhindered group. The steric hindrance refers to a blocked rotational motion of the aryl subunit around the bond connecting this moiety to the meso-position of the BODIPY core. The energy barriers related to this rotation were simulated by DFT calculations. As follows from the relatively low rotational barrier calculated to about 17 kcal/mol, a free rotation is only possible for sterically unhindered compounds. Rotational barriers of more than 40 kcal/mol determined for the sterically hindered compounds suggest an effective freezing of the rotational motion in These molecules. With the aid of temperature-dependent spectroscopic measurements, we could show that the ability to rotate directly affects the optical properties of our set of BODIPY dyes. This accounts for the strong temperature dependence of the fluorescence of the sterically unhindered compounds which show a drastic decrease in fluorescence quantum yield and a significant shortening in fluorescence lifetime upon heating. The optical properties of the sterically hindered compounds, however, are barely affected by temperature. Our results suggest a nonradiative deactivation of the first excited singlet state of the sterically unhindered compounds caused by a conical intersection of the potential energy surfaces of the Ground and first excited state which is accessible by rotation of the meso-subunit. This is in good agreement with previously reported deactivation mechanisms. In addition, our results suggest the presence of a second nonradiative depopulation pathway of the first excited singlet state which is particularly relevant for the sterically hindered compounds.