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Eingeladener Vortrag
- nein (42)
Natürliche und künstliche Alterung von Polymeren - Bericht über die XXII. Donauländergespräche
(2002)
Adaption of the Acid Dew and Fog (ADF) Test for Service Life Predicitons of Aircraft Coatings
(2003)
While artificial weathering is a long-established tool to investigate long-term behaviour of polymers at outdoor conditions, the use of chemiluminescence as a highly sensitive and broadly applicable sensor for the effected change is a recent addition. This combination of artificial weathering with chemiluminescence could already be successfully applied to differentiate and evaluate long-term stability of various real use polymeric building materials relatively to each other and promises to be a useful tool for a variety of other polymeric materials as well.
Adaption of the acid dew and fog (ADF) test for service life predicitons of aircraft coatings
(2003)
Degradation effects of automotive coatings after weathering as detected by thermoluminescence
(2004)
Adaption of the Acid Dew and Fog (ADF) Test for Service Life Predictions of Aircraft Coatings
(2003)
Grundsätzliches zur Frage der "UV-Beständigkeit" bzw. der "Lichtbeständigkeit" polymerer Werkstoffe
(2013)
Photo-oxidative ageing of polymers under defined exposure (UV, humidity) was investigated from two points of view: a) the ageing process Starts from the topmost surface and penetrates slowly towards bulk and b) radicals play an important role among ageing. Therefore, X-ray photoelectron (XPS) and electron spin resonance (ESR) spectroscopy were applied to show both, the progressive incorporation of oxygen during in-situ UV irradiation (XPS) and the formation of radicals (ESR) in the polymer. The intensity of ESR Signals served as measure for radical concentration. The Validation of this correlation was checked for polyethylenes (PE) equipped with different concentrations of Hostavin N30 UV stabilizer.
The outdoor weathering of polymers is mainly due to UV radiation, water, Pollution, humidity, temperature etc. To understand the effects of weathering, simulated tests need to be undertaken in lab scale. Such tests must be quite efficient and similar to the effects of natural weathering. This paper mainly focuses on the effects of UV radiation along with humidity on LDPE.
To determine a polymer’s spectral response of photo degradation, two main methods have been established. The so-called “filter technique” uses polychromatic radiation, which is filtered by a set of various sharp cut-on filters. This procedure provides separated reading points of an activation spectrum of the investigated material. With the "spectrographic technique” a specimen is irradiated with pectrally dispersed radiation, locally quasi monochromatically, and the local property changes.are related to the radiant exposure at the respective wavelengths. A third method, the irradiation of specimens with quasi monochromatic radiation behind interference filters, is rarely used.
These methods have advantages and disadvantages and therefore, there are limits for conclusions from these spectral data. Concerning the quasi monochromatic Irradiation of specimens the development of new UV radiation sources looks promising.
With the rapid development of inexpensive UV Light-emitting diodes (LEDs), new : sources of nearly monochromatic radiation in the UV ränge are available, even down to about 250 nm. To determine the spectral response, the use of such UV-LEDs in TO-18 ) and TO-39 metal cases combines the advantages of low cost and energy efficiency, stable spectral irradiance, temperature.and humidity control, larger specimen areas, and an easy and stable analysis.
Combinations of different UV LEDs are also discussed as replacement for xenon arc ' radiation sources, see patent application EP01528388A1.
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.
Chemiluminescence (CL) is a sensitive method of investigating the thermo-oxidative stability of polymers in the early stages of degradation. Therefore, CL measurements were applied to different automotive coatings to evaluate their degradation behavior during artificial weathering. In this work, CL measurements were carried out for different automotive coatings to follow their degradation behavior during artificial weathering. The CL emission depends on sample-specific parameters like stabilizer, matrix, or hardener; experimental parameters like the oxygen partial pressure; and exposure parameters like the duration of weathering. The potential of CL could be demonstrated by classifying materials into categories of good, medium, and low degradation performance at a much earlier stage of weathering exposure than in combination with the usual visual detection of weathering effects.
Eine Verkürzung der Dauer von Bewitterungsversuchen kann durch eine empfindlichere Detektion der Bewitterungseffekte erreicht werden als sie konventionell benützt wird. Eine solche besonders empfindliche Detektionsmethode stellt die Chemilumineszenz dar. Die Verkürzung durch empfindliche Detektion muss jedoch gleichzeitig der Bedingung genügen, ausreichend gute Rangkorrelation zu Bewitterungseffekten unter Anwendungsbedingungen zu zeigen. In diesem Spannungsfeld sollen die Möglichkeiten der Chemiluminiszenz-Detektion beleuchtet werden.
Accelerated weathering test for plastics and coatings that are exposed to acidic precipitation
(2009)
Due to the occurrence of acidic precipitation, and due to the fact that polymers and stabilizers may be sensititve to acids, it is important to have a laboratory test that combines weathering exposure with acidic exposure. The loss of stabilization caused by an acid damage of stabilizing system gets evident only over the weathering progress. For solid samples, for wich mostly the surface properties are relevant, the "Acid Dew and Fog Test" (ADF test) was established. For woven or tufted materials, the "Acid Rain Test" (AR test) was developed. The proposed weathering tests aim at plastics as well as at coatings.
The thermo-oxidative stability of commercially available polymer optical fibers (POFs) and their components (cores and claddings) was investigated. All the bare POFs (core and cladding only) studied here were based on poly(methyl methacrylate) (PMMA) core. The fibers were exposed to 100 °C/low humidity for about 4200 h. Chemiluminescence (CL) technique was applied to investigate the thermo-oxidative stability and for measuring the transmission loss during exposure a prototype device called multiplexer was used. POFs exhibited variation in thermo-oxidative stability although they possessed identical core material PMMA. This was due to difference in the chemical compositions of claddings. Claddings were more susceptible to the thermo-oxidative degradation compared to cores. The thermo-oxidative degradation of both the cladding and the core was found in POFs as a result of climatic exposure. POFs showed an early drop-off followed by a slow decline of transmission. The early drop-off of transmission was attributed to physical changes like thermal expansion and the slow decline of transmission to chemical changes like oxidative degradation of POFs. A good linear relationship between optical transmission stability and thermo-oxidative stability of POFs was established from these studies.
Ansätze zur Testverkürzung
(2009)
chemiluminescence studies on the thermooxidative stability of poly(1,4-phenyl phenylene vinylene)
(1996)
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.
Combined impact of ultraviolet and chemical fluids on high-density polyethylene packaging material
(2012)
To investigate the ageing behaviour of filled plastic containers outdoors, square cuts of the wall of two high-density polyethylene (HDPE) types were exposed to ultraviolet (UV) radiation at their front side and to specific liquid chemicals (de-ionized water, surfactant or White Spirit) at their back. The UV radiant exposure at the front side was 80 MJ/m².
To compare the actions of the different exposures, separate dark backside fluid exposures were performed, in parallel. Besides, UV weathering was carried out until a UV radiant exposure of 325 MJ/m², being roughly comparable to outdoor exposure of one year in Northern Australia.
An unpigmented HDPE included in the investigation gave no sufficient protection for the White Spirit. In addition, it showed clear degradation after several of these exposures. In combination with the White Spirit, an increase of carbonyl bonds was measured, presumably assignable to degradation products of the White Spirit.
For a pigmented HDPE material, with the implemented combined exposures, no relevant damage was observed, within applied the exposure period.
Scrap tyres are widely reused in the form of granules as infill materials or component of sub-base layers in construction of sporting grounds such as synthetic turf areas and athletic track surfaces. The recycled rubber may contain organic and inorganic pollutants due to the presence of vulcanisation catalysts, stabilisers and other additives which can be released into soil and groundwater in the case of outdoor sports facilities. In order to evaluate the amount of potentially mobile pollutants, leaching tests can be employed. This study aimed particularly at the investigation of the feasibility of column tests using complete synthetic surface flooring or turf system assemblies. The release of zinc and polycyclic aromatic hydrocarbons (PAH) leached from components of sports surfaces containing recycled rubber granules was considered. Additionally, batch tests on coated and uncoated styrene butadiene rubber (SBR) granules aged by artificial weathering were performed to indicate its possible influence on the leaching behaviour of zinc and PAH. The chosen approach of column tests simulating typical complete synthetic sports surface installations has been proven to be feasible and robust. The time-dependent leaching behaviour and interactions between single components can be evaluated by column tests. Zinc was the most relevant contaminant in the eluates and its leachability was enhanced after accelerated ageing by artificial weathering. Leachable PAH were found in relatively low but well detectable amounts which increase by ageing as well.
Die Umweltwirkungen auf ein Material werden als Überlapp der Funktionskurven von Materialempfindlichkeit und einwirkenden Umweltparametern betrachtet. Wenn entweder die Empfindlichkeit oder die Beanspruchungen Null sind, ergibt sich auch keine Umweltwirkung und bei beidseitig Werten größer Null das jeweilige Produkt der beiden. Die Akkumulation der nicht-reversiblen Effekte über die Zeit und allen Eigenschaftsänderungen entspricht der Alterung des Materials für den jeweiligen Expositionszeitraum.
Die digitale Umweltsimulation gliedert sich hier in drei Teilaspekte. Ein erster, rein materialwissenschaftlicher Teil hat die Aufgabe, alle relevanten Materialempfindlichkeiten experimentell zu quantifizieren. Ein zweiter – unter Umständen numerischer Teil – hat die Aufgabe, das Bauteil und seine Einbaulage zu digitalisieren und aus den makroskopischen Umgebungsbedingungen die relevanten mikroklimatischen Umweltparameter für alle Oberflächen- oder Volumenelemente zu bestimmen. In einem dritten Teil werden die Einwirkungen über den betrachteten Zeitraum berechnet und kumuliert. Dieses Konzept, das auf den so genannten Expositions-Reaktions-Funktionen (ERF) basiert, wird an Beispielen der Photoxidation erläutert. Dieses Vorgehen wurde schon beim ViPQuali-Projekt als Numerische Umweltsimulation umgesetzt.
Überprüft werden muss das Modell unbedingt an einer realitätsnahen Validierungsbeanspruchung. Hier werden die ermittelten ERFs mit über den kompletten Beanspruchungszeitraum geloggten Umweltparametern gekoppelt, um die berechnete mit der experimentell erfahrenen Alterungswirkung zu vergleichen. Nur so kann sichergestellt sein, dass alle für die Anwendungsumgebung relevanten Materialempfindlichkeiten einbezogen wurden.
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.
A liquid crystalline mainchain conjugated polymer for polarized electroluminescence applications
(1997)
Polarized fluorescence and orientational order parameters of a liquid crystalline conjugated polymer
(1999)
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.
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.
In the present study, a simple approach was used to investigate the effect of UV-exposure on two high density Polyethylene materials (PE-HD), commonly used for storage tanks, on fuel sorption behavior and colonization by microorganisms. The aim was to investigate whether the sorption behavior of the fuels (diesel/biodiesel) and the colonization by microorganisms, frequently occurring in the fuel, is affected and may lead to undesirable or safety-relevant material changes. We showed that the UV-irradiation leads to significant changes of the sorption behavior due to chemi-crystallization and crosslinking. The fuel Sorption is affected by the UV-induced formation of polar carbonyl and hydroxyl groups predominantly occurring at the surface. With respect to microbial colonization behavior for Bacillus subtilis and Pseudomonas aeruginosa, isolated from a contaminated diesel sample, differences of the initial adhesion could be shown depending on the initial type of polyethylene as well as on the degree of UV-induced degradation.
In previous papers, we investigated the influence of biodiesel or diesel on mechanical properties of a high-density polyethylene (PE-HD) for tank applications using Charpy impact tests and dynamicmechanical analysis (DMA). In this work, covering two more PE-HD materials, we extend our study to addressing the tensile properties, especially changes of Young's modulus, after immersion in biodiesel or diesel at 60 °C. As we cover sorption and desorption behavior, during desorption, i.e. storage at 60 °C in a circulating air oven, ageing or degradation phenomena were also observed and characterized in some detail using spectral reflectance measurements and FT-IR spectroscopy. The results obtained here support the concept of co-oxidation, i.e. the faster oxidation of the PE-HD matrix if the samples were previously saturated with biodiesel, itself easily oxidizable.
Transport und Lagerung flüssiger Chemikalien erfolgen häufig in HDPE-Behältern. Diese Behälter müssen Bauteilprüfungen bestehen, die mechanische und chemische Beanspruchungen kombinieren. UV-Beanspruchungen sind kein Bestandteil der Zulassungsprüfungen; gefordert wird aber eine ausreichende UV-Stabilisierung. Inwiefern diese UV-Stabilisierung aber abhängig vom jeweiligen Füllgut ist, soll hier untersucht werden.
Vorgestellt wird der experimentelle Aufbau zur kombinierten Beanspruchung von Kunststoffproben durch UV-Strahlung und flüssige Chemikalien. Aufgrund des Gefährdungspotenzials sind dabei entsprechende Sicherheitsvorgaben einzuhalten. Ziel ist die Bewertung synergistischer Effekte beider Einzelbeanspruchungen. Die Wirksamkeit verschiedener Stabilisierungskonzepte bei Beanspruchung durch 55 %-ige Salpetersäure wird beleuchtet. Es wird anschaulich gezeigt, dass nur pigmentiertes HDPE ausreichende Stabilität aufweist.
Die Grenzen der Oberflächentemperaturen von Proben, die der natürlichen oder einer künstlichen Globalstrahlung ausgesetzt sind, können grob mit sog. Schwarzstandard Thermometern BST oder Weißstandard Thermometern WST ermittelt werden [ 1a) ].
Um einige Mängel der aktuellen Konstruktion zu beseitigen, wird ein neues Konzept dieser Thermometer vorgeschlagen, das sie weniger träge und ihre physikalischen Eigenschaften ähnlicher denen einer 5 mm dicken Polymerplatte macht. Es wird auch gezeigt, dass eine Anforderung an die Reaktionszeit von weniger als 1 min in EN 513 unrealistisch ist.
After several months of operation, many photovoltaic (PV) modules develop a discolouration defect called snail trails which appear as irregular dark traces across the cells. These traces are caused by silver nanoparticles accumulating within the encapsulation foil directly above the grid finger. In this work we systematically investigate combinations of encapsulation and back-sheet foils with respect to their susceptibility for snail trails. We can show that certain additive compositions within the encapsulation and back sheet foils are critical for the formation of the discolouring silver nanoparticles. We suggest a reaction model explaining the formation of snail trails from a chemical point of view. This fundamental understanding allows the rapid testing of foils for their snail trail sensitivity as well as the special design of resistant foils.
Jerrycans made from three different types of high-density polyethylene (HDPE) were exposed outdoors, for one Berlin summer season. They were filled with a 55 percent nitric acid solution (HN03), pure water, or air, and half of them were protected from sunlight by an UV absorbing canvas. Thus, the separate effects of UV radiation and nitric acid could be compared to the combined impact. Combined impact was mainly affected by decomposition of nitric acid, resulting in presence of reactive nitrogen oxides, increased oxygen partial pressure, and UV radiation energy, simultaneously in vapour phase.
To investigate the degradation effects after the outdoor exposure, jerrycans were exposed to a so called hydraulic internal pressure test, similar to an approval test for dangerous goods packaging. After combined impact of UV radiation and nitric acid, internal pressure tests showed very fast failures, whereas after separate impacts no remarkable deteriorations were observed, compared to unaged jerrycans.
Temperature is an important parameter in weathering tests. In many (photo-)chemical degradation processes a Variation of the specimen temperature by A t = + 1 °C can cause a Variation of AP(property change) by ± 8%.
Since the early eighties it is well known that some types of black panel thermometers can show temperatures that are far below the maximum surface temperature of a black specimen. Although, there were precise requirements for the black coating of the BPT, a replacement by a white coating - depending on the design of the BPT - did not really change the temperature shown by the thermometer. There was no correlation between the BPT and the specimen surface temperature.
In Europe and later at ISO the so-called black- and white-standard thermometers BST/WST were introduced. Now, there are BST and WST (ISO) and there are thermally uninsulated and insulated BPT and WPT (ASTM), partly for artificial or for outdoor exposure. And there are other adventurous procedures to determine surface temperatures.
The different types of thermometers and different procedures will be discussed and it will be shown that there is no procedure which establishes a correlation between outdoor surface temperatures and surface temperatures in artificial exposure tests.