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Eingeladener Vortrag
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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.
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.
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.
The aim of the joint project ViPQuali (Virtual Product Qualification) was to describe a components ageing behaviour in a given environment, by numerical simulation.
Having chosen polypropylene (PP) as the material, which does not show sensitivity to moisture, the relevant weathering parameters of the doseresponse functions could be limited to spectral irradiance and temperature.
In artificial irradiation tests, for PP plates of varied stabiliser content, spectral sensitivity as well as temperature dependence of irradiation-caused crack formation was quantified. For that purpose, samples were exposed both to artificial weathering tests at various constant temperatures and to spectrally resolved irradiation. The temperature dependence could be modelled by an Arrhenius fit. For fitting the spectral sensitivity, a plateau function was chosen. Subsequently, the stabiliser content was parameterised and extrapolated.
The formed dose–response functions were incorporated into a Computational Fluid Dynamics (CFD) software program, simulating the environment of a sample within a Phoenix-exposed IP/DP (Instrument Panel/Door Panel box) box, based on sun position and weather conditions, including radiation interactions. Observed local effects as well as the general ageing advance of PP hats are compared with respect to simulation and experiment.
Resulting from this project, for this most simple example of PP of varied stabiliser content, the time to failure can be estimated for each weathering exposure environment with known time-resolved irradiance and temperature conditions.
The optical transmission stability was investigated for commercially available polymer optical fibers (POFs) which were exposed to a climate of 92°C and 95% relative humidity for about 3300 h. The optical transmission stability of POFs was correlated to their thermooxidative stability. POFs possessed identical core material, poly(methyl methacrylate), but they differed in the materials used for the claddings. The optical transmission was measured online using a prototype device called multiplexer. The chemiluminescence (CL) technique was applied to characterize the thermooxidative stability and degradation of POFs. CL analysis reveals the thermooxidative degradation of bare POFs (core and cladding), predominantly of the claddings, as a result of climatic exposure. Ultraviolet-visible transmittance measurements demonstrated more changes in the claddings as compared to the cores due to degradation. The CL and optical measurements data indicated that the optical transmission stability of POFs was dependent mainly on the thermooxidative stability of the claddings and their chemical compositions.
Accelerated weathering test for plastics and coatings that are exposed to acidic precipitation
(2008)
Chemiluminescence for the early detection of weathering effects of coatings - Part I: Fundamentals
(2010)
For polypropylene of varied stabilization, spectral sensitivity as well as temperature dependence of irradiation caused crack formation was determined in artificial irradiation tests. UV radiant exposure HUV necessary to generate crack formation was measured both in spectrally dispersed irradiation and artificial irradiation in a Fluorescent UV lamp device. Dependencies were fitted to a plateau function and an Arrhenius function, respectively, to describe the action of irradiation by response functions. Applied to weather data from Phoenix, the results were compared with respective outdoor exposure results.
Degradation of poly(phenylphenylene-vinylene)-films during illumination and thermal treatment
(1994)
Für Polypropylen unterschiedlicher Stabilisierung wurden in künstlichen Bestrahlungstests sowohl die spektrale Empfindlichkeit als auch die Temperaturabhängigkeit der Rissbildung quantitativ ermittelt. Dafür wurde die Dauer bis zur Rissbildung sowohl bei spektraler Bestrahlung als auch bei Bestrahlung in einem UV-Leuchtstofflampengerät bei verschiedenen Temperaturen bestimmt.
Die Temperaturabhängigkeit konnte als Arrhenius-Abhängigkeit beschrieben werden; das Wirkungsspektrum wurde an eine Stufenfunktion angepasst. Anschließend wurde auch noch der Einfluss des Stabilisatorgehalts als Potenzfit parametrisiert. Die Einzelabhängigkeiten wurden zu einer Gesamtfunktion der Wirkungen in Abhängigkeit der Dosis zusammengesetzt, die es ermöglicht die Wirkungen unterschiedlicher Dosiskombinationen abzuschätzen.
Zur Validierung der Dosis-Wirkungsfunktionen wurden Freibewitterungsergebnisse aus Phoenix/Arizona herangezogen. Mit der Dosis, die sich aus den Wetterdaten dieser Freibewitterung ergibt, wurden anhand der Dosis-Wirkungs-Funktionen die jeweiligen Lebensdauern errechnet und mit dem experimentell bestimmten Versagen in der Freibewitterung verglichen.
Die Arbeiten erfolgten im Rahmen des ViPQuali-Projektes mit dem Ziel der Bestimmung der Materialkenngrößen.
Der Anteil von Polymeren als Funktions- und Konstruktionswerkstoffe in dauerhaften medizinischen Anwendungen steigt beständig. Derartige Materialien müssen den mechanischen, biologischen und chemischen Bedingungen im Körper widerstehen (u.a. Abrieb, Hydrolyse, Degradation) und gleichzeitig gut verträglich sein. Der sichere Einsatz von polymeren Materialien erfordert die Kenntnisse über ihre Langzeitstabilität unter verschiedenen äußeren Bedingungen. Diese sind nicht nur beeinflusst durch die unmittelbare Umgebung in vivo, sondern auch durch die Historie der verwendeten Materialien. Dazu zählen u. a. erhöhte Temperaturen unter sauerstoffhaltiger Atmosphäre während der Verarbeitung oder die Exposition von ionisierender Strahlung oder reaktiven Radikalen während der Sterilisation.
Ingenieurbauwerke wie Brücken, hoch beanspruchte Verkehrsflächen oder auch Hochhäuser und deren Bauwerksteile wie z.B. Hochhausfassaden werden aus technischen und ästhetischen Gründen durch Fugen in Einzelabschnitte unterteilt. Zur Sicherstellung der Gebrauchsfähigkeit und zum Schutz des Gesamtbauwerks, aber in zunehmendem Maße auch zur statisch-konstruktiven Anbindung der Bauwerksteile, werden diese Fugenspalte in aller Regel durch spezielle Fugenfüllsysteme verschlossen. Aufgrund der hohen Sicherheitsrelevanz bei Fugenfüllungen im Glasfassadenbau fordert das Baurecht auch bei diesen Bauprodukten als Voraussetzung für die baupraktische Verwendbarkeit neben dem Nachweis der Funktionsfähigkeit auch den Nachweis der Dauerhaftigkeit. Da die hierfür bekannten Nachweismethoden zur Dauerhaftigkeit keine allgemeine Zulassungsakzeptanz finden, kann das ästhetische, bauphysikalische und ökonomische Potential von modernen geklebten Ganzglasfassaden (sogenannte SSG-Fassaden) in der Baupraxis der Bundesrepublik Deutschland derzeit nicht ausgenutzt werden. Grund dafür sind die ungenügend erfassten und in den Bewertungsverfahren simulierten Wechselwirkungen derartiger Baukonstruktionen mit der Umwelt. In diesem Beitrag soll am Beispiel moderner Fugen im Glasfassadenbau (SSG-Fassaden) eine ganzheitliche gebrauchsbezogene Versuchsmethodik zur kontrollierten Ansprache der Funktionsfähigkeit und Dauerhaftigkeit von Fugensystemen unter realitätsnah und reproduzierbar simulierten Umwelteinwirkungen vorgestellt werden. Dazu werden die maßgebenden Umwelteinflüsse und die Quantifizierung der daraus folgenden Beanspruchungen auf derartige Fugensysteme dargestellt. Basierend darauf werden eine repräsentative Beanspruchungsfunktion zur Nachstellung der maßgebenden Umwelteinflüsse und Beanspruchungen auf das System Tragrahmen - Fugenfüllung- Glasscheibe sowie eine geeignete Probendimensionierung abgeleitet. In der Konsequenz werden die Erkenntnisse in den Aufbau einer neuartigen komplexen Versuchseinrichtung überführt. Funktionsprinzip und Leistungsparameter dieser Anlage zur Umweltsimulation werden vorgestellt. Die Möglichkeiten der Systemkennzeichnung werden vorgestellt. Erste Versuchsergebnisse zeigen das Potential der neuartigen Bewertungsmethodik auf, die Kunst der Fuge im Bauwesen gebrauchsorientiert weiter zu entwickeln.
The surface temperature of test specimens exposed to natural and artificial solar radiation are roughly ascertained with black standard thermometers BST and white standard thermometers WST. For the calibration of these thermometers a new European Standard prEN 16465 was published in 2015, describing the well-known contact method and a new contactless method with a pyrometer. It can be confirmed that the temperature calibrations according to the two methods provide different calibration results which are not interchangeable (which is already stated in the scope of this standard). The described contactless method to determine the surface temperature 'under radiation load' results in clearly too high temperatures. This paper tries to highlighting the reasons.
A new irradiation device for the exposure of plastic products is presented. Developed in the BAM division 3.1 "Dangerous Goods Packaging" it can be used for artificial UV irradiation of plastic Containers filled with hazardous liquids.
Present regulations and tests only investigate the exposure effects of UV and of media separately, but as the damaging effect is expected to be synergistic for at least some media, a combined test was looked for.
A chamber of 60 cm by 60 cm base area and 1 m height gives space for up to 40 cm wide objects. Two fluorescent UV lamp arrays are arranged on opposite walls, separated from the chamber by quartz glass panes. By continuously rotating the exposure object by means of a rotary disc that the object is placed on, spatial irradiation homogeneity is achieved over the exposure duration. The spectral irradiance of the chosen UVA 340 nm lamps gives the best match of global solar radiation in the short wavelength ränge. The close arrangement of the UVA lamps (15 each side) results in 60 W m'2 UV irradiance.
Constant temperature is adjusted to typically 40 °C by the control of the fan speed. This temperature is chosen, as it is the required temperature for three week storage of filled polyethylene Containers, for proving Chemical compatibility in the field of dangerous goods. To ensure homogeneity, an interiorfan provides for air circulation.
Häufig ist es wünschenswert, für neue Materialien oder Anwendungen künstliche Bewitterungsverfahren zu benutzen, die auf die spezifischen Anforderungen besser zugeschnitten sind, als es bei bestehenden standardisierten Verfahren der Fall ist. Nachdem man die spezifischen Parameter der Beanspruchung unter Anwendungsbedingungen und die spezifische Empfindlichkeit des Materials erfasst hat, beginnt ein Prozess, der als „Test Tailoring“ häufig abstrakt verwendet, auf den aber nur selten näher eingegangen wird. Genau dieser Prozess soll hier am Beispiel der Entwicklung eines künstlichen Bewitterungstests unter saurer Beaufschlagung, dem in der BAM entwickelten Acid Dew and Fog Test, beispielhaft erläutert werden.
Additively manufactured test specimens made of polyamide 12 (PA 12) by Laser Sintering (LS) as well as of acrylnitril-butadien-styrol (ABS) by Fused Layer Modeling (FLM), were tested with active thermography. For this, two different excitation methods (flash and impulse excitation) were used and compared, regarding the suitability for the detection of constructed and imprinted defects. To increase the quality of the thermograms, data processing methods like thermal signal reconstruction (TSR) and Fourier-Transformation were applied. Furthermore, the long-term stability of the probes towards environmental stress, like UV-radiation, heat, water contact and frost is being investigated in the presented project with artificial weathering tests.
Es wird ein Verfahren zur Charakterisierung der Beständigkeit und Langzeitstabilität von additiv gefertigten Kunststoff-Bauteilen vorgestellt. Dabei sollen die Prüfkörper über 2000 Stunden künstlich bewittert und währenddessen die Änderungen der Eigenschaften der Bauteile zerstörungsfrei untersucht werden.
Mit additiven Fertigungsverfahren hergestellte Bauteile und Produkte aus Kunststoffen werden zunehmend nicht mehr nur als Prototypen, sondern als voll funktionsfähige Bauteile und Produkte gefertigt. Bedingt durch die Fertigungsprozesse und den schichtweisen Aufbau resultieren physikalische Materialeigenschaften, die stark von den Fertigungsparametern abhängen und zudem anisotrop sind. Von den Fertigungsparametern werden auch die Oberflächeneigenschaften beeinflusst, sodass zu erwarten ist, dass sich die Beständigkeit gegenüber äußeren Umwelteinflüssen bei additiv gefertigten Bauteilen von der konventionell gefertigter unterscheiden kann. Nachfolgend wird daher die Entwicklung eines Qualitätssicherungskonzeptes basierend auf spektroskopischen und zerstörungsfreien Prüfverfahren vorgestellt, in dem der Alterungsprozess von mittels Fused Deposition Modelling (FDM) und mittels Lasersintering (LS) hergestellten Probekörpern untersucht wird.
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.
Exposure response function for a quantitative prediction of weathering caused aging of polyethylene
(2019)
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.
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.
The impact fracture behavior of two common high-density polyethylene grades for container applications were intensively studied by the instrumented Charpy impact test after well-defined exposure to UV-irradiation. Individual stages of the impact event, such as crack initiation and crack propagation energy as well as maximum impact load, were investigated from the recorded load–deflection curves. UV-induced material property changes were further investigated by infrared spectroscopy, differential scanning calorimetry, and dynamic-mechanical analysis as well as density measurements. Based on the results of the Charpy impact test, three indicators were identified to describe the extend of photooxidation on high-density polyethylene: (a) a reduced Charpy impact strength—at least to half of its initial value for a distinctly brittle impact fracture, (b) a marked decrease in the crack propagation contribution to the impact strength, and (c) an increase of the brittle features of the fracture surface.
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.
Weathering reference materials (WRMs) are used to characterize the harshness of an exposure, aiming on either reproducibility of a specific exposure or on the comparability between various kinds of natural or artificial weathering exposure.
The materials that are used as weathering reference materials differ in their sensitivities (as well as in interactions and interferences of the latter), conditioned by the different processes which lead to the respective property change. It is also essential to take into account the necessary measurement equipment for the respective property change, in order to allow timely intervention.
What are the key issues on choosing a weathering reference material?
What can be learned from the weathering reference materials, investigated so far?
Possibilities and limitations are discussed on the basis of existing weathering reference materials. Conclusions are drawn, for establishing new weathering reference materials.
On the basis of a lot of investigation on the spectral sensitivity of photo degradation of plastics and on the underestimated influence of temperature and relative humidity on degradation processes a new type of weathering device was presented at the end of the seventies:
It was a combination of a radiation source with fluorescent UV lamps and a precise climatic cabinet.
The radiation emission from a combination of four different types of fluorescent UV lamps was superimposed on the specimen surfaces in the climatic cabinet to match the UV part of solar radiation as closely as possible. Air temperature was controlled to within ± 1 °C, and relative humidity to within ± 5 %RH.
As the lamps’ emission is focussed on the UV range almost no radiation heating of the sample occurs. Therefore, the temperature of the sample, which is the quantity of consideration for the degradation, is nearly identical with the chamber’s air temperature, which is the quantity to be controlled. Also, therefore, high humidity can be obtained on the sample surface. The limitation of the emission to the UV range is sufficient for the study of the polymer matrix.
This type of weathering device offers an exactness of microclimatic control of the sample’s surface, which should be a standard for weathering devices. Even now it is the only weathering device which generates pure relative humidity (without aerosol).
To improve on the classic radiometric sensor with radiometric measurement [ ] here a new UV-sensor characteristic for effective UV is proposed that no longer applies equal weighting of spectral irradiation into the UV irradiance value but rather aims at approaching a weighting according to a typical spectral sensitivity curve of polymers. This curve resembles the erythema curve of the skin which is the basis of the UV-index.
For the use of the sensor it would be desirable to keep it in the artificial weathering device for the complete weathering test (including rain phases) while the same sensor should also be applicable for the monitoring of outdoor weathering exposures.
A first application of this kind of weighted measurement and a comparison with radiometric measurements accompanied with polymer ageing results will be presented together with conclusions for a future effective UV irradiance sensor.
Das vorgestellte Projekt beschäftigt sich mit den optischen, thermophysikalischen und mechanischen Materialeigenschaften von additiv gefertigten Kunststoffteilen und deren Alterung. Dazu wurden mittels Fused Layer Modeling (FLM) Probekörper aus ABS hergestellt, die anschließend für drei Monate einer künstlichen Bewitterung unterzogen wurden. Die dabei erzeugte definierte Alterung wurde nach drei Zeitabschnitten jeweils mit zerstörungsfreien Methoden charakterisiert. Dabei wurde neben den spektroskopischen Standardmethoden auch die aktive Thermografie eingesetzt. Die Ergebnisse zeigen, dass sich mittels der Thermografie sowohl chemische Veränderungen als auch mechanische Schädigungen (Fehlstellen) darstellen lassen. Die Bewitterung beeinflusst die Teiltransparenz der Proben zumindest im sichtbaren Spektralbereich, was bei der Charakterisierung der Fehlstellen, die mittels optisch angeregter aktiver Thermografie detektiert wurden, berücksichtigt werden muss.
Additiv gefertigte Prüfkörper aus Polyamid 12 (Laser Sinter Verfahren) und Acrylnitril-Butadien-Styrol (Fused Layer Modeling Verfahren) wurden über 2000 Stunden künstlich bewittert und ihr Alterungsverhalten untersucht. Die Ergebnisse wurden anschließend mit denen von Prüfkörpern verglichen, welche auf dieselbe Weise künstlich bewittert, aber mittels konventionellem KunststoffSpritzguss hergestellt wurden.
Additively manufactured test specimens made of polyamide 12 (PA 12) by Laser Sintering as well as of acrylonitrile butadiene styrene (ABS) by Fused Layer Modelling, were characterised with active thermography directly after manufacturing and after artificial weathering. For this, two different excitation methods (flash and pulse heating) were used and compared, regarding their suitability for the detection of constructed and imprinted defects inside the test specimens. To increase the quality of the thermograms, data processing methods like thermal signal reconstruction (TSR) and Fourier Transformation after TSR were applied. To further investigate the long-term stability of the additively manufactured test specimens towards environmental stress, like UV radiation, heat, humidity, water contact and frost with active thermography, an artificial weathering test over 2000 hours (~3 months) was applied to the specimens. The monitoring of the changes in the optical properties of the weathered plastics was supplemented by spectral reflectance and UV/VIS spectroscopy.
Einfluss von Feuchte und Nässe auf die Witterungs-induzierte Alterung am Beispiel eines Polyurethans
(2017)
Bei der Bewitterung von Polymeren kommt es auf molekularer Ebene zur Alterung, die sich in verschiedenen Eigenschaften als unterschiedlich starke Änderung äußert. Art und Geschwindigkeit dieser molekularen Alterung und die damit einhergehenden Eigenschaftsänderungen hängen dabei neben einer Reihe anderer Einflussfaktoren von der Art und Intensität der Beanspruchung ab.
In diesem Beitrag soll der relative Einfluss des Wassers als Feuchte und Nässe unter den Beanspruchungsfaktoren untersucht werden. Die Unterscheidung von Luftfeuchte und Nässe bezüglich ihrer Wirkung ist dabei notwendig, weil die stehende Nässe zusätzliche Extraktionswirkung besitzt und auch die verfügbare Sauerstoffmenge beeinflusst.
Dazu wurde ein Polymer, das im Rahmen des BAM-internen Projektes PolyComp untersucht wird, künstlich bewittert. Hierzu wurde ein Fluoreszenzlampengerät mit UV-A 340 nm Leuchtstoffröhren verwendet, in dessen Probenraum durch zusätzliche Kammern die gleichzeitige Bewitterung unter drei unterschiedlichen Feuchte-Varianten realisiert wurde (bei konstanter Temperatur):
- UV und trocken
- UV und hohe Luftfeuchte
- UV und stehende Nässe.
Das gleichzeitige Einwirken der einzelnen Einflussfaktoren kann dabei konkurrierende oder aufeinander folgende chemische Reaktionen und physikalische Prozesse und somit ein anderes Ergebnis bewirken, als wenn sie isoliert nacheinander auf eine Probe eingewirkt hätten.
Über die erwähnten Varianten hinaus kann auch noch der spezifische Einfluss der UV-Strahlung mit untersucht werden, weil die Proben im Bereich ihrer Befestigung verdeckt sind.
Die Methodik und erste Ergebnisse dieser Untersuchung werden präsentiert.
Einfluss von Feuchte und Nässe auf die Witterungs-induzierte Alterung am Beispiel eines Polyurethans
(2017)
In diesem Beitrag soll der relative Einfluss des Wassers als Feuchte und Nässe unter den Beanspruchungsfaktoren untersucht werden. Die Unterscheidung von Luftfeuchte und Nässe bezüglich ihrer Wirkung ist dabei notwendig, weil die stehende Nässe zusätzliche Extraktionswirkung besitzt und auch die verfügbare Sauerstoffmenge beeinflusst.
Dazu wurde ein Polymer, das im Rahmen des BAM-internen Projektes PolyComp untersucht wird, künstlich bewittert. Hierzu wurde ein Fluoreszenzlampengerät mit UV-A 340 nm Leuchtstoffröhren verwendet, in dessen Probenraum durch zusätzliche Kammern die gleichzeitige Bewitterung unter drei unterschiedlichen Feuchte-Varianten realisiert wurde (bei konstanter Temperatur):
- UV und trocken
- UV und hohe Luftfeuchte
- UV und stehende Nässe
Das gleichzeitige Einwirken der einzelnen Einflussfaktoren kann dabei konkurrierende oder aufeinander folgende chemische Reaktionen und physikalische Prozesse und somit ein anderes Ergebnis bewirken, als wenn sie isoliert nacheinander auf eine Probe eingewirkt hätten.
Über die erwähnten Varianten hinaus kann auch noch der spezifische Einfluss der UV-Strahlung mit untersucht werden, weil die Proben im Bereich ihrer Befestigung verdeckt sind.
Die Methodik und erste Ergebnisse dieser Untersuchung werden präsentiert.
Quantitative Auswertemöglichkeiten bei der spektralen Bestrahlung – Berechnung des Wirkungsspektrums
(2017)
Für die Bewertung des Wellenlängeneinflusses auf die Alterungsvorgänge bei der Bestrahlung UV- oder lichtempfindlicher Materialien kann die Methode der spektralen Bestrahlung angewendet werden. Im Prinzip wird dabei das linear dispergierte Spektrum einer Strahlenquelle mit kontinuierlichem Spektrum (z.B. Xe-Lampe) auf eine Probenoberfläche abgebildet, so dass Ort einer Materialänderung und Wellenlänge der Bestrahlung einander zugeordnet werden können. Nachfolgende lokal-auflösende Analysemethoden ermitteln eine Eigenschaftsänderung an einem spezifischen Ort der Probe, aus dem sich dann die Bestrahlungswellenlänge ergibt.
Der verwendete Aufbau wird beschrieben. Es wird an einem ausgewählten Beispiel gezeigt, wie durch geeignete Anbindung eines Messsystems zur Bestimmung der spektralen Bestrahlungsstärke und ortsaufgelöste Messungen der Eigenschaftsänderungen eine quantitative Auswertung realisiert werden kann. Der Einfluss nichtlinearer Alterungsverläufe wird diskutiert. Grenzen der Methode werden aufgezeigt und Erweiterungsmöglichkeiten dargestellt.
Quantitative Auswertemöglichkeiten bei der spektralen Bestrahlung – Berechnung des Wirkungsspektrums
(2017)
Für die Bewertung des Wellenlängeneinflusses auf die Alterungsvorgänge bei der Bestrahlung UV- oder lichtempfindlicher Materialien kann die Methode der spektralen Bestrahlung angewendet werden. Im Prinzip wird dabei das linear dispergierte Spektrum einer Strahlenquelle mit kontinuierlichem Spektrum (z.B. Xe-Lampe) auf eine Probenoberfläche abgebildet, so dass Ort einer Materialänderung und Wellenlänge der Bestrahlung einander zugeordnet werden können. Nachfolgende lokal-auflösende Analysemethoden ermitteln eine Eigenschaftsänderung an einem spezifischen Ort der Probe, aus dem sich dann die Bestrahlungswellenlänge ergibt.
Der verwendete Aufbau wird beschrieben. Es wird an einem ausgewählten Beispiel gezeigt, wie durch geeignete Anbindung eines Messsystems zur Bestimmung der spektralen Bestrahlungsstärke und ortsaufgelöste Messungen der Eigenschaftsänderungen eine quantitative Auswertung realisiert werden kann. Der Einfluss nichtlinearer Alterungsverläufe wird diskutiert. Grenzen der Methode werden aufgezeigt und Erweiterungsmöglichkeiten dargestellt.
Discoloration Effects of High-Dose gamma-Irradiation and Long-Term Thermal Aging of (U) HMW-PE
(2017)
Two polyethylene types with ultra-high (UHMWPE) and high molecular weight (HMW-PE) used as neutron radiation shielding materials in casks for radioactive waste were irradiated with doses up to 600 kGy using a 60Co gammasource. Subsequently, thermal aging at 125∘C was applied for up to one year. Degradation effects in the materials were characterized using colorimetry, UV-Visspectroscopy, IR spectroscopy, and DSC. Both materials exhibited a yellowing upon irradiation.The discoloration of UHMW-PE disappeared again after thermal aging.Therefore, the yellowing is assumed to originate fromannealable color centers in the formof free radicals that are trapped in the crystalline regions of the polymer and recombine at elevated temperatures. For the antioxidantcontaining HMWPE, yellowing was observed after both irradiation and thermal aging. The color change was correlated mainly to decomposition products of the antioxidant in addition to trapped radicals as in UHMW-PE. Additionally, black spots appeared after thermal aging of HMW-PE.
Outdoor exposure tests are a common tool to evaluate the weathering resistance of a polymeric material or component. However, they have only a limited validity, mainly due to the limited reproducibility of the weather as well as of the bad adaptability to other exposure sites. Typically, an outdoor exposure is characterized by the measured radiant exposure; sometimes averaged temperature data are added. These can be – separately – related to long-term annual means, to get an idea on the severity of the exposure.
However, as for polymeric ageing, irradiance and temperature act simultaneously, such severity of an outdoor exposure could be better described by a computed property change of a similar material, which is calculated from the hourly irradiance and temperature values on the base of established exposure response functions.
In this way, various outdoor exposures are evaluated. For several exposure sites, annual deviations of the ageing amount are related to annual mean values, to evaluate the weathering reproducibility at the exposure site. Additionally, correlations to relevant weather parameters are illuminated. Also some specific exposure conditions, such as tilt angle, are tested.
Compared to the use of weathering reference materials, this procedure unfavourably depends on the availability of a suited control as well as on the quality of the established exposure response function. In contrast, it enables a later exposure evaluation, on the base of documented weather data, if for instance no reference material was exposed.