7.5 Technische Eigenschaften von Polymerwerkstoffen
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Elastomers, such as hydrogenated acrylonitrile-butadiene rubber (HNBR) are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. These high filler loadings sometimes cause deterioration of the physical properties of the material. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings (3 phr) to reduce the total amount of filler or boost performance.1,2,3 In former studies nanofiller achieved increased flame retardancy at very low lowdings.4,5,6 The dispersion of the nanofiller is essential for the properties of the nanocomposites.7 The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing and subsequent conventional two-roll milling.
SEM and TEM micrographs and rheological measurements revealed that the MLG nanoparticles were well dispersed in the HNBR matrix. In the HNBR nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr ATH or 15 phr CB + 3 phr ATH and achieved large consistent improvement in curing, rheological and mechanical properties of the HNBR. The nanocomposites with partial replaced CB reduced the filler loading up to 60% without any deterioration of the properties. The HNBR/MLG nanocomposites achieved an even higher Young’s modulus, hardness and thermal conductivity. MLG achieved advanced flame retardancy by improving the protection layer. The layer is created during the burning phase and acted as an afterglow suppressor. This study proposed the combination of ATH with MLG as a promising approach to reduce the amount of filler, in addition to improving the mechanical properties and fire performance of HNBR rubbers.
Elastomers are used in a wide range of automotive and railway applications. However, a severe drawback of most rubbers are their high flammability. Therefore, flame retardants (FRs) are added to improve the performance in fire. Generally, rubber composites are filled with high amounts of mineral fillers such as aluminium trihydroxide (ATH) to fulfil fire safety regulations. These high loadings may cause deterioration of the physical properties of the material. This work shows the implementation of two new strategies to achieve the modern demands on non-toxic FRs and the reduction of fillers.
The first approach was the implementation of multilayer graphene (MLG), acting as a multifunctional filler, reinforcing agent and FR. The study presents filler combinations with a systematic variation of the fillers carbon black (CB), MLG and ATH. The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing. Afterwards the master batch was compounded into the rubber in a two-roll milling. MLG substituted high amounts of the conventional filler CB, leading to reduced filler loadings and a consistent improvement in curing, mechanical and FR properties.
The second strategy was the combination of phosphorous-containing FRs with a potential new polymeric char promoting agent polyaniline (PANI). Char promoting additives such as pentaerythritol (PER) improve the effectiveness of the FR system. The combination of ammonium polyphosphate (APP) with PER was successfully investigated for natural and styrene-butadiene rubber composites. This work investigates the flame retardancy of the combination of FRs with PANI and its capability to act as a char/barrier promoter in EPDM.
The morphology of the rubbers and homogenously dispersion of MLG was investigated via scanning/transmission electron microscope (SEM/TEM) micrographs. Rheological and mechanical measurements assessed the influence of the fillers on the physical properties of the rubber composites. Characterization via thermogravimetric analysis (TGA) led to a broader understanding of the decomposition. In order to determine the flame retardancy effect of these materials, a multi-methodical approach was selected. Limiting oxygen index (LOI) and UL-94 were used to quantify the flammability of the rubber composites. The cone calorimeter provided information about the fire behaviour in forced flaming conditions. Residues were investigated via elementary analysis and XPS to clarify the composition of the remaining material. Glow-Wire and FMVSS 302 tests revealed significant results in terms of flame retardancy. The flame retardancy investigation of rubber composites, combinations of ATH with MLG and ATH with phosphorous-containing FRs, broaden the horizons of rubber flame retardancy solutions. By examining alternate FR formulations and their effect on mechanical and physical properties of the rubber, new insight into the range of applicable additives for rubber composites may be won.
Polymeric membranes represent a low-cost, energy efficient solution for gas separation. Recently polymers of intrinsic microporosity (PIMs) have emerged as prestigious membrane materials featuring a large concentration of pores smaller than 1 nm, a BET surface area larger than 700 m2/g and high gas permeability and selectivity. Unusual chain structure combining rigid segments with sites of contortion gives rise to the intrinsic microporosity. However, this novel class of glassy polymers are prone to pronounced physical aging. The initial microporous structures approach a denser state via local small scale fluctuataions, leading to a dramatic reduction in the gas permeabilities. For the first time, dielectric relaxation spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate three representative PIMs with a systematic change in chain rigidity: PIM-EA-TB 〉 PIM-1 〉 PIM-MDPH-TB. The molecular mobility, the charge transport and their response upon heating (aging) in the polymers were measured in a broad temperature range through isothermal frequency scans during different heating / cooling cycles. Multiple dielectric processes following Arrhenius behavior were observed for the investigated polymers. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxation phenomena were discussed and attempted to be correlated with the structural features of PIMs. Moreover, all PIMs showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature far below the glass transition temperature of PIMs is explained in terms of the loosely packed microporous structure and the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone.
High performance polymers of intrinsic microporosity (PIMs) have emerged as novel materials with broad applications from gas separation to electronic devices. Sufficiently rigid, even contorted polymer chains show only limited molecular mobility, therefore undergo inefficient packing and give rise to intrinsic microporosity with pore size generally smaller than 1 nm and BET surface areas larger than 700 m2/g. Further performance optimization and long-term stability of devices incorporating PIMs rely on our understanding of structure-processing-property relationships and physical aging, in which glass transition plays a key role. Up to now no glass transition temperature (Tg) of PIMs could be detected with conventional thermal analysis techniques before degradation. Decoupling the time scales responsible for the glass transition and the thermal decomposition is a reliable strategy to overcome this. This was achieved by employing fast scanning calorimetry (FSC) based on a chip sensor, which is capable to heat and cool a small sample (ng-range) with ultrafast rates of several ten thousand K/s. FSC provides definitive evidence of glass transition of a series of PIMs with a special consideration on the chain rigidity. The determined glass transition temperature of these PIMs follows the order of the rigidity of their backbone structures. FSC provides the first clear-cut experimental evidence of the glass transition of PIM-EA-TB with a Tg of 663 K, PIM-1 of 644 K and PIM-DMDPH-TB of 630 K at a heating rate of 1Χ104 K/s. Local fluctuations are featured in glass transition of highly rigid PIMs. As conformational changes are prevented by the backbone rigidity, the glass transition must rather be assigned to local small scale fluctuations.
Das EU Projekt TREEADS „A Holistic Fire Management Ecosystem for Prevention, Detection and Restoration of Environmental
Desasters” beschäftigt sich mit der Erforschung der drei Phasen „Prävention und Bereitschaft“, „Detektion und Reaktion“ und
„Aufforsten und Anpassen“ der Waldbrandverhütung. Im Projekt gibt es acht ausgewiesene Pilotregionen, in denen Deutschland
auch mit einer Pilotregion in Sachsen-Anhalt bzw. in Brandenburg vertreten ist. Unsere Arbeit auf Charakterisierung des Waldbodens und numerische Simulation wird vorgestellt.
For the purpose of increasing payload and reduce freight cost, lightweight composite tank containers used for Transportation have been progressively developed during the last years. Compared to conventionally produced cylindrical steel tanks, the fiber-reinforced solutions allow greater flexibility in the tank design. Despite a number of further material-related benefits of fiber-reinforced composites as non-conductive and non-magnetic behavior as well as corrosion resistance and high strength, the optimization of their thermal degradation properties during combustion is still a challenge. To improve the fire performance of lightweight composite containers, special intumescent fire protection coatings can be applied onto the outside tank surface. This paper presents fire tests on glass-fiber-reinforced plastic transport tanks with complex geometries sheltered with different surface-applied fire protection systems. To evaluate the fire resistance of the tank structures, a fiber optic monitoring system was developed. This system is based on distributed temperature measurements using high-Resolution optical backscatter reflectometry and pointwise reference measurements using fiber Bragg gratings. Thereby, all the fiber optic sensors were directly integrated in the composite layer structure of the tanks. The focus of the presented work is on the demonstration of capability of fiber optic monitoring system in such high-temperature application. Moreover, the fiber optic measurements provide new insights into the efficiency of intumescent coating applied for fire protection of fiber-reinforced plastic transport tanks.
Recent facade fires worldwide have driven change in regulations for façade fire safety in different parts of the world. The Grenfell Tower fire 2017 in London triggered a thorough investigation of many aspects of the fire. One investigation was about the UK building regulations from Dame Judith Hackett. This investigation compares the UK with the situation other parts of the world. Key findings of the review of building regulations by Judith Hackett are:
In den letzten Jahrzehnten wurde die Degradation der polymeren Matrix von flammgeschützten Polymeren eingehend untersucht. Erst in den letzten Jahren jedoch hat sich die Frage der Lebensdauer der Funktionalität des Flammschutzes selbst als wichtige Fragestellung herauskristallisiert, z.B. bei Kabeln. Deshalb sollte diese Fragestellung durch systematisch-variierte künstliche Klima- und Bewitterungstests an flammgeschützten Polymerwerkstoffen untersucht werden.
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.
Bei der Bestrahlung und Bewitterung von polymeren Werkstoffen wird die Degradation durch eine Absorption von Strahlung initiiert und meistens durch weitere Klimagrößen, wie z.B. Wärme, Feuchte und atmosphärische Gase beeinflusst. Die Messung einer effektiven Bestrahlungsstärke und ihre zeitliche Integration sind deshalb von großer Bedeutung und zwar sowohl für die Kontrolle der Funktion des Bewitterungs- oder Bestrahlungsgerätes als auch als zusätzliche Angabe der wirkenden Beanspruchung.
Photochemische Prozesse werden beim Sehen oder allgemeiner bei Farbstoffen schon durch sichtbare (VIS) Strahlung, dagegen bei der Erythembildung der Haut und der Photodegradation von Polymeren erst durch die energiereicheren Photonen der ultravioletten (UV) Strahlung initiiert. Die spektrale Empfindlichkeit des Auges und die Erythembildung sind im VIS- bzw. UV-Bereich sehr stark wellenlängenabhängig, was durch die Angabe der mit der spektralen Hellempfindlichkeit V(λ) des Auges bewerteten VIS-Strahlung in Lux (lx) bzw. die mit der Erythem-Wirkfunktion Serythem bewertete UV Strahlung als dimensionsloser UV-Index berücksichtigt wird. Spektrale Empfindlichkeiten.
Die Photodegradation von Polymeren ist im UV-Bereich ebenfalls stark wellenlängenabhängig, was bisher bei der radiometrischen UV-Messung nicht berücksichtigt wurde. Seit Mitte der 70er Jahre, als die lx- bzw lxh- Messung bei der Strahlungsbeanspruchung langsam durch die Ermittlung der radiometrischen UV-Bestrahlungsstärke bzw. der UV-Bestrahlung im gesamten UV-Bereich abgelöst wurde, gab es hier bei der Bewitterungsprüfung keine weiteren Fortschritte auf dem Gebiet der Charakterisierung der Strahlungsbeanspruchung im UV-Bereich.
Seit Jahren liegen zahlreiche Ergebnisse über die spektrale Empfindlichkeit von Photo-degradationsprozessen vor, die zeigen, dass die spektrale Empfindlichkeit im Bereich der Globalstrahlung an der kurzwelligen Grenze bei ca. 300 nm, am größten ist und im langwelligen UV-Bereich bei ca. 400 nm gegen Null geht. Die Messungen der radiometrischen Größen UV-Gesamtbestrahlungsstärke und UV-Gesamtbestrahlung erfasst deshalb über weite Wellenlängenbereiche Strahlungsanteile, die für die Photodegradation bedeutungslos sind und mittelt über potenziell bedeutsame Änderungen im kurzwelligen UV-Bereich hinweg.
Es wird das Konzept eines neuen UV-Radiometers vorgestellt, dessen spektrale Empfindlichkeit einer mittleren spektralen Empfindlichkeit der Photodegradation von Polymeren entspricht. Die effektive UV-Bestrahlungsstärke und UV-Bestrahlung kann dadurch wesentlich genauer erfasst werden.
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.
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.
Genormte künstliche Bewitterungstests sind häufig nicht spezifisch für die Anwendungssituation oder das Material. Das macht die Entwicklung spezifischer Tests erforderlich. Für deren Entwicklung müssen Maximalparameter der Anwendungssituation bekannt sein, womit dann der künstliche Test formuliert wird und dessen Bedingungen werden dann solange optimiert, bis die Korrelation der Effekte von natürlichem und künstlichem Test ausreichend ist.
Für Untersuchungen der Freisetzung kann der verbleibende Rest in der Probe und/oder die freigesetzte Menge in Luft, Boden, Wasser bestimmt werden.
Im ersten Beispiel der Witterungswirkung wurde die Freisetzung von Kohlenstoff-Nanoröhrchen (CNT) aus Polymer-Kompositen untersucht (unter Verwendung von empfindlich-nachweisbarer radioaktiver 14C-Markierung für einzelne CNT-Partikel), in einem zweiten die Freisetzung von anorganischen und organischen Bestandteilen aus elastomeren Bestandteilen von Sportböden (Bahnen und Kunstrasen) in Wasser.
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.
In den letzten Jahrzehnten wurde die Degradation der polymeren Matrix von flammgeschützten Polymeren eingehend untersucht. Erst in den letzten Jahren jedoch hat sich die Frage der Lebensdauer der Funktionalität des Flammschutzes selbst als wichtige Fragestellung herauskristallisiert, z.B. bei Kabeln. Deshalb sollte diese Fragestellung durch systematisch-variierte künstliche Klima- und Bewitterungstests an flammgeschützten Polymerwerkstoffen untersucht werden
The individual and collective impacts of additives in melt dripping behaviour were studied under UL 94 vertical test conditions. A set of polyamide 6 (PA6) based materials compounded with melamine cyanurate (MCA) – a ˝dripping agent˝ – and glass fibre (GF) – a ˝non-dripping agent˝ - was investigated in detail. Dripping quantification was carried out during first and second ignition. The materials and their drops were investigated with respect to thermal decomposition, melt viscosity, and others properties. PA6 with V-2 classification improves to V-0 when MCA is added; and is worsened to HB in presence of glass fibre. Together, PA6/GF/MCA achieved V-2. The non-flaming drops of PA6/MCA are formed by oligomeric fragments. The flaming drops of PA6/GF contain a high amount of glass fibre. The dripping behaviour of PA6/GF/MCA under fire is a complex response of the specimen, but not explained by an easy superposition of the materials’ properties. The dripping behaviour is influenced by the interaction and concurrence of the different phenomena.
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).
Packaging containers for dangerous goods that include aggressive liquids require that any packaging material that is based on high-density polyethylene has a high degree of stability and durability. This work is focused on testing the environmental stress cracking of the high-density polyethylenes used for such containers in contact with crop protection formulations, in particular, two model liquids established in Germany as standardized test media representatives for crop protection formulations containing the various admixtures typical for such products. One of the liquids is water-based and contains mostly surface-active ingredients, while the other is solvent-based and includes some emulsifiers. Originally established for pin impression tests, these model liquids and their individual components were here used for the first time as environmental media in the Full Notch Creep Test, which addresses the resistance against environmental stress cracking. The Full Notch Creep Test was carried out on five high-density polyethylene types with both model liquids, and also on one selected material with its components. The evaluation was focused on the fracture surface structures, which were visualized by a scanning electron microscope and by optical in situ imaging of the notch opening. While the water-based model liquid and its surface-active individual components induced environmental stress cracking with the characteristic pattern for a craze-crack mechanism and so-called brittle fracture on the surface, the solvent-based model liquid and its soluble ingredients exhibited rather ductile failure behavior, caused by the plasticizing effect on the polymer that reduced the yield stress of the high-density polyethylene.
For both cases, fracture surface analysis, together with side views of the crack opening, showed a clear relation between surface pattern, notch deformation (e.g., by blunting), or crack opening due to crack growth with time to failure and the solubility of the liquids in high-density polyethylene.
Polyethylen hoher Dichte (PE-HD) ist ein weit verbreitetes Material für Transportbehälter, die oft für eine längere Nutzungsdauer vorgesehen sind. Insbesondere in diesem Fall können mikroskopische Schäden im Material auch weit unterhalb der Streckgrenze auftreten, die durch eine Spannungskonzentration verursacht werden, deren Ursprung in intrinsischen Materialfehlern oder äußeren Kratzern liegt. Mit fortschreitender Schädigung bilden sich Rissstrukturen, die von verstreckten Fibrillen aufgespannt werden, bis es zum Versagen dieser Fibrillen kommt und sich der Riss ausbreitet. Dieser Schadensmechanismus des langsamen Risswachstums kann durch eine Vielzahl von Umgebungsmedien beschleunigt werden und wird dann als "environmental stress cracking" (ESC) bezeichnet. Eine international normierte Methode zur Validierung der Spannungsrissbeständigkeit von PE-HD Materialien ist der „Full Notch Creep Test“ (FNCT).
Anhand von Bruchflächenauswertungen mittels Rasterelektronenmikroskopie und Laser-Scanning-Mikroskopie, werden die typischen Schädigungsstrukturen des ESC sichtbar. Die fibrillierten Strukturen des ESC auf der Bruchfläche von PE-HD ergeben sich besonders bei oberflächenaktiven wässrigen Umgebungsmedien. In Lösungsmittel-Umgebungsmedien, im Zusammenspiel mit PE-HD, kommt es aufgrund der plastifizierenden Wirkung zur Herabsetzung der Streckspannung und Bruchflächen aus dem FNCT veranschaulichen keine signifikanten Anzeichen des Schädigungsmechanismus ESC.
Molecular orientation has a significant effect on the material properties of polymers. Preferential orientation of the microstructure (polymer chains or crystallites) in a specific direction or plane often enhances the material properties, especially if the high-strength covalent bonds are primarily exposed to loads instead of the weaker van der Waals bonds. However, the orientation-dependent microstructure and its mechanical behavior is in general already well understood by many scientific studies [1-3]. Isotropic materials are frequently required for an intrinsic material characterization without prevailing processing-induced properties, as is the case for Full Notch Creep Test (FNCT) [4] addressing environmental stress cracking (ESC) in high-density polyethylene (PE-HD) [5, 6]. Since ESC is one of the major limiting issues for long-term performance of PE-HD pipes and containers [7], which in contrast have a production-related preferential orientated microstructure due to extrusion or extrusion blow molding, it is important to additionally investigate the ESC resistance of such anisotropic microstructure.
Investigations of the slow crack growth (SCG) with respect to the molecular orientation generally obtain a factor of 1.2 up to 4.7 between crack growth perpendicular to the extrusion direction and crack growth parallel to the extrusion direction 8. Based on FNCT investigations with an aqueous detergent solution as environmental medium, hot pressed sheets with isotropic morphology are compared with extruded sheets from which specimens with different orientation angles are taken. However, the time to failure obtained by FNCT is also significantly influenced by the different cooling conditions under which the final morphology is formed. The tendency of the specimen to fail due to ESC is investigated as a function of environmental medium temperature. For a more detailed analysis of the affecting parameters in the manufacturing process, the ESC resistance is discussed considering the differences in crystallinity as revealed by thermal analysis.
Currently, the Full Notch Creep Test (FNCT) [1] method is used by material suppliers and end users in industry for the approval of container and pipe materials based on high-density polyethylene (PE-HD). The resistance to environmental stress cracking (ESC) of the material is evaluated using the time to failure of the specimen in an aqueous solution of a detergent [2, 3]. Usually specimens made of sheets with isotropic material properties, manufactured by hot pressing, are employed in order to obtain intrinsic properties of the material in terms of ESC failure. In contrast, the processes used in manufacturing to form containers and pipes, such as extrusion blow molding or extrusion, impose anisotropic properties to the material. These are mostly due to a microstructural orientation (polymer chains or crystallites) [4]. Furthermore, the different cooling conditions significantly affect the size distribution of crystallites as well as the overall morphology. It is therefore essential to understand the influence of process-induced material characteristics on failure due to ESC.
A large number of studies on material properties as a function of microstructural preferential orientation have already been conducted [5-7]. However, effects on ESC as the major failure mechanism of containers and pipes are still rather unexplored [8, 9]. The most important factor is whether primarily intramolecular high-strength covalent bonds or the substantially weaker intermolecular van der Waals forces are predominantly loaded.
In addition to the widely established classification by time to failure, the strain or crack opening displacement (COD) provides valuable information about the evolution and progression of damage as a function of time [10, 11]. Optical strain measurement using digital image correlation allows the differences in COD for isotropic and different angles of orientation of anisotropic specimens to be discussed. Also, a post-fracture surface analysis provides clarification on the craze-crack mechanism of the ESC. These different ESC-related properties of extruded and hot-pressed specimens have been investigated at different environmental medium temperatures and different initial stresses to provide a broad characterization of the fracture behavior of PE-HD.
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) composites usually demands intermediate-scale or full-scale testing. In this study a bench-scale test is presented as practicable and efficient method to assess the improvement in structural integrity of CFRP with different protective coatings during fire.
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) composites usually demands intermediate-scale or full-scale testing. In this study, a bench-scale test is presented as a practicable and efficient method to assess the improvement in structural integrity of CFRP with different protective interlayers during fire.
Fire stability is one of the biggest issues of carbon fibre reinforced polymer (CFRP) composites, particularly when they are using in load bearing applications. As soon as the glass transition temperature of polymer matrix (100-200°C) is achieved, the composite loses its structural integrity, what leads to the distortion and failure. The principal fire stability test is based on simultaneous application of fire and mechanical load. Since the carbon fibres can transfer the tensile loads quite well, the compression load is chosen as a required mechanical load for a test. The fire tests were preceded by a static load test at room temperature to determine ultimate failure load. The specimen was loaded with a compression force until the failure load was reached, which was observed as a buckling. For the fire tests, 10% of compression failure load and direct flame of a fully developed fire (heat flux ≈ 180 kW m-2) were applied simultaneously to the specimen, while the time to failure was measured.
The possibilities of bench-scale fire stability testing were presented by investigating new types of laminate structures, which exhibit promising flame retardancy and fireproof properties. The new approach of CFRP laminate differs with a protective concept. Every system consists of two different interlayers (titanium foil, thermoplastic foil PEI, ceramic layer WHIPOX, rubber tape Pyrostat, basalt fibres and kenaf fibres), where the one layer constitutes the fireproof protection, that delays the rise of temperature in the rest of laminate, and the second layer provides very good structural connection with carbon fibre layers, thus improves the mechanical integrity of CFRP composite in fire.
The time to failure of CFRP composite was 17s. Protective systems significantly enhance the fire stability and increased time to failure by 3 to 10 times. Thicker specimens showed longer resistance time, however CFRP laminate with ceramic layer and titanium foil presented outstanding results and the best performance. The protection with Kenaf and basalt fibres offered a natural fibre solution with also good fire resistance performance
Although bench-scale tests are limited with respect to assessing the performance of components and structures, they are valuable in the assessment of different materials concepts. Furthermore, the reduced effort of conducting bench-scale test (lower costs, time, personnel resources) makes it more practical and effective.
Bench-scale fire stability testing - Protective layers in carbon fibre reinforced polymer laminates
(2023)
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) composites usually demands intermediate-scale or full-scale testing. In this study, a bench-scale test is presented as a practicable and efficient method to assess the improvement in structural integrity of CFRP with different protective interlayers during fire.
FR additives were incorporated during tanning process. The mode of action of an intumescent system and each component individually, was methodically investigated in a semi-finished leather. Vertical flammability test results showed that the investigated semi-finished leather satisfies the regulations of the Federal Aviation Administration; in addition, afterglow time is strong minimized and forced fire behavior pointed out an important reduction on smoke production.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. These polymers are characterized by a high permeability and reasonable permselectivity. The latter point is somehow surprising because for microporous systems a more Knudson-like diffusion is expected then a size dependent temperature activated sieving process. It was argued in the framework of a random gate model that molecular fluctuations on a time scale from ps to ns are responsible for the permselectivity.
Here series of polymers of intrinsic microporosity (PIMs) as well as microporous polynorbornenes with bulky Si side groups and a rigid backbone are considered. The polymers have different microporosity characterized by high BET surface area values.
First inelastic time-of-flight neutron scattering measurements were carried out to investigate the low frequency density of state (VDOS). The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. It was found that the frequency of the maximum position of the Boson peak correlates with the BET surface area value.
Secondly elastic scans as well as quasielastic neutron scattering measurements by a combination of neutron time-of-flight and backscattering have been out. A low temperature relaxation process was found for both polymers. This process was assigned to the methyl group rotation. It was analysed in terms of a jump diffusion in a three-fold potential. The analysis of the dependence of the elastic incoherent structure factor on the scattering vector yields the number of methyl groups which might be immobilized.
The neutron scattering experiments were accompanied by fast scanning calorimetry and broadband dielectric investigations as well as atomistic molecular dynamic simulations.
Thermoplastic polyurethane - How thespecific two-stage decompositioncontrols its fire behavior
(2018)
Thermoplastic polyurethanes (TPUs) are one of the major classes of thermoplastic elastomers used in the cable and wire industry. Due to their chemical structure, they are considered as linear block copolymers with alternating hard and soft segments. This specific structure is not only responsible for the excellent mechanical properties of TPU like high tensile strength or abrasion resistance, but it also influences the pyrolysis and burning behavior. TPU is a highly flammable polymer which forms liquid pool fires or burning drops which results in intensive flame spread. Because of that, TPU often does not meet the strict requirements for indoor applications given by the cable market.
Under thermal stress, TPU decomposes in a specific way. At first, the hard segments decompose and the material becomes soft and melts. Subsequently, pool fires are formed and melted material burns extensively. There are not many works addressing this problem in detail especially in terms of suitable flame retardant solutions. It is crucial to understand at which stage the flame retardants are working and how they affect the thermal decomposition of TPU. Hence, the focus of this work was put on the identification of the reactions occurring during each stage of TPU decomposition and the contribution of released products to the effective heat of combustion (EHC). Moreover, the detailed analysis of the melt dripping behavior was performed to better understand the influence of the decomposition degree on the viscosity.
The use of melamine cyanurate (MC) in combination with other additives was reported to be a promising flame retardant solution for TPU, especially in cable jacket applications. Hence, the combinations of MC with various flame retardants were used in TPU (Elastollan® 1185A10) and were investigated in terms of fire behavior, flammability, pyrolysis and decomposition products. As flame retardants, common ones were used including aluminum trihydrate (ATH), melamine polyphosphate (MPP), or aluminum diethylphosphinate (AlPi). Moreover, commercial product TPU-FR (Elastollan® 1185A10FHF) was investigated as a reference.
The residual post-fire mechanical properties of fiber-reinforced epoxy composites are influenced by their fire residues after burning. This study uses intumescent/low-melting glass flame retardants to tailor fire residues in epoxy resin. Processibility of prepregs and their quality are analysed for transfer of the flame-retardant epoxy resins to layered glass-fiber reinforced composites. Minimal effects were found on the pre-fire flexural strengths of the composites due to low loading of the flame retardants. However, when transferred to glass-fiber reinforced composites, the fire residues diminish significantly. Further studies are required to improve theoretical and experimental estimations of the post-fire mechanics of the composites.
The transfer of flame-retardant epoxy resin formulations to composites for structural and lightweight applications in the energy and transport sector can be complex and requires systematic investigation. Here, uncoated and silane-coated ammonium polyphosphate (APP, Si-APP) intumescent compounds are transferred to prepregs using a Bisphenol A diglycidyl ether (DGEBA) resin matrix to 0/90o bidirectional glass fibers with an aerial weight of 600 g/m2. Inorganic silicates (InSi) are added to improve the fire residues of the composites after combustion and the total amount of flame retardants in the resin formulations was 10% by weight. The prepregs' fiber volume content (FVC) is corroborated using in-process measurements and thermogravimetric analysis. This was found to be approximately 60% for the composites containing APP, which is ideal for load-bearing applications with high mechanical strength. However, the Si-APP containing prepregs showed an inconsistent FVC potentially due to interactions with the commercial sizing of the glass fibers. The composites subsequently prepared are analysed for potential filtration effects of the additives via SEM after immobilization in a cured resin and platinum sputtering. The inter-laminar shear strength and the mechanical strength of the composites are compared via three-point bending tests. Additionally, the fire performance of the composites is analysed using cone calorimetry. It was found there was minimal impact of the loading of the flame retardants on the delamination of the composites and the flexural strength. However, the high density of the glass fibers possibly results in a suppression of the mode of action of the flame retardants in the composites. Therefore, the fire residues of the composites are further compared using SEM, and the flame-retardant modes of action upon transfer are investigated.
The residual post-fire mechanical properties of fiber-reinforced epoxy composites are influenced by their fire residues after burning. This study uses intumescent/low-melting glass flame retardants to tailor fire residues in epoxy resin. Processibility of prepregs and their quality are analysed for transfer of the flame-retardant epoxy resins to layered glass-fiber reinforced composites. Minimal effects were found on the pre-fire flexural strengths of the composites due to low loading of the flame retardants. However, when transferred to glass-fiber reinforced composites, the fire residues diminish significantly. Further studies are required to improve theoretical and experimental estimations of the post-fire mechanics of the composites.
Natural Rubber Nanocomposites via Optimized Latex Premixing and Conventional Technical Processing
(2021)
Creation of highly functional materials and replacement of high amounts of conventional fillers are driving forces for the development of nanocomposites. Besides the type and properties of nanoparticles, their dispersing in the elastomeric matrix and the stability of this dispersion through all processing steps are the
main factors for the resulting performance of the produced material. Therefore, a preparation chain via latex premixing to a highly filled masterbatch, followed by conventional technical processing is to be developed.
Three types of carbon-based particles are characterized as such (SEM, Raman Spectroscopy, BET specific surface area) and in combination with natural rubber, as nanocomposites (TEM. Hardness, Abrasion resistance, Compression set, Cone calorimetry).
All of the studied particles lead to an improvement in the investigated mechanical properties, the extent of reinforcement depends strongly on the specific surface of the particle interacting with the elastomeric matrix in combination with their shape.
2D layered nanoparticles enable a distinct reduction of filler loadings in rubber compounds combined with a boost in performance due to their high surface to volume ratio. They often enable unique property profiles providing a great potential as effective fillers in rubber, especially by enhancing mechanical and barrier properties.
As the best possible incorporation into the elastomer matrix is crucial for the efficiency of the nanofiller, dispersing and exfoliation of the nanoparticles without formation of agglomerates usually constitutes an outstanding challenge - especially when using conventional processing methods. Laboratory-scale approaches for highly dispersed nanocomposites sometimes solve this problem, but these are often too energy and time consuming and provide no scale up possibility for real applications. Therefore, a latex premixing process was established to produce highly filled masterbatches, enabling the processing with conventional techniques.
The presence of nanoparticles greatly impacts the behavior of elastomeric compounds, besides affecting the properties of the final product also the processing is influenced (rheology, crosslinking).
In this study, nanocomposites of natural rubber and multilayer graphene (MLG) were prepared via a latex masterbatch route. Different strategies for masterbatch premixing are compared (stirring vs. ultrasonication, coagulation vs. drying). Dispersion and exfoliation of MLG were determined by transmission electron microscopy. The reinforcing effect of MLG affects the viscosity while the dispersed graphene layers may also act as diffusion barrier/absorbent for the crosslinking agents. In contrast to that, MLG forms physical crosslinks in the final product. Swelling measurements and differential scanning calorimetry allow a differentiation between chemical and physical network links. Different technical properties of the nanocomposites were measured with respect to mechanical and application relevant behavior.
The incorporation of nanoscale particles into elastomers enable a boost in performance and/or a distinct reduction of conventional filler loadings due to their high surface to volume ratio. 2D layered nanoparticles like graphene and graphene-related materials provide a great potential as effective fillers in rubber, especially by enhancing mechanical and barrier properties. The type and properties of the nanoparticles, their interface and the elastomeric matrix materials influence the technical behavior, and therefore the potential application fields of such rubber nanocomposites. Especially crucial for the efficiency of the nanofiller, however, is its best possible incorporation into the elastomer. The dispersing of nanoparticles without agglomerates usually constitutes a challenge when using conventional two-roll milling or internal mixing. Academic approaches for highly dispersed nanocomposites solve this problem but are often energy and time consuming with no feasible scale up possibility. Therefore, an ultrasonic assisted NR latex premixing process was established to produce highly filled masterbatches, enabling the main processing with conventional rubber processing techniques.
Two carbon-based nanoparticles with similar specific surface areas were investigated and incorporated in natural rubber as nanocomposites: A commercially available multilayer graphene (MLG) and a nanoscale carbon black (nCB). The mentioned premixed masterbatches were further processed to nanocomposites by the addition of matrix NR, two-roll milling, and hot pressing (vulcanization). By this procedure an increase in Young’s modulus of 157% (MLG) and 71% (nCB) could be obtained at a concentration level of 3 phr. As anisotropic material behavior was observable for the nanocomposites containing MLG, different measurement methods were investigated to quantify the orientation of the nanoparticles in the nanocomposites: Sorption measurements (swelling in 2 dimensions), hardness and dynamical mechanical analysis (in-plane vs. cross-plane), X-Ray diffraction and transmission and scanning electron microscopy.
For centuries, churches, secular buildings and museums have been furnished with valuable works of art. Many works of art are UV- and light-sensitive. It is well known that especially UV radiation causes damage and discoloration in paintings, textiles, plastics, wood and other materials. In particular, the wavelengths between 280 and 410 nm cause color changes, embrittlement or destruction of e.g. plastics over time. Therefore, strongly UV-absorbing glasses are advantageous for architecture and are necessary for the protection of cultural assets. As restorers in all disciplines become more and more aware, the demands placed on buildings and their furnishings in terms of climate are becoming increasingly detailed and precise. The aim in each case is to preserve the valuable artwork.
For some years now, the industry has been offering the protection of cultural objects by installing special UV-protective glasses. Currently, UV protection for church buildings is realized by laminated safety glass equipped with appropriate UV-protective plastic films. Technically, this always means a second pane of glass in front of the windows, which is installed outside the building. This creates climatic gaps that are difficult to control and deterioration due to ageing effects can be expected. At the same time, this protective glazing is not invisible and has a considerable aesthetic influence on the interior and exterior appearance of the building. Meanwhile, the preservation of historical monuments accepts such aesthetic cuts on buildings in order to protect the artwork in the interior from UV light. To this day, however, the long-term durability of UV protection provided by inserted plastic films is still controversial.
To date the only available alternative on the market is a mouth-blown UV protection glass which uses a so-called overlay to provide UV protection. This shows that UV protection can also be achieved by glasses without plastic films thus realizing an exclusive inorganic protection which normally is more stable than a polymeric one. So far there are not enough studies to prove long-term durability.
The aim of this project is to provide existing glazing or new glazing to be created with a highly transparent layer that ensures this UV-protective filter function below 400 nm. The glass coating is to be applied to the glass over a large area and fired into the surface like a classic ceramic enamel paint with the same technics. In addition, it should be long-term durable in its function. It means, that the glass has to be fused at temperatures below 630 °C during the firing process, its chemical durability has to be high, its coefficient of thermal expansion has to be as close as the one of the substrate (usually float glass) and the glass has to absorb the UV-radiation within a thin thickness (thinner as 100 µm).
In this project, the long-term durability of commercial UV-protective glasses is examined. New low melting glasses containing UV-absorbing ions are being developed. Their UV-absorption as a thin layer is analyzed as well as their chemical durability and their thermal properties.
We are grateful to BMWI for the financial support in the frame of the Central Innovation Programme for SMEs (ZIM).
The chapter gives a brief introduction to (nano)compositecomposite materials having the focus on polymer-based nanocomposites. The different dimensionalities of nanoparticles are introduced, along with their distribution in the matrix.
Different application fields of polymer-based nanocomposites, like flame retardancy, filled rubbers, nanofilled thermosets and thermoplastics, separation membranes and nanodielectrics, are considered in greater detail.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering where the data are discussed with regard to both the q- and the temperature dependence.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in green gas separation membranes and as active materials for electronic applicatons. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analysed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
Die Forderung, dass der Flammschutz von Kunststoffen nicht nur zum bei der Herstellung der jeweiligen Produkte, sondern auch über die gesamte Einsatzdauer im geforderten Maß wirksam ist, stellt eine große Aufgabe dar. Ferner ist die Anforderung für viele Produkte in der Praxis neu, da bisher vor allem der Einfluss der Flammschutzmittel auf die Stabilität der Polymerwerkstoffe, nicht aber die Stabilität des Flammschutzes untersucht wurde. Das Langzeitverhalten halogenfreier Systeme ist bis heute wenig untersucht, insbesondere weil Phosphor- und Stickstoff-basierte Systeme die oxidative Beständigkeit von Polymeren weniger zu beeinflussen scheinen als halogenhaltige FSM. Die Frage, wie zuverlässig der Flammschutz wirkt, wenn Kunststoffe einige Jahre im Innen- und Außenbereich im Einsatz sind und dabei wechselnden Beanspruchungen ausgesetzt waren, wurde bislang nur vereinzelt untersucht. Mögliche Auswirkungen von Witterungseinflüssen auf flammgeschützte Polymerwerkstoffe sind, dass die Flammschutzmittel selbst abbauen, ausgewaschen werden, oder auch durch Wechselwirkung mit den eingesetzten Additiven oder mit den Alterungsprodukten der Polymermatrix in ihrer Wirkung nachlassen. Hier bestand großer Forschungsbedarf, um an den Punkt zu gelangen, die Beständigkeit der Flammschutzeigenschaften eines Produktes über seine gesamte Lebensdauer zuverlässig garantieren zu können. Diese Fragestellung greift das durchgeführte Forschungsvorhaben auf.
Ziel war die Untersuchung der Langzeitstabilität der Flammschutzwirkung von halogenfrei flammgeschützten Polymerwerkstoffen unter diversen Witterungseinflüssen. Dazu wurden die Schädigungsmechanismen der Polymerwerkstoffe und der Flammschutzmittel sowie die auftretenden Wechselwirkungen analysiert, um ein Verständnis für die ablaufenden Prozesse zu entwickeln und Empfehlung für die Reduzierung der Alterung zu erarbeiten. Gegenstand der Untersuchungen waren anwendungsrelevante Flammschutz-Konzepte, die miteinander verglichen wurden. Die Erarbeitung von Struktur-Eigenschafts-Beziehungen ermöglichte die Beschreibung der Empfindlichkeiten und den Vergleich zwischen den Systemen. Darauf basierend wurden für die FSM spezifische Leitlinien für die Optimierung der Langzeitstabilität des Flammschutzes erstellt.
The dataset provided in this repository comprises data obtained from a series of full-notch creep tests (FNCT) performed on selected high-density polyethylene (PE-HD) materials (for further details, see section 1 Materials in this document) in accordance with the corresponding standard ISO 16770.
The FNCT is one of the mechanical testing procedures used to characterize polymer materials with respect to their environmental stress cracking (ESC) behavior. It is widely applied for PE-HD materials, that are predominantly used for pipe and container applications. It is based on the determination of the time to failure for a test specimen under constant mechanical load in a well-defined and temperature controlled liquid environment. The test device used here also allows for continuous monitoring of applied force, specimen elongation and temperature.
Polyethylen hoher Dichte (PE-HD) wird als Werkstoff für Rohre und Behälter für den Transport und zur Lagerung von Gefahrgütern verwendet. Für die Beurteilung und technische Freigabe dieser Materialien ist insbesondere das Verständnis des Schädigungsmechanismus des langsamen, umgebungsbedingten Spannungsrisses (engl.: „environmental stress cracking“, ESC) essentiell. ESC tritt bei relativ geringen auf einen Werkstoff einwirkenden mechanischen Spannungen auf. An lokalen Fehlstellen (z.B. Defekte, Inhomogenitäten, Kerben) beginnend wächst ein Riss langsam durch das Material und führt nach gewisser Zeit zu einem charakteristischen, pseudo-spröden Bruch. Dabei wird das Risswachstum durch äußere Medieneinwirkung zusätzlich entscheidend beeinflusst. Dieses langsame Risswachstum wird als Hauptursache für das plötzliche und unerwartete Versagen von Polymerwerkstoffen angesehen.
Eine etablierte Prüfmethode zur Bewertung des Materialverhaltens gegenüber dieses Schädigungsmechanismus ist der Full-Notch Creep Test (FNCT), der für PE-HD Behältermaterialien üblicherweise unter Verwendung von wässrigen Netzmittellösungen (Arkopal N 100) durchgeführt wird. Die aus dem FNCT erhaltene Standzeit dient dabei als Bewertungskriterium für verschiedene PE-HD-Werkstoffe. In einer Studie wurden neben einer typischen Arkopal-N-100-Netzmittellösung praktisch relevante, organische Flüssigkeiten wie Biodiesel und Diesel als Testmedien verwendet, um deren Einfluss auf das ESC-Verhalten von PE-HD-Behältermaterialien zu charakterisieren. Neben der klassischen Standzeit-Auswertung erfolgte eine erweiterte Bruchflächenanalyse mittels Licht- (LM), Laserscanning- (LSM) und Rasterelektronenmikroskopie (REM). Insbesondere die LSM erlaubt eine schnelle und einfache Unterscheidung pseudo-spröder und duktiler Bruchbilder, die zur Beurteilung der Repräsentativität des FNCT für das dem Spannungsriss zugrundeliegenden langsamen Risswachstum von Bedeutung ist.
As the well-known damage mechanisms slow crack growth (SCG) and environmental stress cracking (ESC) are the major causes for possible failure of polyolefin-based materials, especially for PE-HD, they are highly relevant and need to be considered thoroughly. Furthermore, due to slight but perceptible differences in damaging effect, a differentiation between SCG and ESC is expedient. SCG appears in “inert” or “neutral” media without a decisive influence of the surrounding medium whereas ESC occurs in “active” media, which influence the failure behavior and time to failure crucially.
To characterize the inherent resistance of the material against those damage mechanisms, the well-established Full-Notch Creep Test (FNCT) is used. In this study, the FNCT – usually applied according to ISO 16770 [3] using a few universal model liquid media and mainly for pipe materials – is extended by investigations with appropriate parameters of selected relevant PE-HD container materials also in real media, such as the topical fuels diesel and biodiesel. The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Especially, mechanical stress and temperature were varied systematically during FNCT and time to failure values, time-dependent elongation data as well as detailed fracture surface analysis by laser scanning microscopy (LSM) were combined for the first time (Fig. 1). Particularly, the fracture surface analysis provides a sound basis to characterize failure behavior, mainly regarding the balance between brittle crack propagation and ductile deformation. Therefore, fracture surface analysis is an essential tool for a decent assessment of SCG and ESC by FNCT measurements.
During their lifetime, polymer components subjected to mechanical loads and environmental influences show a loss of their mechanical properties required for their specific applications. In this respect, the craze-crack damage mechanism slow crack growth (SCG) is relevant for PE-HD components used in high-performance applications such as pipes and containers for the storage and transport of dangerous goods. SCG is considered to be the major failure mechanism in polyolefins and it typically occurs suddenly and unexpectedly. Due to the fields of application, SCG is a safety relevant issue. To test for the resistance of PE-HD pipe and container materials against SCG, the full-notch creep test (FNCT) is widely applied in Europe. In this study, SCG phenomena in PE-HD are investigated in detail based on an improved FNCT, especially including the consideration of the influence of environmental liquids effecting the damage mechanism. Using an enhanced fracture surface and a crack propagation analysis with imaging techniques such as light microscopy (LM), laser scanning microscopy (LSM), X-ray computed tomography (CT-scan) and scanning electron microscopy (SEM), detailed data concerning SCG are obtained.
The combined application of FNCT and such imaging techniques is explicitly advantageous and recommended to gain important information on damage occurring to PE-HD induced by mechanical stress and the influence of environmental liquids, which is essential within the Fourth Industry Revolution.
The full-notch creep test (FNCT) is a common method to evaluate the environmental stress cracking (ESC) behavior of high-density polyethylene (PE-HD) container materials . The test procedure as specified in ISO 16770 provides a comparative measure of the resistance against ESC using the time to failure of specimens mechanically loaded in a well-defined liquid environment. Since the craze-crack damage mechanism underlying the ESC process is associated with brittle failure, the occurrence of globally brittle fracture surfaces is a prerequisite to consider an FNCT measurement as representative for ESC . Therefore, an optical evaluation of FNCT fracture surfaces concerning their brittleness is essential. Due to the experimental setup, an inevitable increase of the true mechanical stress and the associated appearance of small ductile parts on fracture surfaces is induced in any case. Hence, an FNCT experiment is considered as 'valid', if the corresponding fracture surface is predominantly brittle . Based on laser scanning microscopy (LSM) height data of FNCT fracture surfaces , a universal and easy-to-use phenomenological criterion was developed to assess the validity of distinct FNCT experiments. This criterion is supposed to facilitate a quick evaluation of FNCT results in practical routine testing.
This is the stable version of the full-notch creep test ontology (OntoFNCT) that ontologically represents the full-notch creep test. OntoFNCT has been developed in accordance with the corresponding test standard ISO 16770:2019-09 Plastics - Determination of environmental stress cracking (ESC) of polyethylene - Full-notch creep test (FNCT).
The OntoFNCT provides conceptualizations that are supposed to be valid for the description of full-notch creep tests and associated data in accordance with the corresponding test standard. By using OntoFNCT for storing full-notch creep test data, all data will be well structured and based on a common vocabulary agreed on by an expert group (generation of FAIR data) which is meant to lead to enhanced data interoperability. This comprises several data categories such as primary data, secondary data and metadata. Data will be human and machine readable. The usage of OntoFNCT facilitates data retrieval and downstream usage. Due to a close connection to the mid-level PMD core ontology (PMDco), the interoperability of full-notch creep test data is enhanced and querying in combination with other aspects and data within the broad field of materials science and engineering (MSE) is facilitated.
The class structure of OntoFNCT forms a comprehensible and semantic layer for unified storage of data generated in a full-notch creep test including the possibility to record data from analysis and re-evaluation. Furthermore, extensive metadata allows to assess data quality and reliability. Following the open world assumption, object properties are deliberately low restrictive and sparse.
Im Rahmen des Forschungsprojektes IGF 20470N wurden Untersuchungen zum Alterungsverhalten von reaktiven Brandschutzsystemen (RBS) auf Stahlbauteilen durchgeführt. Mithilfe der Ergebnisse einer umfangreichen Literaturrecherche sowie experimentellen und numerischen Untersuchungen sollte ein Vorschlag für ein Prüfkonzept zum Nachweis einer Nutzungsdauer von RBS von mehr als 10 Jahren auf Basis von Kurzzeitversuchen abgeleitet werden. Dabei setzt die Bewertung des Alterungsverhaltens von RBS voraus, dass die Mechanismen der Alterung hinreichend bekannt sind.
Dafür wurden zunächst systematisch Daten von Kurz- und Langzeitversuchen von nationalen Zulassungsprüfungen der letzten Jahrzehnte ausgewertet. Anschließend wurden umfangreiche experimentelle Untersuchungen an einer wasserbasierten sowie einer epoxidharzbasierten Richtrezeptur durchgeführt. Da aus der Literatur bekannt ist, dass die Einflüsse der Bewitterung zu einer Veränderung der Konzentration der Bestandteile innerhalb der Beschichtung führen können, wurden Untersuchungen mit Mangelrezepturen durchgeführt, wobei systematisch einzelne Bestandteile reduziert wurden. Neben optischen Untersuchungen wurden thermoanalytische Verfahren (DSC-TG-, ATR-FTIR-, Elementar-, Farbanalyse) angewandt sowie Brandversuche an beschichteten Stahlplatten durchgeführt. Des Weiteren wurden die Richtrezepturen den beschleunigten Kurzzeitversuchen gemäß EAD 350402-00-1106 (2017) unterzogen, welche die Zulassung von Produkten auf europäischer Ebene regelt. Für die wasserbasierte Richtrezeptur wurden die Bewitterung für den feuchten Innenraum (Typ Z1) mehrfach wiederholt (1x, 3x, 6x). Für die epoxidharzbasierte Richtrezeptur entsprach die Bewitterung dem Zyklus für die Außenanwendung (Typ X). In Brandversuchen sowie thermoanalytischen und optischen Untersuchungen wurde das Alterungsverhalten sowie die thermische Schutzwirkung analysiert.
Anschließend wurden numerische Simulationen von Stahlbauteilen mit gealterten RBS durchgeführt und anhand der experimentellen Untersuchungen validiert. Mithilfe der numerischen Modelle kann eine Bewertung der thermischen Schutzwirkung von Stahlbauteilen mit gealterten RBS vorgenommen werden.
Mithilfe der gesammelten Erkenntnisse wurde ein Vorschlag für ein Prüfkonzept für den Nachweis einer Nutzungsdauer von mehr als 10 Jahren abgeleitet. Das Prüfkonzept besteht dabei aus einem Katalog von Möglichkeiten, die aktuellen Zulassungsprüfungen auf europäischer Ebene für eine Nutzungsdauer von 10 Jahren auf einen längeren Zeitraum zu erweitern.
Polyurethane (PU) bilden eine der vielseitigsten Klassen der Polymerwerkstoffe. Kein anderer Kunststoff wird sowohl als Thermoplast, als Elastomer wie auch als Duroplast verarbeitet und eingesetzt. Entsprechend vielfältig sind auch die Anforderungen an den Flammschutz. Je nach Material und Anwendung müssen spezifische Brandnormen erfüllt werden. Der vorliegende Aufsatz gibt einen Überblick über die verfügbaren Ansätze, um durch geeignete Auswahl der Rohstoffe und der Flammschutzmittel diese verschiedensten Anforderungen an das Brandverhalten zu erfüllen.