7.5 Technische Eigenschaften von Polymerwerkstoffen
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Eingeladener Vortrag
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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.
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.
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 presentation gives an overview of actual research adtivities in the field of flame retardant polymers. Details are selected illuminating the scientific topic beyond the state of the art. Different concepts are illustrated with own results obtained in different Research projects over the last 15 years.
Hydroliquefaction is a possible pathway to produce liquid transportation fuels from solid feedstocks like coal or biomass. Though much effort has been put into the investigation of maximizing the oil yield using expensive catalysts and pasting oils in batch setups, little is known about how to commercialize the process. This work aims at the demonstration of lignin hydroliquefaction under conditions interesting for commercial operation. The results from hydroliquefaction experiments of two different lignin types using a cheap iron-based catalyst and anthracene oil as the pasting oil in a semibatch system are presented here. Oil yields of above 50% are reached without observing coke formation. Extensive analyses of the feedstocks and product oils were performed. The process supplies high-quality oil, while differences in the decomposition path of both lignin types are observed. An high heating value of 39 400 J/g and H/C and O/C ratios of up to 1.6 and 0.1, respectively, are detected for the produced bio-oils.
Bare steel constructions are often integrated in modern buildings. Intumescent coatings are widely used to protect the steel from heating up too quickly in a case of fire. As the functionality of intumescent coatings decreases with the impact of weathering processes, it is important to understand the mechanisms of material degradation to maintain long durability. The weathering-induced degradation behavior of a water-borne intumescent coating was examined, and the weakest points of the formulation were identified by a systematic approach. Resulting from this investigation, adjustments to the formula were made, leading to improved weathering resistance.
Most synthetic polymers have a high fire load, and as a result, they require flame retardants (FRs) to ensure their safe use. Phosphorus plays an important role in flame retardancy and has the potential to replace halogenated variants, which are assumed to be harmful to the environment and health. Among phosphorus-based FRs, there exists a trend towards polymeric, high molar mass molecules with complex molecular architectures. In this project, we synthesized a novel series of so-called phosphorus-based hyperbranched polymeric FRs and investigated their use as multifunctional additives to high-performance polymers, i.e. epoxy resins. By cleverly designing the chemical structure to contain varying amounts of P-O and P-N bonds, new insight into the chemical mechanism of flame retardancy was gained, and by comparing the hyperbranched polymers to their monomeric counterparts, a greater understanding of the role of complex architecture was won. This talk aims at presenting some of these results and proposes chemical mechanisms that illustrate what role these novel hyperbranched flame retardants play in molecular firefighting.
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:
Polymers of intrinsic microporosity (PIMs) have recently emerged as novel materials for a broad range of high-performance applications from gas separation to electronic devices. The very rigid, contorted polymer chains show only limited molecular mobility and therefore pack inefficiently giving rise to intrinsic microporosity with pore sizes generally smaller than 1 nm resulting in BET surface areas larger than 700 m2/g. Using conventional thermal analysis techniques, no glass transition temperature (Tg) of PIMs could be unambiguously detected up to now. Employing fast scanning calorimetry (FSC) based on a one chip sensor, decoupling the time scales responsible for the glass transition and the thermal decomposition is a reliable strategy to overcome this limitation. The FSC device is capable to heat and cool a small sample (ng-range) with ultrafast rates of several ten thousand K/s. Evidence of a glass transition is obtained for a series of PIMs with different chain rigidities. Local small-scale fluctuations are held responsible for the glass transition of highly rigid PIMs rather than segmental motions as in conventional polymers.
Es wurden Prüfkörper aus additiver Fertigung mittels Laser Sinter Verfahren (Polyamid 12, PA 12) und Fused Layer Modeling (Acrylnitril-Butadien-Styrol, ABS) sowie Prüfkörper aus dem Kunststoff-Spritzguss Verfahren (PA 12 und ABS) über 2000 Stunden künstlich bewittert. Vor, während und nach der Bewitterung erfolgte eine zerstörungsfreie Prüfung mittels Thermografie, optischer Mikroskopie und spektralen Methoden (UV/VIS-Spektroskopie und spektrale Reflexion), um den Alterungsfortschritt zu untersuchen und Schäden durch die künstliche Bewitterung sowie eingedruckte Defekte zu identifizieren und zu detektieren.
Zusätzlich wurden zerstörende Zugprüfungen vorgenommen, welche mit einer IR-Kamera verfolgt wurden. Auf diese Weise konnten lokale Temperaturänderungen, hervorgerufen durch elastische sowie plastische Verformungen, zeitaufgelöst erfasst und ausgewertet werden.
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.
The main flame retardant modes of action are known, nevertheless in practise the detailed scientific understanding usually falls short, when it comes to modern multicomponent systems, the important tiny optimizations, or quantifying in terms of specific fire properties. The description of the flame retardant modes of action remains usually vague and fragmentary. This talk tries to deliver thought-provoking impulses how the understanding of the fire behaviour and flame retardancy can be utilized to direct the development of future flame retardant polymer products. Some overseen details are picked up as well as rethinking of concepts memorised long ago is encouraged to discover something new. Furthermore, the talk tries to fill the gap between flame retardant modes of action and fire performance constituting a product. This talk promotes the evidence-based development of flame retardant polymers.
Weathering reference materials 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 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.
First phosphorus AB2 monomer for flame-retardant hyperbranched polyphosphoesters: AB2vs. A2 + B3
(2019)
Branched polymers are an important class of polymers with a high number of terminal groups, lower viscosity compared to their linear analogs and higher miscibility, which makes them especially interesting for flame retardant applications, where the flame retardants (FR) are blended with another polymer matrix. Hyperbranched polyphosphoesters (hbPPEs) are gaining more and more interest in the field of flame retardancy, as low molar mass FRs often have the disadvantage of blooming out or leaching, which is not desired in consumer products. Here, we present the first phosphorus-based AB2 monomer for the synthesis of hbPPEs and assess its flame-retardant performance in an epoxy resin compared to a hbPPE synthesized by an A2 + B3 approach. The hbPPE synthesized from an AB2 monomer exhibited a slightly higher performance compared to a similar hbPPE, which was prepared by A2 + B3 polyaddition, probably due to its higher phosphorus content.
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.
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() des Auges bewerteten VIS-Strahlung in Lux (lx) bzw. die mit der Erythem-Wirkfunktion bewertete UV Strahlung als dimensionsloser UV-Index berücksichtigt wird. Spektrale Empfindlichkeiten.
Die Photodegradation von Polymeren ist im UV-Bereich ebenfalls stark wellenlängenab-hängig, was bisher 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 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-Gesamt-bestrahlungsstärke und UV-Gesamtbestrahlung erfasst deshalb über weite Wellen-längenbereiche 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.
This work investigates the fire phenomena of rigid polyurethane foams (RPUFs) in detail. To elucidate structure-property relationships, systematically varied sets of materials were prepared covering polyurethane, polyisocyanurate-polyurethane and flame retarded polyurethane foams. Advanced cone calorimeter investigations provide insight into the fire behavior under forced flaming conditions. Thermocouples inside specimens give information about the temperature gradient during combustion. Furthermore, fire phenomena were characterized using cross sections of quenched samples and the scanning electron microscope. By using a Multi methodological approach and systematically varied sets of foam materials, new insights into the burning of RPUFs were won. For the flame retarded foams, the dominant flame retardant mode of action changed with density. PIR foams exhibited a cellular structure in the residue leading to the superior fire performance compared to polyurethane foams. The understanding of fire phenomena contributes to future development of tailored flame retardant strategies for RPUFs.
We synthesized a library of phosphorus-based flame retardants (phosphates and phosphoramides of low and high molar mass) and investigated their behavior in two epoxy resins (one aliphatic and one aromatic).
The pyrolytic and burning behavior of the two resins (via TGA, TG-FTIR, Hot stage FTIR, Py-GC/MS, PCFC, DSC, LOI, UL-94, Cone calorimeter) are analyzed and compared to the results of flame retardant (FR)-containing composites. A decomposition pathway incorporating the identified modes of action and known chemical mechanisms is proposed. The overlap of decomposition temperature (Tdec) ranges of matrix and FR determines the efficacy of the system. Low molar mass FRs strongly impact material properties like Tg but are very reactive, and high molar mass variants are more thermally stable. Varying PeO and PeN content of the FR affects decomposition, but the chemical structure of the matrix also guides FR behavior. Thus, phosphates afford lower fire load and heat release in aliphatic epoxy resins, and phosphoramides can act as additives in an aromatic matrix or a reactive FRs in aliphatic ones. The chemical structure and the structure-property relationship of both FR and matrix are central to FR performance and must be viewed not as two separate but as one codependent system.
The current trend for future flame retardants (FRs) goes to novel efficient halogen-free materials, due to the ban of several halogenated FRs. Among the most promising alternatives are phosphorus-based FRs, and of those, polymeric materials with complex shape have been recently reported. Herein, we present novel halogen-free aromatic and aliphatic hyperbranched polyphosphoesters (hbPPEs), which were synthesized by olefin Metathesis polymerization and investigated them as a FR in epoxy resins. We compare their efficiency (aliphatic vs. aromatic) and further assess the differences between the monomeric compounds and the hbPPEs. The decomposition and vaporizing behavior of a compound is an important factor in its flame-retardant behavior, but also the interaction with the pyrolyzing matrix has a significant influence on the performance. Therefore, the challenge in designing a FR is to optimize the chemical structure and its decomposition pathway to the matrix, with regards to time and temperature. This behavior becomes obvious in this study, and explains the superior gas phase activity of the aliphatic FRs.
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.
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.
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.
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).
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.
Whereas the degradation of flame retardant polymers has been discussed since decades, only more recently, the lifetime of the flame retardancy itself becomes an important factor, e.g. for cables used as building products. In this work, several kinds of accelerated artificial ageing tests are performed simulating different environmental exposures and thus highlighting different degradation mechanisms: artificial accelerated weathering, climatic chamber, water immersion, salt spray chamber, and autoclave test. The durability is expected to be different for different flame-retardant materials. Thus, various sets of halogen-free fire-retarded polymers were investigated: ethylene vinyl acetate (EVA) with aluminum hydroxide (ATH), boehmite and synergists, ester-based and ether-based thermoplastic polyurethane (TPU) with melamine cyanurate (MC), aluminum diethylphosphinate (AlPi), and boehmite, and glass fiber reinforced polyamide 66 (PA66) with AlPi-based mixtures.
Intensive degradation of the surface was observed, e.g. yielding discoloration and yellowing, EVA showed cracking when weathered. Changes in chemical structure was investigated by ATR-FTIR. The flammability was investigated with the cone calorimeter, UL-94 classification, and oxygen index (LOI). The flame retardancy of most of the materials studied degraded only slightly for the investigated exposure times. EVA/ATH achieved an improved LOI due to flame retardants agglomeration at the surface. Sets of materials, based on EVA and TPU, were also investigated as cable jackets. While flame retarded EVA exhibited no dripping during burning, TPU flame-retarded with MC cables showed pronounced melt-dripping. Cone calorimeter tests were carried out using cable rafts as well as our self-made cable module test, simulating a vertical bundle of cables at the bench scale. The comparison of different fire tests, different exposure conditions, and different materials carved out the specific degradation phenomena with respect to each of these parameters.
Most of this work was supported by the IGF Project (18926 N) of the Fördergemeinschaft für das Süddeutsche Kunststoff-Zentrum e.V., supported by the AiF within the framework of the program “Förderung der Industriellen Gemeinschaftsforschung (IGF)” of the German Federal Ministry for Economic Affairs and Energy based on a decision of the Deutschen Bundestag.
A central challenge to ensure the sustainable production and use of nanotechnologies is to understand and effectively control the risks along the industrial innovation value chain. Knowledge about nanotechnology processes and nanosafety issues (hazards, fate, risk...) is growing rapidly but the effective use of this knowledge for risk management by market actors is lagging behind.
EC4SafeNano (European Centre for Risk Management and Safe Innovation in Nanomaterials and Nanotechnologies) promotes a harmonized vision of expertise in risk assessment and management for the public and private sectors to enable the safe development and commercialization of nanotechnology.
EC4SafeNano is operated together by major European risk institutes with the support of numerous associated partners, gathering all stakeholders involved in Nanomaterials and Nanotechnologies (regulators, industry, society, research, service providers...).
In a case study the surface chemical transformations upon 2 different ageing procedures (long-term UV irradiation or swimming pool water) of a representative set of titanium dioxide nanoparticles has been investigated. The materials have been analyzed by various analytical techniques. Each method addresses different aspects of the complex endpoint surface chemistry. The multi technique approach allows evaluation of the capabilities and limitations of the applied methods regarding their suitability to address the endpoint surface chemistry and their sensitivity to identify even small surface chemical transformations.
Results:
- To obtain a comprehensive picture, it is insufficient to concentrate on a single analysis technique.
- By using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in combination with principal component analysis (PCA) it was possible to identify even subtle changes in the surface chemistry of the investigated materials.
- A general trend that was observed for the UV-aged samples is the decrease of organic material on the nanomaterial surface.
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 723623.
To quantify the evacuation process, evacuation practitioners use engineering egress data describing the occupant movement characteristics. These data are typically based to young and fit populations. However, the movement abilities of occupants who might be involved in evacuations are becoming more variable—with the building populations of today typically including increasing numbers of individuals: with impairments or who are otherwise elderly or generally less mobile. Thus, there will be an increasing proportion of building occupants with reduced ability to egress. For safe evacuation, there is therefore a need to provide valid Engineering egress data considering pedestrians with disabilities. Gwynne and Boyce recently compiled a series of data sets related to the evacuation process to support practitioner activities in the chapter Engineering Data in the SFPE Handbook of Fire Protection Engineering. This paper supplements these data sets by providing information on and presenting data obtained from additional research related to the premovement and horizontal movement of participants with physical-, cognitive-, or age-related disabilities. The aim is to provide an overview of currently available data sets related to, and key factors affecting the egress performance of, mixed ability populations which could be used to guide fire safety engineering decisions in the context of building design.
Flame-retarded biocomposites of thermoplastic starch and natural fibres are successfully processed according to state-of-the-art extrusion and injection moulding. Using agave fibres and henequen fibres recovered from local industrial waste is a convincing contribution to sustainability. A systematically varied set of biocomposites is investigated comprehensively, e.g. electron microscopy is used for characterizing the morphology, rheology for the melt viscosity, tensile and impact resistance for the mechanical properties, thermal analysis for the pyrolysis, UL 94 burning chamber and oxygen index for the flammability, and cone calorimeter for the fire behaviour. Achieving sufficient mechanical properties was not the goal in our pre-competitive study but may be tackled by adding compatibilizer in future. The combination of well-dispersed natural fibres, aluminium diethylphosphinate (AlPi) and a special silicone synergist (Si) is proposed as promising innovative route for V-classified biocomposites. The flame-retardancy modes of action in the gas phase (fuel dilution and flame inhibition) and in the condensed phase (charring, protective layer formation) are discussed in detail, as is the role of combining the ingredients. This work is a convincing proof of principle of how to prepare industrial-waste fibres biocomposites, to apply the synergistic combination of AlPi and Si for future flame-retarded technical polymer materials that are based on renewable resources and compostable.
A promising approach for the further improvement of fire detection techniques is the inclusion of fire gases in the characteristics used to detect a fire. A screening of sample materials representative for common first burning items and their gas release under different ignition conditions was performed to gain an overview of possible target gas candidates. Different fire scenarios were investigated to evaluate fire gases produced in early stages of fire development, their time of appearance and concentration development using the vitiated mass loss calorimeter and a heating plate setup in the single burning item test chamber.
Im Rahmen des BMBF geförderten Verbundprojekts „TEBRAS – Konzepte und Techniken zur Branderkennung, Bekämpfung und Selbstrettung in der frühesten Brandphase“ arbeiten sechs Partner aus der Wissenschaft und der Industrie gemeinsam an Lösungen zur schnelleren Branddetektion und Bekämpfung. Ausgehend von Brandschadenstatistiken werden zunächst häufige Brandentstehungsszenarien, Brandursachen und die beteiligten Objekte und Materialien identifiziert. Auf dieser Basis wird ein Testszenario entwickelt, das es erlaubt, einen repräsentativen Entstehungsbrand unter definierten Testbedingungen zu untersuchen. Typische Brandkenngrößen werden anhand der ausgewählten Referenzszenarios des Schwelbrands einer Mischbrandkrippe vorgestellt. Der Fokus liegt dabei auf den freigesetzten Brandgasen.
Im Rahmen des BMBF geförderten Verbundprojekts „TEBRAS – Konzepte und Techniken zur Branderkennung, Bekämpfung und Selbstrettung in der frühesten Brandphase“ arbeiten sechs Partner aus der Wissenschaft und der Industrie gemeinsam an Lösungen zur schnelleren Branddetektion und Bekämpfung. Ausgehend von Brandschadenstatistiken werden zunächst häufige Brandentstehungsszenarien, Brandursachen und die beteiligten Objekte und Materialien identifiziert. Auf dieser Basis wird ein Testszenario entwickelt, das es erlaubt, einen repräsentativen Entstehungsbrand unter definierten Testbedingungen zu untersuchen. Typische Brandkenngrößen werden anhand der ausgewählten Referenzszenarios des Schwelbrands einer Mischbrandkrippe vorgestellt. Der Fokus liegt dabei auf den freigesetzten Brandgasen.
We successfully synthesized multifunctional P-based hyperbranched polymeric flame retardants (hb-FRs) with varying oxygen-to-nitrogen (O : N) content and characterized them via 1H and 31P NMR and GPC. Their miscibility in epoxy resins (EP) and impact on glass-transition temperatures (Tg) were determined via differential scanning calorimetry (DSC). Using thermogravimetric and evolved gas Analysis (TGA, TG-FTIR), pyrolysis gas chromatography/mass spectrometry (Py-GC-MS), hot stage FTIR, flammability tests UL-94 and LOI, fire testing via cone calorimetry, residue analysis via scanning electron microscopy (SEM) and elemental analysis, detailed decomposition mechanisms and modes of action are proposed. hb-polymeric FRs have improved miscibility and thermal stability, leading to high FR performance even at low loadings. Polymeric, complex FRs increase flame retardancy, mitigate negative effects of low molecular weight variants, and can compete with commercial aromatic FRs. The results illustrate the role played by the chemical structure in flame retardancy and highlight the potential of hb-FRs as multifunctional additives.
Evakuierungsübung Werkstatt: positives Ergebnis
Evakuierungsübung Wohnbereich: Optimierungspotential identifiziert
•Lange Evakuierungszeiten
•Vorzeitige Rückkehr in das Gebäude / Freigabe
•Gefährdungsbeurteilungen
•Einweisung / regelmäßige Übung Assistenzmittel
•Intensivierung der Zusammenarbeit / Abstimmung mit örtlicher Feuerwehr
Emergency exits as bottlenecks in escape routes are important for designing traffic facilities. Especially the fundamental diagram is a crucial performance criterion for assessment of pedestrians' safety in facilities and an important basis for calculation methods. For this reason, several studies were performed during the last decades which focus on the quantification of movement through bottlenecks. These studies were usually conducted with populations of homogeneous characteristics to reduce influencing variables and for reasons of practicability.
Studies which consider heterogeneous characteristics in performance parameters are rarely available. In response and to reduce this lack of data a series of well-controlled large-scale movement studies considering pedestrians with different disabilities was carried out.
Crisis management, particularly the evacuation of handicapped People during a fire scenario presents a highly demanding challenge for nursing staff and rescue forces on site. The German research Project SiME is an interdisciplinary cooperation of university and non-university research institutions as well as medium-sized companies, which work together to develop strategies to manage such critical scenarios. In the SiME project, which is funded by the German Federal Ministry of Education and Research, evacuation characteristics of pedestrians with physical, mental or age-related disabilities are investigated to fit consisting numerical evacuation models with data. One of the major tasks of the OvGU was to set up a database of scenarios related to fire, explosion or substance releases in the working and living environment of handicapped people. Therefore, more than 463 fire Events occurring over the last decade in Germany were documented in this database and categorized by a suitable assignment of characteristics e.g. location of fire, ignition source, number of fatalities and injured.
The evaluated data were the basis for carrying out a quantitative risk analysis. Thus event trees were set up for different integrative infrastructures with which occurrence probabilities for different scenarios could be calculated for each path. The extent of damage, as a quantity describing the impact, was assumed to be personal injury or death or serious injury. By a risk assessment critical Scenarios could be derived from the risk analysis.
Emergency exits as bottlenecks in escape routes are important for designing traffic facilities. Especially the fundamental diagram is a crucial performance criterion for assessment of pedestrians' safety in facilities and an important basis for calculation methods. For this reason, several studies were performed during the last decades which focus on the quantification of movement through bottlenecks. These studies were usually conducted with populations of homogeneous characteristics to reduce influencing variables and for reasons of practicability.
Studies which consider heterogeneous characteristics in performance parameters are rarely available. In response and to reduce this lack of data a series of well-controlled large-scale movement studies considering pedestrians with different disabilities was carried out.
Several attempts have been made in the past to develop a European harmonized testing and assessment method for façades before the European commission decided to publish a call for tender on the topic. A project consortium from five countries (Sweden, UK, France, Germany and Hungary) applied to the call for tender and was contracted to develop a European approach to assess the fire performance of façades. 24 sub-contractors and 14 stakeholder entities were part of the project.
The objective of the European project was to address a request from the Standing Committee of Construction (SCC) to provide EC Member States regulators with a means to regulate the fire performance of façade systems based on a European approach agreed by SCC. In addressing this objective, the project team was asked to consider a number of issues which are presented and discussed.
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 1,2. This investigation compares the UK with the situation other parts of the world.
Crisis management, particularly the evacuation of handicapped people during a fire scenario presents a highly demanding challenge for nursing staff and rescue forces on site. The German research Project SiME is an interdisciplinary cooperation of university and non-university research institutions as well as medium-sized companies, which work together to develop strategies to manage such critical scenarios. In the SiME project, which is funded by the German Federal Ministry of Education and Research, evacuation characteristics of pedestrians with physical, mental or age-related disabilities are investigated to fit consisting numerical evacuation models with data. One of the major tasks of the OvGU was to set up a database of scenarios related to fire, explosion or substance releases in the working and living environment of handicapped people. Therefore, more than 463 fire Events occurring over the last decade in Germany were documented in this database and categorized by a suitable assignment of characteristics e.g. location of fire, ignition source, number of fatalities and injured.
In this study included:
The consideration of a façade kit as a construction product
The consideration of a façade as a part of a specific building. In some national regulations this would mean that detailing such as
window openings may also need to be considered.
Fire scenario identification for each of the Member States that regulate for the fire performance of the façade system based on alternative assessment methods.
Emergency exits as bottlenecks in escape routes are important for designing traffic facilities. Particularly, the capacity estimation is a crucial performance criterion for assessment of pedestrians' safety in built environments. For this reason, several studies were performed during the last decades which focus on the quantification of movement through corridors and bottlenecks. These studies were usually conducted with populations of homogeneous characteristics to reduce influencing variables and for reasons of practicability. Studies which consider heterogeneous characteristics in performance parameters are rarely available. In response and to reduce this lack of data a series of well-controlled large-scale movement studies considering pedestrians using different types of wheelchairs was carried out. As a result it is shown that the empirical relations are strongly affected by the presence of participants with visible disabilities (such as wheelchair users). We observed an adaption of the overall movement speeds to the movement speeds of participants using a wheelchair, even for low densities and free flow scenarios. Flow and movement speed are in a complex relation and do not depend on density only. In our studies, the concept of specific flow fits for the nondisabled subpopulation but it is not valid for scenario considering wheelchair users in the population.
Polyether and -ester urethanes (PU) were exposed to artificial weathering at 40 °C and artificial UV radiation in a weathering chamber. In 3 parallel exposures, humidity was varied between dry, humid, and wet conditions. Material alteration was investigated by various analytical techniques like size exclusion chromatography
(SEC), liquid chromatography-infrared spectroscopy (LC-FTIR), thermal-desorption gas chromatography-mass spectrometry (TD-GC-MS), fluorescence mapping and dynamic mechanical analysis (DMA). Our results show that depending on the weathering conditions, different degradation effects can be observed. By means of SEC an initial strong decrease of the molar masses and a broadening of the mass distributions was found. After a material dependent time span this was followed by a plateau where molar mass changes were less significant. A minor moisture-dependent degradation effect was only found for polyester PU. Fluorescence measurements on two materials revealed an increase in the luminescence intensity upon weathering process reaching a saturation level after about 500 h. The changes in the optical properties observed after different exposure conditions and times were very similar. The TD-GC-MS data showed the fate of the stabilizers and antioxidant in the course of weathering. LC-FTIR measurements revealed a change in peak intensities and the ratio of urethane and carbonyl bands.
Polymers of Intrinsic Microporosity (PIMs) of high performance have developed as materials with a wide application range in gas separation and other energy-related fields. Further optimization and long-term behavior of devices with PIMs require an understanding of the structure-property relationships including physical aging. In this context the glass transi-tion plays a central role, but with conventional thermal analysis a glass transition is usually not detectable for PIMs be-fore their thermal decomposition. Fast scanning calorimetry provides evidence of the glass transition for a series of PIMs, as the time scales responsible for thermal degradation and for the glass transition are decoupled by employing ultrafast heating rates of tens of thousands K s-1. The investigated PIMs were chosen considering the chain rigidity. The estimated glass transition temperatures follow the order of the rigidity of the backbone of the PIMs.
Elastomers are used in almost all areas of industrial applications, such as tires, engine mounts, bridge bearings, seals or coatings. During their use in operation, they are exposed to different environmental influences. These include, in particular, climatic factors such as air oxygen, high temperatures, light (UV radiation) and the influence of media (e.g. oils, fuels). A very important result of these factors is the chemical ageing of elastomers. In this case, the elastomer degenerates and changes its chemical structure in the aged regions, which leads to an irreversible change in the material properties in connection with the reduction in its usability. In this paper, chemical ageing of nitrile butadiene rubber (NBR) is investigated. Especially in case of thermo-oxidative ageing at elevated operating temperatures, the ageing processes run inhomogeneously. These effects are known as diffusion-limited oxidation (DLO) and are associated with the diffusion–reaction behaviour of atmospheric oxygen with the elastomer network. For these reasons, NBR samples are artificially aged in air and subjected to different experimental methods, which are presented and discussed. Additional results from inhomogeneous mechanical tests and permeation tests indicate the causes of the DLO-effect, show the influence of chemical ageing and are subsequently used for parameter identification in relation to the diffusion–reaction equation. A continuum-mechanical modelling approach is also presented here, which describes the finite hyperelasticity, diffusion–reaction processes as well as chemical degradation and reformation of the elastomer network. This multifield problem leads to a system of partial and ordinary differential equations and constitutive equations and is solved within the finite element method.
A series of new flame retardants (FR) based on dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) incorporating acrylates and benzoquinone were developed previously. In this study, we examine the fire behavior of the new flame retardants in polyisocyanurate (PIR) foams. The foam characteristics, thermal decomposition, and fire behavior are investigated. The fire properties of the foams containing BPPO-based derivatives were found to depend on the chemical structure of the substituents. We also compare our results to state-of-the-art non-halogenated FR such as triphenylphosphate and chemically similar phosphinate, i.e. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO), based derivatives to discuss the role of the phosphorus oxidation state.
This paper is based mainly on the results of two different projects performed in the group of the author recently (2016-2019). The three external partners involved in these two projects are competent in the preparation of FPUF (ICL IP America), RPUF (Department of Industrial Engineering, Padova University), and TPU (Fraunhofer-Institut für Betriebsfestigkeit und Systemzuverlässigkeit LBF, Darmstadt) as well as for the specimen preparation. Systematically varied sets of materials were prepared as the key basic for scientific discussion, varying the kind and combination of flame retardant, PUR structure, density, and blowing agent.
A multimethodical approach based on thermogravimetry (TGA), TGA coupled with evolved gas analysis (TGA-FTIR) and pyrolysis GC-MS was used for investigating the pyrolysis. The flammability was addressed using oxygen index (OI) and testing in UL 94 burning chamber in vertical and horizontal set-up. The fire behaviour was addressed by using a cone calorimeter. Beyond these methods according to the state of the art, key experiments were performed. We addressed the dripping and the two-stage burning of TPU using a self-designed apparatus and specific data evaluation, the foam burning through quenching burning samples, using different special sample holders, and measuring temperature profiles within the burning foams. The investigation is made round by intensive analysis of the fire residues, such as comprehensive investigation of the morphology.
Result on the pyrolysis (TGA-FTIR, Pyrolysis-GC/MS), flammability (UL 94, LOI), and fire behaviour (cone calorimeter) of TPU and flame retardant TPUs are shown. We discuss in detail the characteristic of PUR decomposition: the low tendency to char, and the specific two step decomposition and how these characteristics control the regimes in fire behaviour. We demonstrate that the different burning regimes are controlled by different pyrolysis products and effective heat of combustions. The resulting formation of pool fires as well as the formation of dripping is discussed in detail. The latter quite important to understand the flame retardancy applied with respect to achieve the UL 94 classification V0 nondripping or V0 non-flaming dripping.
Rigid and flexible PUR foams and their flame retarded versions are investigated for different densities. Water and pentane-blown foams are compared as well as PUR and polyisocyanurate-polyurethane (PIR) foams. Horizontal testing in the cone calorimeter is used and the vertical foam specimen holder as well. Self-designed set-ups within the cone calorimeter enable a better inside in the pyrolysis front running through the foam samples as well as the development of the temperature gradient inside the foam during the fire test. The morphology change during burning was characterised by the means of quenching burning foams with liquid nitrogen and investigating the cross sections with scanning electron microscope. In sum, a rather comprehensive study was performed to work out the principle fire phenomena controlling the fire behaviour of PUR foams in a very systematic and significant way.
Promising flame retardancy approaches are discussed. The importance of either combining the drain of fuel and flame inhibition or charring into an effective protection layer/multicellular structure is underlined.
This contribution focusses the general conclusions and trends. It tries to increase the understanding of the specific and demanding challenge to develop flame retardant PUR materials.
Our approach includes the preparation of blends of preferably liquid-crystalline polyesters with Lignin, but also the synthesis of new polyesters with Lignin-related monomer units.
While most studies employ pulped Lignin directly, we first purified the Kraft Lignin by fractionation, followed by chemical modification of the terminal OH groups. Acetylation results in the reduction of glass transition temperatures (Tg) below 200°C, improved processability in the melt with complete melting of the Lignin sample, and higher thermostability.
These Lignin fractions were melt-mixed in a mini-twin-screw extruder with polyesters. The chemical structure of the polyesters was systematically varied between poly(ethylene terephthalate), (PET); poly(ethylene terephthalate-co-oxybenzoate), (PET/HBA); liquid crystalline polyesters with fully aromatic structure; and polyesters with Lignin-related monomers like ferulic and vanillic acid). The polymer influence on the blending behavior with Lignin was examined. SEM revealed phase-separated blends with partial compatibilization of the phases indicated by the shift of Tg’s. The influence of the polyester and the Lignin on decomposition and combustion was accessed by thermogravimetry (TGA), TGA-FTIR and pyrolysis-combustion flow calorimetry (PCFC) and compared to the decomposition of polyesters. The main focus was to achieve melt-spinnable blends for fibres with improved flame retardancy or as precursors for carbon fibers. Blends of Lignin fractions with the aromatic-aliphatic polyesters (here preferably PET/HBA) were successfully spun into fibers with lab-scale melt-spinning equipment. X-ray measurements revealed orientation of the fibers with Lignin. The E-moduli raised with increasing purity of the Lignin fractions (e.g., by removal of reducing sugars).
The structure of the polymer matrix determines the decomposition and combustion behavior of the blends with Lignin. Incorporation of aliphatic subunits reduces the amount of remaining char formed in TGA and PCFC from about 40-45 wt% for fully aromatic polyesters to 18-25 wt% for semiaromatic polyesters (at almost comparable carbon content in the polymer), while the maximum temperature of combustion decreased from 480-530°C for the former to 410-465°C for the latter. Lignin fractionation and acetylation yields samples with high char content (36 wt%) and extremely low heat release capacity (80-90 kJ/gK) with combustion maximum temperature at 405°C. Lignin/ PET/HBA blends combine the low HRC with intermediate char and offer interesting opportunities for polyester fibers with improved flame retardancy without adding P-containing FRs.
The flame retardancy behavior was explored by limiting oxygen index measurements on injection-molded parts and fibers.
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.
As a potential substitute for currently used halogenated flame retardants we explored the synthesis of dibenzo[d,f][1,3,2]dioxaphosphepine 6-oxide (BPPO) and derivatives. BPPO is a cyclic phosphonate and was synthesized by a simple, three-component condensation using 2,2´-biphenol, phosphorus trichloride and water by improving a procedure given by Natchev. Subsequently, BPPO was employed in phospha-Michael additions in line with the known synthesis of DOPO-compounds to double bonds. These reactions result in novel phosphorus-containing compounds with flame retardant activíty. The chemical structure of the unsaturated compounds was systematically varied yielding non-reactive flame retardants (without functional groups) from acrylates and diesters, and reactive (with functional groups) flame retardants from p-benzoquinone. The use of the phosphonate BPPO and its derivatives as flame retarding additives has not been described yet. The BPPO ring is highly reactive. Therefore, it is supposed that it mainly acts in the gas phase.
The new phosphonates were applied as additives for improving the flame retardancy of rigid PUR/PIR foams with triethyl phosphate (TEP) as plasticizer. The foam characteristics like density, cell integrity, pore size and mechanical properties were investigated. The burning properties of the foams were analyzed in the vertical flame spread according to DIN 4102 and by cone calorimetry. The relevant parameters depended on the phosphorus content, which is illustrated for PIR foams with ethyl 3-(6-oxidodibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)propanoate (X, Z = H; Y = OEt; EA-BPPO) as FR additive.
At comparable P-content, the EA-BPPO additive reached the PHHR-values of the benchmark foam with TEP and triphenyl phosphate as FR additive. With increased P-content the values were further reduced. TML and MARHE parameters showed a similar tendency. The FR additives dispersed well in the formulation and had no significant influence on foam density, cell integrity and pore size compared to the reference sample.
Nowadays, various polymeric materials are used in E&E applications with sufficient flame retardance by adding rather different flame retardants. It doesn’t matter whether cables are used outdoor or are installed indoor as building products, the weathering exposures such as UV radiation, humidity and variation in temperature occur and influence the flame-retardant property. Recently, the lifetime of the flame retardance itself becomes an increasingly important factor. In this work, several devices were used to perform accelerated artificial ageing simulating different environment exposures.
The comprehensive and global understanding of the durability of flame retardance in dependence on the weathering or ageing conditions is still a matter of discussion. Therefore, the weathering resistance of various halogen-free fire-retarded polymers was investigated in this work. Polymeric systems with different kinds of fire retardants were chosen, including various fire retardant mechanisms. Ethylene Vinyl Acetate (EVA) blends with high amounts of inorganic flame retardant such as aluminum hydroxide (ATH), boehmite and synergists, which mainly dilutes the polymer resin work as heat sink and cooling agent, and enhance residue formation was examined. Thermoplastic Polyurethane (TPU) was modified with melamine cyanurate (MC), which mainly acts by changed melt flow and dripping behavior as well as fuel dilution. Additionally, aluminum diethylphosphinate and boehmite are induced as assistant flame retardant. Furthermore, glass fiber reinforced Polyamide 66 (PA) was investigated containing different kinds of aluminum diethylphosphinate based flame retardant mixtures, which acts by flame inhibition and additional char formation.
The degradation of the surface was analyzed after the different weathering conditions. Most of the specimens exhibited an intensive material degradation at the top surface accompanied by a distinct discoloration, e.g. getting darker or showing yellowing. The weathering of the EVA samples lead to numerous cracks (already) after 4000 h. The corresponding changes in the chemical structure was investigated by ATR FT-IR for all materials.
The flammability was investigated by cone calorimeter, UL-94 burning chamber, and oxygen index (LOI) using plate and bar specimens. The flame retardance of most of the materials studied degrades only slightly or were rather stable for the investigated exposure times. Interestingly, also some opposite results were found. EVA modified by different inorganic flame retardants such as ATH achieved higher LOI after exposing in the humidity chamber and the accelerated oxidation under water in the autoclaves. It is suggested that the particle size of ATH and boehmite plays an important role, when these flame retardants agglomerate at the surface during accelerated weathering.
Both materials, EVA and TPU, were also investigated as cable jackets. While EVA modified with inorganic flame retardants exhibits low-smoke and non-dripping fire behavior, TPU flame-retarded with MC yields cables with pronounced melt-dripping. Cone calorimeter tests were carried out using cable rafts of the size of 100 mm * 100 mm as well as our self-made cable module test, which simulates the vertical full-scale test of a bundle of cables at the bench-scale. Both methods were used to investigate the weathering resistance of the flame retardance in cables. The results of the cable module test for the flame-retarded EVA cables were only slightly affected even when a long time hydrothermal ageing was carried out. This is because of inorganic residue which just delays the fire growth but does not extinguish. However, for the flame-retarded TPU cable jackets, the cable module test exhibited an accelerated fire spread and a melt-dripping behavior which was promoted by weathering exposure.