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Eingeladener Vortrag
- nein (42)
In this paper, we demonstrate the effects of radiation exposures of polymeric materials with UV-A 340 nm lamps (ISO 4892-3, Type 1A) at -10 °C in comparison to an irradiation at +50 °C using a Global UV Test 200 fluorescent lamp device from Weiss Umwelttechnik GmbH, which incorporates an active cooling appliance. While the effects at -10 °C actually are lower than at + 50°C their extent was clearly beyond expectations.
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.
Aufgrund des tieferen Eindringens der solaren Strahlung treten bei transparenten und bei transluzenten (durchscheinenden) Kunststoffen veränderte Bedingungen gegenüber opaken Proben auf. Dies kann zu speziellen Effekten und damit zu einem abweichenden Bewitterungsverhalten führen. Auch aus Mangel an geeigneten Normen werden diese Effekte häufig vernachlässigt. Deshalb initiiert der DIN-FNK auf ISO-Ebene ein entsprechendes Dokument.
Die Norm ist in der Form eines Technical Reports geplant. In einem ersten Teil sollen die Besonderheiten transparenter oder transluzenter Kunststoffe erläutert werden, um den Nutzer für mögliche Probleme zu sensibilisieren. Im zweiten Teil werden Empfehlungen für Bestrahlung oder Bewitterung herausgearbeitet. In einem dritten Teil geht es dann um Besonderheiten bei der Messung von Eigenschaftsänderungen transparenter bzw. transluzenter Kunststoffe. In informativen Anhängen sollen verschiedene Beispiele die Thematik illustrieren.
The site of Schöningen (Germany), dated to ca. 300,000 years ago, yielded the earliest large-scale record of humanly-made wooden tools. These include wooden spears and shorter double-pointed sticks, discovered in association with herbivores that were hunted and butchered along a lakeshore. Wooden tools have not been systematically analysed to the same standard as other Palaeolithic technologies, such as lithic or bone tools. Our multianalytical study includes micro-CT scanning, 3-dimensional microscopy, and Fourier transform infrared spectroscopy, supporting a systematic technological and taphonomic analysis, thus setting a new standard for wooden tool analysis. In illustrating the biography of one of Schöningen’s double-pointed sticks, we demonstrate new human behaviours for this time period, including sophisticated woodworking techniques. The hominins selected a spruce branch which they then debarked and shaped into an aerodynamic and ergonomic tool. They likely seasoned the wood to avoid cracking and warping. After a long period of use, it was probably lost while hunting, and was then rapidly buried in mud. Taphonomic alterations include damage from trampling, fungal attack, root damage and compression. Through our detailed analysis we show that Middle Pleistocene humans had a rich awareness of raw material properties, and possessed sophisticated woodworking skills. Alongside new detailed morphometrics of the object, an ethnographic review supports a primary function as a throwing stick for hunting, indicating potential hunting strategies and social contexts including for communal hunts involving children. The Schöningen throwing sticks may have been used to strategically disadvantage larger ungulates, potentially from distances of up to 30 metres. They also demonstrate that the hominins were technologically capable of capturing smaller fast prey and avian fauna, a behaviour evidenced at contemporaneous Middle Pleistocene archaeological sites.
Die Umweltwirkungen auf ein Material werden als Überlapp der Funktionskurven von Materialempfindlichkeit und einwirkenden Umweltparametern betrachtet. Wenn entweder die Empfindlichkeit oder die Beanspruchungen Null sind, ergibt sich auch keine Umweltwirkung und bei beidseitig Werten größer Null das jeweilige Produkt der beiden. Die Akkumulation der nicht-reversiblen Effekte über die Zeit und allen Eigenschaftsänderungen entspricht der Alterung des Materials für den jeweiligen Expositionszeitraum.
Die digitale Umweltsimulation gliedert sich hier in drei Teilaspekte. Ein erster, rein materialwissenschaftlicher Teil hat die Aufgabe, alle relevanten Materialempfindlichkeiten experimentell zu quantifizieren. Ein zweiter – unter Umständen numerischer Teil – hat die Aufgabe, das Bauteil und seine Einbaulage zu digitalisieren und aus den makroskopischen Umgebungsbedingungen die relevanten mikroklimatischen Umweltparameter für alle Oberflächen- oder Volumenelemente zu bestimmen. In einem dritten Teil werden die Einwirkungen über den betrachteten Zeitraum berechnet und kumuliert. Dieses Konzept, das auf den so genannten Expositions-Reaktions-Funktionen (ERF) basiert, wird an Beispielen der Photoxidation erläutert. Dieses Vorgehen wurde schon beim ViPQuali-Projekt als Numerische Umweltsimulation umgesetzt.
Überprüft werden muss das Modell unbedingt an einer realitätsnahen Validierungsbeanspruchung. Hier werden die ermittelten ERFs mit über den kompletten Beanspruchungszeitraum geloggten Umweltparametern gekoppelt, um die berechnete mit der experimentell erfahrenen Alterungswirkung zu vergleichen. Nur so kann sichergestellt sein, dass alle für die Anwendungsumgebung relevanten Materialempfindlichkeiten einbezogen wurden.
Unpigmented HDPE jerrycans filled with nitric acid (55%) and water respectively had been exposed to outdoor conditions for one Berlin summer season. As both liquids underwent equal temperature progression, exposure effects of UV radiation and nitric acid as well as of their combination can be separated and compared. On the basis of various property changes after these exposures, synergistic action is evaluated and compared to a damaged Intermediate Bulk Container (IBC) from a transport accident.
It is found that carbonyl formation goes along with lightness increase in color measurement due to microcracking and with a worsening in mechanical behavior, all of them showing synergistic effects of UV and nitric acid exposure. In contrast, embedding nitrogen compounds goes along with yellowing of the material but cannot be correlated to oxidation.
The reason for intensified damaging is the decomposition of the 55-percent nitric acid and formation of nitrogen oxides even at ambient temperatures, caused by UV radiation. Thus, damaging effects become similar to those caused by fuming nitric acid exposure at temperatures above 60 °C, with the result of strong oxidative degradation of the polyethylene.
In contrast, exclusive exposure to the 55-percent nitric acid at 40 °C does not cause any failure.
It can therefore be assumed that also the damaged IBC had been exposed to both UV radiation and nitric acid, probably outdoors.
Size-exclusion chromatography (SEC) was used to monitor changes of the molecular masses of thermoplastic polyether – and polyester urethane (TPU) exposed to thermal, hydrolytic, and photo-oxidative (UV) Degradation conditions for several days. The thermal treatment was performed at elevated temperatures (100–200 °C) under oxidative (air) as well as non-oxidative (nitrogen) conditions to evaluate the specific influence of oxygen on the degradation. At higher temperatures (≥175 °C) a fast decrease of the molecular masses of both PU accompanied by a high degree of crosslinking was found. At lower temperatures (≤150 °C) the polymers remained widely unaffected by thermal degradation within the investigated degradation interval of up to two weeks. Surprisingly, the influence of oxygen (air) was found to be less distinct. In contrast to that, UV treatment at 25 °C at less than 10% rel. humidity (RH) resulted in a fast crosslinking, whereas the molecular masses of both PU decreased slower than for thermal treatments. The depth of penetration of the UV radiation was estimated using 3D printed PU samples with different thicknesses. Hydrolysis based degradation effects were less significant. Only slight molecular mass changes were detected at temperatures ≤80 °C within a time span of 14 days, while no crosslinking could be measured. Considering the degradation results at the investigated exposure parameters, it could be shown that esterbased PU in general exhibits a significant higher stability compared to ether-based materials.
Investigation on the Durability of a Polypropylene Geotextile under Artificial Aging Scenarios
(2024)
Geosynthetics are widely used in various civil engineering applications, such as geotextiles in coastal protection, and display a sustainable alternative to natural mineral materials. However, the full benefits of using geosynthetics can only be gained with a long service lifetime of the products. With the use of added stabilizers to the polymers, service lifetimes can be achieved in the range of 100 years. Therefore, accelerated aging methods are needed for the assessment of the long-term performance of geotextiles. In the present study, the behavior of geosynthetic materials made of polypropylene was investigated under artificial aging conditions involving elevated temperatures ranging from 30 to 80 °C, increased oxygen pressures ranging from 10 to 50 bar in water-filled autoclaves, and UV irradiation under atmospheric conditions. ATR-IR spectroscopy was employed to detect the increase in the carbonyl index over various aging durations, indicating the oxidative degradation of the geotextile. The most pronounced increase was observed in the case of aging through UV irradiation, followed by thermal aging. Elevated pressure, on the other hand, had a lower impact on oxidation. High-temperature size exclusion chromatography was utilized to follow the reduction in molar mass under different degradation conditions, and the results were consistent with those obtained from ATR-IR spectroscopy. In polyolefins such as polypropylene, Hindered Amine Stabilizers (HAS) are used to suppress oxidation caused by UV radiation. The quantitative analysis of HAS was carried out using a UV/Vis method and HPLC. The degradation of UV stabilizers during the aging of geotextiles is responsible for the oxidation and the reduction in the molar mass of polypropylene. From the results, it can be concluded that applications of PP geotextile without soil or sand cover might cause the risk of the formation of microplastic particles. Material selection, design, and maintenance of the construction must follow best practices, including the system’s removal or replacement at end-of-life. Otherwise, a sustainable use of geotextiles in civil engineering is not possible.
The durability of flame retardancy is a challenge for cables over long lifetimes. The degradation of flame retardance is investigated in two kinds of exposures, artificial weathering and humidity. In this basic study, typical mineral flame retardants in two polymers frequently used in cable jackets are investigated to get the fundamental picture. Aluminum hydroxide (ATH) and magnesium hydroxide (MDH) are compared in ethylene‐vinyl acetate (EVA), and further in EVA and linear low‐density polyethylene (LLDPE) cables containing the same ATH. The changes in chemical structure at the surface are studied through attenuated total reflectance Fourier transform infrared spectroscopy (ATR‐FTIR), the formation of cracks, and changes in color are investigated. The cone calorimeter and a bench scale fire testing cable module are utilized to evaluate the fire behavior of the cables. Although the flame retardancy deteriorated slightly, it survived harsh exposure conditions for 2000 h. Compared to EVA/MDH and LLDPE/ATH, the fire behavior of EVA/ATH is the least sensitive. Taken together, all of the results converge to estimate that there will be no problem with flame retardancy performance, for materials subjected to natural exposure for several years; the durability of fire retardancy is questionable for longer periods, and thus requires further investigation.
Influence of Weathering on the Stability of Flame Retardancy in Polymeric Materials for Outdoor Use
(2009)
Influence of weathering on the stability of flame retardancy in polymeric materials for outdoor use
(2009)
We report the selective ring opening copolymerisation (ROCOP) of
oxetane and phthalic thioanhydride by a heterobimetallic Cr(III)K
catalyst precisely yielding semi-crystalline alternating poly(esteralt-
thioesters) which show improved degradability due to the
thioester links in the polymer backbone.
Multilayer Graphene (MLG), a nanoparticle with a specific surface of BET = 250 m²/g and thus made of only approximately 10 graphene sheets, is proposed as a nanofiller for rubbers. When homogenously dispersed, it works at low loadings enabling the replacement of carbon black (CB), increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and mechanical properties of different rubbers, as shown for Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR), and Styrene-Butadiene Rubber (SBR). A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The later shown by the reduction in heat release rate in the cone calorimeter. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as a multifunctional nanofiller and seems to be quite ready for rubber development.
The influence of weathering on the fire retardancy of polymers is investigated by means of a cone calorimeter test, before and after artificial weathering. The surface degradation was monitored using different techniques (ATR–FTIR, microscopy, colour measurement). Different kinds of polymeric materials were chosen, all as they are used in practice: polycarbonate (PC) blends, polyamide (PA) and polypropylene (PP) flame-retarded with arylphosphate, melamine cyanurate (MC) and intumescent formulation based on ammonium polyphosphate (APP), respectively.
All samples show material degradation at the surface due to weathering. No significant weathering influence occurs on the flame retardancy when it is a bulk property, as was observed for aryl phosphates in PC blends and MC in PA. When the fire retardancy is dominated by a surface mechanism, dependence on the duration of weathering is detected: for intumescent formulations based on ammonium APP in PP, a worsening in the formation of the intumescent network was observed.
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.
The thermo-oxidative degradation of a polymeric optical cable is investigated by chemiluminescence, The results are reliable and reproducible. Two distinct processes are reported marked by a peak and a plateau behavior versus the time, respectively. Both processes are ruled by thermally activated processes. Beside the dependencies of temperature and time, the influence of absorbed water is discussed. Chemiluminescence is proposed as a promising candidate for a suitable testing method assessing the thermo-oxidative stability of plastic optical fibers and cables. it requires not more than a simple one-day testing procedure and has the advantage that it can be carried out even within the lo cv temperature ranges of the cables' intended use.
Polarized fluorescence and orientational order parameters of a liquid-crystalline conjugated polymer
(1999)
We report a study of the orientational order of aligned thin films of the liquid crystalline conjugated polymer poly(9,9-dioctylfluorene). Steady state polarized fluorescence measurements were used to determine the orientational order parameter <P2> and <P4>. The influence of intermolecular and intramolecular excitation energy transfer on the degree of polarization is discussed. The role of film morphology is also examined by comparison of the results for glassy and crystalline films.
A liquid crystalline mainchain conjugated polymer for polarized electroluminescence applications
(1997)
Polarized fluorescence and orientational order parameters of a liquid crystalline conjugated polymer
(1999)
The excitation energy transfer (EET) of a bichromophoric cross-shaped molecule was investigated by stationary polarized fluorescence spectroscopy in the solid state. For this purpose 2,2[prime],7,7[prime]-tetrakis(biphenyl-4-yl)-9,9[prime]-spirobifluorene was embedded in a polymeric bisphenol-A-polycarbonate (PC) matrix. The dependence of the fluorescence on concentration and wavelength was determined. The role of the intermolecular and intramolecular EET is dealt with separately and discussed by means of the degree of polarization. The intermolecular excitation energy transfer is described in terms of a Förster transfer mechanism. The intramolecular transfer is prevented for the zero-point vibrational levels by the molecular cross-shaped structure, but is found for a wide range of wavelength, presumably based on vibrationally excited states.
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
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.
Recycled plastic granules of high-density polyethylene, polyvinyl chloride and polystyrene the size of microplastics were exposed to artificial aging conditions (2000 h; photooxidative and thermo-oxidative) to simulate their fate outdoors. Their potential to leach into water during the aging process was investigated using column percolation tests.
Aging-related changes on the surface of the material were characterised by IR measurements indicating oxidation reactions with the formation of new adsorption bands (C=O, C–O and OH), especially in the case of photooxidative aging.
These findings were confirmed by the identification of leachable organic compounds. Leaching of total organic carbon, Cl, Ca, Cu and Zn is clearly affected by changes due to aging, and their release is increased after photooxidative aging.
In general, exposure to photooxidative conditions shows a greater influence on aging and thus on leaching and seems to be the more important mechanism for the aging of microplastic in the environment. Comparison with the total content of inorganic species revealed that, for most elements, less than 3% of the total content is released after 2000 h of photooxidative aging.
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.
A phosphaphenanthrene and triazinetrione group containing flame retardant (TAD) is combined with organically modified montmorillonite (OMMT) in epoxy resin thermosets (EP) to improve the performance of the flame-retardant system. When only 1 wt% OMMT/4 wt% TAD is introduced into the EP, the limited oxygen index (LOI) rises from 26% to 36.9% and a V-0 rating is achieved in a UL 94 test. The decomposition and pyrolysis products in the gas phase and condensed phase were characterized using thermogravimetry-Fourier transform infrared spectroscopy (TG-FTIR). The influence on the decomposition of EP, such as the increase in char yield, is limited with the incorporation of OMMT; a large amount of the phosphorus is released into the gas phase. The flame-retardant effect evaluation based on cone calorimeter data testified that OMMT improves the protective-barrier effect of the fire residue of OMMT/TAD/EP on the macroscopic scale, while TAD mainly causes flame inhibition. The fire residues showed a corresponding macroscopic appearance (digital photo) and microstructure (scanning electron microscope [SEM] results). The protective barrier effect of OMMT and the flame-inhibition effect of TAD combined to exert a superior flame-retardant effect, resulting in sufficient flame-retardant performance of OMMT/TAD/EP
High loadings of carbon black (CB) are usually used to achieve the properties demanded of rubber compounds. In recent years, distinct nanoparticles have been investigated to replace CB in whole or in part, in order to reduce the necessary filler content or to improve performance. Multilayer graphene (MLG) is a nanoparticle made of just 10 graphene sheets and has recently become commercially available for mass-product nanocomposites. Three phr (part for hundred rubbers) of MLG are added to chlorine isobutyl isoprene rubber (CIIR)/CB composites in order to replace part of the CB. The incorporation of just 3 phr MLG triples the Young’s modulus of CIIR; the same effect is obtained with 20 phr CB. The simultaneous presence of three MLG and CB also delivers remarkable properties, e.g. adding three MLG and 20 phr CB increased the hardness as much as adding 40 phr CB. A comprehensive study is presented, showing the influence on a variety of mechanical properties. The potential of the MLG/CB combination is illustrated to reduce the filler content or to boost performance, respectively. Apart from the remarkable mechanical properties, the CIIR/CB/MLG nanocomposites showed an increase in weathering resistance.
Elastomers are usually reinforced and employed in different applications. Various different nanoparticles, including layered silicates, carbon nanotubes, and expanded graphite, are currently being used as nanofiller. Multilayer Graphene (MLG) is proposed as promising nanofiller to improve the functional properties of Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR) and Styrene–Butadiene Rubber (SBR) at low concentrations. MLG is constituted by only approximately 10 graphene sheets. Nanocomposites with extremely low MLG content (3 phr) showed evident improvement in rheological, mechanical and curing properties. The Young's modulus of the nanocomposites increased more than twice in comparison with the unfilled rubbers. MLG also improved the weathering resistance of the different rubbers. The nanocomposites conserved their initial mechanical properties against weathering exposure.
A siloxane compound (MVC) and a bi-group phosphaphenanthrene/triazine compound (TGD) were employed in epoxy thermosets to explore high-efficiency flame retardant systems. With only 1wt% MVC and 3wt% TGD, an epoxy thermoset passed UL 94 V-0 rating test and achieved a limiting oxygen index value of 34.0%, exhibiting an excellent flame retardant effect. The MVC/TGD system not only decreased the peak value of heat release rate and effective heat of combustion but also imparted an improved charring ability to thermosets, thereby outstandingly reducing the flammability of 1%MVC/3%TGD/EP. Compared with the fire performance of 4%TGD/EP and 4%MVC/EP, the MVC/TGD system showed an obvious flame retardant synergistic effect, mainly depending on the general improvement of flame inhibition, charring and barrier effects of the thermoset during combustion. Evolved gas analysis combinedwith condensed-phase pyrolysis product Analysis jointly revealed the details of the changed pyrolysis mode.
Scientific publications addressing the durability of the flame retardance of cables during their long-term application are rare and our understanding lacks. Three commercial flame retardants, aluminum hydroxide, aluminum diethyl phosphinate (AlPi-Et), and intumescent flame retardant based on ammonium polyphosphate, applied in ethylene-vinyl acetate copolymer (EVA) model cables, are investigated. Different artificial aging scenarios were applied: accelerated weathering (UV-irradiation/temperature/rain phases), humidity exposure (elevated temperature/humidity), and salt spray exposure. The deterioration of cables’ surface and flame retardancy were monitored through imaging, color measurements, attenuated total reflectance Fourier transform infrared spectroscopy, and cone calorimeter investigations. Significant degradation of the materials’ surface occurred. The flame retardant EVA cables are most sensitive to humidity exposure; the cable with AlPi-Et is the most sensitive to the artificial aging scenarios. Nevertheless, substantial flame retardance persisted after being subjected for 2000 h, which indicates that the equivalent influence of natural exposure is limited for several years, but less so for long-term use.
A systematic approach was used to investigate the weathering-induced degradation of a common water–based intumescent coating. In this study, the coatings are intended for humid indoor applications on steel substrates. The coating contains ammonium polyphosphate, pentaerythritol, melamine, and polyvinyl acetate. By replacing each ingredient with a less water-soluble substance, the most vulnerable substances, polyvinyl acetate and pentaerythritol, were identified. Furthermore, the weathering resistance of the system was improved by exchanging the ingredients. The coatings were stressed by artificial weathering tests and evaluated by fire tests. Thermogravimetry and Fourier-transform infrared spectroscopy were used to study the thermal decomposition. This study lays the foundation for the development of a new generation of water-based intumescent coatings.
Die komplexe Wirkung von Schimmelpilz und Klima auf Polymeroberflächen und ihre Simulation im Labor
(2004)
Multilayer graphene/chlorine-isobutene-isoprene rubber nanocomposites: the effect of dispersion
(2016)
Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The Dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine-isobutene- isoprene rubber (CIIR) on a two-roll mill did not result in substantial enhancement of the material properties. In contrast, by pre-mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two-roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young’s moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure.
As the results of a 14 weeks outdoor exposure of a series of automotive coatings in South Florida, the panels were found to be overgrown with an almost closed layer of mildew. Pinholes remained as permanent surface damage after removing the mildew mycelium. The extent of the damage differed in dependence of the kind of the coating. By tracing the images and profiles of the coating surfaces systematically over all phases of weathering and the subsequent cleaning procedure, a connection between formation of pinholes and mildew growth could be found. Outdoor weathering tests in other regions of Florida as well as in Europe and Australia showed that pinholes caused by mildew attack could also be found in all other locations, but always to a lower extent than in South Florida. The standardised mildew tests EN ISO 846 and MIL-STD 810F for laboratory exposure failed to reproduce the formation of pinholes.