7.5 Technische Eigenschaften von Polymerwerkstoffen
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Eingeladener Vortrag
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This Special Issue of Fire and Materials brings together a Collection of papers that were presented at the 2016 Interflam conference in the Fire & Facades session along with recent submissions to the Fire and Materials Journal that are very relevant to the Fire and Facades subject. Having attended the Interflam conference, all Fire and Materials Journal editors who attended realised the importance of this topic. We felt it important that this session content would both be reviewed and made available to a wider audience and that it was timely that we featured this increasing important topic in our journal. Accordingly, authors of selected papers were invited to update and extend their papers for journal submission, and other appropriate peer review papers subsequently submitted to the journal were included in the collection.
High-throughput fire tests and weathering-induced degradation behaviour of intumescent coatings
(2018)
In this work, the weathering-induced degradation of intumescent coatings was investigated by a systematic and comprehensive approach. A mechanism is revealed that is proposed to be responsible for the loss of function of intumescent coatings induced by weathering.
First, the thermal decomposition of artificially weathered intumescent coatings was examined. To get a better understanding of the weathering and ageing phenomena, the degradation behaviour of the single ingredients during the weathering process was investigated, as well as their chemical and physical interactions. For the systematic approach, the materials that are essential for intumescence (ammonium polyphosphate, pentaerythritol, titanium dioxide, melamine and the binder) are treated with moisture, elevated temperature and UV radiation.
Thermogravimetry (TG) and IR spectroscopy were used to compare the initial samples with their different grades of weathering. We demonstrate that ammonium polyphosphate, melamine and the binder are mainly responsible for the ageing process. Further, it was demonstrated that TG and IR spectroscopy are suitable measuring methods to detect the effects of weathering on intumescent coatings.
Finally, a small-scale fire test procedure is introduced. Based on the reduction of the sample size, up to 50 samples can be tested in a single fire test. The results of this fire test have the same quality as the results from standard intermediate fire tests corresponding to DIN 4102-8.
Der Beitrag versucht sich an der Herausforderung, trotz beschränktem zeitlichen Rahmen einen ansprechenden Spagat zwischen umfangreichem Überblick und wissenschaftlichem Verständnis und so eine unabhängige und unparteiliche Einführung in Thematik flammgeschützte PUR-Schäume zu geben. Er kann sicherlich nicht individuelle Antworten oder konkrete Entwicklungsziele wie neue Rezepturvorschläge liefern, aber hofft zum Hintergrund und als Handwerkzeugs für das Aufstellen und Überdenken von Entwicklungsstrategien beizutragen.
Evaluation of evacuation process is common separated by two phases: pre-movement and movement-phase. Individual capabilities of pedestrians have an impact on both and therefore on the time required for safe escape. In view of evaluating the evacuation process, characteristics of realistic movements of pedestrians involved are needed, but so far such data are mainly available for individuals with unrestricted evacuation capabilities only.
Due to the lack of available data, parameter studies in an assisted living for people with disabilities were performed to explore the movement during evacuation. Preparation times for assistance (n = 10), unimpeded walking speeds (n = 34) depending on the assistance devices in the plane as well as walking speeds on stairs (n = 11) were focussed.
Time to prepare an assistance device for utilisation depends significantly on the kind of device type. Further on, practical experience in handling the devices for assistance has an impact on the preparation time. In contrast to the results of the preparation times, any relation on assistance devices were investigated for the unimpeded walking speed in the plane. A remarkable decrease of walking speed on stairs was observed which is independent from the utilised assistance device.
The presented data improve and extend the insufficient engineering data base and raised up questions regarding the complexity of considering pedestrians movement with impairments in evacuation planning.
Recent bus fires in Europe, such as the bus fire in France 2015 with 43 fatalities and the bus fire in Germany 2017 with 19 fatalities, show that these fires can be very hazardous and time for escape can be too short. Recently, several fire safety measures came into force for busses. Engine compartment suppression systems will be mandatory for all busses in Europe. This is a big step in fire safety as about 80 % of fires start in the engine compartment. However, in several recent bus fires a time of less than 5 minutes has been reported from detection of the fire to a fully developed fire. As normally many people are on board of a bus, a bus fire is not comparable to fire in a home. Especially for people with reduced mobility or for fires after a collision the available times for escape are too short. When the fire service is on scene the transition to a fully developed fire might have happened already. Passengers who are not able to escape in this short period of time mostly cannot be rescued by the fire service even with quick response times because of the dramatic fire development. Fires that do not start in the engine compartment but develop in the cabin are rarer but extremely dangerous because fire and smoke spread very rapidly. The reason for the fast fire and smoke development in the cabin are the materials which are used. Over the last tens of years materials in busses had major developments. The amount of plastic in the cabin has grown significantly. In a modern coach the biggest fire load often is not the fuel anymore but the interior materials.
Bus fire safety is mainly regulated by ECE regulations R 118 and R 107. A comparison with European standards for trains shows that for trains, in contrast to busses, a holistic fire concept exists. Fire scenarios as well as escape scenarios and passenger behaviour are taken into account, resulting in fire safety regulations on a high level compared with bus regulations. In contrast to regulations for train materials no limits for heat or smoke production are given for bus materials. Larger heat release values promote more rapid fire spread. Also smoke production and toxicity are key factors in fires. The smoke reduces the visibility in the case of fire, and together with the toxicity of the smoke can make escape from the vehicle impossible. Figure 1 shows the remains of the bus from the recent severe bus fire in Germany in 2017.
As a result of experience with real cases and results from research projects we think it is necessary to develop a holistic fire safety concept for busses as it exists for other transport means like railways. The fire safety concept should include vehicle configuration and design as well as areas of use, e.g. use in cities, use in long-distance traffic on motorways and use in tunnels.
Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentaneand water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate Polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m3. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent.
Es wird ein Verfahren zur Charakterisierung der Beständigkeit und
Langzeitstabilität von additiv gefertigten Kunststoff-Bauteilen vorgestellt. Dabei sollen die Prüfkörper über 2000 Stunden künstlich bewittert und währenddessen die Änderungen der Eigenschaften der Bauteile zerstörungsfrei untersucht werden.
Häufig ist es wünschenswert, für neue Materialien oder Anwendungen künstliche Bewitterungsverfahren zu benutzen, die auf die spezifischen Anforderungen besser zugeschnitten sind, als es bei bestehenden standardisierten Verfahren der Fall ist. Nachdem man die spezifischen Parameter der Beanspruchung unter Anwendungsbedingungen und die spezifische Empfindlichkeit des Materials erfasst hat, beginnt ein Prozess, der als „Test Tailoring“ häufig abstrakt verwendet, auf den aber nur selten näher eingegangen wird. Genau dieser Prozess soll hier am Beispiel der Entwicklung eines künstlichen Bewitterungstests unter saurer Beaufschlagung, dem in der BAM entwickelten Acid Dew and Fog Test, beispielhaft erläutert werden.
Benefits of hyperbranched structure:
Molecular weight, miscibility, number of FR groups, end-group functionalization, glass transition temperature, decreased PBT.
Examples of hyperbranched FRs:
Charring agent, silicone, triazine, etc.
Systematic study of effect of chemical surrounding and impact of Complex shape of phosphorus-based hyperbranched polymers on flame retardant efficacy in epoxy resins.
Evaluation of evacuation process is common separated by two phases: pre-movement and movement-phase. Individual capabilities of pedestrians have an impact on both and therefore on the time required for safe escape. In view of evaluating the evacuation process, characteristics of realistic movements of pedestrians involved are needed, but so far such data are mainly available for individuals with unrestricted evacuation capabilities only.
Due to the lack of available data, parameter studies in an assisted living for people with disabilities were performed to explore the movement during evacuation. Preparation times for assistance (n=10), unimpeded walking speeds (n=34) depending on the assistance devices in the plane as well as walking speeds on stairs (n=11) were focussed.
Time to prepare an assistance device for utilisation depends significantly on the kind of device type. Further on, practical experience in handling the devices for assistance has an impact on the preparation time. In contrast to the results of the preparation times, any relation on assistance devices were investigated for the unimpeded walking speed in the plane. A remarkable decrease of walking speed on stairs was observed which is independent from the utilised assistance device.
The presented data improve and extend the insufficient engineering data base and raised up questions regarding the complexity of considering pedestrians movement with impairments in evacuation planning.
Evaluation of evacuation process is common separated by two phases: pre-movement and movement-phase. Individual capabilities of pedestrians have an impact on both and therefore on the time required for safe escape. In view of evaluating the evacuation process, characteristics of realistic movements of pedestrians involved are needed, but so far such data are mainly available for individuals with unrestricted evacuation capabilities only.
Due to the lack of available data, parameter studies in an assisted living for people with disabilities were performed to explore the movement during evacuation. Preparation times for assistance (n=10), unimpeded walking speeds (n=34) depending on the assistance devices in the plane as well as walking speeds on stairs (n=11) were focussed.
Time to prepare an assistance device for utilisation depends significantly on the kind of device type. Further on, practical experience in handling the devices for assistance has an impact on the preparation time. In contrast to the results of the preparation times, any relation on assistance devices were investigated for the unimpeded walking speed in the plane. A remarkable decrease of walking speed on stairs was observed which is independent from the utilised assistance device.
The presented data improve and extend the insufficient engineering data base and raised up questions regarding the complexity of considering pedestrians movement with impairments in evacuation planning.
Understanding movement in heterogeneous groups is important for a meaningful evaluation of evacuation prediction and for a proper design of buildings. The understanding of interactions and influencing factors in heterogeneous groups on key performance figures is fundamental for a safe design. This contribution presents results of experimental studies on movement of a crowd through a bottleneck involving participants with and without disabilities. High precise trajectories of the attendees extracted from video recordings were used to calculate density and velocity of the participants. Besides the well-established fundamental diagram new insights into the individual relation between density and velocity are discussed. A complex structure and considerate behaviour in movement implicates a strong influence of the heterogeneity on key performance values of safe movement.
Understanding movement in heterogeneous groups is important for a meaningful evaluation of evacuation prediction and for a proper design of buildings. The understanding of interactions and influencing factors in heterogeneous groups on key performance figures is fundamental for a safe design. This contribution presents results of experimental studies on movement of a crowd through a bottleneck involving participants with and without disabilities. High precise trajectories of the attendees extracted from video recordings were used to calculate density and velocity of the participants. Besides the well-established fundamental diagram new insights into the individual relation between density and velocity are discussed. A complex structure and considerate behaviour in movement implicates a strong influence of the heterogeneity on key performance values of safe movement.
In case of a vehicle fire, an installed LPG (liquefied petroleum gas) tank with a malfunctioning safety device poses severe hazards. To investigate the consequences in case of tank failure, we conducted 16 tests with toroidal shaped LPG vehicle tanks. Three tanks were used for a Hydraulic Burst Test under standard conditions. Another three tanks were equipped with a statutory safety device and were subjected to a gasoline pool fire. The safety device prevented tank failure, as intended. To generate a statistically valid dataset on tank failure, ten tanks without safety devices were exposed to a gasoline pool fire. Five tanks were filled to a level of 20 %; the re-maining five were filled to a level of 100 %. In order to gain information on the heating process, three tem-perature readings at the tank surface, and three nearby flame temperatures were recorded. At distances of l = (7; 9; 11) m to the tank, the overpressure of the shock wave induced by the tank failure and the unsteady tem-peratures were measured. All ten tanks failed within a time of t < 5 min in a BLEVE (boiling liquid expanding vapor explosion). Seven of these resulted directly in a catastrophic failure. The other three resulted in partial failure followed by catastrophic failure. A near field overpressure at a distance of l = 7 m of up to p = 0.27 bar was measured. All ten tests showed massive fragmentation of the tank mantle. In total, 50 fragments were found. These 50 fragments make-up 88.6 % of the original tank mass. Each fragment was georeferenced and weighed. Fragment throwing distances of l > 250 m occurred. For the tanks with a fill level of 20 %, the average number of fragments was twice as high as it was for the tanks that were filled completely.
The present study aims to investigate the use of geopolymer mortars as passive fire protection system for steel structures. Coal fly ashes were used as aluminosilicate source and perlite was employed as aggregate to obtain a lightweight system. In addition, a geopolymer mortar containing quartz aggregate was produced for comparison. The geopolymer mortars were applied on stainless steel plates and exposed to both, cellulosic and hydrocarbon standard fire curves, according to ISO 834-1 and EN 1363-2, respectively. Acoustic emission measurements were conducted to analyze cracking phenomena during the high temperature exposure. The resulting temperature-time curves showed that the investigated system is effective in retarding the temperature rise of the steel plates. When the cellulosic fire curve was applied, a 20 mm [0.79 in.] thick layer of lightweight geopolymer mortar protected the steel substrate from reaching the critical temperature of 500 °C [932 °F] for at least 30 minutes, avoiding the rapid decrease of its mechanical properties and thus representing an important safety measure against accidental fires. No spalling phenomena on heating were detected; however, significant cracking was observed on cooling.
Flexible polyurethane foams with densities of 40 ± 2 kg m−3 were prepared by combining different ecofriendly fillers such as layered double hydroxides (LDH) and kraft lignin (a byproduct of the pulp and paper industry) with a phosphorous polyol (E560) in order to study their effect on the mechanical performance and fire behavior of the foams. Two series of foams were prepared, some containing lignin or LDH separately, and some with a combination of both: one of the series was prepared without E560 (0E foam series) and the other with 5 parts per hundred of E560 polyol (5E series). The use of fillers resulted in increased viscosity of the reactive mixture, requiring higher blowing agent content in order to hold the density of the foams constant. It was observed that urea phase segregation was favored in the series of 0E foams due to their lower viscosity than the 5E series. This had consequent effects on the resilience, compression force deflection and compression set of these foams. In terms of fire behavior it was observed that while the limiting oxygen index decreased, cone calorimeter results showed that the combination of lignin, LDH and E560 decreased the heat release of the foams. In addition, the combination of fillers and E560 contributed to increase the viscosity of the pyrolysis products, preventing the dripping of the molten polymer, which is a key factor in flame propagation towards adjacent objects in fire scenarios.
Thermoplastic polyurethane - How thespecific two-stage decompositioncontrols its fire behavior
(2018)
Thermoplastic polyurethanes (TPUs) are one of the major classes of thermoplastic elastomers used in the cable and wire industry. Due to their chemical structure, they are considered as linear block copolymers with alternating hard and soft segments. This specific structure is not only responsible for the excellent mechanical properties of TPU like high tensile strength or abrasion resistance, but it also influences the pyrolysis and burning behavior. TPU is a highly flammable polymer which forms liquid pool fires or burning drops which results in intensive flame spread. Because of that, TPU often does not meet the strict requirements for indoor applications given by the cable market.
Under thermal stress, TPU decomposes in a specific way. At first, the hard segments decompose and the material becomes soft and melts. Subsequently, pool fires are formed and melted material burns extensively. There are not many works addressing this problem in detail especially in terms of suitable flame retardant solutions. It is crucial to understand at which stage the flame retardants are working and how they affect the thermal decomposition of TPU. Hence, the focus of this work was put on the identification of the reactions occurring during each stage of TPU decomposition and the contribution of released products to the effective heat of combustion (EHC). Moreover, the detailed analysis of the melt dripping behavior was performed to better understand the influence of the decomposition degree on the viscosity.
The use of melamine cyanurate (MC) in combination with other additives was reported to be a promising flame retardant solution for TPU, especially in cable jacket applications. Hence, the combinations of MC with various flame retardants were used in TPU (Elastollan® 1185A10) and were investigated in terms of fire behavior, flammability, pyrolysis and decomposition products. As flame retardants, common ones were used including aluminum trihydrate (ATH), melamine polyphosphate (MPP), or aluminum diethylphosphinate (AlPi). Moreover, commercial product TPU-FR (Elastollan® 1185A10FHF) was investigated as a reference.
The Role of Decomposition Temperature for Flame Redartancy Mode of Action in the Condensed Phase
(2018)
Condensed-phase mechanisms play a major role in fire-retardant polymers. Generations of development have followed the concept of charring to improve fire properties. Whereas the principal reactions are believed to be known, the specific description for multicomponent systems is lacking, as is the picture across different systems. One important aspect in achieving, adjusting and optimising flame retardancy in the condensed phase is exploiting chemical reactions between the pyrolysing polymer and flame retardant at the right place, time and temperature. It is the aim of this contribution to address the role of the decomposition temperature of both flame retardant and polymer by the means of two examples: First, aryl phosphates in Polycarbonate/ Acrylonitrile-Butadiene-Styrene (PC/ABS) blends, where the reaction with the early stage decomposition products of PC is controlling the flame retardancy mechanism in the condensed phase. Second, a comprehensive set of phosphorus flame retardants in thermosets and their corresponding carbon fibre reinforced composites based on two different epoxy systems. Both examples show that key reactions between intermediate decomposition products only occur when the decomposition temperature ranges correspond to each other. The systems can be shifted towards condensed phase activity such as charring or inorganic glass formation as well as towards phosphorus release and thus flame inhibition in the gas phase. Changing the role of flame retardancy mechanisms also influence the efficiency in the achieved flame retardancy.
Elastomers are used in a wide range of automotive and railway applications. However, a severe drawback of most rubbers are their high flammability. Therefore, flame retardants (FRs) are added to improve the performance in fire. Generally, rubber composites are filled with high amounts of mineral fillers such as aluminium trihydroxide (ATH) to fulfil fire safety regulations. These high loadings may cause deterioration of the physical properties of the material. This work shows the implementation of two new strategies to achieve the modern demands on non-toxic FRs and the reduction of fillers.
The first approach was the implementation of multilayer graphene (MLG), acting as a multifunctional filler, reinforcing agent and FR. The study presents filler combinations with a systematic variation of the fillers carbon black (CB), MLG and ATH. The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing. Afterwards the master batch was compounded into the rubber in a two-roll milling. MLG substituted high amounts of the conventional filler CB, leading to reduced filler loadings and a consistent improvement in curing, mechanical and FR properties.
The second strategy was the combination of phosphorous-containing FRs with a potential new polymeric char promoting agent polyaniline (PANI). Char promoting additives such as pentaerythritol (PER) improve the effectiveness of the FR system. The combination of ammonium polyphosphate (APP) with PER was successfully investigated for natural and styrene-butadiene rubber composites. This work investigates the flame retardancy of the combination of FRs with PANI and its capability to act as a char/barrier promoter in EPDM.
The morphology of the rubbers and homogenously dispersion of MLG was investigated via scanning/transmission electron microscope (SEM/TEM) micrographs. Rheological and mechanical measurements assessed the influence of the fillers on the physical properties of the rubber composites. Characterization via thermogravimetric analysis (TGA) led to a broader understanding of the decomposition. In order to determine the flame retardancy effect of these materials, a multi-methodical approach was selected. Limiting oxygen index (LOI) and UL-94 were used to quantify the flammability of the rubber composites. The cone calorimeter provided information about the fire behaviour in forced flaming conditions. Residues were investigated via elementary analysis and XPS to clarify the composition of the remaining material. Glow-Wire and FMVSS 302 tests revealed significant results in terms of flame retardancy. The flame retardancy investigation of rubber composites, combinations of ATH with MLG and ATH with phosphorous-containing FRs, broaden the horizons of rubber flame retardancy solutions. By examining alternate FR formulations and their effect on mechanical and physical properties of the rubber, new insight into the range of applicable additives for rubber composites may be won.
The need to develop effective flame retardants that retain polymer properties and are safe for consumers and the environment is a continuous challenge for material scientists. While halogenated flame retardants were once commonplace, the shift to non-halogenated materials has steadily progressed due to concerns over impact on health and the environment. One prominent group of flame retardants has become a viable alternative for halogenated materials, namely phosphorus-based flame retardants. The chemical versatility of phosphorus-based flame retardants and the ability to work as reactive or additive compounds makes them ideally suited for modern materials. There exists a trend toward complex, polymeric, and multifunction flame retardants, as these materials show greater flame retardancy performance than low molecular weight counterparts and affect material properties to a much lesser extent.
One group of organophosphorus flame retardants that shows great potential for high-performance polymers like epoxy resins are hyperbranched phosphorus-based polymers. These additives exhibit great miscibility with the polymer matrix and a significantly decreased diffusion through the material, which greatly reduce leaching or blooming out of the matrix. Moreover, the material’s thermal stability remains intact at elevated temperatures due to its low impact on the glass transition temperature. Finally, following market trends and legislation such as the guidelines for the Restriction of Hazardous Substances Directive implemented by REACH (Registration, Evaluation, Authorization and Restriction of Chemicals) in the EU, these macromolecules are non-accumulating, non-toxic and have a lower risk of leeching or blooming from the matrix, further reducing environmental impact.
The work presented herein focusses on two distinct parts studying hyperbranched polymeric flame retardants and their corresponding monomeric compounds.
The first part, involving the low molecular weight components, investigated the role of the chemical surrounding of phosphorus in terms of flame retardant efficacy. Here, a systematic variance of the surrounding of phosphorus was investigated: by changing the ratio of oxygen to nitrogen (4:0 until 1:3), four materials, namely phosphoester (4:0), phosphoramidate (3:1), phosphorodiamidate (2:2), and phosphoramide (1:3), were synthesized, characterized, and finally added to Bisphenol A based epoxy resins (10 wt.-% loading). Pyrolysis investigations showed that low molecular weight components volatize at lower temperatures than the polymer matrix. Additionally, cone calorimeter measurements and TGA-FTIR investigations show trends in respect to FR efficacy in pyrolysis and full flaming conditions.
The second part involves the hyperbranched variants of the monomeric counterparts and investigates the role of complex shape on flame retardant efficacy. By comparing the low to the high molecular weight compounds, the influence of the complex shape becomes apparent and can be quantified. Cone calorimeter measurements show an increase in flame retardancy for some materials, while for others, the mode of action is altered.
By implementing a multi-methodical approach, various flame retardancy aspects, from pyrolysis behavior in the gas and condensed phase, to ignitability / reaction-to-small-flame performance, to action in forced flammability experiments, are identified and quantified, allowing for a clearer understanding of the behavior in fire of these novel flame retardants. By comprehending the roles of chemical composition and complex shape, it opens the path for new and effective multifunctional, polymeric flame retardants with decreased PBT, higher miscibility, and low impact on Tg.
This work is funded by the Deutsche Forschungsgemeinschaft (DFG: SCHA 730/15-1; WU 750/8-1).
PE-HD as a polymeric fuel storage tank material: Photooxidation, fuel sorption and long-term storage
(2018)
High-density polyethylene (PE-HD) is a commodity thermoplastic polymer which is typically used for packing of dangerous goods. Its good resistance against photooxidation, fuels, chemicals and other environmental factors in addition to low production costs makes PE-HD attractive for fuel storage applications. Typical engine fuels stored in polymer tanks are petrol, diesel and biodiesel that receives increasing attention as proper alternative to fossil fuels. One of the major problems with biodiesel is its susceptibility to oxidize due to its chemical composition of unsaturated fatty acids which also can cause polymer degradation.
The aim of this study is to investigate the influence of different environmental factors, UV radiation and commonly stored fuels, on the mechanical, physical and chemical properties of two types of PE-HD polymers (stabilized and non-stabilized). The influence on the mechanical properties was tested by Charpy and tensile tests, chemical and physical properties were evaluated by Fourier-transform infrared spectroscopy (FTIR) and by dynamical mechanical analysis (DMA) tests. Samples were characterized after varying exposure time of UV radiation and after fully and partially immersion in biodiesel. In addition, similar experiments were conducted using diesel for comparison.
The first documentation of fuel biodeterioration dates back to the late 19th century. However, extensive studies concerning the microbial fuel contamination started in 1980’s. Polymeric fuel storage tanks containing diesel and biodiesel provide environmental conditions for microbial growth. Several studies demonstrated that bacteria, which were found in contaminated fuel systems, can use fuels as macronutrient; but such bacteria can also cause microbiologically influenced corrosion and fouling.
The aim of this study is to investigate the initial attachment behavior of bacteria, isolated from a diesel contamination, on neat and photooxidized high-density polyethylene (PE-HD). Two common PE-HD’s, less- and biodiesel-stabilized, were radiated to UV light representing a tank exposed to sunlight. The effect of photooxidiation on PE-HD’s surface were characterized chemically by Fourier-transform infrared spectroscopy (FTIR). The attached bacteria Pseudomonas aeruginosa and Bacillus subtilis on the polymer surface were evaluated by fluorescence microscopy and colony-forming unit tests (CFU).
Different imaging techniques were employed to monitor Full Notch Creep Test (FNCT) experiments addressing environmental stress cracking in more detail. The FNCT is a well-established test method to assess slow crack growth and environmental stress cracking of polymer materials, especially polyethylene. The standard test procedure, as specified in ISO 16770, provides a simple comparative measure of the resistance to crack growth of a certain material based on the overall time to failure when loaded with a well-defined mechanical stress and immersed in a liquid medium promoting crack propagation.
Destructive techniques which require a direct view on the free fracture surface, such as light microscopy and laser scanning microscopy, are compared to non-destructive techniques, i.e. scanning acoustic microscopy and xray micro computed tomography. All methods allow the determination of an effective crack length. Based on a series of FNCT specimens progressively damaged for varied Durations under standard test conditions, the estimation of crack propagation rates is also enabled. Despite systematic deviations related to the respective Imaging techniques, this nevertheless provides a valuable tool for the detailed evaluation of the FNCT and its further development.
Editorial façade fire safety
(2018)
This Special Issue of Fire and Materials brings together a collection of papers that were presented at the 2016 Interflam conference in the Fire & Facades session along with recent submissions to the Fire and Materials Journal that are very relevant to the Fire and Facades subject. Having attended the Interflam conference, all Fire and Materials Journal editors who attended realised the importance of this topic. We felt it important that this session content would both be reviewed and made available to a wider audience and that it was timely that we featured this increasing important topic in our journal. Accordingly, authors of selected papers were invited to update and extend their papers for journal submission, and other appropriate peer review papers subsequently submitted to the Journal were included in the collection.
As part of energy‐efficient renovations or for the construction of new buildings often external thermal insulation composite (ETIC) are used. In 2015, in Germany almost 37 million square meters were installed. But several fires involving ETIC systems with polystyrene foam (EPS) insulation in Germany led to an extensive discussion about fire safety of such systems. A collection initiated by the Frankfurt fire service of façade fires which include polystyrene insulation foam1 shows that more than two thirds of all reported fires started in front of buildings. In half of these fires burning waste containers were the first burning objects. Consequently, German building authorities called for tests of existing approved ETIC systems with EPS insulation in a fire Scenario representing a burning waste container. As these tests revealed weaknesses in the existing ETIC systems measures were introduced to enhance the systems. However, the recently introduced German test standard DIN 4102‐20 does not take These changes into account. The DIN test represents a fire where flames emerge an opening but is downscaled regarding the size of the fire load and therefore does not represent a fully developed fire in a room. In ETIC systems with EPS insulation, the render is an important factor for the fire performance of these systems as collapse of the render usually leads to very rapid fire development. Intermediate scale tests with ETICs specimens indicate that mechanical damages of the render weaken the System significantly. Challenges and possible measures to enhance fire safety of ETIC systems are discussed.
The effects of weathering exposure on unfilled and filled thermoplastic polyurethanes (TPU) materials are described as performed under different humidity conditions. For this purpose, a weathering device was used with UV-A 340 nm lamps at a constant temperature of 40 °C. The effects of environmental (UV and humidity condition) degradation on the frictional properties of TPU materials are presented along with surface analyses to characterize the chemistry of the degradative process. Photooxidative degradation of unfilled polymer leads to deterioration of physical and mechanical properties, which affects its tribological behavior significantly. Due to crosslinking, the stiffness of the material increases, reducing drastically the friction coefficient of unfilled TPUs. The frictional behavior of glass fiber reinforced TPU is less affected by radiation.
The ubiquity of polymeric materials in daily life Comes with an increased fire risk, and sustained research into efficient flame retardants is key to ensuring the safety of the populace and material goods from accidental fires. Phosphorus, a versatile and effective element for use in flame retardants, has the potential to supersede the halogenated variants that are still widely used today: current formulations employ a variety of modes of action and methods of implementation, as additives or as reactants, to solve the task of developing flameretarding polymeric materials. Phosphorus-based flame retardants can act in both the gas and condensed phase during a fire. This Review investigates how current phosphorus chemistry helps in reducing the flammability of polymers, and addresses the future of sustainable, efficient, and safe phosphorus-based flame-retardants from renewable sources.
The rapid mass calorimeter (RMC) was used as a screening tool based on accelerated fire testing to assess flame-retarded thermoplastic polyurethane (TPU). The reliability of RMC results was proven with the cone calorimeter as reference fire test. The influence of melamine cyanurate (MC) concentration on the fire performance of TPU was investigated, along with some flame-retardant combinations such as MC with aluminium diethylphosphinate (AlPi), aluminium trihydrate (ATH), and melamine polyphosphate (MPP). The two-stage burning behaviour of TPU was investigated in detail; the first stage corresponds mainly to the hard segments' decomposition and has a much lower effective heat of combustion (EHC) than the second stage, in which mainly the soft segments decompose and an intensive liquid pool fire is observed in the cone calorimeter set-up. In addition to fire testing with the cone calorimeter, RMC, and UL 94 flammability tests, the decomposition of the materials was investigated using thermogravimetric analysis coupled with infrared spectrometry (TGeFTIR). TPU/MC/AlPi shows the most promising results, achieving V-0 classification in UL 94 and reducing the extreme peak heat release rate (PHRR) of the liquid pool fire from 3154 kW/m2 to 635 kW/m2. Using MC/AlPi/MPP enhances the latter PHRR reduction further. The decomposition products identified in the gas phase via TGeFTIR reveal specific MCeAlPi eMPP interactions, as they differ from products seen in systems with MC/AlPi or MC/MPP. Correlations between RMC and cone calorimeter results were examined and presented in the final part of the paper. Several characteristics correlate strongly, pointing out that RMC is a reliable high-throughput fire testing method to screen multicomponent flame-retardant solutions in TPU.
To save weight and resources lightweight tanks with complex geometries made of glass-fibre reinforced plastics (GFRP) are a promising innovation for the transportation of dangerous goods. To realise the use of polymer tanks for such applications, their fire safety must be guaranteed. This paper presents solutions to protect fibre-reinforced plastic tanks from fire. The fire resistance of six GFRP tanks with different fire protection systems was tested in an outdoor full-scale fire test facility according to the regulation stipulated in the ADR (European agreement concerning the national carriage of dangerous goods by road). All tanks feature a complex geometry and a holding capacity of 1100 litres. The fire protection systems are composed of specialised resins as well as two intumescent coatings. All systems had a protective impact. The best results were achieved by the epoxy based intumescent coating, which was able to prolong the time needed to reach 150 °C inside the tank by 20 min. The emergence of a temperature holding point inside the tank due to condensation effects was observed at temperatures around 100 °C.
The individual and collective impacts of additives in melt dripping behaviour were studied under UL 94 vertical test conditions. A set of polyamide 6 (PA6) based materials compounded with melamine cyanurate (MCA) – a ˝dripping agent˝ – and glass fibre (GF) – a ˝non-dripping agent˝ - was investigated in detail. Dripping quantification was carried out during first and second ignition. The materials and their drops were investigated with respect to thermal decomposition, melt viscosity, and others properties. PA6 with V-2 classification improves to V-0 when MCA is added; and is worsened to HB in presence of glass fibre. Together, PA6/GF/MCA achieved V-2. The non-flaming drops of PA6/MCA are formed by oligomeric fragments. The flaming drops of PA6/GF contain a high amount of glass fibre. The dripping behaviour of PA6/GF/MCA under fire is a complex response of the specimen, but not explained by an easy superposition of the materials’ properties. The dripping behaviour is influenced by the interaction and concurrence of the different phenomena.
Elastomers, such as hydrogenated acrylonitrile-butadiene rubber (HNBR) are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. These high filler loadings sometimes cause deterioration of the physical properties of the material. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings (3 phr) to reduce the total amount of filler or boost performance.1,2,3 In former studies nanofiller achieved increased flame retardancy at very low lowdings.4,5,6 The dispersion of the nanofiller is essential for the properties of the nanocomposites.7 The nanocomposites were prepared via master batch by an ultrasonically assisted solution mixing and subsequent conventional two-roll milling.
SEM and TEM micrographs and rheological measurements revealed that the MLG nanoparticles were well dispersed in the HNBR matrix. In the HNBR nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr ATH or 15 phr CB + 3 phr ATH and achieved large consistent improvement in curing, rheological and mechanical properties of the HNBR. The nanocomposites with partial replaced CB reduced the filler loading up to 60% without any deterioration of the properties. The HNBR/MLG nanocomposites achieved an even higher Young’s modulus, hardness and thermal conductivity. MLG achieved advanced flame retardancy by improving the protection layer. The layer is created during the burning phase and acted as an afterglow suppressor. This study proposed the combination of ATH with MLG as a promising approach to reduce the amount of filler, in addition to improving the mechanical properties and fire performance of HNBR rubbers.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering where the data are discussed with regard to both the q- and the temperature dependence.
Häufig ist es wünschenswert, für neue Materialien oder Anwendungen künstliche Bewitterungsverfahren zu benutzen, die auf die spezifischen Anforderungen besser zugeschnitten sind, als es bei bestehenden standardisierten Verfahren der Fall ist. Nachdem man die spezifischen Parameter der Beanspruchung unter Anwendungsbedingungen und die spezifische Empfindlichkeit des Materials erfasst hat, beginnt ein Prozess, der als „Test Tailoring“ häufig abstrakt verwendet, auf den aber nur selten näher eingegangen wird. Genau dieser Prozess soll hier am Beispiel der Entwicklung eines künstlichen Bewitterungstests unter saurer Beaufschlagung, dem in der BAM entwickelten Acid Dew and Fog Test, beispielhaft erläutert werden.
Additively manufactured test specimens made of polyamide 12 (PA 12) by Laser Sintering (LS) as well as of acrylnitril-butadien-styrol (ABS) by Fused Layer Modeling (FLM), were tested with active thermography. For this, two different excitation methods (flash and impulse excitation) were used and compared, regarding the suitability for the detection of constructed and imprinted defects. To increase the quality of the thermograms, data processing methods like thermal signal reconstruction (TSR) and Fourier-Transformation were applied. Furthermore, the long-term stability of the probes towards environmental stress, like UV-radiation, heat, water contact and frost is being investigated in the presented project with artificial weathering tests.
After introducing into the activities and competence of BAM in the field of fire science, several aspects of successful and tailored flame retardancy of polyolefins are discussed. The talk gives an overview of the works relevant for developing flame retardant polyolefins performed in the working group flame retardancy of polymers. The hypothesis of conservation of effective heat of combustion is proposed. The role of charring, inert fillers, protection layer, and intumescence is assessed for flame retarded polyolefins. Distinct routes of optimization sketched. Examples of controlling the dripping and melt flow to obtain the desired fire behaviour are discussed. Finally the cable modul for the cone calorimeter is presented.
Die Bundesanstalt für Materialforschung und -prüfung (BAM) ist eine Ressortforschungseinrichtung, die zum Schutz von Mensch, Umwelt und Sachgüter, forscht, prüft und berät. Im Fokus aller Tätigkeiten in der Materialwissenschaft, der Werkstofftechnik und der Chemie steht dabei die technische Sicherheit von Produkten und Prozessen. Dazu werden Substanzen, Werkstoffe, Bauteile, Komponenten und Anlagen sowie natürliche und technische Systeme erforscht und auf sicheren Umgang oder Betrieb geprüft und bewertet. Schwerpunkt des Vortrages sind multimodale Polymeranalytik, nanoskalige Sensormaterialien und die Charakterisierung von technischen Eigenschaften von Polymeren sowie ihre Alterung und Umweltrelevanz.
Steel tension rod systems consist of tension rods, fork connectors and associated intersection or connecting plates. They are used for truss systems, bracings or suspensions owing to slender design and increased economic efficiency. In case of fire, beside the tension rods themselves, the connection parts require appropriate fire protection. The use of intumescent fire protection coatings prevents a rapid heating of the steel and helps to ensure the load-carrying capacity of the structures. Because the connection components of the tension rod systems feature surface curvature as well as a complex geometry, high demand is placed on the intumescence and thermal protection effectiveness of the reactive fire protection coatings. Experimental studies were carried out to investigate the performance of intumescent coatings applied to the components of tension rod systems. The examined aspects include the foaming and cracking behaviour of the intumescent coatings, the influence of different dry film thicknesses (DFT), the heating rate of the steel connecting parts in comparison to the tension rods, as well as the mounting orientation of the tension rods together with their associated fork connectors. The results show that a decrease in the surface curvature and/or an increase in the mass concentration of the steel components lead to a lower heating rate of the steel. Moreover, the performance of the intumescent coating on tension rod systems is influenced by the mounting orientation of the steel components.
Steel tension rod systems consist of tension rods, fork connectors and associated intersection or connecting plates. They are used for truss systems, bracings or suspensions owing to slender design and increased economic efficiency. In case of fire, beside the tension rods themselves, the connection parts require appropriate fire protection. The use of intumescent fire protection coatings prevents a rapid heating of the steel and helps to ensure the load-carrying capacity of the structures. Because the connection components of the tension rod systems feature surface curvature as well as a complex geometry, high demand is placed on the intumescence and thermal protection effectiveness of the reactive fire protection coatings. Experimental studies were carried out to investigate the performance of intumescent coatings applied to the components of tension rod systems. The examined aspects include the foaming and cracking behaviour of the intumescent coatings, the influence of different dry film thicknesses (DFT), the heating rate of the steel connecting parts in comparison to the tension rods, as well as the mounting orientation of the tension rods together with their associated fork connectors. The results show that a decrease in the surface curvature and/or an increase in the mass concentration of the steel components lead to a lower heating rate of the steel. Moreover, the performance of the intumescent coating on tension rod systems is influenced by the mounting orientation of the steel components.
From halogenated flame retardants to non-halogenated to nanocomposites, each milestone in flame retardancy research led to an increase in performance and safety. With the rise of ceramic precursors in flame retardants, a new field of applications in extreme fire scenarios has become accessible. Intumescent coatings combined with precursors for ceramics show a high temperature transition to a ceramic foam, which provides much better fire resistance than conventional coatings at temperatures beyond 1200°C. Even a protection at 2000 °C for several minutes can be achieved. Combining the expansion property of traditional intumescent coatings with a ceramification at high temperatures leads to high-performance coatings, whose unique properties may prove useful for emergency insulation systems for re-entry bodies in the aerospace industry or special fire protection applications.
In this study, the protection performance in extreme fire conditions, the development of the expansion and the following ceramic transition of a high-performance coating are investigated. To this end, a small scale high-performance burner setup was created. The coated (2.5/4 mm) steel plates (75 x 75 x 2 mm) were exposed to direct flame treatment of a propane-oxygen-burner controlled by two flow controllers. During the test, temperatures above of 1800 °C were reached and steel and flame temperature were recorded. Fire tests of different durations (1, 2.5, 5, 10 and 20 min) were performed. The residues of the different development stages were analysed with non-destructive µ-computed tomography and scanning electron microscopy. The 3D images of the computed tomography provide an insight into the developing cell structure and state of ceramification of the residues.
The demands for modern flame retardants are higher than ever: a flame retardant must function effectively in a certain polymer matrix and avoid critical alterations to the material’s properties. Ideally, a flame retardant additive should be easily miscible and show no sign of leaching or blooming from the matrix. Additionally, the flame retardant should be non-toxic, non-accumulating and biocompatible. Hyperbranched polymers are a promising group of multifunctional flame retardants which fulfill these demands: their complex shape enables high miscibility and avoids leaching or blooming, while their high molecular weight potentially increases biocompatibility and lowers accumulation and toxicity. Moreover, they exhibit a low impact on polymer properties and a good flame retardant performance.
This work examines the efficacy and mode of action of phosphorus-based hyperbranched polymeric flame retardants in bisphenol A-based epoxy matrices. To investigate the effect of the complex shape, the hyperbranched polymers are compared to their corresponding monomeric variants. Furthermore, the materials are synthesized to contain systematically varying oxygen-to-nitrogen ratios, allowing for new insight into what role the chemical surrounding of phosphorous plays in flame retardant efficacy.
Using a multi-methodical approach, including thermogravimetric analysis coupled with Fourier transform infrared spectroscopy (FTIR), hot stage FTIR, micro combustion calorimetry, differential scanning calorimetry, oxygen index (LOI), UL-94 tests and cone calorimetry experiments, the decomposition mechanisms and the flame retardant modes of action of these flame retardants in epoxy resins are investigated, shedding new light on the chemistry of flame retardancy.
Studien zur Erforschung von Kenngrößen der Bewegung von Personen wurden in der Vergangenheit meistens mit jungen und fitten Menschen durchgeführt. In Folge des demographischen Wandels und der Anforderungen an barrierefreies Bauen stellt sich die Frage, ob die so ermittelten Kenngrößen der Bewegung auch auf heterogene Personengruppen übertragen werden können. Da bei der Berechnung von Räumungszeiten zunehmend Ingenieurmethoden eingesetzt werden, deren Ergebnisse ganz wesentlich von den zu Grunde gelegten Bewegungsparametern, wie z. B. der freien Gehgeschwindigkeit, abhängen, hat die Validität der Kenngrößen maßgeblichen Einfluss auf die sicherheitstechnische Evaluation von Gebäuden und Versammlungsstätten.
In diesem Artikel wird anhand aktueller Forschungsergebnisse aus Bewegungsstudien, an denen Menschen mit und ohne Beeinträchtigungen teilgenommen haben, der Einfluss der Heterogenität auf Kenngrößen der Bewegung vorgestellt. Darüber hinaus werden die Besonderheiten des Studienablaufs und die Möglichkeiten und Grenzen der Untersuchungsmethode dargestellt. Die Untersuchungen bestätigen, dass die Berücksichtigung besonderer Personengruppen signifikanten Einfluss auf die Kenngrößen der Bewegung hat und daher die Ergebnisse der Ingenieurmethoden beeinflusst und zukünftig bei heterogenen Personengruppen beachtet werden muss.
Intumescent coatings for fire protection offer advantages over (non-intumescent) cementitious coatings and boards regarding speed of construction, architectural aesthetics, sometimes costs, and other features. However, conventional organic intumescent coatings as well as soluble silicate (waterglass) coatings form foams with low mechanical stability, and the latter coatings generally suffer from low resistance against humidity. Therefore, the search for novel intumescent coatings for more demanding conditions (e.g., abrasive environments) is a necessity in the context of steadily increasing requirements of society and industry.
In this contribution, we present results on intumescent aluminosilicate coatings for fire protection that form foams with significantly increased mechanical strength. Two base formulations, a metakaolin/silica-based mix, adapted from Krivenko et al., and a silica/corundum-based mix, developed at Curtin University, as well as formulations modified with additives (Al(OH)3, Mg(OH)2, B2O3, Na2B4O7), were applied to steel plates (75 mm × 75 mm) and exposed to simulated fire conditions (fire curve according to ISO 834-1:1999). Temperature-time curves were recorded to assess the degree at which the coatings insulated the substrate. In addition, XRD, TG, oscillatory rheometry, and SEM were employed to characterise the coatings.
The coatings were observed to partly expand during hardening due to H2 formation. When the hardened coatings were exposed to elevated temperatures they intumesced as expected, with the degree and nature of expansion dependent on the formulation. Oscillatory rheometry provided insights into the intumescent processes in an apparently brittle material. It revealed that the hardened aluminosilicate coatings became viscous (loss factor > 1) at 75–225 °C, in the temperature range of major water release, as opposed to a “standard” metakaolin-based geopolymer, which continued to behave as a solid. This explains the intumes¬cent behavior of the coatings, i.e. further expansion and foam formation. Microstructural analysis confirmed pore expansion and coalescence; XRD showed that the phases formed after heating (max. temperature ~840 °C) were of ceramic-type.
The fire protection (defined here as the time for the steel substrate to reach the critical temperature of 500 °C) depended mainly on the thick¬ness of the fully expanded coating, i.e. after intumescence. An alumino¬silicate coating free of additives with an original thickness of 12 mm was able to protect the steel for >30 min. The addition of 10 % anhydrous borax (Na2B4O7) caused a significant improvement, such that an original coating thickness of only 6 mm was sufficient to protect the steel for ~30 min. This was caused by the formation of sodium metaborate dihydrate (NaB(OH)4) in the coating that led to a significantly extended dehydration plateau in the temperature-time curve at ~100 °C during the fire exposure.
Studien zur Erforschung von Kenngrößen der Bewegung von Personen wurden in der Vergangenheit meistens mit jungen und fitten Menschen durchgeführt. In Folge des demographischen Wandels und der Anforderungen an barrierefreies Bauen stellt sich die Frage, ob die so ermittelten Kenngrößen der Bewegung auch auf heterogene Personengruppen übertragen werden können. Da bei der Berechnung von Räumungszeiten zunehmend Ingenieurmethoden eingesetzt werden, deren Ergebnisse ganz wesentlich von den zu Grunde gelegten Bewegungsparametern, wie z. B. der freien Gehgeschwindigkeit, abhängen, hat die Validität der Kenngrößen maßgeblichen Einfluss auf die sicherheitstechnische Evaluation von Gebäuden und Versammlungsstätten.
In diesem Artikel wird anhand aktueller Forschungsergebnisse aus Bewegungsstudien, an denen Menschen mit und ohne Beeinträchtigungen teilgenommen haben, der Einfluss der Heterogenität auf Kenngrößen der Bewegung vorgestellt. Darüber hinaus werden die Besonderheiten des Studienablaufs und die Möglichkeiten und Grenzen der Untersuchungsmethode dargestellt. Die Untersuchungen bestätigen, dass die Berücksichtigung besonderer Personengruppen signifikanten Einfluss auf die Kenngrößen der Bewegung hat und daher die Ergebnisse der Ingenieurmethoden beeinflusst und zukünftig bei heterogenen Personengruppen beachtet werden muss.
Mit additiven Fertigungsverfahren hergestellte Bauteile und Produkte aus Kunststoffen werden zunehmend nicht mehr nur als Prototypen, sondern als voll funktionsfähige Bauteile und Produkte gefertigt. Bedingt durch die Fertigungsprozesse und den schichtweisen Aufbau resultieren physikalische Materialeigenschaften, die stark von den Fertigungsparametern abhängen und zudem anisotrop sind. Von den Fertigungsparametern werden auch die Oberflächeneigenschaften beeinflusst, sodass zu erwarten ist, dass sich die Beständigkeit gegenüber äußeren Umwelteinflüssen bei additiv gefertigten Bauteilen von der konventionell gefertigter unterscheiden kann. Nachfolgend wird daher die Entwicklung eines Qualitätssicherungskonzeptes basierend auf spektroskopischen und zerstörungsfreien Prüfverfahren vorgestellt, in dem der Alterungsprozess von mittels Fused Deposition Modelling (FDM) und mittels Lasersintering (LS) hergestellten Probekörpern untersucht wird.
Mit additiven Fertigungsverfahren hergestellte Bauteile und Produkte aus Kunststoffen werden zunehmend nicht mehr nur als Prototypen, sondern als voll funktionsfähige Bauteile und Produkte gefertigt. Bedingt durch die Fertigungsprozesse und den schichtweisen Aufbau resultieren physikalische Materialeigenschaften, die stark von den Fertigungsparametern abhängen und zudem anisotrop sind. Von den Fertigungsparametern werden auch die Oberflächeneigenschaften beeinflusst, sodass zu erwarten ist, dass sich die Beständigkeit gegenüber äußeren Umwelteinflüssen bei additiv gefertigten Bauteilen von der konventionell gefertigter unterscheiden kann. Nachfolgend wird daher die Entwicklung eines Qualitätssicherungskonzeptes basierend auf spektroskopischen und zerstörungsfreien Prüfverfahren vorgestellt, in dem der Alterungsprozess von mittels Fused Deposition Modelling (FDM) und mittels Lasersintering (LS) hergestellten Probekörpern untersucht wird.
Polymers with intrinsic microporosity (PIMs) represent a novel, innovative class of materials with great potential in various applications from high-performance gas separation membranes to electronic devices. Here for the first time, for PIM-1, as the archetypal PIM, fast scanning calorimetry provides definitive evidence for a glass transition (Tg=715 K, heating rate 3·10^4 K/s) by decoupling the time-scales responsible for glass transition and decomposition. As the rigid molecular structure of PIM-1 prevents any conformational changes, small-scale bend and flex fluctuations must be considered the origin of its glass transition. This result has strong implications for the fundamental understanding of the glass transition and for the physical aging of PIMs and other complex polymers, both topical problems of materials science.
Thermoplastic starch polymer blends as biodegradable materials are well known and used mainly as packaging material. In order to exploit new application fields for these materials, additional properties such as flame retardancy or increased mechanical strength are required. This work focuses on the flammability and fire behavior of a thermoplastic starch/polyester blend reinforced with natural fibers derived from Mexican industry processes wastes, such as keratin fibers from the tannery industry or coconut fibers[1]. Different fiber contents as well as combinations of varying contents of aluminum trihydroxide, expandable graphite or ammonium polyphosphate were tested in LOI, UL94, cone calorimeter and TG-FTIR in order to investigate and assess the concentration dependence of the fibers and flame retardants as well as synergistic effects between both components. In combination with ammonium polyphosphate, the coconut fibers induce a synergistic effect by reinforcing the char residue and creating a more stable heat barrier during forced flaming combustion in the cone calorimeter. Synergism is also observed in the oxygen test. The recycling of otherwise wasted material is a true challenge in material development, thus this work is a first step in the direction of sustainable and biodegradable materials.
Es wird ein Verfahren zur Charakterisierung der Beständigkeit und Langzeitstabilität von additiv gefertigten Kunststoff-Bauteilen vorgestellt. Dabei sollen die Prüfkörper über 2000 Stunden künstlich bewittert und währenddessen die Änderungen der Eigenschaften der Bauteile zerstörungsfrei untersucht werden.
This study evaluates the efficacy of compressed air foam (CAF) in comparison to common fire extinguishing media. Newly developed mixed-material burning cribs were used as a normative fire load for extinguishing tests to accurately represent the significantly elevated utilization of synthetic materials in everyday life. A series of outdoor experiments was carried out to analyze the effectiveness of the fire extinguishing medium CAF using synthetical class-A foaming agents from two different manufacturers, and compared them to water and waterfoam solution as a function of the extinguishing distance. In a second series, performed inside a fire room, the efficiency of CAF-usage in indoor fires was evaluated. Moreover, the results of the indoor test series provided information about the composition of smoke gases based on the kind of extinguishing tactic used to suppress the fire. The results showed that under the tested conditions CAF suppressed fire more effectively than both water and water with foaming agents. CAF was able to wet areas hardly accessible to other extinguishing media, and due to its various simultaneously occurring effects and its compact jet with high kinetic energy, it cooled down temperatures more efficiently than water or water-foam solution.
In der Vergangenheit wurden Kenngrößen der Bewegung von Menschen zumeist in Studien gewonnen, die mit jungen und fitten Menschen durchgeführt wurden (z. B. Studierende oder Soldaten). Aufgrund des demographischen Wandels und aktueller Entwicklungen im Kontext der Barrierefreiheit stellt sich jedoch die Frage, ob die in diesen Studien gewonnen Kenngrößen, z. B. freie Gehgeschwindigkeiten, ohne weiteres auch auf heterogene Personengruppen übertragen werden können.
Bei der Bewertung der Sicherheit von Menschen, z. B. in Wohneinheiten, Verwaltungsgebäuden und Versammlungsstätten, kommen heute Ingenieurmethoden zum Einsatz, welche auf den oben genannten Kenngrößen basieren. Insofern ist es erforderlich, Menschen mit und ohne Beeinträchtigungen bei den Bewegungsstudien zu berücksichtigen. Im vorliegenden Artikel werden aktuelle Ergebnisse solcher Studien vorgestellt. Zudem werden Besonderheiten sowie Grenzen und Möglichkeiten der Untersuchungsmethode herausgearbeitet.
As the well-known damage mechanisms slow crack growth (SCG) and environmental stress cracking (ESC) are the major causes for possible failure of polyolefin-based materials, especially for PE-HD, they are highly relevant and need to be considered thoroughly. Furthermore, due to slight but perceptible differences in damaging effect, a differentiation between SCG and ESC is expedient. SCG appears in “inert” or “neutral” media without a decisive influence of the surrounding medium whereas ESC occurs in “active” media, which influence the failure behavior and time to failure crucially.
To characterize the inherent resistance of the material against those damage mechanisms, the well-established Full-Notch Creep Test (FNCT) is used. In this study, the FNCT – usually applied according to ISO 16770 [3] using a few universal model liquid media and mainly for pipe materials – is extended by investigations with appropriate parameters of selected relevant PE-HD container materials also in real media, such as the topical fuels diesel and biodiesel. The investigations were performed using a novel FNCT-device with 12 individual sub-stations, each equipped with individual electronic stress and temperature control and continuous online monitoring of the specimen elongation.
Especially, mechanical stress and temperature were varied systematically during FNCT and time to failure values, time-dependent elongation data as well as detailed fracture surface analysis by laser scanning microscopy (LSM) were combined for the first time (Fig. 1). Particularly, the fracture surface analysis provides a sound basis to characterize failure behavior, mainly regarding the balance between brittle crack propagation and ductile deformation. Therefore, fracture surface analysis is an essential tool for a decent assessment of SCG and ESC by FNCT measurements.
Es wird ein Verfahren zur Charakterisierung der Beständigkeit und Langzeitstabilität von additiv gefertigten Kunststoff-Bauteilen vorgestellt. Dabei sollen die Prüfkörper über 2000 Stunden künstlich bewittert und währenddessen die Änderungen der Eigenschaften der Bauteile zerstörungsfrei untersucht werden. Die Erkenntnisse dienen für die Entwicklung einer Strategie für eine Qualitätskontrolle von additiv gefertigten Kunststoffteilen.
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.
Elastomers are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings, 3 parts per hundred rubber (phr) to reduce the total amount of filler or boost performance in hydrogenated acrylonitrilebutadiene rubber (HNBR). In the HNBR/MLG nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr aluminum trihydroxide (ATH), or 15 phr CB + 3 phr ATH. The nanocomposites were prepared via master batch by ultrasonically assisted solution mixing and subsequent conventional two-roll milling. A comprehensive study is presented, illustrating the impact of MLG on curing and mechanical properties; e.g. replacing 2.5 phr ATH with 3 phr MLG increased the Young's modulus by over 60% and hardness by 10%, while improving flame retardancy, and reducing the total heat evolved by 10%. MLG is a multifunctional filler, as demonstrated by various enhancements in terms of the mechanical and flame retardancy properties of the rubber composites.
Polyesters with 9,10-dihydro-9-oxy-10-phosphaphenanthrene-10-oxide-containing comonomers are synthesized aiming to improve the flame retardancy of aliphatic polyesters such as poly(butylene succinate) and poly(butylene sebacate). The influence of the chemical structure on the thermal decomposition and pyrolysis is examined using a combination of thermogravimetric analysis (TGA), TGA-Fourier transform infrared (FTIR) spectroscopy, pyrolysis-gas chromatography/mass spectrometry, and microscale combustion flow calorimetry. Thermal decomposition pathways are derived and used to select suitable candidates as flame retardants for PBS. The fire behavior of the selected polymers is evaluated by forced-flaming combustion in a cone calorimeter. The materials show two modes of action for flame retardancy: strong flame inhibition due to the release of a variety of molecules combined with charring in the solid state.
Laboratory studies with pedestrians could depend strongly on Initial conditions. Comparisons of the results of such studies require to distinguish carefully between homoge neous and heterogeneous populations.
A series of well-controlled laboratory studies were performed with participants with and without impairments. Individual pedestrian movement through a corridor and a bottleneck of all participants was recorded by wide-angle HD-cameras and the trajectories of each participant was extracted automatically by using PeTrack.
This contribution shows that considering participants with impairments in laboratory studies of pedestrian movement is feasible and reports preliminary the inuences of movement. Preliminary analyses imply two main conclusions and a preliminary forecast: _rst, social behaviour in laboratory studies is considerately and respectful; we did not observe altruistic behaviour; but considerately behaviour may encourage a reduced capacity at bottlenecks. Second, technical devices to improve movement require space and reduce capacity.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. 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 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. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.