7.5 Technische Eigenschaften von Polymerwerkstoffen
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- 7 Bauwerkssicherheit (28)
- 7.5 Technische Eigenschaften von Polymerwerkstoffen (28)
- 5 Werkstofftechnik (4)
- 5.3 Polymere Verbundwerkstoffe (4)
- 6 Materialchemie (3)
- 6.6 Physik und chemische Analytik der Polymere (2)
- 2 Prozess- und Anlagensicherheit (1)
- 2.1 Sicherheit von Energieträgern (1)
- 5.5 Materialmodellierung (1)
- 6.1 Oberflächen- und Dünnschichtanalyse (1)
Polymeric membranes represent a low-cost, energy efficient solution for gas separation. Recently polymers of intrinsic microporosity (PIMs) have emerged as prestigious membrane materials featuring a large concentration of pores smaller than 1 nm, a BET surface area larger than 700 m2/g and high gas permeability and selectivity. Unusual chain structure combining rigid segments with sites of contortion gives rise to the intrinsic microporosity. However, this novel class of glassy polymers are prone to pronounced physical aging. The initial microporous structures approach a denser state via local small scale fluctuataions, leading to a dramatic reduction in the gas permeabilities. For the first time, dielectric relaxation spectroscopy with state-of-the-art high-resolution analyzers was employed to investigate three representative PIMs with a systematic change in chain rigidity: PIM-EA-TB 〉 PIM-1 〉 PIM-MDPH-TB. The molecular mobility, the charge transport and their response upon heating (aging) in the polymers were measured in a broad temperature range through isothermal frequency scans during different heating / cooling cycles. Multiple dielectric processes following Arrhenius behavior were observed for the investigated polymers. Local fluctuations, Maxwell-Wagner-Sillars (MWS) polarization and structural relaxation phenomena were discussed and attempted to be correlated with the structural features of PIMs. Moreover, all PIMs showed conductivity in the glassy state. The significant increase in the conductivity with increasing temperature far below the glass transition temperature of PIMs is explained in terms of the loosely packed microporous structure and the formation of local intermolecular agglomerates due to interaction of π-electrons in aromatic moieties of the polymer backbone.
Das EU Projekt TREEADS „A Holistic Fire Management Ecosystem for Prevention, Detection and Restoration of Environmental
Desasters” beschäftigt sich mit der Erforschung der drei Phasen „Prävention und Bereitschaft“, „Detektion und Reaktion“ und
„Aufforsten und Anpassen“ der Waldbrandverhütung. Im Projekt gibt es acht ausgewiesene Pilotregionen, in denen Deutschland
auch mit einer Pilotregion in Sachsen-Anhalt bzw. in Brandenburg vertreten ist. Unsere Arbeit auf Charakterisierung des Waldbodens und numerische Simulation wird vorgestellt.
Molecular orientation has a significant effect on the material properties of polymers. Preferential orientation of the microstructure (polymer chains or crystallites) in a specific direction or plane often enhances the material properties, especially if the high-strength covalent bonds are primarily exposed to loads instead of the weaker van der Waals bonds. However, the orientation-dependent microstructure and its mechanical behavior is in general already well understood by many scientific studies [1-3]. Isotropic materials are frequently required for an intrinsic material characterization without prevailing processing-induced properties, as is the case for Full Notch Creep Test (FNCT) [4] addressing environmental stress cracking (ESC) in high-density polyethylene (PE-HD) [5, 6]. Since ESC is one of the major limiting issues for long-term performance of PE-HD pipes and containers [7], which in contrast have a production-related preferential orientated microstructure due to extrusion or extrusion blow molding, it is important to additionally investigate the ESC resistance of such anisotropic microstructure.
Investigations of the slow crack growth (SCG) with respect to the molecular orientation generally obtain a factor of 1.2 up to 4.7 between crack growth perpendicular to the extrusion direction and crack growth parallel to the extrusion direction 8. Based on FNCT investigations with an aqueous detergent solution as environmental medium, hot pressed sheets with isotropic morphology are compared with extruded sheets from which specimens with different orientation angles are taken. However, the time to failure obtained by FNCT is also significantly influenced by the different cooling conditions under which the final morphology is formed. The tendency of the specimen to fail due to ESC is investigated as a function of environmental medium temperature. For a more detailed analysis of the affecting parameters in the manufacturing process, the ESC resistance is discussed considering the differences in crystallinity as revealed by thermal analysis.
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) composites usually demands intermediate-scale or full-scale testing. In this study a bench-scale test is presented as practicable and efficient method to assess the improvement in structural integrity of CFRP with different protective coatings during fire.
Bench-scale fire stability testing - Protective layers in carbon fibre reinforced polymer laminates
(2023)
Fire resistance testing of components made of carbon fibre reinforced polymers (CFRP) composites usually demands intermediate-scale or full-scale testing. In this study, a bench-scale test is presented as a practicable and efficient method to assess the improvement in structural integrity of CFRP with different protective interlayers during fire.
FR additives were incorporated during tanning process. The mode of action of an intumescent system and each component individually, was methodically investigated in a semi-finished leather. Vertical flammability test results showed that the investigated semi-finished leather satisfies the regulations of the Federal Aviation Administration; in addition, afterglow time is strong minimized and forced fire behavior pointed out an important reduction on smoke production.
The transfer of flame-retardant epoxy resin formulations to composites for structural and lightweight applications in the energy and transport sector can be complex and requires systematic investigation. Here, uncoated and silane-coated ammonium polyphosphate (APP, Si-APP) intumescent compounds are transferred to prepregs using a Bisphenol A diglycidyl ether (DGEBA) resin matrix to 0/90o bidirectional glass fibers with an aerial weight of 600 g/m2. Inorganic silicates (InSi) are added to improve the fire residues of the composites after combustion and the total amount of flame retardants in the resin formulations was 10% by weight. The prepregs' fiber volume content (FVC) is corroborated using in-process measurements and thermogravimetric analysis. This was found to be approximately 60% for the composites containing APP, which is ideal for load-bearing applications with high mechanical strength. However, the Si-APP containing prepregs showed an inconsistent FVC potentially due to interactions with the commercial sizing of the glass fibers. The composites subsequently prepared are analysed for potential filtration effects of the additives via SEM after immobilization in a cured resin and platinum sputtering. The inter-laminar shear strength and the mechanical strength of the composites are compared via three-point bending tests. Additionally, the fire performance of the composites is analysed using cone calorimetry. It was found there was minimal impact of the loading of the flame retardants on the delamination of the composites and the flexural strength. However, the high density of the glass fibers possibly results in a suppression of the mode of action of the flame retardants in the composites. Therefore, the fire residues of the composites are further compared using SEM, and the flame-retardant modes of action upon transfer are investigated.
The residual post-fire mechanical properties of fiber-reinforced epoxy composites are influenced by their fire residues after burning. This study uses intumescent/low-melting glass flame retardants to tailor fire residues in epoxy resin. Processibility of prepregs and their quality are analysed for transfer of the flame-retardant epoxy resins to layered glass-fiber reinforced composites. Minimal effects were found on the pre-fire flexural strengths of the composites due to low loading of the flame retardants. However, when transferred to glass-fiber reinforced composites, the fire residues diminish significantly. Further studies are required to improve theoretical and experimental estimations of the post-fire mechanics of the composites.
Natural Rubber Nanocomposites via Optimized Latex Premixing and Conventional Technical Processing
(2021)
Creation of highly functional materials and replacement of high amounts of conventional fillers are driving forces for the development of nanocomposites. Besides the type and properties of nanoparticles, their dispersing in the elastomeric matrix and the stability of this dispersion through all processing steps are the
main factors for the resulting performance of the produced material. Therefore, a preparation chain via latex premixing to a highly filled masterbatch, followed by conventional technical processing is to be developed.
Three types of carbon-based particles are characterized as such (SEM, Raman Spectroscopy, BET specific surface area) and in combination with natural rubber, as nanocomposites (TEM. Hardness, Abrasion resistance, Compression set, Cone calorimetry).
All of the studied particles lead to an improvement in the investigated mechanical properties, the extent of reinforcement depends strongly on the specific surface of the particle interacting with the elastomeric matrix in combination with their shape.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, by means of inelastic neutron scattering, the vibrational density of states (VDOS) and the molecular mobility were investigated for PIM-1, the prototypical polymer with intrinsic microporosity. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid).
The measured data show the characteristic low frequency excess contribution to the VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers.
Elastic fixed window scans were measured on a neutron backscattering spectrometer to have an overview about the molecular dynamics at a time scale of ca. 1 ns. The temperature dependence of the estimated mean squared displacement shows a step-like increase in the temperature range from 100 K to 250 K indicating the onset of some molecular mobility. The nature of this motional process was analyzed in detail by quasielastic neutron scattering combining Time-of-Flight and backscattering where the data are discussed with regard to both the q- and the temperature dependence.
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.
The full-notch creep test (FNCT) is a common method to evaluate the environmental stress cracking (ESC) behavior of high-density polyethylene (PE-HD) container materials . The test procedure as specified in ISO 16770 provides a comparative measure of the resistance against ESC using the time to failure of specimens mechanically loaded in a well-defined liquid environment. Since the craze-crack damage mechanism underlying the ESC process is associated with brittle failure, the occurrence of globally brittle fracture surfaces is a prerequisite to consider an FNCT measurement as representative for ESC . Therefore, an optical evaluation of FNCT fracture surfaces concerning their brittleness is essential. Due to the experimental setup, an inevitable increase of the true mechanical stress and the associated appearance of small ductile parts on fracture surfaces is induced in any case. Hence, an FNCT experiment is considered as 'valid', if the corresponding fracture surface is predominantly brittle . Based on laser scanning microscopy (LSM) height data of FNCT fracture surfaces , a universal and easy-to-use phenomenological criterion was developed to assess the validity of distinct FNCT experiments. This criterion is supposed to facilitate a quick evaluation of FNCT results in practical routine testing.
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.
Our approach includes the preparation of blends of preferably liquid-crystalline polyesters with Lignin, but also the synthesis of new polyesters with Lignin-related monomer units.
While most studies employ pulped Lignin directly, we first purified the Kraft Lignin by fractionation, followed by chemical modification of the terminal OH groups. Acetylation results in the reduction of glass transition temperatures (Tg) below 200°C, improved processability in the melt with complete melting of the Lignin sample, and higher thermostability.
These Lignin fractions were melt-mixed in a mini-twin-screw extruder with polyesters. The chemical structure of the polyesters was systematically varied between poly(ethylene terephthalate), (PET); poly(ethylene terephthalate-co-oxybenzoate), (PET/HBA); liquid crystalline polyesters with fully aromatic structure; and polyesters with Lignin-related monomers like ferulic and vanillic acid). The polymer influence on the blending behavior with Lignin was examined. SEM revealed phase-separated blends with partial compatibilization of the phases indicated by the shift of Tg’s. The influence of the polyester and the Lignin on decomposition and combustion was accessed by thermogravimetry (TGA), TGA-FTIR and pyrolysis-combustion flow calorimetry (PCFC) and compared to the decomposition of polyesters. The main focus was to achieve melt-spinnable blends for fibres with improved flame retardancy or as precursors for carbon fibers. Blends of Lignin fractions with the aromatic-aliphatic polyesters (here preferably PET/HBA) were successfully spun into fibers with lab-scale melt-spinning equipment. X-ray measurements revealed orientation of the fibers with Lignin. The E-moduli raised with increasing purity of the Lignin fractions (e.g., by removal of reducing sugars).
The structure of the polymer matrix determines the decomposition and combustion behavior of the blends with Lignin. Incorporation of aliphatic subunits reduces the amount of remaining char formed in TGA and PCFC from about 40-45 wt% for fully aromatic polyesters to 18-25 wt% for semiaromatic polyesters (at almost comparable carbon content in the polymer), while the maximum temperature of combustion decreased from 480-530°C for the former to 410-465°C for the latter. Lignin fractionation and acetylation yields samples with high char content (36 wt%) and extremely low heat release capacity (80-90 kJ/gK) with combustion maximum temperature at 405°C. Lignin/ PET/HBA blends combine the low HRC with intermediate char and offer interesting opportunities for polyester fibers with improved flame retardancy without adding P-containing FRs.
The flame retardancy behavior was explored by limiting oxygen index measurements on injection-molded parts and fibers.
A central challenge to ensure the sustainable production and use of nanotechnologies is to understand and effectively control the risks along the industrial innovation value chain. Knowledge about nanotechnology processes and nanosafety issues (hazards, fate, risk...) is growing rapidly but the effective use of this knowledge for risk management by market actors is lagging behind.
EC4SafeNano (European Centre for Risk Management and Safe Innovation in Nanomaterials and Nanotechnologies) promotes a harmonized vision of expertise in risk assessment and management for the public and private sectors to enable the safe development and commercialization of nanotechnology.
EC4SafeNano is operated together by major European risk institutes with the support of numerous associated partners, gathering all stakeholders involved in Nanomaterials and Nanotechnologies (regulators, industry, society, research, service providers...).
In a case study the surface chemical transformations upon 2 different ageing procedures (long-term UV irradiation or swimming pool water) of a representative set of titanium dioxide nanoparticles has been investigated. The materials have been analyzed by various analytical techniques. Each method addresses different aspects of the complex endpoint surface chemistry. The multi technique approach allows evaluation of the capabilities and limitations of the applied methods regarding their suitability to address the endpoint surface chemistry and their sensitivity to identify even small surface chemical transformations.
Results:
- To obtain a comprehensive picture, it is insufficient to concentrate on a single analysis technique.
- By using time-of-flight secondary ion mass spectrometry (ToF-SIMS) in combination with principal component analysis (PCA) it was possible to identify even subtle changes in the surface chemistry of the investigated materials.
- A general trend that was observed for the UV-aged samples is the decrease of organic material on the nanomaterial surface.
This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 723623.
Behälter aus hochdichtem Polyethylen (PE-HD) werden zur Lagerung und für den Transport von Kraftstoffen eingesetzt. Beim Kontakt beider Medien diffundiert der Kraftstoff in das Polymer, erhöht dessen Volumen und Duktilität und ändert damit das Fließverhalten des Polymers unter Zugbelastung. Zudem weist PE-HD in Luft im verstreckten Bereich das sogenannte strain-whitening (Lichtstreuung) auf, während in Diesel gelagertes PE-HD optisch transparent wird. Zur Untersuchung dieses Phänomens wurden ortsaufgelöste Röntgenrefraktion und –diffraktion (Topographie) eingesetzt. Aus Sicht der molekularen Struktur (Diffraktion) weisen die beiden Probentypen keine Unterschiede auf: im verstreckten Bereich liegt eine „Fasertextur“ der Polymerketten in Belastungsrichtung vor, im unverstreckten Bereich nahezu ideale Isotropie. Die für mikroskopische Strukturen empfindliche Röntgenrefraktion zeigt außerdem für die Probe in Luft im verstreckten Bereich eine ausgeprägte Orientierung von Grenzflächen in Zugrichtung, während die in Diesel gelagerte Probe keine Grenzflächen zeigt. In Analogie zum optischen Verhalten bewirken die ähnlichen Brechungsindizes beider Medien im Röntgenbereich, dass eindiffundierter Diesel als Immersionsflüssigkeit die Brechungseigenschaften herabsetzt.
Polyesters with DOPO substituents can be successfully synthesized with 10-[2,5-Bis(2-hydroxyethoxy)phenyl]-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ-glycolether) and DOPO-substituted dimethyl succinate (PIta). These polyester materials show an effective flame retardancy which can be fine-tuned by the chemical structure of the polyester backbone.
Fire resistance of fiber-reinforced polymers (FRPs) has been an important area of research for many years since FRPs are mainly used in the transportation and construction sectors. This study presents the fire behavior, and mechanical performance between the flame retarded pure epoxy resin and flame retarded glass-fiber composites before, during, and after a fire event. This enables a deeper understanding of the transferability of flame retardants on composite materials.
This study presents the processability, fire behavior, and mechanical performance between the flame retarded pure epoxy resin and flame retarded glass-fiber-reinforced plastic before, during, and after a fire event. This enables a deeper understanding of the transferability of flame retardants, modes of action, char enhancement, and flame inhibition on composite materials
The influence of pressure sensitive adhesive (PSA) tapes as adhesive layers on the burning behaviour of bonded materials has been investigated. Single-sided tapes as an outer connection between construction materials have large influence on flammability, flame spread and fire resistance. In contrast, double sided tapes only take a small impact on the flammability but can drasticly change the burning behaviour in developing fires.
Brände zerstören immer wieder wichtige Kulturgüter und gefährden nationales Kulturerbe. Das Projekt BRAWA erarbeitet neue Strategien und innovative Technologien, um die Brandsicherheit historischer Gebäude zu erhöhen. Dabei basiert das Konzept auf der Vernetzung von Sensoren, die bereits beim Auftreten bestimmter Gase in der Frühphase der Brandentstehung Alarm auslösen. Durch ein neuartiges Helferkonzept soll eine frühe Branderkennung und -bekämpfung ermöglicht werden.
A promising approach for the further improvement of fire detection techniques is the inclusion of fire gases in the characteristics used to detect a fire. A screening of sample materials representative for common first burning items and their gas release under different ignition conditions was performed to gain an overview of possible target gas candidates. Different fire scenarios were investigated to evaluate fire gases produced in early stages of fire development, their time of appearance and concentration development using the vitiated mass loss calorimeter and a heating plate setup in the single burning item test chamber.
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.
A commercially available bio epoxy resin with kenaf fibers and halogen free inorganic and organic flame retardants, respectively, is investigated concerning its thermal stability and fire performance. Particular attention has been paid to the difference of short fibers, fiber mats and woven
materials.
Multifunctional Graphene in Flame Retarded Polybutadiene/ Chloroprene/ Carbon Black Composites
(2021)
Multilayer graphene is investigated as a multifunctional nanofiller to polybutadiene/ chloroprene rubbers (BR/CR) that partially substitutes carbon black (CB) and aluminum trihydroxide (ATH). Loadings of only 3 parts per hundred rubber (phr) MLG replaced 15 phr of CB and/or 3 phr of ATH in BR/CR nanocomposites. Mechanical and fire behavior were investigated, and results point to improved rheological, curing and mechanical properties of MLG-containing rubber composites.
Thermal runaway investigations were performed by subjecting single and double NMC pouch cells to thermal abuse condition inside an air-tight reactor vessel with an internal volume of 100 dm³. The study was divided into two series. The findings revealed the thermal runaway-induced explosion in the cells results in a rate of temperature increase greater than 10 K/s. The highest gaseous production was achieved at a range of 90 – 100% SOC and higher battery capacities 0.79 L/Wh (Series 1, 10 Ah cell) and 0.87 L/Wh (Series 2, 32 Ah cell). The investigation showed between 25 m³ and 84 m³ of explosible gas mixture could be released from electric vehicles of nominal useable electrical energy from 32 kWh up to 108 kWh at thermal runaway. It was also found that, the release of these explosible gases could undergo a secondary explosion.