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Several investigation groups have studied the flame-retardancy modes of action and properties of epoxy resins in the past; nevertheless, the selection of suitable flame retardants for epoxy resins remains challenging, and the transfer to fiber composites is difficult. The addition of flame retardants and glass fibers (GFs) to a polymeric system in a fire scenario changes the polymer's pyrolytic path and burning characteristics, reduces the heat released in the combustion, and suppresses the modes of action in the condensed and gas phase. In this study, the thermal analysis, flammability, fire behavior, residue analysis, fire stability, and quantification of modes of action of three different systems with three halogen-free flame retardants (melamine polyphosphate (MPP), ammonium polyphosphate (APP), and silane ammonium polyphosphate (SiAPP)) and three different types of GFs (unidirectional (UD), bidirectional (BD), and woven roving (WR)) will be compared with pure epoxy resin as a reference.
Revolutionizing our polymer industry for adaption to a sustainable carbon circular economy has become one of today’s most demanding challenges. Exploiting renewable resources to replace fossil-fuel—based plastics with biopolymers such as poly(lactic acid) (PLA) is inevitable while using waste streams as a raw material resource at least is promising. When it comes to using PLA as technical polymer, its high flammability must be addressed by flame retardants compatible with the thermoplastic processing of PLA and its compostability. This study proposes microalgae enriched with phosphorus from wastewater (P-Algae) as an elegant way towards a kind of sustainable organophosphorus flame retardant. The concept is demonstrated by investigating the processing, pyrolysis, flammability, and fire behavior of PLA/P-Algae, while varying the P-Algae content and comparing P-Algae with four alternative bio-fillers (phosphorylated lignin, biochar, thermally treated sewage sludge, and metal phytate) with different P-contents as meaningful benchmarks.
Efficient flame retardancy is often achieved only when applying synergistic multicomponent systems. Flame retardants are combined or used together with adjuvants or synergists to enhance their efficiency, reduce the amount required, or reduce the costs; fibers and fillers contribute to fire properties crucially. Although the main flame-retardant modes of action are known, the detailed scientific understanding usually falls short, when it comes to complex synergistic multicomponent systems, the important tiny optimizations, or quantifying in terms of specific fire properties. This paper tries to illuminate the concept of synergistic flame retardants. The need for the multicomponent approach and the main phenomena are described. Thought-provoking impulses are delivered on how the understanding of multicomponent systems promotes the evidence-based development of future flame retardant polymeric materials. Multicomponent systems are discussed in their capacity as general powerful strategy for achieving and optimizing flame retardant polymeric materials.
This paper is based mainly on the overall conclusions and concrete results of several projects performed in the group of the author. Thanks to my (former) students and co-operation partners in these projects. Thanks for financing to DFG (Scha 730/8-1 Scha 730/8-2, Br 3376/1-1, Scha 730/19-1), AiF IGF (438 ZN, 17833N/2, 19078 N/2), and BMBF (03X0111C, 01DN16040).
Replacing antimony trioxide (ATO) in flame retardant formulations is an urgent task due to its toxicity. There are indications that calcium hypophosphite (CaP) may be a promising replacement. This study investigates the decomposition, fire behavior, and smoke release of brominated flame-retarded acrylonitrile butadiene styrene (ABS) under various fire scenarios like ignition, developing fire and smoldering, while replacing ATO with CaP and CaP/talc. Adding 4 wt.-% of talc to CaP formulations showed beneficial effects on flammability due to changes in the viscosity and barrier properties. Synergism between 8 wt.-% talc and CaP improved the protective layer in the developing fire scenario, resulting in a ∼60 % decrease in the peak of heat release rate and reduction of ∼21 % in total smoke production (ref. ABS+Br+ATO). With a conventional index of toxicity (CIT) of below 0.75, ABS+Br+CaP passes the highest requirements according to EN 45545-2. Overall, the CaP/talc materials improve flame retardancy, show less smoke emission under forced flaming conditions, and prevent chronic intoxication and environmental pollution through smoke particles contaminated with antimony.
Combining buffing leather fibers from industrial waste streams with ammonium polyphosphate and bentonite clay is proposed as a flame-retardant additive for polypropylene. The paper addresses how they can be processed into attractive composites with the desired mechanical properties. Buffing leather fibers function as a multifunctional bio-filler and as a synergist for the flame retardant, resulting in fire retardancy successful enough to increase the oxygen index (LOI) by up to 7 vol.-% and to achieve a V0 UL 94 classification. Impressively reduced heat release rates are obtained in the cone calorimeter at 50 kW/m2 irradiation; for instance, the maximum average rate heat evolved (MARHE) drops from 765 to below 200 kW m 2. The synergistic effects are quantified and shown to be very strong for LOI and MARHE. This work opens the door to use waste buffing leather fibers as a promising multifunctional and synergistic bio-filler.
To ensure fire safety, polymers are filled with flame retardants and smoke suppressants. To meet the highest requirements, it is essential to understand the decomposition of those polymeric materials. This study reveals interactions between polymer, smoke suppressants, and flame retardants, and discusses their impact on the materials’ flame retardancy, smoke emission, smoke toxicity, and particle emission in conventional loadings to provide deeper general understanding. Low melting oxide glass, melem, spherical silica, sepiolite, melamine polyphosphate, and boehmite in an aluminum diethylphosphinate flame-retarded polyamide 6.6 were investigated. All smoke suppressants improve the protective layer and act as an adjuvant. Silica and melem performed best under forced flaming conditions. Spherical silica reduces the peak of heat release rate by 39% and the total heat evolved by 14%, whereas 10 wt% melem lowers the total smoke production by 41%. Melem alters the mode of action of aluminum diethylphosphinate from gas to more condensed phase activity. This change reduces flame inhibition and hence smoke toxicity, but further improves the protective layer due to charring reactions in the decomposition mechanism. In addition, the sizes of the smoke particles decrease because of the prolonged time in the pyrolytic zone. This study highlights that interactions between polymer, flame retardants, and smoke suppressants can significantly determine the smoking and burning behavior.
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.
Short overview is given of BAM's research within the topic "Flame Retardancy of Polymeric Materials". Fire science is identified as a crucial compentenc of BAM following our mission "Safety in Technology and Chemistry". In the area of polymers we work interdisciplinary, in the dimensions from nm to 2m, and we love to combine experiment and simulation. Multimethodical examples are given to describe the burning phenomena and flame-retardant modes of action. Further some examples are presented for tailored bench-scale fire testing and assessing concepts. Our goal is to provide the fundaments for a evidenced-based development of future materials.
Only the nano-scaled structure of the nanocomposite and the dispersion of nanoparticles within the polymer matrix harbor multifunctional potential including superior fire retardancy. Thus, this chapter focuses on the dispersion of nanoplates, based mainly on studies of layered silicates and graphene/graphene-related nanoplates. The nanostructure and properties of the nanocomposites are dependent mainly on thermodynamic and kinetic factors during preparation. Improving nano-dispersion often directly improves flame retardancy. Therefore, the modification of the nanoplates as well as the preparation of nanocomposites becomes very important to control this dispersion. The dispersion of nanoplates functions as a prerequisite for the formation of an efficient protective layer, changing the melt flow and dripping behavior, or the improvement of the char properties.
Main message: Sustainability, or in other words, exploiting environmental conservation for the economic welfare and prosperity for all, would revolutionise the plastics industry were it to become predominant practice as a linear, fossil-fuel–based economy is switched to a carbon circular economy. Food for though is given by dint of a critical overview of the current trends in sustainable flame-retardant polymeric materials.
Introduction:
Transforming the plastics industry into a carbon circular economy over the next 30 years requires an immediate revolution entailing the development of cutting-edge materials and the planning of future industrial production plants. Hence, the innovative field of flame-retardant polymeric materials should lend its strength to drive this challenge. Visionary solutions are proposed to inspire us, while the implementation of economically feasible concepts can take us forward into the future.
Experimental The synthesis, processing, polymer analysis, thermal analysis, and investigation of fire behaviour from our own research are performed according to the state of the art, mostly in accordance with the pertinent ISO standards. Indeed, some of our equipment is part of the accredited lab; for the other methods we fulfil equivalent quality standards in terms of maintenance, calibration, participation in round robins, etc. Work steps such as the synthesis or preparation of new materials are usually outsourced or done with partners that have the relevant core competence. The talk also presents examples from other groups whose experimental is described in the corresponding scientific papers.
Results and Discussion An overview of current trends towards producing sustainable, flame-retardant polymeric materials is presented, using examples from the literature and by sketching our own projects performed in recent years. The examples are structured along a common theme leading from the use of old and new natural materials with some intrinsic flame retardancy, via flame-retardant biopolymers and biocomposites, to using renewable sources for flame retardants with the objective of exploiting natural sources available as industrial waste streams. Natural flame retardants and adjuvants are highlighted, although the status of most may be assessed as merely motivating our vision. Nevertheless, there are natural material streams finding their way into polymer mass production as fillers, adjuvants, polymers, or renewable educt sources. Natural substances originating from industrial waste streams open the door to sustainable solutions, because they are often available at low cost and avoid competition for land with farming or virgin forests. Aside from this main topic, remarks will address the recycling of flame-retarded polymeric materials; vitrimers are mentioned as a potential material for recyclable thermosets. At the end of the day, only convincing property profiles will prevail both for exploiting renewable sources and circular design, including cost effectiveness, sufficient availability, consistent quality, processibility, mechanical properties, and flame retardancy. However, sustainability must not be merely tolerated as an additional demand, but should instead be recognized as a solution, because sustainability aspires to ensure our economic welfare now and in the future.
Acknowledgement:
The examples shown from own project were supported by funding grants: BMBF WTZ: 01DN16040, DFG Scha 730/19-1, VW-Stiftung: Experiment No: 97437, DFG Scha 730/20-1, BMBF KMU Innovativ 031B1289B.