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Flame Retardants for Polymeric Materials
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Flame Retardants for Polymeric Materials

A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Advanced Composites".

Deadline for manuscript submissions: closed (31 October 2021) | Viewed by 20190

Special Issue Editors

Dr. Vera Realinho

E-Mail Website
Guest Editor
Department of Materials Science and Engineering, School of Industrial, Aerospace and Audiovisual Engineering (ESEIAAT), Universitat Politècnica de Catalunya (UPC BarcelonaTech), Terrassa Campus, Building TR5. C. Colom 11, E-08222 Terrassa, Barcelona, Spain
Interests: polymer clay nanocomposites; nanocomposite foams; multifunctional materials; flame retardancy of polymers
Special Issues, Collections and Topics in MDPI journals
Dr. Laia Haurie

E-Mail Website
Guest Editor
Department of Architectural Technology, Barcelona School of Building Construction (EPSEB), Universitat Politècnica de Catalunya (UPC BarcelonaTech), Av. Doctor Marañon 44, 08028 Barcelona, Spain
Interests: fire reaction and fire resistance of building materials; bio-based materials; flame retardancy of wood and lignocellulosic materials
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Flame retardants have been developed and widely used to reduce the inherent high flammability of synthetic and/or natural-based polymers. They play an important role in the fire performance of such materials used in a broad range of applications, such as in textiles, coatings, foams, civil infrastructures, and electronic and electric devices, among others.

The development of novel efficient and environmentally-friendly flame-retardant additives that can promote an optimal fire and mechanical performances has attracted a great deal of interest in recent years. For that, different approaches such as flame retardants’ surface functionalization and/or micro-encapsulation, polymers’ chemical modification, polymer blends, and/or the use of compatibilizers have been employed. Despite the great progress achieved of late, further research on the development of novel flame-retardant polymers and biopolymers, new strategies for flame retardancy, and the development of new green flame retardants with high performances and environmental sustainability is continually underway.

This Special Issue, entitled “Flame Retardants for Polymeric Materials” aims to provide an excellent opportunity to publish your latest advances in these research fields. Full papers, review articles, and communications are all welcome.

Dr. Vera Realinho
Dr. Laia Haurie
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2600 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • flame retardancy
  • flame retardants
  • bio-flame retardants
  • thermoplastic and thermoset polymers
  • bio-based materials
  • mechanical properties
  • compatibilization
  • environmental sustainability

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Published Papers (6 papers)

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Research

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19 pages, 7532 KiB  
Article
Characterization and Properties of Water-Blown Rigid Polyurethane Foams Reinforced with Silane-Modified Nanosepiolites Functionalized with Graphite
by Mercedes Santiago-Calvo, María Carracedo-Pérez, María Luisa Puertas, Antonio Esteban-Cubillo, Julio Santaren, Fernando Villafañe and Miguel-Ángel Rodríguez-Pérez
Materials 2022, 15(1), 381; https://doi.org/10.3390/ma15010381 - 5 Jan 2022
Cited by 5 | Viewed by 3316
Abstract
In the present study, a promising flame retardant consisting of 80 wt% silane-modified nanosepiolites functionalized with 20 wt% graphite (SFG) is used to obtain a synergistic effect principally focussed on the thermal stability of water-blown rigid polyurethane (RPU) foams. Density, microcellular structure, thermal [...] Read more.
In the present study, a promising flame retardant consisting of 80 wt% silane-modified nanosepiolites functionalized with 20 wt% graphite (SFG) is used to obtain a synergistic effect principally focussed on the thermal stability of water-blown rigid polyurethane (RPU) foams. Density, microcellular structure, thermal stability and thermal conductivity are examined for RPU foams reinforced with different contents of SFG (0, as reference material, 2, 4 and 6 wt%). The sample with 6 wt% SFG presents a slightly thermal stability improvement, although its cellular structure is deteriorated in comparison with the reference material. Furthermore, the influence of SFG particles on chemical reactions during the foaming process is studied by FTIR spectroscopy. The information obtained from the chemical reactions and from isocyanate consumption is used to optimize the formulation of the foam with 6 wt% SFG. Additionally, in order to determine the effects of functionalization on SFG, foams containing only silane-modified nanosepiolites, only graphite, or silane-modified nanosepiolites and graphite added separately are studied here as well. In conclusion, the inclusion of SFG in RPU foams allows the best performance to be achieved. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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13 pages, 6886 KiB  
Article
Graphene Nanoplatelets Hybrid Flame Retardant Containing Ionic Liquid and Ammonium Polyphosphate for Modified Bismaleimide Resin: Excellent Flame Retardancy, Thermal Stability, Water Resistance and Unique Dielectric Properties
by Yan Wang, Xining Jia, Hui Shi, Jianwei Hao, Hongqiang Qu and Jingyu Wang
Materials 2021, 14(21), 6406; https://doi.org/10.3390/ma14216406 - 26 Oct 2021
Cited by 8 | Viewed by 2138
Abstract
To achieve the requirements of modified bismaleimide resin composites in electronic industry and high energy storage devices, flame retardancy, water resistance and dielectric properties must be improved. Hence, a highly efficient multifunctional graphene nanoplatelets hybrid flame retardant is prepared by ionic liquid graphite [...] Read more.
To achieve the requirements of modified bismaleimide resin composites in electronic industry and high energy storage devices, flame retardancy, water resistance and dielectric properties must be improved. Hence, a highly efficient multifunctional graphene nanoplatelets hybrid flame retardant is prepared by ionic liquid graphite and ammonium polyphosphate. The preparation processes of the flame retardants are simple, low energy consumption and follow the green chemical concept of 100% utilization of raw materials, compared with chemical stripping. The bismaleimide resin containing 10 wt.% of the flame retardant show good flame retardancy, resulting in the limiting oxygen index increases to above 43%, and the peak heat release rate, total heat release and total smoke release decrease by 41.8%, 47.8% and 52.3%, respectively. After soaking, mass loss percentage of the modified bismaleimide resin only decreases by 0.96%, the dielectric constant of the composite increases by 39.4%, and the dielectric loss decreases with the increase of frequency. The hybrid flame retardants show multifunctional effect in the modified bismaleimide resin, due to the physical barrier, the chemical char-formation, hydrophobicity and strong conductivity attributed to co-work of Graphene nanoplatelets, ammonium polyphosphate and ionic liquid. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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14 pages, 3004 KiB  
Article
Changes in Human Erythrocyte Exposed to Organophosphate Flame Retardants: Tris(2-chloroethyl) Phosphate and Tris(1-chloro-2-propyl) Phosphate
by Bożena Bukowska
Materials 2021, 14(13), 3675; https://doi.org/10.3390/ma14133675 - 1 Jul 2021
Cited by 5 | Viewed by 2797
Abstract
Tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCPP) are the main representatives of organophosphate flame retardants (OPFRs). The exposure of humans to OPFRs present in air, water, and food leads to their occurrence in the circulation. Thus far, no report has been published about [...] Read more.
Tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCPP) are the main representatives of organophosphate flame retardants (OPFRs). The exposure of humans to OPFRs present in air, water, and food leads to their occurrence in the circulation. Thus far, no report has been published about the influence of these retardants on non-nucleated cells like mature erythrocytes. Therefore, the impact of TCEP and TCPP (in concentrations determined in human blood as well as potentially present in the human body after intoxication) on human erythrocytes was evaluated. In this study, the effect of TCEP and TCPP on the levels of methemoglobin, reduced glutathione (GHS), and reactive oxygen species (ROS), as well as the activity of antioxidative enzymes, was assessed. Moreover, morphological, hemolytic, and apoptotic alterations in red blood cells were examined. Erythrocytes were incubated for 24 h with retardants in concentrations ranging from 0.001 to 1000 μg/mL. This study has revealed that the tested flame retardants only in very high concentrations disturbed redox balance; increased ROS and methemoglobin levels; and induced morphological changes, hemolysis, and eryptosis in the studied cells. The tested compounds have not changed the activity of the antioxidative system in erythrocytes. TCPP exhibited a stronger oxidative, eryptotic, and hemolytic potential than TCEP in human red blood cells. Comparison of these findings with hitherto published data confirms a much lower toxicity of OPFRs in comparison with brominated flame retardants. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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10 pages, 2037 KiB  
Article
α-Aminophosphonate Derivatives for Enhanced Flame Retardant Properties in Epoxy Resin
by Melissa K. Stanfield, Jeronimo Carrascal, Luke C. Henderson and Daniel J. Eyckens
Materials 2021, 14(12), 3230; https://doi.org/10.3390/ma14123230 - 11 Jun 2021
Cited by 6 | Viewed by 2286
Abstract
This work demonstrates the introduction of various α-aminophosphonate compounds to an epoxy resin system, thereby improving flame retardance properties. The α-aminophosphonate scaffold allows for covalent incorporation (via the secondary amine) of the compounds into the polymer network. This work explores the synergistic effect [...] Read more.
This work demonstrates the introduction of various α-aminophosphonate compounds to an epoxy resin system, thereby improving flame retardance properties. The α-aminophosphonate scaffold allows for covalent incorporation (via the secondary amine) of the compounds into the polymer network. This work explores the synergistic effect of phosphorus and halogens (such as fluorine) to improve flame retardancy. The compounds were all prepared and isolated in analytical purity and in good yield (95%). Epoxy samples were prepared, individually incorporating each compound. Thermogravimetric analysis showed an increased char yield, indicating an improved thermal resistance (with respect to the control sample). Limiting oxygen index for the control polymer was 28.0% ± 0.31% and it increased to 34.6% ± 0.33% for the fluorinated derivative. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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14 pages, 4479 KiB  
Article
An Extremely Efficient Silylated Benzensulfonate Flame Retardant for Polycarbonate
by Xiaodong Lu, Qiang Yao, Weihong Cao and Tianbo Tang
Materials 2020, 13(16), 3550; https://doi.org/10.3390/ma13163550 - 12 Aug 2020
Cited by 14 | Viewed by 3143
Abstract
An extremely efficient flame retardant with low water solubility has been developed for bisphenol-A based polycarbonate. Potassium trimethylsilylbenzenesulfonate (KTSS) combining trimethylsilyl and sulfonate groups in its molecule is 7 times less water soluble and 5 times more effective in flame retardancy than potassium [...] Read more.
An extremely efficient flame retardant with low water solubility has been developed for bisphenol-A based polycarbonate. Potassium trimethylsilylbenzenesulfonate (KTSS) combining trimethylsilyl and sulfonate groups in its molecule is 7 times less water soluble and 5 times more effective in flame retardancy than potassium benzenesulfonylbenzenesulfonate (KSS), the commercial workhorse for polycarbonate (PC). At a loading of 0.02%, KTSS enables PC to achieve a solid UL-94 V0 rating and a limiting oxygen index (LOI) value of 34.4%, representing an increase of 8.5 units. The extremely high efficiency of KTSS stems from its great migration ability to the burning polymer surface facilitated by trimethylsilyl group, its timely release of active alkaline species that promote the charring process of PC, and the stabilization of char by silicon. In addition to the exceptional flame retardancy, PC/KTSS retains excellent physical properties of PC. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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Review

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29 pages, 4233 KiB  
Review
Flame Retardancy of Biobased Composites—Research Development
by Anna Sienkiewicz and Piotr Czub
Materials 2020, 13(22), 5253; https://doi.org/10.3390/ma13225253 - 20 Nov 2020
Cited by 42 | Viewed by 5296
Abstract
Due to the thermal and fire sensitivity of polymer bio-composite materials, especially in the case of plant-based fillers applied for them, next to intensive research on the better mechanical performance of composites, it is extremely important to improve their reaction to fire. This [...] Read more.
Due to the thermal and fire sensitivity of polymer bio-composite materials, especially in the case of plant-based fillers applied for them, next to intensive research on the better mechanical performance of composites, it is extremely important to improve their reaction to fire. This is necessary due to the current widespread practical use of bio-based composites. The first part of this work relates to an overview of the most commonly used techniques and different approaches towards the increasing the fire resistance of petrochemical-based polymeric materials. The next few sections present commonly used methods of reducing the flammability of polymers and characterize the most frequently used compounds. It is highlighted that despite adverse health effects in animals and humans, some of mentioned fire retardants (such as halogenated organic derivatives e.g., hexabromocyclododecane, polybrominated diphenyl ether) are unfortunately also still in use, even for bio-composite materials. The most recent studies related to the development of the flame retardation of polymeric materials are then summarized. Particular attention is paid to the issue of flame retardation of bio-based polymer composites and the specifics of reducing the flammability of these materials. Strategies for retarding composites are discussed on examples of particular bio-polymers (such as: polylactide, polyhydroxyalkanoates or polyamide-11), as well as polymers obtained on the basis of natural raw materials (e.g., bio-based polyurethanes or bio-based epoxies). The advantages and disadvantages of these strategies, as well as the flame retardants used in them, are highlighted. Full article
(This article belongs to the Special Issue Flame Retardants for Polymeric Materials)
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