Flame-Retardant Polymer Composites II

A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Composites and Nanocomposites".

Deadline for manuscript submissions: 31 December 2024 | Viewed by 9431

Special Issue Editors


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Guest Editor
IMT Mines Alès, 30100 Alès, France
Interests: flame retardancy; polymers; mineral fillers; additive manufacturing; polymer composites
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Guest Editor
IMT Mines Ales, Centre des Matériaux des Mines d’Alès (C2MA), 6 Avenue de Clavières, CEDEX, 30319 Alès, France
Interests: flame retardancy; fire behavior; thermal degradation of polymers
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Polymer composites are extensively employed in various industrial applications, such as transport, wind energy production, aerospace, defense and electronics, among others. Moreover, these materials are often associated with fire hazards, limiting their utilization in some industries, such as transport and defense. Therefore, the flammability of composites must be evaluated and, if required, flame retardants, nanofillers, inorganic particles or other additives should be employed in order to enhance their fire behavior.

Flame-retarded polymer composites can be obtained via various processing routes, such as injection molding, thermo compression or additive manufacturing (AM). Recently, the utilization of AM has expanded the applicative potential of polymer composites because it enables the production of extremely complex parts. However, some composites are not suitable for AM due to the specificities of these technologies. Furthermore, some additives are prone to affecting the functional properties of the composites, regardless of the processing route. Thus, composites and additives should be carefully selected in order to avoid problems during processing, and effective flame-retardant systems should be chosen or developed in order to meet the requirements of the new applications.

Hence, this Special Issue aims to identify the most recent scientific advancements in the flame retardancy of polymer composites processed through various routes, as well developments in the characterization of the flame retardancy mechanism.

Dr. Marcos Batistella
Prof. Dr. Laurent Ferry
Guest Editors

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Keywords

  • polymer composites
  • fire behavior
  • additive manufacturing
  • injection molding
  • thermocompression
  • flame retardancy
  • inorganic fillers

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Published Papers (8 papers)

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Research

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18 pages, 6151 KiB  
Article
Enhancing the Fire Resistance of Ablative Materials: Role of the Polymeric Matrix and Silicon Carbide Reinforcement
by Juana Abenojar, Sara López de Armentia and Miguel Angel Martínez
Polymers 2024, 16(17), 2454; https://doi.org/10.3390/polym16172454 - 29 Aug 2024
Viewed by 532
Abstract
The primary characteristic of ablative materials is their fire resistance. This study explored the development of cost-effective ablative materials formed into application-specific shapes by using a polymer matrix reinforced with ceramic powder. A thermoplastic (polypropylene; PP) and a thermoset (polyester; UPE) matrix were [...] Read more.
The primary characteristic of ablative materials is their fire resistance. This study explored the development of cost-effective ablative materials formed into application-specific shapes by using a polymer matrix reinforced with ceramic powder. A thermoplastic (polypropylene; PP) and a thermoset (polyester; UPE) matrix were used to manufacture ablative materials with 50 wt% silicon carbide (SiC) particles. The reference composites (50 wt% SiC) were compared to those with 1 and 3 wt% short glass fibers (0.5 mm length) and to composites using a 1 and 3 wt% glass fiber mesh. Fire resistance was tested using a butane flame (900 °C) and by measuring the transmitted heat with a thermocouple. Results showed that the type of polymer matrix (PP or UPE) did not influence fire resistance. Composites with short glass fibers had a fire-resistance time of 100 s, while those with glass fiber mesh tripled this resistance time. The novelty of this work lies in the exploration of a specific type of material with unique percentages of SiC not previously studied. The aim is to develop a low-cost coating for industrial warehouses that has improved fire-protective properties, maintains lower temperatures, and enhances the wear and impact resistance. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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17 pages, 5685 KiB  
Article
Harnessing Enhanced Flame Retardancy in Rigid Polyurethane Composite Foams through Hemp Seed Oil-Derived Natural Fillers
by Mansi Ahir, Chandan Bodhak and Ram K. Gupta
Polymers 2024, 16(11), 1584; https://doi.org/10.3390/polym16111584 - 3 Jun 2024
Cited by 2 | Viewed by 604
Abstract
Over the past few decades, polymer composites have received significant interest and become protagonists due to their enhanced properties and wide range of applications. Herein, we examined the impact of filler and flame retardants in hemp seed oil-based rigid polyurethane foam (RPUF) composites’ [...] Read more.
Over the past few decades, polymer composites have received significant interest and become protagonists due to their enhanced properties and wide range of applications. Herein, we examined the impact of filler and flame retardants in hemp seed oil-based rigid polyurethane foam (RPUF) composites’ performance. Firstly, the hemp seed oil (HSO) was converted to a corresponding epoxy analog, followed by a ring-opening reaction to synthesize hemp bio-polyols. The hemp polyol was then reacted with diisocyanate in the presence of commercial polyols and other foaming components to produce RPUF in a single step. In addition, different fillers like microcrystalline cellulose, alkaline lignin, titanium dioxide, and melamine (as a flame retardant) were used in different wt.% ratios to fabricate composite foam. The mechanical characteristics, thermal degradation behavior, cellular morphology, apparent density, flammability, and closed-cell contents of the generated composite foams were examined. An initial screening of different fillers revealed that microcrystalline cellulose significantly improves the mechanical strength up to 318 kPa. The effect of melamine as a flame retardant in composite foam was also examined, which shows the highest compression strength of 447 kPa. Significantly better anti-flaming qualities than those of neat foam based on HSO have been reflected using 22.15 wt.% of melamine, with the lowest burning time of 4.1 s and weight loss of 1.88 wt.%. All the composite foams showed about 90% closed-cell content. The present work illustrates the assembly of a filler-based polyurethane foam composite with anti-flaming properties from bio-based feedstocks with high-performance applications. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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21 pages, 19175 KiB  
Article
Synthesis of a Novel P/N-Triazine-Containing Ring Flame Retardant and Its Application in Epoxy Resin
by Yi Yu, Junlei Chen, Anxin Ding, Changzeng Wang, Yunfei Wang and Ling Yang
Polymers 2024, 16(7), 871; https://doi.org/10.3390/polym16070871 - 22 Mar 2024
Viewed by 1075
Abstract
To meet the environmental protection and flame retardancy requirements for epoxy resins (EPs) in certain fields, in this study, a novel triazine-ring-containing DOPO-derived compound (VDPD), derived from vanillin, 2,4-Diamino-6-phenyl-1,3,5-triazine, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), was synthesized using a one-pot method. Flame-retardant epoxy resin (FREP) was [...] Read more.
To meet the environmental protection and flame retardancy requirements for epoxy resins (EPs) in certain fields, in this study, a novel triazine-ring-containing DOPO-derived compound (VDPD), derived from vanillin, 2,4-Diamino-6-phenyl-1,3,5-triazine, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), was synthesized using a one-pot method. Flame-retardant epoxy resin (FREP) was prepared by adding various ratios of VDPD to EP and curing with 4,4-diaminodiphenylmethane (DDM). The curing behavior, thermal stability, mechanical properties, and flame-retardant properties of the FREP were examined in various tests. According to the results, when the amount of VDPD added to the EP increased, the glass transition temperature of the FREP decreased linearly, and the flame-retardant properties gradually improved. With a 0.4 wt.% P content, the vertical burning rating of EP/DDM/VDPD-0.4 (according to the theoretical content of VDPD) reached the V-0 level, and the LOI value reached 33.1%. In addition, the results of a CCT showed that the peak heat release rate (PHRR) of EP/DDM/VDPD-0.4 decreased by 32% in comparison with that of the EP. Furthermore, compared with those of the EP, the tensile strength of EP/DDM/VDPD-0.4 decreased from 80.2 MPa to 74.3 MPa, only decreasing by 6 MPa, and the tensile modulus increased. Overall, VDPD can maintain the mechanical properties of EP and effectively improve its flame-retardant properties. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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18 pages, 5968 KiB  
Article
The Flame Retardant and Mechanical Properties of the Epoxy Modified by an Efficient DOPO-Based Flame Retardant
by Pengyu Li, Jihui Wang, Changzeng Wang, Chengxin Xu and Aiqing Ni
Polymers 2024, 16(5), 631; https://doi.org/10.3390/polym16050631 - 26 Feb 2024
Cited by 4 | Viewed by 2022
Abstract
Currently, the mechanical performance reduction caused by excessive phosphorus content in the halogen-free flame-retardant EP has been an obstacle to its extensive application. This study presents the effective synthesis of a novel flame-retardant BDD with great efficiency, achieving an optimum phosphorus level of [...] Read more.
Currently, the mechanical performance reduction caused by excessive phosphorus content in the halogen-free flame-retardant EP has been an obstacle to its extensive application. This study presents the effective synthesis of a novel flame-retardant BDD with great efficiency, achieving an optimum phosphorus level of merely 0.25 wt %. The structure of BDD was verified by FTIR, 1H NMR, 31P NMR and XPS spectra. To investigate the flame-retardant properties of BDD, several EPs with various phosphorus levels were synthesized. The addition of phosphorus to the EP significantly increases its LOI value from 25.8% to 33.4% at a phosphorus level of 0.25 wt%. Additionally, the resin achieves a V-0 grade in the UL 94 test. The P-HRR and THR of the modified resin measured by the cone calorimeter are also significantly reduced. At the same time, the addition of a modest quantity of BDD has a minimal impact on the mechanical properties of epoxy resin. This study shows that the removal of hydroxyl groups significantly enhances the fire resistance of phosphate-based flame retardants, thereby providing a novel approach to synthesizing efficient flame retardants. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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26 pages, 3965 KiB  
Article
Elaboration of Thermally Performing Polyurethane Foams, Based on Biopolyols, with Thermal Insulating Applications
by Pedro Luis De Hoyos-Martinez, Sebastian Barriga Mendez, Eriz Corro Martinez, De-Yi Wang and Jalel Labidi
Polymers 2024, 16(2), 258; https://doi.org/10.3390/polym16020258 - 16 Jan 2024
Cited by 2 | Viewed by 1562
Abstract
In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a [...] Read more.
In this work, biobased rigid polyurethane foams (PUFs) were developed with the aim of achieving thermal and fireproofing properties that can compete with those of the commercially available products. First, the synthesis of a biopolyol from a wood residue by means of a scaled-up process with suitable yield and reaction conditions was carried out. This biopolyol was able to substitute completely the synthetic polyols that are typically employed within a polyurethane formulation. Different formulations were developed to assess the effect of two flame retardants, namely, polyhedral oligomeric silsesquioxane (POSS) and amino polyphosphate (APP), in terms of their thermal properties and degradation and their fireproofing mechanism. The structure and the thermal degradation of the different formulations was evaluated via Fourier Transformed Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Likewise, the performance of the different PUF formulations was studied and compared to that of an industrial PUF. From these results, it can be highlighted that the addition of the flame retardants into the formulation showed an improvement in the results of the UL-94 vertical burning test and the LOI. Moreover, the fireproofing performance of the biobased formulations was comparable to that of the industrial one. In addition to that, it can be remarked that the biobased formulations displayed an excellent performance as thermal insulators (0.02371–0.02149 W·m−1·K−1), which was even slightly higher than that of the industrial one. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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18 pages, 6760 KiB  
Article
Preparation of High-Transparency Phosphenanthrene-Based Flame Retardants and Studies of Their Flame-Retardant Properties
by Tao Zhang and Yong Liu
Polymers 2023, 15(24), 4665; https://doi.org/10.3390/polym15244665 - 11 Dec 2023
Cited by 2 | Viewed by 1300
Abstract
Transparency is an important property for polymer flame retardants, especially epoxy resin (EP) flame retardants, and flame-retardant epoxy resins that maintain a high transparency and low chromatic aberration play important roles in the optical, lighting, and energy industries. Herein, a DOPO-based flame retardant [...] Read more.
Transparency is an important property for polymer flame retardants, especially epoxy resin (EP) flame retardants, and flame-retardant epoxy resins that maintain a high transparency and low chromatic aberration play important roles in the optical, lighting, and energy industries. Herein, a DOPO-based flame retardant 6,6′-((sulfonylbis(4,1-phenylene))bis(oxy))bis(dibenzo[c,e][1,2]oxaphosphinine 6-oxide) with a high transparency and low chromatic aberration was prepared via the classical Atherton–Todd reaction and named SBPDOPO. Its chemical structure was characterized with Fourier IR spectroscopy and NMR spectroscopy. An EP loaded with 7 wt% SBPDOPO passed the UL-94 V-0 rating with an LOI value of 32.1%, and the peak heat release rate, total heat release, and total smoke production were reduced by 34.1%, 31.6%, and 27.7%, respectively, compared with those of pure EP. In addition, the addition of SBPDOPO improved the thermal stability, residual mass, and glass transition temperature of the EP. On this basis, the EP containing 7 wt% SBPDOPO maintained a high transparency and low color aberration, with a transmittance of 94% relative to that of pure EP and a color aberration ΔE of 1.63. Finally, the flame-retardant mechanism of SBPDOPO was analyzed, which demonstrated that it exerted both gas-phase and condensed-phase flame-retardant effects, and that SBPDOPO/EP had high potential for application scenarios in which both flame retardancy and transparency are needed. SBPDOPO/EP has great potential for applications requiring both flame retardancy and transparency. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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Review

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22 pages, 50109 KiB  
Review
MXene Based Flame Retardant and Electrically Conductive Polymer Coatings
by Bo Lin, Ao Li, Ivan Miguel De Cachinho Cordeiro, Ming Jia, Yuan Xien Lee, Anthony Chun Yin Yuen, Cheng Wang, Wei Wang and Guan Heng Yeoh
Polymers 2024, 16(17), 2461; https://doi.org/10.3390/polym16172461 - 29 Aug 2024
Viewed by 755
Abstract
Modern polymer coatings possess tremendous multifunctionalities and have attracted immense research interest in recent decades. However, with the expeditious development of technologies and industries, there is a vast demand for the flame retardancy and electrical conductivity of engineered polymer coatings. Traditional functional materials [...] Read more.
Modern polymer coatings possess tremendous multifunctionalities and have attracted immense research interest in recent decades. However, with the expeditious development of technologies and industries, there is a vast demand for the flame retardancy and electrical conductivity of engineered polymer coatings. Traditional functional materials that render the polymer coatings with these properties require a sophisticated fabrication process, and their high mass gains can be a critical issue for weight-sensitive applications. In recent years, massive research has been conducted on a newly emerged two-dimensional (2D) nanosize material family, MXene. Due to the excellent electrical conductivity, flame retardancy, and lightweightness, investigations have been launched to synthesise MXene-based polymer coatings. Consequently, we performed a step-by-step review of MXene-involved polymer coatings, from solely attaching MXene to the substrate surface to the multilayered coating of modified MXene with other components. This review examines the performances of the fire safety enhancement and electrical conductivity as well as the feasibility of the manufacturing procedures of the as-prepared polymer composites. Additionally, the fabricated polymer coatings’ dual property mechanisms are well-demonstrated. Finally, the prospect of MXene participating in polymer coatings to render flame retardancy and electrical conductivity is forecasted. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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25 pages, 6020 KiB  
Review
Recent Advances in Fire-Retardant Silicone Rubber Composites
by Yi-Hao Tang, Jun Liu, Zuan-Yu Chen, Yang Li, Cheng-Fei Cao, Guo-Dong Zhang and Long-Cheng Tang
Polymers 2024, 16(17), 2442; https://doi.org/10.3390/polym16172442 - 28 Aug 2024
Viewed by 692
Abstract
Silicone rubber (SR), as one kind of highly valuable rubber material, has been widely used in many fields, e.g., construction, transportation, the electronics industry, automobiles, aviation, and biology, owing to its attractive properties, including high- and low-temperature resistance, weathering resistance, chemical stability, and [...] Read more.
Silicone rubber (SR), as one kind of highly valuable rubber material, has been widely used in many fields, e.g., construction, transportation, the electronics industry, automobiles, aviation, and biology, owing to its attractive properties, including high- and low-temperature resistance, weathering resistance, chemical stability, and electrical isolation, as well as transparency. Unfortunately, the inherent flammability of SR largely restricts its practical application in many fields that have high standard requirements for flame retardancy. Throughout the last decade, a series of flame-retardant strategies have been adopted which enhance the flame retardancy of SR and even enhance its other key properties, such as mechanical properties and thermal stability. This comprehensive review systematically reviewed the recent research advances in flame-retarded SR materials and summarized and introduced the up-to-date design of different types of flame retardants and their effects on flame-retardant properties and other performances of SR. In addition, the related flame-retardant mechanisms of the as-prepared flame-retardant SR materials are analyzed and presented. Moreover, key challenges associated with these various types of FRs are discussed, and future development directions are also proposed. Full article
(This article belongs to the Special Issue Flame-Retardant Polymer Composites II)
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