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Fire-Safe Polymer Composites: Structure and Application

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

Deadline for manuscript submissions: closed (5 March 2022) | Viewed by 28528

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Special Issue Editors

Dr. Zhi Li

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Guest Editor

School of Materials Science and Engineering, Chongqing Jiaotong University, Chongqing 400074, China
Interests: multifunctional flame-retardant polymer composites; flame-retardant mechanism; fire-safe solid polymer electrolytes for lithium batteries; hybrid assembly of micro/nano fillers toward fire-safe application; flame sensors

Dr. Jun Sun

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Guest Editor

Center for Fire Safety Materials, Beijing University of Chemical Technology, Beijing, China
Interests: flame-retardant materials; nanocomposites; multifunctional flame-retardant polymers; bio-based flame retardants
Special Issues, Collections and Topics in MDPI journals

Dr. Yongqian Shi

E-Mail Website
Guest Editor

School of Environment and Safety Engineering, Fuzhou University, Fuzhou 350116, China
Interests: multifunctional flame-retardant polymer composites; hybrid assembly of micro/nanofillers toward fire-safe application

Special Issue Information

Dear Colleagues,

Fire safety arouses increasing concern due to its versatility and the destructiveness of fire. Newly emerging fire retardants based on novel molecule design as well as the rational construction of the hierarchical nano-assembly by the prevailing MOFs, Mxenes, and black phosphorous nanosheets demonstrate excellent performance. Particularly, specific application fields (e.g., lithium-ion batteries, fabrics, and road pavement materials) have been involved in the distinct fire-retardant treatment and design under the regulatory requirements. The fire safety in some featured scenarios such as in tunnels, coal mines, and forests that are associated with the spread of fire is within the scope of this Special Issue. Papers reporting on sensors to intelligently detect fire occurrence are desirable for inclusion in this Special Issue. Above all, this Special Issue of Polymers aims to collectively disseminate the state-of-the-art research concerning fire-safe polymer composites and applications in manifold fields toward deepening the scientific and technological understanding of fire-safe conceptualization, fire-suppression mechanisms, and fire-protection applications.

People are subject to fire threats in occasions where flammable polymers or components suffer heat shock. Aiming to address this issue, synthetic fire retardants or fire-retardant treatments are employed to fulfil the fire test standard. Recent progress pertaining to the fire-retardant design on the basis of newly emerging nanomaterials, highly efficient phosphorus/nitrogen-based molecules, biobased fire retardants, novel fire-retardant modes of action as well as featured application fields inject new vigor for the development of fire-retardant materials. Additionally, the fire safety requirements imposed by the mandatory industry protocols guild the utilization of fire-retardant technology in specific applications, such as lithium-ion battery materials, fabrics, and pavement materials. A faster fire-hazard response speed and recognizable signal enabled by fire alarm design presents an equivalent position for life rescue. Multifunctional reinforcement (e.g., self-healing, thermal conductivity and photo-thermal response), along with improved fire retardancy represent the current trends in the field. We invite the research and industry communities to contribute to this Special Issue by submitting reviews or research articles. The topics of interest include but are not limited to:

Phosphorous-based fire retardants;
Nano-structured fire retardants;
Fire assessments;
Fire-retardant modes of action;
Ignition behaviors;
Smoke suppression;
Fire simulation;
Fire reaction;
Fire toxicity;
Fire-retardant composites;
Multifunctional fire-retardant polymers;
Fire protection of construction materials;
Functional fire-safe road pavement materials;
Fire-retardant fabrics;
Fire-resistant coatings;
Fire-retardant phase change materials;
Fire-retardant battery materials;
Fire-sensing coating and structure;
Biobased intrinsic flame-retardant polymers;
Biobased fire retardants;
Fire-retardant fiber-reinforced polymer composites;
Fire safety of tunnels;
Fire safety of coal mines;
Fire protection of woods.

Dr. Zhi Li
Dr. Jun Sun
Dr. Yongqian Shi
Guest Editors

Manuscript Submission Information

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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. Polymers 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 2700 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

fire retardant
additive
polymer
composite
nanocomposite
fiber-reinforced polymer composites
coating
fabric
foam
synergism
fire-retardant mechanism
thermal stability
smoke suppression
ignition
multifunctional
preparation
biobased
fire alarm
black phosphorous
metal-organic frameworks
road pavement materials
construction materials
tunnels
coal mines
woods
flame simulation

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Published Papers (9 papers)

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Research

17 pages, 7051 KiB

Open AccessArticle

A Phosphorous-Containing Bio-Based Furfurylamine Type Benzoxazine and Its Application in Bisphenol-A Type Benzoxazine Resins: Preparation, Thermal Properties and Flammability

by Chunxia Zhao, Zhangmei Sun, Jixuan Wei, Yuntao Li, Dong Xiang, Yuanpeng Wu and Yusheng Que

Polymers 2022, 14(8), 1597; https://doi.org/10.3390/polym14081597 - 14 Apr 2022

Cited by 12 | Viewed by 2312

Abstract

Polybenzoxazine (PBa) composites based on phosphorous-containing bio-based furfurylamine type benzoxazines (D-fu) and bisphenol-A type benzoxazines (Ba) were developed for flame retardation. The structure of D-fu was analyzed by Fourier transform infrared (FTIR) spectroscopy and ¹H-NMR spectroscopy. The curing temperature of Ba/D-fu mixtures was systematically studied by differential scanning calorimetry (DSC). Thermogravimetric analysis (TGA) demonstrated the excellent char formation ability of the PBa composites with the addition of phosphorous-containing D-fu. The flame retardancy of the PBa composite materials was tested by the limited oxygen index (LOI), vertical burning test (UL-94) and cone calorimeter (CONE). The LOI and UL-94 level of PBa/PD-fu-5% reached 34 and V0 rate, respectively. Notably, the incorporation of 5% D-fu into PBa led to a decrease of 21.9% at the peak of the heat-release rate and a mass-loss reduction of 8.0%. Moreover, the fire performance index increased, which demonstrated that the introduction of D-fu can diminish fire occurrence. The role of D-fu in the condensed and gas phases for the fire-resistant mechanism of the PBa matrix was supported by SEM-EDS and TGA/infrared spectrometry (TG-FTIR), respectively. Dynamic mechanical analysis (DMA) revealed that the Tg of PBa flame-retardant composites was around 230 °C. Therefore, PBa composites are promising fire-retardant polymers that can be applied as high-performance functional materials. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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13 pages, 7160 KiB

Open AccessArticle

Preparation of Magnesium Hydroxide Flame Retardant from Hydromagnesite and Enhance the Flame Retardant Performance of EVA

by Ling-Li Jiao, Peng-Cheng Zhao, Zhi-Qi Liu, Qing-Shan Wu, Dong-Qiang Yan, Yi-Lan Li, Yu-Nan Chen and Ji-Sheng Li

Polymers 2022, 14(8), 1567; https://doi.org/10.3390/polym14081567 - 12 Apr 2022

Cited by 27 | Viewed by 3762

Abstract

In this study, hydromagnesite, a rare natural hydrated alkaline magnesium carbonate, was used to synthesize magnesium hydroxide (MH) as a flame retardant for ethylene-vinyl acetate (EVA) to enhance its fire resistance and smoke suppression. Various concentrations of sodium hydroxide (NaOH) were used to alter the morphology and the flame-retardant efficiency of synthesized MH. EVA/MH composites were prepared through melt blending, and the influence of NaOH on the flame retardancy and mechanical properties was investigated by means of the limiting oxygen index (LOI), cone calorimeter test (CCT) and tensile test. The flame retardancy results demonstrated that composites exhibited remarkably improved flame retardant properties after introducing MH, reflected by an increase in the LOI value from 20% for neat EVA to roughly 38%. Additionally, the peak of heat release rate (pHRR), the total heat release (THR) and the peak of the smoke production rate for EVA3 were decreased by 37.6%, 20.7% and 44.4% compared with neat EVA, respectively. In the meantime, increasing char residues were also observed. The incorporation of different MH concentrations had a limited effect on the mechanical properties of the EVA/MH composites. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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19 pages, 36691 KiB

Open AccessArticle

Mechanically Robust and Flame-Retardant Polylactide Composites Based on In Situ Formation of Crosslinked Network Structure by DCP and TAIC

by Yajun Chen, Xingde Wu, Mengqi Li, Lijun Qian and Hongfu Zhou

Polymers 2022, 14(2), 308; https://doi.org/10.3390/polym14020308 - 13 Jan 2022

Cited by 10 | Viewed by 2180

Abstract

The addition of intumescent flame retardant to PLA can greatly improve the flame retardancy of the material and inhibit the dripping, but the major drawback is the adverse impact of the mechanical properties of the material. In this study, we found that the flame retardant and mechanical properties of the materials can be improved simultaneously by constructing a cross-linked structure. Firstly, a cross-linking flame-retardant PLA structure was designed by adding 0.9 wt% DCP and 0.3 wt% TAIC. After that, different characterization methods including torque, melt flow rate, molecular weight and gel content were used to clarify the formation of crosslinking structures. Results showed that the torque of 0.9DCP/0.3TAIC/FRPLA increased by 307% and the melt flow rate decreased by 77.8%. The gel content of 0.9DCP/0.3TAIC/FRPLA was 30.8%, indicating the formation of cross-linked structures. Then, the mechanical properties and flame retardant performance were studied. Results showed that, compared with FRPLA, the tensile strength, elongation at break and impact strength of 0.9DCP/0.3TAIC/FRPLA increased by 34.8%, 82.6% and 42.9%, respectively. The flame retardancy test results showed that 0.9DCP/0.3TAIC/FRPLA had a very high LOI (the limiting oxygen index) value of 39.2% and passed the UL94 V-0 level without dripping. Finally, the crosslinking reaction mechanism, flame retardant mechanism and the reasons for the improvement of mechanical properties were studied and described. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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11 pages, 3830 KiB

Open AccessEditor’s ChoiceArticle

Study on the Flame Retardancy and Hazard Evaluation of Poly(acrylonitrile-co-vinylidene chloride) Fibers by the Addition of Antimony-Based Flame Retardants

by Hyelim Kim, Ji-Su Kim and Wonyoung Jeong

Polymers 2022, 14(1), 42; https://doi.org/10.3390/polym14010042 - 23 Dec 2021

Cited by 4 | Viewed by 2887

Abstract

Antimony oxide (ATO) is used mainly as a flame retardant, but it is classified as a hazardous substance. Therefore, regulations on the use of antimony trioxide (ATO(3)) and antimony pentoxide (ATO(5)) in textile products are being developed. Accordingly, there is a need for alternative flame retardants. In this study, antimony tetroxide (ATO(4)), which has higher thermal stability and resistance to acids and alkalis than ATO(3) or ATO(5), was selected to assess its use as an alternative flame retardant. First, ATO(3) or ATO(4) were added to poly(acrylonitrile-co-vinylidene chloride) (PANVDC), and the film and wet-spun fiber were prepared. The PANVDC film with flame retardants was prepared to evaluate the flame retardancy and the mechanism of action of the flame retardants. Flame retardancy analysis showed that a limiting oxygen index of 31.2% was obtained when ATO(4) was added, which was higher than when ATO(3) was used. Subsequently, PANVDC fibers with antimony oxide were manufactured and showed improved mechanical and thermal properties when ATO(4) was used, compared to when ATO(3) was tested. In addition, migration analysis due to antimony in the fiber confirmed that the elution amount was below the acceptable standard when PANVDC fibers with ATO(4) were added. Therefore, based on these results, the flame-retardant and thermal properties of antimony tetroxide were superior to antimony trioxide, and it was confirmed that ATO(4) could be used as an alternative flame retardant to ATO(3). Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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16 pages, 6236 KiB

Open AccessArticle

Comparative Study of Fire Resistance and Char Formation of Intumescent Fire-Retardant Coatings Reinforced with Three Types of Shell Bio-Fillers

by Feiyue Wang, Hui Liu and Long Yan

Polymers 2021, 13(24), 4333; https://doi.org/10.3390/polym13244333 - 10 Dec 2021

Cited by 14 | Viewed by 3828

Abstract

Three types of shell bio-fillers, including eggshell (CES), conch shell (CHS) and clamshell (CMS), were prepared by cleaning, ultrasonication and pulverizing processes of biowastes, and then applied to intumescent fire-retardant coatings. The effects of shell bio-fillers with different polymorphs on the fire resistance and char-forming of intumescent fire-retardant coatings were investigated by cone calorimeter test, fire protection tests, smoke density test, thermogravimetric analysis (TG), and the fire resistance and char-forming mechanism of bio-fillers in intumescent fire-retardant coatings were proposed. The results show that three kinds of bio-fillers exert an excellent synergistic effect on enhancing the fire resistance and char-forming properties of the intumescent fire-retardant coatings, while clamshell has the best synergistic efficiency among the bio-fillers. Especially, IFRC-CMS coating containing 3 wt% clamshell shows the best fire protection performance and lowest smoke production and heat release, which offers an equilibrium backside temperature of 134.6 °C at 900 s, a flame-spread rating of 14.4, and a smoke density rating value of 22.8%. The synergistic efficiency of bio-fillers in the intumescent coatings depends on the polymorphs of CaCO₃ in bio-fillers, and aragonite CaCO₃ shows a higher synergistic efficiency compared to calcite CaCO₃ and the mixture of aragonite and calcite CaCO₃. The CMS composed of aragonite shows the best synergistic effect, CHS composed of aragonite and calcite comes second, and CES composed of calcite has the weakest synergistic effect. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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15 pages, 6516 KiB

Open AccessArticle

Polybenzoxazine Resins with Cellulose Phosphide: Preparation, Flame Retardancy and Mechanisms

by Hui Li, Zhangmei Sun, Chunxia Zhao, Yuntao Li, Dong Xiang, Yuanpeng Wu, Jixuan Wei and Yusheng Que

Polymers 2021, 13(24), 4288; https://doi.org/10.3390/polym13244288 - 7 Dec 2021

Cited by 7 | Viewed by 2699

Abstract

Phosphated cellulose (PCF) was synthesized based on urea, phosphated acid and cellulose. The structure of the PCF was confirmed by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy coupled with the Energy Dispersive Spectrometer (SEM-EDS). Benzoxazine (Ba)/PCF hybrid materials were fabricated and thermally cured to prepare polybenzoxazine composites (PBa/PCF). The effects of PCF on the curing temperature of Ba were analyzed through differential scanning calorimetry (DSC). The thermogravimetric (TGA) results demonstrated an increased char residue of 50% for the PBa composites incorporating PCF-5% compared with the pure PBa. The peak heat release rate (PHRR) and total heat release (THR) values of the PBa/PCF-5% composites clearly decreased by 58.1% and 16.5% compared to those of the pristine PBa. The smoke released from the PBa/PCF system significantly reduced with the loading of PCF. Moreover, the limited oxygen index (LOI) and vertical burning test level (UL-94) of PBa/PCF-5% reached up to 31 and V0. The flame retardant mechanism of the PCF in the PBa matrix was investigated TG-FTIR and char residues analysis. Finally, the dynamical mechanical analysis (DMA) results demonstrated that the Tg of the PBa/PCF composites was approximately 230 °C, which does not affect further applications of PBa composites. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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18 pages, 5244 KiB

Open AccessArticle

Fire Resistance, Thermal and Anti-Ageing Properties of Transparent Fire-Retardant Coatings Modified with Different Molecular Weights of Polyethylene Glycol Borate

by Long Yan, Xinyu Tang, Xiaojiang Xie and Zhisheng Xu

Polymers 2021, 13(23), 4206; https://doi.org/10.3390/polym13234206 - 30 Nov 2021

Cited by 10 | Viewed by 2810

Abstract

Four kinds of polyethylene glycol borate (PEG-BA) with different molecular weights were grafted into cyclic phosphate ester (PEA) to obtain flexible phosphate esters (PPBs), and then applied in amino resin to obtain a series of transparent intumescent fire-retardant coatings. The comprehensive properties of the transparent coatings containing different molecular weights of PEG-BA were investigated by various analytical instruments. The transparency and mechanical analyses indicate that the presence of PEG-BA slightly decreases the optical transparency of the coatings but improves the flexibility and adhesion classification of the coatings. The results from fire protection and cone calorimeter tests show that low molecular weight of PEG-BA exerts a positive flame-retarded effect in the coatings, while high molecular weight of PEG800-BA behaves against flame-retarded effect. Thermogravimetric and char residue analyses show that the incorporation of low molecular weight of PEG-BA clearly increases the thermal stability and residual weight of the coatings and generates a more compact and stable intumescent char on the surface of the coatings, thus resulting in superior synergistic flame-retarded effect. In particular, MPPB1 coating containing PEG200-BA exerts the best flame-retarded effect and highest residual weight of 36.3% at 700 °C, which has 57.6% reduction in flame spread rate and 23.9% reduction in total heat release compared to those of MPPB0 without PEG-BA. Accelerated ageing test shows that low molecular weight of PEG-BA promotes to enhance the durability of structural stability and fire resistance of the coatings, while PEG800-BA with high molecular weight weakens the ageing resistance. In summary, the fire-resistant and anti-ageing efficiencies of PEG-BA in the coatings depend on its molecular weight, which present the order of PEG200-BA > PEG400-BA > PEG600-BA > PEG800-BA. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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17 pages, 74881 KiB

Open AccessArticle

Surface Functionalization of Black Phosphorus via Amine Compounds and Its Impacts on the Flame Retardancy and Thermal Decomposition Behaviors of Epoxy Resin

by Shaoling Lin, Boqing Tao, Xiaomin Zhao, Guohua Chen and De-Yi Wang

Polymers 2021, 13(21), 3635; https://doi.org/10.3390/polym13213635 - 21 Oct 2021

Cited by 11 | Viewed by 2837

Abstract

Recently, lots of effort has been placed into stabilizing black phosphorus (BP) in the air to improve its compatibility with polymers. Herein, BP was chemically functionalized by aliphatic amine (DETA), aromatic amine (PPDA) and cyclamine (Pid) via a nucleophilic substitution reaction, aiming to develop an intensively reactive BP flame retardant for epoxy resin (EP). The -NH₂ group on BP-DETA, BP-PPDA and BP-Pid reacted with the epoxide group at different temperatures. The lowest temperature was about 150 °C for BP-DETA. The impacts of three BP-NH₂ were compared on the flame retardancy and thermal decomposition of EP. At 5 wt% loading, EP/BP-NH₂ all passed UL 94 V 0 rating. The limiting oxygen index (LOI) of EP/BP-PPDA was as high as 32.3%. The heat release rate (HRR) of EP/BP-DETA greatly decreased by 46% and char residue increased by 73.8%, whereas HRR of EP/BP-Pid decreased by 11.5% and char residue increased by 50.8%, compared with EP. Average effective heat of combustion (av-EHC) of EP/BP-Pid was lower than that of EP/BP-DETA and EP/BP-PPDA. In view of the flame-retardant mechanism, BP nanosheets functionalized with aliphatic amine and aromatic amine played a dominant role in the condensed phase, while BP functionalized with cyclamine was more effective in the gas phase. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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12 pages, 3798 KiB

Open AccessArticle

The Preparation and Characterization of Polylactic Acid Composites with Chitin-Based Intumescent Flame Retardants

by Xiaodong Jin, Suping Cui, Shibing Sun, Jun Sun and Sheng Zhang

Polymers 2021, 13(20), 3513; https://doi.org/10.3390/polym13203513 - 13 Oct 2021

Cited by 23 | Viewed by 3479

Abstract

In this work, a novel intumescent flame retardant (IFR) system was fabricated by the introduction of chitin as a green charring agent, ammonium polyphosphate (APP) as the acid source, and melamine (MEL) as the gas source. The obtained chitin-based IFR was then incorporated into a polylactic acid (PLA) matrix using melt compounding. The fire resistance of PLA/chitin composites was investigated via the limiting oxygen index (LOI), UL-94 vertical burning, and cone calorimeter (CONE) tests. The results demonstrated that the combination of 10%APP, 5%chitin and 5%MEL could result in a 26.0% LOI, a V-0 rating after UL and a 51.2% reduction in the peak heat release rate during the CONE test. Based on the mechanism analysis from both the morphology and the chemical structure of the char, it was suggested that chitin was a promising candidate as a charring agent for chitin reacted with APP and MEL with the formation of an intumescent layer on the surface. Full article

(This article belongs to the Special Issue Fire-Safe Polymer Composites: Structure and Application)

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