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Advance in Polymer Composites: Fire Protection and Thermal Management

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

Deadline for manuscript submissions: 1 June 2024 | Viewed by 8220

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Dr. Fei Xiao

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Guest Editor

School of Safety Science and Emergency Management, Wuhan University of Technology, Wuhan 430070, China
Interests: bio-based polymer; flame retardancy; intumescence; fire protection; solid-state NMR

Dr. Fubin Luo

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Engineering Research Center of Polymer Green Recycling of Ministry of Education, Fujian Normal University, Fu Zhou, China
Interests: polymer composites; thermal conductivity; flame retardancy; polymer recycling

Dr. Ke Sun

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1. Institute of Intelligent Manufacturing Technology, Shenzhen Polytechnic, 4089 Shahe West Road, Shenzhen 518055, China
2. Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China
Interests: photopolymerization; photoinitiators; stimuli-responsive materials; organic/polymer photoelectronic functional materials; nanoscience; intelligent manufacturing
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Special Issue Information

Dear Colleagues,

We are pleased to invite you to submit your original research to this Polymers Special Issue entitled “Advance in Polymer Composites: Fire Protection and Thermal Management. The aim of this Special Issue is to provide an excellent opportunity for publishing the latest advances, including all aspects of research related to the fire protection, fire retardancy, thermal stability, and thermal management of polymer composites. This Special Issue is open to researchers and authors who wish to submit their research and review articles exploring experimental and numerical analyses in those fields. We encourage sending manuscripts containing scientific findings within the broad fields of the fire protection and thermal management of polymer composites.

Dr. Fei Xiao
Dr. Fubin Luo
Dr. Ke Sun
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. 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

polymers
composites
fire protection
flame retardant
bio-based flame retardants
thermal conductivity
phonon scattering
thermal management
fire testing
simulation modelling and design
thermal degradation
thermal interface materials

Published Papers (9 papers)

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Research

20 pages, 7400 KiB

Open AccessArticle

Cage Nanofillers’ Influence on Fire Hazard and Toxic Gases Emitted during Thermal Decomposition of Polyurethane Foam

by Arkadiusz Głowacki, Przemysław Rybiński, Monika Żelezik and Ulugbek Zakirovich Mirkhodjaev

Polymers 2024, 16(5), 645; https://doi.org/10.3390/polym16050645 - 27 Feb 2024

Viewed by 592

Abstract

Polyurethane (PUR), as an engineering polymer, is widely used in many sectors of industries. However, the high fire risks associated with PUR, including the smoke density, a high heat release rate, and the toxicity of combustion products limit its applications in many fields. This paper presents the influence of silsesquioxane fillers, alone and in a synergistic system with halogen-free flame-retardant compounds, on reducing the fire hazard of polyurethane foams. The flammability of PUR composites was determined with the use of a pyrolysis combustion flow calorimeter (PCFC) and a cone calorimeter. The flammability results were supplemented with smoke emission values obtained with the use of a smoke density chamber (SDC) and toxicometric indexes. Toxicometric indexes were determined with the use of an innovative method consisting of a thermo-balance connected to a gas analyzer with the use of a heated transfer line. The obtained test results clearly indicate that the used silsesquioxane compounds, especially in combination with organic phosphorus compounds, reduced the fire risk, as expressed by parameters such as the maximum heat release rate (HRRmax), the total heat release rate (THR), and the maximum smoke density (SDmax). The flame-retardant non-halogen system also reduced the amounts of toxic gases emitted during the decomposition of PUR, especially NOx, HCN, NH₃, CO and CO₂. According to the literature review, complex studies on the fire hazard of a system of POSS–phosphorus compounds in the PUR matrix have not been published yet. This article presents the complex results of studies, indicating that the POSS–phosphorous compound system can be treated as an alternative to toxic halogen flame-retardant compounds in order to decrease the fire hazard of PUR foam. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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17 pages, 16643 KiB

Open AccessArticle

Synergistic Modification of Polyformaldehyde by Biobased Calcium Magnesium Bi-Ionic Melamine Phytate with Intumescent Flame Retardant

by Shike Lu, Xueting Chen, Bin Zhang, Zhehong Lu, Wei Jiang, Xiaomin Fang, Jiantong Li, Baoying Liu, Tao Ding and Yuanqing Xu

Polymers 2024, 16(5), 614; https://doi.org/10.3390/polym16050614 - 23 Feb 2024

Viewed by 645

Abstract

Intumescent flame retardants (IFRs) are mainly composed of ammonium polyphosphate (APP), melamine (ME), and some macromolecular char-forming agents. The traditional IFR still has some defects in practical application, such as poor compatibility with the matrix and low flame-retardant efficiency. In order to explore the best balance between flame retardancy and mechanical properties of flame-retardant polyformaldehyde (POM) composite, a biobased calcium magnesium bi-ionic melamine phytate (DPM) synergist was prepared based on renewable biomass polyphosphate phytic acid (PA), and its synergistic system with IFRs was applied to an intumescent flame-retardant POM system. POM/IFR systems can only pass the V-1 grade of the vertical combustion test (UL-94) if they have a limited oxygen index (LOI) of only 48.5%. When part of an IFR was replaced by DPM, the flame retardancy of the composite was significantly improved, and the POM/IFR/4 wt%DPM system reached the V-0 grade of UL-94, and the LOI reached 59.1%. Compared with pure POM, the PkHRR and THR of the POM/IFR/4 wt%DPM system decreased by 61.5% and 51.2%, respectively. Compared with the POM/IFR system, the PkHRR and THR of the POM/IFR/4 wt%DPM system were decreased by 20.8% and 27.5%, respectively, and carbon residue was increased by 37.2%. The mechanical properties of the composite also showed a continuous upward trend with the increase in DPM introduction. It is shown that the introduction of DPM not only greatly reduces the heat release rate and heat release amount of the intumescent flame-retardant POM system, reducing the fire hazard, but it also effectively improves the compatibility between the filler and the matrix and improves the mechanical properties of the composite. It provides a new approach for developing a new single-component multifunctional flame retardant or synergist for intumescent flame-retardant POM systems. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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12 pages, 9342 KiB

Open AccessArticle

Flame-Retardant Thermoplastic Polyether Ester/Aluminum Butylmethylphosphinate/Phenolphthalein Composites with Enhanced Mechanical Properties and Antidripping

by Xue Yang, Yan Zhang, Jia Chen, Liyong Zou, Xuesong Xing, Kangran Zhang, Jiyan Liu and Xueqing Liu

Polymers 2024, 16(4), 552; https://doi.org/10.3390/polym16040552 - 18 Feb 2024

Viewed by 588

Abstract

Aluminum butylmethylphosphinate AiBMP as a flame retardant and phenolphthalein as a synergistic agent were applied in a thermoplastic polyester elastomer (TPEE)) in the current study. The thermal properties, flame retardancy, crystallization and mechanical properties of TPEE/AiMBP with or without phenolphthalein were investigated using various characterizations, including the limiting oxygen index (LOI), vertical burning test (UL 94), thermogravimetric analysis TG, differential scanning calorimetry, microcombustion calorimeter (MCC), scanning electron microscopy (SEM), and mechanical tests. The results revealed that AiBMP alone is an efficient flame retardant of TPEE. Adding 15 wt.% AiBMP increases the LOI value of TPEE from 20% to 36%. The formula TPEE-15 AiBMP passed the UL 94 V-0 rating with no dripping occurring. The MCC test shows that AiBMP depresses the heat release of TPEE. In comparison with pure TPEE, the heat release rate at peak temperature and the heat release capacity of TPEE-15AiBMP are reduced by 46.1% and 55.5%, respectively. With the phenolphthalein added, the formula TPEE/13AiBMP/2Ph shows a higher char yield at high temperatures (>600 °C), and the char layer is stronger and more condensed than TPEE-15AiBMP.The tensile strength and elongation at break values of TPEE-13AiBMP-2Ph are increased by 29.63% and 4.8% in comparison with TPEE-15AiBMP. The SEM morphology of the fracture surface of the sample shows that phenolphthalein acts as a plasticizer to improve the dispersion of AiBMP within the matrix. The good char charming ability of phenolphthalein itself and improved dispersion of AiBMP make the TPEE composites achieve both satisfying flame retardancy and high mechanical properties. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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14 pages, 3864 KiB

Open AccessArticle

Preparation and Characterization of Chloroprene Latexes Modified with Vinyl-POSS

by Junhua Chen, Zhenxian Wu, Qingwei Wang, Chuanghui Yang, Jinlian Chen, He Zhang, Yinping Wu, Dong-Yu Zhu and Xiangying Hao

Polymers 2024, 16(4), 462; https://doi.org/10.3390/polym16040462 - 7 Feb 2024

Viewed by 745

Abstract

Water-based chloroprene latex is a solvent-free, environmentally friendly adhesive. Currently, its market demand is growing rapidly. However, there are problems such as a lack of heat resistance and poor mechanical properties, which limit its application. The introduction of vinyl-POSS (OVS) into the resin structure can effectively improve the thermal stability of chloroprene adhesives. In this paper, modified waterborne chloroprene latex was prepared by copolymerization of methyl methacrylate and OVS with chloroprene latex. The results showed that vinyl-POSS was successfully grafted onto the main chain of the waterborne chloroprene latex, and the modified waterborne chloroprene latex had good storage stability. With the increase in vinyl-POSS, the tensile strength of the chloroprene latex firstly increased and then decreased, the tensile property (peel strength of 20.2 kgf) was maintained well at a high temperature (100 °C), and the thermal stability of the chloroprene latex was improved. When the addition amount was 4%, the comprehensive mechanical properties were their best. This study provides a new idea for the construction of a new and efficient waterborne chloroprene latex system and provides more fields for the practical application of waterborne chloroprene latex. This newly developed vinyl-POSS modified chloroprene latex has great application potential for use in home furniture, bags, and seat cushions. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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15 pages, 5044 KiB

Open AccessArticle

Development of a UiO-66 Based Waterborne Flame-Retardant Coating for PC/ABS Material

by Shaojun Chen, Youhan Zeng, Weifeng Bi, Haitao Zhuo and Haiqiang Zhong

Polymers 2024, 16(2), 275; https://doi.org/10.3390/polym16020275 - 19 Jan 2024

Viewed by 679

Abstract

The flame-retardancy of polymeric materials has garnered great interest. Most of the flame retardants used in copolymers are functionalized additives, which can deteriorate the intrinsic properties of these materials. As a new type of flame retardant, functionalized metal–organic frameworks (MOFs) can be used in surface coatings of polymers. To reduce the flammability, a mixture of phytic acid, multi-wall carbon nanotubes, zirconium-based MOFs, and UiO-66 was coated on a PC/ABS substrate. The structure of the UiO-66-based flame retardant was established by FT-IR, XRD, XPS, and SEM. The flammable properties of coated PC/ABS materials were assessed by LOI, a vertical combustion test, TGA, CCT, and Raman spectroscopy. The presence of a UiO-66-based coating on the PC/ABS surface resulted in a good flame-retardant performance. Heat release and smoke generation were significantly reduced. Importantly, the structure and mechanical properties of PC/ABS were less impacted by the presence of the flame-retardant coating. Hence, this work presents a new strategy for the development of high-performance PC/ABC materials with both excellent flame-retardancy and good mechanical properties. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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15 pages, 2814 KiB

Open AccessArticle

Synthesis and Characterization of Pressure-Sensitive Adhesives Based on a Naphthyl Curing Agent

by Junhua Chen, Shiting Li, Xuan Wang, Lili Fang, Dingding Huang, Lin Ke, Jinlian Chen, Qingwei Wang, He Zhang, Yinping Wu, Dongyu Zhu, Chunsheng Li and Xiangying Hao

Polymers 2023, 15(23), 4516; https://doi.org/10.3390/polym15234516 - 24 Nov 2023

Viewed by 925

Abstract

The incorporation of a naphthyl curing agent (NCA) can enhance the thermal stability of pressure-sensitive adhesives (PSAs). In this study, a PSA matrix was synthesized using a solution polymerization process and consisted of butyl acrylate, acrylic acid, and an ethyl acrylate within an acrylic copolymer. Benzoyl peroxide was used as an initiator during the synthesis. To facilitate the UV curing of the solvent-borne PSAs, glycidyl methacrylate was added to introduce unsaturated carbon double bonds. The resulting UV-curable acrylic PSA tapes exhibited longer holding times at high temperatures (150 °C) compared to uncross-linked PSA tapes, without leaving any residues on the substrate surface. The thermal stability of the PSA was further enhanced by adding more NCA and increasing the UV dosage. This may be attributed to the formation of cross-linking networks within the polymer matrix at higher doses. The researchers successfully balanced the adhesion performance and thermal stability by modifying the amount of NCA and UV radiation, despite the peel strength declining and the holding duration shortening. This research also investigated the effects of cross-linking density on gel content, molecular weight, glass transition temperature, and other properties of the PSAs. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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17 pages, 12747 KiB

Open AccessArticle

Analyzing Temperature Distribution Patterns on the Facing and Backside Surface: Investigating Combustion Performance of Flame-Retardant Particle Boards Using Aluminum Hypophosphite, Intumescent, and Magnesium Hydroxide Flame Retardants

by Fangya Pan, Hongyu Jia, Yuxiang Huang, Zhilin Chen, Shanqing Liang and Peng Jiang

Polymers 2023, 15(23), 4479; https://doi.org/10.3390/polym15234479 - 21 Nov 2023

Cited by 2 | Viewed by 871

Abstract

Particle boards are manufactured through a hot pressing process using wood materials (natural polymer materials) and adhesive, which find common usage in indoor decorative finishing materials. Flame-retardant particleboard, crucial for fire safety in such applications, undergoes performance analysis that includes assessing temperature distribution across its facing surface and temperature increase on the backside surface during facade combustion, yielding critical insights into fire scenario development. In this study, a compact flame spread apparatus is utilized to examine the flame retardancy and combustion behavior of particle boards, with a specific emphasis on the application of cost-effective flame retardants, encompassing aluminum hypophosphite (ALHP), an intumescent flame retardant (IFR) comprising ammonium polyphosphate (APP), melamine (MEL), and Dipentaerythritol (DPE), alongside magnesium hydroxide (MDH), and their associated combustion characteristics. The D_300°C values, representing the vertical distance from the ignition point (IP) to P_300°C (the temperature point at 300 °C farthest from IP), are measured using a compact temperature distribution measurement platform. For MDH/PB, APP + MEL + DPE/PB, and ALHP/PB samples, the respective D_300°C values of 145.79 mm, 117.81 mm, and 118.57 mm indicate reductions of 11.11%, 28.17%, and 27.71%, compared to the untreated sample’s value of 164.02 mm. The particle boards treated with ALHP, IFR, and MDH demonstrated distinct flame-retardant mechanisms. MDH/PB relied on the thermal decomposition of MDH to produce MgO and H₂O for flame retardancy, while APP + MEL + DPE/PB achieved flame retardancy through a cross-linked structure with char expansion, polyphosphate, and pyrophosphate during combustion. On the other hand, ALHP/PB attained flame retardancy by reacting with wood materials and adhesives, forming a stable condensed P-N-C structure. This study serves as a performance reference for the production of cost-effective flame-resistant particleboards and offers a practical method for assessing its fire-resistant properties when used as a decorative finishing material on facades in real fire situations. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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11 pages, 32463 KiB

Open AccessArticle

A Study of the Phosphorylcholine Polymer Coating of a Polymethylpentene Hollow Fiber Membrane

by Feihua Ye, Zhisheng Chen, Chunsheng Li, Junhua Chen and Guobin Yi

Polymers 2023, 15(13), 2881; https://doi.org/10.3390/polym15132881 - 29 Jun 2023

Cited by 1 | Viewed by 1159

Abstract

A phosphorylcholine polymer (poly(MPC–co–BMA–co–TSMA), PMBT) was prepared by free radical polymerization and coated on the surface of the polymethylpentene hollow fiber membrane (PMP–HFM). ATR–FTIR and SEM analyses showed that the PMBT polymer containing phosphorylcholine groups was uniformly coated on the surface of the PMP–HFM. Thermogravimetric analysis showed that the PMBT had the best stability when the molar percentage of MPC monomer in the polymer was 35%. The swelling test and static contact angle test indicated that the coating had excellent hydrophilic properties. The fluorescence test results showed that the coating could resist dissolution with 90% (v/v%) ethanol solution and 1% (w/v%) SDS solution. The PMBT coating was shown to be able to decrease platelet adherence to the surface of the hollow fiber membrane, and lower the risk of blood clotting; it had good blood compatibility in tests of whole blood contact and platelet adhesion. These results show that the PMBT polymer may be coated on the surface of the PMP–HFM, and is helpful for improving the blood compatibility of membrane oxygenation. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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13 pages, 3923 KiB

Open AccessArticle

Exploration of the Fire-Retardant Potential of Microencapsulated Ammonium Polyphosphate in Epoxy Vitrimer Containing Dynamic Disulfide Bonds

by Wenlong Shao, Tongbing Li, Fei Xiao, Fubin Luo, Yong Qiu, Yanyan Liu, Bihe Yuan and Kaiyuan Li

Polymers 2023, 15(13), 2839; https://doi.org/10.3390/polym15132839 - 27 Jun 2023

Cited by 2 | Viewed by 1219

Abstract

Epoxy vitrimers appear as a promising alternative to common epoxy thermoset composites. Nevertheless, the possibilities of applying these materials are limited due to their high flammability which may cause high fire risks. To date, the flame-retardant epoxy vitrimer systems reported in the literature almost all rely on intrinsic flame retardancy to achieve high fire safety; however, the complex and expensive synthesis process hinders their large-scale application. In this work, disulfide-based epoxy vitrimer (EPV) was fabricated with 4, 4′-dithiodianiline as the curing agent, and microencapsulated ammonium polyphosphate (MFAPP) was employed as a potential additive flame retardant to improve their fire retardancy. As a comparative study, common epoxy (EP) composites were also prepared using 4,4′-diaminodiphenylmethane as the curing agent. The results showed that the introduction of dynamic disulfide bonds led to a reduction in the initial thermal decomposition temperature of EPV by around 70 °C compared to EP. Moreover, the addition of 7.5 wt.% of MFAPP endowed EP with excellent fire performance: the LOI value was as high as 29.9% and the V-0 rating was achieved in the UL-94 test (3.2 mm). However, under the same loading, although EPV/MFAPP7.5% showed obvious anti-dripping performance, it did not reach any rating in the UL-94 test. The flame-retardant mechanisms in the condensed phase were evaluated using SEM-EDS, XPS, and Raman spectroscopy. The results showed that the residue of EPV/MFAPP7.5% presented numerous holes during burning, which failed to form a continuous and dense char layer as a physical barrier resulting in relatively poor flame retardancy compared to EP/MFAPP7.5%. Full article

(This article belongs to the Special Issue Advance in Polymer Composites: Fire Protection and Thermal Management)

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