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Polymers
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Fire and Polymers
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Fire and Polymers (Closed)

A topical collection in Polymers (ISSN 2073-4360). This collection belongs to the section "Polymer Applications".

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Editors

Dr. Henri Vahabi

E-Mail Website
Collection Editor
Optical Materials, Photonics and Systems Laboratory (LMOPS), Université de Lorraine, F-57000 Metz, France
Interests: flame retardancy; thermal degradation; biobased flame retardants; biopolymers; aging of flame retardant and polymers; fiber-reinforced composites
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Mohammad Reza Saeb

E-Mail Website
Collection Editor
Department of Polymer Technology, Faculty of Chemistry, Gdańsk University of Technology, G. Narutowicza 11/12, 80-233 Gdańsk, Poland
Interests: biodegradable polymers; biomaterials; materials science; polymer blends; poly-mer nanocomposites; waste management; polymer recycling; rubber recycling; green processing; sustainable polymers
Special Issues, Collections and Topics in MDPI journals
Prof. Dr. Giulio Malucelli

E-Mail Website
Collection Editor
Department of Applied Science and Technology, Politecnico di Torino, I-10129 Torino, Italy
Interests: hybrid O/I systems; sol–gel processes; biomacromolecules; biopolymers; flame retardance; structure–property–processing relationships; thermal degradation; polymer (nano)composites
Special Issues, Collections and Topics in MDPI journals

Topical Collection Information

Dear Colleagues,

Research on flame retardancy of polymer systems as well as developing architecturally designed flame retardant polymers has experienced a tremendous upward trend in the last decade.  In parallel with such ascending trend in the number of publications, it has been attempted by the national and international committees/organizations to define and implement into practice some new directives, legislations and rules to reduce consequences caused by fire. There is no denying that polymers are building blocks of constructions and structures, in both industrial and social media. For instance, nowadays, polymers as coatings, color, or decorative topcoat layers are used in tall buildings and towers thanks to their lightness, anti-corrosive nature, and decorative character. On the other hand, hazardous features of using polymers in leading fire from the surface of the structures to the bulk of buildings, where people live or are doing their job must be cared by developing innovative flame retardant polymer composites. To rely on this necessity, as well as to integrate research on this topic, Polymers as a prestigious journal working in the field of polymer science and technology, dedicated “Fire and Polymers” as a collection part.
The mission for this collection is to find and make directed the articles on the subject of innovative polymer-based flame retardant systems, which are being received by polymers, towards a scientific committee. The collection editors are specifically working on flame retardant polymers and fire retardancy of polymer composites, having a comprehensive view over the quality of works. This collection provides the readers and authors with an active and dynamic atmosphere to keep them updated about new progress in the field. Original regular papers, Review Papers, and Short Communications, are possible kinds of manuscript that can be submitted by authors.
Topics include, but are not limited to:

  • Synthesis and design of flame retardant additives for polymers
  • Development and characterization of flame retardant polymer blends and composites
  • Strategy for additive manufacturing for flame retardant polymers
  • Assessment of the performances of flame retardant polymers
  • Environmental impact of flame retardant polymers
  • Modelling and simulation of flame retardancy mechanism in polymer systems
  • Flame retardancy of polymeric fibers and textiles
  • Recycling of flame retardant polymer composites
  • Green flame retardant polymer composites
  • Flame retardant polymer coatings and thin films

Dr. Henri Vahabi
Prof. Dr. Mohammad Reza Saeb
Prof. Dr. Giulio Malucelli
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 collection 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

  • flame retardants
  • polymers
  • polymer composites
  • polymer coatings and thin films
  • fibers and fabrics
  • nanocomposites
  • fire resistance
  • fire testing
  • fire modelling
  • fire safety regulation
  • heat release
  • flame retardant ecological issues
  • smoke
  • combustion
  • biobased polymers
  • biobased flame retardants

Related Special Issues

Published Papers (79 papers)

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2024

Jump to: 2023, 2022, 2021, 2020, 2019, 2018, 2016, 2015, 2014

12 pages, 1416 KiB  
Article
A New Sight of Ozone Usage in Textile: Improving Flame Retardant Properties
by Semiha Eren, İdil Yiğit, Kadriye Kutlay, Zehra Kaya, Cansu Basrık and Hüseyin Aksel Eren
Polymers 2024, 16(6), 735; https://doi.org/10.3390/polym16060735 - 07 Mar 2024
Viewed by 557
Abstract
Ozone, widely recognized as an environmentally friendly gas, is extensively used in various textile industry applications. These include pre-treatment processes like bleaching and desizing, as well as creating pattern and vintage effects, wastewater clarification, and surface modification. This study focuses on ozone as [...] Read more.
Ozone, widely recognized as an environmentally friendly gas, is extensively used in various textile industry applications. These include pre-treatment processes like bleaching and desizing, as well as creating pattern and vintage effects, wastewater clarification, and surface modification. This study focuses on ozone as a novel solution to a specific challenge: addressing the reduction in flame retardancy properties experienced by flame-retardant (FR) polyester fabrics during post-treatment processes in the production line. Experimentation involved subjecting the fabrics to ozonation and exploring different combinations of ozone flow rates and treatment durations. Mechanical and functional properties of the fabrics were examined, with flammability tested according to International Maritime Organization (IMO) standards. Notably, treatment with a 5 L/min ozone flow rate, a 7.01 g/h ozone concentration ratio, and a duration of 10 min showed significant improvements in IMO values, ensuring compliance with required standards. Furthermore, treated samples underwent comprehensive tests for fastness and strength, yielding results within acceptable ranges. Fourier-transform infrared (FT-IR) and thermogravimetric analysis (TGA) measurements were conducted to evaluate the impact of ozonation. FT-IR results indicated that the presence of C-H groups associated with dyestuff contributed to decreased flame retardancy in the original fabric post-dyeing. However, these groups were effectively eliminated through ozonation, thereby enhancing the fabric’s flame retardancy. Full article
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2023

Jump to: 2024, 2022, 2021, 2020, 2019, 2018, 2016, 2015, 2014

18 pages, 64270 KiB  
Communication
Flame Retardancy Index (FRI) for Polymer Materials Ranking
by Henri Vahabi, Elnaz Movahedifar, Baljinder K. Kandola and Mohammad Reza Saeb
Polymers 2023, 15(11), 2422; https://doi.org/10.3390/polym15112422 - 23 May 2023
Cited by 7 | Viewed by 2195
Abstract
In 2019, we introduced Flame Retardancy Index (FRI) as a universal dimensionless index for the classification of flame-retardant polymer materials (Polymers, 2019, 11(3), 407). FRI simply takes the peak of Heat Release Rate (pHRR), Total Heat Release (THR), and [...] Read more.
In 2019, we introduced Flame Retardancy Index (FRI) as a universal dimensionless index for the classification of flame-retardant polymer materials (Polymers, 2019, 11(3), 407). FRI simply takes the peak of Heat Release Rate (pHRR), Total Heat Release (THR), and Time-To-Ignition (ti) from cone calorimetry data and quantifies the flame retardancy performance of polymer composites with respect to the blank polymer (the reference sample) on a logarithmic scale, as of Poor (FRI ˂ 100), Good (100 ≤ FRI ˂ 101), or Excellent (FRI ≥ 101). Although initially applied to categorize thermoplastic composites, the versatility of FRI was later verified upon analyzing several sets of data collected from investigations/reports on thermoset composites. Over four years from the time FRI was introduced, we have adequate proof of FRI reliability for polymer materials ranking in terms of flame retardancy performance. Since the mission of FRI was to roughly classify flame-retardant polymer materials, its simplicity of usage and fast performance quantification were highly valued. Herein, we answered the question “does inclusion of additional cone calorimetry parameters, e.g., the time to pHRR (tp), affect the predictability of FRI?”. In this regard, we defined new variants to evaluate classification capability and variation interval of FRI. We also defined the Flammability Index (FI) based on Pyrolysis Combustion Flow Calorimetry (PCFC) data to invite specialists for analysis of the relationship between the FRI and FI, which may deepen our understanding of the flame retardancy mechanisms of the condensed and gas phases. Full article
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2 pages, 563 KiB  
Editorial
Sustainable Flame-Retardant Additives for Polymers: Future Perspectives
by Mohammad Reza Saeb and Henri Vahabi
Polymers 2023, 15(6), 1469; https://doi.org/10.3390/polym15061469 - 16 Mar 2023
Viewed by 1150
Abstract
The increased use of plastics, particularly in terms of the use of polymers in electronics and electrical devices commonly used in homes, offices, schools, restaurants, and vehicles, has caused increased fire risks [...] Full article
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2022

Jump to: 2024, 2023, 2021, 2020, 2019, 2018, 2016, 2015, 2014

13 pages, 5552 KiB  
Article
Effect of the Current on the Fire Characteristics of Overloaded Polyvinyl Chloride Copper Wires
by Zhe Li, Qingwen Lin, Yang Li, Huifei Lyu, Huaibin Wang and Junli Sun
Polymers 2022, 14(21), 4766; https://doi.org/10.3390/polym14214766 - 07 Nov 2022
Cited by 2 | Viewed by 1417
Abstract
In this study, the fire behavior variation of unenergized polyvinyl chloride (PVC) copper wires subjected to overload with different currents was investigated by a cone calorimeter. Overload currents were selected from 1 times safe-rated current (Ie) to 3.5 times I [...] Read more.
In this study, the fire behavior variation of unenergized polyvinyl chloride (PVC) copper wires subjected to overload with different currents was investigated by a cone calorimeter. Overload currents were selected from 1 times safe-rated current (Ie) to 3.5 times Ie to obtain tested sample wires. The mass fraction, time to ignition (TTI), heat release rate (HRR), gas emission, and residue were measured. If the current flowing through the wire increased up to 3.5 times Ie, the TTI of this unenergized wire increased drastically and the peak HRR (pHRR) decreased notably so that the flame growing index (FGI) reduced considerably. When the wire carried less than three times Ie, the FGI remained stable. For all overloaded PVC copper wires, the increase in the heat flux resulted in a higher pHRR and a lower burning duration. However, regardless of the external heat flux exposure, the FGI of copper wires overloaded at 3.5 times Ie was lower than that of copper wires carrying less than other times Ie. Moreover, the consumption of O2 and generation of CO2 as the heat flux varied were consistent with that of the HRR. Opposed to expectation, the flame propagation of unenergized PVC copper wires would decline in a fire, if the wire has been damaged by overload with some currents. Full article
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2021

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16 pages, 1989 KiB  
Article
Expandable Graphite for Flame Retardant PA6 Applications
by Florian Tomiak, Klaus Rathberger, Angelina Schöffel and Dietmar Drummer
Polymers 2021, 13(16), 2733; https://doi.org/10.3390/polym13162733 - 15 Aug 2021
Cited by 11 | Viewed by 3081
Abstract
A new expandable graphite (EG) type was studied as a flame retardant additive in Polyamide 6 (PA6). The fire behavior was characterized by a cone calorimeter using external heat fluxes of 35, 50 and 65 kW/m2, limiting the oxygen index (LOI) [...] Read more.
A new expandable graphite (EG) type was studied as a flame retardant additive in Polyamide 6 (PA6). The fire behavior was characterized by a cone calorimeter using external heat fluxes of 35, 50 and 65 kW/m2, limiting the oxygen index (LOI) and UL-94 burning tests. Additionally, electric and thermal conductivity as well as rheological properties were characterized to provide a general property overview. Fire tests were conducted using dry and humid conditioned samples. Cone Calorimeter tests showed a minimum filling degree of 15 wt.% (8.6 vol.%) EG was required to achieve a significant fire inhibiting effect in PA6 independent of the sample condition. UL-94 fire tests show a V0 classification at filling degrees greater than 20 wt.% (humid) and 25 wt.% (dry), although the associated LOI values of 39% and 38% demonstrate good flammability inhibition. Correlation analyses were conducted to identify major influences given by the sample condition for most important key figures measured in cone calorimeter tests. Accordingly, humid-conditioned samples containing between 2.5 (PA6 + 25 wt.% EG) and 4.2 wt.% (PA6) water were found to reduce the total heat evolved (THE) on average by 16% and the total smoke production (TSP) on average by 22%. Full article
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16 pages, 1792 KiB  
Article
A Synergistic Flame Retardant System Based on Expandable Graphite, Aluminum (Diethyl-)Polyphospinate and Melamine Polyphosphate for Polyamide 6
by Florian Tomiak, Angelina Schoeffel, Klaus Rathberger and Dietmar Drummer
Polymers 2021, 13(16), 2712; https://doi.org/10.3390/polym13162712 - 13 Aug 2021
Cited by 12 | Viewed by 2701
Abstract
Expandable graphite (EG), aluminum (diethyl)polyphosphinate (AlPi) and melamine polyphophate (MPP) was used as flame retardant multi-material additive in a polyamide 6 (PA6) matrix. Flame inhabitation performances were conducted by cone calorimeter, LOI and UL-94 tests, synergisms identified analyzed by TGA-FTIR and TGA-GC/MS and [...] Read more.
Expandable graphite (EG), aluminum (diethyl)polyphosphinate (AlPi) and melamine polyphophate (MPP) was used as flame retardant multi-material additive in a polyamide 6 (PA6) matrix. Flame inhabitation performances were conducted by cone calorimeter, LOI and UL-94 tests, synergisms identified analyzed by TGA-FTIR and TGA-GC/MS and effects found were comprehensively discussed. SEM images were used for char residue characterization. For PA6 containing 20 wt.% EG and 5 wt.% AlPi/MPP (3:2), a well working synergism in limiting oxygen indices could be identified exhibiting the highest oxygen index (OI) measured: 46%. The study shows that the synergism due to the partial substitution of EG by AlPi/MPP can be attributed to two effects: (1) When PA6/AlPi/MPP mixtures decompose predominantly CO2 evaporates in early decomposition stages. CO2 evaporations was found to be sensitive to the heating rate applied, whereas specifically high heating rates increased the CO2 yield measured. (2) Solid decomposition products of AlPi/MPP act as “glue” between expanded graphite and thus increase the mechanical residue stability. Full article
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14 pages, 3809 KiB  
Article
Suppression of Smoldering of Calcium Alginate Flame-Retardant Paper by Flame-Retardant Polyamide-66
by Kai Xu, Xing Tian, Ying Cao, Yaqi He, Yanzhi Xia and Fengyu Quan
Polymers 2021, 13(3), 430; https://doi.org/10.3390/polym13030430 - 29 Jan 2021
Cited by 13 | Viewed by 2300
Abstract
Calcium alginate (Ca-Alg) fibers are renewable fibers obtained from the ocean with essential flame retardancy, which have recently been applied as components of flame-retardant paper. However, the application of Ca-Alg fibers is limited because of their tendency to smolder. Therefore, composites papers were [...] Read more.
Calcium alginate (Ca-Alg) fibers are renewable fibers obtained from the ocean with essential flame retardancy, which have recently been applied as components of flame-retardant paper. However, the application of Ca-Alg fibers is limited because of their tendency to smolder. Therefore, composites papers were fabricated by blending using flame-retardant polyamide-66 (FR-PA), with a 5 wt% content of phosphorous flame retardant, which will form molten carbon during combustion. When the FR-PA content is 30% of the composite paper, FR-PA forms a compact carbon layer on the surface of the Ca-Alg fibers during combustion, which isolates the mass/heat transfer and effectively suppresses the smoldering of Ca-Alg. This consists of a condensed flame retardant mechanism. Furthermore, the combustion and thermal degradation behavior of paper were analyzed by cone calorimetry (CONE), TG and TG-IR. Ca-Alg in the composite paper decomposed and released CO2 before ignition, which delayed the ignition time. Simultaneously, the FR-PA contained in the composite paper effectively inhibited the combustion of volatile combustibles in the gas phase. Overall, FR-PA and Ca-Alg improve the thermal stability of the composite paper in different temperature regions under air atmosphere. Ca-Alg reduces the formation of aromatic products and NH3 in the composite paper under N2 atmosphere. Ca-Alg-based paper with excellent flame retardancy was successfully prepared. Full article
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2020

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14 pages, 3695 KiB  
Article
Effect of the B:Zn:H2O Molar Ratio on the Properties of Poly(Vinyl Acetate) and Zinc Borate-Based Intumescent Coating Materials Exposed to a Quasi-Real Cellulosic Fire
by Jakub Łopiński, Beata Schmidt, Yongping Bai and Krzysztof Kowalczyk
Polymers 2020, 12(11), 2542; https://doi.org/10.3390/polym12112542 - 30 Oct 2020
Cited by 3 | Viewed by 1874
Abstract
In order to investigate an influence of the B:Zn:H2O molar ratio on the fire protection efficiency of poly(vinyl acetate)-based thermoplastic intumescent coating materials (ICs), systems containing ammonium polyphosphate, melamine, pentaerythritol and different types of zinc borates (ZBs) were tested in a [...] Read more.
In order to investigate an influence of the B:Zn:H2O molar ratio on the fire protection efficiency of poly(vinyl acetate)-based thermoplastic intumescent coating materials (ICs), systems containing ammonium polyphosphate, melamine, pentaerythritol and different types of zinc borates (ZBs) were tested in a vertical position in quasi-real fire conditions. 3ZnO·2B2O3·6H2O (ZB6), 2ZnO·3B2O3·3.5H2O (ZB3.5) or 3ZnO·2B2O3 (ZB0) were added in amounts of 1–10 wt. parts/100 wt. parts of the other coating components mixture. Char formation processes and thermal insulation features were investigated using an open-flame furnace heated according to the cellulosic fire curve. Thermogravimetric features (DTG), chemical structures (FTIR) and mechanical strength of the ICs and the chars were analyzed as well. It was revealed that the type and dose of the ZBs significantly affect thermal insulation time (TIT) (up to 450 °C of a steel substrate) and sagging (SI) of the fire-heated coatings as well as the compressive strength of the created chars. The highest TIT value (+89%) was noted for the sample with 2.5 wt. parts of ZB3.5 while the lowest SI (−65%) was observed for the coatings containing 10 wt. parts of the hydrated borates (i.e., ZB3.5 or ZB6). The best mechanical strength was registered for the sample filled with the anhydrous modifier (3 wt. parts of ZB0). The presented results show that the ICs with the proper ZBs can be used for effective fire protection of vertically positioned steel elements. Full article
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16 pages, 6249 KiB  
Article
Flame-Retardant Mechanism and Mechanical Properties of Wet-Spun Poly(acrylonitrile-co-vinylidene chloride) Fibers with Antimony Trioxide and Zinc Hydroxystannate
by Ji Su Kim, Ji Eun Song, Daeyoung Lim, Heejoon Ahn and Wonyoung Jeong
Polymers 2020, 12(11), 2442; https://doi.org/10.3390/polym12112442 - 22 Oct 2020
Cited by 8 | Viewed by 2627
Abstract
To produce flame retardant poly(acrylonitrile-co-vinylidene chloride) (PANVDC) fibers with limiting oxygen index (LOI) values above 28%, flame retardants are added to fibers. Because antimony trioxide (ATO) used widely for PANVDC is suspected as a carcinogen, non-toxic zinc hydroxystannate (ZHS) could be the alternative [...] Read more.
To produce flame retardant poly(acrylonitrile-co-vinylidene chloride) (PANVDC) fibers with limiting oxygen index (LOI) values above 28%, flame retardants are added to fibers. Because antimony trioxide (ATO) used widely for PANVDC is suspected as a carcinogen, non-toxic zinc hydroxystannate (ZHS) could be the alternative for reduction of ATO usage. Moreover, a flame retardant efficiency of the combination of ATO with ZHS could be expected because it was reported that ATO resists flame in the gas phase, whereas ZHS reacts in the condensed phase. Therefore, this study discussed the flame retardant mechanisms of ATO and ZHS in PANVDC, and evaluated the efficiency of the combination. PANVDC fibers with ATO and ZHS in 15 phr were produced by wet spinning. When ZHS was added, a more cyclized structure was detected (e.g., 1-methylnaphthalene) through pyrolysis−gas chromatography-mass spectrometry (Py-GC/MS). As a result of SEM-EDX analysis, Sb and Cl hardly remained in char layers of PANVDC-ATO; meanwhile, Zn, Sn, and Cl remained in that of PANVDC-ZHS. This implied that SbCl3 from reaction of ATO and HCl reacts in the gas phase, whereas ZnCl2 and SnCl2 from ZHS and HCl promotes the cyclization reaction of PANVDC in the condensed phase. The LOI values of PANVDC, PANVDC-ATO, and PANVDC-ZHS were 26.4%, 29.0%, and 33.5%, respectively. This suggests that ZHS is a highly effective for PANVDC. Meanwhile, the LOI of PANVDC containing ATO-ZHS mixture is 31.0%. The combination of ATO and ZHS exhibited no efficiency. The addition of ATO and ZHS slightly reduced the tenacities of the fibers, respectively, 3.11 and 3.75 from 4.42 g/den. Full article
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20 pages, 10603 KiB  
Article
The Toxicological Testing and Thermal Decomposition of Drive and Transport Belts Made of Thermoplastic Multilayer Polymer Materials
by Piotr Krawiec, Łukasz Warguła, Daniel Małozięć, Piotr Kaczmarzyk, Anna Dziechciarz and Dorota Czarnecka-Komorowska
Polymers 2020, 12(10), 2232; https://doi.org/10.3390/polym12102232 - 28 Sep 2020
Cited by 23 | Viewed by 3201
Abstract
The article presents the potential impact of flat drive and transport belts on people’s safety during a fire. The analysis distinguished belts made of classically used fabric–rubber composite materials reinforced with cord and currently used multilayer polymer composites. Moreover, the products’ multilayers during [...] Read more.
The article presents the potential impact of flat drive and transport belts on people’s safety during a fire. The analysis distinguished belts made of classically used fabric–rubber composite materials reinforced with cord and currently used multilayer polymer composites. Moreover, the products’ multilayers during the thermal decomposition and combustion can be a source of emissions for unpredictable and toxic substances with different concentrations and compositions. In the evaluation of the compared belts, a testing methodology was used to determine the toxicometric indicators (WLC50SM) on the basis of which it was possible to determine the toxicity of thermal decomposition and combustion products in agreement with the standards in force in several countries of the EU and Russia. The analysis was carried out on the basis of the registration of emissions of chemical compounds during the thermal decomposition and combustion of polymer materials at three different temperatures. Moreover, the degradation kinetics of the polymeric belts by using the thermogravimetric (TGA) technique was evaluated. Test results have shown that products of thermal decomposition resulting from the neoprene (NE22), leder leder (LL2), thermoplastic connection (TC), and extra high top cower (XH) belts can be characterized as moderately toxic or toxic. Their toxicity significantly increases with the increasing temperature of thermal decomposition or combustion, especially above 450 °C. The results showed that the belts made of several layers of polyamide can be considered the least toxic in fire conditions. The TGA results showed that NBR/PA/PA/NBR belt made with two layers of polyamide and the acrylonitrile–butadiene rubber has the highest thermal stability in comparison to other belts. Full article
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25 pages, 2124 KiB  
Review
The Potential for Bio-Sustainable Organobromine-Containing Flame Retardant Formulations for Textile Applications—A Review
by A Richard Horrocks
Polymers 2020, 12(9), 2160; https://doi.org/10.3390/polym12092160 - 22 Sep 2020
Cited by 29 | Viewed by 4400
Abstract
This review considers the challenge of developing sustainable organobromine flame retardants (BrFRs) and alternative synergists to the predominantly used antimony III oxide. Current BrFR efficiencies are reviewed for textile coatings and back-coatings with a focus on furnishing and similar fabrics covering underlying flammable [...] Read more.
This review considers the challenge of developing sustainable organobromine flame retardants (BrFRs) and alternative synergists to the predominantly used antimony III oxide. Current BrFR efficiencies are reviewed for textile coatings and back-coatings with a focus on furnishing and similar fabrics covering underlying flammable fillings, such as flexible polyurethane foam. The difficulty of replacing them with non-halogen-containing systems is also reviewed with major disadvantages including their extreme specificity with regard to a given textile type and poor durability.The possibility of replacing currently used BrFRs for textiles structures that mimic naturally occurring organobromine-containing species is discussed, noting that of the nearly 2000 such species identified in both marine and terrestrial environments, a significant number are functionalised polybrominated diphenyl ethers, which form part of a series of little understood biosynthetic biodegradation cycles.The continued use of antimony III oxide as synergist and possible replacement by alternatives, such as the commercially available zinc stannates and the recently identified zinc tungstate, are discussed. Both are effective as synergists and smoke suppressants, but unlike Sb203, they have efficiencies dependent on BrFR chemistry and polymer matrix or textile structure. Furthermore, their effectiveness in textile coatings has yet to be more fully assessed.In conclusion, it is proposed that the future of sustainable BrFRs should be based on naturally occurring polybrominated structures developed in conjunction with non-toxic, smoke-suppressing synergists such as the zinc stannates or zinc tungstate, which have been carefully tailored for given polymeric and textile substrates. Full article
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17 pages, 6866 KiB  
Article
Flammability Characteristics and Mechanical Properties of Casein Based Polymeric Composites
by Hanbin Lee, Nam Kyeun Kim, Daeseung Jung and Debes Bhattacharyya
Polymers 2020, 12(9), 2078; https://doi.org/10.3390/polym12092078 - 12 Sep 2020
Cited by 11 | Viewed by 2694
Abstract
Even though casein has an intrinsic potential ability to act as a flame retardant (FR) additive, the research regarding the FR performance of casein filled polymeric composites has not been thoroughly conducted. In the present work, two commercial casein products, such as lactic [...] Read more.
Even though casein has an intrinsic potential ability to act as a flame retardant (FR) additive, the research regarding the FR performance of casein filled polymeric composites has not been thoroughly conducted. In the present work, two commercial casein products, such as lactic casein 720 (LAC) and sodium casein 180 (SC), were chosen to investigate their effects on the performances of the polypropylene (PP) composites. The melt compounding and compression moulding processes were employed to fabricate these casein-based composites. Ammonium polyphosphate (APP) was also selected to explore its combined effects in conjunction with casein on the composite’s flammability. The cone calorimeter results showed that the addition of casein significantly reduced (66%) the peak heat release rate (PHRR) of the composite compared to that of neat PP. In particular, the combination of LAC and APP led to the formation of more compact and rigid char compared to that for SC based sample; hence, a further reduction (80%) in PHRR and self-extinguishment under a vertical burn test were accomplished. Moreover, the tensile modulus of the composite improved (23%) by the combined effects of LAC and APP. The overall research outcome has established the potential of casein as a natural protein FR reducing a polymer’s flammability. Full article
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10 pages, 1942 KiB  
Article
A Kinetic Analysis of the Thermal Degradation Behaviours of Some Bio-Based Substrates
by Ananya Thomas, Khalid Moinuddin, Svetlana Tretsiakova-McNally and Paul Joseph
Polymers 2020, 12(8), 1830; https://doi.org/10.3390/polym12081830 - 15 Aug 2020
Cited by 9 | Viewed by 2537
Abstract
In the present paper, we report on a detailed study regarding the thermal degradation behaviours of some bio-sourced substrates. These were previously identified as the base materials in the formulations for fireproofing wood plaques through our investigations. The substrates included: β-cyclodextrin, dextran, potato [...] Read more.
In the present paper, we report on a detailed study regarding the thermal degradation behaviours of some bio-sourced substrates. These were previously identified as the base materials in the formulations for fireproofing wood plaques through our investigations. The substrates included: β-cyclodextrin, dextran, potato starch, agar-agar, tamarind kernel powder and chitosan. For deducing the Arrhenius parameters from thermograms obtained through routine thermogravimetric analyses (TGA), we used the standard Flynn–Wall–Ozawa (FWO) method and employed an in-house developed proprietary software. In the former case, five different heating rates were used, whereas in the latter case, the data from one dynamic heating regime were utilized. Given that the FWO method is essentially based on a model-free approach that also makes use of multiple heating rates, it can be considered in the present context as superior to the one that is dependent on a single heating rate. It is also relevant to note here that the values of energy of activation (Ea) obtained in each case should only be considered as apparent values at best. Furthermore, some useful, but limited, correlations were identified between the Ea values and the relevant parameters obtained earlier by us from pyrolysis combustion flow calorimetry (PCFC). Full article
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17 pages, 3854 KiB  
Article
Mechanistic Aspects of Condensed- and Gaseous-Phase Activities of Some Phosphorus-Containing Fire Retardants
by Ananya Thomas, Malavika Arun, Khalid Moinuddin and Paul Joseph
Polymers 2020, 12(8), 1801; https://doi.org/10.3390/polym12081801 - 11 Aug 2020
Cited by 7 | Viewed by 2255
Abstract
As a part of our ongoing investigations on passively fire protecting polymeric materials, we have been employing both reactive and additive routes involving phosphorus-containing compounds. These included inorganic and organic substances, and in the latter case, the phosphorus-bearing groups differed in terms of [...] Read more.
As a part of our ongoing investigations on passively fire protecting polymeric materials, we have been employing both reactive and additive routes involving phosphorus-containing compounds. These included inorganic and organic substances, and in the latter case, the phosphorus-bearing groups differed in terms of the chemical environments (phosphite, phosphate, phosphine, phosphine oxide and phosphonate ester) and oxidation state of the P atom (i.e., III, or V). The overall flammability profiles of wood substrates coated with the phosphorus-containing compounds were obtained through cone calorimetric measurements. The elemental composition, morphology and chemical natures of the char residues, obtained from the cone tests, were analysed through a variety of spectroscopic, chromatographic and spectrometric means. From the complementary information, obtained through these analyses, some probable mechanistic pathways that underpin the condensed- and gaseous-phase activities of the different additives are suggested. It was found that the inorganic solid additive, i.e., (NH4)2HPO4, underwent a two-step degradation, yielding ammonia gas and phosphoric acid. Furthermore, the liquid additives, owing to their volatility as compared to the solid ones, showed a relatively higher presence in the vapour phase than volatile fragments emanating from the latter ones (i.e., from phosphine and the phosphine oxides). Full article
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22 pages, 6532 KiB  
Article
A Case Study of Polyether Ether Ketone (I): Investigating the Thermal and Fire Behavior of a High-Performance Material
by Aditya Ramgobin, Gaëlle Fontaine and Serge Bourbigot
Polymers 2020, 12(8), 1789; https://doi.org/10.3390/polym12081789 - 10 Aug 2020
Cited by 21 | Viewed by 2743
Abstract
The thermal and fire behaviors of a high-performance polymeric material—polyether ether ketone (PEEK) was investigated. The TG plots of PEEK under different oxygen concentrations revealed that the initial step of thermal decomposition does not greatly depend on the oxygen level. However, oxygen concentration [...] Read more.
The thermal and fire behaviors of a high-performance polymeric material—polyether ether ketone (PEEK) was investigated. The TG plots of PEEK under different oxygen concentrations revealed that the initial step of thermal decomposition does not greatly depend on the oxygen level. However, oxygen concentration plays a major role in the subsequent decomposition steps. In order to understand the thermal decomposition mechanism of PEEK several methods were employed, i.e., pyrolysis–gas chromatography–mass spectrometry (Py–GC–MS), thermogravimetric analysis (TGA) coupled with a Fourier-transform infrared spectrometer (FTIR). It was observed that the initial decomposition step of the material may lead to the release of noncombustible gases and the formation of a highly crosslinked graphite-like carbonaceous structure. Moreover, during the mass loss cone calorimetry test, PEEK has shown excellent charring and fire resistance when it is subjected to an incident heat flux of 50 kW/m². Based on the fire behavior and the identification of pyrolysis gases evolved during the decomposition of PEEK, the enhanced fire resistance of PEEK was assigned to the dilution of the flammable decomposition gases as well as the formation of a protective graphite-like charred structure during its decomposition. Moreover, at 60 kW/m², ignition occurred more quickly. This is because a higher rate of release of decomposition products is achieved at such a heat flux, causing a higher concentration of combustibles, thus an earlier ignition. However, the peak of heat release rate of the material did not exceed 125 kW/m². Full article
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23 pages, 5183 KiB  
Article
Enhanced Biodegradation/Photodegradation of Organophosphorus Fire Retardant Using an Integrated Method of Modified Pharmacophore Model with Molecular Dynamics and Polarizable Continuum Model
by Jiawen Yang, Qing Li and Yu Li
Polymers 2020, 12(8), 1672; https://doi.org/10.3390/polym12081672 - 27 Jul 2020
Cited by 12 | Viewed by 2894
Abstract
A comprehensive 3D-quantitative structure–activity relationship (QSAR) pharmacophore model was constructed using the values of comprehensive biodegradation/photodegradation effects of 17 organophosphorus flame retardants (OPFRs) evaluated by a normalization method to modify OPFRs with high biodegradation/photodegradation, taking tris(chloro-isopropyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) [...] Read more.
A comprehensive 3D-quantitative structure–activity relationship (QSAR) pharmacophore model was constructed using the values of comprehensive biodegradation/photodegradation effects of 17 organophosphorus flame retardants (OPFRs) evaluated by a normalization method to modify OPFRs with high biodegradation/photodegradation, taking tris(chloro-isopropyl) phosphate (TCPP), tris(2-chloroethyl) phosphate (TCEP) and tris(1-chloro-2-propyl) phosphate (TCIPP)—which occur frequently in the environment, and are the most difficult to degrade as target molecules. OPFR-derivative molecules TCPP–OH shows the highest improvement in biodegradation and photodegradation (55.48% and 46.37%, respectively). On simulating the biodegradation path and photodegradation path, it is found that the energy barrier of TCPP–OH for phosphate bond cleavage is reduced by 15.73% and 52.52% compared to TCPP after modification, respectively. Finally, in order to further significantly improve its biodegradability and photodegradation, the efficiency enhancement in the biodegradation and photodegradation of TCPP–OH are analyzed under the simulated environment by molecular dynamics and polarizable continuum model, respectively. The results of molecular dynamics show that the biodegradation efficiency of the TCPP–OH increased by 75.52% compared to TCPP. The UV spectral transition energy (4.07 eV) of TCPP–OH under the influence of hydrogen peroxide solvation effect is 44.23% lower than the actual transition energy (7.29 eV) of TCPP. Full article
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20 pages, 7261 KiB  
Article
A Case Study of Polyetheretherketone (II): Playing with Oxygen Concentration and Modeling Thermal Decomposition of a High-Performance Material
by Aditya Ramgobin, Gaëlle Fontaine and Serge Bourbigot
Polymers 2020, 12(7), 1577; https://doi.org/10.3390/polym12071577 - 16 Jul 2020
Cited by 10 | Viewed by 2632
Abstract
Kinetic decomposition models for the thermal decomposition of a high-performance polymeric material (polyetheretherketone, PEEK) were determined from specific techniques. Experimental data from thermogravimetric analysis (TGA) and previously elucidated decomposition mechanisms were combined with a numerical simulating tool to establish a comprehensive kinetic model [...] Read more.
Kinetic decomposition models for the thermal decomposition of a high-performance polymeric material (polyetheretherketone, PEEK) were determined from specific techniques. Experimental data from thermogravimetric analysis (TGA) and previously elucidated decomposition mechanisms were combined with a numerical simulating tool to establish a comprehensive kinetic model for the decomposition of PEEK under three atmospheres: nitrogen, 2% oxygen, and synthetic air. Multistepped kinetic models with subsequent and competitive reactions were established by taking into consideration the different types of reactions that may occur during the thermal decomposition of the material (chain scission, thermo-oxidation, char formation). The decomposition products and decomposition mechanism of PEEK which were established in our previous report allowed for the elucidation of the kinetic decomposition models. A three-stepped kinetic thermal decomposition pathway was a good fit to model the thermal decomposition of PEEK under nitrogen. The kinetic model involved an autocatalytic type of reaction followed by competitive and successive nth order reactions. Such types of models were set up for the evaluation of the kinetics of the thermal decomposition of PEEK under 2% oxygen and in air, leading to models with satisfactory fidelity. Full article
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16 pages, 3881 KiB  
Article
Application of Plasma Activation in Flame-Retardant Treatment for Cotton Fabric
by Huong Nguyen Thi, Khanh Vu Thi Hong, Thanh Ngo Ha and Duy-Nam Phan
Polymers 2020, 12(7), 1575; https://doi.org/10.3390/polym12071575 - 16 Jul 2020
Cited by 16 | Viewed by 3458
Abstract
Cotton fabric treated by Pyrovatex CP New (PCN) and Knittex FFRC (K-FFRC) using the Pad-dry-cure method showed an excellent fire-retardant effect. However, it needed to be cured at high temperatures for a long time leading to a high loss of mechanical strength. In [...] Read more.
Cotton fabric treated by Pyrovatex CP New (PCN) and Knittex FFRC (K-FFRC) using the Pad-dry-cure method showed an excellent fire-retardant effect. However, it needed to be cured at high temperatures for a long time leading to a high loss of mechanical strength. In this study, atmospheric-pressure dielectric barrier discharge (APDBD) plasma was applied to the cotton fabric, which then was treated by flame retardants (FRs) using the pad–dry-cure method. The purpose was to have a flame-retardant cotton fabric (limiting oxygen index (LOI) ≥ 25) and a mechanical loss of the treated fabric due to the curing step as low as possible. To achieve this goal, 10 experiments were performed. The vertical flammability characteristics, LOI value and tensile strength of the treated fabrics were measured. A response model between the LOI values of the treated fabric and two studied variables (temperature and time of the curing step) was found. It was predicted that the optimal temperature and time-to-cure to achieve LOI of 25 was at 160 °C for 90 s, while the flame-retardant treatment process without plasma pretreatment, was at 180 °C and 114 s. Although the curing temperature and the time have decreased significantly, the loss of mechanical strength of the treated fabric is still high. The tensile strength and scanning electron microscopy (SEM) images of the fabric after plasma activation show that the plasma treatment itself also damages the mechanical strength of the fabric. X-ray photoelectron spectroscopy (XPS) spectra of the fabric after plasma activation and energy-dispersive spectroscopy (EDS) analysis of the flame retardant-treated (FRT) fabric clarified the role of plasma activation in this study. Full article
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16 pages, 2175 KiB  
Article
Potential Synergism between Novel Metal Complexes and Polymeric Brominated Flame Retardants in Polyamide 6.6
by Alistair F. Holdsworth, A. Richard Horrocks and Baljinder K. Kandola
Polymers 2020, 12(7), 1543; https://doi.org/10.3390/polym12071543 - 13 Jul 2020
Cited by 10 | Viewed by 2545
Abstract
While environmental concerns have caused polymeric brominated primary flame retardants (PolyBrFRs) to be effective replacement monomeric species, few alternatives for antimony trioxide (ATO) have been developed beyond the zinc stannates (ZnSs). Previous research, which explored the interactions of aluminium (AlW), tin (II) (SnW) [...] Read more.
While environmental concerns have caused polymeric brominated primary flame retardants (PolyBrFRs) to be effective replacement monomeric species, few alternatives for antimony trioxide (ATO) have been developed beyond the zinc stannates (ZnSs). Previous research, which explored the interactions of aluminium (AlW), tin (II) (SnW) and zinc (ZnW) tungstates with several phosphorus-containing flame retardants in polyamide 6.6 (PA66), is extended to two PolyBrFRs: brominated polystyrene (BrPS), and poly(pentabromobenzyl acrylate) (BrPBz). On assessing the effect of each tungstate on the thermal degradation and flammability in combination with each PolyBrFR using TGA, UL94, LOI, cone calorimetry and TGA-FTIR, only ZnW and SnW showed significant increases in LOI (>26 vol.%). Both ZnW-BrPS- and ZnW-BrPBz-containing formulations yielded average UL94 ratings ≥ V-2 and TGA char residues (corrected for metals content at 500 °C) in air > 15 wt.%. BrPS-containing samples, especially those containing ZnW and SnW, generated peak heat release rates approximately 50% lower than the equivalent BrPBz samples. These reductions did not correlate with respective increases in LOI, suggesting that tungstate-PolyBrFR combinations influence pre-ignition differently to post-ignition behaviour. Calculated synergistic effectivities indicate that ZnW functions as a synergist in both pre- and post-ignition stages, especially with BrPS. TGA-FTIR and char analyses showed that, in addition to the vapour-phase activity normally associated with PolyBrFRs, condensed-phase processes occurred, especially for the ZnW-PolyBrFR combinations. Additionally, ZnW demonstrated significant smoke-suppressing properties comparable with zinc stannate (ZnS). Full article
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14 pages, 3811 KiB  
Article
Preparation and Mechanism of Flame-Retardant Cotton Fabric with Phosphoramidate Siloxane Polymer through Multistep Coating
by Denghui Xu, Shijie Wang, Yimin Wang, Yun Liu, Chaohong Dong, Zhiming Jiang and Ping Zhu
Polymers 2020, 12(7), 1538; https://doi.org/10.3390/polym12071538 - 12 Jul 2020
Cited by 23 | Viewed by 3215
Abstract
To improve the water solubility of phosphoramidate siloxane and decrease the amount of flame-retardant additives used in the functional coating for cotton fabrics, a water-soluble phosphoramidate siloxane polymer (PDTSP) was synthesized by sol-gel technology and flame-retardant cotton fabrics were prepared with a multistep [...] Read more.
To improve the water solubility of phosphoramidate siloxane and decrease the amount of flame-retardant additives used in the functional coating for cotton fabrics, a water-soluble phosphoramidate siloxane polymer (PDTSP) was synthesized by sol-gel technology and flame-retardant cotton fabrics were prepared with a multistep coating process. A vertical flammability test, limited oxygen index (LOI), thermogravimetric analysis, and cone calorimetry were performed to investigate the thermal behavior and flame retardancy of PDTSP-coated fabrics. The coated cotton fabrics and their char residues after combustion were studied by attenuated total reflection infrared spectroscopy (FTIR-ATR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). All results presented that PDTSP-coated cotton fabrics had good flame retardancy and char-forming properties. PDTSP coating was demonstrated to posess gas-phase flame-retardant mechanism as well as a condensed phase flame-retardant mechanism, which can be confirmed by thermogravimetric analysis-Fourier transform infrared spectroscopy (TG-IR) and cone calorimetry test. Also, the preparation process had little effect on the tensile strength of cotton fabrics, although the air permeability and whiteness had a slight decrease. After different washing cycles, the coated samples still maintained good char-forming properties. Full article
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15 pages, 4949 KiB  
Article
Effects of a Reactive Phosphorus–Sulfur Containing Flame-Retardant Monomer on the Flame Retardancy and Thermal and Mechanical Properties of Unsaturated Polyester Resin
by Kang Dai, Zhenzhen Deng, Guyue Liu, Yutong Wu, Wenbin Xu and Yuan Hu
Polymers 2020, 12(7), 1441; https://doi.org/10.3390/polym12071441 - 27 Jun 2020
Cited by 16 | Viewed by 3415
Abstract
A novel reactive phosphorus and sulfur-containing monomer (bis(acryloxyethyldiphenylphosphate)sulfone, BADPS) was synthesized to enhance the comprehensive performance of unsaturated polyester resin (UPR), and corresponding flame-retardant unsaturated polyester resins (FR-UPRs) with various amounts of BADPS were prepared by radical bulk polymerization. The flame retardancy and [...] Read more.
A novel reactive phosphorus and sulfur-containing monomer (bis(acryloxyethyldiphenylphosphate)sulfone, BADPS) was synthesized to enhance the comprehensive performance of unsaturated polyester resin (UPR), and corresponding flame-retardant unsaturated polyester resins (FR-UPRs) with various amounts of BADPS were prepared by radical bulk polymerization. The flame retardancy and thermal and mechanical properties of the UPR samples were investigated by limiting oxygen index (LOI) measurements, cone calorimetry, differential scanning calorimetry (DSC), a thermogravimetric analysis (TGA), and a tension test. The results showed that the introduction of BADPS remarkably enhanced the flame resistance and high-temperature stability, as well as the tensile performance of UPR. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), and Raman spectroscopy studies revealed that BADPS can efficaciously promote the formation of UPR char residue with an improved microstructure and increased graphitization degree, which enhancedthe high-temperature stability and char yield of UPR. Additionally, a thermogravimetry-Fourier transform infrared (TG-FTIR) analysis corroborated that the evolution of combustible volatiles from UPR decomposition was substantially restrained by the incorporation of BADPS, which is beneficial for the suppression of fire hazards in UPR. Full article
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17 pages, 5816 KiB  
Review
Flame Retardancy of Bio-Based Polyurethanes: Opportunities and Challenges
by Henri Vahabi, Hadi Rastin, Elnaz Movahedifar, Karina Antoun, Nicolas Brosse and Mohammad Reza Saeb
Polymers 2020, 12(6), 1234; https://doi.org/10.3390/polym12061234 - 29 May 2020
Cited by 78 | Viewed by 6938
Abstract
Sustainable polymers are emerging fast and have received much more attention in recent years compared to petro-sourced polymers. However, they inherently have low-quality properties, such as poor mechanical properties, and inadequate performance, such as high flammability. In general, two methods have been considered [...] Read more.
Sustainable polymers are emerging fast and have received much more attention in recent years compared to petro-sourced polymers. However, they inherently have low-quality properties, such as poor mechanical properties, and inadequate performance, such as high flammability. In general, two methods have been considered to tackle such drawbacks: (i) reinforcement of sustainable polymers with additives; and (ii) modification of chemical structure by architectural manipulation so as to modify polymers for advanced applications. Development and management of bio-based polyurethanes with flame-retardant properties have been at the core of attention in recent years. Bio-based polyurethanes are currently prepared from renewable, bio-based sources such as vegetable oils. They are used in a wide range of applications including coatings and foams. However, they are highly flammable, and their further development is dependent on their flame retardancy. The aim of the present review is to investigate recent advances in the development of flame-retardant bio-based polyurethanes. Chemical structures of bio-based flame-retardant polyurethanes have been studied and explained from the point of view of flame retardancy. Moreover, various strategies for improving the flame retardancy of bio-based polyurethanes as well as reactive and additive flame-retardant solutions are discussed. Full article
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15 pages, 3797 KiB  
Article
A Flame-Retardant Phytic-Acid-Based LbL-Coating for Cotton Using Polyvinylamine
by Olga Zilke, Dennis Plohl, Klaus Opwis, Thomas Mayer-Gall and Jochen Stefan Gutmann
Polymers 2020, 12(5), 1202; https://doi.org/10.3390/polym12051202 - 25 May 2020
Cited by 30 | Viewed by 4373
Abstract
Phytic acid (PA), as a natural source of phosphorus, was immobilized on cotton (CO) in a layer-by-layer (LbL) approach with polyvinylamine (PVAm) as the oppositely charged electrolyte to create a partly bio-based flame-retardant finish. PVAm was employed as a synthetic nitrogen source with [...] Read more.
Phytic acid (PA), as a natural source of phosphorus, was immobilized on cotton (CO) in a layer-by-layer (LbL) approach with polyvinylamine (PVAm) as the oppositely charged electrolyte to create a partly bio-based flame-retardant finish. PVAm was employed as a synthetic nitrogen source with the highest density of amine groups of all polymers. Vertical flame tests revealed a flame-retardant behavior with no afterflame and afterglow time for a coating of 15 bilayers (BL) containing 2% phosphorus and 1.4% nitrogen. The coating achieved a molar P:N ratio of 3:5. Microscale combustion calorimetry (MCC) analyses affirmed the flame test findings by a decrease in peak heat release rate (pkHRR) by more than 60% relative to unfinished CO. Thermogravimetric analyses (TGA) and MCC measurements exhibited a shifted CO peak to lower temperatures indicating proceeding reactions to form an isolating char on the surface. Fourier transform infrared spectroscopy (FTIR) coupled online with a TGA system, allowed the identification of a decreased amount of acrolein, methanol, carbon monoxide and formaldehyde during sample pyrolysis and a higher amount of released water. Thereby the toxicity of released volatiles was reduced. Our results prove that PA enables a different reaction by catalyzing cellulosic dehydration, which results in the formation of a protective char on the surface of the burned fabric. Full article
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14 pages, 11699 KiB  
Article
Poly (vinyl alcohol)/β-Cyclodextrin Composite Fiber with Good Flame Retardant and Super-Smoke Suppression Properties
by Cheng-Yuan Xing, Shi-Lin Zeng, Shi-Kai Qi, Meng-Jin Jiang, Long Xu, Li Chen, Sheng Zhang and Bang-Jing Li
Polymers 2020, 12(5), 1078; https://doi.org/10.3390/polym12051078 - 08 May 2020
Cited by 15 | Viewed by 3548
Abstract
Fibers with good flame retardant (FR) and smoke suppression performances are highly desirable for the purpose of eliminating fire hazard. This study developed a novel FR fiber by wet-spinning poly (vinyl alcohol)/β-cyclodextrin (PVA/βCD) composite fiber and crosslinking it with hexamethylene diisocyanate (HDI). βCDs [...] Read more.
Fibers with good flame retardant (FR) and smoke suppression performances are highly desirable for the purpose of eliminating fire hazard. This study developed a novel FR fiber by wet-spinning poly (vinyl alcohol)/β-cyclodextrin (PVA/βCD) composite fiber and crosslinking it with hexamethylene diisocyanate (HDI). βCDs showed good compatibility with PVA matrix, and the resulting PVA/CD/HDI fibers showed mechanical strength at the same level as natural cotton fiber. The PVA/CD/HDI fibers also showed excellent flame retardance (the LOI value of PVA/CD/HDI could reach 41.7%, and their peak of heat release (PHRR) could be reduced by up to 77.7% by neat PVA), and super-smoke suppression (the value of total smoke production (TSP) was only 28.6% compared to PVA). These dramatic reductions of fire hazard were ascribed to the char formation of βCD and crosslinking structure of PVA/CD/HDI, which formed a compact char layer during combustion, thus preventing heat transmission and smoke release. Full article
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31 pages, 13538 KiB  
Review
Biomolecules as Flame Retardant Additives for Polymers: A Review
by Daniel A. Villamil Watson and David A. Schiraldi
Polymers 2020, 12(4), 849; https://doi.org/10.3390/polym12040849 - 07 Apr 2020
Cited by 57 | Viewed by 7093
Abstract
Biological molecules can be obtained from natural sources or from commercial waste streams and can serve as effective feedstocks for a wide range of polymer products. From foams to epoxies and composites to bulk plastics, biomolecules show processability, thermal stability, and mechanical adaptations [...] Read more.
Biological molecules can be obtained from natural sources or from commercial waste streams and can serve as effective feedstocks for a wide range of polymer products. From foams to epoxies and composites to bulk plastics, biomolecules show processability, thermal stability, and mechanical adaptations to fulfill current material requirements. This paper summarizes the known bio-sourced (or bio-derived), environmentally safe, thermo-oxidative, and flame retardant (BEST-FR) additives from animal tissues, plant fibers, food waste, and other natural resources. The flammability, flame retardance, and—where available—effects on polymer matrix’s mechanical properties of these materials will be presented. Their method of incorporation into the matrix, and the matrices for which the BEST-FR should be applicable will also be made known if reported. Lastly, a review on terminology and testing methodology is provided with comments on future developments in the field. Full article
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15 pages, 12996 KiB  
Article
Phytic Acid and Biochar: An Effective All Bio-Sourced Flame Retardant Formulation for Cotton Fabrics
by Marco Barbalini, Mattia Bartoli, Alberto Tagliaferro and Giulio Malucelli
Polymers 2020, 12(4), 811; https://doi.org/10.3390/polym12040811 - 04 Apr 2020
Cited by 53 | Viewed by 4083
Abstract
Flame retardant systems based on bio-sourced products combine quite high fire performances with the low environmental impact related to their synthesis and exploitation. In this context, this work describes a new all bio-sourced flame retardant system designed and applied to cotton fabrics. In [...] Read more.
Flame retardant systems based on bio-sourced products combine quite high fire performances with the low environmental impact related to their synthesis and exploitation. In this context, this work describes a new all bio-sourced flame retardant system designed and applied to cotton fabrics. In particular, it consists of phytic acid (PA), a phosphorus-based naturally occurring molecule extracted from different plant tissues, in combination with biochar (BC), a carbon-rich solid product obtained from the thermo-chemical conversion of biomasses in an oxygen-limited environment. PA and BC were mixed together at a 1:1 weight ratio in an aqueous medium, and applied to cotton at different loadings. As revealed by flammability and forced combustion tests, this bio-sourced system was able to provide significant improvements in flame retardance of cotton, even limiting the final dry add-on on the treated fabrics at 8 wt.% only. The so-treated fabrics were capable to achieve self-extinction in both horizontal and vertical flame spread tests; besides, they did not ignite under the exposure to 35 kW/m2 irradiative heat flux. Conversely, the proposed flame retardant treatment did not show a high washing fastness, though the washed flame retarded fabrics still exhibited a better flame retardant behavior than untreated cotton. Full article
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13 pages, 3710 KiB  
Article
Synthesis of Novel Polymeric Acrylate-Based Flame Retardants Containing Two Phosphorus Groups in Different Chemical Environments and Their Influence on the Flammability of Poly (Lactic Acid)
by Jacob Sag, Philipp Kukla, Daniela Goedderz, Hendrik Roch, Stephan Kabasci, Manfred Döring and Frank Schönberger
Polymers 2020, 12(4), 778; https://doi.org/10.3390/polym12040778 - 01 Apr 2020
Cited by 14 | Viewed by 3961
Abstract
Novel polymeric acrylate-based flame retardants (FR 1–4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations [...] Read more.
Novel polymeric acrylate-based flame retardants (FR 1–4) containing two phosphorus groups in different chemical environments were synthesized in three steps and characterized via nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and mass spectrometry (MS). Polylactic acid (PLA) formulations with the synthesized compounds were investigated to evaluate the efficiency of these flame retardants and their mode of action by using TGA, UL94, and cone calorimetry. In order to compare the results a flame retardant polyester containing only one phosphorus group (ItaP) was also investigated in PLA regarding its flame inhibiting effect. Since the fire behavior depends not only on the mode of action of the flame retardants but also strongly on physical phenomena like melt dripping, the flame retardants were also incorporated into PLA with higher viscosity. In the UL94 vertical burning test setup, 10% of the novel flame retardants (FR 1–4) is sufficient to reach a V-0 rating in both PLA types, while a loading of 15% of ItaP is not enough to reach the same classification. Despite their different structure, TGA and cone calorimetry results confirmed a gas phase mechanism mainly responsible for the highly efficient flame retardancy for all compounds. Finally, cone calorimetry tests of the flame retardant PLA with two heat fluxes showed different flame inhibiting efficiencies for different fire scenarios. Full article
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15 pages, 2879 KiB  
Article
Waterborne Intumescent Coatings Containing Industrial and Bio-Fillers for Fire Protection of Timber Materials
by Abderrahman Aqlibous, Svetlana Tretsiakova-McNally and Talal Fateh
Polymers 2020, 12(4), 757; https://doi.org/10.3390/polym12040757 - 31 Mar 2020
Cited by 19 | Viewed by 3789
Abstract
Flammability and combustion of softwood treated with intumescent coatings were studied in the present work. The formulations applied onto wood surfaces contained different ratios of industrial fillers, titanium dioxide TiO2 and aluminium trihydroxide Al(OH)3, and/or bio-fillers, eggshell and rice husk [...] Read more.
Flammability and combustion of softwood treated with intumescent coatings were studied in the present work. The formulations applied onto wood surfaces contained different ratios of industrial fillers, titanium dioxide TiO2 and aluminium trihydroxide Al(OH)3, and/or bio-fillers, eggshell and rice husk ash. Combustion behaviours of unprotected and protected wood samples have been examined with the aid of cone calorimetry performed under the varied levels of thermal flux ranging from 30 to 50 kW/m². The char residues obtained after the completion of cone calorimetry test at 40 kW/m² were analysed by the Raman spectroscopy. The fire protective properties of the studied coatings were strongly influenced by the nature of the fillers as well as by the intensity of thermal irradiance. The incorporation of bio-based fillers into the water-based intumescent formulations significantly improved fire resistance of wood substrates. For example, at 30 kW/m², the Effective Heat of Combustion was reduced by more than 40%, whilst the average Peak to Heat Release Rate had dropped from 193.2 to 150.3 kW/m² for the wood sample protected with the formulation incorporating two industrial and two bio-fillers. Moreover, an application of the studied coatings resulted in a notable reduction of the back surface temperature of the wood specimens. Full article
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18 pages, 4629 KiB  
Article
Effect of Different Flame-Retardant Bridged DOPO Derivatives on Properties of in Situ Produced Fiber-Forming Polyamide 6
by Jelena Vasiljević, Marija Čolović, Nataša Čelan Korošin, Matic Šobak, Žiga Štirn and Ivan Jerman
Polymers 2020, 12(3), 657; https://doi.org/10.3390/polym12030657 - 13 Mar 2020
Cited by 30 | Viewed by 5340
Abstract
The production of sustainable and effective flame retardant (FR) polyamide 6 (PA6) fibrous materials requires the establishment of a novel approach for the production of polyamide 6/FR nanodispersed systems. This research work explores the influence of three different flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives [...] Read more.
The production of sustainable and effective flame retardant (FR) polyamide 6 (PA6) fibrous materials requires the establishment of a novel approach for the production of polyamide 6/FR nanodispersed systems. This research work explores the influence of three different flame-retardant bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives on the comprehensive properties of in situ produced PA6/FR systems. To this end, in situ water-catalyzed ring-opening polymerization of ε-caprolactam was conducted in the presence of three different bridged DOPO derivatives, e.g., one P−N bond phosphonamidate derivative and two P−C bond phosphinate derivatives. The selected bridged DOPO derivatives mainly act in the gas phase at the temperatures that relatively match the PA6 pyrolysis specifics. The effects of the FRs on the dispersion state, morphological, molecular, structural, melt-rheological, and thermal properties of the in situ synthesized PA6 were evaluated. The specific advantage of this approach is one-step production of PA6 with uniformly distributed nanodispersed FR, which was obtained in the case of all three applied FRs. However, the applied FRs differently interacted with monomer and polymer during the polymerization, which was reflected in the length of PA6 chains, crystalline structure, and melt-rheological properties. The applied FRs provided a comparable effect on the thermal stability of PA6 and stabilization of the PA6/FR systems above 450 °C in the oxygen-assisted pyrolysis. However, only with the specifically designed FR molecule were the comprehensive properties of the fiber-forming PA6 satisfied for the continuous conduction of the melt-spinning process. Full article
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14 pages, 3634 KiB  
Article
Thermal and Calorimetric Evaluations of Some Chemically Modified Carbohydrate-Based Substrates with Phosphorus-Containing Groups
by Ananya Thomas, Paul Joseph, Khalid Moinuddin, Haijin Zhu and Svetlana Tretsiakova-McNally
Polymers 2020, 12(3), 588; https://doi.org/10.3390/polym12030588 - 05 Mar 2020
Cited by 7 | Viewed by 2606
Abstract
In the present article, we report on the chemical modifications of some carbohydrate-based substrates, such as potato starch, dextran, β-cyclodextrin, agar agar and tamarind, by reacting with diethylchlorophosphate (DECP), in dispersions in dichloromethane (DCM), in the presence of triethylamine (TEA) as the base. [...] Read more.
In the present article, we report on the chemical modifications of some carbohydrate-based substrates, such as potato starch, dextran, β-cyclodextrin, agar agar and tamarind, by reacting with diethylchlorophosphate (DECP), in dispersions in dichloromethane (DCM), in the presence of triethylamine (TEA) as the base. The modified substrates, after recovery and purification, were analyzed for their chemical constitutions, thermal stabilities and calorimetric properties using a variety of analytical techniques. These included: solid-state 31P NMR, inductively coupled plasma-optical emission spectroscopy (ICP-OES), thermogravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The unmodified counterparts were also subjected to the same set of analyses with a view to serving as controls. Phosphorus analyses, primarily through ICP-OES on the recovered samples, showed different degrees of incorporation. Such observations were optionally verified through solid-state 31P NMR spectroscopy. The thermograms of the modified substrates were noticeably different from the unmodified counterparts, both in terms of the general profiles and the amounts of char residues produced. Such observations correlated well with the relevant parameters obtained through PCFC runs. Overall, the modified systems containing phosphorus were found to be less combustible than the parent substrates, and thus can be considered as promising matrices for environmentally benign fire-resistant coatings. Full article
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17 pages, 9849 KiB  
Article
Ammonium Polyphosphate with High Specific Surface Area by Assembling Zeolite Imidazole Framework in EVA Resin: Significant Mechanical Properties, Migration Resistance, and Flame Retardancy
by Jingyu Wang, Hui Shi, Pinlie Zhu, Yuanjie Wei and Jianwei Hao
Polymers 2020, 12(3), 534; https://doi.org/10.3390/polym12030534 - 02 Mar 2020
Cited by 15 | Viewed by 3567
Abstract
A zeolite imidazole framework (ZIF-67) was assembled onto the surface of ammonium polyphosphate (APP) for preparing a series multifunctional flame-retardant APP-ZIFs. The assembly mechanism, chemical structure, chemical compositions, morphology, and specific surface area of APP-ZIFs were characterized. The typical APPZ1 and APPZ4 were [...] Read more.
A zeolite imidazole framework (ZIF-67) was assembled onto the surface of ammonium polyphosphate (APP) for preparing a series multifunctional flame-retardant APP-ZIFs. The assembly mechanism, chemical structure, chemical compositions, morphology, and specific surface area of APP-ZIFs were characterized. The typical APPZ1 and APPZ4 were selected as intumescent flame retardants with dipentaerythritol (DPER) because of their superior unit catalytic efficiency of cobalt by thermogravimetric analysis. APPZ1 and APPZ4 possessed 6.8 and 92.1 times the specific surface area of untreated APP, which could significantly enhance the interfacial interaction, mechanical properties, and migration resistance when using in ethylene-vinyl acetate (EVA). With 25% loading, 25% APPZ4/DPER achieved a limiting oxygen index value of 29.4% and a UL 94 V-0 rating, whereas 25% APP/DPER achieved a limiting oxygen index value of only 26.2% and a V-2 rating, respectively. The peak of the heat release rate, smoke production rate, and CO production rate respectively decreased by 34.7%, 39.0%, and 40.1%, while the char residue increased by 91.7%. These significant improvements were attributed to the catalytic graphitization by nano cobalt phosphate and the formation of a more protective char barrier comprised of graphite-like carbon. Full article
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18 pages, 4705 KiB  
Article
Alkylation of Aromatic Compounds with Pentabromobenzyl Bromide and Tetrabromoxylene Dibromide as a New Route to High Molecular Weight Brominated Flame Retardants
by Mark Gelmont, Michael Yuzefovitch, David Yoffe, Eyal Eden and Sergei Levchik
Polymers 2020, 12(2), 352; https://doi.org/10.3390/polym12020352 - 06 Feb 2020
Cited by 7 | Viewed by 2977
Abstract
In the view of many national and international human health and environmental regulations, polymeric flame retardants are sustainable products. In this work, a series of high molecular weight and polymeric brominated flame retardants are synthesized by the alkylation of aromatic molecules or the [...] Read more.
In the view of many national and international human health and environmental regulations, polymeric flame retardants are sustainable products. In this work, a series of high molecular weight and polymeric brominated flame retardants are synthesized by the alkylation of aromatic molecules or the alkylation of aromatic polymers with pentabromobenzyl bromide (PBBB) or tetrabromoxylylene dibromide (TBXDB). The flame retardants prepared via the alkylation of toluene or diphenylethane with PBBB were found to be not truly polymeric but had high Mw > 1400. However, the alkylation of the same aromatic molecules by a mixture of PBBB and TBXDP resulted in polymeric flame retardants with Mw > 130,000. Two other polymeric flame retardants were prepared by the alkylation of aromatic polymers (polyphenylene ether or polystyrene) with PBBB. It was found that the new flame retardants had a high bromine content of more than 68%. They showed high thermal stability with the onset of thermal decomposition above 360 °C and a maximum rate of weight loss at about 375–410 °C. The newly synthesized flame retardants were tested in different thermoplastics. Flame retardant efficiency and physical properties were comparable or better than the reference commercial flame retardants. Full article
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15 pages, 3997 KiB  
Article
Flame-Retardant Performance of Transparent and Tensile-Strength-Enhanced Epoxy Resins
by Liang Li and Zaisheng Cai
Polymers 2020, 12(2), 317; https://doi.org/10.3390/polym12020317 - 04 Feb 2020
Cited by 24 | Viewed by 3427
Abstract
In this study, a flame-retardant additive with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) groups denoted DSD was successfully synthesized from DOPO, 4,4′-diaminodiphenyl sulfone (DDS), and salicylaldehyde. The chemical structure of DSD was characterized by FTIR–ATR, NMR, and elemental analysis. DSD was used as an amine curing agent, [...] Read more.
In this study, a flame-retardant additive with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) groups denoted DSD was successfully synthesized from DOPO, 4,4′-diaminodiphenyl sulfone (DDS), and salicylaldehyde. The chemical structure of DSD was characterized by FTIR–ATR, NMR, and elemental analysis. DSD was used as an amine curing agent, and the transparent, tensile strength-enhanced epoxy resins named EP–DSD were prepared via thermal curing reactions among the diglycidyl ether of bisphenol A (DGEBA), 4,4′-diaminodiphenylmethane (DDM), and DSD. The flame-retardancy of composites was studied by the limiting oxygen index (LOI) and UL-94 test. The LOI values of EP–DSD composites increased from 30.7% for a content of 3 wt % to 35.4% for a content of 9 wt %. When the content of DSD reached 6 wt %, a V-0 rating under the UL-94 vertical test was achieved. SEM photographs of char residues after the UL-94 test indicate that an intumescent and tight char layer with a porous structure inside was formed. The TGA results revealed that EP–DSD thermosets decomposed ahead of time. The graphitization degree of the residual chars was also investigated by laser Raman spectroscopy. The measurement of tensile strength at breaking point shows that the loading of DSD increases the tensile strength of epoxy thermosets. Py-GC/MS analysis shows the presence of phosphorus fragments released during EP–DSD thermal decomposition, which could act as free radical inhibitors in the gas phase. Owing to the promotion of the formation of intumescent and compact char residues in the condensed phase and nonflammable phosphorus fragments formed from the decomposition of DOPO groups, EP–DSD composites displayed obvious flame-retardancy. Full article
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12 pages, 1793 KiB  
Article
Synthesis of Lignin-Based Polyacid Catalyst and Its Utilization to Improve Water Resistance of Urea–formaldehyde Resins
by Shishuai Gao, Yupeng Liu, Chunpeng Wang, Fuxiang Chu, Feng Xu and Daihui Zhang
Polymers 2020, 12(1), 175; https://doi.org/10.3390/polym12010175 - 09 Jan 2020
Cited by 28 | Viewed by 4840
Abstract
In this study, a lignin-based polyacid catalyst was synthesized via two steps to enhance water resistance of urea–formaldehyde (UF) resins. The first steps involved a hydroxymethylation reaction to increase the hydroxyl content in lignin. Then, hydroxymethylated lignins were reacted with maleic anhydride to [...] Read more.
In this study, a lignin-based polyacid catalyst was synthesized via two steps to enhance water resistance of urea–formaldehyde (UF) resins. The first steps involved a hydroxymethylation reaction to increase the hydroxyl content in lignin. Then, hydroxymethylated lignins were reacted with maleic anhydride to form maleated lignin-based polyacids. The acid groups were expected to function as acid catalysts to catalyze the curing process of UF resin. In order to elucidate the structural variation, 3-methoxy-4-hydroxyphenylpropane as a typical guaiacol lignin structural unit was used as a model compound to observe the hydroxymethylation and the reaction with maleic anhydride analyzed by 1H and 13C NMR. After the structural analysis of synthesized lignin-based polyacid by FTIR and 13C NMR, it was used to produce UF resin as an adhesive in plywood and medium density fiberboard (MDF) production, respectively. The results showed that when the addition of lignin-based polyacid was 5% in plywood, it could effectively improve the water resistance of UF resins as compared to commercial additive NH4Cl. It also exhibited a lower formaldehyde emission. Like plywood, lignin-based catalysts used in medium density fiberboard production could not only maintain the mechanical properties, but also inhibit the water adsorption of fiberboards. Full article
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16 pages, 5327 KiB  
Article
Enhancement of Flame Retardancy of Colorless and Transparent Semi-Alicyclic Polyimide Film from Hydrogenated-BPDA and 4,4′-oxydianiline via the Incorporation of Phosphazene Oligomer
by Xiao Wu, Ganglan Jiang, Yan Zhang, Lin Wu, Yanjiang Jia, Yaoyao Tan, Jingang Liu and Xiumin Zhang
Polymers 2020, 12(1), 90; https://doi.org/10.3390/polym12010090 - 03 Jan 2020
Cited by 10 | Viewed by 3424
Abstract
Enhancement of flame retardancy of a colorless and transparent semi-alicyclic polyimide (PI) film was carried out by the incorporation of phosphazene (PPZ) flame retardant (FR). For this purpose, PI-1 matrix was first synthesized from hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and 4,4′-oxydianiline (ODA). The soluble [...] Read more.
Enhancement of flame retardancy of a colorless and transparent semi-alicyclic polyimide (PI) film was carried out by the incorporation of phosphazene (PPZ) flame retardant (FR). For this purpose, PI-1 matrix was first synthesized from hydrogenated 3,3′,4,4′-biphenyltetracarboxylic dianhydride (HBPDA) and 4,4′-oxydianiline (ODA). The soluble PI-1 resin was dissolved in N,N-dimethylacetamide (DMAc) to afford the PI-1 solution, which was then physically blended with PPZ FR with the loading amounts in the range of 0–25 wt.%. The PPZ FR exhibited good miscibility with the PI-1 matrix when its proportion was lower than 10 wt.% in the composite films. PI-3 composite film with the PPZ loading of 10 wt.% showed an optical transmittance of 75% at the wavelength of 450 nm with a thickness of 50 μm. More importantly, PI-3 exhibited a flame retardancy class of UL 94 VTM-0 and reduced total heat release (THR), heat release rate (HRR), smoke production rate (SPR), and rate of smoke release (RSR) values during combustion compared with the original PI-1 film. In addition, PI-3 film had a limiting oxygen index (LOI) of 30.9%, which is much higher than that of PI-1 matrix (LOI: 20.1%). Finally, incorporation of PPZ FR decreased the thermal stability of the PI films. The 10% weight loss temperature (T10%) and the glass transition temperature (Tg) of the PI-3 film were 411.6 °C and 227.4 °C, respectively, which were lower than those of the PI-1 matrix (T10%: 487.3 °C; Tg: 260.6 °C) Full article
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2019

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9 pages, 849 KiB  
Article
Incorporation of Comonomer exo-5-(Diphenylphosphato)Isosorbide-2-endo-Acrylate to Generate Flame Retardant Poly(Styrene)
by Bob A. Howell and Yoseph G. Daniel
Polymers 2019, 11(12), 2038; https://doi.org/10.3390/polym11122038 - 09 Dec 2019
Cited by 14 | Viewed by 3094
Abstract
A phosphorus containing acrylate monomer has been constructed from isosorbide, a renewable biomaterial. Treatment of isosorbide with diphenylchlorophosphate generates a mixture of phosphorus esters from which exo-5-(diphenylphosphato)isosorbide-2-endo-ol may be isolated using column chromatography. Conversion of the alcohol to the corresponding [...] Read more.
A phosphorus containing acrylate monomer has been constructed from isosorbide, a renewable biomaterial. Treatment of isosorbide with diphenylchlorophosphate generates a mixture of phosphorus esters from which exo-5-(diphenylphosphato)isosorbide-2-endo-ol may be isolated using column chromatography. Conversion of the alcohol to the corresponding acrylate by treatment with acroyl chloride provides a reactive acryloyl monomer containing a diphenylphosphato unit. Copolymerization of this monomer, at levels to provide 1% or 2% phosphorus incorporation, with styrene generates a polymer with substantially diminished flammability compared to that for styrene homopolymer. Full article
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12 pages, 5058 KiB  
Article
One-Step Synthesis of Highly Efficient Oligo(phenylphosphonic Dihydroxypropyl Silicone Oil) Flame Retardant for Polycarbonate
by Yihui Qiao, Yanbin Wang, Menghao Zou, Dehuan Xu, Yingtong Pan, Zhonglin Luo and Biaobing Wang
Polymers 2019, 11(12), 1977; https://doi.org/10.3390/polym11121977 - 01 Dec 2019
Cited by 9 | Viewed by 3361
Abstract
A highly efficient flame retardant and smoke suppression oligomer, oligo(phenylphosphonic dihydroxypropyl silicone oil) (PPSO), was synthesized by a one-step reaction. The chemical structure of PPSO was confirmed by Fourier transform infrared (FTIR), 31P nuclear magnetic resonance (31P NMR), and 29 [...] Read more.
A highly efficient flame retardant and smoke suppression oligomer, oligo(phenylphosphonic dihydroxypropyl silicone oil) (PPSO), was synthesized by a one-step reaction. The chemical structure of PPSO was confirmed by Fourier transform infrared (FTIR), 31P nuclear magnetic resonance (31P NMR), and 29Si nuclear magnetic resonance (29Si NMR). The flame-retardant effect of PPSO on the polycarbonate (PC) matrix was investigated by limiting oxygen index, UL-94 vertical burning test, and cone calorimetry, respectively. The results showed that PC/PPSO composites passed UL-94 V-0 rate testing with only 1.3 wt. % PPSO. Furthermore, the incorporation of PPSO can suppress the release of smoke. The flame-retardant mechanism was also investigated via thermogravimetric analysis-fourier transform infrared spectroscopy (TG-FTIR), field-emission scanning electronic microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. From the result of pyrolysis gas and char residue, PPSO played a synergistic flame-retardant mechanism including the gas phase and the condensed phase. Full article
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14 pages, 9601 KiB  
Article
An Alginate Hybrid Sponge with High Thermal Stability: Its Flame Retardant Properties and Mechanism
by Yuhuan Jiang, Xuening Pang, Yujia Deng, Xiaolu Sun, Xihui Zhao, Peng Xu, Peiyuan Shao, Lei Zhang, Qun Li and Zichao Li
Polymers 2019, 11(12), 1973; https://doi.org/10.3390/polym11121973 - 30 Nov 2019
Cited by 18 | Viewed by 3912
Abstract
The worldwide applications of polyurethane (PU) and polystyrene (PS) sponge materials have been causing massive non-renewable resource consumption and huge loss of property and life due to its high flammability. Finding a biodegradable and regenerative sponge material with desirable thermal and flame retardant [...] Read more.
The worldwide applications of polyurethane (PU) and polystyrene (PS) sponge materials have been causing massive non-renewable resource consumption and huge loss of property and life due to its high flammability. Finding a biodegradable and regenerative sponge material with desirable thermal and flame retardant properties remains challenging to date. In this study, bio-based, renewable calcium alginate hybrid sponge materials (CAS) with high thermal stability and flame retardancy were fabricated through a simple, eco-friendly, in situ, chemical-foaming process at room temperature, followed by a facile and economical post-cross-linking method to obtain the organic-inorganic (CaCO3) hybrid materials. The microstructure of CAS showed desirable porous networks with a porosity rate of 70.3%, indicating that a great amount of raw materials can be saved to achieve remarkable cost control. The sponge materials reached a limiting oxygen index (LOI) of 39, which was greatly improved compared with common sponge. Moreover, with only 5% calcium carbonate content, the initial thermal degradation temperature of CAS was increased by 70 °C (from 150 to 220 °C), compared to that of calcium alginate, which met the requirements of high-temperature resistant and nonflammable materials. The thermal degradation mechanism of CAS was supposed based on the experimental data. The combined results suggest promising prospects for the application of CAS in a range of fields and the sponge materials provide an alternative for the commonly used PU and PS sponge materials. Full article
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15 pages, 4543 KiB  
Article
A Study of the Thermal Degradation and Combustion Characteristics of Some Materials Commonly Used in the Construction Sector
by Javier Arturo Piedrahita Solorzano, Khalid Abu Mohammad Moinuddin, Svetlana Tretsiakova-McNally and Paul Joseph
Polymers 2019, 11(11), 1833; https://doi.org/10.3390/polym11111833 - 07 Nov 2019
Cited by 10 | Viewed by 3297
Abstract
In the present work, some materials that are commonly used in the construction industry were studied with regard to their thermal degradation characteristics and combustion attributes. These included façade materials for pre-fabricated houses, such as the layers of cross-laminated timber (CLT) and the [...] Read more.
In the present work, some materials that are commonly used in the construction industry were studied with regard to their thermal degradation characteristics and combustion attributes. These included façade materials for pre-fabricated houses, such as the layers of cross-laminated timber (CLT) and the inner core of aluminium composite panels (ACPs). The relevant investigations were carried out by employing thermo-gravimetric analysis (TGA) and pyrolysis combustion flow calorimetry (PCFC). The Arrhenius parameters and the associated calorimetric quantities, i.e., heat release rates, temperature to the peak heat release rate, heats of combustion, heat release capacities, and char yields, were also evaluated. These parameters showed that CLT is more fire retarded than the polymeric internal core of ACP façade materials. Furthermore, some valuable correlations among the various test quantities were found. For instance, a good correlation exists between the general profiles of the thermograms obtained through TGA runs and the heat release rate (HRR) traces from PCFC measurements. Depending on the nature of the materials, the char yields measured by PCFC can be 4–20 times higher than the ones obtained through TGA. Full article
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12 pages, 8326 KiB  
Article
A Novel Inherently Flame-Retardant Composite Based on Zinc Alginate/Nano-Cu2O
by Peng Xu, Peiyuan Shao, Qing Zhang, Wen Cheng, Zichao Li and Qun Li
Polymers 2019, 11(10), 1575; https://doi.org/10.3390/polym11101575 - 27 Sep 2019
Cited by 16 | Viewed by 2936
Abstract
A novel flame-retardant composite material based on zinc alginate (ZnAlg) and nano-cuprous oxide (Cu2O) was prepared through a simple, eco-friendly freeze-drying process and a sol-gel method. The composites were characterized and their combustion and flammability behavior were tested. The composites had [...] Read more.
A novel flame-retardant composite material based on zinc alginate (ZnAlg) and nano-cuprous oxide (Cu2O) was prepared through a simple, eco-friendly freeze-drying process and a sol-gel method. The composites were characterized and their combustion and flammability behavior were tested. The composites had high thermal stability and achieved nearly non-flammability with a limiting oxygen index (LOI) of 58. The results show remarkable improvement of flame-retardant properties in the ZnAlg/Cu2O composites, compared to ZnAlg. Furthermore, the pyrolysis behavior was determined by pyrolysis–gas chromatography–mass spectrometry (Py-GC-MS) and the flame-retardant mechanism was proposed based on the combined experimental results. The prepared composites show promising application prospects in building materials and the textile industry. Full article
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10 pages, 1399 KiB  
Communication
Flame Retardancy Index for Thermoplastic Composites
by Henri Vahabi, Baljinder K. Kandola and Mohammad Reza Saeb
Polymers 2019, 11(3), 407; https://doi.org/10.3390/polym11030407 - 01 Mar 2019
Cited by 197 | Viewed by 6448
Abstract
Flame Retardancy Index, FRI, was defined as a simple yet universal dimensionless criterion born out of cone calorimetry data on thermoplastic composites and then put into practice for quantifying the flame retardancy performance of different polymer composites on a set of reliable [...] Read more.
Flame Retardancy Index, FRI, was defined as a simple yet universal dimensionless criterion born out of cone calorimetry data on thermoplastic composites and then put into practice for quantifying the flame retardancy performance of different polymer composites on a set of reliable data. Four types of thermoplastic composites filled with a wide variety of flame retardant additives were chosen for making comparative evaluations regardless of the type and loading level of the additive as well as the irradiance flux. The main features of cone calorimetry including peak of Heat Release Rate (pHRR), Total Heat Release (THR), and Time-To-Ignition (TTI) served to calculate a dimensionless measure that reflects an improvement in the flame retardancy of nominated thermoplastic composites with respect to the neat thermoplastic, quantitatively. A meaningful trend was observed among well-classified ranges of FRI quantities calculated for the studied dataset on thermoplastic composites by which “Poor”, “Good”, and “Excellent” flame retardancy performances were explicitly defined and exhibited on logarithmic scales of FRI axis. The proposed index remains adaptable to thermoplastic systems whatever the polymer or additive is. Full article
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14 pages, 6330 KiB  
Article
Investigation of the Structure-Property Effect of Phosphorus-Containing Polysulfone on Decomposition and Flame Retardant Epoxy Resin Composites
by Wei Zhao, Yongxiang Li, Qiushi Li, Yiliang Wang and Gong Wang
Polymers 2019, 11(2), 380; https://doi.org/10.3390/polym11020380 - 21 Feb 2019
Cited by 9 | Viewed by 3806
Abstract
The flame retardant modification of epoxy (EP) is of great signification for aerospace, automotive, marine, and energy industries. In this study, a series of EP composites containing different variations of phosphorus-containing polysulfone (with a phosphorus content of approximately 1.25 wt %) were obtained. [...] Read more.
The flame retardant modification of epoxy (EP) is of great signification for aerospace, automotive, marine, and energy industries. In this study, a series of EP composites containing different variations of phosphorus-containing polysulfone (with a phosphorus content of approximately 1.25 wt %) were obtained. The obtained EP/polysulfone composites had a high glass transition temperature (Tg) and high flame retardancy. The influence of phosphorus-containing compounds (ArPN2, ArPO2, ArOPN2 and ArOPO2) on the thermal properties and flame retardancy of EP/polysulfone composites was investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), a UL-94 vertical burning test, and cone calorimeter tests. The phosphorus-containing polysulfone enhanced the thermal stability of EP. The more stable porous char layer, less flammable gases, and a lower apparent activation energy at a high degree of conversion demonstrated the high gas inhibition effect of phosphorus-containing compounds. Moreover, the gas inhibition effect of polysulfone with a P–C bond was more efficient than the polysulfone with a P–O–C bond. The potential for optimizing flame retardancy while maintaining a high Tg is highlighted in this study. The flame-retardant EP/polysulfone composites with high thermal stability broaden the application field of epoxy. Full article
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25 pages, 6339 KiB  
Article
Phosphorus Containing Polyacrylamides as Flame Retardants for Epoxy-Based Composites in Aviation
by Lara Greiner, Philipp Kukla, Sebastian Eibl and Manfred Döring
Polymers 2019, 11(2), 284; https://doi.org/10.3390/polym11020284 - 08 Feb 2019
Cited by 30 | Viewed by 4854
Abstract
Novel polymeric flame retardants based on two acrylamides and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 5,5-dimethyl-[1,3,2]dioxaphosphinane-2-oxide (DDPO) are described for several applications in HexFlow® RTM6, a high-performance epoxy resin. Neat resin samples and carbon fiber-reinforced composites were tested for their glass transition temperatures (dynamic mechanical [...] Read more.
Novel polymeric flame retardants based on two acrylamides and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) or 5,5-dimethyl-[1,3,2]dioxaphosphinane-2-oxide (DDPO) are described for several applications in HexFlow® RTM6, a high-performance epoxy resin. Neat resin samples and carbon fiber-reinforced composites were tested for their glass transition temperatures (dynamic mechanical analysis), thermal stability (thermogravimetric analyses), flammability (UL94) and flame-retardant performance (Cone Calorimetry). Additionally, the fiber degradation occurring during combustion of carbon fiber-reinforced epoxy resins was observed by scanning electron microscopy to show the fiber protecting effect of these flame retardants. Whereas DOPO-containing polyacrylamides acting mainly in the gas phase showed the best flame retardant efficiency, DDPO-containing polyacrylamides acting mainly in the condensed phase showed the best fiber protection. A mixed polyacrylamide was synthesized to combine these effects. This thermoplastic is soluble in the resin and, therefore, suitable for injection molding processes. Interlaminar shear strength measurements showed no negative effect of the flame retardant. The versatility of these flame retardants is shown by investigations dealing with boehmite as synergist in neat resin samples. Full article
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17 pages, 21239 KiB  
Article
Novel Oligo-Ester-Ether-Diol Prepared by Waste Poly(ethylene terephthalate) Glycolysis and Its Use in Preparing Thermally Stable and Flame Retardant Polyurethane Foam
by Cuong N. Hoang, Chi T. Pham, Thu M. Dang, DongQuy Hoang, Pyoung-Chan Lee, Soo-Jung Kang and Jinhwan Kim
Polymers 2019, 11(2), 236; https://doi.org/10.3390/polym11020236 - 01 Feb 2019
Cited by 25 | Viewed by 5435
Abstract
Rigid polyurethane foam (PUF) was successfully prepared from a novel oligo-ester-ether-diol obtained from the glycolysis of waste poly(ethylene terephthalate) (PET) bottles via reaction with diethylene glycol (DEG) in the presence of ZnSO4·7H2O. The LC-MS analysis of the oligodiol enabled [...] Read more.
Rigid polyurethane foam (PUF) was successfully prepared from a novel oligo-ester-ether-diol obtained from the glycolysis of waste poly(ethylene terephthalate) (PET) bottles via reaction with diethylene glycol (DEG) in the presence of ZnSO4·7H2O. The LC-MS analysis of the oligodiol enabled us to identify 67 chemical homologous structures that were composed of zero to four terephthalate (T) ester units and two to twelve monoethylene glycol (M) ether units. The flame retardant, morphological, compression, and thermal properties of rigid PUFs with and without triphenyl phosphate (TPP) were determined. The Tg values showed that TPP played a role of not only being a flame retardant, but also a plasticizer. PUF with a rather low TPP loading had an excellent flame retardancy and high thermal stability. A loading of 10 wt % TPP not only achieved a UL-94 V-0 rating, but also obtained an LOI value of 21%. Meanwhile, the PUF without a flame retardant did not achieve a UL-94 HB rating; the sample completely burned to the holder clamp and yielded a low LOI value (17%). The fire properties measured with the cone calorimeter were also discussed, and the results further proved that the flame retardancy of the PUF with the addition of TPP was improved significantly. The polymeric material meets the demands of density and compression strength for commercial PUF, as well as the needs of environmental development. The current study may help overcome the drawback of intrinsic high flammability and enlarge the fire safety applications of materials with a high percentage of recycled PET. Full article
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16 pages, 9415 KiB  
Article
Electrostatic-Interaction-Driven Assembly of Binary Hybrids towards Fire-Safe Epoxy Resin Nanocomposites
by Lu Liu, Wei Wang, Yongqian Shi, Libi Fu, Lulu Xu and Bin Yu
Polymers 2019, 11(2), 229; https://doi.org/10.3390/polym11020229 - 01 Feb 2019
Cited by 11 | Viewed by 3338
Abstract
Manganese dioxide (MnO2), as a promising green material, has recently attracted considerable attention of researchers from various fields. In this work, a facile method was introduced to prepare binary hybrids by fabricating three-dimensional (3D) zinc hydroxystannate (ZHS) cubes on two-dimensional (2D) [...] Read more.
Manganese dioxide (MnO2), as a promising green material, has recently attracted considerable attention of researchers from various fields. In this work, a facile method was introduced to prepare binary hybrids by fabricating three-dimensional (3D) zinc hydroxystannate (ZHS) cubes on two-dimensional (2D) MnO2 nanosheets towards excellent flame retardancy and toxic effluent elimination of epoxy (EP) resin. Microstructural analysis confirmed that the morphologies and structures of MnO2@ZHS binary hybrids were well characterized, implying the successful synthesis. Additionally, the morphological characterization indicated that MnO2@ZHS binary hybrids could achieve satisfactory interfacial interaction with the EP matrix and be well dispersed in nanocomposites. Cone calorimeter test suggested that MnO2@ZHS binary hybrids effectively suppressed the peak of heat release rate and total heat release of EP nanocomposites, performing better than MnO2 or ZHS alone. Condensed-phase analysis revealed that MnO2@ZHS binary hybrids could promote the char density and graphitization degree of char residues and thereby successfully retard the permeation of oxygen and flammable gases. Moreover, through the analysis of gas phase, it can be concluded that MnO2@ZHS binary hybrids could efficiently suppress the production of toxic gases during the degradation of EP nanocomposites. This work implies that the construction of 2D/3D binary hybrids with an interfacial interaction is an effective way to fabricate high-performance flame retardants for EP. Full article
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31 pages, 3917 KiB  
Review
Recent Advances in Bio-Based Flame Retardant Additives for Synthetic Polymeric Materials
by Christopher E. Hobbs
Polymers 2019, 11(2), 224; https://doi.org/10.3390/polym11020224 - 31 Jan 2019
Cited by 116 | Viewed by 10357
Abstract
It would be difficult to imagine how modern life across the globe would operate in the absence of synthetic polymers. Although these materials (mostly in the form of plastics) have revolutionized our daily lives, there are consequences to their use, one of these [...] Read more.
It would be difficult to imagine how modern life across the globe would operate in the absence of synthetic polymers. Although these materials (mostly in the form of plastics) have revolutionized our daily lives, there are consequences to their use, one of these being their high levels of flammability. For this reason, research into the development of flame retardant (FR) additives for these materials is of tremendous importance. However, many of the FRs prepared are problematic due to their negative impacts on human health and the environment. Furthermore, their preparations are neither green nor sustainable since they require typical organic synthetic processes that rely on fossil fuels. Because of this, the need to develop more sustainable and non-toxic options is vital. Many research groups have turned their attention to preparing new bio-based FR additives for synthetic polymers. This review explores some of the recent examples made in this field. Full article
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26 pages, 13148 KiB  
Article
Mechanism of Heat Transfer through Porous Media of Inorganic Intumescent Coating in Cone Calorimeter Testing
by Sungwook Kang, J. Yoon Choi and Sengkwan Choi
Polymers 2019, 11(2), 221; https://doi.org/10.3390/polym11020221 - 29 Jan 2019
Cited by 31 | Viewed by 5799
Abstract
This work discusses the heat transfer process through a particular form of porous media: an inorganic-based intumescent coating in full-expansion state. Although the thermal mechanism in porous media has been vigorously studied for polymeric/ceramic/metallic foams, less information is available on its application with [...] Read more.
This work discusses the heat transfer process through a particular form of porous media: an inorganic-based intumescent coating in full-expansion state. Although the thermal mechanism in porous media has been vigorously studied for polymeric/ceramic/metallic foams, less information is available on its application with intumescent-type polymers. This examination demonstrates the procedure of (1) the optimisation of the coating’s internal multicellular structure for numerical modelling, based on topological analyses; (2) the finite element simulation for the coating-sample tested with cone calorimetry; and (3) the quantitative evaluation of the thermal insulation performance of its porous structure by adopting effective thermal conductivity. The modelling technique was verified using measurable data from the cone calorimeter tests. Consistent agreement between the numerical predictions and experimental measurements was achieved over the whole steel-substrate temperature history, based on the clarified thermal boundaries of the specimen and modelling of the combined conduction-radiation transfer. This numerical approach exhibits the impacts of porosity, pore-size, and external thermal load on the medium’s performance, as well as the individual contributions of the component heat transfer modes to the overall process. The full understanding of this thermal mechanism can contribute to the enhancement and optimisation of the thermal insulation performance of a porous-type refractory polymer. Full article
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13 pages, 4463 KiB  
Article
Correlation of Montmorillonite Sheet Thickness and Flame Retardant Behavior of a Chitosan–Montmorillonite Nanosheet Membrane Assembled on Flexible Polyurethane Foam
by Peng Chen, Yunliang Zhao, Wei Wang, Tingting Zhang and Shaoxian Song
Polymers 2019, 11(2), 213; https://doi.org/10.3390/polym11020213 - 26 Jan 2019
Cited by 24 | Viewed by 4034
Abstract
Polymer–clay membranes constructed via the layer-by-layer (LbL) assembly, with a nanobrick wall structure, are known to exhibit high flame retardancy. In this work, chitosan–montmorillonite nanosheet (CH–MMTNS) membranes with different thickness of MMTNS were constructed to suppress the flammability of flexible polyurethane (FPU) foam. [...] Read more.
Polymer–clay membranes constructed via the layer-by-layer (LbL) assembly, with a nanobrick wall structure, are known to exhibit high flame retardancy. In this work, chitosan–montmorillonite nanosheet (CH–MMTNS) membranes with different thickness of MMTNS were constructed to suppress the flammability of flexible polyurethane (FPU) foam. It was found that a thinner MMTNS membrane was more efficient in terms of reducing the flammability of the FPU foam. This was because such MMTNS membrane could deposit cheek by jowl and form a dense CH–MMTNS membrane on the foam surface, thus greatly limiting the translation of heat, oxygen, and volatile gases. In contrast, a thicker MMTNS constructed a fragmentary CH–MMTNS membrane on the coated foam surface, due to its greater gravity and weaker electrostatic attraction of chitosan; thus, the flame retardancy of a thick MMTNS membrane was lower. Moreover, the finding of different deposition behaviors of MMTNS membranes with different thickness may suggest improvements for the application of clay with the LbL assembly technology. Full article
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14 pages, 7040 KiB  
Article
Fabrication and Application of Black Phosphorene/Graphene Composite Material as a Flame Retardant
by Xinlin Ren, Yi Mei, Peichao Lian, Delong Xie, Weibin Deng, Yaling Wen and Yong Luo
Polymers 2019, 11(2), 193; https://doi.org/10.3390/polym11020193 - 22 Jan 2019
Cited by 36 | Viewed by 4070
Abstract
A simple and novel route is developed for fabricating BP-based composite materials to improve the thermo-stability, flame retardant performances, and mechanical performances of polymers. Black phosphorene (BP) has outstanding flame retardant properties, however, it causes the mechanical degradation of waterborne polyurethane (WPU). In [...] Read more.
A simple and novel route is developed for fabricating BP-based composite materials to improve the thermo-stability, flame retardant performances, and mechanical performances of polymers. Black phosphorene (BP) has outstanding flame retardant properties, however, it causes the mechanical degradation of waterborne polyurethane (WPU). In order to solve this problem, the graphene is introduced to fabricate the black phosphorene/graphene (BP/G) composite material by high-pressure nano-homogenizer machine (HNHM). The structure, thermo-stability, flame retardant properties, and mechanical performance of composites are analyzed by a series of tests. The structure characterization results show that the BP/G composite material can distribute uniformly into the WPU. The addition of BP/G significantly improves the residues of WPU in both of TG analysis (5.64%) and cone calorimeter (CC) test (12.50%), which indicate that the BP/G can effectively restrict the degradation of WPU under high temperature. The CC test indicates that BP/G/WPU has a lower peak release rate (PHRR) and total heat release (THR), which decrease by 48.18% and 38.63%, respectively, than that of the pure WPU, respectively. The mechanical analysis presents that the Young’s modulus of the BP/G/WPU has an increase of seven times more than that of the BP/WPU, which indicates that the introduce of graphene can effectively improve the mechanical properties of BP/WPU. Full article
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18 pages, 6970 KiB  
Article
Valorization of Industrial Lignin as Biobased Carbon Source in Fire Retardant System for Polyamide 11 Blends
by Neeraj Mandlekar, Aurélie Cayla, François Rault, Stéphane Giraud, Fabien Salaün and Jinping Guan
Polymers 2019, 11(1), 180; https://doi.org/10.3390/polym11010180 - 21 Jan 2019
Cited by 19 | Viewed by 4842
Abstract
In this study, two different types of industrial lignin (i.e., lignosulphonate lignin (LL) and kraft lignin (DL)) were exploited as charring agents with phosphorus-based flame retardants for polyamide 11 (PA11). The effect of lignins on the thermal stability and fire behavior of PA11 [...] Read more.
In this study, two different types of industrial lignin (i.e., lignosulphonate lignin (LL) and kraft lignin (DL)) were exploited as charring agents with phosphorus-based flame retardants for polyamide 11 (PA11). The effect of lignins on the thermal stability and fire behavior of PA11 combined with phosphinate additives (namely, aluminum phosphinate (AlP) and zinc phosphinate (ZnP)) has been studied by thermogravimetric analysis (TGA), UL 94 vertical flame spread, and cone calorimetry tests. Various blends of flame retarded PA11 were prepared by melt process using a twin-screw extruder. Thermogravimetric analyses showed that the LL containing ternary blends are able to provide higher thermal stability, as well as a developed char residue. The decomposition of the phosphinates led to the formation of phosphate compounds in the condensed phase, which promotes the formation of a stable char. Flammability tests showed that LL/ZnP ternary blends were able to achieve self-extinction and V-1 classification; the other formulations showed a strong melt dripping and higher burning. In addition to this, cone calorimetry results showed that the most enhanced behavior was found when 10 wt % of LL and AlP were combined, which strongly reduced PHRR (−74%) and THR (−22%), due to the interaction between LL and AlP, which not only promotes char formation but also confers the stability to char in the condensed phase. Full article
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2018

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16 pages, 2374 KiB  
Article
Investigation of the Flammability and Thermal Stability of Halogen-Free Intumescent System in Biopolymer Composites Containing Biobased Carbonization Agent and Mechanism of Their Char Formation
by Muhammad Maqsood and Gunnar Seide
Polymers 2019, 11(1), 48; https://doi.org/10.3390/polym11010048 - 30 Dec 2018
Cited by 50 | Viewed by 5146
Abstract
Starch, being a polyhydric compound with its natural charring ability, is an ideal candidate to serve as a carbonization agent in an intumescent system. This charring ability of starch, if accompanied by an acidic source, can generate an effective intumescent flame retardant (IFR) [...] Read more.
Starch, being a polyhydric compound with its natural charring ability, is an ideal candidate to serve as a carbonization agent in an intumescent system. This charring ability of starch, if accompanied by an acidic source, can generate an effective intumescent flame retardant (IFR) system, but the performance of starch-based composites in an IFR system has not been tested in detail. Here, we describe a PLA-based IFR system consisting of ammonium polyphosphate (APP) as acidic source and cornstarch as carbon source. We prepared different formulations by melt compounding followed by molding into sheets by hot pressing. The thermal behavior and surface morphology of the composites was investigated by thermogravimetric analysis and scanning electron microscopy respectively. We also conducted limiting oxygen index (LOI), UL-94, and cone calorimetry tests to characterize the flame-retardant properties. Cone calorimetry revealed a 66% reduction in the peak heat release rate of the IFR composites compared to pure PLA and indicated the development of an intumescent structure by leaving a residual mass of 43% relative to the initial mass of the sample. A mechanism of char formation has also been discussed in detail. Full article
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22 pages, 50821 KiB  
Article
Fire Phenomena of Rigid Polyurethane Foams
by Martin Günther, Alessandra Lorenzetti and Bernhard Schartel
Polymers 2018, 10(10), 1166; https://doi.org/10.3390/polym10101166 - 19 Oct 2018
Cited by 58 | Viewed by 7835
Abstract
Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentane- and [...] Read more.
Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentane- and water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m3. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent. Full article
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14 pages, 5314 KiB  
Article
Development of a Semiglobal Reaction Mechanism for the Thermal Decomposition of a Polymer Containing Reactive Flame Retardants: Application to Glass-Fiber-Reinforced Polybutylene Terephthalate Blended with Aluminum Diethyl Phosphinate and Melamine Polyphosphate
by Yan Ding, Stanislav I. Stoliarov and Roland H. Kraemer
Polymers 2018, 10(10), 1137; https://doi.org/10.3390/polym10101137 - 12 Oct 2018
Cited by 22 | Viewed by 5265
Abstract
This work details a methodology for parameterization of the kinetics and thermodynamics of the thermal decomposition of polymers blended with reactive additives. This methodology employs Thermogravimetric Analysis, Differential Scanning Calorimetry, Microscale Combustion Calorimetry, and inverse numerical modeling of these experiments. Blends of glass-fiber-reinforced [...] Read more.
This work details a methodology for parameterization of the kinetics and thermodynamics of the thermal decomposition of polymers blended with reactive additives. This methodology employs Thermogravimetric Analysis, Differential Scanning Calorimetry, Microscale Combustion Calorimetry, and inverse numerical modeling of these experiments. Blends of glass-fiber-reinforced polybutylene terephthalate (PBT) with aluminum diethyl phosphinate and melamine polyphosphate were used to demonstrate this methodology. These additives represent a potent solution for imparting flame retardancy to PBT. The resulting lumped-species reaction model consisted of a set of first- and second-order (two-component) reactions that defined the rate of gaseous pyrolyzate production. The heats of reaction, heat capacities of the condensed-phase reactants and products, and heats of combustion of the gaseous products were also determined. The model was shown to reproduce all aforementioned experiments with a high degree of detail. The model also captured changes in the material behavior with changes in the additive concentrations. Second-order reactions between the material constituents were found to be necessary to reproduce these changes successfully. The development of such models is an essential milestone toward the intelligent design of flame retardant materials and solid fuels. Full article
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15 pages, 3025 KiB  
Article
Some Key Factors Influencing the Flame Retardancy of EDA-DOPO Containing Flexible Polyurethane Foams
by Agnieszka Przystas, Milijana Jovic, Khalifah A. Salmeia, Daniel Rentsch, Laurent Ferry, Henri Mispreuve, Heribert Perler and Sabyasachi Gaan
Polymers 2018, 10(10), 1115; https://doi.org/10.3390/polym10101115 - 09 Oct 2018
Cited by 26 | Viewed by 4388
Abstract
The role of various additives (emulsifier, anti-dripping agent) and formulation procedures (pre-dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6′-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams has been investigated in this work. For comparison, the flame retardancy of [...] Read more.
The role of various additives (emulsifier, anti-dripping agent) and formulation procedures (pre-dispersion of solid additives in polyol via milling) which influence the flame retardancy of 6,6′-[ethan-1,2-diylbis(azandiyl)]bis(6H-dibenzo[c,e][1,2]oxaphosphin-6-oxid) (EDA-DOPO) containing flexible polyurethane foams has been investigated in this work. For comparison, the flame retardancy of two additional structurally-analogous bridged 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO)-based compounds, i.e., ethanolamine-DOPO (ETA-DOPO) and ethylene glycol-DOPO (EG-DOPO) were also evaluated together with EDA-DOPO in flexible PU foams of various formulations. The flame retardancy of these three bridged-DOPO compounds depends on the type of PU formulation. For certain PU formulations containing EDA-DOPO, lower fire performance was observed. Addition of emulsifier and polytetrafluoroethylene (PTFE) to these PU formulations influenced positively the flame retardancy of EDA-DOPO/PU foams. In addition, dispersion of EDA-DOPO and PTFE via milling in polyol improved the flame retardancy of the PU foams. Mechanistic studies performed using a microscale combustion calorimeter (MCC) and its coupling to FTIR showed no difference in the combustion efficiency of the bridged-DOPO compounds in PU foams. From MCC experiments it can be concluded that these bridged-DOPO compounds and their decomposition products may work primarily in the gas phase as flame inhibitors. The physiochemical behavior of additives in PU formulation responsible for the improvement in the flame retardancy of PU foams was further investigated by studying the dripping behavior of the PU foams in the UL 94 HB test. A high-speed camera was used to study the dripping behavior in the UL 94 HB test and results indicate a considerable reduction of the total number of melt drips and flaming drips for the flame retardant formulations. This reduction in melt drips and flaming drips during the UL 94 HB tests help PU foams achieve higher fire classification. Full article
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13 pages, 1146 KiB  
Article
Flame Retardancy of Low-Viscosity Epoxy Resins and Their Carbon Fibre Reinforced Composites via a Combined Solid and Gas Phase Mechanism
by Ákos Pomázi, Beáta Szolnoki and Andrea Toldy
Polymers 2018, 10(10), 1081; https://doi.org/10.3390/polym10101081 - 29 Sep 2018
Cited by 22 | Viewed by 4848
Abstract
Low viscosity, potentially renewable aliphatic epoxy resins, appropriate for processing with injection techniques were flame retarded with the use of resorcinol bis(diphenyl phosphate) (RDP), acting predominantly in the gas phase, ammonium polyphosphate (APP), acting in the solid phase, and their combination. Samples of [...] Read more.
Low viscosity, potentially renewable aliphatic epoxy resins, appropriate for processing with injection techniques were flame retarded with the use of resorcinol bis(diphenyl phosphate) (RDP), acting predominantly in the gas phase, ammonium polyphosphate (APP), acting in the solid phase, and their combination. Samples of gradually increasing phosphorus (P) content (1%, 2%, 3%, 4%, and 5%) and mixed formulations with 2% P from APP and 2% P from RDP were prepared. The fire retardancy of matrix and carbon fibre reinforced samples was examined by limiting oxygen index (LOI), UL-94 tests, and mass loss calorimetry. The thermal stability of the matrices was investigated by thermogravimetric analysis, whereas the effect of flame retardants (FRs) on the crosslinking process and glass transition temperature was evaluated by differential scanning calorimetry in matrices and by dynamic mechanical analysis in composites. According to the results, although the trifunctional glycerol -based (GER) and the tetrafunctional pentaerythritol-based (PER) epoxy resins have a similar initial LOI and horizontal burning rate, GER has an approximately 1.5 times higher peak of heat release rate (pHRR) than PER. At least 4% P content is necessary to reach a reasonable improvement in fire performance in these resin transfer molding (RTM)-compatible systems and with the same FR-content PER reaches better fire performance. RDP has an early gas phase effect at the beginning of degradation, while later on the solid phase action of APP prevails, although in composites hindered by the reinforcing carbon fibres. In PER composites, the combination of APP and RDP had a synergistic effect, leading to a pHRR of 218 kW/m2 and total heat release of 18.2 MJ/m2. Full article
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16 pages, 21129 KiB  
Article
Intumescent Polymer Metal Laminates for Fire Protection
by Laura Geoffroy, Fabienne Samyn, Maude Jimenez and Serge Bourbigot
Polymers 2018, 10(9), 995; https://doi.org/10.3390/polym10090995 - 06 Sep 2018
Cited by 14 | Viewed by 5508
Abstract
Intumescent paints are applied on materials to protect them against fire, but the development of novel chemistries has reached some limits. Recently, the concept of “Polymer Metal Laminates,” consisting of alternating thin aluminum foils and thin epoxy resin layers has been proven efficient [...] Read more.
Intumescent paints are applied on materials to protect them against fire, but the development of novel chemistries has reached some limits. Recently, the concept of “Polymer Metal Laminates,” consisting of alternating thin aluminum foils and thin epoxy resin layers has been proven efficient against fire, due to the delamination between layers during burning. In this paper, both concepts were considered to design “Intumescent Polymer Metal Laminates” (IPML), i.e., successive thin layers of aluminum foils and intumescent coatings. Three different intumescent coatings were selected to prepare ten-plies IPML glued onto steel substrates. The IPMLs were characterized using optical microscopy, and their efficiency towards fire was evaluated using a burn-through test. Thermal profiles obtained were compared to those obtained for a monolayer of intumescent paint. For two of three coatings, the use of IPML revealed a clear improvement at the beginning of the test, with the slopes of the curves being dramatically decreased. Characterizations (expansion measurements, microscopic analyses, in situ temperature, and thermal measurements) were carried out on the different samples. It is suggested that the polymer metal laminates (PML) design, delays the carbonization of the residue. This work highlighted that design is as important as the chemistry of the formulation, to obtain an effective fire barrier. Full article
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2016

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2515 KiB  
Article
New Flexible Flame Retardant Coatings Based on Siloxane Resin and Ethylene-Vinyl Chloride Copolymer
by Dorota Wesolek, Ryszard Gasiorowski, Szymon Rojewski, Judyta Walentowska and Rafał Wojcik
Polymers 2016, 8(12), 419; https://doi.org/10.3390/polym8120419 - 02 Dec 2016
Cited by 7 | Viewed by 8314
Abstract
This work presents the effectiveness of a phosphorus-containing flame retardant based on siloxane resin and ethylene-vinyl chloride copolymer as a back-coating of fabrics. The possibility of improving flame retardant efficiency of this composition by introducing fumed silica, montmorillonite, carbon nanotubes, and graphite was [...] Read more.
This work presents the effectiveness of a phosphorus-containing flame retardant based on siloxane resin and ethylene-vinyl chloride copolymer as a back-coating of fabrics. The possibility of improving flame retardant efficiency of this composition by introducing fumed silica, montmorillonite, carbon nanotubes, and graphite was evaluated. The effect of each additive on the efficiency of the composition was examined separately. Flammability tests of flame retardant-coated fabrics (natural and synthetic) were carried out using pyrolysis combustion flow calorimetry (PCFC), cone calorimetry, and limiting oxygen index determination. An assessment of the ignitability of upholstered furniture containing flame retardant fabric, resistance to washing, antifungal activity, and some of the utility properties of the final newly-developed flame-retardant coating was conducted. Full article
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1800 KiB  
Article
Structure–Property Studies on a New Family of Halogen Free Flame Retardants Based on Sulfenamide and Related Structures
by Teija Tirri, Melanie Aubert, Weronika Pawelec, Anton Holappa and Carl-Eric Wilén
Polymers 2016, 8(10), 360; https://doi.org/10.3390/polym8100360 - 14 Oct 2016
Cited by 16 | Viewed by 8030
Abstract
A wide variety of molecules containing S–N or S–N–S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It [...] Read more.
A wide variety of molecules containing S–N or S–N–S cores were synthesized, and their flame retardant properties in polypropylene (PP), low density polyethylene (LDPE) and polystyrene (PS) were investigated. In addition, polymers or oligomers bearing the sulfenamide functionality (SN) were also synthesized. It was shown that this radical generator family based on sulfenamides is very versatile in terms of structural modifications, and the thermal decomposition range can be easily adjusted by changing the R groups attached to the core. The thermal stabilities of the different sulfenamides were examined by thermogravimetric analysis (TGA). Radicals generated by the homolytic cleavage of the S–N or S–N–S bonds at an elevated temperature can effectively interact with the intermediate products of polymer thermolysis and provide excellent flame retardant properties. The choice of most suitable SN-structure varies depending on the polymer type. For polypropylene DIN 4102-1 B2 and UL94 VTM-2 classifications were achieved with only 0.5 to 1 wt % of sulfenamide, and, in some cases, no flaming dripping was observed. Also for LDPE thin films, sulfenamides offered the DIN 4102-1 B2 rating at low dosage. In the case of polystyrene, the very stringent UL94 V-0 classification was even achieved at a loading of 5 wt % of sulfenamide. Full article
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2880 KiB  
Review
Recent Advances in the Design of Water Based-Flame Retardant Coatings for Polyester and Polyester-Cotton Blends
by Jenny Alongi, Federico Carosio and Paul Kiekens
Polymers 2016, 8(10), 357; https://doi.org/10.3390/polym8100357 - 11 Oct 2016
Cited by 39 | Viewed by 8378
Abstract
Over the last ten years a new trend of research activities regarding the flame retardancy of polymeric materials has arisen. Indeed, the continuous search for new flame retardant systems able to replace the traditional approaches has encouraged alternative solutions, mainly centred on nanotechnology. [...] Read more.
Over the last ten years a new trend of research activities regarding the flame retardancy of polymeric materials has arisen. Indeed, the continuous search for new flame retardant systems able to replace the traditional approaches has encouraged alternative solutions, mainly centred on nanotechnology. In this context, the deposition of nanostructured coatings on fabrics appears to be the most appealing and performance suitable approach. To this aim, different strategies can be exploited: from the deposition of a single monolayer consisting of inorganic nanoparticles (single-step adsorption) to the building-up of more complex architectures derived from layer by layer assembly (multi-step adsorption). The present paper aims to review the application of such systems in the field of polyester and polyester-cotton blend fabrics. The results collated by the authors are discussed and compared with those published in the literature on the basis of the different deposition methods adopted. A critical analysis of the advantages and disadvantages exhibited by these approaches is also presented. Full article
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1311 KiB  
Article
Comparative Analysis of the Thermal Insulation of Traditional and Newly Designed Protective Clothing for Foundry Workers
by Iwona Frydrych, Agnieszka Cichocka, Paulina Gilewicz and Justyna Dominiak
Polymers 2016, 8(10), 348; https://doi.org/10.3390/polym8100348 - 23 Sep 2016
Cited by 8 | Viewed by 6542
Abstract
An objective of the undertaken research was checking the applicability of aluminized basalt fabrics for the production of clothing for foundry workers. The results of flammability, the resistance to contact, convective and radiation heat, as well as the resistance to big molten metal [...] Read more.
An objective of the undertaken research was checking the applicability of aluminized basalt fabrics for the production of clothing for foundry workers. The results of flammability, the resistance to contact, convective and radiation heat, as well as the resistance to big molten metal splashes confirmed the thesis of applicability of the packages with the use of aluminized basalt fabric content for the assumed purpose; therefore, such protective clothing was produced. Thermal comfort of foundry workers is very important and related to many factors, i.e., the structure of the protective clothing package, the number of layers, their thickness, the distance between the body and appropriate underwear. In the paper, a comparison of the results of thermal insulation measurement of two kinds of protective clothing is presented: the traditional one made of aluminized glass fabrics and the new one made of aluminized basalt fabrics. Measurements of clothing thermal insulation were conducted using a thermal manikin dressed in the protective clothing and three kinds of underwear products covering the upper and lower part of the manikin. Full article
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2908 KiB  
Article
Factors for Consideration in an Open-Flame Test for Assessing Fire Blocking Performance of Barrier Fabrics
by Shonali Nazaré, William M. Pitts, John Shields and Rick Davis
Polymers 2016, 8(9), 342; https://doi.org/10.3390/polym8090342 - 19 Sep 2016
Cited by 7 | Viewed by 6953
Abstract
The main objective of the work reported here is to assess factors that could affect the outcome of a proposed open flame test for barrier fabrics (BF-open flame test). The BF-open flame test characterizes barrier effectiveness by monitoring the ignition of a flexible [...] Read more.
The main objective of the work reported here is to assess factors that could affect the outcome of a proposed open flame test for barrier fabrics (BF-open flame test). The BF-open flame test characterizes barrier effectiveness by monitoring the ignition of a flexible polyurethane foam (FPUF) layer placed in contact with the upper side of the barrier fabric, exposed to a burner flame from below. Particular attention is given to the factors that influence the ignitibility of the FPUF, including thermal resistance, permeability, and structural integrity of the barrier fabrics (BFs). A number of barrier fabrics, displaying a wide range of the properties, are tested with the BF-open flame test. Visual observations of the FPUF burning behavior and BF char patterns, in addition to heat flux measurements on the unexposed side of the barrier fabrics, are used to assess the protective performance of the BF specimen under the open flame test conditions. The temperature and heat transfer measurements on the unexposed side of the BF and subsequent ranking of BFs for their thermal protective performance suggest that the BF-open flame test does not differentiate barrier fabrics based on their heat transfer properties. A similar conclusion is reached with regard to BF permeability characterized at room temperature. However, the outcome of this BF-open flame test is found to be heavily influenced by the structural integrity of thermally degraded BF. The BF-open flame test, in its current form, only ignited FPUF when structural failure of the barrier was observed. Full article
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2747 KiB  
Article
PLA with Intumescent System Containing Lignin and Ammonium Polyphosphate for Flame Retardant Textile
by Aurélie Cayla, François Rault, Stéphane Giraud, Fabien Salaün, Vanessa Fierro and Alain Celzard
Polymers 2016, 8(9), 331; https://doi.org/10.3390/polym8090331 - 05 Sep 2016
Cited by 110 | Viewed by 13564
Abstract
Using bio-based polymers to replace of polymers from petrochemicals in the manufacture of textile fibers is a possible way to improve sustainable development for the textile industry. Polylactic acid (PLA) is one of the available bio-based polymers. One way to improve the fire [...] Read more.
Using bio-based polymers to replace of polymers from petrochemicals in the manufacture of textile fibers is a possible way to improve sustainable development for the textile industry. Polylactic acid (PLA) is one of the available bio-based polymers. One way to improve the fire behavior of this bio-based polymer is to add an intumescent formulation mainly composed of acid and carbon sources. In order to optimize the amount of bio-based product in the final material composition, lignin from wood waste was selected as the carbon source. Different formulations of and/or ammonium polyphosphate (AP) were prepared by melt extrusion and then hot-pressed into sheets. The thermal properties (thermogravimetric analyses (TGA) and differential scanning calorimetry (DSC)) and fire properties (UL-94) were measured. The spinnability of the various composites was evaluated. The mechanical properties and physical aspect (microscopy) of PLA multifilaments with lignin (LK) were checked. A PLA multifilament with up to 10 wt % of intumescent formulation was processed, and the fire behavior of PLA fabrics with lignin/AP formulation was studied by cone calorimeter. Full article
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2314 KiB  
Article
Toxic Combustion Product Yields as a Function of Equivalence Ratio and Flame Retardants in Under-Ventilated Fires: Bench-Large-Scale Comparisons
by David A. Purser
Polymers 2016, 8(9), 330; https://doi.org/10.3390/polym8090330 - 03 Sep 2016
Cited by 21 | Viewed by 6961
Abstract
In large-scale compartment fires; combustion product yields vary with combustion conditions mainly in relation to the fuel:air equivalence ratio (Φ) and the effects of gas-phase flame retardants. Yields of products of inefficient combustion; including the major toxic products CO; HCN and organic irritants; [...] Read more.
In large-scale compartment fires; combustion product yields vary with combustion conditions mainly in relation to the fuel:air equivalence ratio (Φ) and the effects of gas-phase flame retardants. Yields of products of inefficient combustion; including the major toxic products CO; HCN and organic irritants; increase considerably as combustion changes from well-ventilated (Φ < 1) to under-ventilated (Φ = 1–3). It is therefore essential that bench-scale toxicity tests reproduce this behaviour across the Φ range. Yield data from repeat compartment fire tests for any specific fuel show some variation on either side of a best-fit curve for CO yield as a function of Φ. In order to quantify the extent to which data from the steady state tube furnace (SSTF [1]; ISO TS19700 [2]) represents compartment fire yields; the range and average deviations of SSTF data for CO yields from the compartment fire best-fit curve were compared to those for direct compartment fire measurements for six different polymeric fuels with textile and non-textile applications and for generic post-flashover fire CO yield data. The average yields; range and standard deviations of the SSTF data around the best-fit compartment fire curves were found to be close to those for the compartment fire data. It is concluded that SSTF data are as good a predictor of compartment fire yields as are repeat compartment fire test data. Full article
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4212 KiB  
Article
Heat Release Property and Fire Performance of the Nomex/Cotton Blend Fabric Treated with a Nonformaldehyde Organophosphorus System
by Charles Q. Yang and Qin Chen
Polymers 2016, 8(9), 327; https://doi.org/10.3390/polym8090327 - 02 Sep 2016
Cited by 4 | Viewed by 7315
Abstract
Blending Nomex® with cotton improves its affordability and serviceability. Because cotton is a highly flammable fiber, Nomex®/cotton blend fabrics containing more than 20% cotton require flame-retardant treatment. In this research, combination of a hydroxyl functional organophosphorus oligmer (HFPO) and 1,2,3,4-butanetetracarboxylic [...] Read more.
Blending Nomex® with cotton improves its affordability and serviceability. Because cotton is a highly flammable fiber, Nomex®/cotton blend fabrics containing more than 20% cotton require flame-retardant treatment. In this research, combination of a hydroxyl functional organophosphorus oligmer (HFPO) and 1,2,3,4-butanetetracarboxylic acid (BTCA) was used for flame retardant finishing of the 65/35 Nomex®/cotton blend woven fabric. The system contains HFPO as a flame retardant, BTCA as a bonding agent, and triethenolamine (TEA) as a reactive additive used to enhance the performance of HFPO/BTCA. Addition of TEA improves the hydrolysis resistance of the HFPO/BTCA crosslinked polymeric network on the blend fabric. Additionally, TEA enhances HFPO’s flame retardant performance by reducing formation of calcium salts and also by providing synergistic nitrogen to the treated blend fabric. The Nomex®/cotton blend fabric treated with the HFPO/BTCA/TEA system shows high flame resistance and high laundering durability at a relatively low HFPO concentration of 8% (w/w). The heat release properties of the treated Nomex®/cotton blend fabric were measured using microscale combustion calorimetry. The functions of BTCA; HFPO and TEA on the Nomex®/cotton blend fabric were elucidated based on the heat release properties, char formation, and fire performance of the treated blend fabric. Full article
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1883 KiB  
Article
Flame Retardancy of Sorbitol Based Bioepoxy via Combined Solid and Gas Phase Action
by Beáta Szolnoki, Katalin Bocz, György Marosi and Andrea Toldy
Polymers 2016, 8(9), 322; https://doi.org/10.3390/polym8090322 - 30 Aug 2016
Cited by 19 | Viewed by 7911
Abstract
Flame-retarded bioepoxy resins were prepared with the application of commercially available sorbitol polyglycidyl ether (SPE). The additive-type flame retardancy of the cycloaliphatic amine-cured SPE was investigated. Three-percent phosphorus (P)-containing samples were prepared with the application of the liquid resorcinol bis(diphenyl phosphate) (RDP), the [...] Read more.
Flame-retarded bioepoxy resins were prepared with the application of commercially available sorbitol polyglycidyl ether (SPE). The additive-type flame retardancy of the cycloaliphatic amine-cured SPE was investigated. Three-percent phosphorus (P)-containing samples were prepared with the application of the liquid resorcinol bis(diphenyl phosphate) (RDP), the solid ammonium polyphosphate (APP), and by combining them. Synergistic effect was found between the inorganic APP and the organophosphorus RDP, when applied in combination: formulations applying RDP or APP alone showed increased limiting oxygen index (LOI) values, however, their UL-94 standard ratings remained HB. When the same amount of P originated from the two additives, V-0, self-extinguishing rating and LOI value of 34% (v/v) was reached. By the combined approach the heat release rate of SPE could be lowered by approximately 60%. The assumed balanced solid and gas phase mechanism was confirmed by thermogravimetric analysis, Fourier transform infrared spectrometry (FTIR) analysis (of the gases formed during laser pyrolysis), attenuated total reflection-infrared spectrometry (ATR-IR) analysis (of the charred residues), as well as by mechanical testing (of the char obtained after combustion). Full article
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6231 KiB  
Review
Recent Advances for Flame Retardancy of Textiles Based on Phosphorus Chemistry
by Khalifah A. Salmeia, Sabyasachi Gaan and Giulio Malucelli
Polymers 2016, 8(9), 319; https://doi.org/10.3390/polym8090319 - 25 Aug 2016
Cited by 186 | Viewed by 19230
Abstract
This paper aims at updating the progress on the phosphorus-based flame retardants specifically designed and developed for fibers and fabrics (particularly referring to cotton, polyester and their blends) over the last five years. Indeed, as clearly depicted by Horrocks in a recent review, [...] Read more.
This paper aims at updating the progress on the phosphorus-based flame retardants specifically designed and developed for fibers and fabrics (particularly referring to cotton, polyester and their blends) over the last five years. Indeed, as clearly depicted by Horrocks in a recent review, the world of flame retardants for textiles is still experiencing some changes that are focused on topics like the improvement of its effectiveness and the replacement of toxic chemical products with counterparts that have low environmental impact and, hence, are more sustainable. In this context, phosphorus-based compounds play a key role and may lead, possibly in combination with silicon- or nitrogen-containing structures, to the design of new, efficient flame retardants for fibers and fabrics. Therefore, this review thoroughly describes the advances and the potentialities offered by the phosphorus-based products recently developed at a lab-scale, highlighting the current limitations, open challenges and some perspectives toward their possible exploitation at a larger scale. Full article
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8668 KiB  
Article
Silica Treatments: A Fire Retardant Strategy for Hemp Fabric/Epoxy Composites
by Francesco Branda, Giulio Malucelli, Massimo Durante, Alessandro Piccolo, Pierluigi Mazzei, Aniello Costantini, Brigida Silvestri, Miriam Pennetta and Aurelio Bifulco
Polymers 2016, 8(8), 313; https://doi.org/10.3390/polym8080313 - 22 Aug 2016
Cited by 43 | Viewed by 9084
Abstract
In this paper, for the first time, inexpensive waterglass solutions are exploited as a new, simple and ecofriendly chemical approach for promoting the formation of a silica-based coating on hemp fabrics, able to act as a thermal shield and to protect the latter [...] Read more.
In this paper, for the first time, inexpensive waterglass solutions are exploited as a new, simple and ecofriendly chemical approach for promoting the formation of a silica-based coating on hemp fabrics, able to act as a thermal shield and to protect the latter from heat sources. Fourier Transform Infrared (FTIR) and solid-state Nuclear Magnetic Resonance (NMR) analysis confirm the formation of –C–O–Si– covalent bonds between the coating and the cellulosic substrate. The proposed waterglass treatment, which is resistant to washing, seems to be very effective for improving the fire behavior of hemp fabric/epoxy composites, also in combination with ammonium polyphosphate. In particular, the exploitation of hemp surface treatment and Ammonium Polyphosphate (APP) addition to epoxy favors a remarkable decrease of the Heat Release Rate (HRR), Total Heat Release (THR), Total Smoke Release (TSR) and Specific Extinction Area (SEA) (respectively by 83%, 35%, 45% and 44%) as compared to untreated hemp/epoxy composites, favoring the formation of a very stable char, as also assessed by Thermogravimetric Analysis (TGA). Because of the low interfacial adhesion between the fabrics and the epoxy matrix, the obtained composites show low strength and stiffness; however, the energy absorbed by the material is higher when using treated hemp. The presence of APP in the epoxy matrix does not affect the mechanical behavior of the composites. Full article
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1090 KiB  
Article
Flammability of Cellulose-Based Fibers and the Effect of Structure of Phosphorus Compounds on Their Flame Retardancy
by Khalifah A. Salmeia, Milijana Jovic, Audrone Ragaisiene, Zaneta Rukuiziene, Rimvydas Milasius, Daiva Mikucioniene and Sabyasachi Gaan
Polymers 2016, 8(8), 293; https://doi.org/10.3390/polym8080293 - 10 Aug 2016
Cited by 49 | Viewed by 9447
Abstract
Cellulose fibers are promoted for use in various textile applications due their sustainable nature. Cellulose-based fibers vary considerably in their mechanical and flammability properties depending on their chemical composition. The chemical composition of a cellulose-based fiber is further dependent on their source (i.e., [...] Read more.
Cellulose fibers are promoted for use in various textile applications due their sustainable nature. Cellulose-based fibers vary considerably in their mechanical and flammability properties depending on their chemical composition. The chemical composition of a cellulose-based fiber is further dependent on their source (i.e., seed, leaf, cane, fruit, wood, bast, and grass). Being organic in nature, cellulose fibers, and their products thereof, pose considerable fire risk. In this work we have compared the flammability properties of cellulose fibers obtained from two different sources (i.e., cotton and peat). Compared to cotton cellulose textiles, peat-based cellulose textiles burn longer with a prominent afterglow which can be attributed to the presence of lignin in its structure. A series of phosphoramidates were synthesized and applied on both cellulose textiles. From thermogravimetric and pyrolysis combustion flow analysis of the treated cellulose, we were able to relate the flame retardant efficacy of the synthesized phosphorus compounds to their chemical structure. The phosphoramidates with methyl phosphoester groups exhibited higher condensed phase flame retardant effects on both types of cellulose textiles investigated in this study. In addition, the bis-phosphoramidates exhibited higher flame retardant efficacy compared to the mono-phosphoramidates. Full article
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1972 KiB  
Article
Flame Retardant Polyamide Fibres: The Challenge of Minimising Flame Retardant Additive Contents with Added Nanoclays
by Richard Horrocks, Ahilan Sitpalan, Chen Zhou and Baljinder K. Kandola
Polymers 2016, 8(8), 288; https://doi.org/10.3390/polym8080288 - 09 Aug 2016
Cited by 35 | Viewed by 7629
Abstract
This work shows that halogen-free, flame retarded polyamide 6 (PA6), fabrics may be produced in which component fibres still have acceptable tensile properties and low levels (preferably ≤10 wt %) of additives by incorporating a nanoclay along with two types of flame retardant [...] Read more.
This work shows that halogen-free, flame retarded polyamide 6 (PA6), fabrics may be produced in which component fibres still have acceptable tensile properties and low levels (preferably ≤10 wt %) of additives by incorporating a nanoclay along with two types of flame retardant formulations. The latter include (i) aluminium diethyl phosphinate (AlPi) at 10 wt %, known to work principally in the vapour phase and (ii) ammonium sulphamate (AS)/dipentaerythritol (DP) system present at 2.5 and 1 wt % respectively, believed to be condense phase active. The nanoclay chosen is an organically modified montmorillonite clay, Cloisite 25A. The effect of each additive system is analysed in terms of its ability to maximise both filament tensile properties relative to 100% PA6 and flame retardant behaviour of knitted fabrics in a vertical orientation. None of the AlPi-containing formulations achieved self-extinguishability, although the presence of nanoclay promoted lower burning and melt dripping rates. The AS/DP-containing formulations with total flame retardant levels of 5.5 wt % or less showed far superior properties and with nanoclay, showed fabric extinction times ≤ 39 s and reduced melt dripping. The tensile and flammability results, supported by thermogravimetric analysis, have been interpreted in terms of the mechanism of action of each flame retardant/nanoclay type. Full article
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2043 KiB  
Article
Key Role of Reinforcing Structures in the Flame Retardant Performance of Self-Reinforced Polypropylene Composites
by Katalin Bocz, Dániel Simon, Tamás Bárány and György Marosi
Polymers 2016, 8(8), 289; https://doi.org/10.3390/polym8080289 - 08 Aug 2016
Cited by 11 | Viewed by 5750
Abstract
The flame retardant synergism between highly stretched polymer fibres and intumescent flame retardant systems was investigated in self-reinforced polypropylene composites. It was found that the structure of reinforcement, such as degree of molecular orientation, fibre alignment and weave type, has a particular effect [...] Read more.
The flame retardant synergism between highly stretched polymer fibres and intumescent flame retardant systems was investigated in self-reinforced polypropylene composites. It was found that the structure of reinforcement, such as degree of molecular orientation, fibre alignment and weave type, has a particular effect on the fire performance of the intumescent system. As little as 7.2 wt % additive content, one third of the amount needed in non-reinforced polypropylene matrix, was sufficient to reach a UL-94 V-0 rating. The best result was found in self-reinforced polypropylene composites reinforced with unidirectional fibres. In addition to the fire retardant performance, the mechanical properties were also evaluated. The maximum was found at optimal consolidation temperature, while the flame retardant additive in the matrix did not influence the mechanical performance up to the investigated 13 wt % concentration. Full article
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9219 KiB  
Article
Application of Flame-Retardant Double-Layered Shell Microcapsules to Nonwoven Polyester
by Chloé Butstraen, Fabien Salaün, Eric Devaux, Stéphane Giraud and Philippe Vroman
Polymers 2016, 8(7), 267; https://doi.org/10.3390/polym8070267 - 22 Jul 2016
Cited by 10 | Viewed by 7871
Abstract
A microencapsulated flame retardant was used in order to produce a flame retardant nonwoven substrate. Melamine-formaldehyde polymer-shell microcapsules, containing Afflamit® PLF 280 (resorcinol bis(diphenyl phosphate)) as the core substance, were coated by an outer thermoplastic wall (polystyrene (PS) or poly(methyl methacrylate)), before [...] Read more.
A microencapsulated flame retardant was used in order to produce a flame retardant nonwoven substrate. Melamine-formaldehyde polymer-shell microcapsules, containing Afflamit® PLF 280 (resorcinol bis(diphenyl phosphate)) as the core substance, were coated by an outer thermoplastic wall (polystyrene (PS) or poly(methyl methacrylate)), before being applied to a core/sheet-type bi-component PET/co-PET spunbond nonwoven substrate using impregnation. The outer wall of the microcapsules was heated to the softening temperature of the thermoplastic shell in order to be bonded onto the textile fibres. The thermal stability of the microcapsules was examined using thermogravimetric analysis. The textile samples were observed with a scanning electron microscope, and the flame retardancy performance was evaluated using the NF P92-504 standard. The results show that the composition of the outer polymeric shell affected the thermal stability of the microcapsules, since the particles with a PS shell are more stable. Furthermore, the microcapsules were more located at the nonwoven surface without affecting the thickness of the samples. Based on the results of the NF P92-504 test, the flame spread rate was relatively low for all of the tested formulations. Only the formulation with a low content of PS was classified M2 while the others were M3. Full article
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13610 KiB  
Article
Adsorption and Flame Retardant Properties of Bio-Based Phytic Acid on Wool Fabric
by Xian-Wei Cheng, Jin-Ping Guan, Guoqiang Chen, Xu-Hong Yang and Ren-Cheng Tang
Polymers 2016, 8(4), 122; https://doi.org/10.3390/polym8040122 - 05 Apr 2016
Cited by 91 | Viewed by 10689
Abstract
Bio-based phytic acid (PA) as a nontoxic naturally occurring compound is a promising prospect for flame-retardant (FR) modifications to polymers. In this work, PA was applied to wool fabric using an exhaustion technique, and the adsorption and FR properties of PA on wool [...] Read more.
Bio-based phytic acid (PA) as a nontoxic naturally occurring compound is a promising prospect for flame-retardant (FR) modifications to polymers. In this work, PA was applied to wool fabric using an exhaustion technique, and the adsorption and FR properties of PA on wool fabric were studied. The flame retardancy of the treated wool fabrics depended greatly on the adsorption quantity of PA, which was related to the pH of treatment solution, immersing temperature and initial PA concentration. The Langmuir adsorption of PA took place due to electrostatic interactions between PA and wool fiber. The limiting oxygen index, vertical burning and pyrolysis combustion flow calorimetry tests revealed that the treated wool fabrics exhibited good flame retardancy. The measurements of the phosphorus content of the burned fabric residues and thermogravimetric analyses suggested that a significant condensed-phase FR action was applicable to the PA treated fabrics. PA treatment was found to have little adverse effect on the whiteness and mechanical performance of wool. Additionally, the washing resistance of the FR fabrics should be further improved. Full article
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2015

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1142 KiB  
Review
An Overview of Mode of Action and Analytical Methods for Evaluation of Gas Phase Activities of Flame Retardants
by Khalifah A. Salmeia, Julien Fage, Shuyu Liang and Sabyasachi Gaan
Polymers 2015, 7(3), 504-526; https://doi.org/10.3390/polym7030504 - 10 Mar 2015
Cited by 108 | Viewed by 13095
Abstract
The latest techniques used to prove, describe and analyze the gas phase activity of a fire retardant used in polymeric materials are briefly reviewed. Classical techniques, such as thermogravimetric analysis or microscale combustion calorimetry, as well as complex and advanced analytical techniques, such [...] Read more.
The latest techniques used to prove, describe and analyze the gas phase activity of a fire retardant used in polymeric materials are briefly reviewed. Classical techniques, such as thermogravimetric analysis or microscale combustion calorimetry, as well as complex and advanced analytical techniques, such as modified microscale combustion calorimeter (MCC), molecular beam mass spectroscopy and vacuum ultra violet (VUV) photoionization spectroscopy coupled with time of flight MS (TOF-MS), are described in this review. The recent advances in analytical techniques help not only in determining the gas phase activity of the flame-retardants but also identify possible reactive species responsible for gas phase flame inhibition. The complete understanding of the decomposition pathways and the flame retardant activity of a flame retardant system is essential for the development of new eco-friendly-tailored flame retardant molecules with high flame retardant efficiency. Full article
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793 KiB  
Article
Pyrolysis Combustion Flow Calorimetry Studies on Some Reactively Modified Polymers
by Svetlana Tretsiakova-McNally and Paul Joseph
Polymers 2015, 7(3), 453-467; https://doi.org/10.3390/polym7030453 - 02 Mar 2015
Cited by 27 | Viewed by 8398
Abstract
As a part of our continuing work to improve the flame retardance of some chain-growth polymers, by employing a reactive route, we have synthesized several unsaturated compounds containing either phosphorus (P), or both phosphorus (P) and nitrogen (N), bearing groups in different chemical [...] Read more.
As a part of our continuing work to improve the flame retardance of some chain-growth polymers, by employing a reactive route, we have synthesized several unsaturated compounds containing either phosphorus (P), or both phosphorus (P) and nitrogen (N), bearing groups in different chemical environments. They included: diethyl(acryloyloxymethyl)phosphonate (DEAMP); diethyl(1-acryloyloxyethyl)phosphonate (DE1AEP); diethyl-2-(acryloyloxy)ethyl phosphate (DEAEP); diethyl-2-(metharyloyloxy)ethyl phosphate (DEMEP); acrylic acid-2-(diethoxyphosphorylamino)ethyl ester (ADEPAE); acrylic acid-2-[(diethoxyphosphoryl)methyl amino]ethyl ester (ADEPMAE). Acrylonitrile (AN), methyl methacrylate (MMA) and styrene (S) were free radically copolymerised with the above mentioned comonomers. The recovered polymers were subjected to routine spectroscopic and thermo-gravimetric analyses. In addition, the combustion behaviours of homopolymers as well as the copolymers containing nominal loadings of P-, or P/N-, groups were, primarily, evaluated using pyrolysis combustion flow calorimetry (PCFC). PCFC has been found to be a very useful screening technique, especially, in establishing the efficacies of the different modifying groups towards flame retarding some base polymeric materials. Values of the heat release capacity (HRC) values normalised to the P contents (wt%) can be considered as useful tool in ranking the various P-containing modifying groups in terms of their efficacies to flame-retard non-halogenated chain-growth polymers considered in the present work. Full article
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1716 KiB  
Article
Flame Retardancy of PA6 Using a Guanidine Sulfamate/Melamine Polyphosphate Mixture
by Mathieu Coquelle, Sophie Duquesne, Mathilde Casetta, Jun Sun, Xiaoyu Gu, Sheng Zhang and Serge Bourbigot
Polymers 2015, 7(2), 316-332; https://doi.org/10.3390/polym7020316 - 13 Feb 2015
Cited by 37 | Viewed by 9117
Abstract
Polyamide 6 (PA6) is a widely-used polymer that could find applications in various sectors, including home textiles, transportation or construction. However, due to its organic nature, PA6 is flammable, and flame-retardant formulations have to be developed to comply with fire safety standards. Recently, [...] Read more.
Polyamide 6 (PA6) is a widely-used polymer that could find applications in various sectors, including home textiles, transportation or construction. However, due to its organic nature, PA6 is flammable, and flame-retardant formulations have to be developed to comply with fire safety standards. Recently, it was proposed to use ammonium sulfamate as an effective flame retardant for PA6, even at low loading content. However, processing issues could occur with this additive considering large-scale production. This paper thus studies the use of another sulfamate salt—guanidine sulfamate (GAS)—and evidences its high efficiency when combined with melamine polyphosphate (MPP) as a flame retardant for PA6. A decrease of the peak of the heat release rate by 30% compared to pure PA6 was obtained using only 5 wt% of a GAS/MPP mixture in a microscale calorimeter. Moreover, PA6 containing the mixture GAS/MPP exhibits a Limiting Oxygen Index (LOI) of 37 vol% and is rated V0 for the UL 94 test (Vertical Burning Test; ASTM D 3801). The mechanisms of degradation were investigated analyzing the gas phase and solid phase when the material degrades. It was proposed that MPP and GAS modify the degradation pathway of PA6, leading to the formation of nitrile end-group-containing molecules. Moreover, the formation of a polyaromatic structure by the reaction of MPP and PA6 was also shown. Full article
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1478 KiB  
Article
Flame Retardance and Physical Properties of Novel Cured Blends of Unsaturated Polyester and Furan Resins
by Baljinder Kaur Kandola, John Russell Ebdon and Kawser Parveen Chowdhury
Polymers 2015, 7(2), 298-315; https://doi.org/10.3390/polym7020298 - 11 Feb 2015
Cited by 41 | Viewed by 11673
Abstract
Novel blends of two furan resins with an unsaturated polyester have been prepared and cured by parallel free radical (for the unsaturated polyester) and acid-catalysed crosslinking (for the furan resin) to give co-cured composite materials. Although these materials have inferior physical properties, such [...] Read more.
Novel blends of two furan resins with an unsaturated polyester have been prepared and cured by parallel free radical (for the unsaturated polyester) and acid-catalysed crosslinking (for the furan resin) to give co-cured composite materials. Although these materials have inferior physical properties, such as low Tg and low storage modulus compared with those of unsaturated polyester and furan resins alone, they show markedly improved flame retardance compared with that of the normally highly flammable unsaturated polyester. This increased flame retardance arises from a condensed phase mechanism in which the furanic component forms a semi-protective char, reducing rates of thermal degradation and total heat release and heat of combustion. The blends also burn with reduced smoke output compared with that from unsaturated polyester alone. Full article
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3795 KiB  
Article
Development of a Halogen Free Flame Retardant Masterbatch for Polypropylene Fibers
by François Rault, Stéphane Giraud, Fabien Salaün and Xavier Almeras
Polymers 2015, 7(2), 220-234; https://doi.org/10.3390/polym7020220 - 09 Feb 2015
Cited by 27 | Viewed by 9271
Abstract
The efficiency of new phosphinates, in combination with melamine cyanurate, was studied using different polypropylene textile structures. The influence of different ratios up to a total amount of 6 wt% in the polypropylene fiber was investigated using the limiting oxygen index (LOI) and [...] Read more.
The efficiency of new phosphinates, in combination with melamine cyanurate, was studied using different polypropylene textile structures. The influence of different ratios up to a total amount of 6 wt% in the polypropylene fiber was investigated using the limiting oxygen index (LOI) and cone calorimeter method for research purposes, while the performances were correlated to the standards FMVSS 302 (Federal Motor Vehicle Safety Standards) and DIN 4102-l (Deutsches Institut für Normung) used more specifically for automotive and building sector. Full article
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2014

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1690 KiB  
Review
A Comparative Analysis of Nanoparticle Adsorption as Fire-Protection Approach for Fabrics
by Jenny Alongi, Jennifer Tata, Federico Carosio, Giuseppe Rosace, Alberto Frache and Giovanni Camino
Polymers 2015, 7(1), 47-68; https://doi.org/10.3390/polym7010047 - 31 Dec 2014
Cited by 45 | Viewed by 6838
Abstract
The present paper critically analyzes the potential for commercially available nanoparticles for enhancing the flame-retardant properties of synthetic and natural fabrics and their corresponding blends. Each nanoparticle has been applied to the fabric through a finishing-like process (namely impregnation/exhausting or, more simply, nanoparticle [...] Read more.
The present paper critically analyzes the potential for commercially available nanoparticles for enhancing the flame-retardant properties of synthetic and natural fabrics and their corresponding blends. Each nanoparticle has been applied to the fabric through a finishing-like process (namely impregnation/exhausting or, more simply, nanoparticle adsorption) in aqueous media and the resulting properties of these fabrics have been assessed in terms of combustion behavior by use of a cone calorimeter under a heat flux of 35 kW/m2. The influence of these nanoparticles on the main combustion parameters of polyester, cotton, and some of their blends has been thoroughly discussed. As a result of this discussion, a flame-retardant efficiency ranking of the nanoparticles under review has been established. Full article
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3836 KiB  
Article
Flame-Retardancy Properties of Intumescent Ammonium Poly(Phosphate) and Mineral Filler Magnesium Hydroxide in Combination with Graphene
by Bettina Dittrich, Karen-Alessa Wartig, Rolf Mülhaupt and Bernhard Schartel
Polymers 2014, 6(11), 2875-2895; https://doi.org/10.3390/polym6112875 - 20 Nov 2014
Cited by 146 | Viewed by 12820
Abstract
Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle’s influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, [...] Read more.
Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle’s influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, fire behavior and mechanical properties were determined. TRGO has a positive effect on the yield stress, which is decreased by both flame-retardants and acts as a synergist with regard to Young’s modulus. The applicability and effects of TRGO as an adjuvant in combination with conventional flame-retardants depends strongly on the particular flame-retardancy mechanism. In the intumescent system, even small concentrations of TRGO change the viscosity of the pyrolysing melt crucially. In case of oxygen index (OI) and UL 94 test, the addition of increasing amounts of TRGO to PP/APP had a negative impact on the oxygen index and the UL 94 classification. Nevertheless, systems with only low amounts (≤1 wt%) of TRGO achieved V-0 classification in the UL 94 test and high oxygen indices (>31 vol%). TRGO strengthens the residue structure of MH and therefore functions as a strong synergist in terms of OI and UL 94 classification (from HB to V-0). Full article
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