2023

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Open AccessCommunication

Flame Retardancy Index (FRI) for Polymer Materials Ranking

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Polymers 2023, 15(11), 2422; https://doi.org/10.3390/polym15112422 - 23 May 2023

Cited by 2 | Viewed by 918

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 (t_i) 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 (t_p), 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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Open AccessEditorial

Sustainable Flame-Retardant Additives for Polymers: Future Perspectives

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Mohammad Reza Saeb

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Henri Vahabi

Polymers 2023, 15(6), 1469; https://doi.org/10.3390/polym15061469 - 16 Mar 2023

Viewed by 819

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

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Open AccessArticle

Effect of the Current on the Fire Characteristics of Overloaded Polyvinyl Chloride Copper Wires

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Polymers 2022, 14(21), 4766; https://doi.org/10.3390/polym14214766 - 07 Nov 2022

Cited by 1 | Viewed by 1038

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 (I_e) 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 (I_e) to 3.5 times I_e 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 I_e, 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 I_e, 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 I_e was lower than that of copper wires carrying less than other times I_e. 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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Open AccessArticle

Expandable Graphite for Flame Retardant PA6 Applications

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Polymers 2021, 13(16), 2733; https://doi.org/10.3390/polym13162733 - 15 Aug 2021

Cited by 8 | Viewed by 2358

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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Open AccessArticle

A Synergistic Flame Retardant System Based on Expandable Graphite, Aluminum (Diethyl-)Polyphospinate and Melamine Polyphosphate for Polyamide 6

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Polymers 2021, 13(16), 2712; https://doi.org/10.3390/polym13162712 - 13 Aug 2021

Cited by 10 | Viewed by 2160

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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Open AccessArticle

Suppression of Smoldering of Calcium Alginate Flame-Retardant Paper by Flame-Retardant Polyamide-66

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Polymers 2021, 13(3), 430; https://doi.org/10.3390/polym13030430 - 29 Jan 2021

Cited by 10 | Viewed by 1884

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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Open AccessArticle

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

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Polymers 2020, 12(11), 2542; https://doi.org/10.3390/polym12112542 - 30 Oct 2020

Cited by 3 | Viewed by 1603

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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Open AccessArticle

Flame-Retardant Mechanism and Mechanical Properties of Wet-Spun Poly(acrylonitrile-co-vinylidene chloride) Fibers with Antimony Trioxide and Zinc Hydroxystannate

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Polymers 2020, 12(11), 2442; https://doi.org/10.3390/polym12112442 - 22 Oct 2020

Cited by 7 | Viewed by 2182

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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Open AccessArticle

The Toxicological Testing and Thermal Decomposition of Drive and Transport Belts Made of Thermoplastic Multilayer Polymer Materials

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Dorota Czarnecka-Komorowska

Polymers 2020, 12(10), 2232; https://doi.org/10.3390/polym12102232 - 28 Sep 2020

Cited by 17 | Viewed by 2795

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 (W_LC50SM) 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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Open AccessEditor’s ChoiceReview

The Potential for Bio-Sustainable Organobromine-Containing Flame Retardant Formulations for Textile Applications—A Review

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A Richard Horrocks

Polymers 2020, 12(9), 2160; https://doi.org/10.3390/polym12092160 - 22 Sep 2020

Cited by 26 | Viewed by 3757

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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Open AccessArticle

Flammability Characteristics and Mechanical Properties of Casein Based Polymeric Composites

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Polymers 2020, 12(9), 2078; https://doi.org/10.3390/polym12092078 - 12 Sep 2020

Cited by 7 | Viewed by 2228

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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Open AccessArticle

A Kinetic Analysis of the Thermal Degradation Behaviours of Some Bio-Based Substrates

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Ananya Thomas

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Khalid Moinuddin

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Svetlana Tretsiakova-McNally

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Paul Joseph

Polymers 2020, 12(8), 1830; https://doi.org/10.3390/polym12081830 - 15 Aug 2020

Cited by 8 | Viewed by 2205

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 (E_a) obtained in each case should only be considered as apparent values at best. Furthermore, some useful, but limited, correlations were identified between the E_a values and the relevant parameters obtained earlier by us from pyrolysis combustion flow calorimetry (PCFC). Full article

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Open AccessArticle

Mechanistic Aspects of Condensed- and Gaseous-Phase Activities of Some Phosphorus-Containing Fire Retardants

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Polymers 2020, 12(8), 1801; https://doi.org/10.3390/polym12081801 - 11 Aug 2020

Cited by 7 | Viewed by 1913

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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Open AccessEditor’s ChoiceArticle

A Case Study of Polyether Ether Ketone (I): Investigating the Thermal and Fire Behavior of a High-Performance Material

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Aditya Ramgobin

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Gaëlle Fontaine

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Serge Bourbigot

Polymers 2020, 12(8), 1789; https://doi.org/10.3390/polym12081789 - 10 Aug 2020

Cited by 17 | Viewed by 2267

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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Open AccessArticle

Enhanced Biodegradation/Photodegradation of Organophosphorus Fire Retardant Using an Integrated Method of Modified Pharmacophore Model with Molecular Dynamics and Polarizable Continuum Model

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Jiawen Yang

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Qing Li

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Yu Li

Polymers 2020, 12(8), 1672; https://doi.org/10.3390/polym12081672 - 27 Jul 2020

Cited by 12 | Viewed by 2509

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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Open AccessEditor’s ChoiceArticle

A Case Study of Polyetheretherketone (II): Playing with Oxygen Concentration and Modeling Thermal Decomposition of a High-Performance Material

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Aditya Ramgobin

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Gaëlle Fontaine

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Serge Bourbigot

Polymers 2020, 12(7), 1577; https://doi.org/10.3390/polym12071577 - 16 Jul 2020

Cited by 8 | Viewed by 2241

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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Open AccessArticle

Application of Plasma Activation in Flame-Retardant Treatment for Cotton Fabric

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Polymers 2020, 12(7), 1575; https://doi.org/10.3390/polym12071575 - 16 Jul 2020

Cited by 11 | Viewed by 2940

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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Open AccessArticle

Potential Synergism between Novel Metal Complexes and Polymeric Brominated Flame Retardants in Polyamide 6.6

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Alistair F. Holdsworth

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A. Richard Horrocks

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Baljinder K. Kandola

Polymers 2020, 12(7), 1543; https://doi.org/10.3390/polym12071543 - 13 Jul 2020

Cited by 10 | Viewed by 2235

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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Open AccessArticle

Preparation and Mechanism of Flame-Retardant Cotton Fabric with Phosphoramidate Siloxane Polymer through Multistep Coating

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Polymers 2020, 12(7), 1538; https://doi.org/10.3390/polym12071538 - 12 Jul 2020

Cited by 20 | Viewed by 2721

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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Open AccessEditor’s ChoiceArticle

Effects of a Reactive Phosphorus–Sulfur Containing Flame-Retardant Monomer on the Flame Retardancy and Thermal and Mechanical Properties of Unsaturated Polyester Resin

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Polymers 2020, 12(7), 1441; https://doi.org/10.3390/polym12071441 - 27 Jun 2020

Cited by 15 | Viewed by 2852

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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Open AccessReview

Flame Retardancy of Bio-Based Polyurethanes: Opportunities and Challenges

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Polymers 2020, 12(6), 1234; https://doi.org/10.3390/polym12061234 - 29 May 2020

Cited by 66 | Viewed by 5621

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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Open AccessArticle

A Flame-Retardant Phytic-Acid-Based LbL-Coating for Cotton Using Polyvinylamine

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Jochen Stefan Gutmann

Polymers 2020, 12(5), 1202; https://doi.org/10.3390/polym12051202 - 25 May 2020

Cited by 21 | Viewed by 3780

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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Open AccessEditor’s ChoiceArticle

Poly (vinyl alcohol)/β-Cyclodextrin Composite Fiber with Good Flame Retardant and Super-Smoke Suppression Properties

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Polymers 2020, 12(5), 1078; https://doi.org/10.3390/polym12051078 - 08 May 2020

Cited by 12 | Viewed by 3102

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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Open AccessReview

Biomolecules as Flame Retardant Additives for Polymers: A Review

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Daniel A. Villamil Watson

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David A. Schiraldi

Polymers 2020, 12(4), 849; https://doi.org/10.3390/polym12040849 - 07 Apr 2020

Cited by 53 | Viewed by 6070

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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Open AccessArticle

Phytic Acid and Biochar: An Effective All Bio-Sourced Flame Retardant Formulation for Cotton Fabrics

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Polymers 2020, 12(4), 811; https://doi.org/10.3390/polym12040811 - 04 Apr 2020

Cited by 40 | Viewed by 3530

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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Open AccessArticle

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)

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Polymers 2020, 12(4), 778; https://doi.org/10.3390/polym12040778 - 01 Apr 2020

Cited by 12 | Viewed by 3392

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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Open AccessArticle

Waterborne Intumescent Coatings Containing Industrial and Bio-Fillers for Fire Protection of Timber Materials

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Abderrahman Aqlibous

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Svetlana Tretsiakova-McNally

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Talal Fateh

Polymers 2020, 12(4), 757; https://doi.org/10.3390/polym12040757 - 31 Mar 2020

Cited by 14 | Viewed by 3070

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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Open AccessArticle

Effect of Different Flame-Retardant Bridged DOPO Derivatives on Properties of in Situ Produced Fiber-Forming Polyamide 6

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Polymers 2020, 12(3), 657; https://doi.org/10.3390/polym12030657 - 13 Mar 2020

Cited by 25 | Viewed by 4791

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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Open AccessArticle

Thermal and Calorimetric Evaluations of Some Chemically Modified Carbohydrate-Based Substrates with Phosphorus-Containing Groups

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Svetlana Tretsiakova-McNally

Polymers 2020, 12(3), 588; https://doi.org/10.3390/polym12030588 - 05 Mar 2020

Cited by 7 | Viewed by 2330

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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Open AccessEditor’s ChoiceArticle

Ammonium Polyphosphate with High Specific Surface Area by Assembling Zeolite Imidazole Framework in EVA Resin: Significant Mechanical Properties, Migration Resistance, and Flame Retardancy

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Polymers 2020, 12(3), 534; https://doi.org/10.3390/polym12030534 - 02 Mar 2020

Cited by 13 | Viewed by 3032

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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Open AccessArticle

Alkylation of Aromatic Compounds with Pentabromobenzyl Bromide and Tetrabromoxylene Dibromide as a New Route to High Molecular Weight Brominated Flame Retardants

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Polymers 2020, 12(2), 352; https://doi.org/10.3390/polym12020352 - 06 Feb 2020

Cited by 5 | Viewed by 2624

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 M_w > 1400. However, the alkylation of the same aromatic molecules by a mixture of PBBB and TBXDP resulted in polymeric flame retardants with M_w > 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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Open AccessArticle

Flame-Retardant Performance of Transparent and Tensile-Strength-Enhanced Epoxy Resins

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Liang Li

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Zaisheng Cai

Polymers 2020, 12(2), 317; https://doi.org/10.3390/polym12020317 - 04 Feb 2020

Cited by 22 | Viewed by 2934

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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Open AccessArticle

Synthesis of Lignin-Based Polyacid Catalyst and Its Utilization to Improve Water Resistance of Urea–formaldehyde Resins

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Polymers 2020, 12(1), 175; https://doi.org/10.3390/polym12010175 - 09 Jan 2020

Cited by 22 | Viewed by 4237

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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Open AccessArticle

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

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Polymers 2020, 12(1), 90; https://doi.org/10.3390/polym12010090 - 03 Jan 2020

Cited by 9 | Viewed by 2970

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 (T_10%) and the glass transition temperature (T_g) of the PI-3 film were 411.6 °C and 227.4 °C, respectively, which were lower than those of the PI-1 matrix (T_10%: 487.3 °C; T_g: 260.6 °C) Full article

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2019

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Open AccessArticle

Incorporation of Comonomer exo-5-(Diphenylphosphato)Isosorbide-2-endo-Acrylate to Generate Flame Retardant Poly(Styrene)

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Bob A. Howell

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Yoseph G. Daniel

Polymers 2019, 11(12), 2038; https://doi.org/10.3390/polym11122038 - 09 Dec 2019

Cited by 14 | Viewed by 2763

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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Open AccessArticle

One-Step Synthesis of Highly Efficient Oligo(phenylphosphonic Dihydroxypropyl Silicone Oil) Flame Retardant for Polycarbonate

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Polymers 2019, 11(12), 1977; https://doi.org/10.3390/polym11121977 - 01 Dec 2019

Cited by 8 | Viewed by 3011

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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Open AccessArticle

An Alginate Hybrid Sponge with High Thermal Stability: Its Flame Retardant Properties and Mechanism

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Polymers 2019, 11(12), 1973; https://doi.org/10.3390/polym11121973 - 30 Nov 2019

Cited by 15 | Viewed by 3438

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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Open AccessArticle

A Study of the Thermal Degradation and Combustion Characteristics of Some Materials Commonly Used in the Construction Sector

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Javier Arturo Piedrahita Solorzano

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Khalid Abu Mohammad Moinuddin

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Svetlana Tretsiakova-McNally

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Paul Joseph

Polymers 2019, 11(11), 1833; https://doi.org/10.3390/polym11111833 - 07 Nov 2019

Cited by 9 | Viewed by 2996

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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Open AccessArticle

A Novel Inherently Flame-Retardant Composite Based on Zinc Alginate/Nano-Cu₂O

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Polymers 2019, 11(10), 1575; https://doi.org/10.3390/polym11101575 - 27 Sep 2019

Cited by 15 | Viewed by 2601

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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Open AccessEditor’s ChoiceCommunication

Flame Retardancy Index for Thermoplastic Composites

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Henri Vahabi

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Baljinder K. Kandola

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Mohammad Reza Saeb

Polymers 2019, 11(3), 407; https://doi.org/10.3390/polym11030407 - 01 Mar 2019

Cited by 167 | Viewed by 5771

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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Open AccessArticle

Investigation of the Structure-Property Effect of Phosphorus-Containing Polysulfone on Decomposition and Flame Retardant Epoxy Resin Composites

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Polymers 2019, 11(2), 380; https://doi.org/10.3390/polym11020380 - 21 Feb 2019

Cited by 9 | Viewed by 3464

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 (T_g) 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 T_g 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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Open AccessEditor’s ChoiceArticle

Phosphorus Containing Polyacrylamides as Flame Retardants for Epoxy-Based Composites in Aviation

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Polymers 2019, 11(2), 284; https://doi.org/10.3390/polym11020284 - 08 Feb 2019

Cited by 30 | Viewed by 4395

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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