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Special Issue "Flame Retardant Polymeric Materials"

A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (31 March 2017)

Special Issue Editor

Guest Editor
Prof. Dr. De-Yi Wang

Head of High Performance Polymer Nanocomposites Group, IMDEA Materials Institute, C/Eric Kandel, 2, 28906 Getafe, Madrid, Spain
Website | E-Mail
Interests: flame retardant polymers; fire behaviors and mechanism; polymer nanocomposites; high performance polymers; functionalized nanomaterials

Special Issue Information

Dear Colleagues,

Nowadays, polymeric material products are ubiquitous in various fields in our day-to-day life, such as electrical/electronics, construction, furniture, transportation, packaging, etc. However, a crucial limitation is that most polymeric materials (both of natural and synthetic polymers) are flammable.  The widespread use of polymeric materials in society brings high fire risk. Based on the data offered by the World Health Organization (WHO) published in 2014, there are 265,000 fire deaths per year worldwide, and 11 million people who have suffered burns that were severe enough to require medical attention. How to improve the fire safety of polymeric materials has become an important concern in the materials science and engineering community.

Unquestionably, the improvement of polymers’ ability to retard fire is a cutting edge topic in the field of materials science and technology. Due to environmental concerns, some halogenated flame-retardants have been phased out. In this context, sustainable, environmentally friendly, high performance flame-retardants and flame-retardant techniques are highly sought.

This Special Issue on “Flame Retardant Polymeric Materials” will compile a variety of emerging novel flame-retardants, new flame-retardant techniques, and some fundamental research or applicative study in the field of fire retardant materials.

Topics to be considered include, but are not limited to:

  • New fire retardants and flame retardant polymers
  • Fire behavior and flame-retardant mechanisms
  • Nanotechnology against fire (nanofillers, nanocoating, etc.)
  • Regulation, tests, toxicity and environmental issues
  • New flame-retardant techniques and approaches

It is my pleasure to invite you to submit a manuscript for this Special Issue. Full papers, communications, and reviews are all welcome.

Prof. Dr. De-Yi Wang
Guest Editor

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 papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Materials is an international peer-reviewed open access monthly 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 1500 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

  • novel flame retardants
  • synthesis and characterization
  • fire behaviors
  • flame retardant mechanism
  • nanomaterials and nanocoating
  • polymer composites and/or nanocomposites

Published Papers (7 papers)

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Research

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Open AccessFeature PaperArticle Improving the Flame Retardant Efficiency of Layer by Layer Coatings Containing Deoxyribonucleic Acid by Post-Diffusion of Hydrotalcite Nanoparticles
Materials 2017, 10(7), 709; doi:10.3390/ma10070709
Received: 29 April 2017 / Revised: 18 June 2017 / Accepted: 23 June 2017 / Published: 27 June 2017
Cited by 1 | PDF Full-text (5957 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
This work deals with the use of hydrotalcite nanoparticle post-diffusion in layer by layer (LbL) coatings with the aim of improving their flame retardant action on cotton. The selected LbL components, which encompass polydiallyldimethylammonium chloride and deoxyribonucleic acid, aim at the deposition of
[...] Read more.
This work deals with the use of hydrotalcite nanoparticle post-diffusion in layer by layer (LbL) coatings with the aim of improving their flame retardant action on cotton. The selected LbL components, which encompass polydiallyldimethylammonium chloride and deoxyribonucleic acid, aim at the deposition of an intumescent coating. Infrared spectra pointed out a super-linear growth of the investigated assembly, indicating the ability to deposit thick coatings while maintaining a relatively low deposition number. A post-diffusion process, performed by exposing the LbL-treated fabrics to two different concentrations of hydrotalcite water suspensions (0.1 or 1 wt %), was carried out to improve the fireproofing efficiency of these coatings. Coatings treated with the lowest concentration suspension partially swelled as a consequence of their structural rearrangements while the use of the highest concentration led to nanoparticle aggregates. Horizontal flame spread tests were used for assessing the achieved flame retardant properties. The post-diffusion performed at the lowest hydrotalcite concentration lowers the minimum number of Bi-Layers required for obtaining cotton self-extinguishment while samples treated with the highest concentration showed detrimental effects on the performances of treated fabrics. This behavior is ascribed to the effects of hydrotalcite particles on the intumescence of LbL coatings, as evidenced by the morphological analyses of post-combustion residues. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Open AccessArticle Thermal Stability and Fire Properties of Salen and Metallosalens as Fire Retardants in Thermoplastic Polyurethane (TPU)
Materials 2017, 10(6), 665; doi:10.3390/ma10060665
Received: 24 April 2017 / Revised: 4 June 2017 / Accepted: 12 June 2017 / Published: 17 June 2017
PDF Full-text (65512 KB) | HTML Full-text | XML Full-text
Abstract
This study deals with the synthesis and evaluation of salen based derivatives as fire retardants in thermoplastic polyurethane. Salens, hydroxysalens and their first row transition metal complexes (salen-M) were synthesized (Copper, Manganese, Nickel and Zinc). They were then incorporated in thermoplastic polyurethane (TPU)
[...] Read more.
This study deals with the synthesis and evaluation of salen based derivatives as fire retardants in thermoplastic polyurethane. Salens, hydroxysalens and their first row transition metal complexes (salen-M) were synthesized (Copper, Manganese, Nickel and Zinc). They were then incorporated in thermoplastic polyurethane (TPU) with a loading as low as 10:1 weight ratio. The thermal stability as well as the fire properties of the formulations were evaluated. Thermogravimetric analysis (TGA) showed that different coordination metals on the salen could induce different decomposition pathways when mixed with TPU. The Pyrolysis Combustion Flow Calorimetry (PCFC) results showed that some M-salen have the ability to significantly decrease the peak heat release rate (−61% compared to neat TPU) and total heat released (−63% compared to neat TPU) when formulated at 10:1 wt % ratio in TPU. Mass Loss Cone Calorimetry (MLC) results have shown that some additives (salen-Cu and salen-Mn) exhibit very promising performance and they are good candidates as flame-retardants for TPU. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Open AccessFeature PaperArticle Flame Retardancy of Carbon Fibre Reinforced Sorbitol Based Bioepoxy Composites with Phosphorus-Containing Additives
Materials 2017, 10(5), 467; doi:10.3390/ma10050467
Received: 5 April 2017 / Revised: 20 April 2017 / Accepted: 23 April 2017 / Published: 27 April 2017
Cited by 1 | PDF Full-text (1797 KB) | HTML Full-text | XML Full-text
Abstract
Carbon fibre reinforced flame-retarded bioepoxy composites were prepared from commercially available sorbitol polyglycidyl ether (SPE) cured with cycloaliphatic amine hardener. Samples containing 1, 2, and 3% phosphorus (P) were prepared using additive type flame retardants (FRs) resorcinol bis(diphenyl phosphate) (RDP), ammonium polyphosphate (APP),
[...] Read more.
Carbon fibre reinforced flame-retarded bioepoxy composites were prepared from commercially available sorbitol polyglycidyl ether (SPE) cured with cycloaliphatic amine hardener. Samples containing 1, 2, and 3% phosphorus (P) were prepared using additive type flame retardants (FRs) resorcinol bis(diphenyl phosphate) (RDP), ammonium polyphosphate (APP), and their combinations. The fire performance of the composites was investigated by limiting oxygen index (LOI), UL-94 tests, and mass loss calorimetry. The effect of FRs on the glass transition temperature, and storage modulus was evaluated by dynamic mechanical analysis (DMA), while the mechanical performance was investigated by tensile, bending, and interlaminar shear measurements, as well as by Charpy impact test. In formulations containing both FRs, the presence of RDP, acting mainly in gas phase, ensured balanced gas and solid-phase mechanism leading to best overall fire performance. APP advantageously compensated the plasticizing (storage modulus and glass transition temperature decreasing) effect of RDP in combined formulations; furthermore, it led to increased tensile strength and Charpy impact energy. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Open AccessArticle Exploring the Modes of Action of Phosphorus-Based Flame Retardants in Polymeric Systems
Materials 2017, 10(5), 455; doi:10.3390/ma10050455
Received: 20 February 2017 / Revised: 12 April 2017 / Accepted: 20 April 2017 / Published: 26 April 2017
Cited by 1 | PDF Full-text (12181 KB) | HTML Full-text | XML Full-text
Abstract
Phosphorus-based flame retardants were incorporated into different, easily preparable matrices, such as polymeric thermoset resins and paraffin as a proposed model for polyolefins and investigated for their flame retardancy performance. The favored mode of action of each flame retardant was identified in each
[...] Read more.
Phosphorus-based flame retardants were incorporated into different, easily preparable matrices, such as polymeric thermoset resins and paraffin as a proposed model for polyolefins and investigated for their flame retardancy performance. The favored mode of action of each flame retardant was identified in each respective system and at each respective concentration. Thermogravimetric analysis was used in combination with infrared spectroscopy of the evolved gas to determine the pyrolysis behavior, residue formation and the release of phosphorus species. Forced flaming tests in the cone calorimeter provided insight into burning behavior and macroscopic residue effects. The results were put into relation to the phosphorus content to reveal correlations between phosphorus concentration in the gas phase and flame inhibition performance, as well as phosphorus concentration in the residue and condensed phase activity. Total heat evolved (fire load) and peak heat release rate were calculated based on changes in the effective heat of combustion and residue, and then compared with the measured values to address the modes of action of the flame retardants quantitatively. The quantification of flame inhibition, charring, and the protective layer effect measure the non-linear flame retardancy effects as functions of the phosphorus concentration. Overall, this screening approach using easily preparable polymer systems provides great insight into the effect of phosphorus in different flame retarded polymers, with regard to polymer structure, phosphorus concentration, and phosphorus species. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Open AccessArticle A Study of the Curing and Flammability Properties of Bisphenol A Epoxy Diacrylate Resin Utilizing a Novel Flame Retardant Monomer, bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl Phosphate
Materials 2017, 10(2), 202; doi:10.3390/ma10020202
Received: 8 December 2016 / Revised: 12 February 2017 / Accepted: 13 February 2017 / Published: 20 February 2017
PDF Full-text (3189 KB) | HTML Full-text | XML Full-text
Abstract
A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate), was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate) and HEA (2-hydroxy ethyl acrylate). DAPP was blended with regular bisphenol A epoxy acrylate (BAEA) in various ratios to yield various phosphorus contents. The
[...] Read more.
A UV-curable, flame-retardant monomer, DAPP (bis[di-acryloyloxyethyl]-p-tert-butyl-phenyl-phosphate), was synthesized based on BPDCP (4-tert-butylphenyl-dichloro phosphate) and HEA (2-hydroxy ethyl acrylate). DAPP was blended with regular bisphenol A epoxy acrylate (BAEA) in various ratios to yield various phosphorus contents. The TGA-IR (thermogravimetric analyzer interface with an infrared spectrometer) results demonstrate that compounding 30 mol % DAPP with BAEA significantly reduced the amount of released CO gas. In contrast, the peak intensity of CO2 is independent of phosphorus content. The limiting oxygen index (LOI), reaching the saturated value of 26, and the heat release rate (HRR) measured using a cone-calorimeter, 156.43 KW/m2, confirm the saturation point when 30 mol % DAPP was compounded into BAEA. A study of the kinetics of pyrolysis reveals that Ea decreases as the phosphorus content increases. Both the TGA-IR and pyrolysis results reveal that the phosphorus compound DAPP is easily decomposed during the initial stage of burning to form an insulating layer, which inhibits further burning of the resin and the consequent release of other flammable gases. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Open AccessArticle Intrinsic Flame-Retardant and Thermally Stable Epoxy Endowed by a Highly Efficient, Multifunctional Curing Agent
Materials 2016, 9(12), 1008; doi:10.3390/ma9121008
Received: 2 November 2016 / Revised: 30 November 2016 / Accepted: 5 December 2016 / Published: 12 December 2016
Cited by 1 | PDF Full-text (7095 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
It is difficult to realize flame retardancy of epoxy without suffering much detriment in thermal stability. To solve the problem, a super-efficient phosphorus-nitrogen-containing reactive-type flame retardant, 10-(hydroxy(4-hydroxyphenyl)methyl)-5,10-dihydrophenophosphazinine-10-oxide (HB-DPPA) is synthesized and characterized. When it is used as a co-curing agent of 4,4′-methylenedianiline (DDM)
[...] Read more.
It is difficult to realize flame retardancy of epoxy without suffering much detriment in thermal stability. To solve the problem, a super-efficient phosphorus-nitrogen-containing reactive-type flame retardant, 10-(hydroxy(4-hydroxyphenyl)methyl)-5,10-dihydrophenophosphazinine-10-oxide (HB-DPPA) is synthesized and characterized. When it is used as a co-curing agent of 4,4′-methylenedianiline (DDM) for curing diglycidyl ether of bisphenol A (DGEBA), the cured epoxy achieves UL-94 V-0 rating with the limiting oxygen index of 29.3%. In this case, the phosphorus content in the system is exceptionally low (0.18 wt %). To the best of our knowledge, it currently has the highest efficiency among similar epoxy systems. Such excellent flame retardancy originates from the exclusive chemical structure of the phenophosphazine moiety, in which the phosphorus element is stabilized by the two adjacent aromatic rings. The action in the condensed phase is enhanced and followed by pressurization of the pyrolytic gases that induces the blowing-out effect during combustion. The cone calorimeter result reveals the formation of a unique intumescent char structure with five discernible layers. Owing to the super-efficient flame retardancy and the rigid molecular structure of HB-DPPA, the flame-retardant epoxy acquires high thermal stability and its initial decomposition temperature only decreases by 4.6 °C as compared with the unmodified one. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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Review

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Open AccessFeature PaperReview Recent Developments in Organophosphorus Flame Retardants Containing P-C Bond and Their Applications
Materials 2017, 10(7), 784; doi:10.3390/ma10070784
Received: 13 May 2017 / Revised: 17 June 2017 / Accepted: 4 July 2017 / Published: 11 July 2017
PDF Full-text (8826 KB) | HTML Full-text | XML Full-text
Abstract
Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010) in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review,
[...] Read more.
Organophosphorus compounds containing P-C bonds are increasingly developed as flame retardant additives due to their excellent thermal and hydrolytic stability and ease of synthesis. The latest development (since 2010) in organophosphorus flame retardants containing P-C bonds summarized in this review. In this review, we have broadly classified such phosphorus compounds based on the carbon unit linked to the phosphorus atom i.e., could be a part of either an aliphatic or an aromatic unit. We have only considered those published literature where a P-C bond was created as a part of synthetic strategy to make either an intermediate or a final organophosphorus compound with an aim to use it as a flame retardant. General synthetic strategies to create P-C bonds are briefly discussed. Most popular synthetic strategies used for developing P-C containing phosphorus based flame retardants include Michael addition, Michaelis–Arbuzov, Friedels–Crafts and Grignard reactions. In general, most flame retardant derivatives discussed in this review have been prepared via a one- to two-step synthetic strategy with relatively high yields greater than 80%. Specific examples of P-C containing flame retardants synthesized via suitable synthetic strategy and their applications on various polymer systems are described in detail. Aliphatic phosphorus compounds being liquids or low melting solids are generally applied in polymers via coatings (cellulose) or are incorporated in the bulk of the polymers (epoxy, polyurethanes) during their polymerization as reactive or non-reactive additives. Substituents on the P atoms and the chemistry of the polymer matrix greatly influence the flame retardant behavior of these compounds (condensed phase vs. the gas phase). Recently, aromatic DOPO based phosphinate flame retardants have been developed with relatively higher thermal stabilities (>250 °C). Such compounds have potential as flame retardants for high temperature processable polymers such as polyesters and polyamides. A vast variety of P-C bond containing efficient flame retardants are being developed; however, further work in terms of their economical synthetic methods, detailed impact on mechanical properties and processability, long term durability and their toxicity and environmental impact is much needed for their potential commercial exploitations. Full article
(This article belongs to the Special Issue Flame Retardant Polymeric Materials)
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