Bio-Based Polyamide 1010 with a Halogen-Free Flame Retardant Based on Melamine–Gallic Acid Complex

This work aims at developing polyamide 1010 (PA1010) composites with improved fire behavior using a halogen-free flame-retardant system based on melamine (Me) and gallic acid (GA) complexes (MA). The MA complexes were formed by hydrogen bonding, starting from 1:2, 1:1, 2:1 Me:GA molar ratios. PA1010 composites were obtained by melt mixing, followed by compression molding. MA provided a plasticizing effect on the PA1010 matrix by decreasing the glass transition temperature. The influence of MA on PA1010 chain packaging was highlighted in the X-ray diffraction patterns, mainly in the amorphous phase, but affected also the α and γ planes. This was reflected in the dynamic mechanical properties by the reduction of the storage modulus. H-bonds occurrence in MA complexes, improved the efficiency in the gaseous form during fire exposure, facilitating the gas formation and finally reflected in thermal stability, thermo-oxidative stability, LOI results, and vertical burning behavior results. PA1010 containing a higher amount of GA in the complex (MA12) displayed a limiting oxygen index (LOI) value of 33.6%, much higher when compared to neat PA1010 (25.8%). Vertical burning tests showed that all the composites can achieve the V-0 rating in contrast with neat PA1010 that has V-2 classification.

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Synthesis of a DOPO-triazine additive and its flame-retardant effect in rigid polyurethane foam

e-Polymers ◽

10.1515/epoly-2019-0024 ◽

2019 ◽

Vol 19 (1) ◽

pp. 235-243 ◽

Cited By ~ 2

Author(s):

Lin Liu ◽

Rui Lv

Keyword(s):

Flame Retardant ◽

Polyurethane Foam ◽

Cell Structure ◽

Rigid Polyurethane Foam ◽

Flame Resistance ◽

Limiting Oxygen Index ◽

Flame Retarded ◽

Flame Retardant Properties ◽

Mechanical Performances ◽

Halogen Free

AbstractA DOPO (9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide)-based halogen-free flame retardant (ODOPM-CYC) was synthesized and incorporated in rigid polyurethane foam (RPUF). The structure of ODOPM-CYC was characterized by Fourier transform infrared spectra (FTIR), 1H NMR and 31P NMR. The effects of ODOPM-CYC on the flame resistance, mechanical performances, thermal properties and cell structure of RPUF were also investigated. The results showed that the incorporation of ODOPM-CYC strikingly enhanced flame retardant properties of RPUF. The flame retarded RPUF acquired a limiting oxygen index (LOI) value of 26% and achieved UL-94 V-0 rating with the phosphorus content of 3 wt%. The smoke production rate (SPR) also showed an obvious decrease and total smoke release (TSR) was 39.8% lower than that of neat RPUF. Besides, the results demonstrated that the incorporation of ODOPM-CYC provided RPUF better thermal stability but did not show any obvious influence on its thermal conductivity.

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Influence of silicon dioxide addition and processing methods on structure, thermal stability and flame retardancy of EVA/NR blend nanocomposite foams

Progress in Rubber Plastics and Recycling Technology ◽

10.1177/1477760620953437 ◽

2020 ◽

pp. 147776062095343

Author(s):

Alif Walong ◽

Bencha Thongnuanchan ◽

Tadamoto Sakai ◽

Natinee Lopattananon

Keyword(s):

Thermal Stability ◽

Silicon Dioxide ◽

Flame Retardant ◽

Flame Retardancy ◽

Layered Silicate ◽

Melt Mixing ◽

Limiting Oxygen Index ◽

Char Layer ◽

Nanocomposite Foams ◽

Silicon Based

Rubber nanocomposite foams based on 60/40 ethylene vinyl acetate (EVA)/natural rubber (NR) were melt-mixed with flame retardant silicon dioxide (SiO2) (20 parts per hundred rubber, phr), and foamed by compression molding process. In this study, the effect of mixing phenomena of SiO2 through two different compounding techniques such as direct mixing (DM) and phase selective mixing (PSM) methods on structure, thermal stability, combustility and flame retardancy of EVA/NR blend nanocomposite foams were investigated. DM method is a melt mixing of EVA, NR, layered silicate and SiO2, followed by foaming. PSM is a new method based on pre-mixing EVA with SiO2, then melt mixing of EVA/SiO2 masterbatch with NR and layered silicate, and finally foaming. Based on TEM technique, it was found that the SiO2 was exclusively located in dispersed NR phase for the sample prepared by DM method, and the SiO2 was preferably dispersed in continuous EVA matrix when PSM method was employed. However, the different mixing methods did not significantly alter their cellular structures. The thermal stability and char residue content of foamed samples with SiO2 increased obviously when compared with those of corresponding foams without SiO2. The results based on limiting oxygen index (LOI) test and oxygen bomb calorimetry indicated that the foams combined with SiO2 had better combustion resistance and flame retardancy due to barrier effect of thermally stable silicon-based char layer. Further, the SiO2 filled foamed system obtained from the PSM method showed a higher degree of improvement in thermal stability, combustion resistance and flame retardancy than that of DM method because the homogeneous dispersion of SiO2 in EVA matrix rather than the selective dispersion in NR phase. This resulted in the continuity of flame retardant EVA/SiO2 phase in the 60/40 EVA/NR nanocomposite foams, which exerted more efficient fire barrier of the silicon-based char layer.

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Self-Extinguishing Resin Transfer Molding Composites Using Non-Fire-Retardant Epoxy Resin

Materials ◽

10.3390/ma11122554 ◽

2018 ◽

Vol 11 (12) ◽

pp. 2554 ◽

Cited By ~ 3

Author(s):

Zhi Geng ◽

Shuaishuai Yang ◽

Lianwang Zhang ◽

Zhenzhen Huang ◽

Qichao Pan ◽

...

Keyword(s):

Flame Retardant ◽

Flame Retardants ◽

Resin Transfer Molding ◽

Fire Retardant ◽

Functional Materials ◽

Building Blocks ◽

Fire Retardancy ◽

Limiting Oxygen Index ◽

Transfer Molding ◽

Halogen Free

Introducing fire-retardant additives or building blocks into resins is a widely adopted method used for improving the fire retardancy of epoxy composites. However, the increase in viscosity and the presence of insoluble additives accompanied by resin modification remain challenges for resin transfer molding (RTM) processing. We developed a robust approach for fabricating self-extinguishing RTM composites using unmodified and flammable resins. To avoid the effects on resin fluidity and processing, we loaded the flame retardant into tackifiers instead of resins. We found that the halogen-free flame retardant, a microencapsulated red phosphorus (MRP) additive, was enriched on fabric surfaces, which endowed the composites with excellent fire retardancy. The composites showed a 79.2% increase in the limiting oxygen index, a 29.2% reduction in heat release during combustion, and could self-extinguish within two seconds after ignition. Almost no effect on the mechanical properties was observed. This approach is simple, inexpensive, and basically applicable to all resins for fabricating RTM composites. This approach adapts insoluble flame retardants to RTM processing. We envision that this approach could be extended to load other functions (radar absorbing, conductivity, etc.) into RTM composites, broadening the application of RTM processing in the field of advanced functional materials.

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Study of a novel co-rotating non-twin screw extruder in processing flame retardant polymer materials

Journal of Polymer Engineering ◽

10.1515/polyeng-2016-0235 ◽

2017 ◽

Vol 37 (8) ◽

pp. 827-835

Author(s):

Song Zhao ◽

Baiping Xu ◽

Liang He ◽

Huiwen Yu ◽

Shouzai Tan

Keyword(s):

Flame Retardant ◽

Mechanical Performance ◽

Acrylonitrile Butadiene Styrene ◽

Operating Conditions ◽

Polymer Materials ◽

Twin Screw Extruder ◽

Screw Extruder ◽

Limiting Oxygen Index ◽

Twin Screw ◽

Halogen Free

Abstract A thorough study was carried out to investigate the priority of a novel co-rotating non-twin screw extruder (NTSE) over a traditional twin screw extruder (TSE) in the mixing process of halogen-free intumescent flame-retardant acrylonitrile-butadiene-styrene (ABS) composites. The homogeneity of the flame-retardant additives of the composites processed by NTSE and TSE under the same operating conditions was characterized by using mechanical performance properties, limiting oxygen index values, UL-94 tests, and thermogravimetric analysis. All the results suggested that NTSE could achieve better mixing of the flame-retardant additives in the polymer matrix than TSE, which was further clarified by the scanning electron microscope pictures.

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Preparation and Properties of Halogen-Free Flame Retardant Polyurethane Foams

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.418-420.540 ◽

2011 ◽

Vol 418-420 ◽

pp. 540-543 ◽

Cited By ~ 2

Author(s):

Ding Meng Chen ◽

Yi Ping Zhao ◽

Jia Jian Yan ◽

Li Chen ◽

Zhi Zhi Dong ◽

...

Keyword(s):

Flame Retardant ◽

Flame Retardants ◽

Oxygen Index ◽

Mechanical Analysis ◽

Polyurethane Foams ◽

Dimethyl Methylphosphonate ◽

Limiting Oxygen Index ◽

Layer Composite ◽

Halogen Free ◽

Thermal Stable

Polyurethane foams (PUFs) filled with several halogen-free flame retardants and composite halogen-free flame retardants were prepared. The flame retardant, thermal stable and mechanical properties of the PUFs were investigated. The results of limiting oxygen index (LOI) and thermogravimetric analysis (TGA) revealed that PUFs filled with dimethyl methylphosphonate (DMMP) had better flame retardancy compared with other flame retardants and DMMP degraded at a low temperature to form several phosphorated acids which accelerated the formation of char layer. Composite flame retardant of DMMP and melamine (MA) had a synergistic effect between phosphorus and nitrogen. The combination of DMMP and MA slightly altered the density of the PUFs. Results from the mechanical analysis revealed that with the increase in concentration of MA in the composite flame retardant of DMMP and MA, the tensile strength of PUFs reduced firstly and then increased up to a constant.

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Fire behavior of halogen-free flame retardant electrical cables with the cone calorimeter

Journal of Hazardous Materials ◽

10.1016/j.jhazmat.2017.08.027 ◽

2018 ◽

Vol 342 ◽

pp. 306-316 ◽

Cited By ~ 31

Author(s):

Romain Meinier ◽

Rodolphe Sonnier ◽

Pascal Zavaleta ◽

Sylvain Suard ◽

Laurent Ferry

Keyword(s):

Flame Retardant ◽

Cone Calorimeter ◽

Fire Behavior ◽

Halogen Free ◽

Electrical Cables

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Synthesis and characterisation of the halogen-free flame retardant and mechanical performance of the retardant epoxies resin

Pigment & Resin Technology ◽

10.1108/prt-02-2016-0021 ◽

2017 ◽

Vol 46 (3) ◽

pp. 172-180 ◽

Cited By ~ 4

Author(s):

Bing Liang ◽

Jiao Lv ◽

Gang Wang ◽

Tsubaki Noritatsu

Keyword(s):

Flame Retardant ◽

Mechanical Performance ◽

Cyanuric Chloride ◽

Proton Nuclear Magnetic Resonance ◽

Flame Resistance ◽

Limiting Oxygen Index ◽

Content Type ◽

Ul 94 ◽

Halogen Free ◽

The Impact

Purpose The purpose of this paper is to prepare a novel halogen-free intumescent flame retardant (IFR) BHPPODC (benzene hydroquinone phosphorous oxy dichloride cyanuric chloride) for application to epoxy resin (EP) and study their mechanical and flame-retardant performance. Design/methodology/approach The IFR was synthesised by phenylphosphonic dichloride, hydroquinone and cyanuric chloride via solvent reaction, and the structure was fully characterised by proton nuclear magnetic resonance (1H-NMR), mass spectrometry (MS) and Fourier transform infrared (FT-IR) spectroscopy. The thermal stability, mechanical and flame properties and morphology of the char layer of the flame-retardant EP was investigated by using thermogravimetric analysis (TGA), tensile and Charpy impact tests, limiting oxygen index (LOI) and vertical burning test (UL-94) and scanning electron microscopy (SEM). Findings Results of the LOI indicated that the halogen-free flame retardant as an additive exhibits very good flame-retardant effects. The results showed that the addition of IFR improved the flame resistance properties of epoxies resin composites, and the residual char ratio at 800°C significantly increased. Research limitations/implications The IFR can be prepared successfully and can improve the flame-retardant performance. Practical implications This contribution can provide a high flame retardant performance and has minimal impact on the mechanical performance of the BHPPODC/EP composition. Originality/value This study showed that flame-retardant BHPPODC has an effective flame effect under optimal conditions. When the 12 Wt.% IFR was added to the EP, the LOI was 29.1 and the UL-94 rank can reach V-0 rank, the tensile strength was 83.86 MPa and the impact strength was 8.82 kJ/m2.

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The Effects of Halogen-Free Flame Retardant Additives in Epoxidized Natural Rubber (ENR)

Advanced Materials Research ◽

10.4028/www.scientific.net/amr.1107.131 ◽

2015 ◽

Vol 1107 ◽

pp. 131-136

Author(s):

A.I.H.Dayang Habibah ◽

Abd Rahim Ruhida

Keyword(s):

Natural Rubber ◽

Flame Retardant ◽

Flame Retardants ◽

Epoxidized Natural Rubber ◽

Standard Type ◽

Limiting Oxygen Index ◽

The Usa ◽

The Difference ◽

Flame Retardant Properties ◽

Halogen Free

Legislation on fire safety requirements especially in the USA and UK has been the driving force behind the use of halogen-free flame retardants (FR) in recent years. The present study describes the effect of inorganic fillers, namely aluminium hydroxides (ATH) on epoxidized natural rubber (ENR) in order to increase its flame retardant capability. Two different types of ATH, a standard type Apyral 60 CD (ATH 60) and a submicron sized Apyral 200 SM (ATH 200) were used. The flame-retardant ENR composite was characterized by limiting oxygen index (LOI), UL-94V, and thermogravimetric analysis (TGA) to study the combustion behavior and thermal stability. The finer particles size (ATH 200) as expected produced better flame retardant properties (measured by LOI) compared to ATH 60; however, the difference between the values is marginal. It was also observed that a combination of 100 pphr ATH 200 and 60 pphr ATH 60 gave the highest LOI value (29.4%) in ENR compounds. The compound was V0 rated in UL-94V burn test. Even at the higher loading, it was also found that the compound exhibited lower viscosity indicating its easier processability.

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Surface Modification of Carbon Microspheres with Guanidine Phosphate and Its Application as a Flame Retardant in PET

Polymers ◽

10.3390/polym12081689 ◽

2020 ◽

Vol 12 (8) ◽

pp. 1689

Author(s):

Shan Jiang ◽

Cheng Ji ◽

Dan Zha ◽

Yonghong Ding ◽

Dun Wu ◽

...

Keyword(s):

Surface Modification ◽

Flame Retardant ◽

Testing Machine ◽

Grain Size Analysis ◽

Size Analysis ◽

Gravimetric Analysis ◽

Carbon Microspheres ◽

Melt Mixing ◽

Limiting Oxygen Index ◽

Guanidine Phosphate

Composites based on polyethylene terephthalate (PET) and surface-modified carbon microspheres (CMSs) were prepared by melt mixing. The surface modification of CMSs was conducted with low-temperature plasma technology first, and a phosphorus-nitrogen flame retardant, guanidine phosphate (GDP), was then grafted onto CMSs. The modification of CMSs was done to improve both the filler dispersity in the PET matrix and the flame-retardant performance of composites. The obtained CMSs-GDP was characterized by FTIR spectra and a scanning electron microscope (SEM). The grafting ratio was characterized and calculated by thermal gravimetric analysis (TGA). The grain size analysis was used to describe the dispersity of CMSs. The mechanical properties of the PET/CMSs-GDP composite were measured using a universal testing machine. The PET/CMSs-GDP composite can achieve a limiting oxygen index (LOI) value of 32.4% and a vertical burning test (UL94) V-0 rating at 3% CMSs-GDP loading.

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Fast-curing halogen-free flame-retardant epoxy resins and their application in glass fiber-reinforced composites

Textile Research Journal ◽

10.1177/0040517518819845 ◽

2018 ◽

Vol 89 (18) ◽

pp. 3700-3707 ◽

Cited By ~ 2

Author(s):

Bo Yang ◽

Yanyun Mao ◽

Yihui Zhang ◽

Yi Wei ◽

Wanshuang Liu ◽

...

Keyword(s):

Glass Fiber ◽

Flame Retardant ◽

Epoxy Resins ◽

Fiber Reinforced Composites ◽

Reinforced Composites ◽

Fiber Reinforced ◽

Epoxy System ◽

Limiting Oxygen Index ◽

Glass Fiber Reinforced ◽

Halogen Free

A series of novel fast-curing halogen-free flame-retardant epoxy resins were formulated and used to prepare glass fiber-reinforced composites. Dynamic mechanical analysis showed that the optimized epoxy system could be completely cured in 0.5 h at 150℃ and had a glass transition temperature ( Tg) of above 130℃. The optimized epoxy system was also used as matrix resin to make glass fiber prepregs and composite panels. The flame-retardant properties of the glass fiber-reinforced composites were investigated, including the limiting oxygen index (LOI) and flaming, smoke and toxicity properties. The glass fiber-reinforced composite had good flame retardancy with a UL-94 V-1 rating and high LOI of ∼36%. More significantly, the composite based on the flame-retardant epoxy resin showed lower smoke density compared with those based on phenolic resins. Finally, the glass fiber prepregs were used to fabricate honeycomb sandwich composites. The peel strength of the epoxy-based composites was almost twice that of the composites based on phenolic resin.

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