Investigations of thermal degradation behavior and fire performance of halogen‐free flame retardant poly(1,4‐butylene terephthalate) composites

This work aims to develop halogen‐free poly(1,4‐butylene terephthalate) (PBT) composites with enhanced flame retardancy using ecofriendly flame retardants, aluminum hypophosphite (AHP) and melamine derivatives (melamine polyphosphate and melamine cyanurate). Microscale combustion calorimetry and thermal gravimetric analysis/infrared spectrometry (TG‐IR) technique were used to investigate the potential fire hazards of these PBT composites. For the PBT composites with the incorporation of AHP and melamine derivatives, the heat release capacity (HRC) which is an indicator of a material fire hazard was significantly reduced, and the intensities of a variety of combustible or toxic gases detected by TG‐IR technique were remarkably decreased. Moreover, a loading of 20 wt % flame retardant mixture fulfilled the PBT composites high limited oxygen index (LOI) and V‐0 classification in UL 94 testing. An intumescent flame retarded mechanism was speculated in this work, because numerous bubble‐like char residues were found on the surface of the samples containing flame retardant mixture after LOI testing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Correlations between pyrolysis combustion flow calorimetry and conventional flammability tests with halogen‐free flame retardant polyolefin compounds

Seven halogen‐free flame retardant (FR) compounds were evaluated using pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry. Performance of wires coated with the compounds was evaluated using industry standard flame tests. The results suggest that time to peak heat release rate (PHRR) and total heat released (THR) in cone calorimetry (and THR and temperature at PHRR in PCFC) be given more attention in FR compound evaluation. Results were analyzed using flame spread theory. As predicted, the lateral flame spread velocity was independent of PHRR and heat release capacity. However, no angular dependence of flame spread velocity was observed. Thus, the thermal theory of ignition and flame spread, which assumes that ignition at the flame front occurs at a particular flame and ignition temperature, provides little insight into the performance of the compounds. However, results are consistent with a heat release rate greater than about 66kW/m² during flame propagation for sustained ignition of insulated wires containing mineral fillers, in agreement with a critical heat release rate criterion for burning. Mineral fillers can reduce heat release rate below the threshold value by lowering the flaming combustion efficiency and fuel content. A rapid screening procedure using PCFC is suggested by logistic regression of the binary (burn/no‐burn) results. Copyright © 2008 John Wiley & Sons, Ltd.     

The effectiveness of magnesium carbonate‐based flame retardants for poly(ethylene‐co‐vinyl acetate) and poly(ethylene‐co‐ethyl acrylate)

In this report we outline recent work on the evaluation of magnesium carbonate‐based flame retardants for polymers commonly used in halogen‐free flame retardant wire and cable applications: poly(ethylene‐co‐vinyl acetate) (EVA) and poly(ethylene‐co‐ethyl acrylate) (EEA). Natural magnesium carbonate (magnesite), synthetic magnesium carbonate (hydromagnesite), and hydromagnesite/huntite blends were combined with EVA or EEA and tested for flame retardancy effectiveness with the cone calorimeter. The flammability results showed that the effectiveness of these carbonates was polymer dependent, suggesting that polymer degradation chemistry played a role in the flammability reduction mechanism. Hydromagnesites were, in general, more effective in reducing flammability, being comparable in performance to magnesium hydroxide. Finally, we report some polymer–clay (organically treated montmorillonite and magadiite) + magnesium carbonate flame retardant results which showed that the nanocomposite yielded mixed results. Specifically, the polymer–clay nanocomposite samples did not always yield the greatest reductions in peak heat release rate. Copyright © 2007 John Wiley & Sons, Ltd.     

Combustion characteristics of halogen‐free flame‐retarded polyethylene containing magnesium hydroxide and some synergists

Halogen‐free flame‐retarded polyethylene materials have been prepared by using magnesium hydroxide (MH) as a flame retardant combined with red phosphorous (RP) and expandable graphite (EG) as synergists. The effects of these additives on the combustion behavior of the filled linear low density polyethylene (LLDPE), such as a limiting oxygen index (LOI), the rate of heat release (RHR), the specific extinction area (SEA), etc., have been studied by the LOI determination and the cone calorimeter test. The results show that RP and EG are good synergists for improving the flame retardancy of LLDPE/MH formulations. In addition, a suitable amount of ethylene and vinyl acetate copolymer (EVA) added in the formulations can increase the LOI values while promoting the char formation and showing almost no effect on the RHR and SEA values. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 206–214, 2001     

Cone calorimetric and thermogravimetric analysis evaluation of halogen‐containing polymer nanocomposites

Halogen‐containing organically modified clay nanocomposites have been prepared and it was found that the presence of bromine enhances the fire retardancy of polystyrene and polypropylene nanocomposites, compared with the virgin polymers. The nanocomposites were evaluated by X‐ray diffraction (XRD), thermogravimetric analysis (TGA) and cone calorimetric measurements. The UL‐94 test gave a V‐0 rating for some samples while cone calorimetry gave a reduced PHRR. Both the amount and identity of the bromine‐containing compound and the mode of preparation, which controls the dispersion, have a significant effect on the results. Bromine‐containing materials, at very low loading, approximately 6% or less bromine, give excellent results when the clay loading was about 3%. Copyright © 2005 John Wiley & Sons, Ltd.     

Environmental issues related to end‐of‐life options of plastics containing brominated flame retardants

Bromine is used as the building block for some of the most effective flame retarding agents available to the plastics industry today. They are used to protect against the risk of accidental fires in a wide range of Electrical and Electronic Equipment (EEE). Brominated flame retardants (BFRs), as all flame retardants, act to decrease the risk of fire by increasing the fire resistance of the materials in which they are applied. There is a perception that BFRs affect adversely the end‐of‐life management of plastics through formation of Polybrominated Dibenzo Dioxins and Dibenzo Furans (PBDD/F). In fact, there exists a wide range of data and practical experience demonstrating that the end‐of‐life management of plastics containing BFRs is fully compliant with legislation setting the strictest limit values for PBDD/F and is fully compatible with an integrated waste management concept. Copyright © 2004 John Wiley & Sons, Ltd.     

Structure−property relationships of halogen‐free flame‐retarded poly(butylene terephthalate) and glass fiber reinforced PBT

Flame retardancy for thermoplastics is a challenging task where chemists and engineers work together to find solutions to improve the burning behavior without strongly influencing other key properties of the material. In this work, the halogen‐free additives aluminum diethylphosphinate (AlPi‐Et) and a mixture of aluminum phosphinate (AlPi) and resorcinol‐bis(di‐2,6‐xylyl phosphate) (AlPi‐H + RXP) are employed in neat and reinforced poly(butylene terephthalate) (PBT), and the morphology, mechanical performance, rheological behavior, and flammability of these materials are compared. Both additives show submicron dimensions but differ in terms of particle and agglomerate sizes und shapes. The overall mechanical performance of the PBT flame‐retarded with AlPi‐Et is lower than that with AlPi‐H‐RXP, due to the presence of larger agglomerates. Moreover, the flow behavior of the AlPi‐Et/PBT materials is dramatically changed as the larger rod‐like primary particles build a percolation threshold. In terms of flammability, both additives perform similar in the UL 94 test and under forced‐flaming combustion. Nevertheless, AlPi‐Et performs better than AlPi‐H + RXP in the LOI test. The concentration required to achieve acceptable flame retardancy ranges above 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Expandable graphite systems for halogen‐free flame‐retarding of polyolefins. I. Flammability characterization and synergistic effect

The use of some types of expandable graphite (EG) as an intumescent flame‐retardant additive in polyolefins was studied using the cone calorimeter test (CCT), thermogravimetric analysis (TGA), the limiting oxygen index (LOI), and the‐UL 94 test and through measurement of EG's mechanical and electrical properties. The present study has shown that some suitable EG systems combined with other organic and inorganic halogen‐free flame‐retardant (HFFR) additives apparently can improve the flame‐retardant capacity with good mechanical properties of polyolefin blends. For linear low‐density polyethylene and/or ethylene vinyl acetate/EG/HFFR blends the limiting oxygen index can reach a rating above 29, and the UL‐94 test can produce a value of V–0. The CCT and TGA data show that the EG and EG/HFFR additives not only promoted the formation of carbonaceous char but also greatly decreased the heat release rate and the effective heat of combustion and increased the residues after burning. The synergistic effect of EG with other HFFR additives, such as zinc borate, the phosphorus–nitrogen compound NP28, and microcapsulated red phosphorus is examined and discussed in detail in this article. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1181–1189, 2001     

Flame retardancy of poly(butylene terephthalate) blended with phosphorous compounds

The thermal degradation and flame retardancy of poly(butylene terephthalate) (PBT) were studied with a focus on the effect of phosphorous compounds. Thermogravimetric analysis, pyrolysis/gas chromatography/mass spectrometry (Py/GC/MS), and elemental analysis were used to analyze the flame retardancy, which were observed by an Underwriters Laboratory UL‐94 test and a cone calorimeter. The 50% degradation temperatures of PBT blends with phosphorous compounds were the same as that of neat PBT. Six scission products were assigned by Py/GC/MS. The burning times of the UL test of several PBT blends were much shorter than that of neat PBT. The relation between flame retardancy and thermal degradation was analyzed with respect to the results of the scission products and the char in burned polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2326–2333, 2004     

Flame retardant performance of various UL94 classified materials exposed to external ignition sources

The flammability of eight halogen‐free styrene resins and one halogen‐containing styrene resin was characterized by UL 94 VB, LOI and cone calorimeter tests. Their burning behaviour was also measured when exposed to three external ignition sources (methenamine tablet, candle, paper ball). Five resins were used for 19″ monitor housings and the others for 25″ TV. The LOI values of UL 94 V‐2, V‐1 and V‐0 rated resins were higher than that of HB. The heat release rate decreased as the UL 94 ratings increased from HB to V‐0. When these resins were exposed to three external ignition sources, UL 94 V‐1 and V‐0 rated resins showed a self‐extinguishing property after removal of the fire and did not cause fire growth in either 19″ monitor or the 25″ TV housings in all cases. However, UL 94 V‐2 and HB rated resins were easily ignited and spread fire by dripping burning trickles. The burning rate of V‐2 resin was slower than that of HB. Copyright © 2004 John Wiley & Sons, Ltd.     

Synergistic effects of exfoliated LDH with some halogen‐free flame retardants in LDPE/EVA/HFMH/LDH nanocomposites

The synergistic effects of exfoliated layered double hydroxides (LDH) with some halogen‐free flame retardant (HFFR) additives, such as hyperfine magnesium hydroxide (HFMH), microencapsulated red phosphorus (MRP), and expandable graphite (EG), in the low‐density polyethylene/ethylene vinyl acetate copolymer/LDH (LDPE/EVA/LDH) nanocomposites have been studied by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermal analysis (TGA and DTG), mechanical properties, limiting oxygen index (LOI), and UL‐94 tests. The XRD results show that EVA as an excellent compatilizer can promote the exfoliation of LDH and homogeneous dispersion of HFMH in the LDPE/EVA/HFMH/LDH nanocomposites prepared by melt‐intercalation method. The TEM images demonstrate that the exfoliated LDH layers can act as synergistic compatilizer and dispersant to make the HFMH particles dispersed homogeneously in the LDPE matrix. The results from the mechanical, LOI, and UL‐94 tests show that the exfoliated LDH layers can also act as the nano‐enhanced and flame retardant synergistic agents and thus increase the tensile strength, LOI values, and UL‐94 rating of the nanocomposites. The morphological structures of charred residues observed by SEM give the positive evidence that the compact charred layers formed from the LDPE/EVA/HFMH/LDH nanocomposites with the exfoliated LDH layers play an important role in the enhancement of flame retardant and mechanical properties. The TGA and DTG data show that the exfoliated LDH layers as excellent flame retardant synergist of MRP or EG can apparently increase the thermal degradation temperature and the charred residues after burning. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of gamma radiation on properties of halogen‐free flame retardant EPDM‐PVMQ rubber blends

In this study, the effects of gamma radiation on properties of ethylene–propylene–diene monomer (EPDM) and its blends with phenyl vinyl methyl silicon rubber (PVMQ) were studied. The samples were irradiated with the dose rate of 171.7 Gy/min, and the total dose was up to 500 kGy. Mechanical properties, electrical insulation, limiting oxygen index (LOI), crosslink density, and ATR‐FTIR spectroscopy of the rubber were carried out to characterize the properties via irradiation. The results indicated that PVMQ acted as an irradiation degradation retarder for EPDM. After a postvulcanized period corresponding to 50 kGy dose, the elongation at break and electrical insulation decreased with LOI unaffected, while the crosslink density and tensile strength presented a complicated change with the increasing of radiation dose. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Low‐temperature synthesis of Mg(OH)2 nanoparticles from MgO as halogen‐free flame retardant for polypropylene

Mg(OH)₂ (MH) nanoparticles were synthesized by hydration of the light‐burned MgO at low temperature (70°C). Effects of additives, such as magnesium nitrate and magnesium acetate, on the size, morphology and agglomeration of MH particles were investigated. MH nanoparticles have platelet‐like structure and approximately 20–40 nm in thicknesses. The supersaturation degree plays an important role in magnesia hydration and is defined. When magnesium acetate was used as the additive, the hydroxyl ion can be homogeneously introduced into the solution. The size and morphology of MH nanoparticles are more homogeneous. Modified by titanate coupling agent, MH nanoparticles were used as the flame retardant for polypropylene (PP). The combustibility, mechanical properties and thermal behaviors of the PP/MH composites were characterized. The mechanical properties of PP/MH composites are not seriously deteriorated with increasing MH content. When the amount of MH fraction reached 65, the limiting oxygen index (LOI) value and UL 94 testing result of MH65 are 33.8 and V‐0 grading, respectively. The onset temperature (T_10%) and the maximum thermal decomposition temperature (T_max) of MH65 separately increased by approximately 100°C and 77°C than those of neat PP. Copyright © 2012 John Wiley & Sons, Ltd.     

Nonhalogen flame retarded poly(butylene terephthalate) composite using aluminum phosphinate and phosphorus‐containing deoxybenzoin polymer

Synergistic charring effect was observed between aluminum diethlyphosphinate (AlPi) and 4,4‐bishydroxydeoxybenzoin‐polyphosphonate (BHDB‐PPN) in the poly(butylene terephthalate) composite. By combining them together, robust UL 94 V0 rating was achieved at 0.8 mm thickness for poly(butylene terephthalate)/AlPi/BHDB‐PPN composite which exhibited better mechanical properties than the samples without BHDB‐PPN. The thermal degradation behavior of BHDB‐PPN was investigated by analyzing its evolution and residues under different temperatures. It was found that the radical termination reaction of formed benzyl group may play a critical role in the high charring capacity of BHDB‐PPN. Part of the volatile diethlyphosphinate fragments reacted with the degradation intermediates from BHDB‐PPN to form big chain structure for further carbonization was a possible reason for the synergistic charring effect between AlPi and BHDB‐PPN. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45537.     

A macromolecular halogen‐free flame retardant and its effect on the properties of thermoplastic polyesters

A halogen‐free flame retardant with a macromolecular structure is presented. Its synthesis proceeds via polymerization of phosphorus‐containing acrylate monomers. The flame retardant was incorporated into poly(ethylene terephthalate) by extrusion. Samples with different concentrations (0.5, 2.5, and 5.0 wt%) as well as a 25 wt% masterbatch were prepared. All samples were transparent and colorless without any visible irregularities. Thermal investigations reveal an unchanged glass transition temperature. Tensile tests show the typical mechanical behavior of poly(ethylene terephthalate), but with an elevated Young's modulus. The burning behavior was investigated by several small‐flame tests in vertical and horizontal orientation, as well as by cone calorimetry. It is shown that samples with 2.5 wt% flame retardant pass the vertical UL94 test (V‐2, 20‐mm flame). The sample cannot be ignited in the horizontal fire test according to FMVSS 302. The oxygen index was measured to 28 vol%. Cone calorimetric measurements show that the effective heat of combustion as well as the total heat evolved is reduced.     

Preparation and characterization of microcapsulated red phosphorus and its flame‐retardant mechanism in halogen‐free flame retardant polyolefins

Microcapsulated red phosphorus (MRP), with a melamine–formaldehyde resin coating layer, was prepared by two‐step coating processes. The physical and chemical properties of MRP were characterized by Fourier‐transform infrared spectroscopy (FTIR), X‐ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) and other measurements. The flame retardant action and mechanism of MRP in the halogen‐free flame retardant (HFFR) polyolefins (PO) blends have been studied using cone calorimeter, limiting oxygen index (LOI), thermogravimetric analysis (TGA) and dynamic FTIR spectroscopy. The results show that the MRP, which is coated with melamine–formaldehyde resin, has a higher ignition point, a considerably lower amount of phosphine evolution and of water absorption compared with red phosphorus (RP) itself. The data observed by cone calorimeter, LOI and TGA measurements from the PO/HFFR blends demonstrated that the MRP can decrease the heat release rate and effective heat of combustion, and increase the thermostability and LOI values of PO materials. The dynamic FTIR results revealed the flame‐retardant mechanism that RP can promote the formation of charred layers with the P–O and P–C complexes in the condensed phase during burning of polymer materials. Copyright © 2003 Society of Chemical Industry     

Flammability characteristics and performance of halogen‐free flame‐retarded polyoxymethylene based on phosphorus–nitrogen synergistic effects

The flammability characteristics and thermal stability of a novel halogen‐free flame‐retardant compounding system based on polyoxymethylene (POM) were studied, and a very effective flame retarding formulation for POM was developed from a combination of ammonium polyphosphate (APP), melamine cyanurate (MC), novolak, and dipentaerythritol. The decomposition behavior of POM compounds was evaluated by thermogravimetric analysis. The compound shows optimal flame retardancy with a limiting oxygen index of 52.8 and flammability rating of UL94 V‐0, when 27 wt % APP, 9 wt % MC, 4 wt % novolak, and 4 wt % dipentaerythritol are simultaneously incorporated into POM. The presence of novolak and dipentaerythritol as char‐forming agents results in a dense and compact multicellular char residue for the test bar after combustion, while Fourier transform infrared spectra confirm a characteristic phosphorous‐ and carbon‐rich char resulting from the APP/MC formulation. The pyrolysis–gas chromatography/mass spectrometry analysis indicates that highly flammable formaldehyde gas, the main pyrolysis product of POM, is annihilated by amide derivatives produced by the pyrolysis of MC, imparting better flame retardancy. The comprehensive flame‐retardant mechanisms based on phosphorus–nitrogen synergism promote the high flame retardancy of POM to reach the nonflammability of V‐0 rating. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Study of a novel halogen‐free flame retardant system through TGA and structure analysis of polymers

Butadiene‐rubber toughened styrene polymers, such as acrylonitrile‐butadiene‐styrene (ABS) copolymer and high impact polystyrene (HIPS), are noncharring polymers. They are generally blended with polycarbonate (PC) or polyphenyleneether (PPE), which are char forming polymers, to improve char forming ability for styrenic blends containing conventional phosphate flame retardants. To achieve cost effective flame retardant system, PET was selected as a potential char‐source for ABS blends through the thermogravimetric analysis (TGA) and chemical structure analysis of various polymers. PET may contribute to the enhancement of flame retardancy of ABS/PET blends, especially in the presence of small amounts of phenol novolac (PN). The effective flame retardancy of this system is believed to be accomplished through the enhancement of interchain reactions by PN. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Recent developments in P(O/S)–N containing flame retardants

Synthesis of organophosphorus compounds containing nitrogen as heteroatom and its application as a flame retardant (FR) have attracted much attention in the academic and industrial communities over the past decade. Such compounds are relatively easy to synthesize and offer advantages such as high thermal stability, which is useful for high temperature processing, improved char stability, density, and yield during the thermal decomposition of polymer, and release phosphorus species active in the flame inhibition process. Though a variety of phosphorus–nitrogen (P–N) compounds can be found in the literature, this review mostly summarizes the recent (since 2013) development in phosphorus (O)-nitrogen containing flame retardants which have been published in peer-reviewed journals. General strategies of synthesizing P(O)–N compounds as FRs from various phosphorus-based starting materials are highlighted in this review. Some of the most common classes of researched P(O)–N containing compounds as FRs include the phosphinamides, phosphonamides, phosphoramides, phosphoramidates, phosphorodiamidates, phosphonamidates and their thio counterparts which are usually obtained via a one- or two-step synthetic strategy. Incorporation of these compounds as FRs in various polymer systems such as polyurethane, epoxy resins, polyamides, cellulose, polylactide, poly(butylene terephthalate), polycarbonates, and acrylonitrile–butadiene–styrene are discussed in detail in this review. Special emphasis on the various fire and thermal performances of the new materials are also summarized. The mechanical performance of new materials and the influence of these additives on polymer processing are also briefly discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47910.     

Synthesis of cerium phenylphosphonate and its synergistic flame retardant effect with decabromodiphenyl oxide in glass‐fiber reinforced poly(ethylene terephthalate)

A lamellar cerium phenylphosphonate (CeHPP) was synthetized through reflux method and it was combined with decabromodiphenyl oxide (DBDPO) to prepare flame retarded poly(ethylene terephthalate) (PET) nanocomposites. Scanning electron microscopy (SEM) and X‐ray diffraction (XRD) showed that CeHPP was a one‐dimensional nanocrystal with the interlamellar distance of 1.57 nm. Thermogravimetric analysis (TGA) indicated that CeHPP had the excellent thermal stability and abundant char residue. Transmission electron micrographs (TEM) revealed that CeHPP dispersed homogenously in both PET and DBDPO phases. CeHPP could form a continuous and compact char layer in PET nanocomposites and had a synergistic effect with DBDPO. The collaboration of 2 wt% CeHPP and 6 wt% DBDPO dramatically improved UL 94 rating (from V‐2 to V‐0) and limiting oxygen index (LOI) value (from 22.9% to 29.1%) for PET. What is more, the mechanical properties were evaluated by tensile tests. POLYM. COMPOS., 35:539–547, 2014. © 2013 Society of Plastics Engineers