Mechanical performance and flame retardancy of polypropylene composites containing zeolite and multiwalled carbon nanotubes

Intumescent‐flame‐retarded polypropylene (PP‐IFR) composites were prepared by the incorporation of methyl hydrogen siloxane treated ammonium polyphosphate and dipentaerythritol in a twin‐screw extruder. The effects of zeolite (Z), multiwalled carbon nanotubes (CNTs), and maleic anhydride grafted polypropylene on the flame retardancy, mechanical properties, and thermal stability of PP‐IFR were investigated. The addition of Z and CNT promoted the flame retardancy of PP‐IFR, and the highest limited oxygen index was 35.6%, obtained on PP‐M‐IFR‐2–Z, for which the heat‐release rate, total heat release, and smoke production rate based on cone calorimetry analyses decreased by 45.0, 51.0, and 66.3%, respectively, in comparison with those values of the PP‐IFR composites. Additionally, scanning electron microscopy analyses showed that there was a good interface interaction between the polypropylene matrix and additives. The flexural, tensile, and impact strengths of the PP‐IFR composites were improved significantly with the incorporation of CNT. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42875.     

Thermal stability,flame retardance,and mechanical properties of polyamide 66 modified by a nitrogen–phosphorous reacting flame retardant

Flame‐retardant polyamide 66 (PA66) was prepared by the polymerization between PA66 prepolymer and N‐benzoic acid (ethyl‐N‐benzoic acid formamide) phosphamide (NENP). Compared with the pure PA66, the flame‐retardant PA66 exhibited better thermal stability, as indicated by thermogravimetric analysis results. The limiting oxygen index was 28% and the UL‐94 test results of the flame‐retardant PA66 indicated a V‐0 rating when the content of the NENP prepolymer was 5 wt %. The flammability and flame‐retardant mechanism of PA66 were also studied with cone calorimetry and scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, respectively. The mechanical properties results show that the flame‐retardant PA66 resin had favorable mechanical properties. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43538.     

Effect of graphite on the flame retardancy and thermal conductivity of P‐N flame retarding PA6

In this article, a novel flame‐retardant polyamide 6 (PA6) was prepared by introducing a halogen‐free flame‐retardant (OP1314). Graphite was added as a flame‐retardant synergistic agent, and the flame retardancy was enhanced, especially the melt‐dripping was forbidden and for the formula of PA6/12 wt % OP1314/5 wt % graphite, UL94 V‐0 grade was reached. Meanwhile, the graphite is also an excellent thermal conductive filler and with the addition of 5 wt % graphite in the flame‐retardant PA6 mixtures, the thermal conductivity (λ) rose to 1.2 W/mK which was nearly three times higher than the flame‐retardant PA6. Due to the good flame retardancy and improved thermal conductivity, the material could be suitable for applications in electronic and electrical devices. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46559.     

The effect of 3D structure design on fire behavior of polyethylene terephthalate glycol containing aluminum hypophosphite and melamine cyanurate

Effect of the shape of 3D printed samples on fire behavior of polyethylene terephthalate glycol (PET-G) and PET-G additivated with a mix of aluminum hypophosphite (AHP) and melamine cyanurate as flame retardant, was investigated. The additives improved fire performance (e.g., maximum average rate of heat emission, total oxygen consumption, heat release rate indices) irrespective of structural complexity, favoring carbonaceous char formation. However, at increasing structural complexity, they promoted higher release of smoke, compared to neat PET-G, because of a change in the prevalent retardation mechanism, which became dominated by the flame inhibition action of AHP. Consequently, the synergistic effect obtained combining the two additives, was hindered. Impact of product design on mechanisms of fire retardation helps in devising engineering solutions aimed at meeting required level of fire-safety performance, which should be tailored to the specific product.     

Flame retardancy and mechanical properties of polyamide 6 with melamine polyphosphate and ionic liquid surfactant‐treated montmorillonite

The mechanical properties and inflammability of polyamide 6 (PA6) nanocomposites incorporated with Montmorillonite organoclay (MMT) modified with thermal stable ionic liquid surfactants were investigated. The compatibility between ionic liquid‐treated MMT and PA6 matrix was improved and the intercalation morphology was achieved, which resulted in the increaseof tensile modulus. However, the addition of organo‐MMTs alone did not improve the inflammability of the PA6 nanocomposite, because of strong melt‐dripping behavior of PA6 matrix. Addition of auxiliary melamine polyphosphate (MPP) intumescent flame retardant to the nanocomposite prevented the melt dripping and enhanced inflammability performance. The enhanced inflammability of PA6/organoclay/MPP nanocomposites was attributed to the synergistic effect between imidazolium or phosphonium organo‐MMTs and intumescent flame retardant MPP. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40648.     

Improvement in mechanical and thermal properties of phenolic foam reinforced with multiwalled carbon nanotubes

Phenolic foams reinforced with pristine and functionalized multiwalled carbon nanotubes (MWCNTs) were fabricated to develop fire‐resistant materials with improved mechanical properties. The influences of the contents of carboxyl multi‐walled carbon nanotubes (MWCNTs‐COOH) and of MWCNTs types on the compressive properties of the composite foams were investigated. The microstructure and detailed failure behavior of MWCNTs/phenolic composite foams were studied using scanning electron microscopy (SEM) and in situ quasistatic compression inside SEM, respectively. In addition, thermal performances were evaluated by thermogravimetric analysis (TGA) and vertical burning method. It is found that as heterogeneous nucleation agents, MWCNTs increase cell density and decrease cell size of the produced foams, and that as reinforcements located in cell walls, MWCNTs impart high strength and stiffness to brittle foams. Moreover, MWCNTs reinforced foams have higher thermal stability than raw foams and exhibit similar excellent resistance to flame, confirming the effectiveness of MWCNTs as stabilizers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1479–1488, 2013     

Polyamide 6 Composites with Melamine Polyphosphate and Layered Silicates: Evaluation of Flame Retardancy and Physical Properties

The potential synergy of melamine polyphosphate and layered silicates for enhancing the flame retardancy and physical properties of polyamide 6 is investigated. Through melt blending, exfoliated nanocomposites were prepared, suffering, however, from polymer degradation. In the presence of the additives, the ability of polyamide 6 to crystallize was restrained and its thermal stability was deteriorated. Nevertheless, the stiffness of the polymer was increased, yet at the expense of ductility. Apart form stiffness, the additives exerted a positive effect on the fire resistance of polyamide 6; melamine polyphosphate and layered silicates cooperated during combustion to provoke the formation of a superficial protective barrier, yielding materials of inferior flammability.

     

Synergistic flame‐retardant effect of phosphaphenanthrene derivative and aluminum diethylphosphinate in glass fiber reinforced polyamide 66

The synergistic flame‐retardant (FR) effect of 1,1′‐bis(4‐hydroxyphenyl)‐metheylene‐bis(9,10‐dihydro‐9‐oxa‐10‐phosphaphenanthrene‐10‐oxide‐2‐hydroxypropan‐1‐yl) (DPOH) and aluminum diethylphosphinate (AlPi) composites on glass fiber reinforced polyamide 66 (PA) was investigated by limiting oxygen index (LOI) tests, vertical burning (UL94) tests, and cone calorimeter tests. DPOH/AlPi system with 1:1 mass ratio increased UL94 ratings, suppressed heat release rate and increased residue yields of PA composites, and DPOH/AlPi system also imposed high LOI values and lower total heat release values to PA composites. All these results verified excellent synergistic FR effect between DPOH and AlPi. The reason of DPOH/AlPi system with higher flame‐retardant efficiency was caused by the quenching effect as good as that of DPOH and also by the higher charring effect than that of AlPi. DPOH/AlPi system possesses good flame retardancy in gas phase and also the strengthened FR effect in condensed phase compared with DPOH and AlPi alone, which led to excellent synergistic FR effect between the two components DPOH and AlPi. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45126.     

Flame retardancy and thermal and mechanical performance of intercalated,layered double hydroxide composites of polyamide 11, aluminum phosphinate,and sulfamic acid

Sulfamic acid‐intercalated MgAl‐layered double hydroxide (SA‐LDH) was prepared and added with aluminum phosphinate (AlPi) into polyamide 11 (PA11). The results showed that AlPi/SA‐LDH made a positive contribution to both flame retardancy and thermostability, and the effect was demonstrated with the limiting oxygen index (LOI), vertical burning tests (UL‐94), cone calorimetry (CONE), and thermogravimetric analysis (TGA). The char morphologies were observed by SEM, and its chemical composition was investigated by Fourier transform infrared spectroscopy (FTIR). The decomposition mechanism was examined by TGA‐FTIR. The results showed that the LOI of PA11 was only 23.0 and cannot pass any UL‐94 rating. The addition of 20% AlPi increased the LOI to 31.5 and passed the UL‐94 V‐1 rating, and AlPi/SA‐LDH 15%/5% increased the LOI to 32.4 and also passed the UL‐94 V‐1 rating. The CONE results revealed that 20% of either AlPi or AlPi/SA‐LDH brought about a 30% decrease in the peak heat release rate (pHRR). The contribution of SA‐LDH to flame behavior was especially reflected in the postponement of pHRR. SEM showed that the char morphologies became denser after SA‐LDH incorporation. The improvement in thermal stability of the AlPi/SA‐LDH combination was documented by TGA in both N₂ and air atmospheres. The mechanical performance deterioration caused by AlPi was partly improved by SA‐LDH. The storage modulus (E′) below the T_g of AlPi/SA‐LDH 15%/5% was about 300 MPa higher than with 20% AlPi. This was attributed to a compatibility improvement. The interaction forces among PA11, AlPi, and SA‐LDH were probed by X‐ray photoelectron spectrometry. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43370.     

Aging studies on flame retardant treated lignocellulosic fibers

The study deals with chemical and flame retardant (FR) treatment of flax fabric. Sheets of flax fabric were subjected to chemical treatments using NaOH and silane coupling agents. A phosphate‐based flame retardant (DAP) was also applied to improve the flammability of the fabric. The effects of the chemical treatments and FR treatments on flax fabric were investigated using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and vertical flame resistance test. Aging studies were carried out by exposing the samples in an environmental chamber at specified conditions for two weeks. The mechanical properties of the fabric, before and after environmental aging, were investigated. Flammability of flax fabric was improved after FR treatment. Thermal studies revealed a shift of decomposition temperature to lower temperatures and an increase in char residue after FR treatment. Despite treatment of the fabric with NaOH and silane, the tensile strength of FR‐treated flax fabric declined by more than 90% after aging for two weeks at 90 °C and 50% RH. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44175.     

Enhancement of flame retardancy and mechanical properties of polyamide 6 by incorporating melamine cyanurate combined with attapulgite

In this study, the nanocomposites are prepared which used polyamide 6 (PA6) composite as matrix, melamine cyanurate (MCA) as fire retardant and attapulgite (AT) as synergistic agent. The mathematical model between MCA content, AT content, and limited oxygen index (LOI) is established by multiple linear regression fitting. The polymer materials are characterized using Fourier transform infrared spectroscopy, X-ray diffraction, Thermogravimetric Analysis, and scanning electron microscopy. Through response surface methodology, the important variables (polymerization time, the content of MCA, and the content of AT) affecting the mechanical strength of composites are modeled. Results demonstrate that when the t is 0.6 h, the AT content is 6.2%, and the MCA content is 11.5%, the mechanical properties of the PA6/MCA/AT composite are up to 44.81 MPa, and the sample passes the UL-94 V-0 flammability rating, and the LOI reaches 27.9%. Therefore, polymers with highly effective flame retardancy and optimal mechanical properties are prepared. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 47298.     

Function of the aryl group in bis DOPO phosphonate on reducing fire hazards of polyamide 6 composites

The increased integration interaction of bis 9,10-dihydro-9-oxa- 10-phospaphenanthrene-10-oxide (DOPO) phosphonate (abbreviated as FR) including ethyl-(FR1), phenethyl-(FR2), naphthalene-(FR3) with the aryl group and hexa-phenoxy-cyclotriphosphazene (HPCP) on flame-retardant polyamide 6 (PA6) were investigated. The role of the aryl group in FR on flame-retarding PA6 was analyzed. Results showed that PA6 composites with greatly reduced fire hazards possessed a high-limiting oxygen index value of 34% and achieved a UL-94 V-0 rating and sharply decreased peak heat release rate by simultaneously adding FR and HPCP. Flame inhibition effect acted as the main mechanism for FR and HPCP in flame-retarding PA6. Gas phase action increased with the number of aryl groups. HPCP played a catalytic effect in the condensed phase. Particularly, the result of residue analysis after cone test implied that char surface with network structure was formed, and the structure became compact and continuous with the increase in the number of aryl groups. Furthermore, the aryl group played an important role in aiding the PA6 composites in the construction of a network protective char layer on the surface during combustion.     

Synthesis,thermal and mechanical behavior of a silicon/phosphorus containing epoxy resin

A liquid silicon/phosphorus containing flame retardant (DOPO–TVS) was synthesized with 9,10‐dihydro‐9‐oxa‐10‐phosphapheanthrene‐10‐oxid (DOPO) and triethoxyvinylsilane (TVS). Meanwhile, a modified epoxy resin (IPTS–EP) was prepared by grafting isocyanate propyl triethoxysilane (IPTS) to the side chain of bisphenol A epoxy resin (EP) through radical polymerization. Finally, the flame retardant (DOPO–TVS) was incorporated into the modified epoxy resin (IPTS–EP) through sol–gel reaction between the ethyoxyl of the two intermediates to obtain the silicon/phosphorus containing epoxy resin. The molecular structures of DOPO–TVS, IPTS–EP and the final modified epoxy resin were confirmed by FTIR spectra and ¹H‐NMR, ³¹P‐NMR. Thermogravimetric analysis (TGA), differential scanning calorimetry, and limiting oxygen index were conducted to explore the thermal properties and flame retardancy of the synthesized epoxy resin. The thermal behavior and flame retardancy were improved. After heating to 600°C in a tube furnace, the char residue of the modified resin containing 10 wt % DOPO–TVS displayed more stable feature compared to that of pure EP, which was observed both by visual inspection and scanning electron microscope (SEM). Moreover, the mechanical performance testing results exhibited the modified epoxy resins possessed elevated tensile properties and fracture toughness which is supported by SEM observation of the tensile fracture section. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42788.     

Property of intrinsic flame retardant epoxy resin cured by functional magnesium organic composite salt and diethylenetriamine

An efficient intrinsic flame retardants composite was prepared by curing epoxy resin with a functional magnesium organic composite salt (FMOCS, 0.685 ± 0.3 nm) and diethylenetriamine (DETA). Curing behavior, thermal and flame‐retardant properties of the cured epoxy resins were systematically investigated by infrared spectrum (FTIR), thermogravimetric analysis (TGA), vertical burning test (UL‐94) and limited oxygen index (LOI) measurement. It was found that flame retardancy and mechanical properties of the cured composite are significantly enhanced compared with DETA/EP. The LOI of the EP reached to 33%, which is much higher than the DETA/EP (19%) or its IFR composite (31%) in the optimal addition of ammonium polyphosphate (APP, 18.69 wt %), pentaerythritol (PER, 6.21 wt %) and FMOCS (3.50 wt %). Furthermore, the mechanical properties of the composite material measurement results to imply that it can enhance tensile strength (150%) and bending strength (88%) rather than DETA/EP, which were tested by impact testing machine and microcomputer control electron universal testing machines. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal aging properties of flame retardant silicone rubber based on melamine cyanurate

In this work, an efficient preparation method for flame retardant silicon rubbers (FRSR) was established with using melamine cyanurate (MCA) as flame retardants. In order to analyze the thermal aging mechanisms and flame retardancy of FRSR, cone calorimetric test (CCT), Fourier transform infrared (FTIR) spectra, scanning electronic microscopy (SEM), and energy dispersive X-ray spectra were performed. Results indicated that the aging time significantly decreases the tensile strength and the elongation at break. SEM images revealed that the porous surface of the aged FRSR provide diffusion path for heat and oxygen, which resulted in a continuously increase in Shore A hardness due to the increase of cross-linking density during the aging process. FTIR spectra further proved that the MCA is well-embedded into samples and cross-linking reaction between free radicals of silicone rubber (SR) and oxygen was occurring during the aging process. Besides, CCT results showed that all FRSR samples before and after thermal aging exhibit excellent flame retardancy with compact and stable char residue layers, effectively hindering the heat transfer and oxygen diffusion. It was expected that our findings could provide important information to fabricate SR with flame retardancy and outstanding long-term thermal-aging resistance.     

Effect of boron‐containing materials on the flammability and thermal degradation of polyamide 6 composites containing melamine

Three different boron‐containing substances—zinc borate (ZnB), borophosphate (BPO₄), and a boron‐ and silicon‐containing oligomer (BSi)—were used to improve the flame retardancy of melamine in a polyamide 6 (PA‐6) matrix. The combustion and thermal degradation characteristics of PA‐6 composites were investigated with the limiting oxygen index (LOI), the UL‐94 standard, thermogravimetric analysis (TGA)/Fourier transform infrared (FTIR) spectroscopy, and differential scanning calorimetry (DSC). A slight increase was seen in the LOI values of a sample containing BSi (1 wt %). BPO₄ at high loadings showed a V0 rating (indicating the best flame retardancy) and slightly lower LOI values in comparison with samples with only melamine. For ZnB and BSi, glassy film and char formation decreased the dripping rate and sublimation of melamine, and this led to low LOIs. According to the TGA–FTIR results, the addition of boron compounds did not change the decomposition product distribution of melamine and PA‐6. The addition of boron compounds affected the flame retardancy by physical means. The TGA data showed that boron compounds and melamine reduced the decomposition temperature of PA‐6. According to the DSC data, the inclusion of boron compounds increased the onset temperature of sublimation of melamine and also affected the flame retardancy negatively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Soluble polyarylates containing phosphorus in main chains with thermal stability

A series of polyarylates containing phosphorus (pho‐PARs) were synthesized from bisphenol A with different molar ratios of bis‐(4‐carboxyphenyl) phenyl phosphine oxide (BCPPO) to terephthalic acid (TPA). When the contents of BCPPO are in the range of 0.4–1.0, the pho‐PARs are readily soluble in a wide range of organic solvents and have the glass transition temperatures of 243.0–260.4°C. The initial degradation temperatures of these pho‐PARs are all above 450°C and their char yields at 800°C under nitrogen atmosphere are in the range of 28.7–33.0%, suggesting they have excellent thermal stability. The results of TG‐FTIR and FT‐IR show the introduction of BCPPO change the decomposition model of the pho‐PARs. The limiting oxygen indexes are at a range of 30.7–34.5%, which suggests that the pho‐PARs are a kind of excellent inherent flame retardant materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3521–3529, 2013     

A novel polyurethane prepolymer as toughening agent: Preparation,characterization, and its influence on mechanical and flame retardant properties of phenolic foam

A novel phosphorus‐ and silicon‐containing polyurethane prepolymer (PSPUP) was synthesized by the chemical reaction of phenyl dichlorophosphate with hydroxy‐terminated polydimethylsiloxane (HTPDMS) and subsequently with toluene‐2,4‐diisocyanate. The structure of PSPUP was confirmed by Fourier transform infrared spectroscopy and ¹H nuclear magnetic resonance. Afterward, a series of phenolic foams (PF) with different loadings of PSPUP toughening agent were prepared. The apparent density and scanning electron microscopy results showed that the addition of PSPUP can increase the apparent density of phenolic foam. The compressive, impact and friability test results showed that the incorporation of PSPUP into PF dramatically improved the compressive strength, impact strength, and reduced the pulverization ratio, indicating the excellent toughening effect of PSPUP. The limiting oxygen index of PSPUP modified phenolic foams remained a high value and the UL‐94 results showed all samples can pass V0 rating, indicating the modified foams still had good flame retardance. The thermal properties of the foams were investigated by thermogravimetric analysis under air atmosphere. Moreover, the thermal degradation behaviors of the PF and PSPUP/PF were investigated by real‐time Fourier transform infrared spectra. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Mechanical property improvement and fire hazard reduction of ammonium polyphosphate microencapsulated in rigid polyurethane foam

Ammonium polyphosphate (APP) is an effective phosphorus-containing flame retardant. But APP also has excellent hygroscopic capacity and decreases the mechanical property of composite. The aim of the study was to microencapsulate APP with polymethyl methacrylate (PMMA) to prepare microencapsulated ammonium polyphosphate (PMAPP) in order to eliminate the harmful effects caused by the mechanical property of composite. The microcapsules are characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and hydroscopicity test and observed by scanning electron microscopy (SEM). Fire hazard of rigid polyurethane foam (RPUF) is evaluated using a cone calorimeter and limited oxygen index test. The mechanical property of RPUF is studied by compressive strength test. The results show that APP has been microencapsulated by PMMA successfully and the shell does not decrease the beneficial effect of APP on fire hazard of RPUF. Furthermore, the shell also reduces the damage of APP on the mechanical property of composite. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48307.     

Reactive,intumescent, halogen‐free flame retardant for polypropylene

A reactive, intumescent, halogen‐free flame retardant, 2‐({9‐[(4,6‐diamino‐1,3,5‐triazin‐2‐yl)amino]‐3,9‐dioxido‐2,4,8,10‐tetraoxa‐3,9‐diphosphaspiro[5.5]undecan‐3‐yl}oxy)ethyl methacrylate (EADP), was synthesized through a simple three‐step reaction from phosphorus oxychloride, pentaerythritol, hydroxyethyl methacrylate, and melamine. EADP exhibited excellent thermal stability and char‐forming ability, as revealed by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The TGA results show that the temperature at 5% weight loss was 297.8°C and the char yield at 700°C was 51.75%. SEM observation revealed that the char showed a continuous and compact surface and a cellular inner structure with different sizes. Composite of polypropylene (PP) with a 25 wt % addition of EADP (PP/EADP25) passed the UL‐94 V‐0 rating and showed a limiting oxygen index value of 31.5. Compared with those of neat PP, the flexural strength and modulus values of PP/EADP25 were somewhat improved, the tensile strength was basically unchanged, and the notched Izod impact strength was slightly decreased. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40054.