Regulating the Localization of Intumescent Flame Retardant for Improving the Flame Retardancy of Ethylene-vinyl Acetate Copolymer Using Polyamide 6 as a Charring Agent

Polyamide 6 (PA6) was employed as a charring agent of intumescent flame retardant (IFR) to improve the flame retardancy of ethylene-vinyl acetate copolymer (EVA). Different processing procedures were used to regulate the localization of IFR in the EVA matrix. Localizations in which IFR was dispersed in the PA6phase or in the EVA phase were prepared. The effect of the localization of IFR on the flame retardancy of EVA was investigated. The limited oxygen index (LOI), vertical burning (UL 94) and cone calorimeter test (CCT)showed that the localization of IFR in the EVA matrix exhibited a remarkable influence on the flame retardancy.Compared with EVA/IFR, a weak improvement in the flame retardancy was observed in the EVA/PA6/IFR blend withthe localization of IFR in the PA6 phase. When IFR was regulated from the PA6 phase to the EVA matrix,a remarkable increase in the flame retardancy was exhibited. The LOI was increased from 27.8%to 32.7%, and the UL 94 vertical rating was increased from V-2 to V-0. Moreover, an approximately 41.36%decrease in the peak heat release rate was exhibited. A continuous and compact intumescent charring layer that formed in the blends with the localization of IFR in the EVA matrix should be responsible for its excellent flame retardancy.

Preparation of Polyurea Elastomer with Flame Retardant, Insulation and Thermal Conductivity Properties

By using 6,6-((sulfonylbis(4,1-phenylene)bis(azanediyl))bis(thiophen-2-ylm-ethylene))bis6H-di-benzo[c,e][1,2]oxaphosphinine 6-oxide(DOPO-N)as phosphorus-nitrogen flame retardant,the polyurea(PUA)with flame retardant properties(PUA/DOPO-N)was prepared.In addition,organically modified montmorillonite(OMMT)and magnesium hydroxide(MH)were used as co-effectors respectively,and the flame retardant PUA(PUA/DOPO-N/OMMT and PUA/DOPO-N/MH)were also prepared.Thermal properties,flame retardant properties,flame retardant mechanism and mechanical properties of PUA/DOPO-N,PUA/DOPO-N/OMMT and PUA/DOPO-N/MH were investigated by thermogravimetric(TG)analysis,limiting oxygen index(LOI),UL 94,cone calorimeter test,scanning electron microscopy(SEM),and tensile test.The results show that the LOI value of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are 27.1%,27.7%,and 28.3%,respectively,and UL 94 V-0 rating is attained.Compared with PUA,the peak heat release rate(pk-HRR),total heat release(THR)and average effective heat combustion(av-EHC)of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH decrease significantly.SEM results indicate that the residual chars of PUA/20%DOPO-N,PUA/18%DOPO-N/2%OMMT and PUA/15%DOPO-N/5%MH are completer and more compact.The complex of DOPO-N/OMMT and DOPO-N/MH have synergistic flame retardancy.The mechanical properties of PUA can be improved by the addition of DOPO-N,DOPO-N/OMMT and DOPO-N/MH,respectively.The insulation performance test shows that the volume resistivity of PUA/20%DOPO-N is 6.25×10^(16)Ω.cm.Furthermore,by using modified boron nitride(MBN)as heat dissipating material,the complex of PUA/MBN was prepared,and the thermal conductivity of PUA/MBN was investigated.The thermal conductivity of PUA/8%MBN complex coating at room temperature is 0.166 W/(M·K),which is a 163%improvement over pure PUA.

Synergistic effect of MXene on the flame retardancy and thermal degradation of intumescent flame retardant biodegradable poly(lactic acid)composites

The effect of Ti3C2 MXene nanosheets on the intumescent flame retardant(IFR)poly(lactic acid)(PLA)composites was investigated among a series of PLA/IFR/MXene,which were prepared by melt blending 0-2.0 wt%MXene,10.0 wt%-12.0 wt%IFR and PLA together.The results of limiting oxygen index(LOI)and vertical burning(UL-94)discover that the combination of 0.5 wt%MXene and 11.5 wt%IFR synergistically improves the fire safety of PLA to reach UL-94 V-0 rating with LOI value of 33.0%.The PLA/IFR/MXene composites perform an obvious reduction in peak of heat release rate(HRR)in cone calorimeter tests(CCTs).Furthermore,the carbon residues after CCTs were characterized by scanning electron microscope(SEM),laser Raman spectroscopy(LRS),X-ray diffraction(XRD)and X-ray photoelectron spectroscopy(XPS).It is demonstrated that both the titanium composition of the MXene structure and the characteristics of the two-dimensional material enhance the PLA/IFR/MXene composite materials’ability to produce a dense barrier layer to resist burnout during thermal degradation.

Synthesis of Organic-Inorganic Hybrid Aluminum Hypophosphite Microspheres Flame Retardant and Its Flame Retardant Research on Thermoplastic Polyurethane

Aluminum hypophosphite microspheres(AHP) were synthesized by hydrothermal method using NaH2PO2·H2O and AlCl3·6H2O as raw materials, and then the AHP microspheres were polymerized by surface polymerization of micro-nanospheres with cyclic cross-linked poly(cyclotriphosphazene-co-4,4'-sulfonyldiphenol)(PZS). A new organic-inorganic poly(phosphonitrile)-modified aluminum hypophosphite microspheres(PZS-AHP) were synthesized by encapsulation and applied to flame retardant thermoplastic polyurethane(TPU). The microstructure and chemical composition of the PZS-AHP microsphere were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy and X-ray spectroscopy. The thermal stability of PZS-AHP microsphere was explored with thermogravimetric analysis. Thermogravimetric data indicate that the PZS-AHP microspheres have excellent thermal stability. The thermal and flame-retarding properties of the TPU composites were evaluated by thermogravimetric(TG), limited oxygen index tests(LOI), and cone calorimeter test(CCT). The TPU composite achieved vertical burning(UL-94) V-0 grade and LOI value reached 29.2% when 10 wt% PZS-AHP was incorporated. Compared with those of pure TPU, the peak heat release rate(pHRR) and total heat release(THR) of TPU/10%PZS-AHP decreased by 82.2% and 42.5%, respectively. The results of CCT indicated that PZS-AHP microsphere could improve the flame retardancy of TPU composites.

Research Progress in Flame Retardant in Flame Retardant Coatings

Flame retardant coatings are functional materials that can serve as decorative and protec-tive substrates in the event of a fire.Flame retardant coatings generally consist of two parts:a base material and a flame retardant agent.A detailed introduction was given to the development of flame retardant coatings in recent years and the flame retardants used in flame retardant coatings.Flame retardants mainly include halogen flame retar-dants,phosphorus nitrogen flame retardants,expansion flame retardants,biomass flame retardants,and graphene flame retardants.The application of flame retardant coatings in the fields of epoxy resin,polyurethane,etc.was elaborated.In addition,the application of new biomass flame retardants and graphene flame retardants was introduced,and the future development of flame retardant coatings and flame retardants was described.

Comparative study on the flame retardancy of CO_(2) and N_(2) during coal adiabatic oxidation process

To test the effectiveness of N_(2) and CO_(2) in preventing coal from spontaneously combusting,researchers used an adiabatic oxidation apparatus to conduct an experiment with different temperature starting points.Non-adsorbed helium(He)was used as a reference gas,and coal and oxygen concentration temperature variations were analyzed after inerting.The results showed that He had the best cooling effect,N_(2) was second,and CO_(2) was the worst.At 70℃and 110℃,the impact of different gases on reducing oxygen concentration and the cooling effect was the same.However,at the starting temperature of 150℃,CO_(2) was less effective in lowering oxygen concentration at the later stage than He and N_(2).N_(2) and CO_(2) can prolong the flame retardation time of inert gas and reduce oxygen displacement with an initial temperature increase.When the starting temperature is the same,N_(2) injection cools coal samples and replaces oxygen more effectively than CO_(2) injection.The flame retardancy of inert gas is the combined result of the cooling effect of inert gas and the replacement of oxygen.These findings are essential for using inert flame retardant technology in the goaf.

An Effective Green Porous Structural Adhesive for Thermal Insulating,Flame-Retardant,and Smoke-Suppressant Expandable Polystyrene Foam

To develop an efficient way to overcome the contradiction among flame retardancy,smoke suppression,and thermal insulation in expanded polystyrene(EPS)foams,which are widely used insulation materials in buildings,a novel"green"porous bio-based flame-retard ant starch(FRS)coating was designed from starch modified with phytic acid(PA)that simultaneously acts as both a flame retardant and an adhesive.This porous FRS coating has open pores,which,in combination with the closed cells formed by EPS beads,create a hierarchically porous structure in FRS-EPS that results in superior thermal insulation with a lower thermal conductivity of 27.0 mW·(m·K)^(-1).The resultant FRS-EPS foam showed extremely low heat-release rates and smoke-production release,indicating excellent fire retardancy and smoke suppression.The specific optical density was as low as 121,which was 80.6%lower than that of neat EPS,at 624.The FRS-EPS also exhibited self-extinguishing behavior in vertical burning tests and had a high limiting oxygen index(LOI)value of 35.5%.More interestingly,after being burnt with an alcohol lamp for 30 min,the top side temperature of the FRS-EPS remained at only 140℃with ignition,thereby exhibiting excellent fire resistance.Mechanism analysis confirmed the intumescent action of FRS,which forms a compact phosphorus-rich hybrid barrier,and the phosphorus-containing compounds that formed in the gas phase contributed to the excellent flame retardancy and smoke suppression of FRS-EPS.This novel porous biomass-based FRS system provides a promising strategy for fabricating polymer foams with excellent flame retardancy,smoke suppression,and thermal insulation.

Effect of dosage of expandable graphite,dimethyl methylphosphonate,triethanolamine,and isocyanate on fluidity,mechanical,and flame retardant properties of polyurethane materials in coal reinforcement

In this study,orthogonal experiments were conducted to investigate the influence of expandable graphite(EG),dimethyl methylphosphonate(DMMP),triethanolamine(TEA),and isocyanate content on the compressive and bonding strengths,oxygen index,and fluidity of rigid polyurethane foam(RPUF).The results revealed that EG significantly increased the oxygen index of RPUF,enlarged the diameter of foam cells,and decreased the cell-closed content in foam;thus,leading to a pressure drop in RPUF.However,excessive EG was capable of reducing the fluidity of polyurethane slurry.TEA exhibited significant influence on the compressive strength of RPUF,which dropped initially,and then increased.DMMP had a remarkable effect on the flame retardant property and compressive strength of RPUF.Compressive strength of RPUF initially displayed an increase followed by a decrease with increasing dosage of DMMP,and achieved the maximum value at DMMP dosage of 4%.DMMP could effectively reduce the diameter of RPUF cells leading to an increase in the percentage of close area in foam.DMMP displayed the flame-retardation effects mainly in the gas phase leading to a significant enhancement in the oxygen index of RPUF.Moreover,the compressive strength and bonding strength of RPUF decrease significantly with the increase of isocyanate content due to the increased blowing efficiency by the CO_2.The oxygen index and flowing length of foam increased with the increase in isocyanate dosage.

A novel high-efficient P/N/Si-containing APP-based flame retardant with a silane coupling agent in its molecular structure for epoxy resin

A flame retardant containing multiple antiflaming elements usually exhibits high-efficient flame retardancy. Here, a novel P/N/Si-containing ammonium polyphosphate derivative(APTES-APP) is synthesized from ammonium polyphosphate(APP) and silane coupling agent(3-aminopropyl)triethoxysilane(APTES)via cation exchange, which is quite different in the chemical structure from APTES-modified APP for retaining silicon hydroxyls. APTES-APP is highly efficient for the epoxy resin. 8%(mass) APTES-APP imparts excellent flame retardancy to the epoxy resin, with a V-0 rating at the UL-94 test(1.6 mm)and an LOI value of 26%(vol). The peak heat release rate and total smoke production of the flameretardant epoxy resin are decreased by 68.1% and 31.3%, respectively. The synergy of P/N/Si contributes to the well-expanded char residue with a strong and dense surface layer, which is a very good barrier against heat and mass transfer. Besides, there is no significant deterioration in the mechanical properties of flame-retardant epoxy resin thanks to silicon hydroxyls forming hydrogen bonds with epoxy molecules. Meanwhile, other molecules can be grafted onto APTES-APP via these silicon hydroxyls, if needed.Briefly, this work has developed a new strategy for amino silane as flame retardants. In conjunction with a low-cost and simple preparation method, APTES-APP has a promising prospect in the high-performance flame-retardant epoxy.

Recent progress in flame retardant technology of battery: A review

As one of the most popular research directions,the application safety of battery technology has attracted more and more attention,researchers in academia and industry are making efforts to develop safer flame retardant battery.The battery consists of electrolyte,separator,electrode and shell,the traditional flame retardant method of battery is to modify the components to improve its flame safety.In this review,varied types of battery flame retardant technology are initially described,including the type of flame-retardants,flame retardant behaviors and flame retardant mechanisms.Latest research progress of various battery flame retardant technologies is summarized.Typical flame retardant approaches and important properties of flame retardant battery are reviewed as well.In addition,the current main challenges of the battery flame retardant technology in both academics and the industrial are analyzed carefully.In the end,the perspectives for future development of battery flame retardant technology are briefly discussed.

Thermal and Thermo-oxidative Degradation of Flame Retardant High Impact Polystyrene with Triphenyl Phosphate and Novolac Epoxy Resin

Thermal and thermo-oxidative decomposition and decomposition kinetics of flame retardant high impact polystyrene （HIPS） with triphenyl phosphate （TPP） and novolac type epoxy resin （NE） were characterized using thermo-gravimetric experiment. And the flammability was determined by limited oxygen indices （LOI）. The LOI results show that TPP and NE had a good synthetic effect on the flame retardancy of HIPS. Compared with pure HIPS, the LOI values of HIPS/NE and HIPS/TPP only increased by about 5%, and the LOI value of HIPS/TPP/NE reached 42.3%, nearly 23% above that of HIPS. All materials showed one main decomposition step, as radical HIPS scission predominated during anaerobic decomposition. TPP increased the activity energy effectively while NE affected the thermal-oxidative degradation more with the help of the char formation. With both TPP and NE, the materials could have a comparable good result of both thermal and thermal-oxidative degradation, which could contribute to their effect on the flame retardancy.

Preparation of a halogen-free P/N/Si flame retardant monomer with reactive siloxy groups and its application in cotton fabrics

A novel halogen-free phosphorus–nitrogen–silicon flame retardant monomer with reactive siloxy groups,N-(diphenylphosphino)-1,1-diphenyl-N-(3-(triethoxysilyl)propyl) phosphinamine(DPTA) has been synthesized and was applied to the fire-resistant finishing of cotton fabrics. The molecular structure of DPTA has been well characterized by elemental analysis, FTIR,1H NMR, and ^(31)P NMR spectroscopies. The chemically-grafted cotton fabrics, which were treated with 25 wt% DPTA, were obtained and confirmed by attenuated total reflectance Fourier infrared spectroscopy(ATR-FTIR). The flame retardancy and thermal property of the treated samples were investigated by limited oxygen index(LOI), vertical flammability test(VFT), thermogravimetric analysis(TGA) and microscale combustion calorimeter(MCC). It is noted that in vertical flammability test, the treated samples extinguished immediately upon removing the ignition source, whereas the untreated one was completely burned out. Furthermore, TGA and MCC tests revealed that the treated samples produced a high char formation and a low heated release during combustion. The surface morphology of the untreated and treated samples and the char residues after LOI tests were observed by scanning electron microscopy(SEM). Therefore, all the results showed that the treated cotton fabrics with 25 wt% DPTA apparently improved the fireresistant and thermal performances.

A biobased flame retardant towards improvement of flame retardancy and mechanical property of ethylene vinyl acetate

A new biobased flame retardant(MHPA)with remarkable compatibility was synthesized via a facile and low-cost neutralization reaction of magnesium hydroxide(MH)and phytic acid(PA).By blending the prepared MHPA into ethylene vinyl acetate(EVA),the fire retardancy,smoke suppression and mechanical properties of the composites were significantly improved.When 50 wt%of MH was added into EVA matrix,the value of limiting oxygen index(LOI)reached 26.1%.Whereas,when 10 wt%MH in the EVA composites(with initial 50 wt%MH)was replaced by MHPA,the resulted EVA composites had a LOI value of 30.8%,indicating high efficiency of addition of MHPA to improve flame retardancy.Moreover,the heat release rate(HRR)and total smoke production(TSP)of the EVA composites reduced by 54.4%and 27.6%,respectively,suggesting that incorporation of MHPA could effectively hinder rapid degradation of EVA composites during burning process.The fire-retardant mechanism may reside in that the MHPA combined with MH can present the excellent carbonization and expansion effects.This study illustrates that the biobased MHPA has a broad application prospect to develop flame-retardant EVA composites.

Levels and distribution of brominated flame retardants in the soil of Harbin in China

This study reports the presence of brominated flame retardants in the topsoil in and around Harbin, a city in northeastern China. Samples of soil were collected from 17 locations in 2006, and the levels of 9 polybrominated diphenylethers （PBDEs 17, 28, 47, 66, 99, 100, 153, 154, and 183） ranged from 2.45 to 55.9 pg/g dry weight （dw） with a mean of 26.3 pg/g dw. These levels are very low comparing with those for some cities in Europe and USA. BDE 209 and hexabromocyclododecane were the two dominant congeners, with mean concentrations of 520 pg/g dw and 1750 pg/g dw, respectively. The concentrations of the total nine PBDE congeners clearly decreased from urban areas to background, but the compositions of individual congeners differed. Proportions of heavier congeners decreased while those of lighter congeners increased, along urban-rural-background transect, providing evidence for an urban fractionation effect. Correlation analysis indicated similar sources for PBDEs, hexabromocyclododecane, and 1,2-bis（2,4,6-tribromophenoxy）-ethane from urban areas but pentabromoethylbenzene was probably present due to long-range atmospheric transport. Principal component analysis was used to determine the characteristics of the relationships among these brominated flame retardants in the field.

Synthesis and thermal stability of a novel phosphorus-nitrogen containing intumescent flame retardant

A novel phosphorus-nitrogen containing intumescent flame retardant （P-N IFR） was prepared via the reaction of dichlor-opentate with N-methylaniline. The structure of the product was confirmed by ^1H NMR, ^31p NMR, MS and IR. TGA analysis showed it has effective thermal stability.

A NEW SYNERGIST FOR INTUMESCENT FLAME RETARDANT POLYPROPYLENE

The synergistic effects of silicotungstic acid (SiW12) as a catalyst in the phosphorus-nitrogen compounds AM-based intumescent flame-retardant (IFR) polypropylene (PP) were studied using the limiting oxygen index (LOI), the UL-94 test, thermogravimetric analysis (TGA), real time Fourier transform infrared (FTIR), laser Raman spectroscopy (LRS). The LOI data show that SiW12 added to PP/IFR systems has a synergistic FR effect with an IFR additive named AM. The TGA data show that SiW12 apparently increases the thermal stability of the PP/IFR systems at high temperature (T > 500degreesC). The FTIR results provide the positive evidence that IFR can improve the thermal stability of PP and SiW12 can induce a higher rate of formation of phosphoric acid and its derivatives. The LRS measurements provide useful information on the carbonaceous microstructures. In short, a suitable amount of SiW12 (1.5 wt%) exerts synergistic effects with the IFR by increasing the LOI value and the thermal stability at high temperature and promoting the formation of charred structures on the burning PP surface.

Preparation and Properties of Bio-Based Flame Retardant Polyvinyl Alcohol

Polyvinyl alcohol (PVA) has been widely used in the fields of medical, food and packaging due to its excellentbiocompatibility, good fiber-forming and film-forming properties. However, the high flammability of PVA hasgreatly limited its wider applications. The flame-retardant PVA was prepared by melt blending of a bio-basedflame retardant (prepared from lignin, phosphoric acid and carbamide) with thermoplastic PVA (TPVA). Thechemical structure, morphology, thermal properties, mechanical properties, fire property and fluidity of thisflame retardant PVA were investigated by Fourier transform infrared spectrometer(FTIR), field emission scanning electron microscope(SEM), thermogravimetric analyzer(TGA), impact tester, universal testing machine,horizontal-vertical burning tester, limiting oxygen indexer(LOI) and melt flow rate meter(MFR). The resultsshowed that the prepared flame retardant had good compatibility with the PVA substrate;The impact strength,melt flow rate, fire property and char residue of this PVA material increased with the content of bio-based flameretardant. When the content of flame retardant was of 20%, the five indices including impact strength, meltflow rate, UL-94 level, LOI and char residual were 11.3 KJ/m^(2), 21.2 g/10 min, V-0 UL-94 level, 33.1%, and19.2%, respectively. This research can promote the high-value utilization of lignin and the application ofPVA in the fields of fire protection.

Novel Bio-based Flame Retardant Systems Derived from Tannic Acid

In this study,tannic acid(TA)was investigated as flame retardant agent for PLA.Different strategies to modify its thermal degradation pathway have been explored in order to improve its charring effect.The first one consists in combining TA with organomodified montmorillonite(oMMT),and enables limiting the thermo-oxidative degradation of TA and promoting the formation of an effective char layer.Flame-retardant(FR)behavior of PLA-based composition has been found to be positively impacted by this combination since a reduction of the peak of Heat Release Rate(PHRR),more important than the value recorded when oMMT and tannic acid are used separately,has been obtained.The second strategy,in which tannic acid was associated with a biosourced phosphorousbased compounds,i.e.metallic phytate salt,evidenced another alternative allowing enhancing TA flame retardant effect at 30 wt%loading content.The third and last strategy explored aims to chemically modify TA via a chemical grafting of phosphoric acid groups.This phosphorylated TA was shown to present the most effective flame-retardant(FR)effect.However,an important reduction of PLA molecular weight was observed.

A Vanillin-Derived,DOPO-Contained Bisphenol as a Reactive Flame Retardant for High-Performance Epoxy Thermosets

Quest for bio-based halogen-free green flame retardant has attracted many concerns in recent years.Herein a reactive functional flame retardant containing phosphorus VDP is synthesized from vanillin,9,10-dihydro-9-oxa-10-phosphophene-10-oxide(DOPO)and phenol via a facile way.VDP is characterized with^(1)H NMR,^(31)P NMR,FTIR and Time of Flight Mass Spectrometry,and used as a new reactive flame retardant for bisphenol epoxy thermosets.Thermogravimetry analysis shows that when the VDP loading is only 0.5P%(based on phosphorus content),the residue increases from 14.2%to 21.1%at 750℃ in N_(2)compare with neat DGEBA.Correspondingly,the limit oxygen index increased to 29.6%,and flame retardancy reaches UL-94 V0 grade.Micro combustion calorimetry(MCC)and cone calorimetry analyses demonstrate that VDP can significantly lower flammability of the epoxy thermoset.With only 0.5P%of VDP,the heat release rate,total heat release rate and smoke production are reduced markedly.At the same time,the mechanical properties of the modified epoxy thermosets are also improved.The impact strength increases by 34%and the flexural strength increased by 23%,with 1.5P%of VDP.In short,VDP not only improves the flame retardancy,but also improves the mechanical properties of the epoxy thermosets.

Preparation and Properties of Bio-Based Flame Retardant L-APP/Poly(L-lactic acid)Composites

Poly(L-lactic acid)(PLLA)is a thermoplastic material with complete degradability,high biocompatibility and excellent mechanical properties.It can replace petroleum-based polymers are currently being used in the fields of packaging,agriculture,textiles,medical and so on.However,PLLA’s extremely flammability greatly limits its wider application.An bio-based flame retardant L-APP/PLLA composites was prepared by melt blending of the L-APP and PLLA.The morphology,impact properties,thermal properties and flame retardant properties of composites were investigated by field emission scanning electron microscope(SEM),impact tester,differential scanning calorimeter(DSC),thermogravimetric analyzer(TGA),limiting oxygen indexer(LOI)and horizontalvertical burning tester.The results showed that the degree of crystallization(X_(c))and LOI of L-APP/PLLA composites increased as increasing of L-APP content.What’s more,the impact strength first increased and then decreased,the glass transition temperature(T_(g))and melting temperature(T_(m))do not changed significantly.The impact strength of composites was 9.1 kJ/m^(2) at a 5 wt%loading for L-APP,which was the highest level.When the content of L-APP was 20%,the LOI was 30.8%,the Xc was 42.3%and the UL-94 level was V-0.This research can promote the value-added utilization of lignin and the application of PLLA in the fields of flame retardant materials.