Intumescent Flame-retardant Modification of Polypropylene/Carbon Fiber Composites

To improve the flame resistance of polypropylene(PP)/carbon fiber(CF)composite materials,triazine char-forming agent(TCA)was compounded with ammonium polyphosphate(APP)or modified APP(CS-APP)in a 2:1 ratio to prepare intumescent flame retardant(IFR)and the modified intumescent flame retardant(CS-IFR)in this paper.Flame retardancy and thermal degradation behaviors of the composites modified by IFR and CS-IFR were characterized by Fourier Transform Infrared(FTIR),contact angle measurement,oxygen index(OI),vertical burning tests(UL-94),thermogravimetric analyer(TGA),and thermogravimetric analyzer coupled with Fourier transform infrared(TG-FTIR).It was found that 25.0 phr of IFR and 24.0 phr of CS-IFR could improve the LOI value of PP/CF composites to 28.3%and 28.9%,respectively.At the same time,a UL-94 V-0 rating was achieved.The experimental results show that the IFR and CS-IFR prepared could effectively improve the flame retardancy and thermostability of PP/CF composites,and they would greatly expand the application range of PP/CF composite materials.

Synthesis of Antistatic Composite Based on Reaction Flame Retarding Unsaturated Polyester Resin

The synthesis of reaction flame retarding unsaturated polyester resin and the flame retarding mechanism are investigated.By taking the synthesis flame retarding unsaturated polyester resin as a base material,glass fibers as reinforced material,under the condition of adding graphite or carbon black respectively,the composites were manufactured.The flame retarding and antistatic properties are also studied.In the experiment,bromide-bearing flame retarding resin decomposed under a high temperature.Compound HBr was set out and retarded or stopped the flame.High concentration of HBr gas wall was formed between gas and solid phrases,which decreased flame.The results show that antistatic property of carbon black is higher than that of graphite.Adding a threshed value of 1% carbon black into composite,the antistatic property is at its highest value.

Synthesis, Characterization and Flame-retardant Properties of Epoxy Resins and AACHH Composites

Flame retardant epoxy resins were prepared by a simple mixed method using ammonium aluminum carbonate hydroxy hydrate （AACHH） as a halogen-free flame retardant. The prepared samples were characterized by X-ray diffraction, thermogravimetric and differential scanning calorimetry, scanning electron microscope and limiting oxygen index（LOI） experiments. Effects of AACHH content on LOI of epoxy resins/AACHH composite and flame retardant mechanism were investigated and discussed. Results show that AACHH exhibites excellent flame-retardant properties in epoxy resin（EP）. When the content of AACHH was 47.4%, the LOI of EP reached 32.2%. Moreover, the initial and terminal decomposition temperature of EP increased by 48 ℃ and 40 ℃, respectively. The flame retarded mechanism of AACHH is due to the synergic flame retardant effects of diluting, cooling, decomposition resisting and obstructing.

Phosphorylated Salicylic Acid as Flame Retardant in Epoxy Resins and Composites

A novel,versatile flame retardant substructure based on phosphorylated salicylic acid(SCP)is described and used in the synthesis of new flame retardants for HexFlow
RTM6,a high-performance epoxy resin used in resin transfer molding processes as composite matrix.The starting material salicylic acid can be obtained from natural sources.SCP as reactive phosphorus chloride is converted with a novolak,a novolak containing 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide(DOPO)substituents or DOPO-hydroquinone to flame retardants with sufficient thermal stability and high char yield.Additionally,these flame retardants are soluble in the resin as well as react into the epoxy network.The determined thermal stability and glass transition temperatures of flame retarded neat resin samples as well as the interlaminar shear strength of corresponding carbon fiber reinforced composite materials showed the applicability of these flame retardants.Neat resin samples and composites were tested for their flammability by UL94 and/or flame-retardant performance by cone calorimetry.All tested flame retardants decrease the peak of heat release rate by up to 54%for neat resin samples.A combination of DOPO and SCP in one flame retardant shows synergistic effects in char formation and the mode of action adapts to neat resin or fiber-reinforced samples,so there is efficient flame retardancy in both cases.Therefore,a tailoring of SCP based flame retardants is possible.Additionally,these flame retardants efficiently reduce fiber degradation during combustion of carbon fiber-reinforced epoxy resins as observed by scanning electron microscopy and energy dispersive X-ray spectroscopy.

Formulating Novel Halogen-Free Synergistic Flame Retardant Epoxy Resins for Vacuum Assisted Resin Infusion Composites

The most common process to manufacture advanced composites is the costly autoclave.One of the out-of-autoclave alternatives is the low-cost vacuum assisted resin infusion(VARI)which produces quality parts with less pollution.Epoxy resin is a widely used composite matrix resin,but its high flammability limits its use as interior composite parts for vehicles.The usual flame retardant for epoxy involves halogen,which is effective but has high smoke toxicity.As a result,halogen-free flame retardant epoxy resin systems become dominant.In this paper,phosphorus flame retardant was combined with benzoxazine(BOZ)to produce synergistic effect and achieve satisfactory flame retardance,as well as mechanical improvement for the epoxy resin.Differential scanning calorimetry(DSC),dynamic mechanical analysis(DMA),thermal gravitational analysis(TGA),the cone calorimeter(CC),and limiting oxygen index(LOI)were used to characterize the resins.The results showed significant improvement on the flame retardance of the synergistically modified resins.Specifically,the carbon residue increased by 113.6%,and the char thickness increased by 6 to 7 times,compared to those of the flammable benchmark resin.The LOI reached 33 and passed the UL94 V-0 vertical burn rating.The modified resins also exhibited adequate stability and viscosity suitable for VARI processes.

Tribological and flame retardant modification of polyamide-6 composite

A series of wear and flame resistant polyamide 6(PA6)composites were prepared using glass fiber(GF)and talc(T)as reinforcer,polytetrafluoroethylene(PTFE)and graphite(Gr)as solid lubricants,red phosphorus(RP)and zinc borate(ZB)as flame retardant.The tribological property,mechanical property,flame retardant property and the flame retardant mechanism were investigated.The tests show that the formula of the wear resistant PA6 composite(WRPA 6)is PA6/GF/T/PTFE/Gr in the ratio of 100/15/5/10/5 by mass.Because this composite exhibits the lowest friction coefficient(0.1429)and no wear mass loss,the introduction of RP and ZB can increase the flame resistance of WRPA6,and the synergistic effect of RP and ZB is obtained.Detailedly,the composite with 4 parts of ZB and 12 parts of RP shows the best flame retardant property,achieving the highest limiting oxygen index(LOI)(30.2 vol%)and a UL94 V-0 rating,and the flame retardant mechanisms may be gas phase along with condense phase mechanism.

Novel wood-plastic composite fabricated via modified steel slag:Preparation,mechanical and flammability properties

A novel method was developed to enhance the utilization rate of steel slag(SS).Through treatment of SS with phosphoric acid and aminopropyl triethoxysilane(KH550),we obtained modified SS(MSS),which was used to prepare MSS/wood-plastic composites(MSS/WPCs)by replacing talcum powder(TP).The composites were fabricated through melting blending and hot pressing.Their mechanical and combustion properties,which comprise heat release,smoke release,and thermal stability,were systematically investigated.MSS can improve the mechanical strength of the composites through grafting reactions between wood powder and thermoplastics.Notably,MSS/WPC#50(16wt%MSS)with an MSS-to-TP mass ratio of 1:1 exhibited optimal comprehensive performance.Compared with those of WPC#0 without MSS,the tensile,flexural,and impact strengths of MSS/WPC#50 were increased by 18.5%,12.8%,and 18.0%,respectively.Moreover,the MSS/WPC#50 sample achieved the highest limited oxygen index of 22.5%,the highest vertical burning rating at the V-1 level,and the lowest horizontal burning rate at 44.2 mm/min.The formation of a dense and stable char layer led to improved thermal stability and a considerable reduction in heat and smoke releases of MSS/WPC#50.However,the partial replacement of TP with MSS slightly compromised the mechanical and flame-retardant properties,possibly due to the weak grafting caused by SS powder agglomeration.These findings suggest the suitability of MSS/WPCs for high-value-added applications as decorative panels indoors or outdoors.

Flame Retardancy Enhancement of Hybrid Composite Material by Using Inorganic Retardants

This study aims to investigate the possibility of improving the flame Retardancy for the hybrid composite material consisting araldite resin (CY223). The hybrid composite was reinforced by hybrid fibers from carbon and Kevlar fibers on woven roving form (45o -0o), by using a surface layer of 4mm thick of Zinc Borate flame retardant. Afterward, the structure was exposed directly to gas flame of 2000oC due to 10 mm and 20mm exposure interval. The retardant layer thermal resistance and protection capability were determined. The study was continued to improve the performance of Zinc Borate layer mixed by 10%, 20% and 30% of Antimony Trioxide. To determine the heat transfer of the composite material the opposite surface temperature method was used. Zinc Borate with (30%) Antimony Trioxide gives the optimized result of the experiment.

A Study on a Magnesium-Based Layered Composite Used as a Flame Retardant for Phenolic Epoxy Resins

The effects of a magnesium-based layered composite on the flammability of a phenolic epoxy resin(EP)are studied.In order to produce the required composite material,first,magnesium hydroxide,aluminum salt and deionized water are mixed into a reactor according to a certain proportion to induce a hydrothermal reaction;then,the feed liquid is filtered out using a solid-liquid separation procedure;finally,the material is dried and crushed.In order to evaluate its effects on the flammability of the EP,first,m-phenylenediamine is added to EP and vacuum defoamation is performed;then,EP is poured into a polytetrafluoroethylene mold,cooled to room temperature and demoulded;finally,the magnesium-based layered composite is added to EP,and its flame retardance is characterized by thermogravimetric analysis,limiting oxygen index and cone calorimetry.The X-ray diffraction patterns show that the baseline of magnesium-based layered composite is stable and the front shape is sharp and symmetrical when the molar ratio of magnesium to aluminium is 3.2:1;with the addition of magnesium-based layered composite,the initial pyrolysis temperature of EP of 10%,15%and 30%magnesium-based layered composite decreases to 318.2°C,317.9°C and 357.1°C,respectively.After the reaction,the amount of residual carbon increases to 0.1%,3.45%and 8.3%,and the limiting oxygen index increases by 28.3%,29.1%and 29.6%,respectively.The maximum heat release rate of cone calorimeter decreases gradually.The optimum molar ratio of Mg:Al for green synthesis is 3.2:1,and the NO_(3)-intercalated magnesium-based layered composite has the best flame retardance properties.

Design of the flame retardant form-stable composite phase change materials for battery thermal management system

Phase change materials have attracted significant attention owing to their promising applications in many aspects.However,it is seriously restricted by some drawbacks such as obvious leakage,relatively low thermal conductivity,and easily flame properties.Herein,a novel flame retardant form-stable composite phase change material(CPCM)with polyethylene glycol/epoxy resin/expanded graphite/magnesium hydroxide/zinc hydroxide(PEG/ER/EG/MH/ZH)has been successfully prepared and utilized in the battery module.The addition of MH and ZH(MH:ZH=1:2)as flame retardant additions can not only greatly improve the flame retardant effect but also maintain the physical and mechanical properties of the polymer.Further,the EG(5%)can provide the graphitization degree of residual char which is beneficial to building a more protective barrier.This designation of CPCM can exhibit leakage-proof,high thermal conductivity(increasing 400%-500%)and prominent flammable retardant performance.Especially at 3C discharge rate,the maximum temperature is controlled below 54.2℃and the temperature difference is maintained within 2.2℃in the battery module,which presents a superior thermal management effect.This work suggests an efficient and feasible approach toward exploiting a multifunctional phase change material for thermal management systems for electric vehicles and energy storage fields.

Dynamic Mechanical Characterizations and Road Performances of Flame Retardant Asphalt Mortars and Concretes

To research the dynamic mechanical properties and road performances of flame retardant asphalt mortars and mixtures, four different asphalt mortars/mixtures were prepared: a reference group and three asphalt mortars/mixtures containing composite flame retardant materials(M-FRs) of different proportions. Temperature sweep, frequency sweep, repeated creep test, force ductility test and bending beam rheological test were carried out to research the dynamic mechanical properties of asphalt mortars containing M-FRs; wheeltracking test, low-temperature bending test and freeze-thaw split test were used to study the road performances of asphalt mixtures containing M-FRs. The results show that high-temperature performances of the three flame retardant asphalt mortars improve greatly, while low-temperature cracking resistances decline. Both hightemperature performances and water stabilities of asphalt mixtures containing M-FRs are quite good and exceed the specification requirements. However, their low-temperature performances decline in different degrees. In summary, besides their good flame retardancy, the flame retardant asphalt mortars and mixtures also exhibit acceptable road performance.

Bio-Based Trivalent Phytate:A Novel Strategy for Enhancing Fire Performance of Rigid Polyurethane Foam Composites

Biomass phytic acid has potential flame retardant value as the main form of phosphorus in plant seeds.In this study,phytate-based flame retardants aluminum phytate(PA-Al)and iron phytate(PA-Fe)were synthesized and characterized.Subsequently,they were introduced into rigid polyurethane foam(RPUF)as flame retardants by one-step water-blown method.The results indicated that RPUF/PA-Fe30 exhibited the highest char residue of 22.1 wt%,significantly higher than 12.4 wt%of RPUF.Cone calorimetry analysis showed that the total heat release(THR)of RPUF/PA-Al30 decreased by 17.0%and total smoke release(TSR)decreased by 22.0%compared with pure RPUF,which were the lowest,demonstrating a low fire risk and good smoke suppression.Thermogravimetric analysis-Fourier transform infrared spectrometer(TG-FTIR)implied the release intensity of flammable gases(hydrocarbons,esters)and toxic gases(isocyanate,CO,aromatic compounds,HCN)of composites was significantly reduced after the addition of PA-Fe.The analysis of char residue indicated that the RPUF composites formed a dense char layer with a high degree of graphitization after the addition of PA-Al/PA-Fe,endowing RPUF composites with excellent mass&heat transmission inhibition effect and fire resistance in the combustion process.

Boron nitride silicone rubber composite foam with low dielectric and high thermal conductivity

Silicone rubber(SR)is widely used in the field of electronic packaging because of its low dielectric properties.In this work,the porosity of the SR was improved,and the dielectric constant of the SR foam was reduced by adding expanded microspheres(EM).Then,the thermal conductivity of the system was improved by combining the modified boron nitride(f-BN).The results showed that after the f-BN was added,the dielectric constant and dielectric loss were much lower than those of pure SR.Micron-sized modified boron nitride(f-mBN)improved the dielectric and thermal conductivity of the SR foam better than that of nano-sized modified boron nitride(f-nBN),but f-nBN improved the volume resistivity,tensile strength,and thermal stability of the SR better than f-mBN.When the mass ratio of f-mBN and fnBN is 2:1,the thermal conductivity of the SR foam reaches the maximum value of 0.808 W·m^(-1)·K^(-1),which is 6.5 times that before the addition.The heat release rate and fire growth index are the lowest,and the improvement in flame retardancy is mainly attributed to the high thermal stability and physical barrier of f-BN.

Flexible and flame-retarding phosphorylated MXene/polypropylene composites for efficient electromagnetic interference shielding

Flame-retardant composites with high electromagnetic interference(EMI)shielding performance are desirable for electronic device packaging.Despite great potential of MXene for high EMI,it still remains a great challenge to develop high-performance flame-retardant polymer/MXene composites with excellent EMI shielding effectiveness because of the poor oxidative stability of MXene.Herein,phosphorylated MXene/polypropylene(PP)composites are prepared by coating phosphorylated MXene on PP fabric followed by spraying polyethylenimine(PEI)and hot-pressing.The phosphorylated MXene proves to be more durable against oxidation than pure MXene due to the protection effect of polyphosphates.Upon hot-pressing,melted PP fibers are fused together at their contact points and thus as-prepared composites are bi-continuous with two interpenetrating phases.The composites show significantly improved thermal stability and flame retardancy relative to pure PP,with a low total heat release(THR)of 3.7 kJ/g and a heat release rate(HRR)of 50.0 W/g,which are reduced by 78%and 87%,respectively.In addition,the composites exhibit a high electrical conductivity of~36,700 S/m and an EMI shielding performance of~90 d B over the whole frequency range of 8–12 GHz with a thickness of~400μm.The as-developed PP/MXene composites hold great promise for reliable protection of next-generation electronic devices working in complex environments.

轨道交通用碳纤维增强环氧树脂复合材料力学与阻燃性能研究

该研究通过热压罐工艺制备3种轨道交通用碳纤维增强环氧树脂复合材料,对其拉伸、层间剪切等力学性能和防火阻燃性能进行测试,为材料的选择与优化提供科学依据。结果表明3种复合材料的0°拉伸强度皆大于1900 MPa,层间剪切强度大于70 MPa,关键力学性能优异,且阻燃等级皆达到EN45545-2:2020 R1 HL3,可满足轨道交通领域典型承力件和次承力件的力学性能及防火安全性的要求。

Enhanced mechanical properties and flame retardancy of short jute fiber/poly(lactic acid)composites with phosphorus-based compound

In this work, a phosphorous-based compound （DOPO-ICN） was obtained by a two-step process. 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide （DOPO） reacted with formaldehyde firstly, followed with reacting with 1,6-hexane diisocyanate （HD1）. The chemical structure of DOPO-ICN was confirmed by Fourier transform infrared spectroscopy （FTIR） and 1H NMR. The influence of DOPO-1CN on the mechanical and flammability properties ofjute/PLA composites was studied. Compared to DOPO, DOPO-ICN improved the tensile, flexural and impact strength of the flame retardant jute/PLA composites. Moreover, the flammability ofjute/PLA composites with different DOPO and DOPO-MA loading was investigated by thermogravimetric analysis （TGA）, UL 94 test and limiting oxygen index （LOI） measurements. The results showed that DOPO-ICN imparted the flame retardancy to the jute/PLA composites.

Flame-retardant Wrapped Ramie Fibers towards Suppressing “Candlewick Effect” of Polypropylene/Ramie Fiber Composites

In this work, a flame-retardant polypropylene（PP）/ramie fiber（RF） composite was prepared. The ramie fibers were wrapped chemically by a phosphorus- and nitrogen-containing flame retardant（FR） produced via in situ condensation reaction so as to suppress their candlewick effect. Fourier transform infrared spectroscopy（FTIR）, X-ray photoelectron spectroscopy（XPS） and scanning electron microscopy（SEM） demonstrated that the ramie fibers wrapped chemically by FR（FR-RF） were obtained successfully. Thermogravimatric test showed that the PP/FR-RF composite had more residue and better thermal stability at high temperatures than the PP/RF composite. Cone calorimeter（CC） results indicated that the peak of heat release rate（PHRR） and total heat release（THR） correspondingly decreased by 23.4% and 12.5% compared with the values of neat PP/RF. The PP/FR-RF composite created a continuous and compact char layer after the combustion. Combining FTIR analysis of char residue after CC test with heat conduction coefficient results, it could be concluded that the charring of FR on RF greatly weakened the candlewick effect of RF, and more char residue in the RF domain facilitated the formation of more continuous and compact char layer in the whole combustion zone, consequently protected PP composites during combustion, resulting in the better flame retardancy of PP/FR-RF composite than that of PP/RF composite.

Polyester-supported Chitosan-Poly(vinylidene fluoride)-Inorganic-Oxide-Nanoparticles Composites with Improved Flame Retardancy and Thermal Stability

Polyester(PET) was pre-activated by atmospheric air plasma and coated by various inorganic oxide nanoparticles(MOx) such as titanium dioxide(TiO2), zinc oxide(ZnO), and silicon oxide(SiO2), using poly(vinylidene fluoride)(PVDF) and chitosan(CT) as binders. The resulting PET-PVDF-MOx-CT composites were thermally compressed and then characterized by scanning electron microscopy, Fourier infrared spectroscopy, thermal gravimetric analysis, and flame retardancy(FR) ability tests. PET modifications resulted in more thermally stable and less harmful composites with weaker hazardous gas release. This was explained in terms of structure compaction that blocks pyrolysis gas emissions.CT incorporation was found to reduce the material susceptibility to oxidation. This judicious procedure also allowed improving flame retardancy ability, by lengthening the combustion delay and slowing the flame propagation. Chitosan also turned out to contribute to a possible synergy with the other polymers present in the synthesized materials. These results provide valuable data that allow understanding the FR phenomena and envisaging low-cost high FR materials from biodegradable raw materials.

Flame Retardant and Mechanical Properties of Wood Powders/PE Composites

The influence law of ammonium polyphosphate(APP) and coupling agents on the mechanical properties and flame retardant properties of wood powder/PE composites were studied by mechanical test and limited oxygen index(LOI) test. The experimental results show that the LOI of composites increased from 18.7%to 26.5%when the content of APP flame retardant was 30%,however the mechanical properties decreased.The maleic anhydride graft PP,titanate and silane coupling agent were used to improve mechanical properties of composites and it was implied that titanate and silane coupling agent can improve the mechanical properties of composites obviously.The limited oxygen index of wood powder/PE composites reached 27.5% when the content of titanate was 2%. Thermogravimetric analysis(TGA) shows that APP promoted charring and increased the amounts of char,thus protecting the inner matrix and increased the amount of residual char at higher temperature. The titanate coupling agent further increased the charring formed and strengthened the thermal stability,so obviously increased the flame retardant of composites.

苯并噁嗪与木质素磺酸钠协同阻燃聚酯复合材料的性能分析

为提高聚对苯二甲酸乙二醇酯(PET)的阻燃性能,以苯并噁嗪(BOZ)和木质素磺酸钠(SLS)为改性材料,制备了以PET为基体的聚酯复合材料。采用扫描电镜观察聚酯复合材料的表面形貌,通过热失重分析、差示扫描量热分析、极限氧指数(LOI)测试和垂直燃烧实验(UL-94)表征聚酯复合材料的热性能和阻燃性能,利用能量色散X射线光谱仪分析残炭情况,并使用电子万能试验机测试力学性能。结果表明:BOZ和SLS在PET基体中没有出现明显的团聚现象;当BOZ和SLS的质量比为1∶0.5、总添加量(质量分数)为10%时,聚酯复合材料的结晶度、熔融温度和残炭量相比纯PET均有所提高;聚酯复合材料的LOI值提高到了26.4%,UL-94等级达到了V-1等级,燃烧时的熔体滴落被有效抑制;残炭分析结果表明,聚酯复合材料的阻燃遵循凝聚相阻燃机理;聚酯复合材料的拉伸强度和断裂伸长率相比纯PET有所下降,但聚酯复合材料的杨氏模量相比纯PET有所提高。该研究可为聚酯复合材料的阻燃研究提供参考。