Enhanced flame retardancy,smoke suppression,and acid resistance of polypropylene/magnesium hydroxide composite by expandable graphite and microencapsulated red phosphorus

Low flame retardant efficiency and poor acid resistance of filled polymer composites are two main drawbacks of magnesium hydroxide (MH) as a flame retardant (FR). To solve these problems, expandable graphite (EG) and microencapsulated red phosphorus (MRP) were introduced into polypropylene/magnesium hydroxide (PP/MH) composite by melt compounding. The obtained PP/MH/EG/MRP quadruple composite was studied regarding its fire behavior as well as acid resistance. Obvious flame retardant synergism among MH, EG, and MRP is found in PP, which diminishes the loading of FR from 63.0 to 37.5 wt% to obtain V-0 rating in UL-94 test and low smoke release. Compact intumescent char with high thermo-oxidative stability was generated on composite surface, which plays a vital role in flame retardancy. The removal of MH by acid erosion on PP/MH/EG/MRP composite surface does not affect production of intumescent char and fire behavior of this composite. The composite displays good fire retardancy, smoke inhibition, and acid resistivity concurrently. This article renders an easy and cheap route to overcome the main faults of MH.     

无卤阻燃聚丙烯材料的研究

用自制的膨胀型阻燃剂(IFR)与成炭剂、无机填料复配和聚丙烯(PP)共混,进行燃烧性能测试,考察了共混体系的燃烧行为;利用锥形量热仪研究了表面处理剂对膨胀阻燃体系的影响;用氧指数(OI)分析了阻燃剂及其他助剂在PP中的阻燃作用。结果表明,该阻燃体系既有较好的阻燃效果,又有抑烟作用。     

An efficient approach to improving fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene composites via incorporating organo‐modified sepiolite

In this work, an efficient approach to improving the fire retardancy and smoke suppression for intumescent flame‐retardant polypropylene (PP) composites is developed via incorporating functionalized sepiolite (organo‐modified sepiolite [ONSep]). The PP composites with different amounts of intumescent flame retardants and ONSep were prepared by melt compounding. The morphology, thermal behavior, fire retardancy, smoke suppression, and mechanical property of flame‐retardant PP composites were studied. The results indicate an appropriate amount of ONSep in the flame‐retardant PP composites can increase thermal degradation temperature and char formation as well as a reduction of the peak heat release rate and total heat release; moreover, the addition of ONSep significantly decreases the CO production, total smoke production, smoke production rate, and smoke temperature. Simultaneously, the impact strength of intumescent flame‐retardant PP composite is also maintained by introducing an appropriate amount of ONSep as compared with that without ONSep.     

New fire‐protective intumescent coatings for wood

Polyurethane coatings are highly flammable, and because of their widespread applications on different substrates (wood, steel, and building materials), there is a need to increase their fire‐safety properties. Intumescent additives sharply suppress the flammability properties of polyurethane coatings. Two problems accompany intumescent additives: their high loading percentage and incompatibility with polyurethane coatings. In this research, we succeeded in increasing the compatibility by mixing intumescent additives with a butyl acrylate polymer and in lowering the flame‐retardant additive loading (up to 20%) by incorporating newly modified montmorillonite. The flammability properties of the new intumescent coatings were characterized with a cone calorimeter. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

磷—溴—硅膨胀阻燃体系在聚丙烯中的协同阻燃作用

采用锥形量热仪研究了磷-溴-硅三种阻燃元素对聚丙烯(PP)释热速度、总烟产量、释热总量、一氧化碳、二氧化碳(Co、CO_2)的释放量等的影响。研究结果表明,含溴阻燃剂阻燃效果显著,但 CO 和总烟产量较高。含磷和氮的膨胀型阻燃剂的 CO 和总烟产量显著降低,但阻燃效果较差,分子筛的加入,可使磷采用锥形量热仪研究了磷-溴-硅三种阻燃元素对聚丙烯(PP)释热速度、总烟产量、释热总量、一氧化碳、二氧化碳(Co、CO_2)的释放量等的影响。研究结果表明,含溴阻燃剂阻燃效果显著,但 CO 和总烟产量较高。含磷和氮的膨胀型阻燃剂的 CO 和总烟产量显著降低,但阻燃效果较差,分子筛的加入,可使磷一溴协同体系的各项阻燃参数得到显著改善,若能将磷氮的膨胀型阻燃剂和分子筛二者结合,少加或不加六溴环卜二烷将是理想的选择。溴协同体系的各项阻燃参数得到显著改善,若能将磷氮的膨胀型阻燃剂和分子筛二者结合,少加或不加六溴环十二烷将是理想的选择。     

Basic magnesium carbonate flame retardants for polypropylene

Magnesium hydroxide and magnesium carbonates have attracted attention as endothermic flame retardants that are sufficiently stable to be incorporated into thermoplastics without decomposition. In this survey, a basic form of magnesium carbonate, magnesium carbonate hydroxide pentahydrate [(MgCO₃)₄ · Mg(OH)₂ · 5H₂O] was evaluated as a flame retardant for polypropylene. This filler (MCHP) has a thermal stability intermediate between that of alumina trihydrate (ATH) and magnesium hydroxide, which is sufficient to allow incorporation into polypropylene without decomposition. The MCHP is most effective at high filler concentrations near 60% where it was found to impart a Limiting Oxygen Index of 28.2 with a V-O rating (no dripping). This is slightly more effective than the flammability ratings for ATH and Mg(OH)₂ under the same conditions. The effectiveness of MCHP was attributed to the large endothermic loss of water of hydration, which also dilutes the combustion gases. This action was further aided by the formation of an intumescent char on the burning surface, which eventually extinguished the flame. Various combinations of magnesium oxide, magnesium hydroxide, magnesium carbonate, and MCHP were evaluated in order to clarify the mechanism of the flame retardant and improve the efficiency of the protective action. However, no synergism was evident, and the flame retardant results were found to be additive. The mechanical properties and processabilities of these highly filled compounds are very sensitive to the type of surface treatment. The method of Savides was employed to compare the burning temperature of the test specimens and to measure the rates of combustion.     

用锥形量热仪研究无卤阻燃HDPE体系的燃烧性

在35kW／m^2热辐照条件下,利用锥形量热仪研究了膨胀型阻燃剂／Mg(OH)2阻燃高密度聚乙烯(HDPE)体系的燃烧性。结果表明：膨胀型阻燃剂／Mg(OH)2能明显降低HDPE的热释放速率、总热释放量、最大生烟速率及总烟释放量。与膨胀型阻燃剂单独使用相比,Mg(OH)2与膨胀型阻燃剂复合使用的阻燃效果明显,总烟释放量减少了38％,总热释放量减少了10％,达到了低发炯、高效阻燃的目的。     

壳聚糖/聚磷酸铵膨胀阻燃PP的阻燃及抑烟性能

为了提高聚丙烯(PP)的阻燃和抑烟性能,将壳聚糖(CS)作为膨胀型阻燃剂的碳源、聚磷酸铵(APP)作为膨胀型阻燃剂的酸源和气源,在此基础上通过熔融共混的方法制备了PP/CS/APP复合材料。采用极限氧指数仪、锥形量热仪等仪器研究了PP/CS/APP复合材料的的抑烟性及阻燃性。研究结果表明:CS/APP添加量为30%时,复合材料的极限氧指数值最大可达28.1%;且复合材料在烟气释放总量、CO和CO_2排放上明显降低,抑烟性得到了提升;热释放速率峰值、平均热释放速率值、平均有效燃烧热值、总热释放量值降低,成炭率升高,PP/CS/APP复合材料更难点燃;火灾性能指数明显提高,阻燃性能得到了大幅度提升,火灾蔓延指数显著减小,同时火灾危险性也相应降低。     

Flame retardation and thermal degradation of intumescent flame‐retarded polypropylene composites containing spirophosphoryldicyandiamide and ammonium polyphosphate

A novel halogen‐free intumescent flame retardant, spirophosphoryldicyandiamide (SPDC), was synthesized and combined with ammonium polyphosphate (APP) to produce a compound intumescent flame retardant (IFR). This material was used in polypropylene (PP) to obtain IFR‐PP systems whose flammability and thermal behavior were studied by the limiting oxygen index (LOI) test, UL‐94, thermogravimetric analysis, and cone calorimetry. In addition, the mechanical properties of the systems were investigated. The results indicated that the compound intumescent flame retardant showed both excellent flame retardancy and antidripping ability for PP when the two main components of the IFR coexisted in appropriate proportions. The optimum flame retardant formulation was SPDC:APP = 3:1, which gave an LOI value of 38.5 and a UL‐94 V‐0 rating. Moreover, the heat release rate, production of CO, smoke production rate, and mass loss rate of the IFR‐PP with the optimum formulation decreased significantly relative to those of pure PP, according to the cone calorimeter analysis. The char residues from the cone calorimetry experiments were observed by scanning electron microscopy, which showed that a homogeneous and compact intumescent char layer was formed. J. VINYL ADDIT. TECHNOL., 2010. © 2010 Society of Plastics Engineers     

Ignition,combustion, toxicity,and fire retardancy of polyurethane foams: A comprehensive review

This review provides insight into the ignition, combustion, smoke, toxicity, and fire‐retardant performance of flexible and rigid polyurethane foams. This review also covers various additive and reactive fire‐retardant approaches adopted to render polyurethane foams fire‐retardant. Literature sources are mostly technical publications, patents, and books published since 1961. It has been found by different workers that polyurethane foams are easily ignitable and highly flammable, support combustion, and burn quite rapidly. They are therefore required to be fire‐retardant for different applications. Polyurethane foams during combustion produce a large quantity of vision‐obscuring smoke. The toxicity of the combustion products is much higher than that of many other manmade polymers because of the high concentrations of hydrogen cyanide and carbon monoxide. Polyurethane foams have been rendered fire‐retardant by the incorporation of phosphorus‐containing compounds, halogen‐containing compounds, nitrogen‐containing additives, silicone‐containing products, and miscellaneous organic and inorganic additives. Some heat‐resistant groups such as carbodiimide‐, isocyanurate‐, and nitrogen‐containing heterocycles formed with polyurethane foams also render urethane foams fire‐retardant. Fire‐retardant additives reduce the flammability, smoke level, and toxicity of polyurethane foams with some degradation in other characteristics. It can be concluded that despite many significant attempts, no commercial solution to the fire retardancy of polyurethane foams without some loss of physical and mechanical properties is available. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effects of additives on fire properties of polyethylene

Low-density polyethylene, with and without an antimony–bromine synergistic fire retardant or aluminium hydroxide, was subjected to standard fire tests and to experiments which determined the smoke and harmful fumes emitted on overheating. Both additives improved most fire properties but the fire retardant increased the smoke generated by intense radiant heat. The onset of smoke, flammable gas, carbon monoxide and acids was generally delayed by the additives. The total amounts and maximum values of these volatiles were lessened. Sample weight and form affect the results of these experiments. Observations during heating show that the additives reduce spreading of the melt, thus reducing the surface area available for oxidation.     

无卤阻燃聚丙烯的研究进展

介绍了水合金属氢氧化物、磷系阻燃剂、膨胀型阻燃剂、硅系阻燃剂和无机层状阻燃剂在聚丙烯无卤阻燃中的研究现状。综述了协同增效剂在氧氧化镁、膨胀型阻燃剂阻燃聚丙烯方面的最新研究进展。指出了当前研究的无卤阻燃剂中的不足,因此合理利用各种阻燃剂间的协同效应、提高阻燃剂的阻燃效率、开发复合型高效阻燃剂是未来聚丙烯阻燃的研发热点。     

Flame‐retardant materials: synergistic effect of halloysite nanotubes on the flammability properties of acrylonitrile–butadiene–styrene composites

Novel well‐dispersed nanocomposites of halloysite nanotubes and acrylonitrile–butadiene–styrene were prepared. The fire retardancy and thermal stability of these new nanocomposites were improved. A synergistic effect was observed between the halloysite nanotubes and an intumescent flame‐retardant system consisting of ammonium polyphosphate, melamine polyphosphate and pentaerythritol in the acrylonitrile–butadiene–styrene composites. The incorporation of the intumescent flame‐retardant material into the halloysite–polymer nanocomposite system also improved the thermal stability and reduced the peak heat release rate by up to 56.2%, and it significantly reduced the emission of CO and CO₂ gases. The morphology and dispersion of the halloysite nanotubes were characterized using scanning and transmission electron microscopy. The thermal stability and flammability properties were investigated using thermogravimetric analysis and cone calorimeter tests. © 2013 Society of Chemical Industry     

Cone calorimeter testing of foam core sandwich panels treated with intumescent paper underneath the veneer (FRV)

Surfaces of novel foam core sandwich panels were adhered with intumescent fire‐retardant paper underneath the veneers (FRV) to improve their flammability properties. The panels were evaluated by means of cone calorimeter test (ASTM E 1354). Variables tested were different surface layer treatments, adhesives used for veneering, surface layer thicknesses, and processing conditions, having the objective of obtaining similar or better flammability as that of solid particle boards. Previous research showed that sandwich panels without FRV compared to panels with FRV generally had much higher heat release rates, somewhat higher heat of combustion and much higher smoke production due to the polymeric foam component of tested panels. The present study shows that using FRV adhered to the surface layer of sandwich panels dramatically improved flammability properties; the best FRV performance resulted from panels produced with thicker face layer (5 mm) and lower press temperature (130°C) and adhered with an acrylic thixotropic adhesive. Such protected foam core particleboard has heat release rate profiles as low as that is typical of commercially available fire‐retardant–treated plywood, thus implying a low flammability rating when tested in accordance with both single burn item (Euro Class B anticipated) and steiner tunnel (North America Class A anticipated) tests.     

A study of the flame‐retardant properties of polypropylene/Al(OH)3/Mg(OH)2 composites

Polymeric materials are used extensively, but their applications are limited because many of them are flammable. Therefore ways to make them flame retardant have received much attention. In this work, polypropylene (PP) was used as the matrix resin, aluminium hydroxide (Al(OH)₃) and magnesium hydroxide (Mg(OH)₂) as flame‐retardant additives and zinc borate (ZB) as a flame‐retardant synergist. PP/Al(OH)₃/Mg(OH)₂ and PP/Al(OH)₃/Mg(OH)₂/ZB flame‐retardant composites were prepared with a twin‐screw extruder. The flame‐retardant properties, i.e. oxygen index (OI), burning velocity and smoke density, of the composites were measured. The results showed that OI increased with an increase of the filler content and decreased with an increase of the filler particle diameter. The burning velocity decreased with an increase of the filler content, while it first increased and then decreased with an increase of the filler particle diameter. The smoke density decreased with an increase of the filler content and increased with an increase of the filler particle diameter. There was a flame‐retardant synergy between Al(OH)₃/Mg(OH)₂ and ZB in the composites, and the smoke suppression effect was marked when ZB was added. Copyright © 2009 Society of Chemical Industry     

Fire behavior and smoke emission of phosphate–based inorganic fire‐retarded polyester resin

The fire behavior and the smoke emission of an unsaturated polyester resin modified by the addition of three phosphorus‐based fire‐retardant materials (ammonium polyphosphate (APP), silane‐coated APP, and melamine pyrophosphate) at two concentration levels (20% w/w, 35% w/w) have been investigated. Scanning electron microscopy, Fourier transform infrared spectroscopy and optical microscopy analysis have been performed to verify the dispersion and the action mechanism of additives within the resin. Results from cone calorimetric tests demonstrated that the incorporation of the fire retardants at 35% w/w has a strong effect on flammability and smoke suppressant properties with respect to both the neat resin and the loaded systems at 20% (w/w). In particular, the smoke formation and smoke parameters are reduced by 50% and 80%, respectively, leading to the conclusion that APP can be used single‐handedly without combination with specific smoke suppressors. Copyright © 2011 John Wiley & Sons, Ltd.     

Development of halogen‐free flame‐retardant thermoplastic elastomer polymer blend

Ethylene‐propylene diene rubber (EPDM) and isotactic polypropylene (iPP) blends have widest industrial applications that require a degree of flame retardancy. Halogen‐free intumescent technology based on phosphorous salt is a significantly advanced approach to make the polymer flame‐retardant. Both ammonium polyphosphate and ethylenediamine phosphate are important intumescent compounds. Their combination with carbonific and spumific agents were studied in binary blends of EPDM/PP. The polymer system was vulcanized online during melt mixing. Intumescent flame‐retardant polymer systems exhibit good flame‐retardancy with optimum comparable physiomechanical, electrical, and fluid resistance properties, including lower smoke emission, which is essential to protect people because the visibility remains unaffected in the event of fire. Pronounced charring and intumescent effect appear to enhance the flame‐retardancy of the polymers. Possible expected intumescent mechanism is proposed based on the nonpyrolysis mechanism for the flame‐retarded polymer and the intumescent components. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 407–415, 2004     

软质PVC阻燃抑烟的研究

介绍了各类阻燃剂(如氢氧化铝、氢氧化镁、锑系、磷系、硼系、钼系)的性能及阻燃机理,并对软质PVC材料的阻燃抑烟性能进行了实验。结果表明：经偶联剂处理过的阻燃剂,由于增强了其与基体的界面结合力。从而使其力学性能得到提高;三氧化钼的用量对聚合物的阻燃效果影响不明显,而随着硼酸锌和三氧化二锑用量的增加,其阻燃效果越来越好。     

PP电缆料无卤阻燃技术的研究与应用进展

综述了用于无卤阻燃聚内烯(PP)电缆料的主要阻燃体系的研究进展,介绍了金属氧化物水合物体系、磷-氮膨胀型阻燃体系、有机硅复合体系和纳米复合材料阻燃体系的开发应用情况。建议加强对无卤阻燃PP电缆料的研究,以开发出力学性能优异的无卤阻燃PP电缆料。     

Effect of glass fibres and fire retardant on the combustion behaviour of composites,glass fibres–poly(butylene terephthalate)

The oxygen index (OI) of poly(butylene terephthalate) (PBT) tends to decrease when it is combined with milled-glass fibres either with or without the sizing treatment. This shows that the previously found apparent increase of flammability of PBT glass fibre composites (GFPBT) as compared to PBT is not due to the introduction of the flammable sizing together with the glass fibres in the polymer which was one suggested explanation in the literature, but rather to the wick and anti-dripping effects of glass fibres. The effectiveness of a typical brominated organic compound-antimony trioxide fire retardant system (FR), as measured by OI, is found to be larger in GFPBT as compared to PBT. A linear increase of the temperature index (TI) of PBT and of GFPBT is observed with increasing concentration of the FR. The fire retardant increases the time to ignite while it decreases the maximum rate of heat release and increases the smoke optical density and CO evolution on burning in the cone calorimeter. The dependence of fire risk and hazard assessement on the combustion model of the combustion test method is discussed for OI and cone calorimeter in the case of PBT, GFPBT and FR corresponding materials. © 1998 John Wiley & Sons, Ltd.