Fire retardant properties of intumescent polypropylene composites filled with calcium carbonate

This study was aimed to investigate the influence of calcium carbonate (CaCO₃), a widely used filler, on the fire retardancy of intumescent polypropylene composites. Two intumescent systems based on (1) mixture of ammonium polyphosphate (APP) and pentaerythritol and (2) surface‐modified APP (m‐APP) were examined. In terms of steady heat release rate, total heat evolved, and fire growth index determined by mass loss calorimetry, m‐APP performed markedly superior to APP‐pentaerythritol. The presence of CaCO₃ in both intumescent formulations caused significant losses in fire retardant performance assessed by mass loss calorimetry, limiting oxygen index and UL‐94 tests. Peak rates of heat release and mass loss during combustion, and total heat evolved on combustion were increased, whereas time to ignition was decreased. Characterization of fire residues ascribed the mechanism of deterioration in fire retardancy to the formation of porous and nonexpanded crystalline calcium phosphate/CaCO₃ residues during combustion rather than the amorphous protective intumescent chars formed in the absence of CaCO₃. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

珍珠岩对水性膨胀型聚氨酯/醋丙防火涂料防火性能的影响

以热固性的聚氨酯-丙烯酸酯乳液和热塑性的醋丙乳液复配为成膜物、聚磷酸铵为酸源、白糖为碳源、双氰胺和磷酸氢二铵为气源、珍珠岩为阻燃协助剂,制备了膨胀型水性防火涂料。采用模拟大板燃烧法对其耐火性能进行了研究,并用数码相机和光学显微镜观察其碳孔状况,结果表明：开孔膨胀珍珠岩对防火涂料的耐火性能有良好的协助作用,经碳层光学照片分析表明添加珍珠岩后也有利于改善膨胀碳层的性能。     

透明膨胀型氨基树脂基阻燃涂料的研究进展及趋势

分析了氨基树脂作为透明膨胀型阻燃涂料成膜物质的优势,综述了透明膨胀型氨基树脂基阻燃涂料的国内外研究进展,提出了现阶段该涂料产品存在的问题,阐述了透明膨胀型氨基树脂基阻燃涂料未来的研究方向。指出了透明膨胀型氨基树脂基阻燃涂料的研究重心已从关注其理化性能和膨胀阻燃性能,逐渐转向探求技术问题出现的根本原因。     

叶蜡石改性膨胀型涂料阻燃性能研究

为了提高木质胶合板的阻燃性能,以聚磷酸铵(APP)-季戊四醇(PER)-尿素为基础配方,叶蜡石粉作为改性添加剂制备膨胀型阻燃涂料(IFRC);采用锥形量热仪、静态接触角测量仪、扫描电镜、X射线衍射仪和拉力机等仪器对试样的阻燃性能、疏水性能和力学性能进行了表征,并且研究了叶蜡石粉含量对所制备涂料性能的影响。结果表明:在膨胀型阻燃涂料中加入适量的叶蜡石可以提高涂料的阻燃效果,当掺加叶蜡石粉的质量分数为2%时,涂料的火灾增长指数(FGI)降低了47%,火灾性能指数(FPI)增加了89%,并且阻燃性能指数(FRI)提高至2.5倍;叶蜡石粉的加入促进涂层在燃烧过程中形成连续致密的炭层结构,并形成了可以有效隔绝氧气和热量的熔融态物质,进一步增强了涂料的阻燃隔热性能;此时涂层的疏水性能和燃烧后木质胶合板的力学性能达到最佳,水接触角增大了8°,拉伸强度提高了45%,断裂伸长率也提高至8.5倍。本文研究结果对木质胶合板阻燃体系涂料配方的开发有一定的参考作用。     

Effects of natural weathering on the fire properties of intumescent fire‐retardant coatings

Fire‐retardant coatings could be one option for providing enhanced protection to buildings during a wildfire, particularly when applied to combustible siding and in under‐eave areas. Limited studies have been conducted on their effectiveness but maintaining adequate performance after weathering has been questioned. This paper reports on a study evaluating the effect of natural weathering on the performance of intumescent‐type fire‐retardant coatings. The main concerns were (a) the reduction of ignition resistance of the coating after weathering and (b) the coating might contribute as a combustible fuel and assist the fire growth after weathering. This study evaluated the performance of 3 intumescent coatings that were exposed to natural weathering conditions for up to 12 months. A bench‐scale evaluation using a cone calorimeter was used to evaluate the performance of the coatings at 3 heat flux levels (30, 50, and 70 kW/m²). Our results showed that weathering exposure reduced the effectiveness of fire protection of intumescent coatings, but the weathered coatings did not act as additional fuels. Weathering orientation showed much less effect on the performance of intumescent coatings in comparison to other parameters. There was statistical evidence that weathering duration, heat flux level, and coating type affected the combustion properties.     

Acrylic-based fire-retardant coatings for steel protection: Employing the concept of in situ ceramization

Traditional intumescent coatings are widely used as passive fire-protective coatings for steel structures as they are capable of expanding in the range of 20–50 times the original thickness thereby providing excellent insulation. However, the fragile nature of such residue and susceptibility to thermo-oxidation given their carbonaceous nature are key problematic issues. The concept of in situ ceramization is explored in this work as a means to form inorganic cohesive char with improved rigidity and thermo-oxidative stability. Coating samples were prepared by incorporating ammonium polyphosphate, talc, Mg(OH)₂, and polydimethylsiloxane as additives into acrylic resin at different weight fractions. Thermal analysis and x-ray diffraction have confirmed the reactions between the additives to form various crystalline magnesium phosphate phases, and to a small extent, silicon phosphate, thereby ensuring the thermo-oxidative stability of the residue. This is reiterated by the fire performance tests (by exposing the coatings to a temperature profile in a furnace similar to ISO 834 fire curve). Despite the advantages of rigid char and its thermo-oxidative stability as a result of formation of inorganic phosphates, the lack of swelling has resulted in relatively poor insulation capabilities of the char, and subsequently, compromised the fire protection times (that are in the range of 45–55 min). However, pyrolysis flow combustion calorimeter results of the coatings are promising and have shown a significant drop of up to 70% in the peak of heat release rate values as compared to neat resin.     

Influence of the pentaerythritol phosphate melamine salt content on the combustion and thermal decomposition process of intumescent flame‐retardant ethylene–vinyl acetate copolymer composites

Pentaerythritol phosphate melamine salt (PPMS) as a single‐molecule intumescent fire retardant was synthesized and characterized. The influence of the PPMS content on the combustion and thermal decomposition processes of intumescent‐flame‐retardant (IFR) ethylene–vinyl acetate copolymer (EVA) composites was studied by limiting oxygen index (LOI) measurement, UL 94 rating testing, cone calorimetry, thermogravimetric analysis, and scanning electron microscopy. The LOI and UL 94 rating results illustrate that PPMS used in EVA improved the flame retardancy of the EVA composites. The cone calorimetry test results show that the addition of PPMS significantly decreased the heat‐release rate, total heat release, and smoke‐production rate and enhanced the residual char fire performance of the EVA composites. The IFR–EVA3 composite showed the lowest heat‐release and smoke‐production rates and the highest char residue; this means that the IFR–EVA3 composite had the best flame retardancy. The thermogravimetry results show that the IFR–EVA composites had more residual char than pure EVA; the char residue yield increased with increasing PPMS content. The analysis results for the char residue structures also illustrated that the addition of PPMS into the EVA resin helped to enhance the fire properties of the char layer and improve the flame retardancy of the EVA composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42148.     

Intumescent char structures and flame‐retardant mechanism of expandable graphite‐based halogen‐free flame‐retardant linear low density polyethylene blends

The structures of the intumescent charred layers formed from expandable graphite (EG)‐based intumescent halogen‐free flame retardant (HFFR) linear low‐density polyethylene (LLDPE) blends and their flame‐retardant mechanism in the condensed phase have been studied by dynamic Fourier transform infrared (FTIR), X‐ray photoelectron spectroscopy (XPS), laser Raman spectroscopy (LRS), scanning electron microscopy (SEM), differential thermal analysis (DTA) and thermal conductivity (TC) measurements. The dynamic FTIR, XPS and LRS data show that the carbonaceous structures of intumescent charred layers consist of EG and various numbers of condensed benzene rings and/or phosphocarbonaceous complexes attached by the P? O? C and P? N bonds or quaternary nitrogen products. The addition of EG can hasten the formation of these phosphocarbonaceous structures. The above results show that the flame‐retardant mechanism in the condensed phase is that the compact char structures, as observed by SEM, slow down heat and mass transfer between the gas and condensed phase and prevent the underlying polymeric substrate from further attack by heat flux in a flame. The DTA and TC data show that carbonaceous charred layers are good heat‐insulating materials, the TC value of which is only about one‐tenth of that of the corresponding blend and that they increase the oxidization temperature and decrease thermal oxidization heat of the LLDPE/EG/HFFR systems. © 2003 Society of Chemical Industry     

Intumescent flame retardant TPO composites: Flame retardant properties and morphology of the charred layer

Intumescent flame retardant thermoplastic polyolefin (TPO) composites were prepared to study the relationships between their structure of charred layer (including of the multicellular intumescent layer and the charry layer) and flame retardant properties. They were characterized using the LOI and UL‐94 test, which indicated that the best fire retardant behavior (V‐0 rating and LOI reach to 28.1%) was obtained at the formulation of TPO/ammonium dihydrogen phosphate/starch (100/60/20). Thermal gravimetric analysis demonstrated that the presence of ammonium dihydrogen phosphate/starch promoted the esterification and carbonization process in lower temperature range while enhancing the thermal stability of intumescent flame retardant TPO in high‐temperature range. Scanning electron microscope and optical microscope were shown that, with combustion time prolonged, the intumescent layers obtained greater number of cells, and the charry layer became more compact while the size of the carbon granules became smaller on the surface. Introduction of starch had an obvious effect on the structure of the intumescent and charry layers. The charry layer of the composites with the content of 20 phr starch was more compact and uniform than that of the composites with 50 phr. The weight ratio of ammonium dihydrogen phosphate to starch in the intumescent flame retardant was fixed as 3 : 1 which cooperated with each other well to promote a compact charry layer and to obtain the better flame retardancy performance. Therefore, the better the charred layers produced, and the better flame retardant properties they obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

一种超薄膨胀型钢结构防火涂料的研制

以磷酸二氢铵、季戊四醇、三聚氰胺及丙烯酸树脂为原料研制了一种超薄膨胀型丙烯酸树脂钢结构防火涂料。并依据国家标准测定了不同配方防火涂料的理化性能和防火性能,分析了防火涂料的作用过程,给出了性能优异的配方设计。     

Synergistic effects of aluminum hydroxide on improving the flame retardancy and smoke suppression properties of transparent intumescent fire-retardant coatings

A series of novel aluminum phosphate ester (APEA) flame retardants were synthesized by the salification of cyclic phosphate ester acid (PEA) with different mass ratios of aluminum hydroxide (ATH) and thoroughly characterized by Fourier transform infrared (FTIR) spectroscopy and ¹H nuclear magnetic resonance spectroscopy. The PEA and APEAs were thoroughly mixed with melamine formaldehyde resin to produce five kinds of transparent fire-retardant coatings. The synergistic effects of ATH on the thermal stability, flame retardancy, and smoke suppression properties of the coatings were investigated by different analytical instruments. The results show that the incorporation of ATH greatly decreases the weight loss, char index, flame spread rating, heat release rate, total heat release, smoke production rate, total smoke release and specific optical density in the coatings applied to plywood boards, which is ascribed to a more compact and intumescent char formed during burning, as determined from digital photographs and scanning electron microscopy images. The synergistic effects of ATH in the coatings depend on the content of ATH, and an excessive amount of ATH diminishes the synergistic effects on the flame retardancy and smoke suppression properties based on fire protection tests and cone calorimeter test. Thermo-gravimetric analysis reveals that the thermal stability and char-forming ability of the coatings gradually improve with increasing loading of ATH. FTIR analysis demonstrates that the incorporation of ATH forms a more phosphorus-rich crosslinked char and aromatic char during burning, thus effectively reducing the mass loss, heat release, and smoke production and exhibiting excellent synergistic flame retardant and smoke suppression effects in the coatings.     

Thermal degradation and fire performance of wood treated with PMUF resin and boron compounds

Plantation Chinese fir wood was modified by low molecular weight phenol melamine urea formaldehyde (PMUF) resin, boron compounds (BB), and the mixture of PMUF/BB (PMUF‐BB), followed by a curing step. The fire performance and thermal degradation of wood was measured by limiting oxygen index instrument, cone calorimeter, and simultaneous thermal analysis. The results showed that the limiting oxygen index increased to 50.7%, 43.5%, and 55.0% for BB, PMUF, and PMUF‐BB samples, respectively. The PMUF resin decreased the heat release rate of wood but increased the total heat release compared with the control samples. The thermal analysis results demonstrated that PMUF resin enhanced the thermal stability of wood, however, had little impact on the residual chars. Combinative treatment with boron compounds could substantially reduce the fire risk for PMUF‐modified wood, making them especially useful for application in public settings.     

超薄膨胀型钢结构防火涂料的研制

以磷酸二氢铵、季戊四醇、三聚氰胺及丙烯酸树脂为原料研制了一种超薄膨胀型丙烯酸树脂钢结构防火涂料。并依据国家标准测定了不同配方防火涂料的理化性能和防火性能,分析了防火涂料的作用过程,并提供了相应的检测标准和测试结果,给出了性能优异的配方。阻燃体系(磷酸二氢铵、季戊四醇、三聚氰胺)的分解温度对防火涂料的性能有明显的影响;该配方使用原料简单、来源丰富、成本低、防火性能好。     

水性环氧乳液改善膨胀型醋丙涂料的防火性能

以聚磷酸铵为酸源、季戊四醇为碳源、双氰胺和磷酸氢二铵为气源、热固性的水性环氧乳液和热塑性的醋-丙乳液复配为成膜物,制备了膨胀型水性防火涂料.采用模拟大板燃烧法对其耐火性能进行了研究,并用傅里叶红外光谱仪(FT - IR)分析灼烧后膨胀炭层的成分,用电子显微镜观察炭层的炭孔状况.结果表明:热固性的水性环氧乳液能有效提高膨胀型醋-丙防火涂料的防火隔热性能.当添加量为6％(质量分数)时,灼烧60 min后,炭层整体强度达到2.26 N/cm2,膨胀倍率为37倍,木板背火温度仅66℃,红外光谱分析表明炭层与木板连接处还有成膜物存在.另外,炭层电镜照片分析表明添加水性环氧乳液后也有利于改善膨胀炭层的质量.     

Construction of multilayer coatings for flame retardancy of ramie fabric using layer‐by‐layer assembly

Complex multilayer coatings composed of α‐zirconium phosphate (ZrP), polyethylenimine (PEI), and ammonium polyphosphate (APP) were constructed via layer‐by‐layer assembly method for flame retardant ramie fabric. Bicomponent PEI/ZrP layers served as insulating barrier coating, and bicomponent PEI/APP layers served as intumescent coating. The flame retardancy of the coated ramie fabric was strongly dependent on the nature of the coatings and the layer‐by‐layer assembly patterns. The coated ramie fabric with inside PEI/ZrP layers and outside PEI/APP layers possessed the most uniform and consistent coating surface morphology, as well as the highest content of N and P elements, resulting in an excellent improvement in flame retardancy of ramie fabrics. When this kind of coated ramie fabric was heated, the inner PEI/ZrP layer effectively prevent oxygen and heat from penetrating into the substrate, and the outer PEI/APP layer exposed to air with good expansion during combustion. The synergistic effect was formed during the combustion process and could impart ramie fabrics with high flame retardancy. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45556.     

Combined effects of layered nanofillers and intumescent flame retardant on thermal and fire behavior of ABS resin

The application of acrylonitrile-butadiene-styrene (ABS) copolymer as construction material is largely restricted by its inherent flammability and the release of a great amount of smoke and toxic gases during combustion. To address this issue, the combination of conventional flame retardants and nanoadditives was proven to be a promising way. Herein, both intumescent flame retardants (IFR) and layered nanofillers, that is, graphene and layered double hydroxide were added into ABS resin. These nanofillers exhibited superior dispersion in the ABS matrix. Thermal and fire behaviors of ABS resin were investigated by thermogravimetry analysis, UL-94 vertical burning test, limiting oxygen index test, and cone calorimetry. The ABS composites containing IFR and layered nanofillers presented remarkable decline in total heat release, peak heat release rate, and volume of toxic effluents released in the burning process compared with those of neat ABS, indicating the significantly improved fire safety of ABS. Moreover, introducing layered nanofillers could further enhance the heat stability and fire safety of the flame-retardant ABS composites, indicating the presence of synergistic effect between IFR and layered nanofillers. The scanning electron microscopy and Raman spectroscopy results confirmed the formation of compact and dense intumescent chars, which could obstruct the spread of heat and mass, and thus improved the heat stability and flame retardancy of ABS resin. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48220.     

Burning rate of solid wood measured in a heat release rate calorimeter

Burning rate is a key factor in modeling fire growth and fire endurance of wood structures. This study investigated the burning rate of selected wood materials as determined by heat release, mass, loss and charring rates. Thick samples of redwood, southern pine, red oak and basswood were tested in a heat release rate calorimeter. Results on ignitability and average heat release, mass loss and charring rates are reported for a heat flux range between 15 and 55 kw m^?2. In this range, burning rate increased linearly with heat flux. Burning rate was very species dependent. Heat release rate was related to mass loss by effective heat of combustion, which also increased with heat flux. Charring rate was related to mass loss rate and original wood density. Important char property data such as yield, density and contraction are reported. A simplified calculation method is proposed for calculating mass loss rate and charring rate based on heat release rate.     

Update for combustion properties of wood components

The combustion properties of various biomass and wood materials from various references and from our laboratory were reanalysed. The net heat of combustion for cellulosic materials was found to be 13.23 kJ/g times the ratio of stoichiometric oxygen mass to fuel mass, r_o, regardless of the material composition. Bomb calorimeter data for original, charred and volatilized material components provide gross heating values, while elemental analysis of the materials for carbon, hydrogen, oxygen and ash provide direct evaluation for r_o. We corrected these data as provided in various references by converting gross heating values to lower heating values and converting elemental compositions, char fractions and r_o to a moisture‐free and ash‐free basis. Some existing formulae were found to disagree with data from vegetation, charred wood with high ash content, and with volatiles from cellulose treated with the fire retardant NaOH. We also established various functional correlations of r_o with elemental compositions, or volatization fractions of untreated and treated materials, or material fractions for cellulose, lignin and extractives, or volatile fractions for tar, combustible gases and inert gases in pure nitrogen carrier gas. An interesting predictive result provides nearly constant heat of combustion while the volatile tar fraction is decreasing and combustible and inert gas fractions are increasing with time during the charring of Douglas‐fir wood. Published in 2002 John Wiley & Sons, Ltd.     

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