Effect of expandable graphite and ammonium polyphosphate on the thermal degradation and weathering of intumescent fire-retardant coating

This research aims to study the effect of ammonium polyphosphate and expandable graphite on the intumescent coating formulations (ICF). The coating presented in this research article is based on carbon source expandable graphite (EG), blowing agent melamine, acid source ammonium polyphosphate (APP), epoxy resin as a binder with polyamide amine. The stability of the developed coating was verified at 950°C for 1-hour fire test. The results showed that the coating is stable and well bond with the steel substrate. The char was characterized by using FESEM, XRD, FTIR, DTA, TGA, XPS, Py-GCMS and Weathering Test. The morphology of the char was studied by SEM of the coating after furnace fire test. XRD and FTIR show the presence of graphite, borophosphate; boron oxide and sassolite in the residual char. TGA and DTG disclosed that EG improved the residual mass of coating. XPS analysis showed the char residue of IF5-APP-EG contains carbon and oxygen contents 47.50 and 40.70, respectively. Py-GCMS analysis described that the IF5-APP-EG released less gaseous compounds. The weathering test illustrated that's the char expansion of coatings samples was decreased due to the presence of a humid environment and UV light. The IF5-APP-EG showed the maximum char expansion, lower substrate temperature and high residual weight among the studied formulations.     

Effect of boric acid and melamine on the intumescent fire‐retardant coating composition for the fire protection of structural steel substrates

Intumescent coating is an insulating material designed to decrease heat transfer to a substrate structure. The coating presented in this research article was based on expandable graphite, ammonium polyphosphate, melamine, and boric acid. Bisphenol A epoxy resin BE‐188 was used as a binder with ACR hardener H‐2310 polyamide amine. Different formulations were developed to study the effect of expansion and heat shielding after fire testing. The coating was tested at 950°C for 1 h. The results show that the coating was stable and well bonded with the substrate. The coating was characterized with thermogravimetric analysis (TGA, Parkin Elmer, Norwalk, CT, 06859, USA), Fourier transform infrared (FTIR, Nicolet 400 D Shimadzu spectrometer) spectroscopy, X‐ray diffraction (XRD, Bruker D8 advance Diffracto meter, Bruker Germany), and scanning electron microscopy (SEM, Carl Zeiss Leo 1430VP, UK). The morphology of char was studied by SEM on the coating after fire testing. XRD and FTIR spectroscopy showed the presence of graphite, boron phosphate, boron oxide, and sassolite in the residual char. TGA (Pyris 1, manufactured by Parkin Elmer, Norwalk, CT, 06859, USA) and differential thermal gravimetric analysis (DTGA) showed that boric acid enhanced the residual weight of the intumescent fire‐retardant coating. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

水性超薄膨胀型钢结构防火涂料的制备

以有机硅改性的丙烯酸酯乳液为基料,多聚磷酸铵(APP)、季戊四醇(PER)、三聚氰胺(MEL)为膨胀阻燃体系,制备水性超薄膨胀型钢结构防火涂料;采用硼酸和可膨胀石墨(EG)改性防火涂料。研究表明,同时用w(硼酸)=4%,w(EG)=5%改性防火涂料,涂层的耐火极限达到93 min,热失质量分析(TGA)测试表明w(硼酸)=4%,w(EG)=5%共同改性的防火涂料在700℃时最终残炭量是44%。扫描电镜(SEM)分析结果表明硼酸/EG改性的残炭层形成了致密的"蜂窝"状结构。     

Effects of inorganic fillers on the performance of the water-based intumescent fire-retardant coating

The purpose of this research was to evaluate the influences of filler type and its content on the performance of a water-based intumescent fire-retardant coating. Three fillers (vermiculite, celite, and aluminum hydroxide) were added to the intumescent paint formulation. The thermal and fire protective properties were studied with thermogravimetric analysis (TGA), torch test, electrical furnace, scanning electron microscopy (SEM), and Fourier transform infrared analysis (FTIR). The results showed that adding fillers into coatings up to 3% could improve the intumescent coating's behavior and increase its endurance against flames. Of the three fillers used, vermiculite showed a better performance in the torch test, attributed to its chemical and physical structure. Vermiculite has low thermal conductivity and is considered an appropriate filler for heat-insulation. The final back-plate temperatures in the torch test for the vermiculite-containing samples were around 100°C–150°C lower than that of other samples. Moreover, vermiculite's addition improved the coating's expansion by 10% compared with the control sample's. The vermiculite sample's char layer morphology showed a uniform cell size distribution, indicating structural robustness. The coating samples successfully transformed polypropylene flammability from highly flammable to V0 level in the UL 94 vertical burning test standard. The results showed that vermiculite could improve intumescent paint's fire resistance and be used as an enhancer in intumescent coating formulations.     

Influence of heat-stable filler on the thermal shielding performance of water-based intumescent fire-resistive coating for structural steel applications

Intumescent coatings are the newest passive fireproofing materials which maintain structural integrity of high-rise buildings in fire events. The present work focuses on the influence of zirconium silicate as a heat-stable filler in intumescent coatings. Different coatings were formulated by varying the zirconium silicate concentration from 1, 3, 5, 8, and 10 on parts per hundred basis (phr). Fire performance of the coatings was then determined by fire test using a Bunsen burner fire flame at 950°C for 1 h. The degradation of coatings was examined by thermogravimetric analysis (TGA). The morphology of the intumescent chars was analyzed by environmental scanning electron microscopy. The char was also examined by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy. XRD confirmed the inertness of zirconium silicate with intumescent ingredients at high temperatures. TGA showed an increase in the weight residue of char at high temperature. The incorporation of zirconium silicate into intumescent coating forms a thermally stable char with better substrate adhesion. EDS analysis confirmed an increase in the antioxidation property of the char, and the fire test also confirmed an increase in char strength of coatings by the incorporation of zirconium silicate.     

可膨胀石墨在膨胀型钢结构防火涂料中的应用

为了改善钢结构防火涂料膨胀炭质层蓬松易脱落和易开裂的缺点,将可膨胀石墨(EG)添加到防火涂料中,通过耐火实验来研究EG对炭质层形貌和钢结构耐火极限的影响。结果表明,EG膨胀后成“蠕虫”状穿插于膨胀炭质层中,起到增强作用,使炭质层结构更致密。热分析结果表明,w(EG) =6 7%时,防火涂料在600℃时的热失重减少了7%;w(EG) =0 5%时,钢结构耐火极限延长了10min。     

新型阻燃体系对木塑防火涂层阻燃性能的影响

采用隔热性能试验、热失重分析(TG)、傅里叶红外光谱分析(FTIR)以及显微分析等方法,研究了两种改性材料膨胀石墨(EG)和云母对膨胀防火涂层防火性能和热降解行为的影响。结果表明:EG与云母加入后不会改变涂层的基本阻燃进程,且会提高膨胀炭质层的热稳定性,涂层的阻燃效果显著改善。     

海泡石和EG对水性膨胀型钢结构防火涂料的影响

采用可膨胀性石墨(EG)和海泡石对传统的APP/PER/MEL膨胀型防火涂料体系进行改性,制备了一种新型水性超薄膨胀型防火涂料,并采用防火性能测试装置、热重分析(TGA)、差热重量分析(DTG)及X射线衍射(XRD)等方法对该防火涂料的耐火性能、热降解过程、炭化层结构进行了研究。热分析结果表明,海泡石与EG复合使用,将充分发挥它们的协同作用:EG在较低温度区域能够延缓炭化层的形成,而海泡石则能够在高温区域阻止炭化层氧化分解,并提高成炭率从而达到阻燃的目的。XRD结果显示,复合使用EG和海泡石能够促进炭化层中TiP2O7的形成,在高温阶段保护炭化层不被氧化。当防火涂料中添加质量分数3%海泡石和质量分数2%EG,涂层厚度为1.0 mm时,钢材的耐火时间达到72 min。     

Influence of nano-boron nitride on anti-aging property of waterborne fire-resistive coatings

The influence of nano-boron nitride (BN) with a multilayered structure on the anti-aging property of fire-resistive coatings was studied. After accelerated weathering for 20 days, the thermal stabilities and fire protection of the coating without nano-BN were significantly decreased, but the coating modified by nano-BN still maintained excellent intumescent effect and fire protection. The results indicated that nano-BN could improve the anti-aging property of the coatings remarkably. FTIR and XPS characterizations suggested that nano-BN with a multilayered structure could prevent the migration behavior of the hydrophilic fire-retardant additives and keep the fixed ratio of those additives in the coating. TGA results demonstrated that nano-BN could effectively enhance the thermal stabilities of the aged coatings and improve the anti-oxidation property of the char layers formed by the coatings. XRD and EDS results proved that the anti-oxidation of the aged coatings under high temperature could be enhanced effectively after adding nano-BN. SEM observations illustrated that nano-BN addition was beneficial to the improvement of the foam structure of the aged coating.     

MoO3与可膨胀石墨改性聚磷酸铵/季戊四醇/三聚氰胺防火涂料研究

采用MoO3、可膨胀石墨(EG)和MoO3/EG对APP/PER/MEL膨胀防火涂料进行改性,制备成改性涂料,运用隔热性能分析和热重分析(TGA)测试改性涂料的耐火极限和残碳率.结合扫描电镜分析结果,探讨MoO.EG和MoO3/EG对涂料耐火性能提高的途径分别为MoO3通过与APP/PER/MEL涂料体系作用提高了涂料残碳率;EG通过自身膨胀产生"蠕虫"结构显著改善了碳层结构;而MoO3/EG则通过MoO3和EG各自的作用,产生了明显的协同增效效果.     

Influences of glass flakes on fire protection and water resistance of waterborne intumescent fire resistive coating for steel structure

Glass flake (GF) was used as a modifier to improve the fire protection and water resistance of waterborne intumescent fire resistive coating. The influences of GF on the properties of the coatings were investigated in detail by using TGA, XRD, X-ray fluorescence spectrometry (XRF), SEM and fire protection test. The TGA results proved that addition of GF could enhance the anti-oxidation of the char layers and increase the residue weights of the coatings. The XRF results indicated that anti-oxidation of the coatings modified by GF was improved. The SEM images demonstrated that addition of GF could improve the foam structure of the coatings. After immersed in water over 600 h, the results showed that the thermal stability and fire protection of the coating without GF were significant decreased, but the coatings modified by GF could still maintain the excellent intumescent effect and fire protection.     

Thermal degradation study of fire resistive coating containing melamine polyphosphate and dipentaerythritol

A melamine polyphosphate (MPP)/dipentaerythritol (DPER) mixture was used as fire retardant additives for preparing waterborne intumescent fire resistive coating. The thermal degradation of the MPP/DPER mixture and of the coating was studied by TGA and FTIR. The resulting char of the coating was investigated by XPS, SEM and energy dispersive spectroscopy (EDS). The results showed that the thermal degradation behavior of the MPP/DPER mixture was similar to that of the coating. They decomposed to nonflammable gases, and formed intumescent char layer containing phosphorus oxide at high temperature. The EDS results proved that the resulting char was gradually oxidized with the temperature increase. The SEM micrographs showed that the average cell size of the char layers became bigger and the cell size distribution became wider as the temperature increased from 500 °C to 800 °C, and this non-uniform char layer could damage the fire protection of the coating.     

海泡石和可膨胀性石墨对水性超薄膨胀型钢结构防火涂料阻燃性能的影响

采用可膨胀性石墨（EG）和海泡石对传统的APP/PER/MEL膨胀型防火涂料体系进行改性,制备了一种新型水性超薄膨胀型防火涂料,并采用防火性能测试装置、热重分析（TGA）、差热重量分析（DTG）及X射线衍射（XRD）等方法对该防火涂料的耐火性能、热降解过程、碳化层结构进行了研究。热分析结果表明,海泡石与EG复合使用,将充分发挥它们的协同作用：EG在较低温度区域能够延缓碳化层的形成,而海泡石则能够在高温区域阻止碳化层氧化分解,并提高成炭率从而达到阻燃的目的。XRD结果显示,复合使用EG和海泡石能够促进碳化层中TiP2O7的形成,在高温阶段保护碳化层不被氧化。当防火涂料中添加3wt%海泡石和2wt%EG,涂层厚度为1mm时,钢材的耐火时间达到72min。     

Thermal degradation study of fire resistive coating containing melamine polyphosphate and dipentaerythritol

A melamine polyphosphate (MPP)/dipentaerythritol (DPER) mixture was used as fire retardant additives for preparing waterborne intumescent fire resistive coating. The thermal degradation of the MPP/DPER mixture and of the coating was studied by TGA and FTIR. The resulting char of the coating was investigated by XPS, SEM and energy dispersive spectroscopy (EDS). The results showed that the thermal degradation behavior of the MPP/DPER mixture was similar to that of the coating. They decomposed to nonflammable gases, and formed intumescent char layer containing phosphorus oxide at high temperature. The EDS results proved that the resulting char was gradually oxidized with the temperature increase. The SEM micrographs showed that the average cell size of the char layers became bigger and the cell size distribution became wider as the temperature increased from 500 °C to 800 °C, and this non-uniform char layer could damage the fire protection of the coating.     

Influence of hydrothermal aging process on components and properties of waterborne fire-resistive coatings

The changes in fire-resistive coatings during the aging process were studied. XPS results proved that the hydrophilic components in fire-resistive coatings migrated from the inside to the outside of the coating in the presence of moisture. This migration behavior changed the compositions and distributions in the coating. The changes of components weakened the intumescent performances of the coating. SEM observations showed that the aging process affected the forming of the foam structure, causing nonuniform distribution of the cells. The thermal stability of the coatings decreased during the aging time. TGA results indicated that the migration behavior also reduced the cooperation between the coating components. XRD spectra showed that less TiP₂O₇ was produced in the char layer after the aging tests, which would reduce the chemical strength of the char layer and the anti-ablation stability under high temperature. EDS results showed that the anti-oxidation property of the coating was also damaged by the aging test.     

Influences of silicone emulsion on fire protection of waterborne intumescent fire-resistive coating

The combination of self-crosslinking polyacrylate emulsion and silicone emulsion was used as a binder for the preparation of waterborne intumescent fire-resistive coatings. The influences of silicone emulsion on fire protection and char formation of the coatings were investigated in detail by means of TGA, SEM, energy dispersive spectroscopy analysis, rheological measurement, and fire protection tests. The results showed that using silicone emulsion improved thermal stability and antioxidation ability of the coating and increased the residue weights of the char layer at high temperature. Furthermore, an appropriate amount of silicone emulsion could improve the rheological property of the mixed binders and be conducive to the increase of the intumescent factor of the coatings, thus improving the fire protection of the coating significantly. However, an excess amount of silicone emulsion can lead to uneven dispersion of silicone emulsion in the mixed binder and cause an uneven distribution of cell size of the char layer.     

水性钢结构防火涂料的制备及其耐火性能研究

以水性树脂为基体,聚磷酸铵(APP)、三聚氰胺(MEL)、季戊四醇(PER)为膨胀阻燃体系,可膨胀石墨(EG)和绢云母为填料制备了水性膨胀型钢结构防火涂料;研究了基体拼合、膨胀阻燃体系、EG与绢云母配比对钢结构防火涂料性能的影响。结果表明:氯偏乳液与纯丙AC261P乳液质量比为22:3,APP、MEL、PER的质量比为4:3:3,可膨胀石墨和绢云母的质量比为5:3时,制备的防火涂料涂层受热膨胀倍率为5.68倍,形成了"蜂窝状"结构的膨胀炭质层,孔洞均匀致密,与钢板粘附性好、强度高,耐火性能好,耐火极限高达2 997 s。     

Study on the preparation and properties of novel transparent fire-resistive coatings

A cyclic polyphosphate (CPPA) was synthesized by the reaction of polyphosphoric acid and pentaerythritol. Polyethylene glycol (PEG) was introduced in the structure of CPPA to improve its solubility in water and ethanol and five kinds of reactive type flame retardants (MCPPA) were obtained. ³¹P NMR, ¹H NMR, FTIR, and TGA were used to characterize the composition and structure of CPPA and MCPPAs. The experimental results showed that there were 25% cyclic P–O–C structures in the product and MCPPA had better carbonization ability than CPPA. Five kinds of transparent fire-resistive coatings were prepared by the mixing of amino resin with five kinds of MCPPAs. The results of the fire protection test showed that both the fire-resistive time of coatings and intumescent factor of char layers decreased with the increase of molecular weight of PEG. The results of TGA and EDS showed that the carbonaceous residue of coatings and the antioxidation ability of char layers also decreased regularly with the increase of molecular weight of PEG. The SEM images demonstrated that the coating prepared with low molecular weight of PEG contributed to dense form structure and narrow distribution of cell size. Above all, the transparent fire-resistive coating prepared with PEG 200 had the best fire retardancy and stable thermal behavior.     

氧化石墨烯提高钢结构水性膨胀防火涂料的防火性能研究

以水性丙烯酸树脂为基体,聚磷酸胺、季戊四醇和三聚氰胺为膨胀阻燃体系,加入少量氧化石墨烯制备水性膨胀防火涂料。采用小板燃烧法研究了氧化石墨烯用量对膨胀型防火涂料的阻燃性能的影响。结果表明:加入极少量氧化石墨烯(<0.01%),可提高涂料的阻燃性,当氧化石墨烯含量在0.005%时,涂层的耐燃时间可达432 s,炭层膨胀高度较未加氧化石墨烯涂层增加了13.04%。结合红外光谱(FT-IR)、X射线衍射(XRD)和扫描电子显微镜(SEM)等表征手段对炭层形貌进行分析可知,加入氧化石墨烯后炭层在300~500 ℃范围的热稳定性提高,燃烧炭层完整密实,隔热性能提高,耐燃时间提高。     

水性超薄膨胀型防火涂料的制备与性能研究

以水性乳液为基体,化学膨胀与物理膨胀相结合的阻燃膨胀体系,其中聚磷酸铵(APP)、三聚氰胺(MEL)、双季戊四醇(DPE)为化学膨胀体系,可膨胀石墨(EG)、石英纤维为物理膨胀体系,制备水性超薄膨胀型防火涂料.考察了基体类型、膨胀阻燃体系配比对水性防火涂料防火性能的影响.结果表明,聚醋酸乙烯酯乳液与纯丙乳液质量为比1∶...