Effects of expandable graphite on char morphology and pyrolysis of epoxy based intumescent fire-retardant coating

The current study was designed to investigate the effects of expandable graphite (EG) on fire protection properties of intumescent fire-retardant coating for steel structures. Several formulations of intumescent coating were prepared and tested according to ISO 834 for char expansion. The chars were found without cracks and bonded with the steel substrate. The results showed that the coating slowly degraded during the test and char remained in contact with vertically tested coated substrate. The coated substrates were also tested for weather resistance using humid and ultraviolet environment. The char was characterized by using FESEM, XRD, FTIR, TGA, and XPS analysis. FESEM examined char morphology of the coatings after furnace fire test. XRD and FTIR showed the presence of graphite, borophosphate; boron oxide and sassolite in the char. TGA and DTGA results disclosed that EG improved the residual mass of coating. XPS analysis showed the percentages of carbon and oxygen are 48.50 and 43.45 in char of formulation with 12.8% EG. The results of weathering test coatings showed decreased in char expansion because of a humidity and UV light. The formulation with 9.8% EG showed the maximum char expansion and high residual mass among the formulations investigated in this study. The weathering tested coated samples showed their capability of fire protection.     

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。     

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.     

Expandable graphite's versatility and synergy with carbon black and ammonium polyphosphate in improving antistatic and fire‐retardant properties of wood flour/polypropylene composites

This study investigated the antistatic and fire‐retardant properties of wood flour/polypropylene composites consisting of carbon black (CB), ammonium polyphosphate (APP), and expandable graphite (EG) through resistance meter measurement, cone calorimetry (CONE), thermogravimetric analysis (TGA), and scanning electron microscopy. Antistatic property testing confirmed a positive effect between CB and EG on discharging electrostatic charge. Electrostatic charge was thus considered able to be conducted between CB particles through EG, which acted as a bridge in the CB/EG ‐ treated composites. The results of CONE tests showed that EG significantly reduced the smoke release of the wood plastic composites (WPCs), including total smoke release (TSR), average specific extinction area (SEA), and production of carbon monoxide. During the WPCs burning process, a compound of EG and APP showed synergistic effects which decreased heat release and fixed the residual char. TGA results demonstrated that combining EG with APP, as opposed to using EG only, effectively increased the residual mass and decreases the initial thermal decomposition temperature of the WPCs. Addition of APP caused the wood flour char by catalyzing at a lower temperature, moreover, EG and APP displayed good synergistic effects on fire inhibition and smoke suppression. POLYM. COMPOS., 38:767–773, 2017. © 2015 Society of Plastics Engineers     

Enhanced fire behavior of rigid polyurethane foam by intumescent flame retardants

Using expandable graphite (EG) and ammonium polyphosphate (APP) as flame retardants, we prepared two series of polyisocyanurate–polyurethane (PIR–PUR) foams (i.e., EG foams filled with different amounts of EG alone and APEG foams containing different amounts of expanded EG and APP) and evaluated the effect of the additives on the physical–mechanical property, fire behavior and thermal stability of the foams based on compressive strength test, limiting oxygen index (LOI), cone calorimeter test, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The addition of EG alone or both EG and APP into the foam greatly influences the physical–mechanical property. The compressive strength of APEG foams is closely related to the apparent density. The LOI value showed good improvement in both EG and APEG foams. The addition of APP in APEG foams gave better fire behavior than the EG foams with an obvious decrease in PHRR and increase in residue. In addition, the TGA curves illustrated that APP might be an effective charring agent to promote char formation. The SEM results showed that the incorporation of APP and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and increased the thermal stability of PIR‐PUR. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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。     

Expandable graphite: A fire retardant additive for polyurethane coatings

The study investigates the mechanism of fire retardancy induced by expandable graphite in a polyurethane coating. A complementary investigation to the spectroscopic study performed previously confirms that little interaction occurs between the matrix and the additive. X‐ray diffraction study demonstrates that the crystalline structure of the graphite is maintained during the intumescent process. The presence of free radicals in the protective shield is then demonstrated but at low concentration compared with classical intumescent systems, such as for example polyurethane/ammonium polyphosphate. Finally, the physical properties of the char are then investigated. Blowing measurement demonstrates the high degree of expansion of the layer which may partially explain the fire retardant performance of expandable graphite in polyurethane. Surface analyses by optical microscopy and optical profilometry also enable a better understanding of the efficiency of expandable graphite. In the absence of a fire retardant additive the coating displays cracks and holes, providing a pathway for oxygen diffusion as well as heat and mass transfer between the flame and the virgin polymer. Both phenomena are limited when expandable graphite is added to polyurethane. Consequently, fire retardancy of expandable graphite results more from a physical than from a chemical action. Copyright © 2003 John Wiley & Sons, Ltd.     

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.     

膨胀石墨在聚乙烯中阻燃协效作用的研究

以膨胀石墨(EG)与聚磷酸铵(APP)复配组成膨胀型阻燃剂，应用于高密度聚乙烯(PE-HD)中。热分析表明APP／FG的添加使得PE-HD材料的热稳定性增强，降解过程变缓，剩炭率增加。氧指数(LOI)结果表明APP／EG具有良好的阻燃协同作用。扫描电镜(SEM)显示APP／EG的加入可使得PE-HD样品生成连续致密的炭层。同时力学性能研究表明APP／EG对材料的力学性能的影响比其它膨胀型阻燃剂要小。     

Fire performance and mechanical properties of acrylonitrile‐butadiene‐styrene copolymer/modified expandable graphite composites

The fire performance and mechanical properties of an acrylonitrile‐butadiene‐styrene (ABS) copolymer compounded with different expandable graphites (EG) and fire retardants were studied by using the limiting oxygen index test, the UL‐94 test, a mechanical test, and a thermogravimetric analysis. The ground EG treated with phosphoric acid and silane could have the great increase of the volume expansion ratio. The addition of the treated EG in ABS significantly enhances the fire performance but decreases the impact strength of ABS. ABS with the treated EG has a much higher impact strength than with the as‐received EG because of the smaller particle size of the treated EG and the better adhesion between the ABS and the treated EG. The addition of modified ammonium polyphosphate or decabromodiphenyl oxide/antimony trioxide can considerably improve the fire performance of ABS/treated EG composites because of a synergistic effect. The V‐0 grade (UL‐94) ABS composite with the limiting oxygen index of 32.5 can be obtained by adding small amounts of the treated EG and modified ammonium polyphosphate into ABS. Thermogravimetric analysis results indicate that the initial vapor release temperatures and the weight loss rates of ABS/EG composites are closely related to their fire performance and affected by the fire retardant used. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

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。     

Preparation of borate–modified expandable graphite and its flame retardancy on acrylonitrile‐butadiene‐styrene resin

A borate‐modified expandable graphite (written as MEG) was prepared through one step intercalating reaction of natural graphite, using KMnO₄ as oxidant, H₂SO₄ and sodium tetraborate as intercalator and assistant intercalator, respectively. The dilatability, structure, element contents, thermal stability, and flame retardancy on acrylonitrile‐butadiene‐styrene (ABS) were investigated. Compared with the normal expandable graphite (written as EG, which was prepared with only H₂SO₄ as intercalator), the results show that MEG exhibits higher expandable property, thermal stability and flame retardancy on ABS. The EDS, FT‐IR, and XRD results reveal that borate has been inserted into graphite layers. With the addition of MEG or EG at a 30 wt%, LOI of 70ABS/30MEG composite improved to 27.9%, 2.2% higher than that of 70ABS/30EG. Moreover, the synergistic effect between MEG and traditional intumescent flame retardant (IFR, consists of ammonium polyphosphate (APP), pentaerythritol (PER), and melamine (MEL) with a mass ratio of 7.5:4.5:3.0) improves the LOI of 70ABS/15MEG/15IFR composite to 32.6%, and the UL‐94 level reaches V‐0. This synergistic efficiency is attributed to the formation of continuous and compact residual char. Addition of MEG together with IFR changes the ABS pyrolysis behavior, and there is not only physical synergy, but also chemical reaction. POLYM. COMPOS., 37:2673–2683, 2016. © 2015 Society of Plastics Engineers     

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。     

Polyurethane coatings based on linseed oil phosphate ester polyols with intumescent flame retardants

The effect of intumescent flame retardants on the properties of polyurethane (PU) coatings based on 2 kinds of phosphate ester polyol was studied. Synthesizing polyols, phosphorylation of epoxidized linseed oil with phosphoric acid was performed in the presence of isopropyl alcohol (IPA polyol) or diethylene glycol butyl ether (DGBE polyol). The obtained polyols were characterized by Fourier transform infrared (FTIR) and ³¹P nuclear magnetic resonance (NMR) spectroscopy. The properties of neat PU coatings based on 2 polyols and those filled with different content (up to 25 wt%) of melamine (Mel), ammonium polyphosphate (APP), and expandable graphite (EG) were studied using thermal gravimetric analysis (TGA), and tensile and cone calorimeter tests. It was found that IPA polyol contained not only phosphate monoesters and diesters, as DGBE polyol, but also phosphate triester and pyrophosphate monoester. Due to this difference, IPA neat and filled coatings had higher tensile characteristics and char residue in a TGA test. Also, the flame retardancy of IPA coatings, compared with that of DGBE coatings, was higher. In a cone calorimeter test, coatings filled with Mel showed a small increase of flame retardancy, but the total smoke release (TSR) of wood samples with coatings decreased noticeably. The effect of APP on the flame retardancy of coatings was higher, but in contrast, the TSR of samples increased with increasing APP content. Even greater decrease of flammability parameters and a simultaneous significant decrease of TSR were shown by the samples with IPA coatings filled with EG.     

PGS@P-N阻燃剂的制备及增强EVA复合材料的 阻燃性能的研究

利用坡缕石表面的羟基，采用化学方法首先将坡缕石（PGS）用磷酸进行了改性，随后通过酸碱中和的方法，将十二胺接枝到磷酸分子上，得到改性的含P、N型复合阻燃剂PGS@P-N。通过SEM、 XRD、 FTIR等方法对所合成阻燃剂PGS@P-N的形貌和结构进行了表征，利用氧指数法(LOI)、垂直燃烧法(UL-94)和锥形量热法(CCT)对复合材料的阻燃性能进行了测试，并对复合材料的力学性能和相容性进行了考察。结果表明：当向EVA中加入质量分数为30%的PGS@P-N/EG后，EVA/PGS@P-N/EG(可膨胀石墨)复合材料的氧指数达到了36.3%，与EVA/PGS/EG比较，接入烷基链后，EVA/PGS@P-N/EG复合材料的断裂伸长率提高了40%。     

可膨胀石墨与含磷阻燃剂在聚氨酯硬泡材料中的应用

通过氧指数仪与锥形量热仪研究了可膨胀石墨（EG）与低聚磷酸酯多元醇（OP550）、二乙基N,N二(2羟乙基)胺基甲基膦酸酯（WSFR 6）2种反应型含磷阻燃剂对聚氨酯硬泡材料（RPUF）阻燃性能的影响。结果表明,在OP550与WSFR 6的存在下,RPUF具有较好的成炭性,且炭层较为致密;添加EG后,体系的阻燃性能进一步提高,当其含量为14 %（质量分数,下同）时,RPUF体系的极限氧指数达到33.6 %,热释放速率峰值降低到106.93 kW/m2。     

Synergistic effect of expandable graphite and aluminum hypophosphite on flame‐retardant properties of rigid polyurethane foam

A series of flame retarding rigid polyurethane foam (RPUF) composites based on expandable graphite (EG) and aluminum hypophosphite (AHP) were prepared by the one‐pot method. The properties were characterized by limiting oxygen index (LOI) test, cone calorimeter test, thermogravimetric analysis (TGA), real‐time Fourier transform‐infrared spectra (RT‐FT‐IR), X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), etc. The results indicate that both EG and AHP could enhance the flame retardency of RPUF composites. Besides, the flame retardant effect of EG was better than that of AHP. The results also show that partial substitution of EG with AHP could improve the flame retardency of RPUF, and EG and AHP presented an excellent synergistic effect on flame retardancy. What is more, compared with RPUF/20EG and RPUF/20AHP, the heat release rate (HRR) and total heat release (THR) of RPUF/15EG/5AHP were lower.TGA results indicate that partial substitution of EG with AHP could improve the char residue which provided better flame retardancy for RPUF composites. The thermal degradation process of RPUF composites and the chemical component of the char residue were investigated by RT‐FT‐IR and XPS. And the results prove that RPUF/15EG/5AHP had higher heat resistance in the later stage. Compared with the RPUF composites filled with EG, a better cell structure and mechanical properties were observed with the substitution of AHP for part of EG. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42842.     

Flammability of EVA/IFR (APP/PER/ZB system) and EVA/IFR/synergist (CaCO3, NG,and EG) composites

Poly(ethylene‐co‐vinyl acetate)/intumescent flame retardant (ammonium polyphosphate/pentaerythritol/zinc borate system) composites‐EVA/IFR (APP/PER/ZB system) and EVA/IFR/Synergist [CaCO₃, natural graphite, or expanded graphite (EG)] composites have been prepared by melting compounding method. The flammability, the combustion process, the quantity of the residual chars, the morphology of the residual chars, and the thermal stability of the chars have been investigated by cone calorimeter, scanning electron microscopy and thermo gravimetric analysis. The results indicate that heat release rate (HRR), total heat released, and total smoke release (TSR) of EVA/IFR (IFR 30 phr) composite decrease to about 67.1, 78.2, and 64% of that of pure EVA, respectively. HRR, THR, and TSR of EVA/IFR/EG (IFR 9 phr, EG 1phr) composite decrease to about 62.1, 76.2, and 44% of that of pure EVA, respectively. The quantity, the thermal stability of residual chars and the char structure are discussed to find the reasons of the phenomenon above. It has been found that the flame retardant of EVA vulcanizates is improved and the fire jeopardizing is dramatically reduced due to the addition of IFR and synergist, which can give some advice to design formulations for practical applications as cable. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012