膨胀型饰面防火涂料现状及进展

简要介绍了膨胀型饰面防火涂料的阻燃原理和分类。阐述了我国饰面型防火涂料的发展现状及最新科研成果,比较国内外饰面型防火涂料的标准,同时对国内新旧标准的变化进行简要的比较。最后,对我国膨胀型饰面防火涂料的发展趋势进行了展望。     

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.     

水性环氧改性丙烯酸防火磁漆的制备

以丙烯酸、丙烯酸丁酯、甲基丙烯酸甲酯、丙烯酸2,4,6-三溴苯酯和环氧树脂（E-44）等为原料合成了水性环氧改性丙烯酸树脂,讨论了丙烯酸2,4,6-三溴苯酯的含量对涂层阻燃性能的影响,E-44、丙烯酸的含量以及中和度对水性环氧改性丙烯酸树脂性能的影响。讨论了阻燃助剂等对涂层阻燃性能的影响。     

Comparative study of the fire protection performance and thermal stability of intumescent fire-retardant coatings filled with three types of clay nano-fillers

The fire protection and thermal stability properties of intumescent fire-retardant coatings filled with three various clay nano-fillers (layer double hydroxide [LDH], montmorillonite [MMT], and sepiolite) were compared by fire protection tests and thermo-gravimetric analysis. The fire protection tests show that the incorporation of three fillers improves the fire protection properties of the intumescent fire-retardant coatings and the addition of 1 wt% sepiolite exhibits the lowest flame spread rating of 9.9 and equilibrium backside temperature of 164.5°C at 900 seconds. TG analysis shows that the incorporation of nano-fillers imparts a considerable enhancement of thermal stability and char formation to the intumescent coatings. Especially, the coating with 1 wt% sepiolite acquires the highest residual weight of 34.2% among the samples. Char residue analysis presents that the introduction of clay nano-fillers plays a positive role in enhancing the compactness and anti-oxidation ability of the char residues, and this positive effect as well as the flame-retardant efficiency depends on the types of clay nano-fillers. The three types of layered clay nano-fillers exhibit synergistic flame-retardant effectiveness in the order of sepiolite > MMT > LDH.     

纳米粒子几何结构对膨胀型防火涂料阻燃和抑烟性能的影响

为了研究纳米粒子几何结构对膨胀型防火涂料阻燃和抑烟性能的影响,以聚磷酸铵(APP)-季戊四醇(PER)-三聚氰胺(MEL)-硼酸三聚氰胺(MB)为阻燃体系,硅丙乳液为成膜物质,分别添加球形纳米二氧化硅(Si O2)、经硅烷偶联剂KH560改性的管状碳纳米管(KH560–CNT)和片状水滑石(LDH)制备了3种水性膨胀型防火涂料。采用小室法、隧道法及模拟大板法研究了涂层的防火阻燃性能,再结合热重分析、扫描电镜分析和能谱分析,考察了涂层的热解性能和炭层结构。结果表明,球形Si O2和片状LDH能有效增强防火涂料的阻燃和抑烟性能,表现出较好的协效作用;管状KH560–CNT则会恶化防火涂料的阻燃和抑烟性能,表现出对抗作用。当纳米填料的质量分数为0.5%时,片状LDH表现出最优的协效作用,火焰传播比值为12.5,烟密度等级为14.1%。这是因为它能促进涂层在燃烧过程中形成更多的含磷和含硼交联结构,有效增强了炭层的致密性、连续性和隔热性能。     

水性聚氨酯涂料的研究与应用

综述了水性聚氨酯（WPU）涂料的性能及其组成，介绍了WPU涂料的种类和改性方法，阐述了其应用领域及进展。     

室外用超薄钢结构防火涂料的研制

以小板燃烧法为评价方法,考察了不同树脂体系、P-C-N阻燃体系、防火颜填料等因素对涂层防火性能的影响规律.通过配方优化以及与自制防火面漆相复合,获得了综合性能佳的室外用超薄型钢结构防火涂料.该产品已通过了国家检验中心的检测,当涂层厚度为1.5mm时,防火时间达96min.     

无机矿物填料增白技术

天然矿物填料的白度是影响产品性能、价格和经济效益的最主要因素之一.在分析影响矿物填料白度主要因素的基础上,介绍了无机矿物填料的增白处理技术、基本原理及其特点.     

膨胀型防火涂料的研究进展

综述了膨胀型防火涂料的发展历程、分类、制备工艺流程及其阻燃机理。对膨胀型防火涂料基体树脂和各种防火助荆（包括成碳剂、脱水成碳催化剂、发泡剂、防火填料和颜料及其它助剂等）的选择方法进行了分析,指出了膨胀型防火涂料的发展动向。     

阴极聚氨酯电泳涂料的漆膜性能研究

以甲苯二异氰酸酯(TDI)、聚合物多元醇(PEA)、亲水剂(MDEA)以及封端剂通过丁酮法合成了阳离子型水性聚氨酯电泳涂料。实验结果表明：亲水剂用量越多，耐水性越差；交联剂用量越多，乳液的柱径越小，粘度越大，漆膜的硬度越高，耐水性越好；离子化试剂的用量越少，耐水性越好，但硬度降低；DSC结果表明丙二酸二乙酯封端的PU漆膜的分解温度为128℃，漆膜的耐水性大于96h，铅笔硬度4H。     

电缆防火涂料阻火有效性试验

根据电缆隧道实际环境,建立电缆水平燃烧试验平台,研究不同火灾荷载和通风速度下,受防火涂料保护电缆延燃长度的变化规律。结果表明:一定风速条件下,电缆延燃长度随敷设宽度增加呈指数增长,可根据隧道内通风速度和电缆束宽度近似预测电缆延燃长度,从而为电缆隧道的防火设计提供依据。     

Effects of inorganic fillers on the shear viscosity and fire retardant performance of waterborne intumescent coatings

In the present work, the effects of inorganic fillers on the fire retardant performance of waterborne intumescent coatings are investigated by thermogravimetry (TG), capillary rheometer, X-ray diffraction spectroscopy (XRD) and fire retardant test, etc. The TG results indicate that the thermal stability of vinyl acetate-vinyl ester of versatic acid copolymer (hereafter VAc-VeoVa) in VAc-VeoVa/Si–Al powder composite or in VAc-VeoVa/Halloysite nanometer-tube (HNTs) composite is improved mainly due to the release of the crystal water in Si–Al powder or HNTs. Capillary rheometer analysis results demonstrate that the VAc-VeoVa/HNTs composite melt possesses the highest shear viscosity, because of the large specific surface area of HNTs and the strong interaction force between HNTs and VAc-VeoVa. Weight loss difference (ΔT) of filler/ammonium polyphosphate (APP) composites show antagonism effects at 300 °C < T < 650 °C and synergistic effects at T > 650 °C. The fire retardant test results show the coatings using TiO₂/Si–Al powder/HNTs (8/1/1) as multiple fillers obtains an intumescent char layer with intumescent ratio of 28.14 and presents excellent fire retardant performance (3327 s). It is found that the high melt viscosity, resulted from the effect of inorganic filler, immobilizes the relaxation and rotation of polymer chain, restricts the intumescent behavior of the coatings, which leads to the formation of an intumescent char layer with lower intumescent ratio and the shortening of the fire retardant time. Moreover, the antagonism effect between filler and APP reduces the catalytic dehydration efficiency of pentaerythritol (PER) and VAc-VeoVa, which, as a result, also affects the final fire retardant performance of coatings.     

无机填料对淀粉胶性能的影响

以斯坦霍尔2步法制备的玉米淀粉胶为研究对象,试验了3种无机填料对淀粉胶稳定性、黏度以及制备的瓦楞纸板在普通环境和潮湿环境中的边压强度和粘合强度的影响。结果表明,加入无机填料可以大幅度提高淀粉胶稳定性;以加入适当无机填料A的淀粉胶制作的瓦楞纸板的边压强度有较大提高。     

Thermal conductivity of intumescent coating char after accelerated aging

This paper presents the results of an experimental and numerical simulation study to obtain thermal conductivity of intumescent coating after accelerated aging. Two types of intumescent coating were used. The main objective of this research was to check the accuracy of a thermal conductivity model for the fully expanded intumescent coating char, which was assumed to depend on the expansion thickness and the bubble size and distribution. By using the model and the measured expanded thicknesses and average bubble diameters for the two types of intumescent coating after different cycles of accelerated aging, the intumescent coating insulated steel plate temperatures were numerically calculated and compared with measured results. The agreement has been found to be generally satisfactory, suggesting that the thermal conductivity model is acceptable. The measured results of intumescent coating expanded thickness and bubble size show that aging has two detrimental effects on the insulation performance of intumescent coating: reducing the expansion thickness and increasing the bubble size, both leading to increased thermal conductivity. Copyright © 2012 John Wiley & Sons, Ltd.     

Effect of boron compounds on fire protection properties of epoxy based intumescent coating

The aim of this study was to investigate the effect of boron compounds on fire protection properties of intumescent coating based on ammonium polyphosphate (APP). Three kinds of boron compounds namely boric acid (BA), zinc borate (ZB) and melamine borate (MB) were used. Total amount of flame retardant additive was kept constant at 30 wt%, and boron compounds were used at three concentrations of 1, 3 and 5 wt%. Thermogravimetric analysis (TGA), Attenuated total reflectance–Fourier transform infrared spectroscopy (ATR‐FTIR) and fire test were conducted for the determining the fire performance of intumescent coating. According to fire test results, BA and MB showed synergistic effect at 1 wt% loading. ZB showed antagonistic effect at all concentrations. Fire protection effect of intumescent coating decreased as the added amount of boron compound increased regardless of boron compound type because of suppression of intumescence. Copyright © 2016 John Wiley & Sons, Ltd.     

无机材料对超薄型钢结构防火涂料性能的影响

介绍了晶须、石墨插层化合物、硅微粉、纳米二氧化硅、二氧化钛、硼酸锌等无机材料对超薄型钢结构防火涂料的防火性能、涂膜质量等理化性能的影响,指出以合适的无机新材料在适当的用量下对传统防火涂料进行必要的改性,是进一步提高超薄型钢结构防火涂料各项性能的有效方法。     

Experimental study on insulative properties of intumescent coating exposed to standard and nonstandard furnace curves

This paper reports the results of an experimental study on two types of intumescent coating exposed to the ISO834 standard fire and three nonstandard fire curves. The nonstandard fires were all less severe than the standard fire. A total of 72 intumescent coating protected steel specimens were tested. The expanded thickness of intumescent char was measured, and the pore feature was observed. Constant thermal conductivity for each specimen was calculated based on the measured steel plate temperature. Thermogravimetric analysis (TGA) test was carried out, and the results show that more gas is trapped within the coating due to better matching of thermal behaviour between gas evolution and polymer viscosity as the rate of heating increases. The constant effective thermal conductivities for the intumescent coating under the nonstandard fires were 65% (type‐W) and 35% (type‐S) higher than that under the standard fire, which resulted in an overestimation of the coating failure time up to 15 and 11 minutes, respectively. Therefore, it is sometimes insecure to use results from standard fire tests guiding the design of coating thickness for steel elements under nonstandard fire conditions.     

新型室温固化水性可剥涂料的开发与应用

以醇为反应介质,双丙酮丙烯酰胺为功能单体,采用自由基聚合,与丙烯酸及丙烯酸酯类单体共聚,用氨水中和成盐,调节pH=8~9,制成含酮羰基的水溶性聚丙烯酸树脂液,再与己二酰肼混合,得到室温交联固化的水性可剥涂料。讨论了亲水单体的种类及用量、溶液pH值、干燥温度对漆膜性能的影响。结果表明,该涂料可采用喷、浸、刷、辊等方法涂用于玻璃陶瓷制品、金属构件、各种漆器、PVC材料等物品表面,作为临时性保护。     

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.     

Design and optimization of an intumescent flame retardant coating using thermal degradation kinetics and Taguchi's experimental design

Two supplementary approaches in terms of thermal degradation kinetics and Taguchi's experimental design were employed toward developing a design effort for intumescent coatings. A model intumescent system including ammonium polyphosphate (APP), pentaerythritol (PER), melamine (MEL), thermoplastic acrylic resin and liquid hydrocarbon resin was chosen and then subjected to thermogravimetric analysis and heat insulation tests to provide experimental data. Kinetic analysis of the thermogravimetric data based on the Friedman and Kissinger methods revealed that activation energy (E_a) and reaction order (n) could be used as parameters to accurately judge whether the selected intumescent components represented coordinated thermal characteristics. Examination of the calculated E_a and n values showed that the decomposition of thermoplastic acrylic resin and liquid hydrocarbon resin occurred first and that the APP, PER and MEL components were degraded immediately after. Such a degradation sequence was quite consistent with the functional mechanism of intumescent systems. In addition, simultaneous implementation of analysis of variance and mean effect assessment on the Taguchi data demonstrated that the designed formulation, based on the optimized coupling of 10 g MEL into APP/PER 25 g/11 g, exhibited the highest fireproofing time among the prepared coating samples. The APP content had the most important contribution to the flame retardant behaviour, and APP versus PER interactions showed the highest severity index. Scanning electron microscopy showed that the higher flame retardancy of the optimized sample was related to the presence of a large number of micropores in the expanded charring layer structure. Copyright © 2012 Society of Chemical Industry