Article(id=1210613547491520966, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.11.009, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1705939200000, receivedDateStr=2024-01-23, revisedDate=1709395200000, revisedDateStr=2024-03-03, acceptedDate=null, acceptedDateStr=null, onlineDate=1766562361834, onlineDateStr=2025-12-24, pubDate=1732032000000, pubDateStr=2024-11-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766562361834, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766562361834, creator=13701087609, updateTime=1766562361834, updator=13701087609, issue=Issue{id=1210613541111984320, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='11', pageStart='1', pageEnd='143', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766562360313, creator=13701087609, updateTime=1766564044072, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620603392987671, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620603392987672, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210613541111984320, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=79, endPage=86, ext={EN=ArticleExt(id=1210613547814482395, articleId=1210613547491520966, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and properties of new ceramifiable intumescent fire protection coatings, columnId=1210613542542241998, journalTitle=Insulating Materials, columnName=Special Issue on Key Materials and Technology for New Energy Vehicles, runingTitle=null, highlight=null, articleAbstract=

A new type of ceramifiable intumescent fire protection coating was prepared by using epoxy resin as the matrix, ammonium polyphosphate as the flame retardant, zinc borate as the flux, and raw vermiculite powder and wollastonite as the refractory fillers. The effects of the compound of four fillers on the properties of ceramifiable intumescent fire protection coating were studied by scanning electron microscope (SEM) and fire resistance test. The results show that ammonium polyphosphate can significantly improve the expansion multiplication rate and thermal insulation performance, zinc borate can effectively enhance the strength and density of the charcoal layer, and raw vermiculite powder and wollastonite can enhance the burn-resistant performance of the charcoal layer and increase the fire resistance time limit at high temperature. When the mass ratio of ammonium polyphosphate, raw vermiculite, zinc borate, and wollastonite is 11∶5∶6∶10, the tensile shear strength is 7.8 MPa, the refractory performance is the best, the fire resistance time limit reaches 10 min, the maximum backsheet temperature is 393℃, and the charcoal layer after burning can withstand a voltage of 1.0 kV.

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以环氧树脂为基体,聚磷酸铵为阻燃剂、硼酸锌为助熔剂、生蛭石粉和硅灰石为耐火填料,制备了一种新型可瓷化膨胀防火涂料。采用扫描电子显微镜(SEM)、耐火性能测试等方法研究4种填料复配对可瓷化膨胀防火涂料性能的影响。结果表明:聚磷酸铵可以显著提高涂层的膨胀倍率和隔热性能,硼酸锌能有效增加炭层的强度和致密度,在高温下生蛭石粉和硅灰石提升了炭层的耐烧性能并增加了耐火时限;当聚磷酸铵、生蛭石、硼酸锌、硅灰石的质量比为11∶5∶6∶10时,样品的拉伸剪切强度为7.8 MPa,耐火性能最好,耐火时限达到了10 min,最高背板温度为393℃,燃烧后的炭层可耐1.0 kV电压。

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王金合(1982-),男(汉族),河北唐山人,副研究员,主要从事功能高分子复合材料的研究。
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洪建婷(1999-),女(汉族),江苏无锡人,硕士生,主要从事可瓷化防火涂料的研究。

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洪建婷(1999-),女(汉族),江苏无锡人,硕士生,主要从事可瓷化防火涂料的研究。

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洪建婷(1999-),女(汉族),江苏无锡人,硕士生,主要从事可瓷化防火涂料的研究。

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Study on effect of fillers and fluxes on the ceramic polyolefin char layer[J]. Synthetic Materials Aging and Application,2023,52(6):12-15., articleTitle=Study on effect of fillers and fluxes on the ceramic polyolefin char layer, refAbstract=null)], funds=[Fund(id=1218964282994246146, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, awardId=202302AB080022, language=CN, fundingSource=云南省新材料重大专项(202302AB080022), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1218964273263460463, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, xref=1, ext=[AuthorCompanyExt(id=1218964273267654767, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, companyId=1218964273263460463, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China), AuthorCompanyExt(id=1218964273276043376, 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articleId=1210613547491520966, language=EN, label=Fig.1, caption=Schematic diagram of homemade equipment for coating fire resistance experiment, figureFileSmall=IbQ46mjmXIULNaJsIuiR5g==, figureFileBig=rU39VNvQ++MtvB94lcU6Eg==, tableContent=null), ArticleFig(id=1218964278955131260, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, label=图1, caption=涂层耐火实验自制装备示意图, figureFileSmall=IbQ46mjmXIULNaJsIuiR5g==, figureFileBig=rU39VNvQ++MtvB94lcU6Eg==, tableContent=null), ArticleFig(id=1218964279080960389, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=EN, label=Fig.2, caption=The macroscopic surface topography of samples after fire resistance test, figureFileSmall=Ia7v/QT45lok7z8RCZSFxg==, figureFileBig=OfEAiHdLeLm0eB8UzRj0LA==, tableContent=null), ArticleFig(id=1218964279240343951, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, 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tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=EN, label=Fig.9, caption=Voltage withstand test results of different samples before and after burning, figureFileSmall=ceyq91AGSKgCbIUSLCcE5w==, figureFileBig=vBRBzXP5kEKxUiggez/hQg==, tableContent=null), ArticleFig(id=1218964280876122588, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, label=图9, caption=不同样品在燃烧前后的耐电压测试结果, figureFileSmall=ceyq91AGSKgCbIUSLCcE5w==, figureFileBig=vBRBzXP5kEKxUiggez/hQg==, tableContent=null), ArticleFig(id=1218964282163773919, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=EN, label=Fig.10, caption=Tensile shear strength of different samples, figureFileSmall=wCvSpRxJ4ZOkagC9Ay6rWg==, figureFileBig=y6C5y21UP/WSEPX4yzDnbQ==, tableContent=null), ArticleFig(id=1218964282323157478, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, label=图10, caption=不同样品的拉伸剪切强度, figureFileSmall=wCvSpRxJ4ZOkagC9Ay6rWg==, figureFileBig=y6C5y21UP/WSEPX4yzDnbQ==, tableContent=null), ArticleFig(id=1218964282444792296, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=EN, label=Fig.11, caption=Schematic diagram of ceramization mechanism of fire protection coating, figureFileSmall=Jz6Hfuod83hRdW16OrJ/3g==, figureFileBig=ryhHGDeWhFQ80EcEqIKvgA==, tableContent=null), ArticleFig(id=1218964282604175857, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, label=图11, caption=防火涂料可瓷化机理示意图, figureFileSmall=Jz6Hfuod83hRdW16OrJ/3g==, figureFileBig=ryhHGDeWhFQ80EcEqIKvgA==, tableContent=null), ArticleFig(id=1218964282679673334, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=EN, label=Table 1, caption=Filler formulation composition for ceramifiable intumescent fire protection coatings, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号APP生蛭石ZB硅灰石总填料量E51树脂593固化剂
APP-008159325414
APP-176127325414
APP-296116325414
APP-3115106325414
APP-413595325414
Vrm-0110138325414
Vrm-1112127325414
Vrm-2115106325414
Vrm-311885325414
Vrm-4111164325414
ZB-0115016325414
WI-0115160325414
ZB/WI-1115412325414
ZB/WI-2115610325414
ZB/WI-311588325414
ZB/WI-4115106325414
ZB/WI-5115124325414
), ArticleFig(id=1218964282792919547, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1210613547491520966, language=CN, label=表1, caption=

可瓷化膨胀防火涂料的填料配方组成

, figureFileSmall=null, figureFileBig=null, tableContent=
样品编号APP生蛭石ZB硅灰石总填料量E51树脂593固化剂
APP-008159325414
APP-176127325414
APP-296116325414
APP-3115106325414
APP-413595325414
Vrm-0110138325414
Vrm-1112127325414
Vrm-2115106325414
Vrm-311885325414
Vrm-4111164325414
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新型可瓷化膨胀防火涂料的制备及性能研究
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洪建婷 1 , 安彤 1 , 陈泽超 1 , 刘立起 1 , 彭雨晴 1 , 李爱军 1 , 徐梦欣 3 , 王金合 2
绝缘材料 | 新能源汽车用关键材料与技术专题 2024,57(11): 79-86
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绝缘材料 | 新能源汽车用关键材料与技术专题 2024, 57(11): 79-86
新型可瓷化膨胀防火涂料的制备及性能研究
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洪建婷1, 安彤1, 陈泽超1, 刘立起1, 彭雨晴1, 李爱军1, 徐梦欣3, 王金合2
作者信息
  • 1上海大学,材料科学与工程学院,上海 200444
  • 2上海大学,理学院,上海 200444
  • 3青岛高新城维实业有限公司,山东 青岛 266000
  • 洪建婷(1999-),女(汉族),江苏无锡人,硕士生,主要从事可瓷化防火涂料的研究。

通讯作者:

王金合(1982-),男(汉族),河北唐山人,副研究员,主要从事功能高分子复合材料的研究。
Preparation and properties of new ceramifiable intumescent fire protection coatings
Jianting HONG1, Tong AN1, Zechao CHEN1, Liqi LIU1, Yuqing PENG1, Aijun LI1, Mengxin XU3, Jinhe WANG2
Affiliations
  • 1School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
  • 2College of Sciences, Shanghai University, Shanghai 200444, China
  • 3Qingdao Gaoxin Chengwei Industry Co., Ltd., Qingdao 266000, China
出版时间: 2024-11-20 doi: 10.16790/j.cnki.1009-9239.im.2024.11.009
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以环氧树脂为基体,聚磷酸铵为阻燃剂、硼酸锌为助熔剂、生蛭石粉和硅灰石为耐火填料,制备了一种新型可瓷化膨胀防火涂料。采用扫描电子显微镜(SEM)、耐火性能测试等方法研究4种填料复配对可瓷化膨胀防火涂料性能的影响。结果表明:聚磷酸铵可以显著提高涂层的膨胀倍率和隔热性能,硼酸锌能有效增加炭层的强度和致密度,在高温下生蛭石粉和硅灰石提升了炭层的耐烧性能并增加了耐火时限;当聚磷酸铵、生蛭石、硼酸锌、硅灰石的质量比为11∶5∶6∶10时,样品的拉伸剪切强度为7.8 MPa,耐火性能最好,耐火时限达到了10 min,最高背板温度为393℃,燃烧后的炭层可耐1.0 kV电压。

可瓷化  /  膨胀  /  防火涂料

A new type of ceramifiable intumescent fire protection coating was prepared by using epoxy resin as the matrix, ammonium polyphosphate as the flame retardant, zinc borate as the flux, and raw vermiculite powder and wollastonite as the refractory fillers. The effects of the compound of four fillers on the properties of ceramifiable intumescent fire protection coating were studied by scanning electron microscope (SEM) and fire resistance test. The results show that ammonium polyphosphate can significantly improve the expansion multiplication rate and thermal insulation performance, zinc borate can effectively enhance the strength and density of the charcoal layer, and raw vermiculite powder and wollastonite can enhance the burn-resistant performance of the charcoal layer and increase the fire resistance time limit at high temperature. When the mass ratio of ammonium polyphosphate, raw vermiculite, zinc borate, and wollastonite is 11∶5∶6∶10, the tensile shear strength is 7.8 MPa, the refractory performance is the best, the fire resistance time limit reaches 10 min, the maximum backsheet temperature is 393℃, and the charcoal layer after burning can withstand a voltage of 1.0 kV.

ceramifiable  /  intumescent  /  fire protection coating
洪建婷, 安彤, 陈泽超, 刘立起, 彭雨晴, 李爱军, 徐梦欣, 王金合. 新型可瓷化膨胀防火涂料的制备及性能研究. 绝缘材料, 2024 , 57 (11) : 79 -86 . DOI: 10.16790/j.cnki.1009-9239.im.2024.11.009
Jianting HONG, Tong AN, Zechao CHEN, Liqi LIU, Yuqing PENG, Aijun LI, Mengxin XU, Jinhe WANG. Preparation and properties of new ceramifiable intumescent fire protection coatings[J]. Insulating Materials, 2024 , 57 (11) : 79 -86 . DOI: 10.16790/j.cnki.1009-9239.im.2024.11.009
随着天然能源的不断开发和利用,加上人们对环境保护的重视程度日益增加,汽车电动化已成为一种重要的发展趋势,而锂离子电池包作为新能源汽车里的核心部件之一,其安全问题是人们关注的重点。锂离子电池包出现故障后可能导致漏电、火灾等危险,对人身安全构成巨大的威胁[1-2]。因此,对锂离子电池包故障起火的防护至关重要。目前,常用防火毡材料作为新能源汽车电池包的防火材料,如云母板、高硅氧棉毡、超细玻璃棉等[3]。虽然防火毡材料可以有效防止热量扩散和阻止火势蔓延,但其在电池包外壳的异形结构上贴合不良,且在车辆施工上有一定局限性。而防火涂料在电池包外壳的异形结构上贴合良好,且施工便捷,可直接喷涂在材料表面,防火性能不亚于防火毡材料,有望成为防火毡材料的替代物[4]。目前防火涂料常用于建筑材料上作为钢结构用防火涂料[5],其中膨胀型防火涂料在火焰的灼烧下会形成一定厚度以气孔为主的连续炭层,可以达到隔热防火的目的[6-7]
动力电池和建筑行业对防火涂层的性能要求因使用场景的不同而有较大差别。首先,电池起火时温度迅速上升至800~1 000℃,最高温度甚至可以达到1 500℃。因此,对于新能源汽车电池包用防火涂料而言,良好的隔热性能和耐高温性能是首要因素,而普通膨胀型防火涂料的耐高温性能不佳,在高温下容易熔融烧穿。其次,由于电池包内空间有限,对于涂层干膜厚度的要求较为苛刻,同时容纳不了高厚度的膨胀炭层,然而普通膨胀型防火涂料主要依靠燃烧后膨胀炭层的高厚度来达到隔热防火的效果,其干膜厚度普遍高于1 mm[8]。再者,电池包故障起火后易产生气流冲击和漏电现象,而普通膨胀型防火涂料燃烧后形成的炭层结构疏松且多孔,不利于抵挡气流冲击且绝缘性能不佳。最后,防火涂料在施工后需要对电池包进行搬运组装,对防火涂料的粘结强度有一定的要求,而普通膨胀型防火涂料的粘结强度较低,通常为1 MPa左右。因此,需要对普通膨胀型防火涂料进行改良,以满足电池包对防火涂料的性能要求。
可陶瓷化聚合物基复合材料(PCCs)结合了有机高分子和无机陶瓷的优良性能,在高温下材料向陶瓷化转变,形成抗冲击陶瓷层并提高材料的耐热性能,起到热防护的作用[9-11]。一般陶瓷化体系主要包括耐火填料、助熔剂和阻燃剂等[12]。LIU W等[13]将滑石粉和聚磷酸铵(APP)加入到环氧树脂(EP)中,制备得到一种非膨胀型可瓷化防火涂料,结果表明其具有良好的阻燃性能,燃烧后残留物稳定性好且机械强度高。杨威等[14]在硼酚醛树脂中加入可瓷化填料MoSi2和低熔点玻璃料,结果表明玻璃料使材料的弯曲强度提高了6.5 MPa,在燃烧时材料表面形成致密熔体结构,烧蚀率降低了10.7%。E PALACIOS等[15]制备了一种海泡石磷酸盐(SepP)并掺入EP中得到了可陶瓷化的复合材料,结果表明该复合材料在高温下形成3D纳米结构的陶瓷网络,形成的陶瓷涂层其抗压强度达到了35 MPa。可瓷化技术不同于传统膨胀防火机制,在高温下不会形成膨胀的炭层来进行隔热,而是形成有一定强度的陶瓷层来抵御气流冲击并提高残留物的稳定性,所得涂料在耐气流冲击性方面优于膨胀型防火涂料。本文拟通过可瓷化技术与传统膨胀防火机制相结合的方法,制备出厚度低于0.5 mm、膨胀倍率可控且有一定绝缘性能的新型可瓷化膨胀防火涂料。
聚磷酸铵(APP),是一种被广泛应用的膨胀型无机磷系阻燃剂,在膨胀型防火涂料的膨胀阻燃体系中是最常见的脱水催化剂,起到促进成炭的作用[16-17]。硼酸锌(ZB),是硼酸盐阻燃剂中最常用的一种,其在凝聚相和气相均可发挥阻燃作用,同时在高温下可熔融形成玻璃态,可作为助熔剂使用[18-19]。生蛭石粉(Vrm),在高温下可使层间的水分子受热汽化,利用压力差使其膨胀从而得到膨胀蛭石,膨胀后的蛭石热导率低,可作为耐火填料[20]。硅灰石(WI)的分子式为CaSiO3,主要成分是SiO2、CaO等,具有良好的介电性能和耐热性能,可作为耐火填料[21]。本研究以环氧树脂为基体、APP为膨胀型阻燃剂、ZB为助熔剂、生蛭石粉和硅灰石为耐火填料,制备一种新型可瓷化膨胀防火涂料并应用于电池包外壳,同时探讨4种填料的复配对防火涂料的耐火性能、膨胀倍率和绝缘性能的影响,并初步提出可瓷化机理。
双酚A型环氧树脂E51(EP,环氧值为0.48~0.54 ep/100 g)、脂肪胺类环氧固化剂593,工业级,江阴万千化学品有限公司;聚磷酸铵(APP,(NH4PO3)nn>1 000,平均粒径为20 µm),工业级,科莱恩化工(中国)有限公司;生蛭石粉(Vrm,平均粒径为325目),工业级,灵寿县旭阳矿业有限公司;硼酸锌(ZB,平均粒径为325目),工业级,山东优索化工科技有限公司;硅灰石粉(WI,平均粒径为15 µm),工业级,江西奥特科技有限公司。
YM-SG65型三辊研磨机,上海屹鸣化工装备有限公司;CJJ-931型数显六联磁力恒温搅拌器,江苏金坛市环宇科学仪器厂;DHG-9076A型电热恒温鼓风干燥箱,上海精宏实验设备有限公司;SZQ湿膜制备器,佛山南北潮电子商务有限公司;QuaNix4200/4500型金属涂层测厚仪,四川思创倍科科技有限公司;572-2型红外测温仪,福禄克电子仪器仪表公司;NO:920便携喷枪、清系220G便携气瓶,义乌市乐拓户外野营用具有限公司;CC2670A型耐电压测试仪,南京长创科技有限公司;SU-1500型扫描电子显微镜,日本HITACHI公司;TY8000型万能试验机,江苏天元测试仪器有限公司。
首先将E51环氧树脂加入烧杯中,然后将膨胀型阻燃剂、耐火填料和助熔剂加入烧杯中得到混合液,将混合液在三辊研磨机中以转速为26、70、145 r/min研磨2~3次进行预分散,使填料充分分散在环氧树脂基体中,最后加入593环氧固化剂,在磁力恒温搅拌器中以500 r/min的转速搅拌分散15 min即制得可瓷化膨胀防火涂料。不同的可瓷化膨胀防火涂料试样中APP、生蛭石粉、ZB和硅灰石粉的用量如表1所示,其中固定基体与填料的质量比不变,具体为mE51m593m总填料=20∶5∶12。
用砂纸将钢板(尺寸为0.7 mm×100 mm×100 mm)打磨至光滑,用乙醇溶液擦拭除去表面的油渍和污垢,放入干燥箱中在80℃下烘干30 min至无乙醇残留,备用。将制备好的可见化膨胀防火涂料用湿膜制备器均匀涂在处理好的钢板上,放入干燥箱中在80℃下固化30 min,制备得到的涂层干膜厚度为0.3~0.4 mm,固化完全后在室温(温度为25℃)下养护5 h。
本文采用自制装备模拟电池发生热失控时的火焰气流冲击,通过红外测温仪记录钢板背面温度的变化来反映涂层的防火性能。自制装备如图1所示,将待测样品垂直固定在铁架台上,钢板附着涂层的一面朝向喷枪,调整样品与喷枪口的距离为(85±15)mm,喷枪孔径为18 mm,气罐中的燃料为丁烷,耗气用量为150 g/h,火焰长度为150~180 mm,保证涂层在900~1 050℃外焰下持续灼烧。在涂层燃烧过程中用红外测温仪在未附着涂层的一面水平测量背板温度,每15 s记录温度数据,待10 min后,关闭喷枪,在燃烧结束后记录各样品的膨胀高度和表面形貌。
通过耐电压测试仪对样品随机取3点在0~3 000 V交流电下测试60 s,保证其漏电流≤3 mA,记录3点间电压值并取平均值。
将待测样品用导电胶粘在铜台上,经喷金处理后用扫描电子显微镜观察样品的微观形貌。
根据GB/T 7124—2008相关要求制备样条,通过万能试验机测量样品的拉伸剪切强度。
图2为不同APP含量的样品在10 min耐火测试后的宏观形貌图。从图2可以看出,随着APP含量的增加,燃烧后的涂层表面逐渐从熔融状变化成有一定强度的膨胀炭层,膨胀炭层越来越致密,膨胀较均匀,膨胀倍率显著增大,但是燃烧后的样品均有不同程度的残缺,燃烧中心处露出钢板。APP-0样品在燃烧后有气体逸出并产生气泡,这是由于在高温下涂层主要由固体粉末组成,基本没有黏稠度,导致产生的气体逸出,没有形成膨胀炭层;APP-2、APP-3和APP-4样品在燃烧后残余物连接在一起形成多孔膨胀炭层,这是由于APP在燃烧过程中熔融覆盖在样品表面,有了黏稠度,有效阻止了气体逸出,从而使炭层膨胀。但由于APP在高温下黏度小,在耐火填料不足的情况下,可能存在被气体撑破的现象,且随着测试时间增加,炭层氧化而变薄,导致样品的耐火性能不佳。
不同APP含量的样品在10 min耐火测试下的钢板背温-时间曲线如图3所示。当燃烧后的炭层完整性被破坏且露出钢板时,此时的钢板背温-时间曲线趋于水平,对应的测试时间即为涂层的耐火时限。从图3可以看出,APP-0和APP-1样品的背温-时间曲线上升趋势与裸钢类似,分别在3 min和7 min时达到耐火时限。相较之前两种样品,APP-2、APP-3和APP-4样品的背温-时间曲线上升速率大幅下降,它们的耐火时限分别为8、8、9.5 min。在高温下APP热分解生成的酸性物质起到促进基体树脂脱水成炭的作用[22],从图2图3可以看出,随着APP含量的增加,膨胀倍率上升,耐火时限增加,当耐火测试达到一定时间时,膨胀炭层的耐烧程度和强度不足以继续支撑,此时样品的隔热性能逐渐劣化,膨胀炭层也随时间的增加逐渐燃烧殆尽,使得背温曲线快速上升。
图4为不同APP含量涂层燃烧后的膨胀倍率和耐火测试7 min时背板温度情况,此图可以直观体现涂层膨胀倍率和隔热性能之间的关系。从图4可以看出,随着APP含量的增加,膨胀倍率呈现不断上升的趋势,增长速率由慢到快,当APP的质量分数由0增加到13%时,涂层的膨胀倍率从8.4增加到19.9。同时,随着涂层膨胀倍率的上升,膨胀高度增加,火焰到背板的距离随之增加,由于炭层间存在孔洞,里面空气的导热系数低,热量损失较大,导致背板温度逐渐下降,涂层的隔热性能增加。当APP质量分数从9%增加到11%时,背板温度下降速率最快,由401℃降为302℃。其中背板温度在APP质量分数为13%时达到最低值,为245℃。可见,燃烧后涂层的膨胀倍率和背板温度呈负相关,同时结合图3分析可以看出,膨胀倍率与涂料的防火性能呈正相关,当APP含量增加时,膨胀倍率上升,耐火时限增加,同一燃烧时间下的背板温度下降,隔热性能增强。
图5图6分别为不同耐火填料和助熔剂含量的样品在10 min耐火测试后的宏观和微观形貌图。从图5中可以看出,Vrm-0~Vrm-4样品虽然燃烧后在燃烧中心处露出钢板,但从残留的膨胀炭层可以看出,随着生蛭石含量的增加,炭层上残留的棕褐色膨胀蛭石愈发明显,在一定程度上可以增加涂层的残留率和耐火时限[20]。此外,WI-0、ZB/WI-2和ZB/WI-3样品在燃烧后表面残留的膨胀炭层较完整,炭层相对致密且有一定强度,未露出钢板,耐火时限达到了10 min。
对比图6(a)(b)可以看出,ZB-0燃烧后残留物被APP连接起来形成网状的炭层,但以气孔为主的发泡炭层较为疏松,而WI-0燃烧后各残留物之间的空隙减小,形成的炭层较为致密,这是由于ZB在高温下熔融成液态使黏稠度提高,并起到桥接和助熔作用,各残留物之间粘结更为紧密,从而使样品的耐烧程度提高。对比图6(b)和(c)可以看出,Vrm-0的炭层相比WI-0更为致密,这是由于生蛭石粉膨胀后粒径变大,与之相比硅灰石的粒径小且比表面积大,增黏性大于生蛭石,在ZB桥接作用下更为致密。从图6(d)可以看出,ZB/WI-2燃烧后形成多孔的膨胀炭层,且相较于ZB-0而言,炭层间的孔隙减小,连接性更强,在一定程度上提高了炭层的耐烧强度。
图7图8分别为耐火填料和助熔剂对膨胀倍率、涂层耐火时限以及背板温度的影响。从图7(a)可以看到,随着生蛭石含量的增加膨胀倍率逐渐上升,且增长率趋于平缓,这是由于不添加生蛭石时,样品在高温下黏度大,而产生的气体不易撑起炭层,导致膨胀倍率低,加入生蛭石后可以适当减小样品的黏度,从而提高膨胀倍率,但当生蛭石含量增加到一定程度时,样品的黏度变化不大,且依靠矿物自身的膨胀对涂层膨胀倍率的影响并不显著;结合图8(a)可以看出,当生蛭石质量分数为5%时,涂层的耐火时限最长,为8 min,最高背板温度为490℃。由图7(b)可以看出,助熔剂ZB对涂层膨胀倍率的影响最大,随着ZB含量的增加,耐火填料间的粘结强度增大,炭层也越致密,膨胀倍率逐渐下降;结合图8(b)可以看出,当ZB和硅灰石的质量比为16∶0时,即WI-0样品,其炭层的微观形貌较为致密,但由于膨胀倍率过小,导致背板温度相对较高,达到了456℃。当ZB和硅灰石的质量比为6∶10时,即ZB/WI-2样品,其耐火性能最佳,耐火时限达到了10 min,最高背板温度为393℃,在燃烧期间形成的膨胀炭层和陶瓷化达到平衡,炭层的致密性增加,耐火性能得到提高。
对耐火时限达到10 min的3个样品进行燃烧前后的绝缘性能测试,结果如图9所示。从图9可以看出,燃烧前,WI-0、ZB/WI-2和ZB/WI-3样品均能通过3.0 kV电压下的绝缘性能测试,这是由于基体树脂具有良好的绝缘性能,加入填料后仍满足3.0 kV电压下的绝缘要求。燃烧后,由于炭层厚度不等,炭层不同位置上的测试值有一定差异,在测试时选取不同厚度位置进行测试,并取均值表示样品的测试值。从图9可以看出,ZB/WI-2样品的绝缘性能最佳,燃烧后的炭层可以通过1.0 kV的耐压测试,且耐受电压比ZB/WI-3样品略高,这是由于ZB/WI-2中的耐火填料含量相对高,块状的膨胀蛭石互相堆叠,同时针尖状的硅灰石在一定程度上对炭层起到补强作用,使炭层间的空隙减少,阻碍了电流的通过,且膨胀倍率也略大于ZB/WI-3样品,测得电压值为空气击穿所需电压,击穿的电压和距离有正比关系。WI-0样品炭层的致密度虽然提高,但耐火填料含量少且膨胀倍率低,同时炭层间还存在细小孔洞,因此耐电压较低,为0.5 kV。
图10为WI-0、ZB/WI-2和ZB/WI-3样品的拉伸剪切强度,由于基体树脂具有良好的粘结性,加入填料后仍保持良好的粘结强度。从图10可以看出,3个样品的拉伸剪切强度均在7 MPa之上,且相差不大。其中,由于WI-0样品中加入大量的ZB,ZB粒径较小且比表面积大,易团聚,在拉伸剪切过程中产生应力集中的概率增加,导致样品在较低拉伸剪切强度下被破坏[18-19],因此拉伸剪切强度最低,仅为7 MPa;ZB/WI-2和ZB/WI-3样品由于ZB和硅灰石的含量相差不大,两者的拉伸剪切强度相同,达到了7.8 MPa,表明制备得到的新型防火涂料粘结强度高。
综合上述讨论,提出了制备得到的新型防火涂料的可瓷化机理,可瓷化机理示意图如图11所示。涂层在高温下燃烧,APP受热分解生成偏磷酸等酸性物质,促进基体树脂脱水成熔融态炭层,并释放N2气体[13];同时片状生蛭石膨胀成块状膨胀蛭石,ZB在高温下分解熔融成液态使黏度增大,和APP在高温下生成的磷酸盐共同将针状耐火填料硅灰石和块状耐火填料膨胀蛭石粘结在一起,产生共晶混合物,高温下形成陶瓷骨架[23]。通过APP初步促进成炭和可瓷化形成陶瓷骨架两者的共同作用,膨胀炭层的致密度和耐火性能有效提高。
涂层燃烧后的膨胀倍率是影响涂层隔热性能最关键的因素,膨胀倍率越大,涂层的隔热性能越好。本研究中APP含量越多的样品,其膨胀倍率越大,ZB可以显著提高炭层的致密性,生蛭石粉和硅灰石的加入有效提高了炭层的耐烧性能,增加了耐火时限。当APP、生蛭石、ZB、硅灰石的质量比为 11∶5∶6∶10时,即ZB/WI-2样品,其拉伸剪切强度为7.8 MPa,且表干厚度为0.3~0.4 mm时,燃烧后的炭层可耐1.0 kV电压,涂层的耐火时限达到了10 min,最高背板温度为393℃,燃烧后形成多孔的膨胀炭层且有陶瓷状残余物,陶瓷状残余物在一定程度上提高了炭层的耐烧性能,制备得到的新型可瓷化膨胀防火涂料在电池包外壳上具有一定的应用潜能。
  • 云南省新材料重大专项(202302AB080022)
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2024年第57卷第11期
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doi: 10.16790/j.cnki.1009-9239.im.2024.11.009
  • 接收时间:2024-01-23
  • 首发时间:2025-12-24
  • 出版时间:2024-11-20
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  • 收稿日期:2024-01-23
  • 修回日期:2024-03-03
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云南省新材料重大专项(202302AB080022)
作者信息
    1上海大学,材料科学与工程学院,上海 200444
    2上海大学,理学院,上海 200444
    3青岛高新城维实业有限公司,山东 青岛 266000

通讯作者:

王金合(1982-),男(汉族),河北唐山人,副研究员,主要从事功能高分子复合材料的研究。
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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