Article(id=1198667062584377708, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198667059954545009, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.04.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1649952000000, receivedDateStr=2022-04-15, revisedDate=1655049600000, revisedDateStr=2022-06-13, acceptedDate=null, acceptedDateStr=null, onlineDate=1763714097876, onlineDateStr=2025-11-21, pubDate=1681920000000, pubDateStr=2023-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763714097876, onlineIssueDateStr=2025-11-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763714097876, creator=13701087609, updateTime=1763714097876, updator=13701087609, issue=Issue{id=1198667059954545009, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='4', pageStart='1', pageEnd='112', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763714097249, creator=13701087609, updateTime=1766563529326, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210618444354023975, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198667059954545009, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210618444354023976, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198667059954545009, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=22, endPage=27, ext={EN=ArticleExt(id=1198667063347741044, articleId=1198667062584377708, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Properties of phosphorus nitrogen aluminum synergistic flame retardant low smoke halogen-free polyolefin materials, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

Ethylene-vinyl acetate copolymer/ethylene-α-olefin copolymer (EVA/POE) was used as the base material, and phosphorus-nitrogen halogen-free flame retardant (HF-601AE) compounded with surface modified aluminum hydroxide (ATH) was used as the flame retardant system, a halogen-free flame retardant polyolefin material for heat shrinkable tube was prepared by melt mixing method. The variation of limiting oxygen index, electrical properties, and mechanical properties of the composites under different ratios were studied, and the flame retardant mechanism of composites was investigated by thermo-gravimetric analysis (TGA) and the morphology characterization of combustion residue carbon. The results show that and the 2# sample prepared with 50 phr polyolefin materials, 35 phr flame retardant HF-601AE, and 20 phr ATH has the best mechanical properties, and the tensile strength is 7.1 MPa, the elongation at break is 502.86%. The limiting oxygen index is 37.2%, which meets the requirements of EN45545-2 R22 HL3 flame retardant grade. The thermogravimetric rate at 371.5℃ reaches -18.11%/min, the carbon residue is low after combustion, and there are no holes and pores in the carbon layer, which indicate that the comprehensive properties are the best.

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以乙烯-醋酸乙烯共聚物/乙烯-α-烯烃的共聚物(EVA/POE)为基材,磷氮系无卤阻燃剂(HF-601AE)复配表面改性氢氧化铝(ATH)为阻燃体系,采用熔融混合法制备一种热缩管用无卤阻燃聚烯烃材料,研究不同配比下复合材料的极限氧指数、力学性能、电性能的变化规律,通过热失重分析(TGA)及对燃烧残炭形貌表征探究复合材料的阻燃机理。结果表明:聚烯烃材料为50份、阻燃剂HF-601AE为35份、ATH为20份制备的2#试样力学性能最优,拉伸强度为7.1 MPa,断裂伸长率为502.86%,极限氧指数为37.2%,满足EN45545-2 R22类HL3阻燃等级要求;在371.5℃时热失重速率达到-18.11%/min,燃烧后残炭量较低,炭层无空穴及孔洞,综合性能最优。

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刘晓播(1972-),男(汉族),吉林省吉林市人,高级工程师,博士,主要从事功能高分子材料的研究。
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=GWzF86qO8Vte34ym8u848Q==, magXml=gswH+BjfzUOxGcHx5hNwpg==, pdfUrl=null, pdf=To1O/DvBYsN7ubFx9DE1ew==, pdfFileSize=6493506, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=7ddj4yIl6GvweS2U2e5XwQ==, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=PK2gx0Rmfh0l8N69xhEVmg==, mapNumber=null, authorCompany=null, fund=null, authors=

吴松金(1980-),男(汉族),广西桂平人,工程师,从事热缩材料产品的开发。

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吴松金(1980-),男(汉族),广西桂平人,工程师,从事热缩材料产品的开发。

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unstructuredReference=赵榕晶,刘亚军,张玲.氢氧化铝无卤阻燃乙烯-醋酸乙烯共聚物的结构与性能[J].中国塑料,2018,32(4):97-102., articleTitle=氢氧化铝无卤阻燃乙烯-醋酸乙烯共聚物的结构与性能, refAbstract=null), Reference(id=1210986277474800360, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, doi=null, pmid=null, pmcid=null, year=2005, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[19], rfOrder=18, authorNames=王建祺, journalName=无卤阻燃聚合物基础与应用, refType=null, unstructuredReference=王建祺.无卤阻燃聚合物基础与应用[M].北京:科学出版社,2005., articleTitle=null, refAbstract=null), Reference(id=1210986277600629487, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, doi=null, pmid=null, pmcid=null, year=2007, volume=35, issue=10, pageStart=68, pageEnd=72, url=null, language=null, rfNumber=[20], rfOrder=19, authorNames=赵成刚, journalName=塑料科技, refType=null, unstructuredReference=赵成刚.环保热缩管研制[J]塑料科技,2007,35(10):68-72., articleTitle=环保热缩管研制, refAbstract=null), Reference(id=1210986277718070007, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, doi=null, pmid=null, pmcid=null, year=2005, volume=null, issue=3, pageStart=320, pageEnd=326, url=null, language=null, rfNumber=[21], rfOrder=20, authorNames=LIZ Z, WANGX G, TANY J, journalName=Fire Science and Technology, refType=null, unstructuredReference=LIZ Z, WANGX G, TANY J.et.al. Synergistic effects and flame-retardant properties of melamine cyanurate with magnesium hydroxide in halogen-free flame-retardant EVA blends[J]. Fire Science and Technology,2005,24,(3):320-326., articleTitle=et.al. Synergistic effects and flame-retardant properties of melamine cyanurate with magnesium hydroxide in halogen-free flame-retardant EVA blends, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1210986270424174930, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, xref=1, ext=[AuthorCompanyExt(id=1210986270432563538, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, companyId=1210986270424174930, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1Changyuan Electronics (Dongguan) Co., Ltd., Dongguan 523793, China), AuthorCompanyExt(id=1210986270436757843, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, companyId=1210986270424174930, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=1长园电子(东莞)有限公司,广东 东莞 523793)]), AuthorCompany(id=1210986270524838234, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, xref=2, ext=[AuthorCompanyExt(id=1210986270533226843, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, companyId=1210986270524838234, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2Shenzhen Woer Heat-Shrinkable material Co., Ltd., Shenzhen 518100, China), AuthorCompanyExt(id=1210986270537421148, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, companyId=1210986270524838234, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=2深圳市沃尔核材股份有限公司,广东 深圳 518100)])], figs=[ArticleFig(id=1210986272647156222, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Fig.1, caption=Mico-morphology of sample combustion carbon layer, figureFileSmall=Yj+Fr2UF7dAklQmbMqdi4w==, figureFileBig=8qXzHqoY41CeUms8GrMLWQ==, tableContent=null), ArticleFig(id=1210986272739430917, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=图1, caption=试样燃烧炭层的微观形貌, figureFileSmall=Yj+Fr2UF7dAklQmbMqdi4w==, figureFileBig=8qXzHqoY41CeUms8GrMLWQ==, tableContent=null), ArticleFig(id=1210986272877842957, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Fig.2, caption=TGA and DTA curves of samples, figureFileSmall=EjELK2I2kG8vsWw7Hcu9Lw==, figureFileBig=dE0HHmKIgnyw/DJLXjXtDQ==, tableContent=null), ArticleFig(id=1210986272940757526, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=图2, caption=试样的TGA/DTA曲线, figureFileSmall=EjELK2I2kG8vsWw7Hcu9Lw==, figureFileBig=dE0HHmKIgnyw/DJLXjXtDQ==, tableContent=null), ArticleFig(id=1210986273037226522, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.1, caption=The main components of sample, figureFileSmall=null, figureFileBig=null, tableContent=
材料种类1#2#3#4#5#
基材5050505050
ATH4035202025
HF-601AE2020403525
加工助剂若干若干若干若干若干
), ArticleFig(id=1210986273125306911, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表1, caption=

试样的主要成分

, figureFileSmall=null, figureFileBig=null, tableContent=
材料种类1#2#3#4#5#
基材5050505050
ATH4035202025
HF-601AE2020403525
加工助剂若干若干若干若干若干
), ArticleFig(id=1210986273238553132, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.2, caption=The limit oxygen index of samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样极限氧指数
1#35.3
2#37.2
3#36.2
4#37.4
5#35.7
), ArticleFig(id=1210986274467484212, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表2, caption=

试样的极限氧指数

, figureFileSmall=null, figureFileBig=null, tableContent=
试样极限氧指数
1#35.3
2#37.2
3#36.2
4#37.4
5#35.7
), ArticleFig(id=1210986274593313336, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.3, caption=The mechanical properties of samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样拉伸强度/MPa断裂伸长率/%
1#6.85500.56
2#7.10502.86
3#5.7879.25
4#5.61381.30
5#6.30463.75
), ArticleFig(id=1210986274710753856, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表3, caption=

试样的力学性能

, figureFileSmall=null, figureFileBig=null, tableContent=
试样拉伸强度/MPa断裂伸长率/%
1#6.85500.56
2#7.10502.86
3#5.7879.25
4#5.61381.30
5#6.30463.75
), ArticleFig(id=1210986274803028551, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.4, caption=The volume resistivity test results of samples, figureFileSmall=null, figureFileBig=null, tableContent=
试样体积电阻率/(Ω·cm)
1#6.88×1014
2#6.49×1014
3#4.12×1015
4#4.39×1015
5#7.41×1014
), ArticleFig(id=1210986274941440593, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表4, caption=

试样的体积电阻率测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
试样体积电阻率/(Ω·cm)
1#6.88×1014
2#6.49×1014
3#4.12×1015
4#4.39×1015
5#7.41×1014
), ArticleFig(id=1210986275050492504, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.5, caption=The EN45545-2 R22 test results of 2# sample, figureFileSmall=null, figureFileBig=null, tableContent=
测试标准测试项目指标测试结果判定
EN ISO 4589-2极限氧指数≥3237.2OK
EN ISO 5659-2烟雾密度≤150146.2OK
NF X 70-100-1及NF X 70-100-2烟雾毒性≤0.750.16OK
), ArticleFig(id=1210986275142767201, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表5, caption=

2#试样EN45545-2 R22测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
测试标准测试项目指标测试结果判定
EN ISO 4589-2极限氧指数≥3237.2OK
EN ISO 5659-2烟雾密度≤150146.2OK
NF X 70-100-1及NF X 70-100-2烟雾毒性≤0.750.16OK
), ArticleFig(id=1210986275230847592, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=EN, label=Tab.6, caption=Thermogravimetric parameters of samples, figureFileSmall=null, figureFileBig=null, tableContent=
项目试样
1#2#3#4#5#
T5%/℃332.0359.4329.2357.9359.0
Tmax1/℃375.9371.5373.0371.5376.5
第1阶段质量损失速率/(%/min)-12.69-18.11-12.17-16.89-12.83
Tmax2/℃474.4475.0481.9475.8474.4
第2阶段质量损失速率/(%/min)-10.52-10.22-8.58-8.71-10.17
残炭量/%21.5020.1820.9219.7723.93
), ArticleFig(id=1210986275318927981, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198667062584377708, language=CN, label=表6, caption=

试样热失重参数

, figureFileSmall=null, figureFileBig=null, tableContent=
项目试样
1#2#3#4#5#
T5%/℃332.0359.4329.2357.9359.0
Tmax1/℃375.9371.5373.0371.5376.5
第1阶段质量损失速率/(%/min)-12.69-18.11-12.17-16.89-12.83
Tmax2/℃474.4475.0481.9475.8474.4
第2阶段质量损失速率/(%/min)-10.52-10.22-8.58-8.71-10.17
残炭量/%21.5020.1820.9219.7723.93
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磷氮铝协同阻燃低烟无卤聚烯烃材料性能研究
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吴松金 1 , 田冠楠 2 , 何洪瑞 1 , 刘晓播 2
绝缘材料 | 材料研究 2023,56(4): 22-27
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绝缘材料 | 材料研究 2023, 56(4): 22-27
磷氮铝协同阻燃低烟无卤聚烯烃材料性能研究
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吴松金1, 田冠楠2, 何洪瑞1, 刘晓播2
作者信息
  • 1长园电子(东莞)有限公司,广东 东莞 523793
  • 2深圳市沃尔核材股份有限公司,广东 深圳 518100
  • 吴松金(1980-),男(汉族),广西桂平人,工程师,从事热缩材料产品的开发。

通讯作者:

刘晓播(1972-),男(汉族),吉林省吉林市人,高级工程师,博士,主要从事功能高分子材料的研究。
Properties of phosphorus nitrogen aluminum synergistic flame retardant low smoke halogen-free polyolefin materials
Songjin WU1, Guannan TIAN2, Hongrui HE1, Xiaobo LIU2
Affiliations
  • 1Changyuan Electronics (Dongguan) Co., Ltd., Dongguan 523793, China
  • 2Shenzhen Woer Heat-Shrinkable material Co., Ltd., Shenzhen 518100, China
出版时间: 2023-04-20 doi: 10.16790/j.cnki.1009-9239.im.2023.04.005
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以乙烯-醋酸乙烯共聚物/乙烯-α-烯烃的共聚物(EVA/POE)为基材,磷氮系无卤阻燃剂(HF-601AE)复配表面改性氢氧化铝(ATH)为阻燃体系,采用熔融混合法制备一种热缩管用无卤阻燃聚烯烃材料,研究不同配比下复合材料的极限氧指数、力学性能、电性能的变化规律,通过热失重分析(TGA)及对燃烧残炭形貌表征探究复合材料的阻燃机理。结果表明:聚烯烃材料为50份、阻燃剂HF-601AE为35份、ATH为20份制备的2#试样力学性能最优,拉伸强度为7.1 MPa,断裂伸长率为502.86%,极限氧指数为37.2%,满足EN45545-2 R22类HL3阻燃等级要求;在371.5℃时热失重速率达到-18.11%/min,燃烧后残炭量较低,炭层无空穴及孔洞,综合性能最优。

极限氧指数  /  无卤阻燃  /  磷氮系阻燃剂  /  氢氧化铝

Ethylene-vinyl acetate copolymer/ethylene-α-olefin copolymer (EVA/POE) was used as the base material, and phosphorus-nitrogen halogen-free flame retardant (HF-601AE) compounded with surface modified aluminum hydroxide (ATH) was used as the flame retardant system, a halogen-free flame retardant polyolefin material for heat shrinkable tube was prepared by melt mixing method. The variation of limiting oxygen index, electrical properties, and mechanical properties of the composites under different ratios were studied, and the flame retardant mechanism of composites was investigated by thermo-gravimetric analysis (TGA) and the morphology characterization of combustion residue carbon. The results show that and the 2# sample prepared with 50 phr polyolefin materials, 35 phr flame retardant HF-601AE, and 20 phr ATH has the best mechanical properties, and the tensile strength is 7.1 MPa, the elongation at break is 502.86%. The limiting oxygen index is 37.2%, which meets the requirements of EN45545-2 R22 HL3 flame retardant grade. The thermogravimetric rate at 371.5℃ reaches -18.11%/min, the carbon residue is low after combustion, and there are no holes and pores in the carbon layer, which indicate that the comprehensive properties are the best.

limiting oxygen index  /  halogen-free flame retardant  /  phosphorus-nitrogen flame retardant  /  aluminum hydroxide
吴松金, 田冠楠, 何洪瑞, 刘晓播. 磷氮铝协同阻燃低烟无卤聚烯烃材料性能研究. 绝缘材料, 2023 , 56 (4) : 22 -27 . DOI: 10.16790/j.cnki.1009-9239.im.2023.04.005
Songjin WU, Guannan TIAN, Hongrui HE, Xiaobo LIU. Properties of phosphorus nitrogen aluminum synergistic flame retardant low smoke halogen-free polyolefin materials[J]. Insulating Materials, 2023 , 56 (4) : 22 -27 . DOI: 10.16790/j.cnki.1009-9239.im.2023.04.005
无卤阻燃材料方面的研究一直以来备受广大学者、科研人员、企业技术人员的关注。无卤阻燃剂的种类有很多,常见的有氢氧化镁、氢氧化铝、红磷、氰尿酸三聚氰胺(MCA)等,但无论是单一无机氢氧化物、镁/铝复配、镁/红磷,或氮系阻燃剂,大量的研究都表明材料往往需要添加大量阻燃剂才能达到很好的阻燃效果。而阻燃剂添加量过大,会造成材料的力学性能损失严重。
科莱恩OP系列无卤阻燃剂,由于其创新性,迅速获得广泛关注,另因其特殊性,往往添加少量就能达到很好的阻燃效果。程宝发等[1]研究聚酰胺6(PA6)/二乙基次磷酸铝(ADP)复合材料的阻燃性能,结果表明,ADP的质量份数为22%时,可使PA6的极限氧指数从22%提高到33.5%,垂直燃烧从V2级提高到V0级。王金泳等[2]研究发现,ADP的热降解是通过C2H5断裂生成C2H4的方式进行,ADP热降解后剩余的含磷固体会残留在固相中,降低气相阻燃能力,ADP热降解的主要裂解产物包括C4H8、P4和C6H12。P4的生成说明ADP中同P相连接的所有化学键都发生断裂,然后这些P原子在N2保护下形成P4。在真实燃烧过程中,由于火焰中有O2等反应性物质的存在,裂解生成的P原子会继续反应生成自由基淬灭剂,而不是生成P4
氢氧化铝/氢氧化镁阻燃剂得到广泛研究和应用,其主要原因在于它们可以作为填充剂、阻燃剂、抑烟剂使用,而且理论和实践研究已非常成熟[3]。文献[4-9]研究阻燃剂对低烟无卤聚烯烃电缆性能的影响,以乙烯-醋酸乙烯共聚物(EVA)、线性低密度聚乙烯(LLDPE)、乙烯和α-烯烃的共聚物(POE)共混物为基体,氢氧化铝、氢氧化镁为阻燃剂。研究表明,随着阻燃剂填充量的增加,试样的拉伸强度和断裂伸长率降低,极限氧指数提高。文献[10-11]研究表明,通过添加大量无机阻燃剂氢氧化物可显著提升复合材料的阻燃性能,但通常会降低复合材料的力学性能,对氢氧化物进行表面改性或添加协效剂,可使复合材料的力学性能得到改善。通常无机阻燃剂的添加量要达到50%以上才能达到较好的阻燃效果[12-13]
氮系阻燃剂以MCA最具代表性,在聚丙烯(PP)阻燃和尼龙(PA)阻燃方面尤为突出,但单独应用于EVA等聚烯烃的阻燃改性时,往往需要大量填充才能使得聚烯烃材料达到较好的阻燃效果,此时其力学性能已太差。
随着无卤阻燃技术发展日渐成熟,阻燃材料的开发已趋于向高阻燃、无卤化、低毒、新技术、多功能化等方面发展[14-15]。我国的轨道交通规模日益庞大,为降低在密闭性更强的环境中运行的轨道车辆线路所用阻燃材料发生火灾的风险,对无卤阻燃材料的要求更为具体和明确,要求材料具有高极限氧指数、低烟密度、低烟毒性等特点。
在此背景下,得出磷氮系阻燃剂、氢氧化铝复配(简称磷氮铝)协同阻燃低烟无卤聚烯烃材料具有理论基础和技术可行性,但目前此类阻燃材料研究并不多[16]。本研究以磷氮铝作为阻燃体系,研究阻燃剂填充量、添加比例对材料阻燃、极限氧指数、力学性能、电性能的影响,以期开发出一款适用于轨道车辆密闭运行环境的无卤阻燃聚烯烃材料。
乙烯-醋酸乙烯共聚物,牌号为EVA630,生产厂家为日本东槽;乙烯-α-烯烃共聚物,牌号为POE 8150,生产厂家为陶氏化学;表面改性氢氧化铝(ATH),牌号为MD-9,粒径Dmax≤10 μm,生产厂家为益阳华晟;磷氮系阻燃剂,牌号为HF-601AE,生产厂家为中山康诺德。
将EVA630、POE8150在双辊开炼机上熔融混合均匀,然后逐次加入ATH、HF-601AE、加工助剂等,制备无卤阻燃复合材料,混炼温度为135℃,打三角包厚度:1 mm 6遍、0.1 mm 6遍,转速为25 r/min,然后以0.3 mm出片。再用平板硫化机在135℃、35 MPa条件下预热3 min,排气2次,加压5 min,冷却至室温。根据实验要求,制得厚度分别为1 mm和3 mm的试样。试样的配方如表1所示。
(1)极限氧指数(LOI):JF-3型氧指数仪,南京市江宁区分析仪器厂,按EN ISO 4589-2进行测试,试样尺寸为140 mm×6.5 mm×3 mm。
(2)力学性能:TM4503型万能试验机,深圳三思纵横科技股份有限公司,按ASTM D638-2014进行测试,拉伸速率为500 mm/min,实验温度为(23±2)℃。试样为Ⅱ型哑铃片,厚度为(1.0±0.1)mm,测量标距长度为25 mm,宽度为6 mm,取5次测试值的平均值作为实验结果。
(3)电性能:TH2684A型绝缘电阻测试仪,江苏同惠电子有限公司,按IEC 93-1983测试试样的体积电阻率,试样尺寸为140 mm×140 mm×1 mm。
(4)EN45545-2、R22 HL3阻燃等级符合性:优选试样送SGS第三方进行测试。
(5)微观形貌分析:SVM-3030型手动影像测量仪,东莞市展康测量科技有限公司,观察5种试样燃烧后的炭貌,并拍照其燃烧后的炭层,放大倍数为500倍。
(6)热失重分析(TGA):TG 209 F3型热重分析仪,耐驰公司,测试在流速为30 mL/min的氮气气氛中进行,升温速率为10℃/min,测试温度为30~800℃。
极限氧指数常用于评价材料的静态阻燃性能,试样的极限氧指数数据见表2。从表2可以看出,2#试样和4#试样(阻燃剂总量为55份)的极限氧指数明显大于其他试样(1#和3#试样的阻燃剂总量为60份),试样的极限氧指数并不随着复配阻燃剂总填充量的增加而增大。这种现象和现有大多数研究氢氧化物阻燃体系的结论有所区别。现有大多数研究结论表明,极限氧指数随着阻燃剂添加比例的增加而增大[17]
原因在于该复合材料的燃烧行为受ATH和HF-601AE相互影响制约,当ATH含量高时,ATH受热分解形成水(吸收复合材料燃烧时产生的热量)、氧化铝膜为主(氧化铝膜起隔绝材料和氧气的接触作用),复合材料燃烧形成的磷酸铝液态膜浓度低或磷元素猝灭剂含量低,对氧化铝膜层的加固程度不足,导致复合材料的极限氧指数不大。
当HF-601AE含量高时,HF-601AE中的磷系阻燃剂组分主要以形成磷酸铝液态膜(起隔阻氧气作用)和磷元素(起猝灭剂作用)为主;HF-601AE中的氮系阻燃剂组分主要以形成氮气(起到稀释材料表面氧浓度的作用)为主,而ATH组分形成的水(吸热)和氧化铝膜(隔阻)效果不明显。而当HF-601AE的添加量过大时,复合材料燃烧形成的磷酸铝液态膜浓度高或磷元素猝灭剂含量高,但同时形成的氮气量也多,会破坏磷酸铝液态膜、氧化铝膜的隔阻效果,这种协效阻燃效果不明显。因此,只有ATH和HF-601AE添加比例达到某个临界比例时,磷、氮、铝三者相互作用为加强的效果时,复合材料的极限氧指数才会更大。
测试试样的力学性能,研究阻燃剂添加量、添加种类对材料力学性能的影响,结果如表3所示。从表3可以看出,当试样阻燃剂添加总量相等时(1#试样和3#试样阻燃剂总量为60份、2#试样和4#试样阻燃剂总量为55份),HF-601AE对复合材料的力学性能损失影响大于ATH。当HF-601AE添加量为40份时,试样的断裂伸长率出现最小值(3#试样),2#试样的力学性能(拉伸强度为7.10 MPa,断裂伸长率为502.86%)在5种试样中最优,阻燃剂总量越少,对复合材料力学性能的影响越小。试样阻燃剂的填充总量对材料的力学性能影响也明显区别于现有研究。
理论上阻燃剂的填充量增加,使得基材树脂大分子链的运动受到更大限制,无机粒子阻碍了应力传递和分子链之间的相对运动[18],复合材料的力学性能应下降。但1#试样和3#试样对比,3#试样的力学性能明显低于1#试样,且同时低于2#、4#、5#试样。5#阻燃剂添加总量最低,但力学性能并不是最高。原因在于ATH/HF-601AE复配体系中,ATH经过表面改性处理,其和基材相容性较好,因此对材料的力学损失影响较小,而HF-601AE与基材的接触界面结合较差,导致相同添加总量的情况下,1#试样比3#试样的力学性能明显要高。通过2#试样和4#试样对比,也得出相同规律。另外两种阻燃剂的粒径尺寸、形状等存在差异,两种不同粒径的材料,只有在相互混合且比例最佳时,堆积密度才最佳,对复合材料力学性能的影响才最小。
通过对试样的体积电阻率进行测试,研究阻燃剂添加量、添加种类对材料电学性能的影响,结果如表4所示。从表4可以看出,2#试样的体积电阻率最低,4#试样的体积电阻率最高。试样的体积电阻率与阻燃剂的添加量或比例变化并不明显,试样满足绝大多数绝缘材料体积电阻率≥1.0×1014 Ω·cm的指标,符合热缩套管产品的体积电阻率要求。
通过对试样的极限氧指数、力学性能、电性能分析,优选2#试样送SGS测试,测试方法标准参考EN45545-2,R22类,结果如表5所示。从表5可以看出,磷氮铝协同阻燃无卤聚烯烃材料的极限氧指数、烟雾密度、烟雾毒性等满足EN45545-2 R22类HL3阻燃等级要求。
为了研究不同阻燃剂添加量、复配比例对复合材料阻燃性能的影响,采用SVM-3030型手动影像测量仪观察材料燃烧后的炭层形貌,放大倍数为500倍,结果如图1所示。
图1可以看出,1#试样燃烧后形成如白雾状的残炭形貌,炭层不坚固,残炭表面有明显的坍塌,形成较大的空洞或孔穴。此时阻燃剂主要成分为ATH,燃烧炭层表面以氧化铝膜为主,HF-601AE的含量低,主要通过ATH燃烧脱水降温、隔阻氧气接触的阻燃机理实现阻燃效果[19-21]。2#试样燃烧后的微观表面和1#相似,但无坍塌现象,炭层更为坚固,表明此时两种阻燃剂的复配协效作用明显,倾向于形成坚固的氧化铝隔膜层为主。原因在于HF-601AE中的磷系阻燃剂燃烧生成的磷酸铝液态膜对ATH燃烧形成的氧化铝膜起到加固作用,同时燃烧分解释放的磷元素起到猝灭剂的作用更为明显;且氮系阻燃剂燃烧形成的氮气量不多,可以起到稀释复合材料燃烧表层氧浓度的作用,但不会对炭层造成明显的破坏影响。3#试样燃烧后的表面无法形成稳定坚固的隔阻层,氧化铝膜层也出现熔塌,此时阻燃剂主要成分为HF-601AE,因其氮系阻燃剂成分燃烧时释放氮气量明显增多,虽然能起到稀释试样表面氧浓度的作用,但同时会破坏磷酸铝液态膜对氧化铝膜的加固效果,反而导致复合材料的阻燃性降低,因此材料的阻燃效果并不好。4#试样燃烧后的残炭形貌更完整,形成的空洞形状相对于1#试样明显要小,表明HF-601AE中磷系阻燃剂燃烧形成的磷酸铝液态膜对ATH起到加速脱水炭化作用。与文献[2]的研究结论一致,随着HF-601AE含量增加,其氮系阻燃剂燃烧产生的氮气量增多,会破坏炭层,从而使试样燃烧表面炭层形成明显的孔穴。但孔穴形成后,燃烧产生的氮气会通过孔穴排出,从而降低对周边炭层的破坏程度,提升了材料的阻燃效果。5#试样的炭层表面和前面4个试样形成的炭层表面有明显的不同,既不能形成完整的氧化铝膜,同时也没有形成连续的炭层、空洞或孔穴。材料的极限氧指数只比1#试样略高,阻燃效果并不好。
图2为1#~5#试样的热失重(TGA/DTA)曲线,相关热失重参数见表6,其中T5%为失重5%时的温度,Tmax1Tmax2分别为材料两个失重阶段最大失重速率对应的温度。
相关研究数据显示,单一的ATH阻燃体系其第1阶段失重峰值温度为320.9~329.3℃[4]。MDH/MCA阻燃体系中,氮系阻燃剂MCA(氰尿酸三聚氰胺)失重峰值温度为365~425℃[21]。二乙基次磷酸铝在燃烧过程中,从360℃开始分解,在高于445℃时,部分二乙基次磷酸铝中乙基链断裂,在448℃达到最大失重速率[2]
图2表6可以看出,1#~5#试样的第1阶段热失重峰值温度范围为371.5℃~376.5℃,和MDH/MCA阻燃体系的第1阶段热失重峰值温度相当。
因此在磷氮铝复配阻燃体系中,对第1阶段热失重峰值起主要贡献作用的是ATH和HF-601AE中的氮系阻燃剂组分。
1#、3#、5#试样在第1阶段的失重速率峰值分别为-12.69、-12.17、-12.83%/min,热失重峰值速率略低于2#试样和4#试样,主要是因为1#、3#、5#试样在第1阶段热失重过程中,HF-601AE分解和ATH分解未能起到加速吸热效果。而2#、4#试样第1阶段热失重速率高,说明复配阻燃剂起到加速吸热作用更明显。第2阶段热失重峰值温度为474.4~481.9℃,主要为聚烯烃降解和氢氧化物降解,同时磷氮阻燃剂中磷系组分分解形成液态磷酸铝和磷酸铝固体物质。第2阶段失重速率峰值为-8.58~-10.52%/min,其中3#和4#试样的失重峰值速率明显低于其他试样,这是因为受ATH含量低影响所致。结合试样配比表可以看出,Tmax2低和ATH含量关联程度更明显。
残炭量也是表征材料热稳定性的一个标准,一般而言残炭量越高,材料的热稳定性越好。而本研究发现,在磷氮铝复配阻燃体系中,结合试样的LOI测试结果,残炭量越低,试样的LOI值反而越高,阻燃性能更好。
(1)通过磷氮铝协同阻燃制备无卤阻燃聚烯烃材料,制备的2#试样(聚烯烃材料为50份、阻燃剂HF-601AE为35份、ATH为20份)极限氧指数为37.2%。
(2)2#试样的力学性能最优,拉伸强度为7.1 MPa、断裂伸长率为502.86%;体积电阻率为6.49×1014 Ω·cm,满足热缩绝缘材料要求,阻燃性符合EN45545-2 R22类HL3等级阻燃要求。
(3)通过TGA分析,2#试样在371.5℃时达到第1阶段的失重峰值,失重速率为-18.11%/min,失重速率最大,失重吸热效果最明显,燃烧后残炭量较低,炭层无空穴和孔洞,综合性能最佳。
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2023年第56卷第4期
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doi: 10.16790/j.cnki.1009-9239.im.2023.04.005
  • 接收时间:2022-04-15
  • 首发时间:2025-11-21
  • 出版时间:2023-04-20
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  • 收稿日期:2022-04-15
  • 修回日期:2022-06-13
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    1长园电子(东莞)有限公司,广东 东莞 523793
    2深圳市沃尔核材股份有限公司,广东 深圳 518100

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刘晓播(1972-),男(汉族),吉林省吉林市人,高级工程师,博士,主要从事功能高分子材料的研究。
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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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