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In this paper, the effects of properties of chopped fiber on the breakdown strength, conductivity, trap characteristics, and mechanical properties of meta-aramid paper were studied. The results show that based on the reference sample of which the fiber diameter is 25 μm, fiber length is 6 mm, crystallization temperature is 300℃, and the ratio of precipitated fibrids and chopped fibers is 7:3, when the fiber diameter increases to 45 μm, the embedding degree of chopped fibers decreases, interface pores appear, and the breakdown and tensile strength of aramid paper can decrease by 16% and 24%, respectively. When the length of fiber increases to 18 mm, chopped fiber morphology shows coiling-type thus forming the "hard-form" interface, the breakdown strength of aramid paper decreases by 63%, while the tensile strength shows little change. When the crystallization temperature decreases to 230℃, the structural stability of chopped fibers reduces, which causes their melting under hot-pressing process, and the breakdown strength and tensile strength decreases by 36% and 50%, respectively. With the increase of proportion of chopped fiber, the breakdown strength of aramid paper increases at first and then decreases, which is along with the change of paper compactness, while the tensile strength of aramid paper increases monotonically with the increase of chopped fiber content, which reflects the necessity of chopped fibers for the stable molding of aramid paper and the weakening effect of excessive chopped fibers on electrical insulation. In addition, the aramid papers with low breakdown strength show a higher conductivity and a shallower trap depth, which can be regarded as reference indexes for the insulation performance of meta-aramid papers.

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本文研究了短切纤维特性对间位芳纶纸击穿强度、电导率、陷阱特性和力学相关性能的影响。结果表明,在参照样品(直径为25 μm、长度为6 mm、结晶温度为300℃、沉析纤维与短切纤维的配比为7∶3)的基础上,纤维直径增加至45 μm会降低沉析对短切纤维的包覆程度,诱发界面孔隙,芳纶纸的击穿强度和拉伸强度降幅可达16%和24%;纤维长度增加至18 mm,会造成短切纤维翘曲并形成“硬质”界面,击穿强度降幅可达63%,拉伸强度则无明显变化;结晶温度降低至230℃,会降低短切纤维结构稳定性,导致其热压熔融,击穿强度和拉伸强度降幅可达36%和50%;当短切纤维配比增加时,芳纶纸的击穿强度随致密度呈先升后降趋势,拉伸强度则随短切纤维含量的增加单调递增,体现了短切纤维对芳纶纸稳定成型的必要性和过量短切纤维对绝缘的削弱作用。此外,低击穿强度芳纶纸会呈现电导率提高和电荷陷阱浅化的现象,可作为芳纶纸绝缘性能判别的参考指标。

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阮浩鸥(1995-),男(汉族),重庆人,博士生,主要从事新型电工绝缘材料改性的研究;

樊思迪(1991-),女(汉族),黑龙江哈尔滨人,特聘副教授,主要从事复合电介质物理特性及储能应用的研究。

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阮浩鸥(1995-),男(汉族),重庆人,博士生,主要从事新型电工绝缘材料改性的研究;

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阮浩鸥(1995-),男(汉族),重庆人,博士生,主要从事新型电工绝缘材料改性的研究;

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樊思迪(1991-),女(汉族),黑龙江哈尔滨人,特聘副教授,主要从事复合电介质物理特性及储能应用的研究。

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Experimental study on damage mechanism of partial discharge of oil-immersed laminated PMIA paper[J]. IEEE Transactions on Dielectrics and Electrical Insulation,2021,28(4):1223-1230., articleTitle=Experimental study on damage mechanism of partial discharge of oil-immersed laminated PMIA paper, refAbstract=null), Reference(id=1217475354726421358, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2020, volume=83, issue=null, pageStart=106358, pageEnd=null, url=null, language=null, rfNumber=[2], rfOrder=1, authorNames=ARROYOO, JALBERTJ, RODRIGUEZE, journalName=Polymer Testing, refType=null, unstructuredReference=ARROYOO, JALBERTJ, RODRIGUEZE, et al. Changes in mechanical properties of impregnated Nomex papers 410 and 910 during accelerated aging[J]. Polymer Testing,2020,83:106358., articleTitle=Changes in mechanical properties of impregnated Nomex papers 410 and 910 during accelerated aging, refAbstract=null), Reference(id=1217475354797724528, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2022, volume=55, issue=2, pageStart=23, pageEnd=27, url=null, language=null, rfNumber=[3], rfOrder=2, authorNames=秦盼亮, 吉永红, 刘嬿, journalName=绝缘材料, refType=null, unstructuredReference=秦盼亮,吉永红,刘嬿,等.牵引电机用国产与进口间位芳纶纸的性能对比研究[J].绝缘材料,2022,55(2):23-27., articleTitle=牵引电机用国产与进口间位芳纶纸的性能对比研究, refAbstract=null), Reference(id=1217475354848056176, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2012, volume=13, issue=3, pageStart=277, pageEnd=281, url=null, language=null, rfNumber=[4], rfOrder=3, authorNames=YAOL, KIMK, KIMJ, journalName=Fibers and Polymers, refType=null, unstructuredReference=YAOL, KIMK, KIMJ. Fabrication of meta-aramid fibrid by precipitation[J]. 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Influence of hot-pressing temperature on the formation of aramid paper[J]. 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Novel poly(m-phenyleneisophthalamide) dielectric composites with enhanced thermal conductivity and breakdown strength utilizing functionalized boron nitride nanosheets[J]. Macromolecular Materials and Engineering,2019,304(11):1900310., articleTitle=Novel poly(m-phenyleneisophthalamide) dielectric composites with enhanced thermal conductivity and breakdown strength utilizing functionalized boron nitride nanosheets, refAbstract=null), Reference(id=1217475356647412602, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2021, volume=13, issue=14, pageStart=16895, pageEnd=16905, url=null, language=null, rfNumber=[12], rfOrder=11, authorNames=TANJ, LUOY, ZHAMGM, journalName=ACS Applied Material & Interfaces, refType=null, unstructuredReference=TANJ, LUOY, ZHAMGM, et al. Dissolving and regeneration of meta-aramid paper: Converting loose structure into consolidated networks with enhanced mechanical and insulation properties[J]. 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The effects of surfactants on the spinnability, structure and properties of dry-jet wet spinning poly(m-phenylene isophalamide) fiber[J]. Fibers and Polymers,2020,21(7):1438-1443., articleTitle=The effects of surfactants on the spinnability, structure and properties of dry-jet wet spinning poly(m-phenylene isophalamide) fiber, refAbstract=null), Reference(id=1217475356974568318, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2020, volume=53, issue=10, pageStart=96, pageEnd=102, url=null, language=null, rfNumber=[16], rfOrder=15, authorNames=吴东乐, 孙胜然, 刘群华, journalName=绝缘材料, refType=null, unstructuredReference=吴东乐,孙胜然,刘群华,等.变压器用绝缘纸击穿强度的多因素协同影响研究[J].绝缘材料,2020,53(10):96-102., articleTitle=变压器用绝缘纸击穿强度的多因素协同影响研究, refAbstract=null), Reference(id=1217475357041677183, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2022, volume=7, issue=1, pageStart=52, pageEnd=63, url=null, language=null, rfNumber=[17], rfOrder=16, authorNames=GAOY, LIJ, XUB, journalName=High Voltage, refType=null, unstructuredReference=GAOY, LIJ, XUB, et al. Effect of chemical corrosion on charge transport behavior in epoxy/Al2O3 nanocomposite irradiated by gamma ray[J]. High Voltage,2022,7(1):52-63., articleTitle=Effect of chemical corrosion on charge transport behavior in epoxy/Al2O3 nanocomposite irradiated by gamma ray, refAbstract=null), Reference(id=1217475357108786048, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2020, volume=22, issue=4, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[18], rfOrder=17, authorNames=RENC, ZHANGC, HUD, journalName=Plasma Science and Technology, refType=null, unstructuredReference=RENC, ZHANGC, HUD, et al. Trap distribution of polymeric materials and its effect on surface flashover in vacuum[J]. 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unstructuredReference=李卫卫,张美云,杨斌,等.芳纶纳米纤维涂布增强间位芳纶纸性能研究[J].中国造纸,2021,40(9):15-22., articleTitle=芳纶纳米纤维涂布增强间位芳纶纸性能研究, refAbstract=null), Reference(id=1217475357377221507, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, doi=null, pmid=null, pmcid=null, year=2015, volume=41, issue=2, pageStart=364, pageEnd=373, url=null, language=null, rfNumber=[21], rfOrder=20, authorNames=廖瑞金, 李萧, 杨丽君, journalName=高电压技术, refType=null, unstructuredReference=廖瑞金,李萧,杨丽君,等.间位芳纶短切纤维/浆粕的配比对芳纶绝缘纸性能的影响[J].高电压技术,2015,41(2):364-373., articleTitle=间位芳纶短切纤维/浆粕的配比对芳纶绝缘纸性能的影响, refAbstract=null)], funds=[Fund(id=1217475354395071333, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, awardId=LAPS202103, language=CN, fundingSource=新能源电力系统国家重点实验室课题(LAPS202103), fundOrder=null, country=null)], companyList=[AuthorCompany(id=1217475345863856777, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, 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纤维命名芳纶纸命名直径/μm长度/mm结晶温度/℃
FC0C025.06300
FD1.5D1.535.06300
FD2D245.06300
FL12L1225.012300
FL18L1825.018300
FT290T29025.06290
FT270T27025.06270
FT250T25025.06250
FT230T23025.06230
), ArticleFig(id=1217475354214716256, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927011397669045, language=CN, label=表1, caption=

短切纤维参数信息

, figureFileSmall=null, figureFileBig=null, tableContent=
纤维命名芳纶纸命名直径/μm长度/mm结晶温度/℃
FC0C025.06300
FD1.5D1.535.06300
FD2D245.06300
FL12L1225.012300
FL18L1825.018300
FT290T29025.06290
FT270T27025.06270
FT250T25025.06250
FT230T23025.06230
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短切纤维特性对间位芳纶纸电气绝缘性能的影响
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阮浩鸥 1 , 律方成 1 , 孙凯旋 1 , 宋景萱 1 , 常小斌 2 , 樊思迪 1
绝缘材料 | 材料研究 2024,57(2): 19-28
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绝缘材料 | 材料研究 2024, 57(2): 19-28
短切纤维特性对间位芳纶纸电气绝缘性能的影响
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阮浩鸥1, 律方成1, 孙凯旋1, 宋景萱1, 常小斌2, 樊思迪1
作者信息
  • 1新能源电力系统国家重点实验室(华北电力大学),北京 102206
  • 2赣州龙邦材料科技有限公司,江西 赣州 341999
  • 阮浩鸥(1995-),男(汉族),重庆人,博士生,主要从事新型电工绝缘材料改性的研究;

    樊思迪(1991-),女(汉族),黑龙江哈尔滨人,特聘副教授,主要从事复合电介质物理特性及储能应用的研究。

Effect of properties of chopped fibers on electrical insulating performance of meta-aramid paper
Haoou RUAN1, Fangcheng LÜ1, Kaixuan SUN1, Jingxuan SONG1, Xiaobin CHANG2, Sidi FAN1
Affiliations
  • 1State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources (NCEPU), Beijing 102206, China
  • 2Ganzhou Longpont Material Technology Co., Ltd., Ganzhou 341999, China
出版时间: 2024-02-20 doi: 10.16790/j.cnki.1009-9239.im.2024.02.003
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本文研究了短切纤维特性对间位芳纶纸击穿强度、电导率、陷阱特性和力学相关性能的影响。结果表明,在参照样品(直径为25 μm、长度为6 mm、结晶温度为300℃、沉析纤维与短切纤维的配比为7∶3)的基础上,纤维直径增加至45 μm会降低沉析对短切纤维的包覆程度,诱发界面孔隙,芳纶纸的击穿强度和拉伸强度降幅可达16%和24%;纤维长度增加至18 mm,会造成短切纤维翘曲并形成“硬质”界面,击穿强度降幅可达63%,拉伸强度则无明显变化;结晶温度降低至230℃,会降低短切纤维结构稳定性,导致其热压熔融,击穿强度和拉伸强度降幅可达36%和50%;当短切纤维配比增加时,芳纶纸的击穿强度随致密度呈先升后降趋势,拉伸强度则随短切纤维含量的增加单调递增,体现了短切纤维对芳纶纸稳定成型的必要性和过量短切纤维对绝缘的削弱作用。此外,低击穿强度芳纶纸会呈现电导率提高和电荷陷阱浅化的现象,可作为芳纶纸绝缘性能判别的参考指标。

间位芳纶纸  /  短切纤维  /  击穿强度  /  电荷陷阱

In this paper, the effects of properties of chopped fiber on the breakdown strength, conductivity, trap characteristics, and mechanical properties of meta-aramid paper were studied. The results show that based on the reference sample of which the fiber diameter is 25 μm, fiber length is 6 mm, crystallization temperature is 300℃, and the ratio of precipitated fibrids and chopped fibers is 7:3, when the fiber diameter increases to 45 μm, the embedding degree of chopped fibers decreases, interface pores appear, and the breakdown and tensile strength of aramid paper can decrease by 16% and 24%, respectively. When the length of fiber increases to 18 mm, chopped fiber morphology shows coiling-type thus forming the "hard-form" interface, the breakdown strength of aramid paper decreases by 63%, while the tensile strength shows little change. When the crystallization temperature decreases to 230℃, the structural stability of chopped fibers reduces, which causes their melting under hot-pressing process, and the breakdown strength and tensile strength decreases by 36% and 50%, respectively. With the increase of proportion of chopped fiber, the breakdown strength of aramid paper increases at first and then decreases, which is along with the change of paper compactness, while the tensile strength of aramid paper increases monotonically with the increase of chopped fiber content, which reflects the necessity of chopped fibers for the stable molding of aramid paper and the weakening effect of excessive chopped fibers on electrical insulation. In addition, the aramid papers with low breakdown strength show a higher conductivity and a shallower trap depth, which can be regarded as reference indexes for the insulation performance of meta-aramid papers.

meta-aramid paper  /  chopped fiber  /  breakdown strength  /  carrier trap
阮浩鸥, 律方成, 孙凯旋, 宋景萱, 常小斌, 樊思迪. 短切纤维特性对间位芳纶纸电气绝缘性能的影响. 绝缘材料, 2024 , 57 (2) : 19 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2024.02.003
Haoou RUAN, Fangcheng LÜ, Kaixuan SUN, Jingxuan SONG, Xiaobin CHANG, Sidi FAN. Effect of properties of chopped fibers on electrical insulating performance of meta-aramid paper[J]. Insulating Materials, 2024 , 57 (2) : 19 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2024.02.003
新能源电力系统中,间位芳纶被视为制作新型绝缘纸的理想材料[1]。与纤维素纸相比,间位芳纶纸具有更高的电气绝缘强度和热力学稳定性,可提升设备绝缘裕度与过载运行能力[2]。目前,市面主流的间位芳纶纸产品是美国杜邦公司研发的Nomex绝缘纸,其中Nomex T410作为一款具有独特性能优势的纯间位芳纶纸,占据了高端绝缘纸市场。目前,承载人身安全和重大经济效益的变电设备如矿用隔爆变压器、高铁牵引变压器、城市枢纽变压器等,须以较大经济代价进口该款绝缘纸[3]。因此,间位芳纶纸的国产化和高性能化成为绝缘材料领域的重要课题。
制备工艺是影响芳纶纸性能的重要因素。从芳纶纸全链条生产路径来看,已有学者对部分关键造纸工艺开展了实验研究。原料调控方面,YAO L等[4]对间位芳纶溶液的沉析工艺进行了探讨,系统性地给出了凝固浴浓度、剪切转速等参数对沉析纤维结构及成纸特性的影响规律;杨军等[5]研究了不同分子量的沉析纤维对芳纶纸性能的影响,发现增加沉析纤维分子量对抗张强度、撕裂强度、断裂伸长率和介电强度有益。湿法抄纸方面,王佩瑶等[6]研究了聚氧化乙烯分散剂对芳纶纤维悬浮液的屈服流变特性及其与成纸均匀度的关系,探索了悬浮液达到临界流态化的条件,提出了高稳定性芳纶纸浆的分散剂调配策略;本课题组[7]研究了纸浆杂质残留对芳纶纸性能的影响,从本征能带和电荷陷阱两个层面揭示了离子型、难溶性及其混合杂质对芳纶纸绝缘性能的削弱机制。热压处理方面,南通大学的YAO L等[8]讨论了热压参数对芳纶纸性能的影响,发现随着热压温度提高,芳纶纸的力学性能呈现先升后降的趋势,揭示了热压温度择优的必要性。陆赵情等[9]研究了热压中的水分残留对芳纶纸性能的影响,发现适当的含水量有助于提升芳纶纸致密度与绝缘性能。已有研究揭示了多项原料方面与造纸方面参数对芳纶纸绝缘及其他性能的影响规律[10-11],却鲜见针对关键芳纶造纸原料——短切纤维的讨论。
短切纤维被视为间位芳纶纸的骨架。为了满足绝缘与力学性能的双向需求,间位芳纶纸被设计为类似“纤维增强树脂(FRP)[12]”的工程结构。短切纤维形态规整,具有高结晶度,可发挥“增强相”的作用,为芳纶纸提供坚韧的支撑骨架。而另一种造纸原料——沉析纤维具有热压易软化、产物致密性好的特点,可保障芳纶纸的基本电气阻隔[13]。借助沉析纤维的软化,可以达成两类纤维的界面粘合,从而制备出以间位芳纶为物质基础,以“短切增强沉析”为结构特征的复合芳纶纸。目前,芳纶造纸工艺难以有效处理短切纤维与沉析纤维的界面缺陷问题,从而导致芳纶纸性能有所下降[14]。在这一技术背景下,短切纤维的制造参数选取显得尤为重要。短切纤维由芳纶聚合溶液通过干喷、湿纺、拉伸、结晶、切割工艺制成,之后以一定配比与沉析纤维混合作为纸浆原料[15]。因此其制造参数主要为纤维直径、长度、结晶温度和配比,探究这些参数对芳纶纸性能的影响规律,对实现芳纶纸绝缘性能的提升具有重要意义。
本文采用控制变量法,研究短切纤维直径、长度、结晶温度和配比对间位芳纶纸结构与性能的影响。从击穿强度、电导率、电荷陷阱3个方面,对间位芳纶纸的电气绝缘性能进行考量。然后根据芳纶纸微观结构特征和力学性能指标,对短切纤维参数引起的电气绝缘性能变化进行阐释。希望研究结果能为国产间位芳纶纸改性提供理论和实验参考。
间位芳纶短切纤维和沉析纤维由赣州龙邦材料科技有限公司提供,涉及9种不同类型的短切纤维,具体命名与短切纤维参数见表1。制备实验中,选取直径25 μm、长度6 mm、结晶温度300℃的短切纤维以30%的质量分数制备而成的芳纶纸为参照样品C0,采用控制变量法开展制备实验,纤维直径取25、35、45 μm,纤维长度取6、12、18 mm,纤维结晶温度取300、290、270、250、230 ℃,短切纤维质量占比取100%、90%、80%、70%、60%、50%。无水乙醇、聚氧化乙烯分散剂购自阿拉丁生化科技有限公司。
取1 940 mL去离子水、2.8 g沉析纤维和60 mL质量分数为0.05%的聚氧化乙烯水溶液,混合于剪切分散机中,以900 r/min的转速分散30 min。之后将浆料转移至纤维疏解器,加入1.2 g短切纤维,以2 500 r/min的转速疏解30 min。将纸浆倒入造纸机筒进行抄造和压榨处理,然后将芳纶纸移至烘箱,在80℃下干燥30 min。最后采用平板硫化机和镀铬钨钢模具,以270℃、10 MPa、15 s的参数热压3次,进行压实处理。上述造纸工艺下,芳纶纸的质量损失率控制在5%以下,芳纶纸厚度为(0.13±0.02) mm,定量控制在32 g/m2
采用扫描电子显微镜(SEM,Zeiss Gemini 300型)观测芳纶纸的微观形貌,制样时,采用尺寸为1 mm×1 mm的方形冲片模具对芳纶纸进行取样,并在测试前分别按照横向、竖向粘贴,以观测芳纶纸的表面与截面,同时喷镀Pt以增强成像。采用标准直径分别为25 mm和75 mm的柱、板电极和交流电压源测试芳纶纸的交流击穿强度,将击穿电压除以击穿点厚度获得击穿强度,每个芳纶纸重复测试9次并进行Weibull拟合[16]
采用三电极法[17]测试芳纶纸的电导率,测试平台如图1(a)所示。测量时下电极电压U为1 kV,加压5 min待电流稳定后读数,据式(1)计算电导率。
δv=ThIv/(πr2U)
式(1)中:Iv为皮安表读数;Th为芳纶纸厚度;r为柱电极半径。
采用等温表面电位衰减法[18]测试芳纶纸的电荷陷阱特性,测试平台如图1(b)所示。测试时芳纶纸置于60℃接地铝箔上,通过5 kV针电晕充电2 min,然后将芳纶纸移至串接静电仪(Trek 3455ET)的探头下(Trek P0864),用数采卡监测表面电位720 s,通过式(2)~(3)推算陷阱曲线参数,包括陷阱深度ET和陷阱密度I(t)。
ET=kBTln(vt)
I(t)=(ε0εr/eTh)tdU/dt
式(2)~(3)中:t为时间;kB为玻尔兹曼常数;T为绝对温度;v为电荷逃逸频率,在直流电场中取4.17×1013 s-1εrε0分别为相对介电常数和真空介电常数。
采用恒速拉伸法测试芳纶纸的拉伸强度和杨氏模量,测试时将芳纶纸裁剪为尺寸为150 mm×25 mm的样条,采用万能试验机(DR-LL-2J型,广东德瑞检测设备有限公司),以100 mm的夹持距离、100 mm/min的拉伸速率进行测试,当断裂处与夹持边的最短距离大于10 mm时,认为测试有效。每组芳纶纸测试3次,取平均值和标准差进行分析。
图2为FC0(直径为25 μm)、FD1.5(直径为35 μm)、FD2(直径为45 μm)短切纤维的SEM图像。从图2可以看出,不同直径纤维的表面光滑度及形态特征相近。
图3为不同直径短切纤维制得芳纶纸的电气绝缘性能测试结果。从图3(a)可以看出,C0芳纶纸的击穿强度为23.4 kV/mm,随着纤维直径增加,击穿强度先缓慢下降然后急剧下降,D1.5的击穿强度为22.9 kV/mm,D2的击穿强度则降至19.7 kV/mm,相比C0下降了16%。从图3(b)可以看出,C0的电导率为1.23×10-16 S/m,随着纤维直径增加,电导率呈递增趋势,其中D2的电导率升至1.15×10-15 S/m,比C0提高了10倍。从图3(c)可以看出,C0的初始电位为3.15 kV,720 s后电位保持率为95%,随着纤维直径增加,初始电位及保持率呈现递减趋势,其中D2的初始电位和720 s后的电位保持率分别下降至2.18 kV和80%。从图3(d)可以看出,C0的深陷阱深度为1.18 eV,深陷阱密度为8.46×1011 eV-1·m-3,浅陷阱深度约为1.07 eV,浅陷阱密度约为7.65×1011 eV-1·m-3。随着纤维直径增加,芳纶纸陷阱曲线发生浅化,深陷阱中心左移且密度降低,同时浅陷阱密度增大。其中D2的深陷阱深度达到1.14 eV,密度降低至5.47×1011 eV-1·m-3,同时,浅陷阱深度变为1.06 eV,密度提高至1.22×1011 eV-1·m-3。上述结果说明,相比直径为25 μm的纤维,直径为35 μm的纤维对芳纶纸电气性能的影响幅度不大,但当纤维直径增加至45 μm时,芳纶纸的电气绝缘性能会被严重削弱,击穿强度的降低幅度可达16%,并伴有电导电流增加和陷阱浅化。
图4为不同直径短切纤维制得芳纶纸的SEM图像,分别用虚线标记了沉析和短切纤维的形态特点。
图4可以看出,C0表面相对平整,短切纤维包埋程度较高,但其表面仍存在大量界面孔隙,这说明造纸工艺无法形成如同FRP的紧密组分粘合,这源于热压中沉析纤维仅发生软化,而非呈现类似树脂的流动状态;同时,短切纤维对压力的过度分担,导致部分短切纤维侧面的沉析纤维无法软化粘结,从而不可避免地形成界面孔隙。同时,C0截面也存在短切纤维脱离和镂空现象,这说明即使在热压方向上,沉析纤维也无法形成连续封闭结构,这源于短切纤维与沉析纤维的相容性不够理想。随着纤维直径增加,芳纶纸的界面缺陷逐渐加重。纸面内孔隙增多,截面中纤维脱离和镂空现象更加严重,D2表面甚至出现了短切纤维裸露,截面出现了短切纤维悬空。上述结果说明,当短切纤维直径增加时,沉析纤维对短切纤维的包覆程度降低,截面观测到的短切纤维脱出区域增多,纤维界面孔隙增加,芳纶纸结构的连续性降低,可认为是造成绝缘下降的原因。
图5为不同短切纤维直径所造芳纶纸的力学性能测试结果。从图5可以看出,C0的弹性模量为1.56 GPa,拉伸强度为33.5 MPa。随着纤维直径增加,芳纶纸的弹性模量和拉伸强度总体呈现递减趋势。D2的弹性模量和拉伸强度分别降低至1.02 GPa和25.3 MPa,相对C0分别下降了35%和24%。相比击穿强度降幅,力学性能的降幅更大,这是因为力学性能与短切网络相关,电气性能则与纤维界面相关。短切纤维直径增加时,纤维界面缺陷呈现先缓后急的递增趋势,当短切纤维质量一定时,纤维直径越大,则纤维数量越少,且随着直径线性增加,单根纤维体积呈二次增加,导致纤维数量骤减,从而影响到纤维网络的均匀性和对局部断裂的约束能力,导致D2的力学性能下降较大。
图6为不同长度短切纤维所造芳纶纸的电气性能测试结果。从图6(a)可以看出,随纤维长度的增加,芳纶纸的击穿强度呈线性递减,其中L18的击穿强度为8.7 kV/mm,相比C0下降约63%。从图6(b)可以看出,随着纤维长度的增加,芳纶纸的电导率呈线性递增,其中L18的电导率为7.78×10-15 S/m,相比C0提高了62倍。从图6(c)可以看出,随着纤维长度增加,芳纶纸的初始电位由C0的2.97 kV下降至L12的1.07 kV和L18的0.24 kV,720 s后电位保持率由96%分别降至28%、6%。从图6(d)可以看出,随着纤维长度的增加,芳纶纸陷阱曲线发生严重浅化。相比于C0,L12深陷阱深度降低至1.11 eV,密度降低至1.29×1011 eV-1·m-3,浅陷阱深度为1.01 eV,密度增加至1.80×1011 eV-1·m-3。L18的深陷阱深度减小至1.08 eV,密度降至小于1×1010 eV-1·m-3。上述结果说明,短切纤维长度增加至12 mm、18 mm时,芳纶纸的击穿强度降幅可达64%,同时伴有明显的电导率提高和电荷陷阱浅化。
图7为不同长度短切纤维制得芳纶纸的SEM图像。从图4(a)(b)图7可以看出,随着短切纤维长度的增加,芳纶纸纤维界面缺陷加重,尤其是L18表面出现了沉析纤维的镂空区域,且产生了短切纤维接触形成的“硬”质界面。上述结果说明,短切纤维过长会导致成纸结构松散,这源于较长纤维在纸浆中的缠绕蜷曲,这也是L18击穿强度大幅下降的原因。
图8为不同长度短切纤维所造的芳纶纸的力学性能测试结果。从图8可以看出,随着纤维长度的增加,芳纶纸的拉伸强度呈递减趋势,L12和L18的拉伸强度分别为28.8 MPa和27.8 MPa,其中L18的拉伸强度相对C0降低了17%。芳纶纸的弹性模量则随纤维长度增加呈先减后增趋势,L12和L18的弹性模量分别为1.36 GPa和1.48 GPa,L12的弹性模量相对C0(1.56 GPa)降低了13%。当纤维长度增加时,力学性能的变化幅度明显小于击穿强度的变化幅度,结合微观表征可解释如下:从力学拉伸的角度看,一根较长的短切纤维蜷曲为多根并排状,和多根较短的短切纤维直接并联,在应变过程中没有较大差异。但从电气绝缘的角度看,采用长度为12 mm和18 mm的纤维将加重纤维界面缺陷程度,甚至产生短切纤维间的硬质界面,进而对芳纶纸的电气绝缘性能产生明显削弱作用。
图9为结晶温度从290℃降至230℃时的短切纤维SEM图。从图9可以看出,随着结晶温度的降低,纤维表面粗糙度增加,出现沟壑状形貌。图10为不同结晶温度下短切纤维的XRD测试结果。从图10可以看出,短切纤维主要在2θ为17.3°、23.5°和27.1°处出现对应(110)、(200)和(211)晶面的衍射峰,降低结晶温度后,衍射峰削弱,表明短切纤维的结晶度有所下降,这是由于较低结晶温度下分子链运动约束较大,更难形成链间氢键和晶体结构[19-20]
图11为不同结晶温度短切纤维所造芳纶纸的电气绝缘性能测试结果。从图11(a)可以看出,随着结晶温度降低,芳纶纸的击穿强度呈先缓后急的递减趋势,T290、T270相对C0(23.4 kV/mm)的降幅不大,但T250和T230降幅明显,击穿强度分别为20.5 kV/mm和15.0 kV/mm,相比C0下降了12%和36%。从图11(b)可以看出,芳纶纸的电导率随结晶温度的变化趋势与击穿强度相反,具有较低击穿强度的T250和T230的电导率分别提升至1.89×10-15 S/m和4.78×10-15 S/m,其中T230的电导率相比C0(1.23×10-16 S/m)提升约38倍。从图11(c)可以看出,随着结晶温度下降,芳纶纸的初始电位和电位保持率均降低,当结晶温度为230℃时,芳纶纸的初始电位为1.57 kV,相比C0(3.15 kV)降低了50%,同时电位保持率下降至59%。从图11(d)可以看出,随着结晶温度降低,芳纶纸的陷阱分布发生浅化,深陷阱深度和密度减小,浅陷阱深度减小,密度略有增加。其中T230的深陷阱深度为1.12 eV,密度为3.46×1011 eV-1·m-3,浅陷阱深度为1.04 eV,密度为1.48×1011 eV-1·m-3,曲线呈现明显的浅陷阱峰,说明绝缘强度受到损伤。上述结果说明,短切纤维结晶温度降至250℃及以下时,芳纶纸的绝缘性能会显著受损。
图12为不同结晶温度短切纤维所造芳纶纸的SEM图像。从图12可以看出,随着结晶温度的降低,界面缺陷先显现出一定程度改善,这源自于略低结晶温度下短切纤维结晶度适度降低,与沉析纤维的结构差异性缩小,界面得到改善。然而,结晶温度进一步降低至250℃和230℃时,短切纤维规整度降低,出现“Y”型畸变,这源于低结晶度纤维在热压中的熔融,也与其在打浆中因结晶度和强度较低产生的劈裂受损有关。不论哪种畸形纤维,都意味着更复杂的界面情况和更易产生孔隙缺陷,同时低结晶温度也会造成纤维本体强度降低。
图13为不同结晶温度短切纤维所造芳纶纸的力学性能测试结果。从图13可以看出,随着结晶温度的降低,芳纶纸的弹性模量和拉伸强度整体呈现先缓后急的递减趋势。当结晶温度高于270℃时,两项力学性能指标降幅较小。当结晶温度低于250℃后,力学性能下降严重,其中T230的强度和模量分别为16.9 MPa和1.13 GPa,分别比C0的拉伸强度(33.5 MPa)和弹性模量(1.56 GPa)下降了50%和28%。上述结果表明,短切纤维结晶温度对芳纶纸电气与力学性能的影响具有阈值跳变特点,跳变点为250℃。结晶温度尚不过低时,短切纤维本体强度下降幅度不大,且因结晶度下降导致与沉析纤维的界面作用得到改善,补偿了本体性能下降带来的绝缘和机械强度削弱,使得T290和T270呈现出与C0相当的性能水平。然而,当结晶温度过低时,主要矛盾转变为纤维本体的严重损伤,畸形纤维引入了过多的界面缺陷,而受损纤维的机械强度也大幅下降,导致T250和T230发生性能骤降。
纤维配比是间位芳纶纸抄造的关键参数。一般情况下,沉析纤维占比提高,芳纶纸致密度、柔顺性乃至抄纸工艺可控性都会提高。但为了均衡芳纶纸的结构强度,纸中须添加足量的短切纤维[21]。本研究以相对常见的7/3(沉析纤维与短切纤维的质量比为7∶3,即C0)作为参照,讨论10/0至5/5的6种配比对芳纶纸性能的影响。
图14为不同纤维配比芳纶纸的绝缘性能测试结果。从图14(a)可以看出,随着短切纤维占比提高,芳纶纸的击穿强度呈先升后降趋势。10/0芳纶纸的击穿强度为27.4 kV/mm,9/1时芳纶纸的击穿强度提高至30.1 kV/mm,比C0(23.4 kV/mm)提升了29%。继续提高短切纤维占比,芳纶纸的击穿强度却逐步下降,5/5时芳纶纸的击穿强度相比9/1时下降了50%,这说明仅掺杂少量短切纤维对提升芳纶纸击穿强度有益。从图14(b)可以看出,当短切纤维占比小于30%时,芳纶纸的电导率随配比变化不明显。当其占比超过40%后,电导率提升幅度变大,6/4和5/5芳纶纸的电导率分别为1.22×10-15 S/m和3.02×10-15 S/m,相对7/3时分别提高了10倍和30倍。从图14(c)可以看出,随着短切纤维占比提升,芳纶纸的初始电位不断降低,5/5时芳纶纸的初始电位低至2.05 kV,同时其电位保持率也降至59%。从图14(d)可以看出,击穿强度低的芳纶纸如6/4和5/5,均呈现出明显的陷阱浅化。而击穿强度相对7/3更高的芳纶纸如9/1、8/2和10/0,则具有更偏深陷阱的曲线特征。从数值上看,7/3的深陷阱深度为1.18 eV,9/1、8/2和10/0的深陷阱深度分别增加至1.25、1.22、1.19 eV,这说明少于3份的短切纤维占比,尤其是9/1芳纶纸维持了良好的深陷阱特性,对载流子束缚力较强。上述结果说明,从电气绝缘的角度,因考虑力学性能而采取的7/3并不是最优配比,9/1具有最高的击穿强度。
图15为不同纤维配比芳纶纸的SEM图。根据一般造纸经验,由于热压过程中短切纤维的形态刚性和沉析纤维可被熔融软化的性质,沉析占比越高的芳纶纸应呈现出更高的致密度和平整度。然而,从图15可以看出,10/0芳纶纸的表面却呈现大量的沉析纤维孔洞,这说明当缺乏短切纤维作为骨架时,沉析芳纶纸在热压中无法维持稳定性;随着短切纤维占比提高,表面致密度先呈现出改善效果, 9/1达到最优,之后开始下降。尤其对于过高短切纤维占比的6/4和5/5芳纶纸,其存在大量短切纤维间的硬质界面,形成了大面积的沉析纤维镂空。
图16为不同纤维配比芳纶纸的力学性能测试结果。从图16可以看出,10/0芳纶纸的拉伸强度和弹性模量分别为11 MPa和1.31 GPa,仅为7/3芳纶纸的33%和84%。随着短切纤维占比增加,芳纶纸的拉伸强度和弹性模量不断增长,但各占比区间内的力学性能增速存在差异。对于9/1芳纶纸,其拉伸强度和弹性模量分别为15.9 MPa和1.33 GPa,相对10/0芳纶纸提升并不明显,这可能是由于短切纤维占比尚且较低,短切纤维无法覆盖整张芳纶纸,造成芳纶纸中存在由纯沉析纤维组成的薄弱区域,限制了芳纶纸整体力学性能提升。当短切占比提高至20%时,拉伸强度和弹性模量大幅改善,分别达到了28.3 MPa和1.481 GPa,说明此时短切纤维网络的连续性增强,芳纶纸由沉析纤维主导的脆性向短切纤维主导的韧性转变。进一步增加短切纤维占比时,两项力学性能指标增速再次放缓,这说明在短切纤维占比较高时,新产生的缺陷折损了芳纶纸的力学性能。结合图15中的界面与短切纤维形态变化可知,高短切纤维占比会产生短切纤维-短切纤维形式的“硬”质界面,同时生成更多的短切纤维-沉析纤维界面孔隙,从而影响芳纶纸的力学性能。
本文采用控制变量法,以短切纤维直径为25 μm、长度为6 mm、结晶温度为300℃、短切纤维占比为30%的参数制备的间位芳纶纸为参照,研究了短切纤维特性及占比对间位芳纶纸电气绝缘性能的影响,得到如下结论。
(1)在短切纤维直径增加至45 μm的过程中,成纸中沉析纤维对短切纤维的包覆度下降,沉析纤维镂空、短切纤维脱出等界面缺陷加剧,导致芳纶纸的击穿强度、拉伸强度降幅达16%、24%,电导率提升了10倍。
(2)在短切纤维长度增加至18 mm的过程中,短切纤维发生蜷绕,产生难以调和的短切纤维间“硬质”界面,由此导致间位芳纶纸的击穿强度降幅达63%,电导率提高了62倍,但因短切纤维网络没有受损,芳纶纸的拉伸强度并未降低。
(3)在纤维结晶温度降低至230℃的过程中,短切纤维结晶度下降,本体结构稳定性减弱,在热压中出现熔融分叉现象,导致击穿强度、拉伸强度降幅达36%和50%,电导率提升了40倍,且性能衰减主要存在于结晶温度低于250℃的芳纶纸中。
(4)在短切纤维占比由0递增至50%的过程中,间位芳纶纸的拉伸强度呈单调递增趋势,而击穿强度则随芳纶纸致密度呈先增后减的趋势,在占比为10%时达到最优,击穿强度相比参照样提升了29%,电导率与参照样接近。
  • 新能源电力系统国家重点实验室课题(LAPS202103)
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2024年第57卷第2期
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doi: 10.16790/j.cnki.1009-9239.im.2024.02.003
  • 接收时间:2022-11-21
  • 首发时间:2025-12-22
  • 出版时间:2024-02-20
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  • 收稿日期:2022-11-21
  • 修回日期:2023-02-16
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新能源电力系统国家重点实验室课题(LAPS202103)
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    1新能源电力系统国家重点实验室(华北电力大学),北京 102206
    2赣州龙邦材料科技有限公司,江西 赣州 341999
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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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