Article(id=1209927480111133657, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927476046860302, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2022.05.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1624809600000, receivedDateStr=2021-06-28, revisedDate=1629907200000, revisedDateStr=2021-08-26, acceptedDate=null, acceptedDateStr=null, onlineDate=1766398790624, onlineDateStr=2025-12-22, pubDate=1652976000000, pubDateStr=2022-05-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766398790624, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766398790624, creator=13701087609, updateTime=1766398790624, updator=13701087609, issue=Issue{id=1209927476046860302, tenantId=1146029695717560320, journalId=1149653034449285133, year='2022', volume='55', issue='5', pageStart='1', pageEnd='122', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766398789655, creator=13701087609, updateTime=1766563075277, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210616539955466501, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927476046860302, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210616539959660806, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209927476046860302, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=19, endPage=26, ext={EN=ArticleExt(id=1209927480362791911, articleId=1209927480111133657, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of Low Temperature Plasma Modification on Properties of Aramid 1313 Fiber/Cellulose Composite Insulating Paper, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

The dielectric constant and dielectric loss of composite insulating paper can be reduced by doping different content of aramid 1313 (PMTA) in the natural cellulose pulp, but the mechanical properties of composite insulating paper are greatly reduced due to the poor combining ability of two fibers. In order to solve this problem, we studied the improvement effect of low-temperature plasma treatment on the binding capacity of two kinds of cellulose emphatically, and tested and analyzed the properties of the prepared composite insulating paper. The results show that the low-temperature plasma treatment can effectively improve the binding force between the two kinds of fibers, so as to make up for the loss of mechanical properties, and it has little influence on the dielectric and breakdown characteristics of the composite insulating paper. The results of SEM and XPS show that the surface of PMTA fiber after low temperature plasma treatment become rough, the polarity functional group increases, the binding force with cellulose matrix increases, and the voids of composite insulating paper sample decreases significantly. The power frequency relative permittivity of the composite insulating paper prepared by doping low temperature plasma treated PMTA in natural cellulose pulp is reduced, while the AC/DC electric strength and volume resistivity remain unchanged, and the tensile strength and elongation at break are compensated to the maximum.

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在天然纤维素浆粕中掺杂不同含量的芳纶1313(PMTA)短切纤维,可降低复合绝缘纸的介电常数及介质损耗,但由于两种纤维的结合能力差,复合绝缘纸样品的力学性能会大幅降低。为解决这一问题,本文重点研究低温等离子体处理对两种纤维素结合能力的提升效果,并对制备得到的复合绝缘纸性能进行测试分析。结果表明:低温等离子体处理可有效提升两种纤维间的结合力,从而弥补力学性能的损失,而且对复合绝缘纸的介电及击穿特性影响不大。SEM和XPS分析结果表明,经低温等离子体处理后的PMTA纤维表面变得粗糙,且极性官能团数量增加,与纤维素基体的结合力增强,复合绝缘纸样品的孔隙明显减少。在天然纤维素桨粕中掺杂低温等离子体处理的PMTA制备的复合绝缘纸样品工频相对介电常数和介质损耗因数均有所降低,交/直流电气强度和体积电阻率基本保持不变,抗张强度和断裂伸长率得到较大补偿。

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邹田甜(1991-),女(汉族),山东威海人,硕士生,研究方向为高压绝缘;

甄珍(1983-),女(汉族),河南信阳人,副教授,研究方向为工业自动化。

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邹田甜(1991-),女(汉族),山东威海人,硕士生,研究方向为高压绝缘;

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邹田甜(1991-),女(汉族),山东威海人,硕士生,研究方向为高压绝缘;

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编号样品配方
P00%PMTA+100%纤维素
P15%未改性PMTA+95%纤维素
P210%未改性PMTA+90%纤维素
P320%未改性PMTA+80%纤维素
P440%未改性PMTA+60%纤维素
P55%改性PMTA+95%纤维素
P610%改性PMTA+90%纤维素
P720%改性PMTA+80%纤维素
P840%改性PMTA+60%纤维素
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绝缘纸样品编号及配方

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编号样品配方
P00%PMTA+100%纤维素
P15%未改性PMTA+95%纤维素
P210%未改性PMTA+90%纤维素
P320%未改性PMTA+80%纤维素
P440%未改性PMTA+60%纤维素
P55%改性PMTA+95%纤维素
P610%改性PMTA+90%纤维素
P720%改性PMTA+80%纤维素
P840%改性PMTA+60%纤维素
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样品εrtanδ/(×10-2)
P04.301.008
P14.150.879
P23.810.821
P33.680.699
P43.330.628
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PMTA/纤维素复合绝缘纸的相对介电常数和介质损耗因数(工频50 Hz)

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样品εrtanδ/(×10-2)
P04.301.008
P14.150.879
P23.810.821
P33.680.699
P43.330.628
), ArticleFig(id=1210884593549447360, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927480111133657, language=EN, label=Tab.3, caption=Relative permittivity and dielectric loss factor of PMTA/cellulose composite insulating papers treated by low temperature plasma (50 Hz), figureFileSmall=null, figureFileBig=null, tableContent=
样品εrtanδ/(×10-2)
P04.301.008
P54.150.820
P63.680.628
P73.720.573
P83.330.499
), ArticleFig(id=1210884593666887877, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927480111133657, language=CN, label=表3, caption=

低温等离子体处理PMTA/纤维素复合纸的相对介电常数和介质损耗因数(工频50 Hz)

, figureFileSmall=null, figureFileBig=null, tableContent=
样品εrtanδ/(×10-2)
P04.301.008
P54.150.820
P63.680.628
P73.720.573
P83.330.499
), ArticleFig(id=1210884593784328398, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927480111133657, language=EN, label=Tab.5, caption=Surface chemical composition of PMTA before and after low temperature plasma treatment, figureFileSmall=null, figureFileBig=null, tableContent=
样品化学组成/%浓度比
CONO和CN和C
未处理PMTA纤维73.9313.267.450.1790.101
处理的PMTA纤维68.4515.5412.390.2270.181
), ArticleFig(id=1210884593884991697, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209927480111133657, language=CN, label=表5, caption=

低温等离子体处理前后PMTA表面化学成分

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样品化学组成/%浓度比
CONO和CN和C
未处理PMTA纤维73.9313.267.450.1790.101
处理的PMTA纤维68.4515.5412.390.2270.181
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低温等离子体改性对芳纶1313纤维/纤维素复合绝缘纸性能的影响
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邹田甜 , 孙传聪 , 熊秋菊 , 甄珍 , 刘威
绝缘材料 | 材料研究 2022,55(5): 19-26
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绝缘材料 | 材料研究 2022, 55(5): 19-26
低温等离子体改性对芳纶1313纤维/纤维素复合绝缘纸性能的影响
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邹田甜, 孙传聪, 熊秋菊, 甄珍, 刘威
作者信息
  • 山东省药品食品职业学院,山东 威海 264200
  • 邹田甜(1991-),女(汉族),山东威海人,硕士生,研究方向为高压绝缘;

    甄珍(1983-),女(汉族),河南信阳人,副教授,研究方向为工业自动化。

Effect of Low Temperature Plasma Modification on Properties of Aramid 1313 Fiber/Cellulose Composite Insulating Paper
Tiantian ZOU, Chuancong SUN, Qiuju XIONG, Zhen ZHEN, Wei LIU
Affiliations
  • Shandong Drug and Food Vocational College, Weihai 264200, China
出版时间: 2022-05-20 doi: 10.16790/j.cnki.1009-9239.im.2022.05.003
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在天然纤维素浆粕中掺杂不同含量的芳纶1313(PMTA)短切纤维,可降低复合绝缘纸的介电常数及介质损耗,但由于两种纤维的结合能力差,复合绝缘纸样品的力学性能会大幅降低。为解决这一问题,本文重点研究低温等离子体处理对两种纤维素结合能力的提升效果,并对制备得到的复合绝缘纸性能进行测试分析。结果表明:低温等离子体处理可有效提升两种纤维间的结合力,从而弥补力学性能的损失,而且对复合绝缘纸的介电及击穿特性影响不大。SEM和XPS分析结果表明,经低温等离子体处理后的PMTA纤维表面变得粗糙,且极性官能团数量增加,与纤维素基体的结合力增强,复合绝缘纸样品的孔隙明显减少。在天然纤维素桨粕中掺杂低温等离子体处理的PMTA制备的复合绝缘纸样品工频相对介电常数和介质损耗因数均有所降低,交/直流电气强度和体积电阻率基本保持不变,抗张强度和断裂伸长率得到较大补偿。

芳纶1313  /  低温等离子体  /  复合绝缘纸  /  介电性能  /  力学性能

The dielectric constant and dielectric loss of composite insulating paper can be reduced by doping different content of aramid 1313 (PMTA) in the natural cellulose pulp, but the mechanical properties of composite insulating paper are greatly reduced due to the poor combining ability of two fibers. In order to solve this problem, we studied the improvement effect of low-temperature plasma treatment on the binding capacity of two kinds of cellulose emphatically, and tested and analyzed the properties of the prepared composite insulating paper. The results show that the low-temperature plasma treatment can effectively improve the binding force between the two kinds of fibers, so as to make up for the loss of mechanical properties, and it has little influence on the dielectric and breakdown characteristics of the composite insulating paper. The results of SEM and XPS show that the surface of PMTA fiber after low temperature plasma treatment become rough, the polarity functional group increases, the binding force with cellulose matrix increases, and the voids of composite insulating paper sample decreases significantly. The power frequency relative permittivity of the composite insulating paper prepared by doping low temperature plasma treated PMTA in natural cellulose pulp is reduced, while the AC/DC electric strength and volume resistivity remain unchanged, and the tensile strength and elongation at break are compensated to the maximum.

aramid 1313  /  low temperature plasma  /  composite insulating paper  /  dielectric properties  /  mechanical properties
邹田甜, 孙传聪, 熊秋菊, 甄珍, 刘威. 低温等离子体改性对芳纶1313纤维/纤维素复合绝缘纸性能的影响. 绝缘材料, 2022 , 55 (5) : 19 -26 . DOI: 10.16790/j.cnki.1009-9239.im.2022.05.003
Tiantian ZOU, Chuancong SUN, Qiuju XIONG, Zhen ZHEN, Wei LIU. Effect of Low Temperature Plasma Modification on Properties of Aramid 1313 Fiber/Cellulose Composite Insulating Paper[J]. Insulating Materials, 2022 , 55 (5) : 19 -26 . DOI: 10.16790/j.cnki.1009-9239.im.2022.05.003
由绝缘纸和绝缘油组成的复合绝缘是油浸式电力设备应用最广泛的内绝缘形式,其中天然纤维素绝缘纸因绝缘及力学性能好、环保可再生以及经济性等优点被广泛应用于油纸绝缘中[1]。木质纤维素经打浆、成型等造纸工艺后制成绝缘纸板,经矿物绝缘油充分浸渍后的介电常数(εboard=4.1~4.8)为矿物绝缘油(εoil≈2.2)的两倍及以上[2]。在交变场强下,绝缘油承担更高的场强,而其电气强度又远小于绝缘纸板,使得变压器中导体与垫块之间的楔形油隙成为内绝缘中一个典型的薄弱环节[3]。降低绝缘纸板的介电常数可以相应减小油隙的场强,尤其对于变压器中0.2 mm左右的小油隙效果更为明显。研究表明[4-5],当绝缘纸介电常数降低至3.5及以下时,油隙中的场强分布可得到明显的改善,电气强度及放电起始电压可得到较大的提高。
有研究通过将低介电常数的聚合物粉末、颗粒纤维或片层结构物质与纤维素纤维进行共混以制备更低介电常数的绝缘纸[6],具有代表性的是日本三菱制纸株式会社于20世纪90年代开发的商品型号为PB-T和PB-TC的两种绝缘纸板,它们是由聚甲基戊烯(PMP)纤维和纤维素通过共混的方式制备而成,其相对介电常数为3.5,与传统绝缘纸板垫片相比击穿电压提升了30%[7]。但由于PMP纤维与天然纤维质量以及亲水性的差异,导致抄造过程中在纤维均匀分散方面遇到较多问题,使得成纸的介质损耗较高,且力学性能难以满足要求[8]。也有研究直接采用低介电常数的聚合物或人工合成纤维材料制备成绝缘纸,可完全替代纤维素绝缘纸[9-10]。例如杜邦公司采用聚间苯二甲酰间苯二胺短切纤维通过人工制备Nomex纸(芳纶1313,PMTA)[11],其介电常数仅为3.0左右,且具有较好的力学性能和热稳定性,是一种非常有前景的绝缘材料,在油浸式电力设备中已经得到了应用,但由于成本较高仅在设备的集热点或重要部位有所应用,未得到大面积的推广。
由于人工合成PMTA纤维在绝缘、力学和热稳定性能方面的优异表现,近年来受到广泛关注。可以将其作为一种增强材料,通过少量添加到基体中实现性能的提升。已有研究表明,在聚酰亚胺、橡胶等聚合物中掺杂少量PMTA可有效提高基体的热稳定性[12]。由于PMTA纤维的极性较弱,也有学者尝试在天然纤维纸浆中添加少量PMTA以降低成纸的介电常数或提高电气强度。然而,研究发现PMTA结构特殊(如图1所示),存在大量苯环,不易移动,使得酰胺基上的氢原子反应活性很差[11],导致其与基体材料的界面结合性不好,在很大程度上影响了复合材料的力学性能。
提高PMTA纤维的表面活性,使其与基体材料更好地结合是当前的研究难点。目前对PMTA纤维的表面改性方法主要有化学法和物理法[13]。化学法是通过化学反应在PMTA表面引入活性基团,如利用乙酸酐试剂的表面蚀刻法、利用硝化反应在苯环上引入硝基的表面接枝法等。然而化学法处理往往反应条件苛刻,尤其是反应时间难以控制,化学试剂的过度处理也会对纤维结构产生破坏,影响其性能的发挥[13]。物理法则主要是通过高速粒子溅射作用,使PMTA表面变得粗糙,从而增大与基体材料间的结合力,常用的物理法有等离子体处理法、超声波法、γ射线法等[14]。与化学法相比,物理法操作简单、无污染、不需要催化剂,更重要的是对纤维无损害,有利于保持PMTA自身的优异性能。
等离子体处理是目前研究最多的一种物理改性PMTA的方法,利用等离子体理化反应来实现PMTA功能的改变。其原理为在低压作用下,分子间距离及分子的自由运动距离会越来越长,同时在电场作用下,分子会发生碰撞形成等离子体,产生辉光放电[15],一方面高速电子撞击PMTA表面产生蚀刻作用提高PMTA表面的粗糙度,另一方面高活性的自由基和离子会破坏PMTA表面的化学键,然后与断键结合形成新的基团,增大纤维的比表面积和表面自由能,从而提高纤维与基体间界面的粘结强度[16]。该方法处理深度仅在数十纳米以内,在改性程度调控方面有独特优势。研究发现[17-18],等离子体改性后的芳纶纤维与树脂、橡胶等材料间的界面抗剪切强度显著提高。这为通过等离子体改性来增大PMTA与纤维素纸基材料间的结合力提供了借鉴,然而目前关于这方面的研究较少。
本研究拟采用低温等离子体处理PMTA,改善其与纤维素基体掺杂时的界面不相容性,进而实现降低绝缘纸介电常数的目的。首先,分别制备低温等离子体处理PMTA/纤维素和未处理PMTA/纤维素复合纸,对比分析低温等离子体改性对增强两种纤维间结合性的有效性。然后,通过测试其性能变化初步研究掺杂配比对复合纸性能的影响,借助扫描电子显微镜(SEM)和X射线光电子能谱(XPS)对绝缘纸的微观形貌和化学元素进行表征,进一步分析低温等离子体处理对提升PMTA改性绝缘纸力学性能的作用机理。
纤维素木浆为俄罗斯进口的未漂针叶木硫酸盐浆;PMTA短切纤维,长度为35 mm,直径约为10 μm,介电常数为2.7(50 Hz),杜邦公司;25#绝缘油,美央环保科技有限公司;丙酮(98%)和乙醇(≥99.5%),上海阿拉丁生化科技有限公司;纸张制备过程中的用水均采用电阻率为18.25 MΩ·cm的去离子水。
为了探究低温等离子体改性处理后的PMTA短切纤维对绝缘纸性能的影响,在实验室中分别制备低温等离子体处理PMTA/纤维素绝缘纸和未处理PMTA/纤维素绝缘纸进行对比。常用的等离子体处理气体包括O2、H2、NH3和惰性气体等[18-19]。因为惰性气体仅对纤维表面有蚀刻作用,不能引入新的官能团,因此本研究不予考虑;而O2环境下会在PMTA中引入-COOH,对其长期热稳定性造成影响;H2的强还原性则多适用于金属表面的处理,因此综合考虑本研究采用NH3作为处理气体[20]。处理过程如下[17-18]:首先用丙酮在75℃下浸泡PMTA短切纤维24 h,去除纤维表面的附着物,取出后用无水乙醇洗涤,去除纤维表面的灰尘、油污等杂质,然后放入100℃的真空烘箱中干燥3 h。将干燥后的PMTA短切纤维放入低温等离子体处理腔内,抽压至3~4 Pa后以30 L/min的流量通入NH3,再抽真空,如此重复以上操作3次,以保证腔体内无其他气体杂质,然后再次向腔体中通入NH3,并保持腔体中的压力恒定为30 Pa。因为处理时间过长或功率过大,等离子体的刻蚀作用会将先前产生的沟槽或引入的极性基团剥离掉;处理时间过短或功率过小,改性效果不明显,所以本研究选择在200 W放电功率下处理15 min。处理完毕后打开射频电源进行放电,取出PMTA备用。
将处理前后的PMTA短切纤维分别与纤维素浆粕按照一定的配比共混,通过解离、过滤、烘干等步骤抄造复合绝缘纸[21],考虑到PMTA掺杂量过低时,对介电性能影响效果较小,而过高时,又会造成力学性能的大幅下降,本研究选择PMTA的质量分数为5%~40%,样品编号及配方如表1所示。制备的绝缘纸手抄片直径为20 cm,平均厚度约为0.13 mm,纤维的密度约为120 g/cm2
为避免样品受潮后极性水分子对电气性能的影响,在测试前对样品进行干燥及真空浸渍等预处理[21]:将直径为3.5 cm的绝缘纸样品在90℃、100 Pa条件下脱气干燥48 h,同时将25#绝缘油在60℃、100 Pa下脱气干燥24 h,随后将绝缘油和纸绝缘按照质量比为20∶1混合后在60℃/100 Pa真空干燥箱中浸渍24 h,备用。
按照IEC 60250-1969,采用Concept 80型宽频介电谱仪测试样品的相对介电常数和介质损耗因数;按照ISO 1924/3:2005采用AT-L-1型拉力试验机测试样品的抗张强度和断裂伸长率;按照IEC 60243-1:2013,采用DRK218型固体绝缘材料电压击穿测定仪测试样品的交/直流电气强度;按照IEC 60093:1980,采用Keithley 6517B型静电计测试样品的体积电阻率。
利用FPMRC-SEM-200型电子显微镜观测和比较PMTA短切纤维在低温等离子体处理前后的形貌变化以及复合绝缘纸的微观形貌。在观察之前,需对所有样品喷镀厚度为25 nm的金层。
利用X射线光电子能谱分析经低温等离子体处理及未经处理的PMTA纤维表面化学成分。用单色Al-K X射线源(H=1 486.6 eV,瓦数为250 W),在1.33×10-11 Pa的分析室中加压获得XPS光谱。
图2为P0~P4样品的介电性能测试结果。从图2可以看出,添加PMTA纤维后的绝缘纸相对介电常数均低于未添加PMTA纤维的绝缘纸,并且随着PMTA短切纤维质量分数的增加呈现逐渐降低的趋势。表2给出了工频(50 Hz)下P0~P4样品的相对介电常数和介质损耗因数。从表2可知,当PMTA纤维的质量分数为5%、10%、20%、40%时,与未添加PMTA纤维的绝缘纸相比,复合绝缘纸的介电常数依次降低了3.5%、11.4%、14.4%、22.6%,介质损耗因数的变化趋势与介电常数表现出相似的规律。这是由于一定量低极性PMTA的添加会导致复合绝缘纸内分子转向极化率减少,从而使其介电常数和介质损耗因数降低。
图3为P0~P4样品的抗张强度及断裂伸长率测试结果。从图3可以看出,与未添加PMTA纤维的绝缘纸相比,PMTA纤维的添加造成复合绝缘纸的抗张强度和断裂伸长率均有不同程度的下降,且添加量越高,下降幅度越大。结果表明,单纯将PMTA和天然纤维进行物理复合,虽然低极性的PMTA降低了复合绝缘纸的介电常数及介质损耗因数,但由于两种纤维无法有效结合,纸的机械强度明显下降,无法满足工程需求。
图4为P5~P8样品的介电性能测试结果,表3给出了工频(50 Hz)下P5~P8样品的相对介电常数和介质损耗因数。从图4可以看出,低温等离子体处理后的PMTA/纤维素绝缘纸的介电常数和介质损耗因数随PMTA含量的变化呈现逐渐降低的趋势。对比表2表3发现,在50 Hz下,两种复合绝缘纸的εr相差不大,但是tanδ有较大差异,低温等离子体处理PMTA后的复合绝缘纸介质损耗因数相比未处理时有不同程度下降,掺杂量越高,下降幅度越大,这可能是因为经低温等离子体处理后PMTA表面的活性官能团增多,与纤维素在界面处的结合强度提高,在电场作用下,两种纤维交界处的界面极化降低,从而使介质损耗降低。
图5为PMTA改性前后复合绝缘纸的抗张强度和断裂伸长率对比图。从图5可以看出,与未改性PMTA/纤维素复合绝缘纸相比,改性后的PMTA/纤维素复合绝缘纸在力学性能上得到了一定的提高。当PMTA的质量分数为10%、20%时,抗张强度分别提升了9.4%、8.5%,断裂伸长率则分别提升了4.2%、4.2%,尽管当PMTA的质量分数达到40%时,力学性能提升幅度更大,但此时复合绝缘纸的力学性能较未添加PMTA纤维的绝缘纸降低太多,已不能满足复合绝缘纸的要求。因此,通过低温等离子体对PMTA改性,可以在不提升绝缘纸介电常数和介质损耗的前提下,在一定程度上补偿力学性能的损失,当改性PMTA质量分数为10%时,复合绝缘纸的抗张强度和断裂伸长率得到了较好的补偿。
体积电阻率和电气强度是表征绝缘纸绝缘性能的重要参数,为进一步探究复合绝缘纸绝缘性能的优劣,对P0、P5~P8样品的体积电阻率和交/直流电气强度进行测试,结果分别如图6图7所示。从图6可以看出,随着改性PMTA纤维掺杂量的增多,样品的体积电阻率呈现先增大后减小的趋势,在改性PMTA的质量分数为5%时,复合绝缘纸比未添加PMTA纤维的绝缘纸具有更高的体积电阻率,且此时介电常数和介质损耗因数下降不明显;当改性PMTA的质量分数为10%和20%时,相比未添加PMTA纤维的绝缘纸,体积电阻率分别降低了3.7%和6.4%,下降幅度较小;当改性PMTA的质量分数超过20%后,体积电阻率下降速率开始变快,下降幅度变大。
图7可以看出,复合绝缘纸的交流电气强度随着改性PMTA纤维掺杂量的增加呈下降趋势,与未添加PMTA纤维的绝缘纸P0相比,P5~P8复合绝缘纸的交流电气强度依次降低了0.9%、4.8%、5.4%、10.4%。随着改性PMTA纤维掺杂量的增加,复合绝缘纸的直流电气强度呈先升高后降低的趋势,其中P5样品的直流电气强度上升了0.9%,P6~P8样品的直流电气强度分别降低了1.8%、1.7%、4.7%。由此可知在低掺杂量时,与未添加PMTA纤维的绝缘纸相比,复合绝缘纸的交/直流电气强度均稍有下降但降幅不大,而当掺杂量超过20%后,交流电气强度下降幅度较明显。
综上,结合2.2中介电常数、介质损耗因数和力学性能的测试结果可知,当改性PMTA的质量分数为5%时,复合绝缘纸的介电常数和介质损耗因数与未添加PMTA纤维的绝缘纸相比降低不显著;当改性PMTA的质量分数为40%时,复合绝缘纸的力学性能急剧下降,不能满足绝缘纸应用要求;当改性PMTA的质量分数为10%和20%时,复合绝缘纸的介电常数和介质损耗因数均有较大幅度的下降,当改性PMTA的质量分数为10%时,复合绝缘纸具有更优的力学性能且此时复合绝缘纸的体积电阻率和电气强度与未添加PMTA纤维的绝缘纸基本相同。因此,掺杂质量分数为10%的低温等离子体改性PMTA纤维对复合绝缘纸的改性效果较优。
图8为未处理PMTA/纤维素复合绝缘纸P3和P4的SEM图。
图8中圆圈内可以看到,纤维素簇及其周围杂散分布着细且短的PMTA纤维,清晰可见两种纤维的边界,且纤维间存在很多大的孔隙,说明两种纤维的界面相容性很差,这是造成力学性能大幅下降的主要原因。进一步观测改性后PMTA/纤维素复合绝缘纸P6的微观形貌,如图9(a)所示,发现尽管与未添加PMTA纤维的绝缘纸(图9(b))相比,复合绝缘纸内纤维素间仍可以看到部分分散的PMTA纤维边界,但与图8相比,此时复合纸表面更加平整,纤维交界处的孔隙变小,说明经过低温等离子体处理后,PMTA与纤维素间的相容性得到改善。
图10为低温等离子体处理前后PMTA纤维的XPS图谱,光谱中的3个主要峰分别对应纤维的C、N、O元素,依次出现在284、400、532 eV附近,表5为等离体处理前后PMTA表面化学成分变化。
图10可以看出,经NH3环境的低温等离子体处理后,纤维中C元素的特征峰强度减弱,而N元素的特征峰强度增强。从表5可知,处理后PMTA纤维中的C元素浓度从73.93%下降到68.45%,N元素浓度则显著升高,从7.45%上升至12.39%,且N和C的浓度比从0.101增大至0.181,O和C的浓度比从0.179增大至0.227。结合图1中PMTA结构式可以看出,C1s由C-C、C=O、C=C、C-N、C-H键组成,N1s由C-N、N-H键组成,改性后C1s降低,而N1s升高,说明C1s中有键断开,如C=O、C-H键等,然后与低温等离子体处理中产生的H+和NH4+重新形成新键,如H-O和N-H,即在PMTA表面引入了新的活性官能团-OH和-NH。纤维素中存在的大量 -OH,与改性的PMTA间的活性基团间可以形成氢键,纤维素和PMTA间通过氢键结合在一起,如图11所示。因此,PMTA纤维与纤维素间的结合力得到增强。
由XPS和SEM的结果可知,NH3环境的低温等离子体处理可以对PMTA表面进行蚀刻,使其表面变得粗糙,同时引入N元素使其表面的极性官能团数量增加,均在一定程度上提升了PMTA与纤维素间的相容性,增大了两种纤维边界处的结合力,补偿了一部分复合绝缘纸力学性能的损失 ,因此经低温等离子处理后的PMTA/纤维素复合纸的力学性能较未处理时有所提高。
(1)通过简单物理混合PMTA纤维可以实现复合绝缘纸介电常数和介质损耗因数的降低,但同时也会造成其力学性能的大幅度下降。
(2)NH3环境下的低温等离子体处理提高了PMTA纤维表面的粗糙度和极性基团浓度,有利于增强PMTA纤维与纤维素基体的结合,在一定程度上补偿了复合绝缘纸力学性能的损失。
(3)10%低温等离子体改性PMTA+90%纤维素制备的复合绝缘纸具有较低的介电常数和介质损耗因数,力学性能损失得到较大补偿,同时兼具较高的交/直流电气强度和体积电阻率。
综上,经低温等离子体改性处理后,PMTA纤维能使复合绝缘纸在保持良好的力学性能、电气强度下,使其介电常数和介质损耗因数大幅下降。但如何在此基础上进一步实现体积电阻率、电气强度和力学性能的提升等问题仍有难度,未来有待进一步展开研究。
  • 国家市场监督管理总局科技计划项目(2019MK045)
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doi: 10.16790/j.cnki.1009-9239.im.2022.05.003
  • 接收时间:2021-06-28
  • 首发时间:2025-12-22
  • 出版时间:2022-05-20
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  • 收稿日期:2021-06-28
  • 修回日期:2021-08-26
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国家市场监督管理总局科技计划项目(2019MK045)
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    山东省药品食品职业学院,山东 威海 264200
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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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