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The ethylene propylene rubber for wind turbine twisting cable insulation needs to have high electrical properties and mechanical strength simultaneously to meet the demanding operating conditions. Different morphologies of zinc oxide nanoparticles doped ethylene propylene rubber samples were prepared to investigate the influence of zinc oxide morphology on the mechanical, electrical, and thermal conductive properties of ethylene propylene rubber. The results show that the larger the specific surface area of zinc oxide nanoparticles, the bigger the crosslinking density of ethylene propylene rubber, while the crystallinity remaines unchanged basically. In terms of mechanical properties, the excessive crosslinking caused by high specific surface area of zinc oxide would slightly decrease the elongation at break and tensile strength of ethylene propylene rubber. In terms of electrical properties, the specific surface area of zinc oxide has little effect on the resistivity, dielectric loss, and breakdown strength at room temperature, but the dielectric constant and breakdown strength at 90℃ increase slightly with the increase of specific surface area of zinc oxide. There is no apparent variation rule in the regulation of thermal conductivity of ethylene propylene rubber by zinc oxide nanoparticles.

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风电扭转电缆绝缘用乙丙橡胶需要同时具备较高的电气性能和机械强度,以满足其严苛的工况要求。本文制备了不同形貌纳米氧化锌掺杂的乙丙橡胶样品,研究纳米氧化锌形貌对乙丙橡胶力学性能、电学性能和导热性能的影响。结果表明:纳米氧化锌的比表面积越大,乙丙橡胶的交联密度越大,但结晶度基本不发生变化;在力学性能方面,大比表面积纳米氧化锌导致的过度交联会稍微降低乙丙橡胶的断裂伸长率和拉伸强度;在电学性能方面,纳米氧化锌比表面积对乙丙橡胶的电阻率、介质损耗和室温电气强度影响不大,但介电常数和90℃电气强度随纳米氧化锌比表面积的增加而稍有提升;纳米氧化锌对乙丙橡胶的导热性能调控没有明显规律。

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李旭(1984-),男(汉族),陕西西安人,高级工程师,主要研究方向为高电压与绝缘技术及高压电器;

吴明(1992-),男(汉族),湖北黄冈人,助理教授,博士,主要研究方向为电工绝缘材料与功能电介质传感。

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李旭(1984-),男(汉族),陕西西安人,高级工程师,主要研究方向为高电压与绝缘技术及高压电器;

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李旭(1984-),男(汉族),陕西西安人,高级工程师,主要研究方向为高电压与绝缘技术及高压电器;

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吴明(1992-),男(汉族),湖北黄冈人,助理教授,博士,主要研究方向为电工绝缘材料与功能电介质传感。

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吴明(1992-),男(汉族),湖北黄冈人,助理教授,博士,主要研究方向为电工绝缘材料与功能电介质传感。

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原料质量份
乙丙橡胶基料95
高岭土60
红丹5
石蜡5
低密聚乙烯5
过氧化二异丙苯3
纳米氧化锌5
抗氧剂1.5
), ArticleFig(id=1211311079892848824, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199644778339074269, language=CN, label=表1, caption=

乙丙橡胶配方

, figureFileSmall=null, figureFileBig=null, tableContent=
原料质量份
乙丙橡胶基料95
高岭土60
红丹5
石蜡5
低密聚乙烯5
过氧化二异丙苯3
纳米氧化锌5
抗氧剂1.5
), ArticleFig(id=1211311079964151994, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199644778339074269, language=EN, label=Tab.2, caption=BET surface area of zinc oxide, figureFileSmall=null, figureFileBig=null, tableContent=
编号比表面积/(m2/g)
1#ZnO4.69
2#ZnO4.20
3#ZnO41.32
4#ZnO17.22
), ArticleFig(id=1211311080077398205, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199644778339074269, language=CN, label=表2, caption=

氧化锌的比表面积

, figureFileSmall=null, figureFileBig=null, tableContent=
编号比表面积/(m2/g)
1#ZnO4.69
2#ZnO4.20
3#ZnO41.32
4#ZnO17.22
), ArticleFig(id=1211311081318912193, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199644778339074269, language=EN, label=Tab.3, caption=Crosslinking density of ethylene propylene rubber regulated by four kinds of nanometer zinc oxide, figureFileSmall=null, figureFileBig=null, tableContent=
编号交联密度/(10-4 mol/cm3)
1#样品2.33
2#样品2.35
3#样品2.69
4#样品2.57
), ArticleFig(id=1211311081406992580, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1199644778339074269, language=CN, label=表3, caption=

4种纳米氧化锌调控的乙丙橡胶交联密度

, figureFileSmall=null, figureFileBig=null, tableContent=
编号交联密度/(10-4 mol/cm3)
1#样品2.33
2#样品2.35
3#样品2.69
4#样品2.57
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纳米氧化锌形貌对风电扭转电缆用乙丙橡胶电气和力学性能的调控研究
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李旭 1 , 李贺 2 , 郭歌 1 , 曹晨 4 , 吴明 2 , 高景晖 2
绝缘材料 | 面向大容量海上风电送出的先进电工材料 2023,56(12): 17-23
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绝缘材料 | 面向大容量海上风电送出的先进电工材料 2023, 56(12): 17-23
纳米氧化锌形貌对风电扭转电缆用乙丙橡胶电气和力学性能的调控研究
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李旭1, 李贺2, 郭歌1, 曹晨4, 吴明2, 高景晖2
作者信息
  • 1国网陕西省电力有限公司,陕西 西安 710048
  • 2西安交通大学 电力设备电气绝缘国家重点 实验室,陕西 西安 710049
  • 3国网陕西省电力有限公司安康水力发电公司,陕西 安康 725000
  • 4国网陕西省电力有限公司商洛供电公司,陕西 商洛 726000
  • 李旭(1984-),男(汉族),陕西西安人,高级工程师,主要研究方向为高电压与绝缘技术及高压电器;

    吴明(1992-),男(汉族),湖北黄冈人,助理教授,博士,主要研究方向为电工绝缘材料与功能电介质传感。

Regulation on electrical and mechanical properties of ethylene-propylene rubber for wind turbine torsion cables by morphology of nano zinc oxide
Xu LI1, He LI2, Ge GUO1, Chen CAO4, Ming WU2, Jinghui GAO2
Affiliations
  • 1State Grid Shaanxi Electric Power Co., Ltd., Xi′an 710048, China
  • 2State Key Lab of Electrical Insulation and Power Equipment, Xi′an Jiaotong University, Xi′an 710049, China
  • 3Ankang Hydropower Company, State Grid Shaanxi Electric Power Co., Ltd., Ankang 725000, China
  • 4Shangluo Power Supply Company, State Grid Shaanxi Electric Power Co., Ltd., Shangluo 726000, China
出版时间: 2023-12-20 doi: 10.16790/j.cnki.1009-9239.im.2023.12.003
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风电扭转电缆绝缘用乙丙橡胶需要同时具备较高的电气性能和机械强度,以满足其严苛的工况要求。本文制备了不同形貌纳米氧化锌掺杂的乙丙橡胶样品,研究纳米氧化锌形貌对乙丙橡胶力学性能、电学性能和导热性能的影响。结果表明:纳米氧化锌的比表面积越大,乙丙橡胶的交联密度越大,但结晶度基本不发生变化;在力学性能方面,大比表面积纳米氧化锌导致的过度交联会稍微降低乙丙橡胶的断裂伸长率和拉伸强度;在电学性能方面,纳米氧化锌比表面积对乙丙橡胶的电阻率、介质损耗和室温电气强度影响不大,但介电常数和90℃电气强度随纳米氧化锌比表面积的增加而稍有提升;纳米氧化锌对乙丙橡胶的导热性能调控没有明显规律。

纳米氧化锌  /  风电扭转电缆  /  乙丙橡胶

The ethylene propylene rubber for wind turbine twisting cable insulation needs to have high electrical properties and mechanical strength simultaneously to meet the demanding operating conditions. Different morphologies of zinc oxide nanoparticles doped ethylene propylene rubber samples were prepared to investigate the influence of zinc oxide morphology on the mechanical, electrical, and thermal conductive properties of ethylene propylene rubber. The results show that the larger the specific surface area of zinc oxide nanoparticles, the bigger the crosslinking density of ethylene propylene rubber, while the crystallinity remaines unchanged basically. In terms of mechanical properties, the excessive crosslinking caused by high specific surface area of zinc oxide would slightly decrease the elongation at break and tensile strength of ethylene propylene rubber. In terms of electrical properties, the specific surface area of zinc oxide has little effect on the resistivity, dielectric loss, and breakdown strength at room temperature, but the dielectric constant and breakdown strength at 90℃ increase slightly with the increase of specific surface area of zinc oxide. There is no apparent variation rule in the regulation of thermal conductivity of ethylene propylene rubber by zinc oxide nanoparticles.

nano zinc oxide  /  wind turbine torsion cables  /  ethylene-propylene rubber
李旭, 李贺, 郭歌, 曹晨, 吴明, 高景晖. 纳米氧化锌形貌对风电扭转电缆用乙丙橡胶电气和力学性能的调控研究. 绝缘材料, 2023 , 56 (12) : 17 -23 . DOI: 10.16790/j.cnki.1009-9239.im.2023.12.003
Xu LI, He LI, Ge GUO, Chen CAO, Ming WU, Jinghui GAO. Regulation on electrical and mechanical properties of ethylene-propylene rubber for wind turbine torsion cables by morphology of nano zinc oxide[J]. Insulating Materials, 2023 , 56 (12) : 17 -23 . DOI: 10.16790/j.cnki.1009-9239.im.2023.12.003
大力发展可再生能源,逐步提高新能源在电力系统中的占比,构建以新能源为主体的新型电力网络,是实现全球能源与环境可持续发展的必然趋势[1]。在不同类型清洁能源中,风能发展最为迅猛,且占有最大的容量比例和市场份额[2]。截至2021年,全球累计风电装机容量超过800 GW,每年新增装机容量呈指数级增长。市场的高速增长促进了风电技术的快速发展,对风电装备技术等提出了更高的要求。
扭转电缆是风力发电机中连接电机和杆塔的重要电力装备,需要同时承受机械、电、热的联合作用,并且在风机容量大型化发展趋势下,扭转电缆的电压等级逐步从35 kV发展至66 kV和110 kV,这对电缆绝缘材料的电气性能和力学性能提出了更高的要求。
三元乙丙橡胶(EPDM)是目前风电扭转电缆主要使用的绝缘材料,它是以乙烯、丙烯和非共轭二烯烃为单体共聚而成的人工合成橡胶[3-4],具有优良的耐热、耐老化、耐腐蚀性能和电绝缘、耐电晕性能,在变压器绝缘垫、绝缘护套和特种电缆等领域具有广泛的应用[5-6]。然而,乙丙橡胶的弹性模量和强度较小,在实际应用过程中,往往需要使用无机填料对乙丙橡胶进行掺杂补强[7-8],同时通过诱发硫化反应促进乙丙橡胶分子之间交联从而形成稳定的三维硫化网络结构,以提高乙丙橡胶的力学性能[9-10]
氧化锌是乙丙橡胶中常用的一种添加剂,一方面它作为无机填料,可对乙丙橡胶的力学性能进行补强;另一方面它作为一种交联促进剂,可促进乙丙橡胶硫化过程中的交联反应[3,11]。近年来,随着纳米氧化锌合成和改性技术的成熟,采用纳米氧化锌作为改性剂逐渐成为乙丙橡胶改性研究领域的热点。然而,这些研究主要关注纳米氧化锌在乙丙橡胶中的分散性以及纳米氧化锌对乙丙橡胶力学性能的调控[12-13]。关于不同种类纳米氧化锌对乙丙橡胶电学性能,特别是对电学和力学性能协同调控的研究还非常少[14]
本文从风电扭转电缆对乙丙橡胶绝缘材料的性能需求出发,研究4种不同几何特征(短柱状、长柱状以及两种不同直径球状)的纳米氧化锌颗粒对风电扭转电缆用乙丙橡胶绝缘材料力学性能和电气性能的改性作用,明确不同种类氧化锌对乙丙橡胶综合性能的影响规律。
本文所用的乙丙橡胶配方体系包括乙丙橡胶基料(陶氏3722)、高岭土(Al2O3·2SiO2·2H2O,美国爱狄希高岭土)、红丹(Pb3O4,陕西缔都医药)、石蜡(中国石化60#)、低密度聚乙烯(LDPE,中国石化7042)、过氧化二异丙苯(DCP阿克苏)、抗氧剂(巴斯夫1010)以及4种不同几何特征纳米氧化锌(济源鲁泰),其中短柱状纳米氧化锌编号命名为1#氧化锌,长柱状纳米氧化锌编号命名为2#氧化锌,球状纳米氧化锌编号命名为3#氧化锌,球状且直径大于3#直径的纳米氧化锌编号命名为4#氧化锌,各原料成分比例如表1所示。其中,高岭土作为补强剂,填充份数较大;红丹作为染色剂的同时有防水作用;石蜡作为软化剂加入,以保证填料混合均匀;LDPE主要与乙丙橡胶体系的结晶度密切相关;DCP和纳米氧化锌是乙丙橡胶交联体系的重要组成,DCP作为交联剂参与整个交联过程,纳米氧化锌作为交联助剂参与其中。
利用哈尔滨哈普电气技术有限责任公司生产的RM200C型转矩流变仪将乙丙橡胶基料与不同添加剂进行混合,在此过程中,改变氧化锌的种类,质量分数统一保持为5%,其他成分比例保持不变,进行4种乙丙橡胶样品的制备,具体操作如下:先按照一定比例将乙丙橡胶基料、高岭土、红丹、石蜡、LDPE、DCP、不同几何特征纳米氧化锌、抗氧剂称量装袋;然后在转矩流变仪中加入一定量的乙丙橡胶基料,温度设置为110℃,转速设置为10 r/min,以清洗仪器,保证没有杂质混入;随后将称量好的乙丙橡胶基料放入仪器中,待乙丙橡胶受热充分后,将LDPE、高岭土、石蜡、抗氧剂依次放入,并提高转速至30 r/min,充分混合15 min;最后将转矩流变仪降温至90℃后加入DCP、不同几何特征纳米氧化锌,混合10 min后取出,得到4种不同种类纳米氧化锌掺杂的乙丙橡胶块状样品。
利用东莞仪通检测设备科技有限公司生产的YT-ML15型平板硫化机将4种乙丙橡胶块状样品压制成片,以实现乙丙橡胶样片的制备,具体操作如下:将混合后的乙丙橡胶块状样品按照模具体积称量,置于模具中,通过钢板和聚酯薄膜将试样固定。整个操作过程中使用两台平板硫化仪,其中一台平板硫化机温度设置为120℃,另一台设置为180℃。先将固定的样品连着模具、钢板一起,放置于120℃的平板硫化机中,预热5 min后,逐步加压,将软化的块状样品压平,压力为20 MPa,继续加热5 min。随后转移至180℃平板硫化机中,压力为20 MPa,交联5 min,循环放气5次,以保证没有气孔产生,再继续加压5 min。交联过程结束后,将样品取出,在空气中迅速冷却至室温。根据模具尺寸得到尺寸为100 mm×100 mm、厚度为0.5 mm的方形试样,以进行后续性能测试。
使用Carl Zeiss公司Gemini SEM 500型场发射扫描电子显微镜观察乙丙橡胶试样的微观形貌,观察前需要将片状样品裁成细条状,在液氮中低温脆断,然后对断面进行喷金处理。利用X射线能谱仪(EDS)对脆断面的元素分布进行测试。使用陕西朗润国际贸易有限公司ASAP 2020 Plus HD88型全自动物理吸附仪(BET)对比表面积进行测试。利用差示扫描量热法(DSC)测试样品的热流曲线并计算结晶度。利用平衡溶胀法测试乙丙橡胶的交联密度,将乙丙橡胶置于环己烷中168 h,当溶剂挤出的弹性收缩力和溶剂渗入橡胶的压力持平时,橡胶的溶胀体积达到极限值,实现溶胀平衡。在橡胶弹性统计论基础上根据Flory-Huggins理论可以得到交联密度的计算公式,即Flory-Rehner公式,如式(1)所示,以此求得样品的交联密度,每组样品测试5个试样,结果取平均值,以保证实验结果的可靠性。
ve=-1vln 1-v2+v2+xv22v213-2v2f
式(1)中:ve为磁化橡胶的交联密度;v2为橡胶相在溶胀后硫化胶中的体积分数;v是溶剂的摩尔体积;x为橡胶与溶剂的相互作用系数;f为橡胶网络的官能度。
依据GB/T 1040.3—2006开展力学性能测试。利用模具将乙丙橡胶样片切割成如图1所示的哑铃形状,使用CMT4503-5kN型电子万能试验机对常温下的乙丙橡胶样品进行拉伸试验,实验温度为25℃,拉伸速率为100 mm/min,传感器选取为大变形传感器,每组试样至少选取5个有效数据,取平均值作为测试结果。
利用实验室常用的交流击穿场强测试系统对乙丙橡胶样片的击穿性能进行测试,电极模块采用柱-柱不锈钢电极,电极的直径均为25 mm。在测试过程中,将整个电极模块置于盛有植物油的恒温油浴箱中,以保证恒温的同时,避免在高电压下出现沿面放电。在实验前,对乙丙橡胶样片进行预处理,用无水酒精擦拭表面,除去灰尘,并在50℃下保温24 h,以消除其机械应力。在测试过程中,采用匀速连续升压的方式进行加压,速率保持为1 kV/s,待电压源发出警报声后停止升压并记录击穿电压值,每组样品进行12次测试,以保证数据的有效性。击穿结束后,擦拭样片表面,对击穿点的厚度进行测试并记录,通过双参数威布尔分布(Weibull)对交流击穿实验结果进行处理,并通过威布尔分布公式计算试样的电气强度,如式(2)所示。
PE=1-exp -Eαβ
式(2)中:E为电场强度(kV/mm);P(E)表示电场强度为E时的累计击穿概率;α为尺度参数,表示失效概率为63.2%时的电气强度;β为形状参数,表示电气强度的分散性。
利用Concept 80型宽带介电谱测试系统,对乙丙橡胶材料的介电性能随温度的变化曲线进行测试。在测试前,需要将乙丙橡胶试样用无水酒精进行擦拭,待晾干后,对试样的两面进行喷金处理,并裁剪成直径为22 mm的圆形薄片。测试过程中的温度范围为-60~80℃,升温速率为1.5℃/min,测试频率为50 Hz。
利用三电极系统对乙丙橡胶样品的电阻率进行测试。直流高压电源选用Spellman公司的SL40PN300/220型高压直流电源,最高输出电压为40 kV,波纹系数为0.1%。电流表选用Keithley公司的6517B型静电计,测试量程为10 aA~21 mA。三电极测试模块选用的高压极直径为45 mm,测量极直径为26 mm,保护极与测量极之间的间隙为3 mm,在电极外还有屏蔽装置以屏蔽电磁干扰。温度控制装置采用恒温温箱来实现温度的变化与控制。
利用Mettler Toledo公司LFA447型导热测量仪对导热系数进行测试。实验前需对所有样片表面喷覆石墨涂层[15],测试过程中取30、60、90℃三个温度点进行测试。
利用扫描电子显微镜对4种氧化锌颗粒的形貌进行观察,其微观形貌如图2所示。从图2可以看出,1#ZnO是尺寸在亚微米级别的短柱状颗粒,对表面形貌图中的颗粒尺寸进行分析计算,得到其平均长度和宽度分别为400 nm和50 nm;2#ZnO是微米级别的长柱状颗粒,其平均长度和宽度分别为700 nm和47 nm,即2#长柱状氧化锌颗粒相较于1#短柱状氧化锌而言,宽度与1#相差不大,而长度比1#更长;3#纳米氧化锌是球状颗粒,测试得到的直径约为15 nm;4#纳米氧化锌也是球状颗粒,直径比3#的大,尺寸约为30 nm,即4#ZnO颗粒的大小约为3#ZnO的2倍。
进一步,利用物理吸附仪对4种氧化锌粉末样品的比表面积进行测试,结果如表2所示。在测试之前,所有粉末样品均经历干燥过筛处理,以保证实验结果的可靠性。从表2可以看出,1#与2#纳米氧化锌的比表面积相差不大,其中1#的比表面积略大,而3#纳米氧化锌的比表面积则远大于其他3种纳米氧化锌,4#纳米氧化锌的比表面积处于中间水平。比表面积与纳米氧化锌的反应活性直接相关,因此4种纳米氧化锌的反应活性从大到小依次为3#、4#、1#、2#。后续将4种纳米氧化锌调控的乙丙橡胶样品分别定义为1#样品、2#样品、3#样品和4#样品。
利用扫描电子显微镜对4种纳米氧化锌调控的乙丙橡胶样片脆断表面进行观察,结果如图3所示。从图3可以看出,4种乙丙橡胶均有高岭土填料分布,但是含量较多的高岭土颗粒粒径也是类似的尺寸水平,与氧化锌颗粒难以区分,因此无法直接通过表面形貌对观察位置的填料种类进行区分。
利用X射线能谱仪对乙丙橡胶断面的元素分布进行测试,发现4种样品表现出类似的规律,其中1#样品的结果如图4所示。测试发现,断面上的Zn元素均保持良好的分散性,说明样品中纳米氧化锌都均匀分散于乙丙橡胶基料中,纳米氧化锌的分散性不会引起后续测试的性能差异。4种样品所表现的性能差异主要由4种纳米氧化锌比表面积的差异引起。
利用平衡溶胀法对4种样品的交联密度进行测试,结果如表3所示。由表3可知,1#样品与2#样品的交联密度差别不大,均处于4组乙丙橡胶中的较低水平,而3#样品的交联密度明显大于其他3组样品,4#样品则略小于3#样品,这一规律与纳米氧化性的比表面积高度相关。高比表面积纳米氧化锌的加入,提供了更多促进交联反应的活性位点,从而能够显著加速乙丙橡胶中的硫化过程,提高乙丙橡胶的交联密度。
通过差示扫描量热仪对乙丙橡胶进行测试,在分析过程中选取测试曲线的二次升温段,如图5(a)所示。图中-45℃附近的台阶对应于乙丙橡胶的玻璃化转变过程,40℃的吸热峰对应于乙丙橡胶体系中石蜡的熔融过程,而95℃附近的吸热峰对应于乙丙橡胶中聚乙烯链段的熔融过程[16-17]。由图5(a)可知,不同种类纳米氧化锌掺杂乙丙橡胶的DSC曲线变化趋势保持一致,表明纳米氧化锌的形貌对乙丙橡胶的基本性质无显著影响。
对95℃附近乙丙橡胶熔融峰的面积进行积分计算,求得乙丙橡胶的结晶度,计算公式如式(3)~(4)所示,计算结果如图5(b)所示。由图5(b)可知,不同样品中聚乙烯链段的结晶度都处于较低水平,整体保持在0.40%附近,变化范围在±0.02%。也就是说,纳米氧化锌种类不会影响乙丙橡胶的结晶过程。
H=dQdtdT 
Xc=HHc×m
式(3)~(4)中:H为焓变,J·g-1dQ/dt为热流, W·g-1T为温度,℃;Xc为结晶度,%;Hc试样完全结晶时的焓变,取290 J·g-1m为对应有机成分的质量分数。
4种纳米氧化锌掺杂乙丙橡胶的室温力学性能测试结果如图6所示。从图6可以看出,1#、3#样品的断裂伸长率最低,分别为440.33%和423.77%,而2#样品的断裂伸长率最大,为532.04%,4#样品的断裂伸长率则处于中间水平,为477.23%。在拉伸强度方面也表现出相同的规律,即1#与3#样品的拉伸强度相差不大,分别为8.31 MPa、8.74 MPa,均处于较低水平,2#样品的拉伸强度最大,为11.88 MPa,4#样品的拉伸强度则处于中间水平,为9.22 MPa。该实验结果说明比表面积大的球状纳米氧化锌颗粒(3#、4#)的加入,不利于乙丙橡胶拉伸性能的提高,这是由于球状纳米氧化锌颗粒的比表面积越大,乙丙橡胶的交联密度越高,硫化胶中的交联点较多,在拉伸过程中自由滑移的分子链减少[18],硫化胶随应力产生形变的能力减弱,胶体依靠形变缓解应力的能力变弱,当拉伸应力超过胶体形变所能承受的范围时,就会发生交联键断裂和分子链断裂,在胶体中形成空隙,对胶体产生破坏,从而导致断裂伸长率和拉伸强度减小。
在室温和高温(90℃)下利用交流击穿平台对4种纳米氧化锌掺杂乙丙橡胶的电气强度进行测试,并利用Weibull分布对实验结果进行计算处理,计算结果如图7所示。从图7可以看出,常温下电气强度最大的是4#样品,为58.08 kV/mm,而电气强度最小的是3#样品,为54.63 kV/mm。高温下电气强度最大的是3#样品,为67.6 kV/mm,而电气强度最小的是2#样品,为63.7 kV/mm。整体而言,4组乙丙橡胶的电气强度差距并不明显,常温下波动在(56±2)kV/mm范围内,高温下波动在(65.5±2)kV/mm范围内。实验结果表明加工过程中乙丙橡胶中的第三单体交联越充分,则残留的双键越少,材料的耐电强度越高[19],因此比表面积较大的3#样品在高温下表现出较高的电气强度。
利用宽带介电谱对4种纳米氧化锌掺杂乙丙橡胶的介电温谱进行测试,结果如图8所示。由图8可知,4种样品的相对介电常数均随温度上升而下降,且在-60℃到80℃区间内,纳米氧化锌的比表面积越大,样品的相对介电常数越高,可能的原因是比表面积的增加会引入更多的纳米氧化锌-乙丙橡胶界面,从而贡献了更多的界面极化。4种样品的介质损耗因数随温度升高呈上升趋势,与纳米氧化锌比表面积没有明显对应关系,且数值都较小,在测试温度范围内tanδ均小于0.013。
图9为4种纳米氧化锌掺杂乙丙橡胶在常温下的电阻率测试结果。由图9可知,4种样品的常温电阻率都在(1.40±0.15)×1015 Ω·m范围内,说明纳米氧化锌形貌对乙丙橡胶的电阻率影响不大,这是因为纳米氧化锌填充量较少,纳米氧化锌粒子都被橡胶大分子包裹隔绝,不会形成导电通道,橡胶材料的电阻率主要由橡胶基体和高填充比例的填料决定。
导热系数表征的是材料导热、散热的能力,良好的导热性能能够保障电缆运行过程中的温度处于正常水平。对4种纳米氧化锌掺杂乙丙橡胶的导热性能进行测试,测试选取30、60、90℃三个温度,测试结果如图10所示。由图10可知,1#和4#样品在3个测试温度下,均具有较高的导热系数,其值为0.30 W/(m·K)左右,2#和3#样品的导热系数较低,在0.15 W/(m·K)左右。样品的导热系数与纳米氧化锌的比表面积、乙丙橡胶的交联密度之间均不存在显性相关关系。
对于有机-无机复合材料而言,无机填料的形貌、用量和分布均会对复合材料的导热系数产生显著影响。同种类的传热填料粒子一般具有球形、片状、纤维状等多种结构,其中晶须对提高橡胶的导热系数最有效,球形最差。通常情况下,填料在有机或者无机基体中的分布状态具有强烈的随机性。即使往基体中加入相同填充量的填料,由于制作工艺的不同,热导率的测试值也会存在一定区别。
(1)纳米氧化锌的比表面积对乙丙橡胶的交联密度有显著影响,比表面积越大,交联密度越大,但结晶度基本保持不变。
(2)大比表面积的纳米氧化锌会导致乙丙橡胶过度交联,从而导致其力学性能劣化。
(3)乙丙橡胶的相对介电常数和高温下的电气强度与掺杂纳米氧化锌比表面积大小呈正相关。
(4)乙丙橡胶的介质损耗、电阻率、导热系数与氧化锌种类无明显对应关系。
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2023年第56卷第12期
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doi: 10.16790/j.cnki.1009-9239.im.2023.12.003
  • 接收时间:2023-05-31
  • 首发时间:2025-11-24
  • 出版时间:2023-12-20
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  • 收稿日期:2023-05-31
  • 修回日期:2023-07-21
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    1国网陕西省电力有限公司,陕西 西安 710048
    2西安交通大学 电力设备电气绝缘国家重点 实验室,陕西 西安 710049
    3国网陕西省电力有限公司安康水力发电公司,陕西 安康 725000
    4国网陕西省电力有限公司商洛供电公司,陕西 商洛 726000
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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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