Article(id=1193556938282726349, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2025.04.002, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1723564800000, receivedDateStr=2024-08-14, revisedDate=1731427200000, revisedDateStr=2024-11-13, acceptedDate=null, acceptedDateStr=null, onlineDate=1762495749302, onlineDateStr=2025-11-07, pubDate=1745078400000, pubDateStr=2025-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1762495749302, onlineIssueDateStr=2025-11-07, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1762495749302, creator=13701087609, updateTime=1762495749302, updator=13701087609, issue=Issue{id=1193556932167431095, tenantId=1146029695717560320, journalId=1149653034449285133, year='2025', volume='58', issue='4', pageStart='1', pageEnd='144', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1762495747843, creator=13701087609, updateTime=1762498255746, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1193567451108573868, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1193567451112768173, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1193556932167431095, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=9, endPage=15, ext={EN=ArticleExt(id=1193556938475664335, articleId=1193556938282726349, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of crystal forms on insulation performances of bi-axial oriented polypropylene film, columnId=1193556932997903294, journalTitle=Insulating Materials, columnName=Advanced Energy Storage Dielectric Special Issue, runingTitle=null, highlight=null, articleAbstract=

Polypropylene (PP) is the most widely used dielectric material for capacitors, improving its insulation performance is of great significance to improve the energy storage density and reliability of capacitors. In this paper, the action law and mechanism of crystal form on breakdown characteristics of films were studied systematically by adding β-nucleating agent to polypropylene resin, so as to obtain the method of improving the insulation performance which can be popularized in industry. Firstly, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) tests were conducted on the polypropylene resin for its aggregate structure. The results show that the crystallization activation energy of polypropylene resin decreases and the crystallinity increases after adding the β-nucleating agent. Secondly, on the basis of the practical application requirements of capacitor dielectric materials, polypropylene resin was bi-axial oriented to obtain bi-axial oriented polypropylene (BOPP) films. It is found that there are no obvious difference in crystal morphology and surface morphology of the resins with different crystal type after stretching,while the electric strength of the BOPP film containing β-nucleating agent is 7.1% lower than that of the BOPP film without β-nucleating agent. Finally, the BOPP films were subjected to vacuum heat treatment at different temperatures for 1 000 h. The electric strength of the two BOPP films increases with the increase of heat treatment temperature, and the electric strength of the film containing β-nucleating agent increases more significantly, which exceeds that of the resin with α-crystal as the main crystal after heat treatment at 120℃. It is speculated that the reason for this result is that the β-crystal is not conducive to the optimal arrangement of molecular chains during the tensile process, resulting in the migration of electrons more easily and thus reduce the electric strength. However, the vacuum heat treatment near the crystallization temperature can promote the movement of molecular chain segments, optimize the aggregation structure, and ultimately make the electric strength incrase.

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聚丙烯(PP)作为最广泛应用的电容器介质材料,提高其绝缘性能对于提升电容器的储能密度和可靠性具有重要意义。本文提出通过在聚丙烯树脂中加入β成核剂,系统研究晶型对薄膜击穿特性的作用规律和机理,从而获得可工业化推广的绝缘性能提升方法。首先,针对聚集态结构,对聚丙烯树脂进行X射线衍射(XRD)和差示扫描量热(DSC)测试。结果表明,加入β成核剂后聚丙烯树脂结晶活化能降低、结晶度提高。其次,基于电容器介质材料的实际应用需求,将聚丙烯树脂进行拉伸制备双向拉伸聚丙烯(BOPP)薄膜,发现不同晶型树脂在拉伸后结晶形态和表面形貌已无明显差异,但含有β成核剂BOPP薄膜的电气强度相比未添加成核剂BOPP薄膜的电气强度低7.1%。最后,对BOPP薄膜在不同温度下进行1 000 h真空热处理,两种BOPP薄膜的电气强度均随热处理温度的升高而增大,并且含β成核剂薄膜的电气强度提升更加显著,在120℃热处理后电气强度反超了α晶为主晶相的树脂。推测出现该结果的原因是由于β晶不利于拉伸过程中分子链的优化排列,导致电子的迁移更容易发生从而降低电气强度,但是在结晶温度附近的真空热处理可以促进分子链段运动,优化聚集态结构,最终使电气强度得到提升。

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姚成(1981-),男(侗族),贵州玉屏人,高级工程师,主要从事电容器及无功补偿的研究。

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姚成(1981-),男(侗族),贵州玉屏人,高级工程师,主要从事电容器及无功补偿的研究。

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姚成(1981-),男(侗族),贵州玉屏人,高级工程师,主要从事电容器及无功补偿的研究。

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晶型对双向拉伸聚丙烯薄膜绝缘特性的影响研究
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姚成 , 刘刚 , 蔡希鹏 , 胡上茂 , 陈喜鹏 , 孟森
绝缘材料 | 先进储能电介质专题 2025,58(4): 9-15
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绝缘材料 | 先进储能电介质专题 2025, 58(4): 9-15
晶型对双向拉伸聚丙烯薄膜绝缘特性的影响研究
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姚成, 刘刚, 蔡希鹏, 胡上茂, 陈喜鹏, 孟森
作者信息
  • 南方电网科学研究院有限责任公司,广东 广州 510663
  • 姚成(1981-),男(侗族),贵州玉屏人,高级工程师,主要从事电容器及无功补偿的研究。

Effect of crystal forms on insulation performances of bi-axial oriented polypropylene film
Cheng YAO, Gang LIU, Xipeng CAI, Shangmao HU, Xipeng CHEN, Sen MENG
Affiliations
  • Southern Power Grid Scientific Research Institute Co., Ltd., Guangzhou 510663, China
出版时间: 2025-04-20 doi: 10.16790/j.cnki.1009-9239.im.2025.04.002
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聚丙烯(PP)作为最广泛应用的电容器介质材料,提高其绝缘性能对于提升电容器的储能密度和可靠性具有重要意义。本文提出通过在聚丙烯树脂中加入β成核剂,系统研究晶型对薄膜击穿特性的作用规律和机理,从而获得可工业化推广的绝缘性能提升方法。首先,针对聚集态结构,对聚丙烯树脂进行X射线衍射(XRD)和差示扫描量热(DSC)测试。结果表明,加入β成核剂后聚丙烯树脂结晶活化能降低、结晶度提高。其次,基于电容器介质材料的实际应用需求,将聚丙烯树脂进行拉伸制备双向拉伸聚丙烯(BOPP)薄膜,发现不同晶型树脂在拉伸后结晶形态和表面形貌已无明显差异,但含有β成核剂BOPP薄膜的电气强度相比未添加成核剂BOPP薄膜的电气强度低7.1%。最后,对BOPP薄膜在不同温度下进行1 000 h真空热处理,两种BOPP薄膜的电气强度均随热处理温度的升高而增大,并且含β成核剂薄膜的电气强度提升更加显著,在120℃热处理后电气强度反超了α晶为主晶相的树脂。推测出现该结果的原因是由于β晶不利于拉伸过程中分子链的优化排列,导致电子的迁移更容易发生从而降低电气强度,但是在结晶温度附近的真空热处理可以促进分子链段运动,优化聚集态结构,最终使电气强度得到提升。

聚丙烯  /  双向拉伸聚丙烯薄膜  /  电容器  /  结晶  /  电气强度  /  β

Polypropylene (PP) is the most widely used dielectric material for capacitors, improving its insulation performance is of great significance to improve the energy storage density and reliability of capacitors. In this paper, the action law and mechanism of crystal form on breakdown characteristics of films were studied systematically by adding β-nucleating agent to polypropylene resin, so as to obtain the method of improving the insulation performance which can be popularized in industry. Firstly, X-ray diffraction (XRD) and differential scanning calorimetry (DSC) tests were conducted on the polypropylene resin for its aggregate structure. The results show that the crystallization activation energy of polypropylene resin decreases and the crystallinity increases after adding the β-nucleating agent. Secondly, on the basis of the practical application requirements of capacitor dielectric materials, polypropylene resin was bi-axial oriented to obtain bi-axial oriented polypropylene (BOPP) films. It is found that there are no obvious difference in crystal morphology and surface morphology of the resins with different crystal type after stretching,while the electric strength of the BOPP film containing β-nucleating agent is 7.1% lower than that of the BOPP film without β-nucleating agent. Finally, the BOPP films were subjected to vacuum heat treatment at different temperatures for 1 000 h. The electric strength of the two BOPP films increases with the increase of heat treatment temperature, and the electric strength of the film containing β-nucleating agent increases more significantly, which exceeds that of the resin with α-crystal as the main crystal after heat treatment at 120℃. It is speculated that the reason for this result is that the β-crystal is not conducive to the optimal arrangement of molecular chains during the tensile process, resulting in the migration of electrons more easily and thus reduce the electric strength. However, the vacuum heat treatment near the crystallization temperature can promote the movement of molecular chain segments, optimize the aggregation structure, and ultimately make the electric strength incrase.

polypropylene  /  BOPP  /  capacitor  /  crystallization  /  electric strength  /  β-crystal
姚成, 刘刚, 蔡希鹏, 胡上茂, 陈喜鹏, 孟森. 晶型对双向拉伸聚丙烯薄膜绝缘特性的影响研究. 绝缘材料, 2025 , 58 (4) : 9 -15 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.002
Cheng YAO, Gang LIU, Xipeng CAI, Shangmao HU, Xipeng CHEN, Sen MENG. Effect of crystal forms on insulation performances of bi-axial oriented polypropylene film[J]. Insulating Materials, 2025 , 58 (4) : 9 -15 . DOI: 10.16790/j.cnki.1009-9239.im.2025.04.002
聚丙烯(PP)具有高电气强度、低介质损耗以及优异的加工性能等特点,被用作电力设备介质材料,广泛应用于高储能密度电容器、热塑性电缆等领域[1]。近年来,随着电压等级的不断提升以及设备逐渐趋于小型化,人们对聚丙烯的绝缘性能提出了更高的要求。在“碳达峰、碳中和”战略目标背景下,柔性直流输电技术的大规模应用推动了电容器的快速发展,这对电容器的储能密度也提出了更高的要求。而提升电容器储能密度的关键途径之一是实现其介质材料——双向拉伸聚丙烯(BOPP)薄膜电气强度的提高。
目前针对提高聚丙烯电气强度的研究主要有两种方法:在聚丙烯中加入有机/无机填料以及对聚丙烯分子结构或聚集态结构进行优化。在众多的改性方法中,纳米复合改性聚丙烯在提高电气强度方面取得了较好的效果[2]。通过引入不同特性的纳米粒子可以改变复合基体的陷阱特性以及松弛极化过程,从而实现对聚丙烯基介质性能的有效调控。例如加入高介电常数的纳米粒子或导体粒子,可以显著提高复合聚丙烯的介电常数[3-4];而电气强度的提高主要是通过改善纳米粒子在聚丙烯基体中的分散性,以及优化纳米粒子周围界面区结构来实现,因此纳米粒子表面改性、构筑“核-壳”结构纳米粒子等方法对于聚丙烯基介质绝缘性能的提升都有显著作用[5-7]。本研究团队通过构筑“聚丙烯/马来酸酐聚丙烯/纳米氧化锆”三元复合聚丙烯,在将聚丙烯电气强度提高43%的同时抑制了介质损耗的激增[8-10]
相比于加入填料的方法,对纯聚丙烯进行结构优化的方法更适用于大规模生产以及经济成本控制[11]。徐明忠等[12]研究了均聚、共聚聚丙烯及其αβ两种晶型的性能,发现均聚β晶型聚丙烯的电性能及结晶性能均优于α晶型聚丙烯;ZHANG W等[13]研究发现在高温条件下引入β晶型的聚丙烯具有更高的电气强度。目前,晶型优化调控的方法在聚丙烯电缆领域显现出了一定的发展潜力,但该方法用于电容器用BOPP薄膜的研究较少。与电缆PP绝缘层不同,电容器用BOPP薄膜是通过对流延薄膜进行双向拉伸得到的,在双向拉伸的过程中其β晶型会转变为α晶型[14],晶型的转变与调控对于BOPP薄膜的性能至关重要。因此,研究聚丙烯树脂初始的结晶形态以及结晶动力学对于BOPP薄膜性能的影响具有重要意义。
本文针对不同结晶形态的聚丙烯树脂开展对比研究,分别测试未加入成核剂PP树脂以及加入β成核剂PP树脂的聚集态结构,将两种树脂进行双向拉伸制备成BOPP薄膜,并开展结晶形态和击穿性能测试,结合不同温度的热处理试验,获得β成核剂对电容器用聚丙烯树脂和BOPP薄膜结构形貌的作用规律,以及对薄膜电学性能的影响机理。
本文所用聚丙烯树脂为同一公司制造的树脂粒料,均为电容器薄膜专用聚丙烯,等规度为98%以上,重均分子量为3.4×105左右。原始树脂编号为PP-A,在PP-A中加入了一定比例的β成核剂,得到的树脂编号为PP-B。对两种树脂采用相同的商业化大规模双向拉伸生产线进行拉伸,得到厚度为6 μm的BOPP薄膜试样,分别编号为BOPP-A和BOPP-B。
对于PP树脂和对应BOPP薄膜的聚集态结构采用X射线衍射(XRD)和差示扫描量热分析(DSC)进行探究,其中XRD所用仪器为Bruker D8 Advance A25型X射线衍射仪,测试条件为常温,测试角度2θ为10°~30°,DSC所用仪器为METTLER DSC 822型差示扫描量热仪,试样质量约为5 mg,将试样置于标准铝坩埚内,在氮气保护下以10℃/min的速率升温至200℃并保温3 min以消除热历史,然后以不同的降温速率结晶,再以10℃/min的速率升温至熔融,记录升温和降温过程中的焓值变化。通过偏光显微镜(POM)对BOPP薄膜的表面形貌结构进行观察。BOPP薄膜的直流击穿测试在常温下进行,使用直径为25 mm的球形铜电极,测试时整个装置包括电极和试样,均浸入绝缘油中,升压速率为1 kV/s,为确保试验数据的可靠性,每组试样至少测试20个击穿点,并对测试结果进行威布尔分布统计。
高分子材料的聚集态结构是指分子链之间排列和堆砌的结构,是决定高分子本体性质的主要因素之一[15]。聚丙烯是由结晶态和非晶态即无定形态共同组成的半结晶材料,因此本文分别采用XRD和DSC对树脂的聚集态结构进行测试表征。图1为PP-A和PP-B试样的X射线衍射图谱。从图1可以看出,两种树脂均在2θ=14.1°、16.2°、16.9°、18.5°和21.2°的位置出现了衍射峰,分别对应晶面(110)、(300)、(040)、(130)和(111)[16]。不同的是PP-A最强的衍射峰位于14.1°,为α晶型的特征峰,而PP-B最强的衍射峰位于16.2°,为β晶型的特征峰,说明两种树脂初始的结晶状态为α晶型与β晶型共存,但加入β成核剂后树脂的主晶相由α晶型转变为β晶型。
根据式(1)所示Turner-Jones公式[17],可以定量计算β晶型在两相共存体系中的占比kβ
k β = H β H β + H α 1 + H α 2 + H α 3
式(1)中:H(β)为晶面(300)衍射峰的强度;H(α 1)、H(α 2)、H(α 3)分别为晶面(110)、(040)、(130)衍射峰的强度。
根据式(1)得到PP-A和PP-B的β晶型占比分别为7.06%和77.4%。
聚丙烯具有3种不同的晶型:分别为α晶型、β晶型以及γ晶型。α晶型是最常见也是最稳定的晶型,大量存在于聚丙烯中。在工业生产中通常生成α晶型的同时常常伴有少量β晶型的生成,β晶型PP的冲击强度、韧性和延展性较α晶型PP更具有优势。与α晶型不同的是,生成大量β晶型需要特定方法诱导,例如“温度梯度”法、剪切诱导法、振动诱导法、添加β成核剂等[18],其中添加β成核剂的方法重复性高,是目前唯一可工业化实施的获取高含量β晶型聚丙烯的方法。因此,在β成核剂的诱导下,PP-B中β晶占比超过了70%。
图2为PP-A和PP-B的DSC熔融曲线测试结果。从图2可以看出,PP-A仅在165℃附近出现了1个熔融峰;而PP-B则在154℃和165℃附近出现了2个熔融峰,其中165℃附近的熔融峰对应α晶型,这主要是由于α晶型具有更高的热力学稳定性,因此其熔融温度更高[10]β晶型属于亚稳态,因此其熔融温度相较α晶型更低,对应154℃处的熔融峰[19]
对熔融曲线进行积分得到熔融峰面积,根据式(2)可以获得两种树脂在10℃/min降温速率下的结晶度。
X c = Δ H s Δ H k × 100 %
式(2)中:X c表示聚合物材料的结晶度;ΔH s为根据熔融峰面积积分得到的熔融焓值;ΔH k为结晶度为100%时的理论熔融焓值,通常聚丙烯取值为209 J/g。
式(2)计算得到PP-A的结晶度为51.88%,PP-B中α晶型和β晶型的结晶度分别为24.1%和34.7%。可见,在β成核剂的作用下PP-B整体具有更高的结晶度。通过DSC测试结果计算得到的β晶型与α晶型结晶度与XRD结果具有一定差异,一方面是由于不同的测试方法导致,另一方面是由于测试样品不同系数,XRD是针对树脂原始状态进行测试,而DSC则是针对消除热历史后采用相同降温速率非等温结晶得到的树脂进行测试。但是两种测试结果共同表明,加入一定量的β成核剂后,聚丙烯树脂的结晶形态为α晶型和β晶型共存,并且β晶型为主晶相。
为了进一步对两种树脂的结晶动力学特性进行研究,将PP-A和PP-B在5、10、15、20℃/min 4种降温速率下进行非等温结晶,测试得到其结晶吸热曲线如图3所示。从图3可以看出,随着降温速率的升高,聚丙烯的结晶温度T c逐渐降低,结晶峰宽度增大。晶体的生长速度取决于链段向晶核扩散和规整堆积的过程,降温速度较快时分子链还未来得及运动排入晶格,导致达到最大结晶速率时所需温度降低、结晶峰变宽。此外,对比两种树脂试样可以发现,在相同的降温速率下,PP-B的结晶温度高于PP-A,这主要是由于β成核剂的作用导致。温度过高时分子热运动剧烈,不利于均相成核,而异相成核则可以在较高的温度下发生,所以PP-B具有较高的结晶温度。
根据非等温结晶的数据,采用Kissinger公式可以计算两种树脂试样的结晶活化能[20]。Kissinger公式如式(3)所示。
l n Φ T p 2 1 T p = Δ E R
式(3)中: Φ表示降温速率,单位为℃/min;T p为对应温度下的结晶峰温度,单位为℃;R为气体常数,取值为8.314 J/(mol·K);ΔE表示聚合物的非等温结晶活化能,单位为kJ/mol。
将不同温度下的1/T p与ln( Φ/T p 2)分别作为x轴和y轴坐标得到图4
图4中4个温度点可通过式(3)进行线性拟合,得到的直线斜率即为ΔE/R。根据斜率计算得到PP-A和PP-B的非等温结晶活化能分别为311.5 kJ/mol和264.7 kJ/mol。非等温结晶活化能越小表示聚合物结晶过程需要克服的能垒越低,即聚合物越容易结晶。PP-B相比PP-A显著降低的非等温结晶活化能正是由于β成核剂促进稳定晶核形成所致。
聚丙烯树脂在经过流延以及双向拉伸后,形成微米级厚度的BOPP薄膜具有更高的电气强度、更好的加工卷绕性能,因此常作为电容器介质材料被广泛应用。BOPP薄膜的绝缘特性直接决定了电容器的储能密度和可靠性,因此有必要对两种树脂拉伸而成的BOPP-A和BOPP-B薄膜试样开展进一步测试研究。图5为BOPP-A和BOPP-B薄膜的X射线衍射谱。
图5可以看出,与图1中两种树脂的衍射图谱不同,经过双向拉伸后两种薄膜试样呈现出几乎完全相同的XRD图谱。这主要是由于在双向拉伸过程中亚稳态的β晶型转变为α晶型[21],因此图5中位于16.2°对应晶面(310)的β晶型特征峰完全消失,仅显示出α晶型的特征峰,说明BOPP薄膜中几乎全部为α晶型。
采用光学显微镜对两种BOPP薄膜试样表面形貌进行观察,结果如图6所示。
图6可以看出,BOPP-A和BOPP-B薄膜具有相似的形貌,即表面呈现出BOPP薄膜特有的“环形山”结晶。对两种薄膜试样随机选取100个结晶环测量其直径,得到的统计结果如图中右上角的柱形统计图所示。BOPP-A薄膜的表面呈现为略小且密的结晶环,环形直径主要集中在50~100 μm;而BOPP-B薄膜则表现为较大且稀疏的环形结晶,环形直径主要集中在50~300 μm。目前关于拉伸前聚丙烯晶型对于拉伸后BOPP薄膜表面结晶形貌影响的研究尚无定论,一些研究认为环形结晶的形成是由于β晶型的密度小于α晶型,拉伸过程中两种晶型密度不同导致薄膜表面分子链堆叠形态和体积发生变化,因此β晶型对于环形结晶至关重要[22];然而也有一些学者认为β晶型并非BOPP环形结晶形成的关键,横穿晶才是决定性因素[23]。环形结晶的形成使得BOPP表面具有粗化结构,相对细密的“环形山”结晶能够促进油浸式电容器在生产过程中空气的抽出、浸渍剂的浸润,因此BOPP薄膜表面形貌对于电容器的性能至关重要。
两种BOPP薄膜试样的XRD和POM的测试结果共同表明,拉伸工艺对BOPP薄膜的形貌结构具有重要影响,不同晶型的树脂在双向拉伸后β晶型均消失,获得了相同的晶型、相近的结晶度和表面形貌等宏观结晶特性。
进一步对BOPP-A和BOPP-B薄膜的绝缘特性进行系统测试。首先对两种薄膜试样在常温下进行直流电气强度测试,为了保证试验可靠性,每组试样至少测试20个击穿点。对测试获得的电气强度进行威布尔(Weibull)分布拟合。Weibull分布的计算公式如式(4)所示[24]
F ( x ) = 1 - e - ( x - c ) β α
式(4)中:x表示试样两端施加的场强;F(x)为外施场强小于x时发生击穿的概率;α为尺度参数,表示击穿概率为63.2%时所对应的电气强度,又称为特征电气强度;β为形状参数,反映数据的分散性,其值越大说明数据的分散性越小;c为位置参数,此处设定c=0。
将BOPP-A和BOPP-B薄膜的电气强度根据式(4)计算拟合,得到的结果如图7所示。
图7可以看出,BOPP-A薄膜击穿水平以及数据的分布特性相比BOPP-B薄膜都更有优势,其特征电气强度达到605.5 kV/mm,比BOPP-B薄膜(563.6 kV/mm)提高了7.4%,形状参数也从6.4提高至7.7。该结果表明,即使是相同的拉伸工艺得到结晶特性高度相似的BOPP薄膜,其原始树脂粒料不同的结晶特性仍对薄膜的击穿特性产生重要影响。结晶度以及通过光学显微镜观察到的表面结晶形貌都是宏观结构的表征,而影响电气强度的电子迁移过程更多是由介质材料的局域态决定的。局部的分子链弯折、堆叠、排列都会影响聚丙烯的陷阱特性,进而影响电子的输运过程。因此推测在两种薄膜的局部区域存在不同的微观结构。
为了进一步阐明BOPP薄膜分子链分布排列对击穿特性的影响规律和机理,本文设计了BOPP薄膜真空热处理试验。将两种BOPP薄膜试样分别置于80、100、120℃的真空烘箱内处理1 000 h,然后在常温下测试其直流击穿特性,测得电气强度如图8所示。从图8可以看出,在经过3个温度热处理后,BOPP-A和BOPP-B薄膜试样的特征电气强度都出现了不同程度的增大,且均随着温度的升高而增大,尤其当温度达到120℃时,两种薄膜试样的电气强度显著增大。另外值得注意的是,相同热处理温度下BOPP-B薄膜的电气强度相比BOPP-A薄膜提升幅度更大,因此二者的差距随温度的升高逐渐减小。在初始状态下,BOPP-B薄膜的电气强度相比BOPP-A薄膜降低了7.1%,这一差距在80℃处理后缩小至4.6%;当热处理温度升高至120℃时,BOPP-B薄膜的电气强度反而大于BOPP-A薄膜的电气强度(673.1 kV/mm),达到了684.4 kV/mm,较BOPP-A薄膜提高了1.7%。
β成核剂使树脂BOPP-B在拉伸前处于β晶型占主导地位的状态,在拉伸过程中发生二次结晶,使得β晶型转变为α晶型。在结晶过程中,分子链选择使生长速率在最短时间内达到最大值的路径,最终快速达到亚稳态,因此BOPP-B薄膜的局部分子链排列有序性相比BOPP-A较低,相应的电气强度也更低。然而,热力学稳定态仍旧是结晶的主要驱动力,因此在高温热处理过程中,β晶型经拉伸后产生的大量亚稳态部分在结晶温度附近会发生优化排列。相比BOPP-A薄膜,BOPP-B薄膜中的β成核剂使其在相同的处理温度下,具有更强的二次结晶动力,对于聚集态结构的优化效果更加显著。一方面优化后的结构中存在于分子链弯折处、原子排列不规则处等位置的电子陷阱特性发生改变,导致促进电子迁移的浅陷阱数量减少;另一方面规则有序的分子排列可以提高分子链段运动能垒,即分子链段难以发生运动,从而抑制电子在分子链间的迁移。最终在热处理后BOPP-B薄膜中电子沿分子链的跳跃过程和在相邻分子链之间的跳跃过程都受到了更显著的抑制,因此电气强度 相比α晶型拉伸后的BOPP-A薄膜有了更明显的提高。
本文针对不同结晶形态的聚丙烯树脂,以及经过双向拉伸后的BOPP薄膜进行系统的测试研究,阐明了β晶型对聚丙烯微观结构和宏观电学性能的影响规律,得到的结论具体如下:
(1)β成核剂的加入使聚丙烯树脂的主晶相由α晶型转变为β晶型,且具有更高的结晶度和较低的非等温结晶活化能。而在经过双向拉伸后,加入β成核剂的PP树脂与未加入β成核剂的PP树脂所获得的BOPP具有几乎相同的聚集态结构,均表现为α晶型且表面呈现“环形山”状的结晶。
(2)聚集态结构几乎相同的BOPP薄膜呈现出不同的击穿特性,β成核剂的加入导致PP拉伸过程中大量分子链的排列处于亚稳态,因此电气强度低于未加入β成核剂的PP树脂拉伸得到的BOPP薄膜。进一步的真空热处理过程使得BOPP薄膜发生重结晶,分子链排列进一步优化,电气强度得到提升。
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doi: 10.16790/j.cnki.1009-9239.im.2025.04.002
  • 接收时间:2024-08-14
  • 首发时间:2025-11-07
  • 出版时间:2025-04-20
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  • 收稿日期:2024-08-14
  • 修回日期:2024-11-13
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    南方电网科学研究院有限责任公司,广东 广州 510663
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2种不同金属材料的力学参数

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total species (%)

Genus
种数
Number of
species
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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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