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Article(id=1198664997678182524, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198664995669110898, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.02.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1647792000000, receivedDateStr=2022-03-21, revisedDate=1651420800000, revisedDateStr=2022-05-02, acceptedDate=null, acceptedDateStr=null, onlineDate=1763713605565, onlineDateStr=2025-11-21, pubDate=1676822400000, pubDateStr=2023-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763713605565, onlineIssueDateStr=2025-11-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763713605565, creator=13701087609, updateTime=1763713605565, updator=13701087609, issue=Issue{id=1198664995669110898, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='2', pageStart='1', pageEnd='117', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763713605086, creator=13701087609, updateTime=1766563346770, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210617678729966036, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198664995669110898, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210617678729966037, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198664995669110898, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=32, endPage=38, ext={EN=ArticleExt(id=1198664999246852261, articleId=1198664997678182524, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Preparation and dielectric properties of ZIF-67/PVDF composite film, columnId=1198664996516360309, journalTitle=Insulating Materials, columnName=Polyimide Film Special Issue, runingTitle=null, highlight=null, articleAbstract=

Improving the performance of dielectric capacitors is one of the effective methods to meet the requirements of miniaturization and integration of circuit components. How to improve the dielectric properties of dielectric composites has attracted extensive attention of researchers. A series of ZIF-67/PVDF composite films were prepared by flowing spread molding using polyvinylidene fluoride (PVDF) as matrix and metal organic frameworks (MOFs), ZIF-67, as filler. The influence of MOF on the microstructure and macroscopic properties of PVDF composites was investigated. The results show that ZIF-67 can induce PVDF to generate more β phase, promote the polarization of matrix, and improve the mechanical and dielectric properties of the composite. When the mass fraction of filler is 5%, the Young's modulus of ZIF-67/PVDF composite film under 40℃ is 1 200 MPa and the breakdown strength is 139.74 kV/mm, both of them are higher than those of pure PVDF. The dielectric constant of ZIF-67/PVDF composite at 100 Hz is 10.39, which is 35.29% higher than that of pure PVDF film, and the dielectric loss can be kept low.

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改善介电电容器性能是满足电路元器件微型化和集成化需求的有效方法之一，如何提高介电复合材料的介电性能引起了研究者们的广泛关注。本文以聚偏氟乙烯（PVDF）为基体，金属有机框架物（MOFs）ZIF-67为填料，通过流延涂膜制备了一系列ZIF-67/PVDF复合薄膜材料，探究MOFs对PVDF基复合材料的微观结构及宏观性能影响。结果表明：ZIF-67可以诱导PVDF生成更多β相，促进基体极化，提高复合材料的力学性能和介电性能。当填料质量分数为5%时，ZIF-67/PVDF复合薄膜40℃下的杨氏模量为1 200 MPa,击穿场强为139.74 kV/mm，两者相较于纯PVDF薄膜均有增长；100 Hz下的介电常数为10.39，比纯PVDF薄膜提高了35.29%，并且能保持较低的介质损耗。

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翁凌（1979-），男（回族），广西桂林人，教授，博士，主要从事聚合物基介电功能复合材料的研究。
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初蕊（1996-），女（汉族），黑龙江齐齐哈尔人，硕士生，主要从事聚合物基介电功能复合材料的研究。

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初蕊（1996-），女（汉族），黑龙江齐齐哈尔人，硕士生，主要从事聚合物基介电功能复合材料的研究。

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初蕊（1996-），女（汉族），黑龙江齐齐哈尔人，硕士生，主要从事聚合物基介电功能复合材料的研究。

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ZIF-67/PVDF复合薄膜的制备及介电性能
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初蕊 1 , 翁凌 1, 2 , 关丽珠 1, 2 , 王小明 1
绝缘材料 | 聚酰亚胺薄膜专题 2023,56(2): 32-38
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绝缘材料 | 聚酰亚胺薄膜专题 2023, 56(2): 32-38
ZIF-67/PVDF复合薄膜的制备及介电性能
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初蕊1, 翁凌1, 2, 关丽珠1, 2, 王小明1
作者信息
  • 1哈尔滨理工大学，材料科学与化学工程学院，黑龙江 哈尔滨 150000
  • 2哈尔滨理工大学，工程电介质及其应用教育部重点实验室，黑龙江 哈尔滨 150000

    • 初蕊（1996-），女（汉族），黑龙江齐齐哈尔人，硕士生，主要从事聚合物基介电功能复合材料的研究。

通讯作者:

翁凌（1979-），男（回族），广西桂林人，教授，博士，主要从事聚合物基介电功能复合材料的研究。
Preparation and dielectric properties of ZIF-67/PVDF composite film
Rui CHU1, Ling WENG1, 2, Lizhu GUAN1, 2, Xiaoming WANG1
Affiliations
  • 1School of Materials Science and Chemical Engineering, Ministry of Education, Harbin University of Science and Technology, Harbin 150000, China
  • 2Key Laboratory of Engineering Dielectric and Its Application, Ministry of Education, Harbin University of Science and Technology, Harbin 150000, China
出版时间: 2023-02-20 doi: 10.16790/j.cnki.1009-9239.im.2023.02.005
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摘要
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改善介电电容器性能是满足电路元器件微型化和集成化需求的有效方法之一，如何提高介电复合材料的介电性能引起了研究者们的广泛关注。本文以聚偏氟乙烯（PVDF）为基体，金属有机框架物（MOFs）ZIF-67为填料，通过流延涂膜制备了一系列ZIF-67/PVDF复合薄膜材料，探究MOFs对PVDF基复合材料的微观结构及宏观性能影响。结果表明：ZIF-67可以诱导PVDF生成更多β相，促进基体极化，提高复合材料的力学性能和介电性能。当填料质量分数为5%时，ZIF-67/PVDF复合薄膜40℃下的杨氏模量为1 200 MPa,击穿场强为139.74 kV/mm，两者相较于纯PVDF薄膜均有增长；100 Hz下的介电常数为10.39，比纯PVDF薄膜提高了35.29%，并且能保持较低的介质损耗。

聚偏氟乙烯  /  金属有机框架  /  介电性能  /  结晶相

Improving the performance of dielectric capacitors is one of the effective methods to meet the requirements of miniaturization and integration of circuit components. How to improve the dielectric properties of dielectric composites has attracted extensive attention of researchers. A series of ZIF-67/PVDF composite films were prepared by flowing spread molding using polyvinylidene fluoride (PVDF) as matrix and metal organic frameworks (MOFs), ZIF-67, as filler. The influence of MOF on the microstructure and macroscopic properties of PVDF composites was investigated. The results show that ZIF-67 can induce PVDF to generate more β phase, promote the polarization of matrix, and improve the mechanical and dielectric properties of the composite. When the mass fraction of filler is 5%, the Young's modulus of ZIF-67/PVDF composite film under 40℃ is 1 200 MPa and the breakdown strength is 139.74 kV/mm, both of them are higher than those of pure PVDF. The dielectric constant of ZIF-67/PVDF composite at 100 Hz is 10.39, which is 35.29% higher than that of pure PVDF film, and the dielectric loss can be kept low.

PVDF  /  MOFs  /  dielectric properties  /  crystallized phase
初蕊, 翁凌, 关丽珠, 王小明. ZIF-67/PVDF复合薄膜的制备及介电性能. 绝缘材料, 2023 , 56 (2) : 32 -38 . DOI: 10.16790/j.cnki.1009-9239.im.2023.02.005
Rui CHU, Ling WENG, Lizhu GUAN, Xiaoming WANG. Preparation and dielectric properties of ZIF-67/PVDF composite film[J]. Insulating Materials, 2023 , 56 (2) : 32 -38 . DOI: 10.16790/j.cnki.1009-9239.im.2023.02.005
正文
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0 引言
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随着电子科学和电子技术的高速发展，电容器作为电子电路中最基本的元器件之一，被广泛应用于各个领域[1-3]。其中，介电电容器因具有功率密度高、快速充放电、使用温度范围宽、循环周期长等优点，表现出了相较于其他类型电容器更加优异的性能，成为了储能材料领域的研究热点[4-7]。传统的介电材料如铁电陶瓷脆性大、加工性能差，导致电容器体积大损耗高[8-9]，而聚合物介电材料具有可加工性好、密度低、脆性低等优点能更好地满足电路元器件集成化和小型化的要求[10-12]。
铁电聚合物聚偏氟乙烯（polyvinylidene fluoride, PVDF）不仅价格低廉、化学稳定性好、密度低、柔韧性好、易加工，而且相较于其他聚合物拥有较高的介电常数、较低的介质损耗，是高储能电介质薄膜材料的理想选择之一[13-15]。金属有机框架物（metal organic frameworks，MOFs）是一类由金属离子及团簇与有机配体自组装形成的有机-无机杂化材料，具有比表面积大、孔隙率高等特点[16-17]。由于结构和组成的可调性[18]，近年来，MOFs成为制备各种功能纳米材料的理想前驱体，广泛应用于如光催化、电催化、水分解等领域[19-22]，并在储能方面也展现了优异的性能[23-24]。
由于MOFs中存在有机配体可以使其更好地与聚合物基体互溶[25]，近年来，研究者尝试将MOFs引入聚合物基体中，制备聚合物基纳米复合材料，在保持聚合物良好力学性能的同时改善复合材料的介电性能。GUO Q等[26]通过水热法制备了UiO-66和UiO-66-NH2两种MOFs，并将这两种MOFs粒子分别加入聚酰亚胺（PI）中，研究发现，与纯PI薄膜相比MOF/PI复合材料的介电性能更好，当UiO-66-NH2的质量分数为20%时，复合材料在100 Hz下的介电常数可达到8.8，约为纯PI薄膜的2.5倍，并且可以保持较低的介质损耗和较高的击穿场强。M FIAZ等[27]将制备的MOFs UiO-66和UiO-66-NH2作为填料加入环氧树脂（EP），对复合材料EP/MOF进行多项电气性能测试，结果表明添加MOFs的环氧树脂比纯环氧树脂有着更低的介质损耗和更高的电气强度。M IMNAS等[28]报道了系列多铁性金属有机骨架材料[(CH3)2NH2][M(HCOO)3]（M=Zn,Cu,Ni,Co,Fe,Mn,Mg）与VDF与三氟乙烯（TrFE）的共聚物P(VDF-TrFE)的纳米复合材料制备方法和介电性能，研究发现在(CH3)2NH2+和金属离子的共同影响下这一系列MOF/P(VDF-TrFE)薄膜的介电常数相比于纯P(VDF-TrFE)薄膜均有提高。YAN Z等[25]制备了一种Zr-MOF，并将其引入PVDF基体中制备了MOF/PVDF复合膜。研究发现PVDF复合材料中的β相含量增加，在填料质量分数为5%时，介电常数提升了105%，同时保持了较低的介质损耗和较好的力学性能。Guan L Z等[29-31]采用两步法合成了Ag-NiMOF和Ag@NiFeMOF纳米片，分别将NiMOF、NiFeMOF、Ag-NiMOF、Ag@NiFeMOF与PVDF复合制备纳米复合薄膜并进行多项测试。结果表明，NiMOF、NiFeMOF、Ag-NiMOF、Ag@NiFeMOF均可以诱导PVDF生成更多的β相，有效提高了复合材料的介电性能。ZHANG L等[32]将MOF-Ni3(HHTP)2接枝到MXene纳米片上，制备了MOF-MXene/PVDF复合材料，在填料质量分数为4.76%时，复合材料在103 Hz下的介电常数达到530，而此时的介质损耗因数仅为0.49。由此可见，将MOFs作为填料制备纳米聚合物基复合材料是现在介电复合材料领域的研究热点之一，具有极大的研究意义和良好的应用前景。
本研究采用以Co离子为金属节点的ZIF-67作为纳米填料引入PVDF基体中，制备ZIF-67/PVDF纳米复合薄膜，探究ZIF-67纳米填料对复合薄膜介电性能和力学性能的影响。
1 实验
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1.1 主要原材料
六水合硝酸钴（Co(NO3)2·6H2O），AR，福晨（天津）化学试剂有限公司；二甲基咪唑（2-MeIM），AR，天津市光复精细化工研究所；甲醇（MeOH）、N,N-二甲基甲酰胺（DMF），均为AR，天津市福宇精细化工有限公司；聚偏氟乙烯（PVDF），分子量为8 000 000 g/mol，法国阿科玛公司。
1.2 设备和仪器
Helios 660型双激光扫描电子显微镜（SEM）、Talos F200S型透射电子显微镜（TEM），美国FEI公司；X’Pert PRO型X-射线衍射仪（XRD），荷兰Panalytical仪器公司；TESCAN MIRA LMS型扫描电子显微镜（SEM），捷克TESCAN公司；Q800型动态热机械分析仪（DMA），美国TA公司；Alpha-A型宽频介电谱分析仪，德国Novocontrol公司；C60/3型高压测试仪，苏州华电电气股份公司。
1.3 样品制备与处理
1.3.1 ZIF-67的制备
将5.82 g六水合硝酸钴溶于200 mL甲醇溶剂中，标记为溶液A；将4.93 g二甲基咪唑溶于200 mL甲醇溶剂中，标记为溶液B。在超声环境下将溶液A缓慢倒入溶液B中，超声搅拌30 min，将紫色溶液常温静置12 h以上，倒去上层澄清液，用甲醇对沉淀物进行多次离心洗涤，结束后将其置于真空干燥箱中60℃条件下真空干燥12 h，得到的紫色粉末即为ZIF-67，其合成机制及结构图如图1所示。
1.3.2 ZIF-67/PVDF的制备
图2是ZIF-67/PVDF复合薄膜的制备流程图。分别称取质量分数为3%、5%、10%、15%的ZIF-67粒子，将其溶于40 mL DMF溶液中，超声搅拌1 h，随后缓慢加入5 g PVDF粉末，使其充分溶解后继续超声搅拌4 h，静置12 h获得粘稠的混合胶液。使用自动涂膜机流延上述混合胶液，形成厚度为40 μm左右的薄膜，并将薄膜置于鼓风干燥箱中80℃条件下干燥3 h，得到紫色的ZIF-67/PVDF薄膜。ZIF-67质量分数为3%、5%、10%、15%的复合薄膜分别命名为3%ZIF-67/PVDF、5%ZIF-67/PVDF、10%ZIF-67/PVDF、15%ZIF-67/PVDF。
1.4 检测方法
采用双激光扫描电子显微镜（SEM）对纳米粒子的形貌和尺寸进行测试；采用X射线衍射仪（XRD）对纳米粒子的组成、复合薄膜的相结构组成进行测试；采用透射电子显微镜（TEM）对纳米粒子的微观形貌进行测试；采用扫描电子显微镜（SEM）对复合薄膜的断面进行测试；采用动态热机械分析仪（DMA）对复合薄膜的热力学性能进行测试；采用宽频介电谱分析仪对复合薄膜的介电频率、介质损耗、电导率随频率的变化进行测试；采用击穿电压测试仪对试样的击穿电压进行测试。
2 结果与分析
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2.1 ZIF-67纳米粒子的结构表征
图3是ZIF-67的SEM图，从图3可以看出，制备的ZIF-67外形呈规则的多面体，这些外形规则的多面体紧密堆垛在一起，可以看出晶粒尺寸整体上是均匀的，表面较为光滑，平均粒径在500 nm左右。部分粒子棱角圆滑可能是由于进行SEM测试前喷金次数过多导致。图4为高倍率下ZIF-67的TEM图，从图4可以看出，ZIF-67的外形棱角分明，并且内部无明显的杂质颗粒。
通过SEM和TEM分析，可以确定实验制备的ZIF-67微观形貌为规则的多面体，特殊形貌使其拥有高的比表面积，为后续复合材料优异的性能奠定了结构基础。
2.2 ZIF-67/PVDF复合薄膜的结构表征
2.2.1 ZIF-67/PVDF复合薄膜的XRD
聚合物PVDF基体的不同结晶相对复合薄膜的介电性能有很大的影响，而ZIF-67的加入会对基体的结晶起到诱导作用。图5为ZIF-67、纯PVDF、5%ZIF-67/PVDF复合薄膜的XRD谱图。
从图5可以看出，实验制备的ZIF-67在2θ为7.31°、10.36°、12.70°、16.40°、17.99°处出现了ZIF-67的特征衍射峰，对应ZIF-67的(011)、(002)、(112)、(013)、(222)晶面，表明ZIF-67制备成功。纯PVDF薄膜在2θ为17.6°、18.3°、19.93°、26.5°时有较强的衍射峰，分别对应PVDF晶体的α(100)、α(020)、γ(110)、α(021)相，说明薄膜中存在较多的α相和γ相。相较于纯PVDF薄膜，ZIF-67/PVDF复合薄膜在2θ为7.31°、10.36°、12.7°时出现新的衍射峰，这与ZIF-67晶体的(011)、(002)、(112)晶面对应。ZIF-67/PVDF复合薄膜的PVDF基体的特征衍射峰强度也有所变化，在PVDF结晶相α(100)、α(020)、γ(110)、α(021)的衍射峰强度与纯PVDF薄膜相比复合体系的峰强度减弱。同时ZIF-67/PVDF复合薄膜在2θ为18.1°和20.26°处出现新的特征峰，与PVDF基体的γ(110)和β(200)相对应，其中PVDF基体中β(200)相的出现表明ZIF-67纳米粒子促进了基体结晶向极性更强的结晶相转变[25,29]。这些差异证明ZIF-67纳米粒子的加入对PVDF基体分子链的有序排列产生了影响，诱导PVDF生成更多的β相，促进了PVDF基体的极化。
从上述晶体的转变现象，推导ZIF-67影响复合材料相变的示意图，如图6所示。多面体结构的ZIF-67纳米粒子与PVDF中的F原子之间存在作用力，影响F原子在PVDF中的排列，从而诱导PVDF生成更多的β相。因此在PVDF基体中引入ZIF-67会对复合材料的性能产生影响。
2.2.2 ZIF-67/PVDF复合薄膜的FTIR
为进一步分析ZIF-67纳米填料对PVDF基体结晶行为的影响，对填料质量分数为5%和10%的ZIF-67/PVDF复合薄膜进行红外测试，结果如图7所示。
从图7可以看出，所有复合体系大体呈现一致的吸收峰，这是由于红外光谱能够检测有机官能团的吸收峰，无机粒子虽不能引起红外吸收峰，但是对基体的结晶相产生影响能使红外谱图发生变化。如ZIF-67/PVDF复合薄膜在510、830、1 270 cm-1附近的峰值强度均略高于纯PVDF薄膜，表明PVDF中的α相向β相转变[25,29-30]，进一步表明ZIF-67纳米粒子的加入会引起结晶相的转变。
2.2.3 ZIF-67/PVDF复合薄膜的断面
图8为ZIF-67/PVDF复合薄膜的断面SEM图。从图8可以看出添加ZIF-67粒子后，粒子镶嵌在PVDF基体中，在粒子与基体的界面处有少许空隙，同时ZIF-67粒子仍保持其特有的多面体结构，表明其结构较为稳定。随着ZIF-67纳米粒子质量分数的增加，ZIF-67/PVDF复合薄膜横截面中纳米粒子数量明显增加。从图8(a)可以看出，在ZIF-67纳米填料质量分数相对较低时，薄膜的断面光滑，纳米粒子在基体中分散均匀，无团聚现象。ZIF-67的比表面积较大，且存在大量氢键，氢键间相互作用吸引，因此随着填料质量分数的增加，纳米粒子的分散性降低，开始出现交叠和团聚等缺陷，如图8(b)所示。从断面扫描图看到PVDF基体中出现了较大孔洞，可能是由于冷冻断裂制样的过程中撕裂薄膜导致填料与基体分离。
2.3 ZIF-67/PVDF复合薄膜的力学性能
图9为PVDF及其复合薄膜的动态力学测试谱图，测试范围为40～170℃。
从图9可以看出，在初始温度为40℃时，5%ZIF-67/PVDF和10%ZIF-67/PVDF的杨氏模量分别为1 200 MPa和957 MPa，相比于纯PVDF薄膜的480 MPa分别增长了150.00%和99.38%。这是由于ZIF-67的比表面积大，纳米粒子表面与PVDF基体相互作用，限制了聚合物分子链的运动，并且ZIF-67的引入诱导PVDF基体产生极性更高的β相，极性基团在分子的连续运动过程中增大了分子间的摩擦力，最终使得ZIF-67/PVDF复合薄膜的分子链运动相较于纯PVDF困难，跟不上外力的变化，呈现较大刚性，杨氏模量增加。
2.4 ZIF-67/PVDF复合薄膜的介电性能
图10和图11分别是ZIF-67/PVDF复合薄膜在室温下测试频率为101～107 Hz时介电常数和介质损耗因数随频率变化的谱图。选取100 Hz的数据对不同质量分数ZIF-67的复合薄膜的介电常数和介质损耗因数进行对比，如图12所示。
从图10可以看出，复合薄膜的介电常数总体上高于纯PVDF薄膜，并且随着ZIF-67质量分数的增加呈现先增大后减小的趋势，这是由于ZIF-67纳米粒子的加入促进了PVDF基体的极化，因此介电常数增大，但是随着ZIF-67质量分数的增加，其分散性降低，使得基体中出现纳米粒子团聚、孔洞等缺陷，因此介电常数反而减小。当频率为100 Hz时，ZIF-67质量分数为5%的复合薄膜介电常数为10.39，相较于纯PVDF薄膜的7.68提高了35.29%。从图11可以看出，复合薄膜的介质损耗因数高于纯PVDF薄膜，并且随着ZIF-67质量分数的增加总体上呈现增加的趋势。这是由于添加的ZIF-67与PVDF基体间会产生界面极化损耗，同时从图8(b)中可以看出，填料过多会使基体中出现缺陷进而产生更多损耗。在频率为100 Hz时，ZIF-67质量分数为5%的复合薄膜的介质损耗因数为0.03。因此在ZIF-67质量分数为5%时ZIF-67/PVDF复合薄膜可以同时得到较高的介电常数和较低的介质损耗因数。
2.5 ZIF-67/PVDF复合薄膜的击穿场强
击穿场强是实际应用中确定介质材料最大能量密度的一个重要参数。因此，在室温直流电场下对复合薄膜的击穿场强进行测试，并采用二参数的Weibull积累分布函数来描述复合薄膜的击穿场强，绘制ln[-ln(1-p)]随击穿场强EB的变化曲线（p为击穿累积概率），最终得到Weibull击穿场强，如图13所示。从图13可以看出，向PVDF基体中添加ZIF-67纳米粒子填料，复合薄膜的击穿场强随着填料添加量的增加而升高。这是由于MOFs是金属离子和有机配体自组装形成的有机-无机杂化材料。ZIF-67中有机框架的存在使ZIF-67/PVDF复合材料相比于纯PVDF具有更好的绝缘稳定性，从而提高了材料的抗电击穿能力[33]。当ZIF-67质量分数为5%时，ZIF-67/PVDF复合薄膜的击穿场强为139.74 kV/mm；当ZIF-67质量分数为15%时，ZIF-67/PVDF复合薄膜的击穿场强为165.28 kV/mm，分别比纯PVDF薄膜的112.95 kV/mm高出23.72%和46.33%。
3 结论
收起
本文制备了典型的MOF材料ZIF-67，并将其引入PVDF基体中制备了ZIF-67/PVDF复合薄膜，通过对系列ZIF-67/PVDF复合薄膜的形貌结构表征和性能测试，得到以下结论：
（1）通过SEM和TEM测试可以看出，ZIF-67颗粒均匀并能在低浓度添加量下良好的分散在PVDF基体中。XRD和FTIR结果表明，ZIF-67可以诱导PVDF生成更多的β相，促进基体极化，进而影响复合材料的性能。
（2）当ZIF-67质量分数为5%时，ZIF-67/PVDF复合薄膜在40℃下的杨氏模量达到1 200 MPa，比纯PVDF薄膜增长了150.00%；100 Hz下的介电常数为10.39，比纯PVDF薄膜提高了35.29%，同时可以保持较低的介质损耗因数0.03；击穿强度为139.74 kV/mm，相较于纯PVDF薄膜的高出23.72%。
综上所述，向PVDF基体中添加ZIF-67制备ZIF-67/PVDF复合薄膜可以改善复合材料的介电性能和力学性能。
基金
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  • 国家自然科学基金资助项目(51677045)
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2023年第56卷第2期
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doi: 10.16790/j.cnki.1009-9239.im.2023.02.005
  • 接收时间：2022-03-21
  • 首发时间：2025-11-21
  • 出版时间：2023-02-20
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  • 收稿日期：2022-03-21
  • 修回日期：2022-05-02
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国家自然科学基金资助项目(51677045)
作者信息
    1哈尔滨理工大学，材料科学与化学工程学院，黑龙江 哈尔滨 150000
    2哈尔滨理工大学，工程电介质及其应用教育部重点实验室，黑龙江 哈尔滨 150000

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翁凌（1979-），男（回族），广西桂林人，教授，博士，主要从事聚合物基介电功能复合材料的研究。
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2种不同金属材料的力学参数
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鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
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