[go: up one dir, main page]

CN104877278B - 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法 - Google Patents

一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法 Download PDF

Info

Publication number
CN104877278B
CN104877278B CN201510365809.9A CN201510365809A CN104877278B CN 104877278 B CN104877278 B CN 104877278B CN 201510365809 A CN201510365809 A CN 201510365809A CN 104877278 B CN104877278 B CN 104877278B
Authority
CN
China
Prior art keywords
pbma
dielectric film
polyvinylidene fluoride
dielectric
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201510365809.9A
Other languages
English (en)
Other versions
CN104877278A (zh
Inventor
王芳辉
孔艳
朱红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN201510365809.9A priority Critical patent/CN104877278B/zh
Publication of CN104877278A publication Critical patent/CN104877278A/zh
Application granted granted Critical
Publication of CN104877278B publication Critical patent/CN104877278B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/16—Homopolymers or copolymers or vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Insulating Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明公开了一种聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜，该膜以含氟聚合物和有机PBMA混合流延成膜。其中复合介电薄膜质量百分比组成为：有机PBMA为10%‑30%，含氟聚合物为70%‑90%。这种复合介电薄膜是具有较高的介电常数，较低的介电损耗的新型介电材料。可以通过控制填料添加比例来制备所需介电常数的复合介电薄膜。该复合薄膜制备工艺简单、复合温度低且对环境友好，具有广泛的应用前景。

Description

一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其 制备方法
技术领域
本发明属于复合介电薄膜领域，特别涉及一种聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜。
背景技术
拥有高介电常数、低介电损耗的聚合物基介电材料因其在储存电能方面有着巨大的潜能而被广泛应用，例如通信设备、电荷存储电容系统、人工肌肉、制动器和航天军事等方面。传统的电介质材料包括无机陶瓷材料和有机高分子材料。常见的无机陶瓷材料，如钛酸钡(BaTiO3)、钛酸铜钙（CCTO）、锆钛酸铅 (PZT) 等，具有非常高的介电常数，但是它们制备工艺复杂、易脆且介电损耗较大。常见的有机高分子材料有聚乙烯、聚丙烯、聚三氟乙烯、环氧树脂等，它们柔性好、介电损耗低、易于加工成膜，但是它们的介电常数相对较低。单一的电介质材料已经难以满足工业化的需要, 因此制备高介电性能的聚合物基复合材料具有非常重要的意义.目前，聚合物基介电材料主要分为以下三种类型：（1）.无机陶瓷材料：如钛酸钡（BaTiO3），其电容较大，介电常数高达6300，但该材料烧结温度高、制备过程复杂、易脆，加工要求高，并且与聚合物相容性差，不易成膜，机械性能差。（2）.导电材料：将石墨烯作为填料添加到PVDF中形成复合材料，在1000Hz复合材料的介电常数是PVDF基体的3倍还多，但是复合材料会受渗流阈值的影响，接近渗流阈值时介电损耗会有很大的提高，同时介电材料突变为导电材料，严重影响其生产应用。（3）.有机复合材料：如聚苯乙烯（PS），通过溶液涂膜的方法制备了PSAN薄膜，薄膜的介电常数为4，介电损耗0.027，储能密度达到6.8J/cm3，柔韧性好，介电损耗低，但是介电常数过小。
发明内容
本发明的主要目的在于提供一种聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜。该复合薄膜具有较好的介电性能。该聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜由PBMA和含氟聚合物组成。其质量百分比组成为：
PBMA 10%-30%
含氟聚合物 70%-90%
所述的聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜，其特征在于，所述有机PBMA为市售商品;
所述含氟聚合物是聚偏氟乙烯-三氟乙烯共聚物[P(VDF-TrFE)]、聚偏氟乙烯-三氟乙烯-氟氯乙烯共聚物[P(VDF-TrFE-CFE)]中的一种。
本发明的另一目的是提供一种聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜的制备方法：
1.将PBMA、含氟聚合物和溶剂N,N-二甲基甲酰胺(DMF)混合后，超声搅拌分散均匀，形成稳定的溶胶；其质量百分比组成为：
PBMA 10%-30%
含氟聚合物 70%-90%
有机PBMA和含氟聚合物总质量与DMF的质量比为1:7-10
2、将步骤1制备的溶胶在模具上80±1℃流延成膜，干燥18±1h，再经过自然冷却、120±1℃退火8±1h，去除残留溶剂，即得到厚度110-150µm的有机填料/聚合物基复合介电薄膜。
根据上述制备方法，在所述的有机PBMA质量比例范围内，调节其质量比例，即制得所需不同介电常数的复合介电薄膜。
本发明具有以下有益效果：
a.该有机PBMA填料克服了背景技术中存在的诸多问题，其具有中级的极化率，表现出较高的介电常数，较低的介电损耗，透明性好，柔韧性较好，具有较高的机械性能。
b. 该填料与基体介电常数相差较小，且与聚合物基底有很好的相容性，故复合介电薄膜具有较好的介电性能，而且其介电损耗没有明显的提升，仍维持在一个较低的位置，是一种新型的高介电复合材料。
c.该薄膜通过调节有机填料PBMA的质量比例，可以明显的改变材料的介电性能，从而制备所需高介电常数薄膜。
d.该薄膜的制备工艺简单、复合温度低且对环境友好，可以根据要求而改变模具的形状大小，从而适用于不同的电子设备、储能材料中。
本发明的复合薄膜，介电性能随着频率的变化相对稳定，没有很大的突变出现。复合薄膜的介电常数能提高到45左右。
具体实施例
下面通过具体的实施方案叙述本发明中产品和制备方法。除非特别说明，本发明中所用的技术手段均为本领域技术人员所公知的方法。另外，实施方案应理解为说明性的，而非限制本发明的范围，本发明的实质和范围仅由权利要求书所限定。对于本领域技术人员而言，在不违背本发明实质和范围的前提下，对这些实施方案中的比例和溶剂等条件进行的各种改变或改动也属于本发明的保护范畴。
以下结合具体实施例对本发明作进一步的说明，但不意味着对本发明保护范围的限制。
实施例1：
a.将0.0100g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯共聚物[P(VDF-TrFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为10%，聚合物为90%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE)复合介电薄膜。在1000Hz时，介电常数能达到16，介电损耗为0.21，击穿场强为322MV/m。
实施例2：
a.将0.0200g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯共聚物[P(VDF-TrFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为20%，聚合物为80%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE)复合介电薄膜。在1000Hz时，介电常数能达到23，介电损耗为0.29，击穿场强为243 MV/m。
实施例3：
a.将0.0300g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯共聚物[P(VDF-TrFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为30%，聚合物为70%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE)复合介电薄膜。在1000Hz时，介电常数能达到21，介电损耗为0.30，击穿场强为259MV/m。
实施例4：
这组实施例为对比实施例。0.1000g聚偏氟乙烯-三氟乙烯共聚物[P(VDF-TrFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，将制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出P(VDF-TrFE)复合介电薄膜。在1000Hz时，介电常数能达到15，介电损耗为0.23，击穿场强为300 MV/m。
实施例5：
a.将0.0100g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯-氯氟乙烯共聚物[P(VDF-TrFE-CFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为10%，聚合物为90%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE-CFE)复合介电薄膜。在1000Hz时，介电常数能达到45，介电损耗为2.5，击穿场强为322 MV/m。
实施例6：
a.将0.0200g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯-氯氟乙烯共聚物[P(VDF-TrFE-CFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为20%，聚合物为80%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE-CFE)复合介电薄膜。在1000Hz时，介电常数能达到34，介电损耗为1.6，击穿场强为203 MV/m。
实施例7：
a.将0.0300g有机PBMA，0.1000g聚偏氟乙烯-三氟乙烯-氯氟乙烯共聚物[P(VDF-TrFE-CFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，该配料比组成为：有机PBMA为30%，聚合物为70%；
b.将步骤a制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出PBMA/ P(VDF-TrFE-CFE)复合介电薄膜。在1000Hz时，介电常数能达到40，介电损耗为1.2，击穿场强为202 MV/m。
实施例8：
这组实施例为对比实施例。0.1000g聚偏氟乙烯-三氟乙烯-氯氟乙烯共聚物[P(VDF-TrFE-CFE)]和1.0005g溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，将制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出P(VDF-TrFE-CFE)复合介电薄膜。在1000Hz时，介电常数能达到35，介电损耗为2.0，击穿场强为294MV/m。
以上对本发明的实施例作了详细说明，所有实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于上述的实施例。

Claims (3)

1.一种聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜,其特征在于，所述复合介电薄膜由含氟聚合物和有机填料PBMA组成，其质量百分比为：有机填料PBMA10%-30%，含氟聚合物70%-90%；所述含氟聚合物为聚偏氟乙烯-三氟乙烯[P(VDF-TrFE)]、聚偏氟乙烯-三氟乙烯-氯氟乙烯[P(VDF-TrFE-CFE)]共聚物中的一种；复合介电薄膜的制备方法为：将PBMA，聚偏氟乙烯基聚合物和溶剂DMF混合后，超声搅拌分散均匀，形成稳定的溶胶，将制备的溶胶在模具上80℃流延成膜，干燥18h；再经过自然冷却、120℃退火8h，即制备出聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜。
2.根据权利要求1所述的聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜，其特征在于，所述有机PBMA为市售商品。
3.根据权利要求2所述的聚甲基丙烯酸正丁酯（PBMA）/聚偏氟乙烯基复合介电薄膜，其特征在于，所述PBMA和含氟聚合物总质量与DMF的质量比为1:7-10。
CN201510365809.9A 2015-06-29 2015-06-29 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法 Expired - Fee Related CN104877278B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510365809.9A CN104877278B (zh) 2015-06-29 2015-06-29 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510365809.9A CN104877278B (zh) 2015-06-29 2015-06-29 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法

Publications (2)

Publication Number Publication Date
CN104877278A CN104877278A (zh) 2015-09-02
CN104877278B true CN104877278B (zh) 2017-08-15

Family

ID=53944975

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510365809.9A Expired - Fee Related CN104877278B (zh) 2015-06-29 2015-06-29 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法

Country Status (1)

Country Link
CN (1) CN104877278B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI771452B (zh) * 2018-07-13 2022-07-21 日商伊雷阿爾史達股份有限公司 壓電材料及壓電材料用組成物
CN109961952A (zh) * 2019-03-27 2019-07-02 哈尔滨理工大学 一种异质结构的多层聚合物基复合储能材料及其制备方法
CN114989464B (zh) * 2022-06-02 2024-02-13 华东师范大学 一种pvdf/pmma复合薄膜及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102004024429A1 (de) * 2004-05-14 2005-12-08 Röhm GmbH & Co. KG Formkörper, enthaltend eine Polymermischung aus schlagzähmodifizierten Poly(meth)-acrylat und Fluorpolymer
DE102007029263A1 (de) * 2007-06-22 2008-12-24 Evonik Röhm Gmbh PMMA/PVDF-Folie mit besonders hoher Witterungsbeständigkeit und hoher UV-Schutzwirkung
FR2966158B1 (fr) * 2010-10-13 2012-10-19 Arkema France Film a base de polymere fluore pour application photovoltaique
CN102140181B (zh) * 2011-01-19 2013-04-17 天津工业大学 聚偏氟乙烯亲水改性膜及其制备方法
CN102382404A (zh) * 2011-09-26 2012-03-21 深圳市科聚新材料有限公司 一种亲水的聚偏氟乙烯复合材料及其制备方法

Also Published As

Publication number Publication date
CN104877278A (zh) 2015-09-02

Similar Documents

Publication Publication Date Title
Li et al. Enhanced energy storage performance of ferroelectric polymer nanocomposites at relatively low electric fields induced by surface modified BaTiO3 nanofibers
CN101712784B (zh) 一种核壳结构填料/聚合物基复合材料及其制备方法
Zhu et al. Poly (vinylidene fluoride) terpolymer and poly (methyl methacrylate) composite films with superior energy storage performance for electrostatic capacitor application
CN105086297B (zh) 一种电储能介质陶瓷/聚合物复合材料及其制备方法
CN110556247A (zh) 一种三明治结构高储能低电导率聚合物基复合薄膜制备方法
CN106633153A (zh) 一种三层结构的聚合物基介电储能纳米复合材料及其制备方法
Su et al. Fabrication and dielectric properties of Na0. 5Bi0. 5Cu3Ti4O12/poly (vinylidene fluoride) composites
CN104877278B (zh) 一种聚甲基丙烯酸正丁酯/聚偏氟乙烯基复合介电薄膜及其制备方法
CN110643129A (zh) 一种聚合物-陶瓷复合电介质储能材料及其制备方法
CN104312062B (zh) 一种储能复合材料的制备方法
KR20170080798A (ko) 그래핀 분산액 및 그래핀-고분자 복합체 제조방법, 및 이를 이용한 배리어 필름 제조방법
CN104277386A (zh) 一种膜电容器用聚偏氟乙烯薄膜
Zheng et al. Methyl methacrylate-co-glycidyl methacrylate-based dielectric films with high breakdown strength and discharge energy density tailored by PVDF
Harami et al. Mixed Matrix Membranes for Sustainable Electrical Energy‐Saving Applications
CN113121936A (zh) 全有机复合材料薄膜及其制备方法和应用
Xie et al. Achieving higher dielectric and energy storage performances of methyl methacrylate-co-glycidyl methacrylate films through the nanocomposite strategy
CN102936351B (zh) 一种聚偏氟乙烯/钛酸钡复合膜材料的制备方法
CN108587007B (zh) 一种叠层结构铁电聚合物基电介质薄膜、及其制备方法和用途
Koroglu et al. hBN/PVDF‐HFP and BNNS/PVDF‐HFP nanocomposites as flexible and lightweight dielectric capacitors: High energy storage performance via electrically insulating nanoparticles
CN101955619A (zh) 一种高储能密度全有机纳米复合薄膜及其制备方法
Wang et al. All-organic Poly (butyl methacrylate)/Poly (vinylidenefluoride-trifluoroethylene) dielectric composites with higher permittivity and low dielectric loss for energy storage application
CN102604280A (zh) 一种混合晶型无机纳米填料/聚合物基复合介电薄膜
CN111253679B (zh) 一种复合材料及其制备方法和应用
CN104558978B (zh) 一种含氟聚合物基介电复合薄膜及其制备方法
CN115966402B (zh) 柔性纳米复合电介质混合液及柔性纳米复合电介质和应用

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20170815