Article(id=1199641486955475494, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.07.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1653148800000, receivedDateStr=2022-05-22, revisedDate=1657468800000, revisedDateStr=2022-07-11, acceptedDate=null, acceptedDateStr=null, onlineDate=1763946418750, onlineDateStr=2025-11-24, pubDate=1689782400000, pubDateStr=2023-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763946418750, onlineIssueDateStr=2025-11-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763946418750, creator=13701087609, updateTime=1763946418750, updator=13701087609, issue=Issue{id=1199641484963181075, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='7', pageStart='1', pageEnd='113', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763946418275, creator=13701087609, updateTime=1766563596176, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210618724747440709, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210618724747440710, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1199641484963181075, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=21, endPage=24, ext={EN=ArticleExt(id=1199641487903388208, articleId=1199641486955475494, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effect of annealing treatment on piezoelectric properties of flexible piezoelectric material poly(vinylidene fluoride)-based dielectrics, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

On the basis of the crystal structure of piezoelectric effect of polyvinylidene fluoride (PVDF) polymer, the effects of different annealing temperatures (60-160℃) on the surface crystal morphology, crystal size, crystallinity, and key dielectric parameters including polarization response curve and piezoelectric coefficient of PVDF film samples were studied. The results show that the sample crystal size and crystallinity increase with the increase of annealing temperature in the range of 60-140℃. The polarization curves show higher residual polarization intensity and hysteresis, and the piezoelectric coefficient increases from 11 pC/N to 27 pC/N with the increase of annealing temperature. When the annealing temperature reaches 160℃, cracks appear on the surface of sample, and consequently the breakdown is easy to occur in the polarization process, and the dispersity of piezoelectric coefficient is large.

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本文从聚偏氟乙烯基聚合物压电效应的晶体结构基础出发,研究不同退火温度(60~160℃)对薄膜样品表面结晶形貌、结晶尺寸、结晶度,以及关键介电参数包括极化响应曲线和压电系数的影响规律。结果表明:在60~140℃范围内,随着退火温度升高,样品结晶尺寸增大、结晶度提高,从而在极化曲线中表现出更高的剩余极化强度和滞回度,同时压电系数随退火温度升高从11 pC/N增大至27 pC/N。而当退火温度达到160℃时,样品表面出现裂痕缺陷,极化过程较容易发生击穿,且压电系数分散性较大。

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高景晖(1984-),男(汉族),陕西西安人,教授,主要从事高电压绝缘技术和功能电介质方面的研究。
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王妍(1992-),女(汉族),陕西宝鸡人,博士,主要从事多种传感材料的研制,接触式、非接触式超声传感器以及柔性传感器的研发。

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王妍(1992-),女(汉族),陕西宝鸡人,博士,主要从事多种传感材料的研制,接触式、非接触式超声传感器以及柔性传感器的研发。

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王妍(1992-),女(汉族),陕西宝鸡人,博士,主要从事多种传感材料的研制,接触式、非接触式超声传感器以及柔性传感器的研发。

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样品命名退火温度/℃退火时间/h
T1601602
T140140
T120120
T100100
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退火实验条件

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T140140
T120120
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T8080
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退火处理对柔性压电材料聚偏氟乙烯基电介质的压电性能影响研究
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王妍 1 , 陈川 1 , 冀晓雨 2 , 刘泳斌 2 , 高景晖 2
绝缘材料 | 材料研究 2023,56(7): 21-24
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绝缘材料 | 材料研究 2023, 56(7): 21-24
退火处理对柔性压电材料聚偏氟乙烯基电介质的压电性能影响研究
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王妍1, 陈川1, 冀晓雨2, 刘泳斌2, 高景晖2
作者信息
  • 1国网智能电网研究院有限公司,北京 102209
  • 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
  • 王妍(1992-),女(汉族),陕西宝鸡人,博士,主要从事多种传感材料的研制,接触式、非接触式超声传感器以及柔性传感器的研发。

通讯作者:

高景晖(1984-),男(汉族),陕西西安人,教授,主要从事高电压绝缘技术和功能电介质方面的研究。
Effect of annealing treatment on piezoelectric properties of flexible piezoelectric material poly(vinylidene fluoride)-based dielectrics
Yan WANG1, Chuan CHEN1, Xiaoyu JI2, Yongbin LIU2, Jinghui GAO2
Affiliations
  • 1State Grid Smart Grid Research Institute Co., Ltd., Beijing 102209, China
  • 2State Key Laboratory of Electrical Insulation and Power Equipment, Xi′an Jiaotong University, Xi′an 710049, China
出版时间: 2023-07-20 doi: 10.16790/j.cnki.1009-9239.im.2023.07.004
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本文从聚偏氟乙烯基聚合物压电效应的晶体结构基础出发,研究不同退火温度(60~160℃)对薄膜样品表面结晶形貌、结晶尺寸、结晶度,以及关键介电参数包括极化响应曲线和压电系数的影响规律。结果表明:在60~140℃范围内,随着退火温度升高,样品结晶尺寸增大、结晶度提高,从而在极化曲线中表现出更高的剩余极化强度和滞回度,同时压电系数随退火温度升高从11 pC/N增大至27 pC/N。而当退火温度达到160℃时,样品表面出现裂痕缺陷,极化过程较容易发生击穿,且压电系数分散性较大。

聚偏氟乙烯  /  柔性压电传感  /  压电系数  /  半结晶聚合物  /  退火

On the basis of the crystal structure of piezoelectric effect of polyvinylidene fluoride (PVDF) polymer, the effects of different annealing temperatures (60-160℃) on the surface crystal morphology, crystal size, crystallinity, and key dielectric parameters including polarization response curve and piezoelectric coefficient of PVDF film samples were studied. The results show that the sample crystal size and crystallinity increase with the increase of annealing temperature in the range of 60-140℃. The polarization curves show higher residual polarization intensity and hysteresis, and the piezoelectric coefficient increases from 11 pC/N to 27 pC/N with the increase of annealing temperature. When the annealing temperature reaches 160℃, cracks appear on the surface of sample, and consequently the breakdown is easy to occur in the polarization process, and the dispersity of piezoelectric coefficient is large.

PVDF  /  flexible piezoelectric sensor  /  piezoelectric coefficient  /  semi-crystalline polymer  /  annealing
王妍, 陈川, 冀晓雨, 刘泳斌, 高景晖. 退火处理对柔性压电材料聚偏氟乙烯基电介质的压电性能影响研究. 绝缘材料, 2023 , 56 (7) : 21 -24 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.004
Yan WANG, Chuan CHEN, Xiaoyu JI, Yongbin LIU, Jinghui GAO. Effect of annealing treatment on piezoelectric properties of flexible piezoelectric material poly(vinylidene fluoride)-based dielectrics[J]. Insulating Materials, 2023 , 56 (7) : 21 -24 . DOI: 10.16790/j.cnki.1009-9239.im.2023.07.004
随着能源互联网的发展,对电网关键电力设备状态感知提出了新的要求,迫切需要对关键电力装备进行全面传感,结合多参量信息融合等手段提高电力能源网络智能感知能力[1]。电力设备局部放电是装备早期故障的典型特征,是感知设备运行状态的重要检测对象。局部放电产生的电、热、声、光等信号是设备状态监测的重要传感参量,通常利用脉冲电流法、特高频检测法、超声波检测法进行参量检测[2-4]。其中,超声波检测法由于具有无电气耦合、容易实现在线监测等优点,被认为是能源互联网局放状态感知的重要传感方法。
目前主流超声传感器敏感压电材料以锆钛酸铅(PZT)陶瓷或单晶的柱状材料为主,其厚度约为10 mm,依靠不锈钢外壳与设备通过螺栓等方式连接固定。虽然超声传感器在变压器、GIS等电力设备中应用初具规模,但这类刚性传感器存在以下问题亟待解决:①介入式安装影响工作状态。传统刚性超声传感器由于体积、质量较大,长期监测通常使用螺栓介入式的安装方法,可能会影响电力电子设备的工作电场和磁场分布;②传感信号质量较差。刚性传感器在异形曲面设备缺陷检测中通常与待测体是以点或者线接触,超声耦合效率低、捕获的信号质量差,难以有效解决现场大量绝缘缺陷和机械缺陷,在检测中容易丢失振动或声信号中的故障特征信息,导致故障的错判或误判;③布置安装局限性大。刚性传感器体积、质量较大,在电力电子设备之间的各类异形连接件部位、狭小空间处难以安装或固定,连接件易掉落磕碰导致灵敏度大幅降低,不便于长期可靠应用[5-9]。同时,目前压电超声传感器件市场全部被国外企业占据,国内超声传感设备尚处起步阶段,但在柔性压电超声器件开发方面国内外都还没有开展深入研究,考虑到电力电子装备的贴敷、传感精度、应用多场景等因素,亟需研究开发电力电子设备用柔性超声传感器件。
聚偏氟乙烯(PVDF)及其共聚物聚偏氟乙烯-三氟乙烯(P(VDF-TrFE))是近年来研究人员十分关注的新型聚合物柔性压电材料[10],其具有高机电耦合系数、高可弯曲性、质量轻等特性,使其在异形曲面电力设备、紧凑空间、聚合物绝缘外壳等条件下具有突出优势,是未来电力设备局放智能监测核心传感材料之一[11-12]。相比现有PZT压电陶瓷(d33约为500 pC/N)而言,PVDF基铁电聚合物(d33约为20 pC/N)压电系数较低,如何有效提高其压电系数是相关研究的重点和难点,也是该类压电传感器应用的瓶颈问题。PVDF基铁电聚合物压电效应结构基础来源于其结晶区β晶型的自发极化偶极矩。因此,研究PVDF基铁电聚合物结晶结构对压电性能的影响,掌握结晶状态的调控方法,是突破其压电性能瓶颈的关键[13-16]
本文以P(VDF-TrFE)材料为研究对象,通过研究对半结晶聚合物结晶状态影响最显著的薄膜退火温度对P(VDF-TrFE)薄膜结晶结构和压电性能的影响规律,阐明结晶结构与压电性能的构效关系,提出薄膜制备的优化退火工艺,为高性能P(VDF-TrFE)柔性压电传感材料开发提供理论依据和实验参考[17-19]
溶质P(VDF-TrFE)(50/50 mol%)为粉状原料,阿科玛公司;溶剂N,N二甲基甲酰胺(DMF),分析纯,阿拉丁(Aladdin)公司。
本文使用溶液流延法制备P(VDF-TrFE)压电薄膜样品。将溶质溶于二甲基甲酰胺(DMF)中,配成质量分数约为5%的溶液;将溶液在50℃下搅拌 5 h,过滤溶液中的杂质;将过滤后的溶液在真空烘箱中处理1 h,除去溶液中的气泡;将真空处理后的溶液静置12 h,以获得稳定的溶液;取适量处理后的溶液流延在玻璃片上,放置在调平后的烘箱内,在60℃下烘干12 h得到薄膜样品。进一步将薄膜样品在烘箱中退火,退火温度为60~160℃,温度范围选择覆盖居里温度和熔融温度之间,退火时间均为2 h,具体退火实验条件及样品命名如表1所示。
利用离子溅射在薄膜上、下表面溅射直径为10 mm的金作为电极,极化条件为70℃油浴,直流100 kV/mm持续1 h,再使用LCR介电谱测试系统连接烘箱,对样品的介电谱进行测试,介电谱测试电压为1 V,温度为40~110℃,频率分别为60、102、103、104、105 Hz。使用扫描电子显微镜(SEM)观察退火后样品的表面形貌。使用X射线衍射法(XRD)表征样品的结晶状态,波长为1.54 Å。使用铁电工作站测试样品极化强度随电场的变化,即电滞回线,最大电场强度为110 kV/mm,频率为100 Hz。使用准静态法测试样品的压电系数(d33)。
P(VDF-TrFE)薄膜的相对介电常数分别在60、102、103、104、105 Hz频率下随温度的变化曲线如图1所示。从图1可以看出,P(VDF-TrFE)介电常数峰值点温度即居里温度为66~73℃,呈现频率弥散的弛豫特征,在居里温度以下时相对介电常数为13~40,相对较低的介电常数(PZT相对介电常数约为2 000)有利于提高压电器件的输出电压灵敏度。
利用扫描电子显微镜观察不同退火温度对 P(VDF-TrFE)薄膜样品表面结晶形貌的影响,实验前在样品表面溅射一层厚度约为20 nm的铂金属导电层,获得的表面显微形貌SEM照片如图2所示。从图2可以看出,随着退火温度上升,样品表面结晶晶片尺寸逐渐增大,结晶致密度也逐渐增大。这可能是由于在该温度区间,P(VDF-TrFE)无定形区分子链在加热条件下运动性能提高,从而在原有晶片表面继续结晶导致晶片生长。然而,在160℃退火的样品表面出现部分裂痕,这可能是由于该温度接近P(VDF-TrFE)材料的熔点。裂痕的出现可能会导致薄膜在高电场极化条件下发生击穿,或者影响样品性能的稳定性。
利用X射线衍射法测量P(VDF-TrFE)薄膜样品结晶区的衍射,表征不同退火温度对样品结晶结构的影响规律,得到不同退火温度的XRD衍射曲线如图3(a)所示,通过衍射曲线计算出的结晶度如图 3(b)所示。从图3可以看出,随着退火温度升高, P(VDF-TrFE)薄膜样品结晶峰值位置逐渐向小角度移动,即2θ减小,表明晶面间距逐渐增大;在60~140℃退火温度范围内结晶度随温度升高而上升,而在160℃退火温度下结晶度下降,这可能是由于样品表面出现微裂痕导致。XRD表征所得结晶结构与上述SEM图像观察表明结晶结果一致,在熔点温度以内退火工艺可以有效提高样品的结晶程度。
由于PVDF基铁电聚合物压电效应结构基础来源于其结晶区β晶型(TTTT)的自发极化偶极矩,同时结晶区αγ晶型可以在极化过程中发生场致相变形成β晶型,而无定形区中分子链无序排列无法形成自发极化偶极矩,因此通过退火处理提升结晶度对提高压电性能具有关键作用。
介质的压电效应本质上为极化强度随外场的变化,因此P(VDF-TrFE)在极化过程后的剩余极化强度(Pr)是决定其压电性能的关键。采用铁电工作站测试P(VDF-TrFE)薄膜样品的电滞回线(即P-E曲线),最大电场强度为110 kV/mm,比较不同退火温度下剩余极化强度的相对大小,结果如图4所示。从图4可以看出,在60~140℃温度范围内,随着退火温度上升,样品的最大极化强度、剩余极化强度和滞回度都呈现上升趋势。其中,T160样品电滞回线在高电场强度位置升压与降压曲线发生交叉,表明样品在高电场下漏电流较大,从而导致测试极化值偏大。这与上述结晶尺寸和结晶度增大相对应,表明退火处理可以提升P(VDF-TrFE)材料的结晶程度并提高剩余极化强度。
利用准静态法测量P(VDF-TrFE)薄膜极化后的压电系数d33,每个退火温度点取3个样品进行测试并取平均值与均方差,结果如图5所示。从图5可以看出,退火温度在60~140℃时,d33随退火温度上升而增大,从约11 pC/N增大至27 pC/N,接近 P(VDF-TrFE) d33的理论值(约为30 pC/N)。而在160℃退火温度下,由于样品表面出现裂痕缺陷导致不同样品测试值出现了较大的均方差,同时样品在极化过程中较容易发生击穿,表明在熔点附近进行退火处理容易导致样品出现缺陷从而产生性能分散性。
综合上述退火温度对P(VDF-TrFE)压电薄膜样品形貌、结晶结构、极化特性和压电系数的影响规律可知,60℃至熔点以下的退火处理可以显著提升介质薄膜的结晶程度,从而提高剩余极化强度和增大压电系数,本实验中在140℃下退火处理可以获得最优压电性能的P(VDF-TrFE)薄膜,其d33可达27 pC/N。
  • 北京市科技计划课题(Z201100004520018)
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2023年第56卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2023.07.004
  • 接收时间:2022-05-22
  • 首发时间:2025-11-24
  • 出版时间:2023-07-20
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  • 收稿日期:2022-05-22
  • 修回日期:2022-07-11
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北京市科技计划课题(Z201100004520018)
作者信息
    1国网智能电网研究院有限公司,北京 102209
    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

通讯作者:

高景晖(1984-),男(汉族),陕西西安人,教授,主要从事高电压绝缘技术和功能电介质方面的研究。
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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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