Article(id=1198664999418822839, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198664995669110898, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.02.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1655049600000, receivedDateStr=2022-06-13, revisedDate=1660492800000, revisedDateStr=2022-08-15, acceptedDate=null, acceptedDateStr=null, onlineDate=1763713605979, onlineDateStr=2025-11-21, pubDate=1676822400000, pubDateStr=2023-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763713605979, onlineIssueDateStr=2025-11-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763713605979, creator=13701087609, updateTime=1763713605979, 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=19, endPage=25, ext={EN=ArticleExt(id=1198664999670481089, articleId=1198664999418822839, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Thermal conductivity testing of polymer films by LFA method, columnId=1198664996516360309, journalTitle=Insulating Materials, columnName=Polyimide Film Special Issue, runingTitle=null, highlight=null, articleAbstract=

The development in the field of electronics and microelectronics has greatly promoted the research on thermally conductive polymer film materials. However, there is a lack of systematic study on both the analyzing technology of thermal conductivity and the testing methods suitable for polymer films. The light/laser flash analysis (LFA) is the most representative method in transient analysis technique. In this paper, the basic principle, testing conditions and application scope of LFA method were systematically introduced. Thermally conductive polyimide films were taken as the representative examples to analyze the key factors on the testing results in detail, including the film thickness, surface quality, pretreatment conditions, instrument parameters, and data analyzing and processing. In addition, the application of LFA method for testing thermal conductivity along different directions of polymer film materials was further discussed. The results show that the thickness accuracy, surface quality, and transparency of the samples will affect the test results, and the pretreatment methods such as gold sputtering or graphite spraying can effectively improve the test accuracy. In addition, the parameter setting and data processing of the testing instrument will affect the shape of temperature-time curve and the fitting results. Thus, it is necessary to reasonably select the appropriate testing conditions according to the characteristics of polymer film samples.

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电子与微电子领域的发展极大地推动了导热聚合物薄膜材料的研究,然而适用于薄膜材料的导热性能分析技术及测试方法仍缺少系统研究。闪光法是最具代表性的瞬态法导热分析技术,本文系统介绍了闪光法的基本原理、测试条件以及适用范围等,并以导热聚酰亚胺薄膜材料为代表,详细分析了聚合物薄膜材料的厚度、表面质量、前处理条件、仪器参数设置以及数据分析处理等因素对测试结果的影响,并探讨了闪光法测试聚合物薄膜材料不同方向导热性能的应用。结果表明:样品的厚度准确性、表面质量、透明性均会影响测试结果,采取溅射镀金和喷涂石墨的预处理方法可有效提高测试准确性。同时,测试仪器的参数设置和数据处理方法会影响温度-时间曲线形状及拟合结果,需要根据聚合物薄膜样品的特性来选择适宜的测试条件。

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邹涛(1976-),女(汉族),江苏常州人,副研究员,主要从事材料热物理性能分析的研究。
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赵瑾(1983-),女(汉族),山东青岛人,助理研究员,主要从事材料热分析、材料热物理性能的测试研究工作。

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赵瑾(1983-),女(汉族),山东青岛人,助理研究员,主要从事材料热分析、材料热物理性能的测试研究工作。

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赵瑾(1983-),女(汉族),山东青岛人,助理研究员,主要从事材料热分析、材料热物理性能的测试研究工作。

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figureFileBig=RBJKg1kisfNT5H6tiMbzyA==, tableContent=null), ArticleFig(id=1210949717521994165, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198664999418822839, language=EN, label=Tab.1, caption=In-plane and out-of-plane thermal conductivity data of representative polymer films reported in literature, figureFileSmall=null, figureFileBig=null, tableContent=
薄膜类型厚度/μm面外导热数据面内导热数据仪器型号参考文献
纯PI薄膜约0.19a约0.23aLFA447[32]
PI/GWFs (12%)约0.34a约3.05aLFA447[32]
PI/BNNS (7%)100约0.28a约2.08aLFA447[33]
PI/BN (50%)270.31a6.61aLFA467
PI/BN (30%)300.54b16.1bLFA467[30]
PI/BN (30%)20000.73b2.81bLFA467[20]
PI/BN (30%)0.72b3.40bLFA447[34]
PVDF/BNNS (33%)28约0.60b10.4bLFA467[10]
纯CNF薄膜30约0.25b4.47bLFA467[35]
CNF/BNNS (25%)301.08b22.67bLFA467[35]
Epoxy/mG/BN (10%/25%)1.27b1.31bLFA467[36]
), ArticleFig(id=1210949717589103030, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1198664999418822839, language=CN, label=表1, caption=

文献报道中代表性聚合物薄膜材料的面内与面外导热数据

, figureFileSmall=null, figureFileBig=null, tableContent=
薄膜类型厚度/μm面外导热数据面内导热数据仪器型号参考文献
纯PI薄膜约0.19a约0.23aLFA447[32]
PI/GWFs (12%)约0.34a约3.05aLFA447[32]
PI/BNNS (7%)100约0.28a约2.08aLFA447[33]
PI/BN (50%)270.31a6.61aLFA467
PI/BN (30%)300.54b16.1bLFA467[30]
PI/BN (30%)20000.73b2.81bLFA467[20]
PI/BN (30%)0.72b3.40bLFA447[34]
PVDF/BNNS (33%)28约0.60b10.4bLFA467[10]
纯CNF薄膜30约0.25b4.47bLFA467[35]
CNF/BNNS (25%)301.08b22.67bLFA467[35]
Epoxy/mG/BN (10%/25%)1.27b1.31bLFA467[36]
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闪光法测试聚合物薄膜材料导热性能的研究
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赵瑾 1 , 高梦岩 2 , 崔芃 1 , 陈宇迪 1 , 张梅 1 , 邹涛 1 , 翟磊 2
绝缘材料 | 聚酰亚胺薄膜专题 2023,56(2): 19-25
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绝缘材料 | 聚酰亚胺薄膜专题 2023, 56(2): 19-25
闪光法测试聚合物薄膜材料导热性能的研究
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赵瑾1, 高梦岩2, 崔芃1, 陈宇迪1, 张梅1, 邹涛1, 翟磊2
作者信息
  • 1北京市科学技术研究院分析测试研究所(北京市理化分析测试中心),有机材料检测技术与质量评价 北京市重点实验室,北京 100089
  • 2中国科学院化学研究所,北京 100190
  • 赵瑾(1983-),女(汉族),山东青岛人,助理研究员,主要从事材料热分析、材料热物理性能的测试研究工作。

通讯作者:

邹涛(1976-),女(汉族),江苏常州人,副研究员,主要从事材料热物理性能分析的研究。
Thermal conductivity testing of polymer films by LFA method
Jin ZHAO1, Mengyan GAO2, Peng CUI1, Yudi CHEN1, Mei ZHANG1, Tao ZOU1, Lei ZHAI2
Affiliations
  • 1Institue of Analysis and Testing, Beijing Academy of Science and Technology (Beijing Center for Physical & Chemical Analysis), Beijing Key Laboratory of Organic Materials Testing Technology & Quality Evaluation, Beijing 100089, China
  • 2Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
出版时间: 2023-02-20 doi: 10.16790/j.cnki.1009-9239.im.2023.02.003
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电子与微电子领域的发展极大地推动了导热聚合物薄膜材料的研究,然而适用于薄膜材料的导热性能分析技术及测试方法仍缺少系统研究。闪光法是最具代表性的瞬态法导热分析技术,本文系统介绍了闪光法的基本原理、测试条件以及适用范围等,并以导热聚酰亚胺薄膜材料为代表,详细分析了聚合物薄膜材料的厚度、表面质量、前处理条件、仪器参数设置以及数据分析处理等因素对测试结果的影响,并探讨了闪光法测试聚合物薄膜材料不同方向导热性能的应用。结果表明:样品的厚度准确性、表面质量、透明性均会影响测试结果,采取溅射镀金和喷涂石墨的预处理方法可有效提高测试准确性。同时,测试仪器的参数设置和数据处理方法会影响温度-时间曲线形状及拟合结果,需要根据聚合物薄膜样品的特性来选择适宜的测试条件。

测试方法  /  闪光法  /  聚合物薄膜  /  导热性能

The development in the field of electronics and microelectronics has greatly promoted the research on thermally conductive polymer film materials. However, there is a lack of systematic study on both the analyzing technology of thermal conductivity and the testing methods suitable for polymer films. The light/laser flash analysis (LFA) is the most representative method in transient analysis technique. In this paper, the basic principle, testing conditions and application scope of LFA method were systematically introduced. Thermally conductive polyimide films were taken as the representative examples to analyze the key factors on the testing results in detail, including the film thickness, surface quality, pretreatment conditions, instrument parameters, and data analyzing and processing. In addition, the application of LFA method for testing thermal conductivity along different directions of polymer film materials was further discussed. The results show that the thickness accuracy, surface quality, and transparency of the samples will affect the test results, and the pretreatment methods such as gold sputtering or graphite spraying can effectively improve the test accuracy. In addition, the parameter setting and data processing of the testing instrument will affect the shape of temperature-time curve and the fitting results. Thus, it is necessary to reasonably select the appropriate testing conditions according to the characteristics of polymer film samples.

testing method  /  light/laser flash analysis (LFA)  /  polymer film  /  thermal conductivity
赵瑾, 高梦岩, 崔芃, 陈宇迪, 张梅, 邹涛, 翟磊. 闪光法测试聚合物薄膜材料导热性能的研究. 绝缘材料, 2023 , 56 (2) : 19 -25 . DOI: 10.16790/j.cnki.1009-9239.im.2023.02.003
Jin ZHAO, Mengyan GAO, Peng CUI, Yudi CHEN, Mei ZHANG, Tao ZOU, Lei ZHAI. Thermal conductivity testing of polymer films by LFA method[J]. Insulating Materials, 2023 , 56 (2) : 19 -25 . DOI: 10.16790/j.cnki.1009-9239.im.2023.02.003
随着电子及微电子器件日益呈现小型化、薄型化和多功能集成化的发展特点,电子产品的运行功率和布线密度大幅增加,使得电子元器件、集成电路在单位体积内产生的热量急剧上升。由此引起的热堆积现象愈发严重,导致电路传输信号的互连延迟、串扰并造成显著能耗,严重影响电子器件的寿命和性能稳定性[1-4]。为及时将热量散出,除采用冷冻法、水循环冷却等外部方法外,提升电路基板或电子封装用聚合物绝缘薄膜材料的导热能力是一种可以从根本上解决散热问题的有效方法[5-8]。因此,开发兼具优异绝缘性和导热性的聚合物薄膜材料已成为国内外研究及应用的热点。
聚酰亚胺(PI)是一类广泛应用于电气、电子、微电子等领域的重要绝缘材料,具有优异的耐热性能、力学性能、绝缘性能、耐化学稳定性[9-12]。然而,传统聚酰亚胺薄膜的导热能力较低,本征导热系数仅为0.1~0.2 W/(m·K),无法满足先进集成电路及微电子器件的快速散热要求,极大限制了聚酰亚胺薄膜材料在光电领域更广泛的应用[13-15]
针对以聚酰亚胺为代表的聚合物绝薄膜材料,国内外学者围绕其导热性能的改善开展了大量研究工作,特别是基于聚合物基体和无机导热填料的导热复合薄膜得到了前所未有的发展[16-22]。在聚合物薄膜材料导热性能受到极大关注的同时,针对薄膜材料导热性能的分析技术以及测试方法的准确性却缺少系统研究。目前,文献报道中关于聚合物材料的导热性能分析的方法种类较多,根据测试原理可分为瞬态法、稳态法、温度波谱法等[23-25]。然而,实际上适用于聚合物薄膜材料导热性能测试的普适性方法却较为单一。
瞬态法导热分析技术是目前最常用于聚合物薄膜材料导热性能测试的方法。该方法的基本原理是在样品的表面施加瞬态或周期性热量,通过记录并计算温度随时间变化的函数,进而获得材料的热扩散系数或导热系数。瞬态法导热分析技术可进一步细分为闪光法(LFA法)、瞬态平面热源法(TPS法)、瞬态热线法以及其他瞬态法等[26-28]。闪光法通过测定相对温升与时间的函数关系即可以确定热扩散系数,不需要测定材料的绝对温度和热量,因此具有测试速度快、适用温度量程宽、对测试样品无损伤等优点,是目前测试聚合物薄膜类样品导热性能的最常用方法。
作为一种瞬态法导热分析技术,闪光法的测试时间较短,由此导致其测试精度偏低,后期还需要缜密、完备的数据分析处理。此外,仪器设备的型号、测试条件、测试样品的厚度与表面质量等均会对导热测试结果产生显著影响。因此,不同文献报道的同类材料的导热数据也没有很好的可比性,难以准确地进行分析比较,严重限制了对聚合物薄膜材料导热行为的客观认识和深入研究。
为此,本文探讨并分析闪光法在聚合物薄膜材料导热性能测试中的应用,系统介绍该测试方法的基本原理、测试条件以及适用范围等,并以在导热聚酰亚胺薄膜材料中的测试为代表,详细讨论测试样品的厚度、表面质量、前处理条件、仪器参数设置以及数据分析处理等对闪光法测试结果的影响。
图1是闪光法的测试装置示意图[26]。测试基本原理是在样品的下方发射瞬时光脉冲,产生的热量通过样品传递至其上表面,利用红外检测器监测样品上表面的温度并得到温升曲线,再根据相应的拟合模型来获得最终的热扩散系数。
闪光法属于对一维热扩散现象的测试方法,可根据样品厚度、固定温度下的热扩散时间即温度升至最大值百分比所需的时间计算得到热扩散系数(α)。要获得材料的导热系数(λ),还需要进一步得到样品的比热容(Cp)和体密度(ρ),并根据式(1)计算。
$\lambda=\alpha \cdot C_{p} \cdot \rho$
采用闪光法测试聚合物薄膜材料的热扩散系数时,虽然测试时间较短,但受到的影响因素却较多,例如测试样品的厚度和前处理、测试仪器的参数设置、测试数据的分析处理等,严重影响最终的测试结果的准确性。
根据闪光法的瞬时测量原理,在对测试条件进行假定简化后,样品的热扩散系数只与样品的厚度(d)、样品被光源照射后温度升至最高温度一半所需的时间(t50)有关,如式(2)所示。
α=0.1388×d2t50
式(2)可以看出,热扩散系数与样品厚度的平方成正比,因此需要准确输入薄膜样品的厚度,薄膜厚度的大小和测量精度将直接影响热扩散系数结果。为减小样品厚度的测试误差,建议采用无接触式的厚度测量方式,精确度可达到0.001 mm。
此外,根据式(2)可以进一步由材料的热扩散系数(α)和半升温时间(t50)推算得到样品的最小厚度(dmin)。例如,对于闪射法导热仪中具有较高数据采集频率的红外检测器,数据采集频率通常为2 MHz,而温升曲线至少需要250个点来完成拟合,因此理论上最小能够检测的t50为0.125 ms。由此可得到进一步计算dmin的公式如式(3)所示。
dmin=α×0.125×10-30.1388
通过式(3),利用已知或预估聚合物薄膜样品的热扩散系数可计算得到样品适于闪光法进行测试的最小样品厚度。聚合物薄膜材料的热扩散系数越小,相应的样品最小厚度就越小;而对于导热能力较高的薄膜材料,允许的样品最小厚度则较大。对于数据采集频率更低的红外检测器,样品厚度需要更大,低于最小厚度的样品将无法准确测试。因此,测试时应注意不同导热能力聚合物薄膜材料的厚度要求,以确保测试准确性。
聚合物薄膜的表面质量会严重影响闪光法的测试结果,薄膜样品表面粗糙度的高低、平整性的好坏会使得导热数据产生严重偏差。对于纯的聚合物薄膜材料,其表面质量往往较好,良好的平整度也使得样品厚度能够进行精确测量。然而,对于掺杂无机填料的聚合物基复合薄膜材料,其表面质量通常较差,特别是填料分散不均导致的表面凸起形貌会导致样品厚度难以精确测量,厚度测试值误差较大且厚度均一性较差。此外,样品较差的表面质量也会严重影响其与传感器、背景材料之间的接触热阻,进而使测试结果产生较大的误差。
图2是纯聚酰亚胺薄膜(PMDA/4,4′-ODA,实验室自制)、不同填料添加量的聚酰亚胺/氮化硼复合薄膜(实验室自制,氮化硼粒径为0.5~2 μm)的热扩散系数对比。
图2可以看出,当氮化硼质量分数为10%时,复合薄膜的热扩散系数高于1.2 mm2/s,远高于未添加导热填料的纯聚酰亚胺薄膜以及导热填料添加量更高的其他复合薄膜。
上述现象并不符合热扩散系数随导热填料添加量增大而逐渐升高的变化趋势,考虑薄膜制备及填料分散工艺的一致性,因此推测氮化硼质量分数为10%的样品表面质量较差,不利于厚度的准确测量,进而影响了热扩散系数的测试结果。为此,通过扫描电镜(SEM)观察了该薄膜表面和断裂横截面的情况,如图3所示,从图3(a)可以看出该样品的表面粗糙度较大,特别是填料颗粒的凸起严重影响了厚度的准确测量。从图3(b)横截面SEM照片可大概推测出,该薄膜样品整体的厚度为13~14 μm,而由于样品表面存在填料颗粒凸起,传统接触式测厚仪实测的样品厚度可能会高达30~40 μm。如前文所述,热扩散系数的测量结果与样品厚度的平方成正比,当测试中输入误测的高厚度值时,将会导致样品实际测试的热扩散系数结果显著偏高。因此,对于厚度较小的薄膜材料,其表面粗糙度越小或平整度越高,测得的厚度就越接近实际热量传递的距离,最终热扩散系数结果的可靠性越好。
聚合物薄膜样品的厚度通常为10~50 μm,受材料制备工艺和引入填料的不同,薄膜材料往往呈现不同的颜色,在可见光区的透光率也不尽相同。闪光法对样品的透明性有一定要求,其中对于无色透明或半透明的聚合物薄膜材料,如果不对样品进行遮光预处理,或采取的预处理方式不当,透过的一部分光脉冲会改变标准的温度响应曲线,影响导热测试结果的可靠性和准确性。
图4给出了具有不同外观颜色的聚酰亚胺基薄膜光学照片及其测试得到的热扩散系数。其中,颜色最深的薄膜样品PI-4、PI-5的测试曲线拟合程度最好,多次测试计算得到的热扩散系数波动最小且有良好重复性;而有一定透光率的样品PI-1测试结果波动较大。为此,对于具有良好透明性的薄膜材料,可对样品采取溅射镀金和喷涂石墨的预处理。特别是对于标准膜样的定值工作需要采用此类预处理方法,以减少人员差异带来的测试误差。
杨莉萍等[29]通过双面镀金再喷涂石墨的方法解决了聚酰亚胺/二氧化硅复合薄膜在导热测试中的透光问题。具体为采用双面溅射镀金消除薄膜透光的影响,再进一步喷涂石墨解决金属表面高反射、低发射的次生问题,以此增强样品正面对激光能量的吸收,并增大样品背面的红外检测信号。研究中聚酰亚胺/二氧化硅复合薄膜的厚度为40 μm,镀金层和石墨层的厚度分别约为2 μm,相比复合薄膜的厚度占比很小,其热导率的影响可忽略不计。研究人员计算了样品中各层的热阻,其中聚酰亚胺薄膜的热阻为2.34×10-4 m2·K/W,镀金层和石墨层引入的总热阻为2.16×10-8 m2·K/W,遮光涂层带来的误差小于0.01%,证实该预处理方法产生的影响很小,可直接测量样品的热扩散系数。
针对透光率较低的薄膜材料,可采取只喷涂石墨的预处理方法,并结合温升曲线分析、反推和多次修正,从而较准确地测量得到其热扩散系数。例如,OU X H等[30]通过在聚酰亚胺(PMDA/ODA)薄膜样品两侧各喷涂一层石墨层,采用闪光法测得了面内和面外热扩散系数,并进一步通过公式计算得到样品的面内和面外导热系数。
闪射法导热仪需要具备明确的参数设置并达到相关要求,例如足够低的脉冲宽度,可低至5 μs以下;数据采集频率不低于2 MHz;温升曲线计算拟合模型具备辐射传热分析类型。在进行闪光法测试时,测试参数诸如电压、脉冲宽度、放大器增益和采样时间等,均会影响测得的温度-时间曲线形状,并对后期曲线的拟合和数据处理造成不同程度干扰。仪器测试参数的选择是否合适会直接影响仪器输出数据点的产生以及数据的可信度。对于不同的聚合物薄膜样品,适用的最优测试参数也不同,需要根据样品特性来确定选择适宜的测试条件。
图5给出了聚酰亚胺/氮化硼复合薄膜在不同型号仪器的测试结果对比,实验选用的导热分析仪器型号分别为德国Netzsch公司LFA467型和LFA447型激光导热仪,两台仪器测试的样品保持一致,均为氮化硼质量分数为0~50%的聚酰亚胺/氮化硼复合薄膜。
图5可以看出,由于两台仪器型号不同,测试时设置的仪器参数也不相同,最终测得的热扩散系数结果差异很大,二者相差2~3倍。其中,LFA447型闪射法导热仪测得的结果明显偏低,而LFA467型闪射法导热仪的测试结果更接近文献[15,20]的报道值。这可能是由于LFA447型闪射法导热仪本身的光源脉冲宽度较长,导致测量厚度薄的样品时,光源脉冲信号与温升信号曲线部分重合,二者无法完全分开。后期采用模型拟合温升信号曲线时会将重合的曲线包含在内,模型中温升的起始时间前移,与实际情况相比t50偏大,因此计算得到的热扩散系数偏小。相比之下,LFA467型闪射法导热仪的光源脉冲宽度可设置为极短,样品的温升信号曲线比较清晰且独立,t50更符合实际情况,因此计算得到的热扩散系数更具有可靠性。无论采用何种型号的闪光法测试仪器,对于厚度较薄的薄膜材料,测试前设置的脉冲宽度参数都建议尽量短,以此保证测试结果的准确性。由此看出,仪器的型号及测试参数会对薄膜样品的导热测试结果产生较大影响。
闪光法的测试数据分析主要涉及温升曲线的解析处理,包括原始数据点的选取和数量、曲线拟合模型及拟合程度等,处理过程中存在较大的主观性,同时实际测试数据也与理论模型存在差异,上述几方面均会影响闪光法的准确性。此外,通过对温升曲线形态的解析,可反推薄膜材料自身属性以及喷涂方法对材料热扩散系数测试的影响。闪光法主要获得材料厚度方向上的温升曲线,其信噪比为3~5倍,较高的信噪比能够获得更好的拟合效果。对测试数据的分析处理可进一步修正喷涂方法、电压值、脉冲宽度,进而得到信噪比更高、更为真实可靠的温升曲线,并得到更完美的拟合结果。
图6是厚度为27 μm的聚合物薄膜样品在不同电压、脉冲等参数设置下的温升曲线拟合效果图。图6(a)中曲线的信噪比并不能满足要求,通过对测试参数进行优化后,同一片薄膜试样的温升曲线的拟合效果更好,如图6(b)所示,计算得到的数据结果也更为准确。
从理论上讲,闪光法可以对聚合物薄膜样品不同方向的导热性能进行测试。通过选用不同的样品尺寸与支架,可实现对样品在薄膜面内方向(X-Y方向,in-plane)和面外方向(Z方向,out-of-plane)上热扩散系数的测试[30-31]
表1列出了文献报道中代表性聚合物薄膜材料的面内与面外导热数据,所有测试均采用闪光法,仪器为LFA447型和LFA467型闪射法导热仪,氮化硼的添加量均为质量百分比。从表1可以看出,由闪光法测试的面外导热数据有较好的可比性,不同文献的测试数据有良好的一致性,而面内导热数据则差异很大,即使同一类薄膜材料也没有很好的可比性。例如,对于PI/BN(30%)薄膜材料,虽然其厚度、制备工艺、测试条件可能会有差别,但不同文献报道的面外导热系数基本均在0.54~0.73 W/(m·K),测试结果表现出较高的可靠性。然而,在面内方向上的测试结果却差异巨大,导热系数最低可为2.81 W/(m·K),最高可达16.1 W/(m·K),严重超出了正常测试波动的范围。
根据测试原理,常规闪光法测得的是聚合物薄膜材料的面外热扩散系数,而针对样品在面内方向上的热扩散系数测试,其原理与面外方向的测试方法基本类似。二者的主要区别在于,对于面内热扩散系数的测试,薄膜样品背面的红外检测器检测的是通过膜材面内半径为14 mm圆周区域的平均温度变化。对于厚度为几十微米的聚合物薄膜材料,水平方向热扩散系数需达到20 mm2/s,才能够检测到足够稳定、拟合效果较好的温升曲线。对于大多数聚合物本征薄膜和掺杂非二维导热填料的复合薄膜材料,水平方向上的热扩散能力有限,红外检测器难以检测到足够稳定的温升信号,通常会使采集的温升曲线扭曲严重,拟合效果不理想。在此种情况下,即使采用了仪器的面内模式进行测试,得到的导热数据也难以准确反映聚合物薄膜材料水平方向上的散热能力,仅能作为参考。
然而,当聚合物薄膜材料的厚度增加到100 μm以上,并且呈现良好的刚性挺度状态时,其面内方向热扩散系数可以采用仪器的多层模式进行测试。具体方法为先将一定厚度、一定硬度的薄膜试样裁剪成相同宽度的样品条,以宽度方向作为热传导方向进行装样并测试,由此可以得到理想的测试结果。
作为最具代表性的瞬态法导热分析技术,闪光法具有测试快捷、样品制备简单且无损伤等特点,被广泛应用于聚合物薄膜材料导热性能的测试。与此同时,闪光法受到众多测试因素影响,能否准确获得样品的热扩散系数对于开展聚合物薄膜导热性能研究至关重要。本文系统探讨了测试样品的厚度、表面质量、前处理条件、仪器参数装置以及数据分析处理对测试结果的影响,总结如下:
(1)聚合物薄膜材料的厚度准确性和表面质量均会直接影响热扩散系数测试结果,同时闪光法对薄膜样品的最小厚度有限制要求。热扩散系数越低的薄膜材料对应的样品最小厚度也越小;薄膜表面粗糙度过大会影响厚度的精确测量,并在测试中带来显著的接触热阻误差。
(2)闪光法对样品的透明性有一定限制要求,对于厚度小于20 μm的无色透明聚合物薄膜材料,需要提前进行遮光预处理。采取溅射镀金和喷涂石墨的预处理方法,可更加有效地解决样品的透光问题,并且不影响导热测试结果的可靠性和准确性。
(3)测试仪器的参数设置和数据处理会影响温度-时间曲线形状及拟合结果,需要根据薄膜样品的特性来合理选择适宜的测试条件。较高的信噪比有助于获得更好的温升曲线拟合效果;闪光法可准确测得薄膜面外方向的热扩散系数,而面内方向的测试取决于试样特点、制样方法及参数设置。
  • 北京市自然科学基金资助项目(2202068)
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2023年第56卷第2期
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doi: 10.16790/j.cnki.1009-9239.im.2023.02.003
  • 接收时间:2022-06-13
  • 首发时间:2025-11-21
  • 出版时间:2023-02-20
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  • 收稿日期:2022-06-13
  • 修回日期:2022-08-15
基金
北京市自然科学基金资助项目(2202068)
作者信息
    1北京市科学技术研究院分析测试研究所(北京市理化分析测试中心),有机材料检测技术与质量评价 北京市重点实验室,北京 100089
    2中国科学院化学研究所,北京 100190

通讯作者:

邹涛(1976-),女(汉族),江苏常州人,副研究员,主要从事材料热物理性能分析的研究。
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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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