Article(id=1241765093759848873, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241765084528181978, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.07.004, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1600358400000, receivedDateStr=2020-09-18, revisedDate=1603987200000, revisedDateStr=2020-10-30, acceptedDate=null, acceptedDateStr=null, onlineDate=1773989469232, onlineDateStr=2026-03-20, pubDate=1626710400000, pubDateStr=2021-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1773989469232, onlineIssueDateStr=2026-03-20, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1773989469231, creator=13701087609, updateTime=1773989469231, updator=13701087609, issue=Issue{id=1241765084528181978, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='7', pageStart='1', pageEnd='120', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1773989467027, creator=13701087609, updateTime=1773989590112, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1241765600834421400, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241765084528181978, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1241765600834421401, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1241765084528181978, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=31, endPage=36, ext={EN=ArticleExt(id=1241765095773114807, articleId=1241765093759848873, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Study on Thermal Conductivity of MWCNTs/T-ZnOw Modified PVB Composites, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

A MWCNTs/T-ZnOw/PVB composite was prepared via solution blending method by using multi-walled carbon nanotubes (MWCNTs) and zinc oxide whisker (T-ZnOw) as fillers and polyvinyl butyral (PVB) as matrix. The thermal diffusivity of the composite was measured by transient electro-thermal technique (TET). The effects of different mass fraction ratio of fillers, heat treatment time and temperature, and ultraviolet accelerated ageing on the thermal conductivity of the composite were investigated. The results show that under the same mass fraction of fillers, the thermal conductivity of the composite increases at first and then decreases with the increase of MWCNTs content. When the heat treatment time is 1 h, with the increase of the heat treatment temperature from 80℃ to 140℃, the thermal conductivity of the composite decreases at first and then increases. When the heat treatment temperature is 140℃, the thermal conductivity increases after heating for 1 h, but it decreases with the extension of heating time. When the composite is accelerated aged by ultraviolet irradiation, the thermal conductivity of the composite decreases with the increase of irradiation time.

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采用溶液共混法制备了以碳纳米管(MWCNTs)、氧化锌晶须(T-ZnOw)为填充材料,以聚乙烯醇缩丁醛(PVB)为基体材料的MWCNTs/T-ZnOw/PVB复合材料,并利用瞬态电热技术(TET)测量了材料的热扩散系数。研究了填料不同质量分数、加热处理时间和温度、紫外线加速老化对复合材料导热性能的影响。结果表明:在填料总质量分数不变的情况下,复合材料的导热系数随着MWCNTs含量的增加先增大后减小。复合材料热处理时间为1 h时,随着热处理温度从80℃上升到140℃,复合材料的导热系数先减小后增大。当复合材料热处理温度为140℃时,加热1 h后导热系数增大,但随着加热时间的延长,导热系数减小。对复合材料进行紫外光照射加速老化,随着光照时间的增加,材料的导热系数呈减小趋势。

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林欢(1983-),女(汉族),山东威海人,副教授,博士,研究方向为微尺度传热。
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孙玉川(1994-),男(汉族),山东潍坊人,硕士生,研究方向为微尺度传热。

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孙玉川(1994-),男(汉族),山东潍坊人,硕士生,研究方向为微尺度传热。

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孙玉川(1994-),男(汉族),山东潍坊人,硕士生,研究方向为微尺度传热。

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articleTitle=热处理对聚丙烯结晶结构和力学性能的影响, refAbstract=null), Reference(id=1245055684782441021, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, doi=null, pmid=null, pmcid=null, year=2006, volume=35, issue=1, pageStart=68, pageEnd=72, url=null, language=null, rfNumber=[19], rfOrder=18, authorNames=曹慧林, 苑会林, 王凤霞, journalName=塑料, refType=null, unstructuredReference=曹慧林,苑会林,王凤霞.聚乙烯醇缩丁醛薄膜老化机理研究[J].塑料,2006,35(1):68-72., articleTitle=聚乙烯醇缩丁醛薄膜老化机理研究, refAbstract=null)], funds=[Fund(id=1245055682714649058, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, awardId=51506106, language=CN, fundingSource=国家自然科学基金资助项目(51506106), fundOrder=null, country=null), Fund(id=1245055682811118056, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, awardId=2017M612225, language=CN, fundingSource=中国博士后科学基金项目(2017M612225), fundOrder=null, country=null), Fund(id=1245055682924364267, 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ArticleFig(id=1245055681766736310, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=EN, label=Fig.6, caption=Effect of heating time on thermal conductivity of materials, figureFileSmall=6Shglujz/6bNT/CkX47vlg==, figureFileBig=P0CFU4d7cLnX+nmpsUmDXQ==, tableContent=null), ArticleFig(id=1245055681846428090, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=CN, label=图6, caption=加热时间对材料导热系数的影响, figureFileSmall=6Shglujz/6bNT/CkX47vlg==, figureFileBig=P0CFU4d7cLnX+nmpsUmDXQ==, tableContent=null), ArticleFig(id=1245055681947091391, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=EN, label=Tab.1, caption=Mass fraction of components in composites, figureFileSmall=null, figureFileBig=null, tableContent=
编号ω(PVB)/%ω(T-ZnOw)/%ω(MWCNTs)/%
110000
2991.00
3990.90.1
4990.70.3
5990.50.5
6990.30.7
7990.10.9
89901.0
), ArticleFig(id=1245055682005811653, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=CN, label=表1, caption=

复合材料各组分的质量分数

, figureFileSmall=null, figureFileBig=null, tableContent=
编号ω(PVB)/%ω(T-ZnOw)/%ω(MWCNTs)/%
110000
2991.00
3990.90.1
4990.70.3
5990.50.5
6990.30.7
7990.10.9
89901.0
), ArticleFig(id=1245055682110669256, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=EN, label=Tab.2, caption=Thermal conductivity of each composite material, figureFileSmall=null, figureFileBig=null, tableContent=
编号长度/μm宽度/μm厚度/μm导热系数/(W/(m·K))
11 067131980.31±0.023
2963911640.28±0.015
38351041390.31±0.021
41 2721811610.35±0.019
51 6741511240.38±0.021
61 5331511130.61±0.022
71 099113790.34±0.018
81 038118820.29±0.013
), ArticleFig(id=1245055682177778122, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=CN, label=表2, caption=

各复合材料的导热系数

, figureFileSmall=null, figureFileBig=null, tableContent=
编号长度/μm宽度/μm厚度/μm导热系数/(W/(m·K))
11 067131980.31±0.023
2963911640.28±0.015
38351041390.31±0.021
41 2721811610.35±0.019
51 6741511240.38±0.021
61 5331511130.61±0.022
71 099113790.34±0.018
81 038118820.29±0.013
), ArticleFig(id=1245055682257469900, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=EN, label=Tab.3, caption=Treatment conditions and results, figureFileSmall=null, figureFileBig=null, tableContent=
编号

长度

/μm

宽度

/μm

厚度

/μm

加热

时间/h

加热

温度/℃

导热系数

/(W/(m·K))

91 53315111300.61±0.022
101 7041721131800.55±0.029
111 27821711311000.51±0.026
121 40918811311200.71±0.025
131 37017011311400.73±0.032
141 62122611321400.56±0.031
151 57519211341400.54±0.025
), ArticleFig(id=1245055682395881935, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=CN, label=表3, caption=

处理工况及结果

, figureFileSmall=null, figureFileBig=null, tableContent=
编号

长度

/μm

宽度

/μm

厚度

/μm

加热

时间/h

加热

温度/℃

导热系数

/(W/(m·K))

91 53315111300.61±0.022
101 7041721131800.55±0.029
111 27821711311000.51±0.026
121 40918811311200.71±0.025
131 37017011311400.73±0.032
141 62122611321400.56±0.031
151 57519211341400.54±0.025
), ArticleFig(id=1245055682483962321, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=EN, label=Tab.4, caption=Effect of UV irradiation on the thermal conductivity of composite materials, figureFileSmall=null, figureFileBig=null, tableContent=
编号

长度

/μm

宽度

/μm

厚度

/μm

光照时间

/d

导热系数

/(W/(m·K))

1-11 0671319800.31±0.023
1-21 47916498300.23±0.016
2-19639116400.28±0.015
2-21 75821640300.27±0.019
6-11 53315111300.61±0.022
6-21 811152179300.51±0.015
8-11 0381188200.29±0.013
8-21 528175121300.23±0.014
), ArticleFig(id=1245055682563654101, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1241765093759848873, language=CN, label=表4, caption=

紫外光照射对复合材料导热系数的影响

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编号

长度

/μm

宽度

/μm

厚度

/μm

光照时间

/d

导热系数

/(W/(m·K))

1-11 0671319800.31±0.023
1-21 47916498300.23±0.016
2-19639116400.28±0.015
2-21 75821640300.27±0.019
6-11 53315111300.61±0.022
6-21 811152179300.51±0.015
8-11 0381188200.29±0.013
8-21 528175121300.23±0.014
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碳纳米管/氧化锌晶须改性聚乙烯醇缩丁醛复合材料导热性能研究
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孙玉川 , 张建伦 , 林欢 , 朱珊珊
绝缘材料 | 材料研究 2021,54(7): 31-36
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绝缘材料 | 材料研究 2021, 54(7): 31-36
碳纳米管/氧化锌晶须改性聚乙烯醇缩丁醛复合材料导热性能研究
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孙玉川, 张建伦, 林欢, 朱珊珊
作者信息
  • 青岛理工大学 环境与市政工程学院,山东 青岛 266033
  • 孙玉川(1994-),男(汉族),山东潍坊人,硕士生,研究方向为微尺度传热。

通讯作者:

林欢(1983-),女(汉族),山东威海人,副教授,博士,研究方向为微尺度传热。
Study on Thermal Conductivity of MWCNTs/T-ZnOw Modified PVB Composites
Yuchuan SUN, Jianlun ZHANG, Huan LIN, Shanshan ZHU
Affiliations
  • School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033, China
出版时间: 2021-07-20 doi: 10.16790/j.cnki.1009-9239.im.2021.07.004
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采用溶液共混法制备了以碳纳米管(MWCNTs)、氧化锌晶须(T-ZnOw)为填充材料,以聚乙烯醇缩丁醛(PVB)为基体材料的MWCNTs/T-ZnOw/PVB复合材料,并利用瞬态电热技术(TET)测量了材料的热扩散系数。研究了填料不同质量分数、加热处理时间和温度、紫外线加速老化对复合材料导热性能的影响。结果表明:在填料总质量分数不变的情况下,复合材料的导热系数随着MWCNTs含量的增加先增大后减小。复合材料热处理时间为1 h时,随着热处理温度从80℃上升到140℃,复合材料的导热系数先减小后增大。当复合材料热处理温度为140℃时,加热1 h后导热系数增大,但随着加热时间的延长,导热系数减小。对复合材料进行紫外光照射加速老化,随着光照时间的增加,材料的导热系数呈减小趋势。

碳纳米管  /  氧化锌晶须  /  聚乙烯醇缩丁醛  /  复合材料  /  瞬态电热技术  /  导热系数

A MWCNTs/T-ZnOw/PVB composite was prepared via solution blending method by using multi-walled carbon nanotubes (MWCNTs) and zinc oxide whisker (T-ZnOw) as fillers and polyvinyl butyral (PVB) as matrix. The thermal diffusivity of the composite was measured by transient electro-thermal technique (TET). The effects of different mass fraction ratio of fillers, heat treatment time and temperature, and ultraviolet accelerated ageing on the thermal conductivity of the composite were investigated. The results show that under the same mass fraction of fillers, the thermal conductivity of the composite increases at first and then decreases with the increase of MWCNTs content. When the heat treatment time is 1 h, with the increase of the heat treatment temperature from 80℃ to 140℃, the thermal conductivity of the composite decreases at first and then increases. When the heat treatment temperature is 140℃, the thermal conductivity increases after heating for 1 h, but it decreases with the extension of heating time. When the composite is accelerated aged by ultraviolet irradiation, the thermal conductivity of the composite decreases with the increase of irradiation time.

multi-walled carbon nanotubes (MWCNTs)  /  zinc oxide whisker (T-ZnOw)  /  polyvinyl butyral (PVB)  /  composite  /  transient electro-thermal technology (TET)  /  thermal conductivity
孙玉川, 张建伦, 林欢, 朱珊珊. 碳纳米管/氧化锌晶须改性聚乙烯醇缩丁醛复合材料导热性能研究. 绝缘材料, 2021 , 54 (7) : 31 -36 . DOI: 10.16790/j.cnki.1009-9239.im.2021.07.004
Yuchuan SUN, Jianlun ZHANG, Huan LIN, Shanshan ZHU. Study on Thermal Conductivity of MWCNTs/T-ZnOw Modified PVB Composites[J]. Insulating Materials, 2021 , 54 (7) : 31 -36 . DOI: 10.16790/j.cnki.1009-9239.im.2021.07.004
在资源日益短缺、环境污染严重的背景下,发展一种清洁、无污染的新能源技术尤为重要。丰富的太阳能是一种具有发展前景的新能源[1],因此将太阳能转化为电能的光伏发电技术应运而生。但是由于太阳能电池不能及时地将热量散出,导致工作温度过高,大幅降低了光伏发电的效率[2]。封装薄膜作为太阳能电池的主要组件[3],在各组件中导热性能最差,导热系数为0.2~0.3 W/(m·K)[4-5]。已有研究表明,硅基太阳能电池温度每升高1℃,转换效率就会降低0.40%~0.73%[6]。并且过高的工作温度将会加速封装材料的老化,而封装材料老化失效是光伏组件寿命缩短的主要原因[7]。因此增强封装薄膜的导热性能,提高光电转换效率,同时减缓封装薄膜的老化,延长光伏系统的使用寿命具有重要意义。
聚乙烯醇缩丁醛(PVB)作为太阳能电池封装材料,具有支撑结构、保护固定电池片、密封等作用。近年来,有许多学者通过对PVB进行改性使其导热性能、抗老化性能、光学性能等得到提升。朱晓亮等[8]用熔融共混法制备出Al2O3/PVB复合材料,结果表明复合材料的导热性能受Al2O3粒径的影响较小,但是随着Al2O3含量的增加,复合材料内部粒子间形成导热链,有效提高了复合材料的导热性能。张帆等[9]将纳米银线(AgNWs)与PVB进行混合,结果表明AgNWs含量的增大能够显著增强复合材料的导热性能,当AgNWs质量分数小于50%时,复合材料的拉伸强度均高于PVB薄膜。张东亮等[10]在合成PVB树脂时通过添加纳米氧化锡锑(ATO)粒子来提高复合材料的紫外屏蔽能力。碳纳米管(MWCNTs)与氧化锌晶须(T-ZnOw)具有优异的导热性能,T-ZnOw在基体中容易形成导热网络,同时T-ZnOw对紫外光具有很强的吸收能力,可以减缓复合材料的老化,提高光伏组件的使用寿命。
本研究通过溶液共混法制备MWCNTs/T-ZnOw/PVB复合材料,通过改性来提高PVB复合材料的导热系数,从而降低光伏组件工作温度,提升光电转换效率,同时增强抗紫外光能力,延长使用寿命。
碳纳米管,型号为TNM3,北京博宇高科新材料公司,该产品制备方法为化学气相沉淀法,其扫描电子显微镜(SEM)图像如图1所示。
氧化锌晶须,白色疏松状粉末,平均针长为30 μm,沪本新材料科技有限公司;PVB,白色粉末,沪本新材料科技有限公司;无水乙醇,分析纯,含量为99.7%,市售。
取一定量PVB粉末与无水乙醇溶液以一定比例混合,并在75℃恒温水浴中充分搅拌,直至形成无色透明黏稠状液体。再称取一定量MWCTs(或T-ZnOw),以一定比例与无水乙醇溶液混合,超声分散30 min得到两种填料的分散液,其中各组分的质量分数如表1所示。将填料分散液与PVB的无水乙醇溶液混合,充分搅拌后,超声分散60 min。将分散后的混合溶液倒入准备好的玻璃器皿中,自然干燥后将膜状复合材料取下,密封保存。
瞬态电热技术(TET)是一种用于测量一维微尺度材料热扩散系数的方法,能够快速、精确、有效地对导体、半导体等材料进行测量,对于绝缘体可以通过在材料表面镀金的方法获得材料的真实热扩散系数,其测量的准确性已经得到了充分的证实[11-13]
TET实验系统如图2所示,将待测样品固定在两个电极之间,置于真空腔体中,微电流源、数字示波器、样品并联连接,通过微电流源将方波脉冲直流电通入样品中,在电流的作用下样品的温度迅速上升,同时样品温度变化会引起电阻的改变,当输入电流一定时,样品两端电压会随着电阻的变化而改变,通过数字示波器记录样品两端的电压。通过电压的变化得到样品温度的变化,进而通过拟合温度与时间曲线来得到样品的热扩散系数,由热扩散系数进一步推导得到样品的导热系数。样品电压与时间的变化关系如图3所示。
试验在真空环境下(真空腔体的真空度小于0.2 Pa)进行,因此可以忽略对流换热对整个试验的影响。为保证热量沿着一维传导,样品的长度远大于宽度和厚度,其控制方程如式(1)所示。
ρcpTt=k2Tx2+q0
式(1)中:ρ为样品的密度;k为导热系数;cp为样品的比热容;q0为单位体积的电加热功率;T为样品平均温度。
样品的平均温度由格林公式积分求解,可表示为式(2)[14]
T(t)=T0+4q0L2kπm=11-exp -(2m-1)2π2αtL2(2m-1)4
式(2)中:L为被测样品的长度;α为样品的热扩散系数;T0为环境温度。
时间趋于无穷大时(t→∞),样品温度沿长度方向趋于稳态,此时样品平均温度如式(3)所示。
T(t)t=T0+q0L212k
样品的归一化温升可表示为式(4)
T*(t)=96π4m=11-exp-2m-12π2αt/L22m-14
最终得到样品两端电压与平均温度的关系如式(5)所示。
Vsample=IR0+Iηq0L212k×T*=IR0+Iη8q0L2kπ4·
m=11-exp-2m-12π2αt/L22m-14
式(5)中:Vsample是示波器记录的样品两端电压;I为通入样品的电流;R0为样品的初始电阻;η为样品电阻温度系数。
因为待测样品为绝缘体,无法通电加热,所以需要对样品进行镀金增加导电性。将放有样品的基台放在磁控溅射镀膜仪中镀金20 nm。镀金后样品的有效热扩散系数可以根据式(6)计算。
αeff=αexpLLorenzTLRAwρcp
式(6)中:αeff为样品的有效热扩散系数;αexp为拟合得到的热扩散系数;R为样品的平均电阻;Aw为样品的横截面积;LLorenz为金薄膜的洛伦兹数。
考虑测量过程中辐射换热会对试验产生一定的影响,样品的真实热扩散系数应等于有效热扩散系数与辐射效应之差,如式(7)所示。
α=αeff-1ρcp8εrσT03DL2π2
式(7)中:εr为样品有效发射率;σ为玻尔兹曼常数;D为样品厚度。由式(7)可知样品的真实热扩散系数与有效热扩散系数之间存在一定的线性关系,可通过改变样品长度推导出辐射作用为0时样品的真实热扩散系数。得到样品的真实热扩散系数后,可由式(8)反推得出样品的导热系数。
α=k/ρcp
因导热填料的质量仅占复合材料总质量的1%,可以用纯PVB的密度和比热容(ρ=1 107 kg/m3cp=1 667 J/(kg·K))[15]来计算得到各样品的导热系数。
将按表1制备好的样品切割成长度远大于其厚度与宽度的尺寸,用无水乙醇将其清洗后悬置于基台上,在磁控溅射镀膜仪中镀金后,用导热银胶将其固定在两端电极上,利用高倍显微镜对样品的尺寸进行多次测量并取平均值。样品在去除辐射和镀金影响后,复合材料的导热系数如表2所示。由表2可知,随着MWCNTs含量的增加,复合材料的导热系数整体上先增大再减小。当MWCNTs和T-ZnOw的质量分数分别为0.7%和0.3%时,复合材料的导热系数最大,达到0.61 W/(m·K)。
样品2相比于纯PVB,复合材料的导热系数并没有得到提升反而减小,这是因为:①基体中MWCNTs含量较少,而含量较多的T-ZnOw不足以在基体中相互连接形成导热网络,对复合材料导热性能的提升影响很小;②当PVB中加入导热填料时,其内部有序排列的分子结构会受到一定的影响,导致材料的结构缺陷增多,使声子缺陷散射得到增强[16]。不完善的导热网络对复合材料导热性能的促进作用弱于结构缺陷对导热性能的抑制作用,最终导致复合材料的导热性能低于纯PVB。
图4为样品5和样品6在不同放大倍数下的微观形貌。从图4(a)可以看出,当T-ZnOw质量分数为0.5%时,T-ZnOw粒子聚集较为明显,MWCNTs不能很好地与T-ZnOw搭接,导热能力受到限制。而从图4(b)可以看出,当T-ZnOw质量分数减小到0.3%时,粒子聚集现象减弱,并且MWCNTs在复合材料中分散均匀,MWCNTs与T-ZnOw之间很好地搭接在一起形成导热网络,有利于复合材料导热性能的提高。
随着MWCNTs质量分数的增加以及T-ZnOw质量分数的逐渐减少,基体内部的导热网络逐渐完善,复合材料的导热性能得到提升。这是因为导热网络中的热量是通过电子来传递的,同时材料本身的声子也会进行热量的传递,此时结构缺陷的抑制作用远远弱于电子和声子的热运输能力,所以材料的导热性能增强。
复合材料的导热系数先增大后减小是因为在导热网络中起骨架作用的T-ZnOw含量减少,导致T-ZnOw间距离过大,MWCNTs无法搭接在上面形成导热网络。另外由于MWCNTs的比表面积大,具有较强的范德华力,成膜晾干的过程中容易发生团聚现象。T-ZnOw含量的减少对MWCNTs团聚的抑制作用也会减弱,导致部分MWCNTs发生团聚现象,材料的导热性能下降。
将样品6在无水乙醇中清洗,待无水乙醇挥发后,放入玻璃培养皿中,在电动鼓风干燥箱中进行热处理,将处理后的样品放在室温中冷却2 h后进行测量,复合材料热处理工况及结果如表3所示。
样品6的热处理时间为1 h,处理温度分别为80、100、120、140℃时的实验结果如图5所示。
图5可知,热处理后复合材料的导热系数呈现先减小后增大的趋势。热处理温度为0~100℃时,导热系数随处理温度的升高而减小,100℃时复合材料的导热系数相比于未热处理时减小了16.4%;热处理温度为140℃时,导热系数最大,相比于未进行热处理时提高了19.7%,但是与120℃时相比导热系数的提升并不明显。
复合材料中基体与填料之间会存在微小孔隙,当热处理温度较低(80~100℃)时,填料与基体的热膨胀系数不同,导致两者的结合度下降,同时带有缺陷的结晶分子链中的链段不足以获得足够的能量进入晶格二次结晶,造成复合材料的导热系数没有增大反而减小[17-18]。当热处理温度超过100℃时,复合材料处于松弛状态,分子链有较大的自由度,此时材料浸润性好,基体与填料重新结合,有较好的结合度。同时随着热处理温度的升高,复合材料获得足够的能量,使缺陷的结晶分子链段进入晶格二次结晶,材料的结晶状况得到改善。结合度和结晶度的提升共同促进了材料导热系数的提升。热处理温度在120~140℃时,导热系数的提升并不明显,这主要是因为在经过120℃的热处理后,材料内部分子链排列规整,晶体结构也较为完善,继续升高温度对导热性能的提升影响不大。
用电动鼓风干燥箱将样品6在140℃的条件下分别热处理0、1、2、4 h,结果如图6所示。
图6可以看出,当热处理温度为140℃时,随着加热时间的增加,材料的导热系数呈现先增大后减小的趋势,材料加热处理1 h时导热系数最大,为0.73 W/(m·K),此时材料内部晶体结构完善,导热系数得到提高。在复合材料的持续加热过程中,PVB分子的侧链和主链受到破坏发生链降解反应,同时羟基被氧化生成羰基,受热过程中最终分解生成自由基[19],使复合材料内部分子结构发生变化,造成复合材料的导热系数减小。
通过用紫外光照射的方法来进行复合材料的加速老化实验,将样品1、样品2、样品6、样品8进行30 d的紫外光照射,空白对照组为相应4种材料不做紫外光照处理,测量结果如表4所示。
表4可以看出,随着紫外光照时间的增加,材料的导热系数呈现下降的趋势,其中样品6经过紫外光照射30 d时导热系数为0.51 W/(m·K),与未进行紫外光照射时相比下降16.4%。紫外光的照射使PVB分子发生了交联反应,随着紫外光照时间的增加,分子链之间发生断裂,复合材料内部晶体结构受到破坏,导致复合材料的导热系数减小。紫外光同时加速了复合材料的老化,使复合材料基体与填料之间的结合度降低,导致界面热阻增大,进一步阻碍了热量的传递,导致复合材料的导热系数变小。
表4还可以看出,样品1因老化较为严重导致导热系数变化最大。含MWCNTs质量分数为1%的样品8因MWCNTs发生团聚现象不能很好地将紫外线电磁波产生的谐振电流消耗而防止复合材料的老化,导致样品8的导热系数变化也较大。含T-ZnOw质量分数为1%的样品2导热系数变化最小,这主要是因为T-ZnOw是一种良好的紫外线吸收剂,能够起到很好的吸收紫外线的作用,同时因为T-ZnOw的须针能够将一部分紫外线散射出去,所以能有效防止复合材料的老化。MWCNTs和T-ZnOw质量分数分别为0.7%和0.3%的样品6在30 d紫外光照射后,仍具有大于其他3种材料的导热系数,说明T-ZnOw和MWCNTs在提高PVB导热系数的同时,还能够起到很好的防止复合材料老化的作用。
(1)保持T-ZnOw和MWCNTs总质量分数为1%,随着MWCNTs含量的增加,复合材料的导热系数先增大后减小。当T-ZnOw和MWCNTs质量分数分别为0.3%和0.7%时,导热系数达到最大值0.61 W/(m·K),比纯PVB的导热系数提高近一倍。
(2)将T-ZnOw和MWCNTs质量分数分别为0.3%和0.7%的复合材料进行热处理,在不同的温度下加热1 h,导热系数先减小后增大。温度为140℃时,导热系数提高了19.7%。在140℃下改变加热时间,结果表明加热1 h后材料的导热系数最大,但是随着加热时间的延长,材料的导热系数减小。
(3)在紫外光加速复合材料老化试验中,4种材料的导热系数虽然有所下降,但是导热系数最大的仍为T-ZnOw和MWCNTs质量分数分别为0.3%和0.7%的复合材料,其导热系数为0.51 W/(m·K)。
  • 国家自然科学基金资助项目(51506106)
  • 中国博士后科学基金项目(2017M612225)
  • 青岛市青年专项基金(18-2-2-72-jch)
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2021年第54卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2021.07.004
  • 接收时间:2020-09-18
  • 首发时间:2026-03-20
  • 出版时间:2021-07-20
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  • 收稿日期:2020-09-18
  • 修回日期:2020-10-30
基金
国家自然科学基金资助项目(51506106)
中国博士后科学基金项目(2017M612225)
青岛市青年专项基金(18-2-2-72-jch)
作者信息
    青岛理工大学 环境与市政工程学院,山东 青岛 266033

通讯作者:

林欢(1983-),女(汉族),山东威海人,副教授,博士,研究方向为微尺度传热。
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2种不同金属材料的力学参数

Family
属数
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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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