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Article(id=1222495717738926636, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1222495713427186326, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.04.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1593273600000, receivedDateStr=2020-06-28, revisedDate=1596643200000, revisedDateStr=2020-08-06, acceptedDate=null, acceptedDateStr=null, onlineDate=1769395291980, onlineDateStr=2026-01-26, pubDate=1618848000000, pubDateStr=2021-04-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1769395291980, onlineIssueDateStr=2026-01-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1769395291980, creator=13041195026, updateTime=1769395291980, updator=13041195026, issue=Issue{id=1222495713427186326, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='4', pageStart='1', pageEnd='108', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1769395290953, creator=13041195026, updateTime=1770971792201, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1229108038972534891, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1222495713427186326, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1229108038972534892, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1222495713427186326, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=14, endPage=20, ext={EN=ArticleExt(id=1222495719752192595, articleId=1222495717738926636, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Molecular Simulation Study on Effect of Nano-Al2O3 Particle on Micro Characteristics of Vegetable Insulating Oil, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

The effect of nano-Al2O3 on the microscopic properties of vegetable insulating oil was studied by molecular simulation, and its result was verified by tests. The mechanism of surface interaction between nano-Al2O3 and vegetable insulating oil molecules was analyzed, models of vegetable insulating oil before and after nano-Al2O3 modification were established. The hydrogen bond, radial distribution function (RDF) of oil molecule, and diffusion coefficient of water molecule were studied, and the thermal ageing experiment was conducted on vegetable insulating oils with different concentration of nano-Al2O3. The results show that compared with the vegetable insulating oil without modification, there are more hydrogen bonds in the modified vegetable insulating model, the peak value of RDF is greater, and the diffusion coefficient of water molecules is smaller. In the process of thermal ageing, the dielectric loss of the modified oil is smaller than that of the unmodified oil, which shows that the nano-Al2O3 modified vegetable insulating oil has excellent stability, and its thermal stability and insulation performance are enhanced.

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采用分子模拟的方法研究了纳米Al2O3对植物绝缘油微观特性的影响，并通过试验加以验证。对纳米Al2O3与植物油分子的表面相互作用机理进行了分析，建立了未改性和改性后的植物油模型，研究分析其中的氢键、油分子的径向分布函数（RDF）和水分子的扩散系数等参数，同时对不同改性浓度纳米Al2O3的植物油进行了热老化实验。结果表明：改性植物油模型中的氢键数量更多，RDF的峰值更大，水分子的扩散系数更小。热老化过程中改性油的介质损耗小于未改性油，表明纳米Al2O3改性植物绝缘油具有优良的稳定性，改性植物绝缘油的热稳定性和绝缘性能得到增强。

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孙长海（1967-），男（汉族），辽宁大连人，教授级高级工程师，主要从事智能微电网关键技术及高电压绝缘技术的研究。

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孙长海（1967-），男（汉族），辽宁大连人，教授级高级工程师，主要从事智能微电网关键技术及高电压绝缘技术的研究。

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孙长海（1967-），男（汉族），辽宁大连人，教授级高级工程师，主要从事智能微电网关键技术及高电压绝缘技术的研究。

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journalId=1149653034449285133, articleId=1222495717738926636, language=EN, label=Tab.1, caption=Fatty acid content in vegetable oil, figureFileSmall=null, figureFileBig=null, tableContent=
脂肪酸

饱和

脂肪酸

单不饱和脂肪酸双不饱和脂肪酸三不饱和脂肪酸
质量分数/%24.750.320.05.0
), ArticleFig(id=1243119747622093133, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1222495717738926636, language=CN, label=表1, caption=

植物油中脂肪酸质量分数

, figureFileSmall=null, figureFileBig=null, tableContent=
脂肪酸

饱和

脂肪酸

单不饱和脂肪酸双不饱和脂肪酸三不饱和脂肪酸
质量分数/%24.750.320.05.0
), ArticleFig(id=1243119747710173520, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1222495717738926636, language=EN, label=Tab.2, caption=System energy of （3×3） superlattice, figureFileSmall=null, figureFileBig=null, tableContent=
温度/℃EtEsEpEIEvEe
70-216 802.612-215 334.909338.161-1 805.864-195 223.624-22 226.450
90-216 655.563-215 299.080411.698-1 768.181-195 205.359-22 218.595
110-216 933.183-215424.063716.134-2 225.254-195 359.580-22 607.184
130-216 736.388-215242.044548.324-2 042.668-195 130.702-22 557.138
150-216 537.213-215228.487510.654-1 819.380-195 189.628-22 119.162
), ArticleFig(id=1243119749220122963, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1222495717738926636, language=CN, label=表2, caption=

（3×3）超晶格的体系能量

, figureFileSmall=null, figureFileBig=null, tableContent=
温度/℃EtEsEpEIEvEe
70-216 802.612-215 334.909338.161-1 805.864-195 223.624-22 226.450
90-216 655.563-215 299.080411.698-1 768.181-195 205.359-22 218.595
110-216 933.183-215424.063716.134-2 225.254-195 359.580-22 607.184
130-216 736.388-215242.044548.324-2 042.668-195 130.702-22 557.138
150-216 537.213-215228.487510.654-1 819.380-195 189.628-22 119.162
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温度/℃EtEsEpEIEvEe
70-1 161 992.769-1 159 531.410563.210-3 024.568-1 020 162.048-142 714.285
90-1 161 995.849-1 159 636.213700.547-3 060.183-1 021 343.002-142 646.888
110-1 161 912.337-1 159 660.312998.654-3 250.678-1 020 326.814-142 576.708
130-1 161 731.823-1 159 545.661802.315-2 988.477-1 020 051.652-142 669.067
150-1 161 690.080-1 159 448.435734.841-2 976.486-1 019 267.195-142 131.972
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（7×7）超晶格的体系能量

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温度/℃EtEsEpEIEvEe
70-1 161 992.769-1 159 531.410563.210-3 024.568-1 020 162.048-142 714.285
90-1 161 995.849-1 159 636.213700.547-3 060.183-1 021 343.002-142 646.888
110-1 161 912.337-1 159 660.312998.654-3 250.678-1 020 326.814-142 576.708
130-1 161 731.823-1 159 545.661802.315-2 988.477-1 020 051.652-142 669.067
150-1 161 690.080-1 159 448.435734.841-2 976.486-1 019 267.195-142 131.972
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模型氢键数量平均键长/Å
未改性植物油1262.356 339 25
改性植物油2052.282 402 36
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纳米Al2O3颗粒对植物绝缘油微观特性影响的分子模拟研究
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孙长海 , 郭佳彬 , 陈百通 , 李天明 , 鞠爽
绝缘材料 | 材料研究 2021,54(4): 14-20
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绝缘材料 | 材料研究 2021, 54(4): 14-20
纳米Al2O3颗粒对植物绝缘油微观特性影响的分子模拟研究
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孙长海, 郭佳彬, 陈百通, 李天明, 鞠爽
作者信息
  • 大连理工大学 电气工程学院，辽宁 大连 116024

    • 孙长海（1967-），男（汉族），辽宁大连人，教授级高级工程师，主要从事智能微电网关键技术及高电压绝缘技术的研究。

Molecular Simulation Study on Effect of Nano-Al2O3 Particle on Micro Characteristics of Vegetable Insulating Oil
Changhai SUN, Jiabin GUO, Baitong CHEN, Tianming LI, Shuang JU
Affiliations
  • School of Electrical Engineering, Dalian University of Technology, Dalian 116024, China
出版时间: 2021-04-20 doi: 10.16790/j.cnki.1009-9239.im.2021.04.003
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摘要
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采用分子模拟的方法研究了纳米Al2O3对植物绝缘油微观特性的影响，并通过试验加以验证。对纳米Al2O3与植物油分子的表面相互作用机理进行了分析，建立了未改性和改性后的植物油模型，研究分析其中的氢键、油分子的径向分布函数（RDF）和水分子的扩散系数等参数，同时对不同改性浓度纳米Al2O3的植物油进行了热老化实验。结果表明：改性植物油模型中的氢键数量更多，RDF的峰值更大，水分子的扩散系数更小。热老化过程中改性油的介质损耗小于未改性油，表明纳米Al2O3改性植物绝缘油具有优良的稳定性，改性植物绝缘油的热稳定性和绝缘性能得到增强。

植物油  /  纳米Al2O3  /  分子模拟

The effect of nano-Al2O3 on the microscopic properties of vegetable insulating oil was studied by molecular simulation, and its result was verified by tests. The mechanism of surface interaction between nano-Al2O3 and vegetable insulating oil molecules was analyzed, models of vegetable insulating oil before and after nano-Al2O3 modification were established. The hydrogen bond, radial distribution function (RDF) of oil molecule, and diffusion coefficient of water molecule were studied, and the thermal ageing experiment was conducted on vegetable insulating oils with different concentration of nano-Al2O3. The results show that compared with the vegetable insulating oil without modification, there are more hydrogen bonds in the modified vegetable insulating model, the peak value of RDF is greater, and the diffusion coefficient of water molecules is smaller. In the process of thermal ageing, the dielectric loss of the modified oil is smaller than that of the unmodified oil, which shows that the nano-Al2O3 modified vegetable insulating oil has excellent stability, and its thermal stability and insulation performance are enhanced.

vegetable oil  /  nano-Al2O3  /  molecular simulation
孙长海, 郭佳彬, 陈百通, 李天明, 鞠爽. 纳米Al2O3颗粒对植物绝缘油微观特性影响的分子模拟研究. 绝缘材料, 2021 , 54 (4) : 14 -20 . DOI: 10.16790/j.cnki.1009-9239.im.2021.04.003
Changhai SUN, Jiabin GUO, Baitong CHEN, Tianming LI, Shuang JU. Molecular Simulation Study on Effect of Nano-Al2O3 Particle on Micro Characteristics of Vegetable Insulating Oil[J]. Insulating Materials, 2021 , 54 (4) : 14 -20 . DOI: 10.16790/j.cnki.1009-9239.im.2021.04.003
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0 引言
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变压器是电网运行中的核心设备，其中变压器油对变压器的安全运行意义重大[1]。最常用的变压器油为矿物油，但是矿石能源日渐枯竭，而且矿物绝缘油一旦泄漏会对环境造成严重污染，植物绝缘油作为一种新型环保材料开始引起人们的关注。相较于矿物油，植物绝缘油有更高的燃点和闪点，同时具有低排碳量、无毒、易降解的生物特性，而且来源广泛，使得植物油成为矿物油的理想替代品。变压器类设备事故统计分析表明[2-3]，变压器油绝缘强度下降是发生安全事故的主要原因，因此进一步提高植物油的绝缘性能对变压器的可靠运行，进而保证电网的长期安全运行具有重要意义。
随着纳米技术的发展，纳米级无机粒子的制备取得了长足发展，国内外学者运用纳米改性技术来提高绝缘油的绝缘性能，取得了很好的成效。国外学者[4-5]发现在矿物绝缘油中加入Fe3O4纳米粒子和SiO2纳米粒子可以提高矿物油的工频击穿电压。陈牧天[6]使用纳米TiO2改性矿物油，发现其工频击穿电压与雷电冲击电压都高于纯油。马智超[7]发现纳米Al2O3与AlN可以提高绝缘油的导热性能。
以上通过纳米颗粒对矿物绝缘油进行改性的研究都取得了较好的效果，但对于纳米改性植物油的研究相对较少。钟宇翔[8]发现在植物油中加入TiO2可以提高植物油的击穿电压，但改性油的介质损耗远大于纯油。杜斌[9]研究了不同粒径的Fe3O4颗粒对植物油绝缘性能的影响，发现在一定粒径范围内Fe3O4的加入可以提高植物油及油纸的击穿电压。近年来分子模拟技术被广泛应用于绝缘材料的微观机理分析，廖瑞金等[10-11]用分子模拟来分析变压器油纸绝缘材料的微观机理，并取得了较大进展；张松[12]使用分子动力学模拟的方法研究了纳米SiO2颗粒对绝缘纸热稳定性的影响机制。
鉴于此，本研究采用分子模拟的方法，进行纳米Al2O3颗粒对植物绝缘油微观特性的影响规律，探索纳米Al2O3颗粒影响植物绝缘油性能的内在机理，从而为进一步研究纳米改性植物油提供理论支撑。
1 植物油与Al2O3的表面相互作用
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1.1 植物油仿真模型构建
植物油原油中的主要成分为甘油三酯，由1个甘油酸分子与3个脂肪酸分子脱水缩合而成[13]。植物油原油中还存在水分、磷脂、蛋白质、游离脂肪酸等其他物质，统称为杂质。为了满足绝缘油的各项性能指标要求，植物油原油需要经过复杂的工艺流程去除原油中的杂质[14]。植物绝缘油是脂肪酸甘油三酯的混合物，不同类型的脂肪酸经过脱水缩合构成的甘油三酯具有不同的理化性质和绝缘稳定性[15]。
根据文献[16]构建植物油分子模型，植物油中各类脂肪酸的质量分数见表1。植物绝缘油中的饱和脂肪酸主要为硬脂酸（C18：0）和棕榈酸（C16：0）；单不饱和脂肪酸主要为油酸（C18：1）；双不饱和脂肪酸与三不饱和脂肪酸主要为亚油酸（C18：2）和亚麻酸（C18：3）。
每个模型由10个甘油三酯分子构成，设置甘油三亚油酸酯分子2个、甘油三硬脂酸酯分子1个、甘油三棕榈酸酯分子1个、甘油三油酸酯分子5个、硬脂酸亚麻酸甘油三酯分子1个。
5种甘油三酯模型经过结构优化和退火处理后如图1所示。
1.2 Al2O3仿真模型构建
建立Al2O3的（012）晶面，并对其进行表面优化，增大表面积，分别建立（3×3）、（4×4）、（5×5）、（6×6）、（7×7）的超晶格表面模型，增大后的表面（3×3）如图2所示，之后将其周期性从2D改为3D。
1.3 复合模型的构建
用MS中的Amorphous Cell模块对植物油单胞进行建模，构建5组植物油无定型模型。所有模型密度均为0.9 g/cm3。能量最小化后用分层建模工具将植物油无定型单胞加到Al2O3的表面上。在Layer1中选择优化后的Al2O3表面，在Layer2中选择构造好的植物油无定型单胞。由于周期边界条件，无定型单胞看起来出现在表面的两侧，因此，植物油层上加入比较大的真空层，这样聚合物就好像只出现在表面层的一边。选择 Layer Details标签部分，将Layer2的真空层加到30.0。图3为（7×7）超晶格Al2O3与植物油层结构的模型，其他晶格尺寸的模型与图3基本相同。
1.4 模拟细节
在分子动力学模拟以及模型优化时，选用COMPASS力场，该力场适用于处理由有机和无机分子构成的体系。为了得到能量较低的模型，首先对5个模型进行结构优化（Geometry optimization）和退火处理（Anneal），结构优化采用Smart方法，退火过程设置5个退火循环，得到能量较低的稳定状态。根据变压器内正常运行温度及可能出现的局部升温，温度范围设定为70～150℃，相邻目标温度间隔20℃。分子动力学模拟采用NVT正则系综，时间为50 ps，积分步长为1 fs，动力学信息收集间隔为500 fs。
1.5 结果分析
1.5.1 体系的能量组成
体系的能量由约束作用能、非键相互作用能和成键相互作用能3部分组成，其中非键相互作用能起主导作用，包括静电能、氢键能以及范德华力作用能[17]。可以使用式（1）计算Al2O3与植物油分子之间的相互作用能。
EI=Et-(Es+Ep)
式（1）中：EI是植物油表面与Al2O3表面相互作用能；Et是Al2O3表面和植物油表面体系的总能量；Es是去掉植物油后Al2O3表面的能量；Ep是去掉Al2O3后植物油表面的能量。表2和表3分别为超晶格（3×3）和（7×7）的植物油与Al2O3的体系能量组成，其他组的能量变化规律与这两组趋势相同。
表2～3中，Ev和Ee分别为范德华力作用能和静电能，可以看出范德华力和静电斥力是植物油分子与Al2O3之间主要的相互作用力，其中范德华作用能（Ev）的占比接近90%，使高分子与纳米粒子能较好地结合在一起。超晶格尺寸不变时，随着温度的升高，体系整体的能量和Al2O3表面的能量比较稳定，波动较小，而植物油表面的能量波动相对较大，而且随着温度升高呈先上升后下降的趋势，进而导致植物油表面与Al2O3表面相互作用能在负方向上随着温度的升高先上升后下降。
1.5.2 体系的结合能
材料的稳定性受金属氧化物表面与聚合物表面结合能的影响很大[18]，结合能越大，材料的稳定性越好，而结合能Eb被定义为相互作用能的负值[19]，如式（2）所示。
Eb=-EI
不同体系在同一温度下的结合能如图4所示。
用MATLAB对同一温度下的结合能与晶格尺寸进行函数关系拟合，结果如式（3）～（7）所示。
y1=exp(7.0607+0.1320x)
y2=exp(7.0188+0.1414x)
y3=exp(7.3936+0.0923x)
y4=exp(7.3036+0.0978x)
y5=exp(7.0755+0.1307x)
为了更准确地分析温度对结合能的影响，对式（3）～（7）进行处理，得到式（8）～（9）。
y=exp(Tt+0.1184x)
Tt=-0.0002t2+0.0441t+4.953
式（8）～（9）中：x为超晶格的尺寸；t为温度；T（t）为温度t对结合能的影响。从式（8）～（9）和图4可以看出，温度为110℃时对结合能的贡献最大。随着晶格尺寸的增加，原子数量增多，体系的总能量负向增长，其中Al2O3表面的能量对体系的能量贡献最大。同时，随着晶格尺寸的增加，植物油分子与Al2O3的接触面积变大，界面间的相互作用能随着晶格面积负增长，结合能正向增长，体系之间的相互作用逐渐增强，说明接触面积越大体系越稳定。由此从微观层面证明了Al2O3易于掺杂到植物油中，且选用比表面积较大的Al2O3纳米粒子制得的改性油稳定性更好。同一尺寸的晶格在70～150℃，体系的结合能呈先增大后减小的趋势，其中在110℃时结合能最大。
2 纳米Al2O3改性植物油的分子模拟
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2.1 模型搭建与模拟细节
使用Material Studio中的Packing任务进行模型搭建，考虑到绝缘油中水分的存在，模型中加入了质量分数为1%的水分子，所有模型密度均设为0.9 g/cm3，所建模型如图5所示。模型中线型模型代表的是植物油分子，水分子和Al2O3用球棍模型表示。
模型构建完成后，同样要对模型进行结构优化和退火处理，以确保模型处于能量最低的稳定状态，之后进行动力学模拟。采用NVT正则系综，温度设定为70℃，模拟时间为250 ps，力场选择COMPASS，积分步长为1 fs，每隔500 fs收集一次动力学信息。
2.2 结果分析
2.2.1 氢键
聚合物分子间形成氢键时，聚合物的熔点和沸点会显著提升，聚合物的热稳定性会提高。与电负性较大的原子成键的氢原子，与邻近的电负性较大的原子之间产生的一种较强的非键作用称为氢键，其本质是强极性键上的氢核与电负性大、含孤电子对的原子之间的静电吸引[20]。一般认为氢键的键能比化学键小得多，与范德华力作用能接近。
目前氢键的定义准则分为能量准则和图形准则[21]，能量准则认为分子之间的相互作用能超过某定值时，即认为分子之间存在氢键。而图形准则认为，除了满足能量要求，两个分子之间还要满足一定的几何规律。相对于能量准则，图形准则的定义更为科学，因此本研究使用文献[22]中的图形准则定义氢键。
按照图形准则定义的氢键如图6所示，其中A为氢键受体，H为氢原子，D为氢键给体，连接H与D之间的是共价键。当受体与氢原子之间的距离rAH小于3Å，并且受体、氢原子、给体之间的夹角θ大于90°时，便认为形成了氢键[22]。
表4统计了两个模型在模拟温度下氢键的数量与平均键长。从表4可以看出，改性油模型中的氢键数量多于未改性油模型，改性油模型中氢键的平均键长小于未改性模型。
径向分布函数（RDF）可以用来分析植物油分子之间氢键的变化情况，其物理意义是距离一个分子r处出现另一个分子的概率，公式表示为式（10）。
gr=4πr2ρ2(r)
式（10）中：r是一个分子距离原点分子的距离；ρ是局部密度。
根据氢键的平均键长，本研究观察了0.20～0.26 nm的径向分布函数，结果如图7所示。从图7可以看出，两个模型油分子的RDF变化趋势基本相同，均在0.217～0.253 nm处出现了尖峰，证实了油分子中存在大量氢键。而改性油模型的RDF峰值比未改性油模型的RDF峰值大，也证明了改性油模型中的氢键数量多于未改性油模型。图8展示了Al2O3周围氢键的情况，其中氢键用蓝色虚线表示。可以看到Al2O3中的O会分别与油分子中的H形成氢键，导致改性油模型中氢键数量增多，而且改性油模型中氢键键长更小，键能更大，所以经过Al2O3纳米粒子改性的植物油模型中的相互作用得以加强，有利于提高热稳定性。
2.2.2 水分子的均方位移
水分的存在会加速绝缘老化、降低介电性能、增大介质损耗，导致绝缘寿命缩短，因此有必要研究纳米粒子改性对植物油中水分子运动的影响规律。水分子的运动状态可以由均方位移（mean square displacement，MSD）表示，其描述了t时刻所有粒子与各自初始点距离的平均值，公式如式（11）所示。
MSD=<|rt-r0|2>
式（11）中，r(t)和r(0)分别为t时刻和初始时刻粒子的位移坐标，其中“< >”表示对组内所有原子进行平均计算。
两组油模型中水分子的MSD曲线见图9。
用Matlab将MSD对时间的曲线线性拟合成y=ax+b的形式，记下斜率a。水分子的扩散系数（D）如式（12）所示。
D=16Nlimt→∞ddt∑i=1Nri(t)-ri(0)2
式（12）中：N是系统中扩散原子的数目；rit和r0t分别表示第i个原子在t时刻与初始时刻的位置向量。式中的微分近似用MSD对时间微分的比率来代替，即曲线的斜率a。因为MSD的值已经对扩散原子数N做了平均，所以式（12）可以简化为式（13）。
D=a6
根据式（3）计算得到未改性油模型中水分子的扩散系数D1为0.065，改性油模型中水分子的扩散系数D2为0.055，说明加入Al2O3纳米颗粒可以延缓水分子的扩散速度。这是因为Al2O3表面的氧原子会形成羟基，周围的水分子会通过氢键与表面羟基结合，从而对水分子有一定的束缚作用，减弱了水分子的运动。
3 试验验证
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3.1 Al2O3改性植物油的制备与稳定性分析
采用两步法制备纳米改性绝缘油，选用FR3植物油为试验用油，纳米粒子选用粒径为20 nm α-Al2O3，表面采用亲油处理。将纯油与纳米粒子放入超声分散仪中分散60 min，得到Al2O3质量浓度分别为0.02、0.04、0.06 g/L的样油。制得的改性油静置10 d后未出现团聚或沉淀的现象。
为进一步验证改性植物油的稳定性，测量了改性植物油的透射系数，透射系数是指透射光通量与入射光通量之比。选择浓度为0.04 g/L的改性油放入比色管中，用一束激光沿着水平方向径直穿过改性油，利用光功率测量仪分别测量透射光强度和入射光强度，比值即为透射系数。首先以高度为变量，测量不同高度下的透射系数变化情况，从比色管底端开始每隔5 cm测量一个值；之后以时间为变量，测量改性油的透射系数随着时间的变化情况，在72 h之内，每6 h测量一次10 cm处改性油的透射系数。测量发现改性植物油在不同高度下的透射系数基本一致，同一高度不同时刻的透射系数也基本上不变。透射系数变化越小，粒子沉降越少，表明制得的Al2O3纳米改性油稳定性良好。
3.2 Al2O3改性植物油的热老化试验
将试验样品在130℃下进行36 d的加速热老化，每6 d取一组样品测量其在工频下的介质损耗因数，得到不同浓度改性绝缘油介质损耗因数随老化时间的变化关系如图10所示。
从图10可以看出，改性植物油的介质损耗因数相较于纯油更小。在加速热老化初期（0～12 d），纯油的介质损耗因数增长速度明显快于纳米改性植物油，而Al2O3纳米粒子本身并不具有抗老化的能力，这是因为Al2O3在热老化的过程中对水分子的束缚作用，降低了脂分子的水解作用，从而提高了植物油的抗老化作用。后期改性油的介质损耗因数增速相对纯油的介质损耗因数增速较大，是因为随着时间的推移，改性油中水分扩散的程度逐渐达到纯油老化前期的程度，但整体上改性油的介质损耗因数还是小于纯油，同时发现3种浓度的改性油中纳米Al2O3浓度为0.04 g/L时抗老化效果最好。
4 结论
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通过分子模拟的方法进行了纳米Al2O3对植物绝缘油的改性研究，并用试验加以验证，具体结论如下：
（1）植物油分子与Al2O3界面间的相互作用能随着晶格面积的增加负向增长，而结合能正向增长，导致体系的稳定性越来越好。同时计算得到了结合能与温度和晶格尺寸之间的关系式，为计算Al2O3表面与植物油分子之间的结合能提供了一条便捷的途径。
（2）改性植物油和水分子中的H与Al2O3中的O形成了氢键，氢键数量增加，且氢键的平均键长更小，键能更大。因此经过Al2O3纳米粒子改性的植物油模型热稳定性得到提高。
（3）改性植物油模型中水分子的扩散系数小于未改性植物油模型，热老化过程中改性油的介质损耗因数小于纯油，表明Al2O3可以延缓水分的扩散速度，提高植物油的绝缘性能，延长植物油的使用寿命。
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doi: 10.16790/j.cnki.1009-9239.im.2021.04.003
  • 接收时间：2020-06-28
  • 首发时间：2026-01-26
  • 出版时间：2021-04-20
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  • 收稿日期：2020-06-28
  • 修回日期：2020-08-06
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    大连理工大学 电气工程学院，辽宁 大连 116024
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2021.04.003
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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