Article(id=1210560433354838141, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210560429043085661, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.07.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1689264000000, receivedDateStr=2023-07-14, revisedDate=1700496000000, revisedDateStr=2023-11-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1766549698436, onlineDateStr=2025-12-24, pubDate=1721404800000, pubDateStr=2024-07-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766549698436, onlineIssueDateStr=2025-12-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766549698436, creator=13701087609, updateTime=1766549698436, updator=13701087609, issue=Issue{id=1210560429043085661, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='7', pageStart='1', pageEnd='142', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766549697408, creator=13701087609, updateTime=1766563951127, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620213532430860, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210560429043085661, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620213532430861, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1210560429043085661, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=36, endPage=42, ext={EN=ArticleExt(id=1210560434084647067, articleId=1210560433354838141, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=A method for improving electric strength of polyethylene by doping tetracyano-benzoquinone dimethane, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

In this paper, tetracyano-benzoquinone dimethane organic small molecules with narrow band gap were introduced, and polyethylene/tetracyano-benzoquinone dimethane composites were prepared by solution blending. The effects of doping content of tetracyano-benzoquinone dimethane on DC breakdown properties, high field conductance and trap distribution properties of the composite were investigated. The results show that the electric strength of the composite increases first and then decreases with the increase of the doping content of tetracyano-benzoquinone dimethane, the addition of tetracyano-benzoquinone dimethane increases the electric strength of polyethylene by a maximum of about 54%, and effectively decreases its conductivity. Trap distribution measurement and quantum chemical simulation confirm that tetracyano-benzoquinone dimethane introduces charge deep traps, enhances the trapping effect of charge carriers, and improves the DC electric strength of polyethylene.

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本文引入具备窄带隙的四氰基苯醌二甲烷有机小分子,通过溶液共混制备了聚乙烯/四氰基苯醌二甲烷复合材料,并考察四氰基苯醌二甲烷掺杂含量对复合材料直流击穿特性、高场电导及陷阱分布特性的影响。结果表明:复合材料的电气强度随着四氰基苯醌二甲烷掺杂含量的增加先升高后降低,四氰基苯醌二甲烷的掺入使聚乙烯的电气强度最大提高了约54%,且有效降低了电导率。陷阱分布测量与量子化学仿真证实四氰基苯醌二甲烷引入了电荷深陷阱,增强了对载流子的捕获作用,使聚乙烯的直流电气强度获得提升。

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钟振芳(1990-),女(汉族),山东莒县人,讲师,主要从事电气绝缘性能提升技术的研究。
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陈纯松(1997-),男(汉族),山东东营人,硕士生,主要从事聚乙烯介电性能提升方法的研究。

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陈纯松(1997-),男(汉族),山东东营人,硕士生,主要从事聚乙烯介电性能提升方法的研究。

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陈纯松(1997-),男(汉族),山东东营人,硕士生,主要从事聚乙烯介电性能提升方法的研究。

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基于四氰基苯醌二甲烷掺杂的聚乙烯电气强度提升方法
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陈纯松 , 王家璇 , 李逸飞 , 朱明晓 , 钟振芳
绝缘材料 | 材料研究 2024,57(7): 36-42
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绝缘材料 | 材料研究 2024, 57(7): 36-42
基于四氰基苯醌二甲烷掺杂的聚乙烯电气强度提升方法
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陈纯松, 王家璇, 李逸飞, 朱明晓, 钟振芳
作者信息
  • 中国石油大学(华东),山东 青岛 266000
  • 陈纯松(1997-),男(汉族),山东东营人,硕士生,主要从事聚乙烯介电性能提升方法的研究。

通讯作者:

钟振芳(1990-),女(汉族),山东莒县人,讲师,主要从事电气绝缘性能提升技术的研究。
A method for improving electric strength of polyethylene by doping tetracyano-benzoquinone dimethane
Chunsong CHEN, Jiaxuan WANG, Yifei LI, Mingxiao ZHU, Zhenfang ZHONG
Affiliations
  • China University of Petroleum (East China), Qingdao 266000, China
出版时间: 2024-07-20 doi: 10.16790/j.cnki.1009-9239.im.2024.07.005
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本文引入具备窄带隙的四氰基苯醌二甲烷有机小分子,通过溶液共混制备了聚乙烯/四氰基苯醌二甲烷复合材料,并考察四氰基苯醌二甲烷掺杂含量对复合材料直流击穿特性、高场电导及陷阱分布特性的影响。结果表明:复合材料的电气强度随着四氰基苯醌二甲烷掺杂含量的增加先升高后降低,四氰基苯醌二甲烷的掺入使聚乙烯的电气强度最大提高了约54%,且有效降低了电导率。陷阱分布测量与量子化学仿真证实四氰基苯醌二甲烷引入了电荷深陷阱,增强了对载流子的捕获作用,使聚乙烯的直流电气强度获得提升。

聚乙烯  /  窄带小分子掺杂  /  介电性能  /  深陷阱  /  仿真建模

In this paper, tetracyano-benzoquinone dimethane organic small molecules with narrow band gap were introduced, and polyethylene/tetracyano-benzoquinone dimethane composites were prepared by solution blending. The effects of doping content of tetracyano-benzoquinone dimethane on DC breakdown properties, high field conductance and trap distribution properties of the composite were investigated. The results show that the electric strength of the composite increases first and then decreases with the increase of the doping content of tetracyano-benzoquinone dimethane, the addition of tetracyano-benzoquinone dimethane increases the electric strength of polyethylene by a maximum of about 54%, and effectively decreases its conductivity. Trap distribution measurement and quantum chemical simulation confirm that tetracyano-benzoquinone dimethane introduces charge deep traps, enhances the trapping effect of charge carriers, and improves the DC electric strength of polyethylene.

polyethylene  /  narrow band small molecule doping  /  dielectric properties  /  deep trap  /  simulation modeling
陈纯松, 王家璇, 李逸飞, 朱明晓, 钟振芳. 基于四氰基苯醌二甲烷掺杂的聚乙烯电气强度提升方法. 绝缘材料, 2024 , 57 (7) : 36 -42 . DOI: 10.16790/j.cnki.1009-9239.im.2024.07.005
Chunsong CHEN, Jiaxuan WANG, Yifei LI, Mingxiao ZHU, Zhenfang ZHONG. A method for improving electric strength of polyethylene by doping tetracyano-benzoquinone dimethane[J]. Insulating Materials, 2024 , 57 (7) : 36 -42 . DOI: 10.16790/j.cnki.1009-9239.im.2024.07.005
聚乙烯具有优异的绝缘性能和力学性能,广泛用作电力电缆的绝缘材料[1-2]。但随着高压直流输电技术的发展,在直流电压作用下,聚乙烯内易积聚空间电荷,导致电场分布畸变,降低其电气强度且加速绝缘老化,因此,对聚乙烯聚合材料绝缘性能的提升具有重要意义。
国内外很多学者针对纳米填料掺杂提升聚乙烯的介电性能开展了研究。张晓虹等[3]研究认为掺杂无机填料引入了深陷阱,提升了聚乙烯的电老化性能,掺杂的填料捕获导带中的自由载流子,从而减弱了高能电子对分子链的冲击,使得放电通道难以形成。R J FLEMING等[4]研究了MgO纳米掺杂对LDPE空间电荷注入的影响,结果表明在高电场下LDPE与MgO的相对介电常数不同产生的深陷阱是抑制空间电荷的原因。肖春等[5]通过研究纳米掺杂聚乙烯的陷阱能级,发现不同含量的Al2O3粉末和MgO粉末均能够使LDPE的陷阱能级明显变深,纳米掺杂可以有效提高深陷阱电荷的俘获概率。YUAN C等[6]在介电聚合物中加入半导电分子填料,证明半导电分子可以通过固定自由电子并阻止空间电荷在介电聚合物中的注入,大幅提高介电聚合物的绝缘性能。需要指出的是,传统的无机填料与聚乙烯基体不兼容,在制备过程中填料容易团聚,导致电场畸变且产生较多的杂质电荷,进一步加速材料的老化,不利于高压直流(HVDC)电缆的稳定运行[7],因此探索新的聚乙烯改性方法具有重要意义。
本文引入具备窄带隙的四氰基苯醌二甲烷有机小分子,通过溶液共混与高温热压法,制备掺杂有机半导体小分子的聚乙烯绝缘薄膜,分析其直流电气强度和高场电导性能,通过等温表面电位衰减法对陷阱分布特征进行分析与探讨。
低密度聚乙烯(LDPE)颗粒,陶氏化学公司;二甲苯(纯度为99%)、有机半导体小分子7,7,8,8-四氰基苯醌二甲烷,阿拉丁化学试剂公司,上述所有化学品均直接使用,未进一步净化与提纯。
将50 mL二甲苯(二甲苯异构体+乙基苯)倒入圆底烧瓶中,加入1 g LDPE颗粒(质量比为50∶1),并加入一定量的四氰基苯醌二甲烷小分子,在95℃下通过磁力搅拌至物料完全混合溶解。混合均匀后,将混合物放入真空干燥箱中,在150℃下加热24 h。再将获得的聚乙烯聚合物样品放到热压机上,加压至15 MPa,设定温度为150℃,热压时间为30 min,制作成薄膜样品。
测量聚乙烯样品的直流电气强度,样品平均厚度为50 μm。将样品置于两个直径为13 mm的铜球状电极之间,通过线性升压法测量击穿电压(升压速率为1 kV/s),得到的电气强度数据采用双参数威布尔分布统计法进行处理与分析。
测量样品的高场电导特征,测试回路如图1所示,由高压源、测量电极、保护电阻以及高精度电流表构成,电极以及试样放在屏蔽箱中。测试前,将测试样品放在真空干燥箱内进行短路24 h处理,短路温度为60℃;测试过程中电压源从初始电压开始,升压步长为500 V,记录加压时间为5 min时电流表的数据。
采用等温表面电位衰减法可以反映聚乙烯高分子复合材料内部陷阱的分布规律[8]。根据电荷衰减的速度,可以确定聚乙烯复合绝缘材料内部陷阱捕获载流子的情况和绝缘层的特性。采用等温表面电位衰减法测量聚乙烯的陷阱分布特征,试验布置如图2所示。电位衰减采用的充电方式为电晕充电放电,在恒温台上采用正极电压通过针尖电极对薄膜样品进行电晕充电放电,恒温台温度为50℃,充电电压为6 kV,充电时间为5 min。充电完成后,利用静电电位计对试样表面的电压进行测量。聚乙烯材料样品的陷阱能级分布曲线由电位衰减曲线拟合而成,拟合公式如式(1)所示。
ET=kTlnγt
式(1)中:ET为表面陷阱能级,eV;k为玻尔兹曼常数,其值为1.38×10-23 J/K;T为绝对温度,K;γ为试图逃逸频率,s-1t为表面电位衰减的时间,s。试图逃逸频率γ可以表示为kT/h,其中h为普朗克常数,其值为6.63×10-34 J·s。
表面陷阱密度与表面电位衰减速率之间的关系如式(2)所示。
NET=εtqef0kTδLdφtdt
式(2)中:N(ET)为陷阱的密度;εL分别为试样的介电常数和厚度;qe为基本电荷量,其值为1.60×10-19 C;φ(t)为表面电位;f0为陷阱的初始占用率,此处假设为1;δ为注入电荷的深度,设为2 μm。
在等温势衰减过程中,较浅圈闭中的电荷比较深圈闭中的电荷更容易脱出。也就是说,电荷的释放时间取决于其陷阱的深度。表面电位衰减曲线可以用双指数方程拟合,如式(3)所示,然后将拟合结果代入式(2),得到陷阱的分布曲线。
φt=a1e-b1t+a2e-b2t
式(3)中:a1a2为拟合参数;b1b2分别表示深陷阱和浅陷阱的衰减时间常数。
采用电声脉冲法(PEA)测量空间电荷分布。在PEA系统中,接地电极接收到的电压信号与空间电荷密度成正比。测量所用内电极和外电极的面积分别为700 cm2和800 cm2,每个样品分别粘贴厚度为50 μm的铝箔作为电极。测量时,施加40 kV/mm电场使样品充分极化1 h,然后关闭电源并短接样品1 h,通过示波器进行空间电荷测量。观察材料的电荷积累以及消散情况,完成空间电荷与陷阱的测试,并对测试结果进行理论分析。
利用Quantum Espresso(QE)软件对纯聚乙烯(PE)和四氰基苯醌二甲烷(C12H4N4)能带结构进行仿真计算。首先进行模型的构建,采用6个C原子的主链作为1个结构单元,采用10 Å×10 Å×10 Å的晶胞得到聚乙烯的模型结构如图3(a)所示,聚乙烯k点选取为(4,4,4,0,0,0)。需要注意的是,由于四氰基苯醌二甲烷小分子是独立存在的,分子之间无相互联系,且QE计算使用的是平面波基组,为了确保计算的准确性,在构建小分子时需要采用1个足够大的晶胞与足够大的截断能,故构建了30 Å×30 Å×30 Å的晶胞,模型如图3(b)所示,计算小分子能级过程中k点取值为(1,1,1,0,0,0)。波函数能量截断能均选取60,电荷密度能量截断均选取400(截断能常用于计算每个原子周围的电子能量最大值),确保建模后小分子之间没有相互作用,且能够满足精度要求。将建立的聚乙烯模型结构进行晶格优化与自洽计算,其中小分子仅需要自洽计算,这是由于其晶胞可以满足实际要求,对得到的结果进行能带与能级的计算,计算过程中使用的赝势是PBE泛函(Perdew-Burke-Ernzerhof)——一种近似的双组分广义梯度近似密度泛函方法。
掺杂不同含量四氰基苯醌二甲烷的聚乙烯样品电气强度测试结果如图4所示。从图4可以看出,纯聚乙烯样品的电气强度为220 kV/mm,在聚乙烯中掺杂少量四氰基苯醌二甲烷时,样品的电气强度随掺杂含量的增加先增大后减小。当掺杂四氰基苯醌二甲烷质量分数为0.07%时,样品的电气强度最大,达到340 kV/mm,相比纯聚乙烯增大了约54%;继续掺杂四氰基苯醌二甲烷时,样品的电气强度开始下降;当掺杂四氰基苯醌二甲烷质量分数为0.3%时,样品的电气强度仅为180 kV/mm,比纯聚乙烯减小了约18%。
分析认为,在较低含量下,小分子极性官能团会引入电荷陷阱,导致电荷被陷阱捕获,此时电荷需要获得足够多的能量才能进行跃迁,从而提升了聚乙烯样品的击穿电压。值得注意的是,随着小分子掺杂量含量的增加,极性官能团过量时,载流子迁移率大幅提升,电荷容易在材料中自由传输到电极两端,使得电气强度降低[9-10],因此四氰基苯醌二甲烷质量分数为0.3%的样品电气强度小于纯聚乙烯样品。
图5为掺杂不同含量四氰基苯醌二甲烷的聚乙烯样品电流密度-电场强度(J-E)特性曲线。从图5可以看出,在电场强度低于15 kV/mm时,除四氰基苯醌二甲烷质量分数为0.07%的样品外,其他样品的J-E曲线斜率较小,电流密度随电场强度变化较小,同时在该电场强度下,电导电流出现一个转折点,在转折点之后J-E曲线斜率增大,意味着电流随着电场强度变大。这可以用空间电荷限制电流(SCLC)理论解释[11],在固态介质中,随着电流密度增加,电场增强效应引起载流子之间的空间电荷积累,导致空间电荷效应逐渐显现,进一步限制了载流子运输[12]。在较低电场下,即加压初期,电介质的伏安特性与欧姆定律[13],当场强上升到某一数值时,阴极注入的载流子浓度变大,由于在聚合物薄膜的禁带能隙中存在很多的局域态,也就是前面提到的陷阱,这些陷阱俘获大量的空间电荷,从而引起空间电荷限制电流,导致电流曲线出现转折,由欧姆电导区进入到空间电荷限制电流区。
掺杂四氰基苯醌二甲烷后聚乙烯样品的电流密度降低,且随掺杂含量的增加先降低后升高,当掺杂四氰基苯醌二甲烷质量分数为0.07%时,电流密度最低,且该样品转折点场强较纯聚乙烯和其他掺杂含量的样品变大。出现上述现象的原因可能是,此时引入的深陷阱密度较高[14],导致俘获载流子的能力较其他样品强,电荷入陷使得转折电压升高。
为了进一步探究样品电气强度提升的原因,通过等温表面电位衰减法测试掺杂不同含量四氰基苯醌二甲烷的聚乙烯样品陷阱分布特征,测试结果如图6图7所示。从图6可以看出,除掺杂四氰基苯醌二甲烷质量分数为0.3%的聚乙烯样品之外,其他样品的电位衰减速率明显低于纯聚乙烯。从图7可以看出,掺杂四氰基苯醌二甲烷的样品引入了新的陷阱能级,且陷阱能级均高于纯聚乙烯,这也证明四氰基苯醌二甲烷小分子在聚乙烯中引入了深陷阱[15],与图6电位衰减曲线相对应。这是由于在聚乙烯材料中引入四氰基苯醌二甲烷小分子掺杂量比较少,而小分子的禁带宽度要比纯聚乙烯窄,二者之间存在能级差,在聚乙烯带隙中引入了深陷阱。深陷阱的引入以及捕获载流子效应[16]的增强导致空间电荷在聚乙烯材料的运输变慢,影响了电荷在聚乙烯内的移动消散平衡过程,因此在电极撤销后,掺杂有机半导体小分子的聚乙烯样品电位衰减速度要明显低于纯聚乙烯。
图7还可以看出,除四氰基苯醌二甲烷掺杂质量分数为0.3%的样品以外,其他样品的深陷阱能级均为1.04~1.06 eV,且掺杂不同含量四氰基苯醌二甲烷的样品陷阱能级大小也不同。绘制深陷阱能级与样品电气强度的关系如图8所示。从图8可以看出,样品的电气强度随深陷阱能级的增大而增大。这是因为深陷阱的引入容易捕获电子,降低聚合物样品内部的载流子浓度与迁移率,削弱了电子的能量,进而减轻了电子对样品内部分子链的冲击,从而提高了电气强度[17]
测试掺杂不同含量四氰基苯醌二甲烷的样品在40 kV/mm场强下的空间电荷分布情况,结果如图9所示。从图9可以看出,掺杂不同含量的四氰基苯醌二甲烷对于空间电荷有不同程度的抑制作用,效果最好的是掺杂四氰基苯醌二甲烷质量分数为0.07%的样品,与前面击穿测试结果相符。
电场作用于纯聚乙烯时,由于大量的晶体粒子导致样品表面电位分布不均,陷阱深度较浅,电极注入样品的电荷随电场流入两极,形成大量的异极性电荷积聚在电极附近,异极性电荷的产生对电场起到一定的加强作用,因而造成试样中积累大量的空间电荷;而在掺杂四氰基苯醌二甲烷的样品中,由于掺杂的四氰基苯醌二甲烷为纳米小颗粒,小分子的存在引入大量的深陷阱,当电荷注入时,大部分电荷会被深陷阱捕获[16],被捕获的电荷留存于电极表面,形成同极性电荷,从而削弱电极的电场,形成电极屏蔽层,在电荷输运过程中载流子容易与深陷阱处的电荷复合,因此表面电荷量较少。
通过前述分析可以看出,空间电荷分布与陷阱分布存在关联性,含深陷阱的样品倾向于产生较低的空间电荷密度。
利用QE软件分别仿真得到聚乙烯能带和四氰基苯醌二甲烷能级结果如图10图11所示。由于PBE密度泛函存在过度屏蔽(over-shielding)的问题,导致计算得到的能带宽度变窄[18],能带间隔拉近,使计算得到的能带比实际略窄。
图10图11可以看出,聚乙烯的能带约为7.0 eV,而四氰基苯醌二甲烷的能级为1.423 8 eV。四氰基苯醌二甲烷小分子和聚乙烯中的空穴形成复合中心,这是引入新的陷阱能级的原因。分子轨道(MOs)是由原子轨道之间的相互杂化作用产生的,描述了原子轨道中电子的波函数特征。通过结合分子中每个原子的原子和杂化轨道的过程,以及自洽场(SCF)方法获得了分子轨道,如图11(b)和(c)所示MOs在LUMO和HOMO位置的分布表明所有的MOs都沿着氰基分布。因此,电子和空穴在跃迁到上层能级时会遇到阻碍,导致电子在该区域相对稳定,很容易被捕获而不能自由移动。表明引入小分子氰基后,电子被吸引并积聚在一起,从而减轻了聚乙烯主链受到的电子冲击。由于带隙的变窄会导致更多的载流子被捕获到新引入的深陷阱中,进而限制载流子的移动,将载流子的能量以一种相对安全的形式释放,从而减轻其对聚乙烯分子链的冲击,不易形成放电轨道,从而提升了样品的电气强度和降低了电导率。
本文制备了聚乙烯/四氰基苯醌二甲烷复合材料,并对其电气强度、高场电导及陷阱分布特征进行测试,得到如下结论:
(1)掺杂四氰基苯醌二甲烷后聚乙烯材料的电气强度提升、电导率降低,且改性效果随掺杂含量的增加先升高后降低,其中掺杂四氰基苯醌二甲烷质量分数为0.07%的样品电气强度较纯聚乙烯提升了约54%。
(2)掺杂四氰基苯醌二甲烷后在聚乙烯内引入了电荷深陷阱,深陷阱可以捕获导带上的载流子,减少载流子密度。
(3)利用DFT理论对聚乙烯和小分子进行建模仿真,发现四氰基苯醌二甲烷的带隙明显低于聚乙烯能带宽度,聚乙烯导带内自由电荷迁移时易被四氰基苯醌二甲烷捕获,形成电荷深陷阱,进而提升了聚乙烯的绝缘性能。
  • 国家自然基金资助项目(52007198)
  • 山东省自然科学基金资助项目(ZR2021ME027)
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2024年第57卷第7期
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doi: 10.16790/j.cnki.1009-9239.im.2024.07.005
  • 接收时间:2023-07-14
  • 首发时间:2025-12-24
  • 出版时间:2024-07-20
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  • 收稿日期:2023-07-14
  • 修回日期:2023-11-21
基金
国家自然基金资助项目(52007198)
山东省自然科学基金资助项目(ZR2021ME027)
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    中国石油大学(华东),山东 青岛 266000

通讯作者:

钟振芳(1990-),女(汉族),山东莒县人,讲师,主要从事电气绝缘性能提升技术的研究。
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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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