Article(id=1198662250547479078, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2023.01.005, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1646668800000, receivedDateStr=2022-03-08, revisedDate=1650297600000, revisedDateStr=2022-04-19, acceptedDate=null, acceptedDateStr=null, onlineDate=1763712950597, onlineDateStr=2025-11-21, pubDate=1674144000000, pubDateStr=2023-01-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1763712950597, onlineIssueDateStr=2025-11-21, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1763712950597, creator=13701087609, updateTime=1763712950597, updator=13701087609, issue=Issue{id=1198662245069713420, tenantId=1146029695717560320, journalId=1149653034449285133, year='2023', volume='56', issue='1', pageStart='1', pageEnd='114', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1763712949292, creator=13701087609, updateTime=1766563309216, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210617521154159057, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210617521154159058, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1198662245069713420, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=23, endPage=28, ext={EN=ArticleExt(id=1198662251046601268, articleId=1198662250547479078, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Effects of thermal oxygen ageing on properties of irradiated EPDM sealing materials and life assessment, columnId=1190369066675179686, journalTitle=Insulating Materials, columnName=Material Research, runingTitle=null, highlight=null, articleAbstract=

The effect of thermal oxygen ageing on the properties of irradiated ethylene propylene diene rubber (EPDM) materials were analyzed, and its theoretical service life was evaluated by analyzing the change rule of compression permanent deformation rate with time. The results show that with the increase of ageing time and ageing temperature, the irradiated EPDM is aged more and more serious, the carbonyl content becomes higher and higher, and the compression set and compression stress relaxation become greater and greater. The SEM results show that the EPDM degrade seriously during ageing process. According to Arrhenius equation, the theoretical life of the irradiated EPDM is 7.58 years at 50℃.

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研究了热氧老化对辐照后三元乙丙橡胶(EPDM)材料性能的影响,并通过分析压缩永久变形率随时间的变化规律,对其理论使用寿命进行评估。结果表明:随着老化时间不断增加与老化温度不断升高,辐照后的EPDM老化越来越严重,羰基含量越来越高,压缩永久变形与压缩应力松弛越来越大;扫描电镜结果表明,老化过程中EPDM降解严重;利用阿伦尼乌斯方程计算得出,辐照后的EPDM在50℃条件下的理论寿命为7.58年。

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李建喜(1983-),男(汉族),江苏太仓人,高级工程师,博士,研究方向为橡塑材料的改性与老化寿命评估。
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周城(1989-),男(汉族),山东泰安人,工程师,博士,研究方向为橡塑材料的改性与老化寿命评估。

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热氧老化对辐照三元乙丙橡胶密封材料性能影响及寿命评估
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周城 1 , 陈夏 1 , 樊亚勤 2 , 金凯峰 1 , 李建喜 1
绝缘材料 | 材料研究 2023,56(1): 23-28
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绝缘材料 | 材料研究 2023, 56(1): 23-28
热氧老化对辐照三元乙丙橡胶密封材料性能影响及寿命评估
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周城1, 陈夏1, 樊亚勤2, 金凯峰1, 李建喜1
作者信息
  • 1中广核三角洲(太仓)检测技术有限公司,江苏 太仓 215400
  • 2中广核高新核材科技(苏州)有限公司,江苏 太仓 215400
  • 周城(1989-),男(汉族),山东泰安人,工程师,博士,研究方向为橡塑材料的改性与老化寿命评估。

通讯作者:

李建喜(1983-),男(汉族),江苏太仓人,高级工程师,博士,研究方向为橡塑材料的改性与老化寿命评估。
Effects of thermal oxygen ageing on properties of irradiated EPDM sealing materials and life assessment
Cheng ZHOU1, Xia CHEN1, Yaqin FAN2, Kaifeng JIN1, Jianxi LI1
Affiliations
  • 1CGN-DELTA (Taicang) Testing Technology Co., Ltd., Taicang 215400, China
  • 2CGN Advanced Materials Technology (Suzhou) Co., Ltd., Taicang 215400, China
出版时间: 2023-01-20 doi: 10.16790/j.cnki.1009-9239.im.2023.01.005
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研究了热氧老化对辐照后三元乙丙橡胶(EPDM)材料性能的影响,并通过分析压缩永久变形率随时间的变化规律,对其理论使用寿命进行评估。结果表明:随着老化时间不断增加与老化温度不断升高,辐照后的EPDM老化越来越严重,羰基含量越来越高,压缩永久变形与压缩应力松弛越来越大;扫描电镜结果表明,老化过程中EPDM降解严重;利用阿伦尼乌斯方程计算得出,辐照后的EPDM在50℃条件下的理论寿命为7.58年。

三元乙丙橡胶  /  热氧-辐照老化  /  压缩永久变形  /  寿命评估

The effect of thermal oxygen ageing on the properties of irradiated ethylene propylene diene rubber (EPDM) materials were analyzed, and its theoretical service life was evaluated by analyzing the change rule of compression permanent deformation rate with time. The results show that with the increase of ageing time and ageing temperature, the irradiated EPDM is aged more and more serious, the carbonyl content becomes higher and higher, and the compression set and compression stress relaxation become greater and greater. The SEM results show that the EPDM degrade seriously during ageing process. According to Arrhenius equation, the theoretical life of the irradiated EPDM is 7.58 years at 50℃.

EPDM  /  thermal oxygen-irradiation ageing  /  compression set  /  life assessment
周城, 陈夏, 樊亚勤, 金凯峰, 李建喜. 热氧老化对辐照三元乙丙橡胶密封材料性能影响及寿命评估. 绝缘材料, 2023 , 56 (1) : 23 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2023.01.005
Cheng ZHOU, Xia CHEN, Yaqin FAN, Kaifeng JIN, Jianxi LI. Effects of thermal oxygen ageing on properties of irradiated EPDM sealing materials and life assessment[J]. Insulating Materials, 2023 , 56 (1) : 23 -28 . DOI: 10.16790/j.cnki.1009-9239.im.2023.01.005
核电作为一种安全、低碳、高效、可大规模利用的能源,具有高效和二氧化碳零排放的优点,对优化能源结构、应对气候变化、建设生态文明等具有重要作用[1]。核电的快速发展对橡胶类高性能密封件(圈)的性能提出了更高的要求,尤其是材料自身的耐辐照、耐老化性能备受关注[2-3]
三元乙丙橡胶(EPDM)具有优异的力学性能和耐热耐久、耐辐照、耐腐蚀性以及良好的电气绝缘、化学稳定性,且价格低廉,在核电站密封材料中备受青睐[4-7]。然而,EPDM密封圈作为一种饱和碳链橡胶,容易受到高温高热、氧、辐照、机械应力、化学试剂等因素的影响,最终导致密封性能、力学性能等失效[8-10]。例如,2017年某核电站主泵停车密封失效,经分析发现是EPDM材质O型圈部分失效导致[11];2018年某核电站主泵径向止推轴承壳体的通风孔漏水,经分析发现是EPDM材质O型圈接触了有机溶剂发生溶胀以及材料老化导致[12]。因此,研究EPDM基密封材料的老化状态及其寿命评估对核电站安全运行、产品验收等方面具有十分重要的借鉴及指导意义。
近年来,对于EPDM材料或产品老化状态及寿命评估的案例有很多[9,13-20],例如,张凯等[13]通过研究不同老化温度和时间下EPDM材质O型圈压缩永久变形的变化规律,得到了密封圈失效时间与温度的关系式,并通过计算得到25℃下该产品能够使用17.8年左右。A KMMLING等[9]对EPDM密封圈在不同温度下进行了长达5年的老化状态研究,以压缩永久变形保留率降到70%作为寿命终点,计算得到该材料在75℃下的寿命为50年。F L LAY[19]研究了热氧以及辐照老化对EPDM密封圈性能的影响,并模拟了该产品在使用19年以及32年后性能的变化规律。然而,对于EPDM的寿命预测及老化状态评估主要是通过研究热氧老化、辐照老化等单一因素进行;由于长时间热氧和辐照共同老化过程存在老化周期长、市场设备少、成本高等因素的影响,关于热氧老化以及辐照老化的共同作用对EPDM老化状态的影响及寿命预测的研究较少。
本文研究热氧老化对辐照老化后EPDM密封材料性能的影响,利用其性能变化规律与老化因素之间的关系及阿伦尼乌斯方程建立寿命预测方程,预测该材料在不同温度下的使用寿命,以期能够尽量模拟热氧与辐照作用对材料性能的影响,并为材料的老化评估与寿命预测提供借鉴。
选用中广核高新核材科技(苏州)有限公司的EPDM密封材料进行研究,实验样品均为未辐照且未老化的样品。首先,对EPDM样品进行500 kGy的辐照(剂量率为4 kGy/h),辐照完成后分别在135、105、90℃下进行长时间老化,定期取样进行性能测试。
采用德国布鲁克公司的TENSOR II型傅里叶红外光谱分析仪进行微观结构表征,采用反射模式,分辨率为4 cm-1,扫描范围为4 000~500 cm-1;采用荷兰飞纳公司的Phenomenon Pro型扫描电子显微镜对老化后样品表面进行观测,样品在真空下喷金处理;采用扬州昌哲试验机械有限公司的CZ-3008型压缩应力松弛仪,按照GB/T 7759.1—2015对材料进行压缩永久变形测试,按照GB/T 1685—2008对材料进行压缩应力松弛测试。
老化过程中由于大分子链段的断裂以及氧化作用,材料内部/表面会产生许多小分子物质,因此对不同温度下老化不同时间的EPDM表面进行红外光谱测试,结果如图1所示。图1中2 920、2 850 cm-1处是主链甲基的非对称及对称伸缩振动峰,1 460 cm-1以及1 380 cm-1处是亚甲基的伸缩振动峰[4,8,21]。从图1可以看出,老化后各样品在1 730 cm-1处出现了羰基的吸收峰,在3 100~3 500 cm-1处出现了羟基的吸收峰,且随着老化时间增加,两峰的强度均越来越大,说明随着老化时间的增加,EPDM老化越严重[21-22]
作为密封用材料除了具有良好的力学性能外,还必须具有良好的耐压缩永久变形性,确保密封性能。分别对辐照-热氧老化后的EPDM进行周期取样及压缩永久变形测试,结果如图2所示。从图2可以看出,材料的压缩永久变形随老化时间增加呈增大趋势,老化温度越高,该现象越明显。这主要是由于辐照以及热氧作用导致材料发生老化,硬度增大,链段之间滑移受到影响,材料回弹性下降[9,19,23]。老化过程中,EPDM主链断裂产生烷基/烷氧基自由基,并进一步与链段上其他氢原子反应,导致生成更多的自由基或交联结构,以此循环往复,材料逐渐老化[4,21]。在后续对EPDM密封材料的寿命评估预测中,将通过该部分相关数据进行计算。
应力松弛是在恒定的温度和应变条件下,材料内部的应力随着时间增加而不断衰减的现象,其本质是分子链段在受力过程中沿着外力方向不断运动,内部分子链发生重排,以减小材料内部应力的过程。EPDM作为一种弹性体,具有明显的应力松弛现象[24-26]图3为老化后EPDM的压缩应力松弛保留率随老化时间的变化曲线。
图3可以看出,随着老化温度升高,应力松弛保留率下降的幅度增大,这是因为老化温度越高,材料老化越严重,老化过程中链段的运动越剧烈,分子间的滑移越大,应力松弛越快,因此应力松弛保留率越小。
为了更加形象地描述EPDM在老化过程中的变化,采用扫描电镜对不同老化条件下的样品进行分析测试。由于样品的老化过程基本一致,因此未对所有样品进行测试,仅选取了部分代表性的样品。图4为不同温度下老化不同时间后EPDM样品的形貌图,图5为通过扫描电镜元素分析得到的不同老化时间下EPDM样品表面氧元素含量。从图4可以看出,未老化的EPDM表面比较光滑,无明显缺陷;随着老化时间不断延长,材料表面逐渐出现大小不一且形状不同的颗粒,这是因为经过辐照与热氧老化后,材料内部助剂向表面迁移、扩散,同时伴随着自身的断链,所以表面越来越粗糙[23,27]。从图5可以看出,随着老化时间增加,材料表面的氧元素含量越来越高。105℃老化后,材料表面的氧元素含量由未老化时的19.0%升高至26.3%,说明材料发生了老化。这是因为辐照及高温老化作用导致EPDM生成一系列自由基,在氧气参与下产生了一系列的过氧化氢水合物、烷基/烷氧基自由基以及羟基自由基等小分子成分,久而久之导致材料含氧量不断升高。
为了更加形象地表征样品在老化过程中的状态变化,对不同老化时间的样品进行白度测试,结果如图6所示。从图6可以看出,随着老化时间增加,样品的白度逐渐下降,同时可以发现,温度越高,样品白度的下降趋势越明显。这是因为在老化过程中材料表面生成了大量的生色基团,如羰基、酯基等,随着老化时间进一步增加以及老化温度升高,样品的分子链氧化降解加剧,样品中生色基团浓度逐渐增大,白度也越来越低[28-29]
EPDM在受到辐照以后,其内部的部分分子链段断裂,生成部分自由基,在热氧的持续作用下,老化进一步加剧。简而言之,其老化机理主要是氧气参与下自由基之间的不断反应,如图7所示[21,30-33]:在EPDM材料老化过程中,首先会产生一系列的过氧化氢水合物、烷基/烷氧基自由基以及羟基自由基等小分子成分;然后,链段被氧化、分解,继续形成较高浓度的过氧化氢水合物,进一步产生大量的自由基;最后,自由基捕获其他链段上的氢原子,继续生成其他的过氧化氢水合物和自由基。众所周知,高聚物断链会导致材料的强度等性能下降,而交联则会导致材料硬化,这对密封材料的使用是不利的;随着老化进行,以上过程重复发生,最终导致材料失效。
为了更好地了解核电用密封件材料的性能及使用寿命,为其维修、更换提供一定的参考依据,本研究利用阿伦尼乌斯方程计算EPDM材料的理论使用寿命。由图2可知,EPDM材料经过辐照老化以及在90、105、135℃下老化后,其压缩永久变形在50%时对应的老化时间分别为4 024、2 100、363 h。根据GB/T 20028—2005[34],高分子材料的老化性能指标与老化温度之间符合阿伦尼乌斯方程,经对数变化以后得到式(1)所示方程。
lnti=ERTi+B
式(1)中:ti为达到某一性能时所用时间;E为活化能;R为摩尔气体常数;Ti为温度;B为常数。
以每个老化温度达到临界老化终点时的对数lnti与相应的测试温度的热力学温度的倒数1/T做图并拟合,拟合后曲线如图8所示。结合图8计算可知,本文研究的EPDM密封材料在50℃下且经过500 kGy辐照后,其理论上可以使用7.58年。
(1)热氧-辐照老化导致EPDM材料发生降解,随老化时间增加与老化温度升高,材料红外光谱中的羰基峰越来越明显,同时压缩永久变形与压缩应力松弛增加,宏观表现为密封性能逐渐失效。
(2)利用压缩永久变形与老化时间的规律,通过阿伦尼乌斯方程计算得到该EPDM材料经过500 kGy辐照后,当环境温度为50℃时的理论使用寿命为7.58年。
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doi: 10.16790/j.cnki.1009-9239.im.2023.01.005
  • 接收时间:2022-03-08
  • 首发时间:2025-11-21
  • 出版时间:2023-01-20
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  • 收稿日期:2022-03-08
  • 修回日期:2022-04-19
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    1中广核三角洲(太仓)检测技术有限公司,江苏 太仓 215400
    2中广核高新核材科技(苏州)有限公司,江苏 太仓 215400

通讯作者:

李建喜(1983-),男(汉族),江苏太仓人,高级工程师,博士,研究方向为橡塑材料的改性与老化寿命评估。
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2种不同金属材料的力学参数

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Percentage of
total species (%)

Genus
种数
Number of
species
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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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