丁羟包覆层老化宏微观特性相关性及贮存寿命预估
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摘要
为了研究固体火箭发动机中丁羟包覆层的宏微观特性相关性并准确预估其材料的贮存寿命,开展了50℃、60℃、70℃和80℃温度下的加速老化试验,建立了交联密度和最大延伸率的相关性函数关系,并用对数模型、幂函数模型和指数模型研究了交联密度随贮存时间的变化规律。以交联密度为老化性能表征量,选用修正Arrhenius法预估了试样的常温贮存寿命。结果表明,α=0.3时的幂函数模型能够较好地描述丁羟包覆层交联密度的变化规律,修正Arrhenius法求得的表观活化能与温度之间具有线性关系。分别以最大延伸率下降50%时的线性函数和二次多项式对应的交联密度值作为失效判据,预估丁羟包覆层的在常温298.15K下的贮存寿命为17.38年和16.14年,结果与用最大延伸率预估的寿命具有很好的一致性,且能够满足包覆层的老化性能要求。
To study the correlation between the macroscopic and microscopic properties of the hydroxyl-terminated polybutadiene inhibitor in solid rocket motor,as well as accurately predict the storage life of the material,accelerated aging tests at 50℃,60℃,70℃ and 80℃ were carried out.The correlation functions about crosslink density and maximum elongation were built,and logarithmic model,power function model and exponential model were used to study how the crosslink density varied with storage time.The crosslink density was selected to describe the aging properties,and the modified Arrhenius method was chosen to predict the storage life of hydroxyl-terminated polybutadiene inhibitor under room temperature.The results show that the power function model withα=0.3 can describe the variation law of crosslink density well.The apparent activation energy of the aging reaction obtained by modified Arrhenius method has a linear relationship with temperature.Taking the crosslink densities as the failure criterion,which are calculated by linear equation and quadratic polynomial respectively when the maximum elongation decrease of 50%,the estimated storage lifetime of the hydroxyl-terminated polybutadiene inhibitor at 298.15 K are 17.38 years and 16.14 years,identical to that when solved with the maximum elongation.Besides,the predicted lifetime can meet the aging performance requirements of the inhibitor.
To study the correlation between the macroscopic and microscopic properties of the hydroxyl-terminated polybutadiene inhibitor in solid rocket motor,as well as accurately predict the storage life of the material,accelerated aging tests at 50℃,60℃,70℃ and 80℃ were carried out.The correlation functions about crosslink density and maximum elongation were built,and logarithmic model,power function model and exponential model were used to study how the crosslink density varied with storage time.The crosslink density was selected to describe the aging properties,and the modified Arrhenius method was chosen to predict the storage life of hydroxyl-terminated polybutadiene inhibitor under room temperature.The results show that the power function model withα=0.3 can describe the variation law of crosslink density well.The apparent activation energy of the aging reaction obtained by modified Arrhenius method has a linear relationship with temperature.Taking the crosslink densities as the failure criterion,which are calculated by linear equation and quadratic polynomial respectively when the maximum elongation decrease of 50%,the estimated storage lifetime of the hydroxyl-terminated polybutadiene inhibitor at 298.15 K are 17.38 years and 16.14 years,identical to that when solved with the maximum elongation.Besides,the predicted lifetime can meet the aging performance requirements of the inhibitor.
引文
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[19]丁世俊,王英英.HTPB贮存老化性能[J].固体火箭技术,2001,24(4):50-55.DING S J,WANG Y Y.Storage aging performance for HTPB[J].Journal of Solid Rocket Technology,2001,24(4):50-55(in Chinese).
[20]毕薇娜.天然橡胶交联密度和动态性能的研究[D].青岛:青岛科技大学,2008.BI W N.Study on the crosslink-density and dynamic properties of NR compound and vulcanizates[D].Qingdao:Qingdao University of Science and Technology,2008(in Chinese).
[21]张焱.密封用硅橡胶老化过程宏微观特性相关性[J].固体火箭技术,2014,40(4):484-487.ZHANG Y.Analysis on pertinence between macroscopical andmicrocosmic performance of silicone rubber[J].Journal of Solid Rocket Technology,2014,40(4):484-487(in Chinese).
[22]张昊,罗怀德,杜娟.线性活化能法预估推进剂贮存寿命研究[J].固体火箭技术,2002,25(2):56-58.ZHANG H,LUO H D,DU J.Linear activation energy method for predicting service life of propellant[J].Journal of Solid Rocket Technology,2002,25(2):56-58(in Chinese).
[23]张检,王海刚.氯丁橡胶的老化和寿命预测研究[J].橡塑技术与装备(塑料),2017,43(16):24-26.ZHANG J,WANG H G.Study on aging and life prediction of chloroprene rubber[J].China Rubber/Plastic Technology and Equipment(Plastics),2017,43(16):24-26(in Chinese).
[24]刘国杰,黑恩成.Arrhenius活化能理论的修正[J].大学化学,2013,28(2):77-80.LIU G J,HEI E C.The modification of Arrhenius activation energy theory[J].University Chemistry,2013,28(2):77-80(in Chinese).
[25]国防科学技术工业委员会.复合固体推进剂高温加速老化试验方法:QJ 2328A-2005[S].北京:北京航标印务中心,2006.China Commission of Science Technology and Industry for National Defense.Test method for temperature accelerated aging of composite solid propellant:QJ 2328A-2005[S].Beijing:Beijing Navigation Mark Printing Center,2006(in Chinese).
[26]盛骤,谢式千,潘承毅.概率论与数理统计[M].北京:高等教育出版社,2001.SHENG Z,XIE S Q,PAN C Y.Probability theory and mathematical statistics[M].Beijing:Higher Education Press,2001(in Chinese).
[27]邱哲明.固体火箭发动机材料与工艺[M].北京:中国宇航出版社,1995.QIU Z M.Solid rocket engine materials and technology[M].Beijing:China Aeronautic Publishing House,1995(in Chinese).
[2]侯林法.复合固体推进剂[M].北京:中国宇航出版社,1994.HOU L F.Composite solid propellant[M].Beijing:China Aeronautic Publishing House,1994(in Chinese).
[3]贾登.三元乙丙橡胶黏结界面变温力学特性及应用研究[D].南京:南京理工大学,2016.JIA D.Research of the temperature-dependent mechanical property of adhesive interface between EPDM films[D].Nanjing:Nanjing University of Science&Technology,2016(in Chinese).
[4]曹付齐,刘志成,李小换.某固体火箭发动机装药加速老化试验与贮存寿命预测[J].航空兵器,2014(4):58-61.CAO F Q,LIU Z C,LI X H.Research on accelerated aging test and storage life prediction of solid rocket motor charge[J].Aero Weaponry,2014(4):58-61(in Chinese).
[5]陈汝训.固体火箭发动机设计与研究[M].北京:中国宇航出版社,1991,460-480.CHEN R X.Design and research of solid rocket engine[M].Beijing:China Aeronautic Publishing House,1991,460-480(in Chinese).
[6]杜永强,郑坚,彭威,等.HTPB推进剂贮存老化建模及寿命预估研究综述[J].化工进展,2016,35(s2):219-224.DU Y Q,ZHENG J,PENG W,et al.Review of research of aging modeling and life prediction for HTPB propellant[J].Chemical Industry and Engineering Progress,2016,35(s2):219-224(in Chinese).
[7]CELINA M,GILLEN K T,ASSINK R A.Accelerated aging and lifetime prediction:Review of non-Arrhenius behavior due to two competing processes[J].Polymer Degradation and Stability,2005,90(3):395-404.
[8]HUANG W,DUANE L.An alternative degradation reliability modeling approach using maximum likelihood estimation[J].IEEE Transactions on Reliability,2005,54(2):310-317.
[9]张兴高.HTPB推进剂贮存老化特性及寿命预估研究[D].长沙:国防科学技术大学,2009.ZHANG X G.Study on the aging properties and storage life prediction of HTPB propellant[D].Changsha:National University of Defense Technology,2009(in Chinese).
[10]高大元,何碧,何松伟,等.Arrhenius方法的局限性讨论[J].含能材料,2006,14(2):132-135.GAO D Y,HE B,HE S W,et al.Discussion on limitation of the Arrhenius methodology[J].Chinese Journal of Energetic Materials,2006,14(2):132-135(in Chinese).
[11]杜永强,郑坚,彭威,等.基于分段老化模型的HTPB推进剂贮存寿命[J].含能材料,2016,24(10):936-940.DU Y Q,ZHENG J,PENG W,et al.Storage life of HTPBpropellant based on segmented aging model[J].Chinese Journal of Energetic Materials,2016,24(10):936-940(in Chinese).
[12]周洁,姚军,宋燕.基于分段非线性Arrhenius的贮存寿命评估方法[J].北京航空航天大学学报,2015,41(4):744-750.ZHOU J,YAO J,SONG Y.Storage life evaluation method based on segmented nonlinear Arrhenius model[J].Journal of Beijing University of Aeronautics and Astronautics,2015,41(4):744-750(in Chinese).
[13]陈海建,滕克难,李波,等.基于修正Arrhenius方法的SRM药柱储存寿命预估[J].弹箭与制导学报,2011,31(4):232-239.CHEN H J,TENG K N,LI B,et al.A research of solid rocket motor grain storage life forecast based on modified Arrhenius method[J].Journal of Projectiles,Rockets,Missiles and Guidance,2011,31(4):232-239(in Chinese).
[14]钱艺华,肖红照,赵耀洪,等.模拟变压器工作环境下的丁腈橡胶老化研究及寿命预测[J].变压器,2017,54(11):19-25.QIAN Y H,XIAO H Z,ZHAO Y H,et al.Lifetime prediction and research on aging of NBR under operating environment of transformer[J].Transformer,2017,54(11):19-25(in Chinese).
[15]ZHANG X,ZHENG J,FANG H M,et al.Surface modified graphene oxide cross-linking hydroxyl-terminated polybutadiene polyurethane:Effects on structure and properties[J].Composites Part A:Applied Science and Manufacturing,2017,103:208-218.
[16]赵菲,毕薇娜,张萍,等.用核磁共振法研究促进剂对硫磺硫化天然橡胶结构的影响[J].合成橡胶工业,2008,31(1):50-53.ZHAO F,BI W N,ZHANG P,et al.Influence of accelerators on structured natural rubber by nuclear magnetic resonance spectroscopy[J].China Synthetic Rubber Industry,2008,31(1):50-53(in Chinese).
[17]中华人民共和国航天工业部.固体发动机燃烧室内绝热、衬层材料拉伸试验方法:QJ 916-1985[S].北京:北京航标印务中心,1986.Ministry of Aerospace Industry of the People’s Republic of China.Tensile test of insulation and inhibitor materials of solid engine combustion chamber:QJ 916-1985[S].Beijing:Beijing Navigation Mark Printing Center,1986(in Chinese).
[18]中华人民共和国国家质量监督检验检疫总局.硫化橡胶或热塑性橡胶热空气加速老化和耐热试验:GB/T 3512-2001[S].北京:中国标准出版社,2002.General Administration of Quality Supervision,Inspection and Quarantine of the People’s Republic of China.Rubber,vulcanized or thermoplastic:Accelerated ageing and heat resistance tests:Air-oven method:GB/T 3512-2001[S].Beijing:China Standards Press,2002(in Chinese).
[19]丁世俊,王英英.HTPB贮存老化性能[J].固体火箭技术,2001,24(4):50-55.DING S J,WANG Y Y.Storage aging performance for HTPB[J].Journal of Solid Rocket Technology,2001,24(4):50-55(in Chinese).
[20]毕薇娜.天然橡胶交联密度和动态性能的研究[D].青岛:青岛科技大学,2008.BI W N.Study on the crosslink-density and dynamic properties of NR compound and vulcanizates[D].Qingdao:Qingdao University of Science and Technology,2008(in Chinese).
[21]张焱.密封用硅橡胶老化过程宏微观特性相关性[J].固体火箭技术,2014,40(4):484-487.ZHANG Y.Analysis on pertinence between macroscopical andmicrocosmic performance of silicone rubber[J].Journal of Solid Rocket Technology,2014,40(4):484-487(in Chinese).
[22]张昊,罗怀德,杜娟.线性活化能法预估推进剂贮存寿命研究[J].固体火箭技术,2002,25(2):56-58.ZHANG H,LUO H D,DU J.Linear activation energy method for predicting service life of propellant[J].Journal of Solid Rocket Technology,2002,25(2):56-58(in Chinese).
[23]张检,王海刚.氯丁橡胶的老化和寿命预测研究[J].橡塑技术与装备(塑料),2017,43(16):24-26.ZHANG J,WANG H G.Study on aging and life prediction of chloroprene rubber[J].China Rubber/Plastic Technology and Equipment(Plastics),2017,43(16):24-26(in Chinese).
[24]刘国杰,黑恩成.Arrhenius活化能理论的修正[J].大学化学,2013,28(2):77-80.LIU G J,HEI E C.The modification of Arrhenius activation energy theory[J].University Chemistry,2013,28(2):77-80(in Chinese).
[25]国防科学技术工业委员会.复合固体推进剂高温加速老化试验方法:QJ 2328A-2005[S].北京:北京航标印务中心,2006.China Commission of Science Technology and Industry for National Defense.Test method for temperature accelerated aging of composite solid propellant:QJ 2328A-2005[S].Beijing:Beijing Navigation Mark Printing Center,2006(in Chinese).
[26]盛骤,谢式千,潘承毅.概率论与数理统计[M].北京:高等教育出版社,2001.SHENG Z,XIE S Q,PAN C Y.Probability theory and mathematical statistics[M].Beijing:Higher Education Press,2001(in Chinese).
[27]邱哲明.固体火箭发动机材料与工艺[M].北京:中国宇航出版社,1995.QIU Z M.Solid rocket engine materials and technology[M].Beijing:China Aeronautic Publishing House,1995(in Chinese).