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HMX不同晶型热膨胀特性及相变的ReaxFF分子动力学模拟

周婷婷 黄风雷

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HMX不同晶型热膨胀特性及相变的ReaxFF分子动力学模拟

周婷婷, 黄风雷

Thermal expansion behaviors and phase transitions of HMX polymorphs via ReaxFF molecular dynamics simulations

Zhou Ting-Ting, Huang Feng-Lei
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  • HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) 晶体不同晶型对温度的响应对于深入认识含能材料在外加载荷下的感度、稳定性、 相变等具有重要意义. 采用ReaxFF-lg势函数和等温等压分子动力学 (NPT-MD) 方法, 研究了-, -和-HMX三种固态晶型在T=303503 K内的晶体结构和分子结构. 结果表明, ReaxFF-lg势函数能够合理地描述HMX晶体的热膨胀行为, 计算得到的晶体结构和热膨胀系数与实验数据比较符合. 三种晶型的线膨胀系数表明, -HMX晶体具有明显的热膨胀各向异性; -HMX晶体c轴的热膨胀特性与a, b轴略有不同; -HMX晶体三个方向的热膨胀特性基本相同. 三种晶型的体膨胀系数为-HMX -HMX HMX, 表明-HMX晶体对温度最敏感, 这可能是-HMX晶体具有更高感度的原因. 在T=443 K时, HMX晶体的晶胞参数突变, 且部分分子构型由椅式转变为船式-椅式. 采用两相热力学模型 (2PT) 得到的亥姆赫兹自由能表明, HMX晶体在 T=423443 K时发生相变. , -和-HMX晶体分别在T=303423 K, T=443503 K和T=363423 K内稳定存在.
    The response to temperature of HMX polymorph is important for understanding the sensitivity, stability, and phase transitions of energetic material. Using ReaxFF-lg with isothermal-isobaric molecular dynamics (NPT-MD) methods, the crystal and molecular structures of -, -, and -HMX crystals in a temperature range of 303-503 K and at atmospheric pressure are investigated. The calculated crystal structures and thermal expansion coefficients are in general agreements with experimental results, indicating that ReaxFF-lg potential can correctly describe the thermal expansion of HMX polymorph. The linear thermal expansion coefficients indicate that the thermal expansion of -HMX is anisotropic, the thermal expansion along c axis is slightly different from those for a and b axes for -HMX, and the thermal expansion along a, b, and c axes are almost the same for -HMX. The volume expansion coefficients for the three phases decrease in the following sequence: -HMX-HMXHMX, showing that -HMX is the most sensitive to temperature in the three crystals, which may be the reason for higher sensitivity of this phase. Sharp changes in lattice parameter and molecular conformation transformation from chair to boat-chair occur for HMX when temperature reaches 443 K. Helmholtz free energy derived from the two-phase thermodynamics (2PT) model suggests a phase transition for HMX at T=423-443 K. The , -, and -HMX crystals are stable in the temperature ranges of 303-423 K, 443-503 K, and 363-423 K, respectively.
    • 基金项目: 国家自然科学基金重点项目(批准号: 10832003)资助的课题.
    • Funds: Project supported by the Key Program of National Natural Science Foundation of China (Grant No. 10832003).
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    Peiris S M, Piermarini G J 2008 Static Compression of Energetic Materails (Berlin: Springer-Verlag) p113-115

    [2]

    Cady H H, Smith L C 1962 Studies on the Polymorphs of HMX. Los Alamos Scientific Laboratory Report, LAMS-2652 TID-4500, Los Alamos National Laboratory, Los Alamos, NM, 1962

    [3]

    Goetz F, Brill T B, Ferraro J R 1978 J. Phys. Chem. 82 1912

    [4]

    Choi C S, Boutin H P 1970 Acta. Cryst. B 26 1235

    [5]

    Main P, Cobbledick R E, Small R W H 1985 Acta. Cryst. C41 1351

    [6]

    Saw C K 2002 Kinetics of HMX and Phase Transitions: Effects of Grain Size at Elevated Temperature. In 12th International Detonation Symposium, San Diego, CA, Aug 11-16, 2002

    [7]

    Herrmann M, Engel W, Eisenreich N 1993 Zeitschrift fr Kristallographie 204 121

    [8]

    Landers A G, Brill T B 1980 J. Phys. Chem. 84 3573

    [9]

    Yoo C S, Cynn H 1999 J. Chem. Phys. 111 10229

    [10]

    Gump J C, Peiris S M 2005 J. Appl. Phys. 97 053513

    [11]

    Cui H L, Ji G F, Chen X R, Zhang Q M, Wei D Q, Zhao F 2010 J. Chem. Eng. Data. 55 3121

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    Sewell T D 1998 J. Appl. Phys. 83 4142

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    Sorescu D C, Rice B M, Thompson D L 1998 J. Phys. Chem. B 102 6692

    [14]

    Zhou T T, Liu Y, Zybin S V, Huang F L, Goddard III W A Equations of State for HMX Polymorphs and Molecular Conformation Transformations from ReaxFF-lg Molecular Dynamics. [to be published]

    [15]

    van Duin A C T, Dasgupta S, Lorant F, Goddard III W A 2001 J. Phys. Chem. A 105 9396

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    van Duin A C T, Zeiri Y, Dubnikova F, Kosloff R, Goddard III W A 2005 J. Am. Chem. Soc. 127 11053

    [17]

    Nomura K I, Kalia R K, Nakano A, Vashishta P, van Duin A C T, Goddard III W A 2007 Phys. Rev. Lett. 99 148303

    [18]

    Zhang L Z, Zybin S V, van Duin A C T, Dasgupta S, Goddard III W A, Kober E M 2009 J. Phys. Chem. A 113 10619

    [19]

    Strachan A, Kober E M, van Duin A C T, Oxgaard J, Goddard III W A 2005 J. Chem. Phys. 122 054502

    [20]

    Strachan A, van Duin A C T, Chakraborty D, Dasgupta S, Goddard III W A 2003 Phys. Rev. Lett. 91 098301

    [21]

    Zybin S V, Goddard III W A, Xu P, van Duin A C T, Thompson A P 2010 Appl. Phys. Lett. 96 081918

    [22]

    Budzien J, Thompson A P, Zybin S V 2009 J. Phys. Chem. B 113 13142

    [23]

    Liu L C, Liu Y, Zybin S V, Goddard III W A 2011 J. Phys. Chem. A 115 (40) 11016

    [24]

    Cobbledick R E, Small R W H 1974 Acta Cryst B 30 1918

    [25]

    Cady H H, Larson A C, Cromer D T 1963 Acta Cryst 16 617

    [26]

    Munday L B, Chung P W, Rice B M, Solares S D 2011 J. Phys. Chem. B 115 4378

    [27]

    Lin S T, Blanco M, Goddard III W A 2003 J. Chem. Phys. 119 11792

    [28]

    Li Y Y, Lin S T, Goddard III W A 2004 J. Am. Chem. Soc. 126 1872

    [29]

    Jang S S, Lin S T, Maiti P K, Blanco M, Goddard III W A, Shuler P, Tang Y C 2004 J. Phys. Chem. B 108 12130

    [30]

    Lin S T, Maiti P K, Goddard III W A 2005 J. Phys. Chem. B 109 8663

    [31]

    Lin S T, Maiti P K, Goddard III W A 2010 J. Phys. Chem. B 114 8191

    [32]

    Pascal T A, Abrol R, Mittal R, Wang Y, Prasadarao N V, Goddard III W A 2010 J. Biol. Chem. 285 37753

    [33]

    Smith G D, Bharadwaj R K 1999 J. Phys. Chem. B 103 3570

  • [1]

    Peiris S M, Piermarini G J 2008 Static Compression of Energetic Materails (Berlin: Springer-Verlag) p113-115

    [2]

    Cady H H, Smith L C 1962 Studies on the Polymorphs of HMX. Los Alamos Scientific Laboratory Report, LAMS-2652 TID-4500, Los Alamos National Laboratory, Los Alamos, NM, 1962

    [3]

    Goetz F, Brill T B, Ferraro J R 1978 J. Phys. Chem. 82 1912

    [4]

    Choi C S, Boutin H P 1970 Acta. Cryst. B 26 1235

    [5]

    Main P, Cobbledick R E, Small R W H 1985 Acta. Cryst. C41 1351

    [6]

    Saw C K 2002 Kinetics of HMX and Phase Transitions: Effects of Grain Size at Elevated Temperature. In 12th International Detonation Symposium, San Diego, CA, Aug 11-16, 2002

    [7]

    Herrmann M, Engel W, Eisenreich N 1993 Zeitschrift fr Kristallographie 204 121

    [8]

    Landers A G, Brill T B 1980 J. Phys. Chem. 84 3573

    [9]

    Yoo C S, Cynn H 1999 J. Chem. Phys. 111 10229

    [10]

    Gump J C, Peiris S M 2005 J. Appl. Phys. 97 053513

    [11]

    Cui H L, Ji G F, Chen X R, Zhang Q M, Wei D Q, Zhao F 2010 J. Chem. Eng. Data. 55 3121

    [12]

    Sewell T D 1998 J. Appl. Phys. 83 4142

    [13]

    Sorescu D C, Rice B M, Thompson D L 1998 J. Phys. Chem. B 102 6692

    [14]

    Zhou T T, Liu Y, Zybin S V, Huang F L, Goddard III W A Equations of State for HMX Polymorphs and Molecular Conformation Transformations from ReaxFF-lg Molecular Dynamics. [to be published]

    [15]

    van Duin A C T, Dasgupta S, Lorant F, Goddard III W A 2001 J. Phys. Chem. A 105 9396

    [16]

    van Duin A C T, Zeiri Y, Dubnikova F, Kosloff R, Goddard III W A 2005 J. Am. Chem. Soc. 127 11053

    [17]

    Nomura K I, Kalia R K, Nakano A, Vashishta P, van Duin A C T, Goddard III W A 2007 Phys. Rev. Lett. 99 148303

    [18]

    Zhang L Z, Zybin S V, van Duin A C T, Dasgupta S, Goddard III W A, Kober E M 2009 J. Phys. Chem. A 113 10619

    [19]

    Strachan A, Kober E M, van Duin A C T, Oxgaard J, Goddard III W A 2005 J. Chem. Phys. 122 054502

    [20]

    Strachan A, van Duin A C T, Chakraborty D, Dasgupta S, Goddard III W A 2003 Phys. Rev. Lett. 91 098301

    [21]

    Zybin S V, Goddard III W A, Xu P, van Duin A C T, Thompson A P 2010 Appl. Phys. Lett. 96 081918

    [22]

    Budzien J, Thompson A P, Zybin S V 2009 J. Phys. Chem. B 113 13142

    [23]

    Liu L C, Liu Y, Zybin S V, Goddard III W A 2011 J. Phys. Chem. A 115 (40) 11016

    [24]

    Cobbledick R E, Small R W H 1974 Acta Cryst B 30 1918

    [25]

    Cady H H, Larson A C, Cromer D T 1963 Acta Cryst 16 617

    [26]

    Munday L B, Chung P W, Rice B M, Solares S D 2011 J. Phys. Chem. B 115 4378

    [27]

    Lin S T, Blanco M, Goddard III W A 2003 J. Chem. Phys. 119 11792

    [28]

    Li Y Y, Lin S T, Goddard III W A 2004 J. Am. Chem. Soc. 126 1872

    [29]

    Jang S S, Lin S T, Maiti P K, Blanco M, Goddard III W A, Shuler P, Tang Y C 2004 J. Phys. Chem. B 108 12130

    [30]

    Lin S T, Maiti P K, Goddard III W A 2005 J. Phys. Chem. B 109 8663

    [31]

    Lin S T, Maiti P K, Goddard III W A 2010 J. Phys. Chem. B 114 8191

    [32]

    Pascal T A, Abrol R, Mittal R, Wang Y, Prasadarao N V, Goddard III W A 2010 J. Biol. Chem. 285 37753

    [33]

    Smith G D, Bharadwaj R K 1999 J. Phys. Chem. B 103 3570

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  • 被引次数: 0
出版历程
  • 收稿日期:  2012-06-07
  • 修回日期:  2012-07-05
  • 刊出日期:  2012-12-05

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