High Pressure Phase Transition of HMX Crystal under Non-Hydrostatic Pressure
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摘要: HMX是一种性能优良的高能炸药，在武器工业中广泛使用。目前，HMX在高压下特别是非静水压下的相变规律仍存在争议。为此，采用不同的传压介质，开展了非静水压下HMX晶体的高压拉曼实验研究。结果表明，HMX晶体分别在4.9、13.9和17.5 GPa发生了结构相变。在13.9 GPa下，HMX开始发生相Ⅱ→相Ⅲ的相变，并在一定的压力范围内两相共存；当压力为17.5 GPa时，出现另一个新相（相Ⅳ），在17.5～23.6 GPa的压力范围内出现相Ⅱ、相Ⅲ和相Ⅳ三相共存现象。HMX晶体在非静水压下的相变路径与准静水压下的相变路径完全不同，非静水压环境下的压力梯度是造成该差异的原因。Abstract: HMX is a high-energy explosive with excellent performance and is widely used in weapons. The phase transition law of HMX, especially under non-hydrostatic pressure, is controversial. In this work, a high-pressure Raman experimental study of HMX crystals under non-hydrostatic pressure was carried out using different pressure-transmitting media. The HMX crystal undergoes three phase transitions at pressures of 4.9, 13.9 and 17.5 GPa, respectively. Under the pressure of 13.9 GPa, HMX began to undergo phase transition from structure Ⅱ to structure Ⅲ, and the two phases existed simultaneously within a certain pressure range; another new phase (structure Ⅳ) began to appear from 17.5 GPa. The three-phase coexistence of structure Ⅱ, structure Ⅲ and structure Ⅳ appeared in the pressure range of 17.5−23.6 GPa. Importantly, the phase transition process of HMX crystals under non-hydrostatic pressure is completely different from the phase transition path under quasi-hydrostatic pressure, and the pressure gradient under non-hydrostatic pressure environment is the reason for the difference.
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Key words:
- HMX crystal /
- Raman spectrum /
- phase transition /
- non-hydrostatic pressure
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图 3 常温常压下β-HMX晶体的拉曼光谱
Figure 3. Raman spectrum of β-HMX crystal at atmospheric pressure and room temperature
图 4 实验1 中HMX晶体的高压拉曼光谱（0～26.1 GPa）
Figure 4. High-pressure Raman spectra of HMX crystal of Exp. 1 (0−26.1 GPa)
图 5 实验1中 HMX晶体的高压拉曼光谱（12.5～23.6 GPa）
Figure 5. High-pressure Raman spectra of HMX crystal of Exp. 1 (12.5−23.6 GPa)
图 6 实验1中压力加载前、后HMX晶体的拉曼光谱
Figure 6. Raman spectra of HMX crystals before loading and after releasing pressure of Exp. 1
图 7 实验2中HMX晶体的高压拉曼光谱（0～15.8 GPa）
Figure 7. High-pressure Raman spectra of HMX crystal of Exp. 2 (0−15.8 GPa)
图 8 实验2中HMX晶体的高压拉曼光谱（15.8～17.6 GPa）
Figure 8. High-pressure Raman spectra of HMX crystal of Exp. 2 (15.8–17.6 GPa)
图 9 高压下实验2和实验1的拉曼光谱对比
Figure 9. Comparison of Raman spectra of Exp. 2 and Exp. 1 under high pressure
表 1 拉曼波数及其归属模式
Table 1. Frequencies of Raman modes of HMX
Wavenumber/cm−1 Assignment Wavenumber/cm−1 Assignment Wavenumber/cm−1 Assignment 94 τ(ring) + γ(N–N) 717 τ(ring) + γ(NO2) 1364 ω(CH2) 127 τ(NO2) 758 γ(NO2) 1416 δ(CH2) 134 831 ν(ring) 1433 152 880 1450 176 949 ν(ring) + ρ(CH2) 1456 182 τ(ring) + γ(N–N) 962 1505 νas(NO2) 231 ν(ring) + τ(ring) 1077 1519 281 1090 1530 314 1165 1555 362 1187 1566 415 1238 νs(NO2) + νs(N–N) 2982 νs(CH2) 436 1263 2992 594 τ(ring) + γ(NO2) 1306 γ(CH2) 3027 νas(CH2) 635 1315 νs(NO2) 3036 658 1346 γ(CH2) Note: as–anti-symmetric; s–symmetric; ν–stretching; δ–deformation motion; τ–torsional motion; γ–deformations involving
one ring and one non-ring bond; ω(XY2)–wag of Y2 atoms out of XY2 plane; ρ(XY2)–rocking in XY2 plane.
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[1] FABBIANI F P A, PULHAM C R. High-pressure studies of pharmaceutical compounds and energetic materials [J]. Chemical Society Reviews, 2006, 35(10): 932–942. doi: 10.1039/b517780b [2] MCCRONE W C. Crystallographic data 36: cyclotetramethylene tetranitramine (HMX) [J]. Analytical Chemistry, 1950, 22(9): 1225–1226. doi: 10.1021/ac60045a050 [3] SHARIA O, TSYSHEVSKY R, KUKLJA M M. Surface-accelerated decomposition of δ-HMX [J]. The Journal of Physical Chemistry Letters, 2013, 4(5): 730–734. doi: 10.1021/jz302166p [4] CHOI C S, BOUTIN H P. A study of the crystal structure of β-cyclotetramethylene tetranitramine by neutron diffraction [J]. Acta Crystallographica Section B, 1970, 26(9): 1235–1240. doi: 10.1107/S0567740870003941 [5] GALLAGHER H G, MILLER J C, SHEEN D B, et al. Mechanical properties of β-HMX [J]. Chemistry Central Journal, 2015, 9: 22. doi: 10.1186/s13065-015-0091-6 [6] LI H, LI Y, BAI L F, et al. Acceleration of δ- to β-HMX-D8 phase retransformation with D2O and intergranular strain evolution in a HMX-based polymer-bonded explosive [J]. The Journal of Physical Chemistry C, 2019, 123(12): 6958–6964. doi: 10.1021/acs.jpcc.8b10002 [7] GOETZ F, BRILL T B, FERRARO J R. Pressure dependence of the Raman and infrared spectra of α-, β-, γ-, and δ- octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine [J]. The Journal of Physical Chemistry, 1978, 82(17): 1912–1917. doi: 10.1021/j100506a011 [8] GAO C, ZHANG X Y, ZHANG C C, et al. Effect of pressure gradient and new phases for 1, 3, 5-trinitrohexahydro-s-triazine (RDX) under high pressures [J]. Physical Chemistry Chemical Physics, 2018, 20(21): 14374–14383. doi: 10.1039/C8CP01192C [9] SUN X Y, WANG X Q, LIANG W T, et al. Pressure-induced conformer modifications and electronic structural changes in 1, 3, 5-triamino-2, 4, 6-trinitrobenzene (TATB) up to 20 GPa [J]. The Journal of Physical Chemistry C, 2018, 122(28): 15861–15867. doi: 10.1021/acs.jpcc.8b03323 [10] DICK J J. A comparison of the shock and static compression curves for four solid explosives [J]. Journal of Energetic Materials, 1983, 1(3): 275–286. doi: 10.1080/07370658308010622 [11] YOO C S, CYNN H. Equation of state, phase transition, decomposition of β-HMX (octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7- tetrazocine) at high pressures [J]. The Journal of Chemical Physics, 1999, 111(22): 10229–10235. doi: 10.1063/1.480341 [12] PRAVICA M, GALLEY M, KIM E, et al. A far- and mid-infrared study of HMX (octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine) under high pressure [J]. Chemical Physics Letters, 2010, 500(1): 28–34. doi: 10.1016/j.cplett.2010.09.072 [13] GAO D X, HUANG J, LIN X H, et al. Phase transitions and chemical reactions of octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine under high pressure and high temperature [J]. RSC Advances, 2019, 9(10): 5825–5833. doi: 10.1039/C8RA10638J [14] SUI Z L, SUN X Y, LIANG W T, et al. Phase confirmation and equation of state of β-HMX under 40 GPa [J]. The Journal of Physical Chemistry C, 2019, 123(50): 30121–30128. doi: 10.1021/acs.jpcc.9b09061 [15] YAN T, WANG J H, LIU Y C, et al. Growth and morphology of 1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetraazacy-clooct ane (HMX) crystal [J]. Journal of Crystal Growth, 2015, 430: 7–13. doi: 10.1016/j.jcrysgro.2015.07.031 [16] BRAND H V, RABIE R L, FUNK D J, et al. Theoretical and experimental study of the vibrational spectra of the α, β, and δ phases of octahydro-1, 3, 5, 7-tetranitro-1, 3, 5, 7-tetrazocine (HMX) [J]. The Journal of Physical Chemistry B, 2002, 106(41): 10594–10604. doi: 10.1021/jp020909z [17] LEVITAS V I, SHVEDOV L K. Low-pressure phase transformation from rhombohedral to cubic BN: experiment and theory [J]. Physical Reviow B, 2002, 65(10): 104109. doi: 10.1103/PhysRevB.65.104109 -
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