Study and Preliminary Application of the Thermochemical Equation of State of C3N4
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摘要: C3N4在超硬材料合成和光催化等领域具有广泛的应用，然而，其在高温高压下的相变和物理行为尚未完全清楚，研究其热化学状态方程十分必要。利用分解相边界及常温压缩线数据，提出了一种定量研究C3N4热化学状态方程的高精度、低成本的新方法。对C3N4的石墨相和正交相建立了三项式热化学状态方程，由此计算的诸多物理量与第一性原理计算结果及实验结果吻合良好，证明了热化学状态方程的可靠性。利用C3N4热化学状态方程，对特定温度压力下C3N4的争议相进行了初步判断。此外，将C3N4热化学状态方程加入新型富氮炸药5,5′-联四唑-1,1′-二氧二羟铵（TKX-50）的爆轰参数计算中，显著降低了TKX-50爆轰参数计算值与实验值之间的误差，为新型炸药爆轰机理研究提供了新的参考方向。Abstract: C3N4 has a wide range of applications in the synthesis of superhard materials and photocatalysis materials, but its phase transitions and physical behaviors under high pressure and high temperature conditions are not fully understood. Therefore, it is necessary to study its thermochemical equation of state. In this paper, we propose a novel, high-precision and low-cost method for quantitatively determining the equation of state of C3N4, based on decomposition phase boundary and compression line at room temperature. We constructs the equation of state for two phases of C3N4, and the corresponding physical quantities match well with first-principles calculations and experimental values, proving the reliability of the equation of state. Based on the equation of state of C3N4, we make a preliminary judgment on the phase state of the controversial points. Furthermore, this study attempts to incorporate the equation of state of C3N4 into the research on the detonation mechanism of novel nitrogen-rich explosives. It significantly reduces the long-standing errors between the calculated values and experimental values of the detonation parameters of the explosives, and provides a new reference direction for the research on the detonation parameter calculations of new explosives.
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Key words:
- C3N4 /
- thermochemical equation of state /
- phase boundary /
- nitrogen-rich explosive
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图 1 C3N4的相图[17]（圆形、正方形、菱形和三角形分别表示石墨、O-C3N4、金刚石和g-C3N4，实线表示石墨与金刚石的边界，虚线表示C3N4的分解相边界）
Figure 1. Phase diagram of C3N4[17] (Circles, squares, diamonds and triangles denote graphite, O-C3N4, diamond and g-C3N4, respectively. Thick solid line represents the boundary between graphite and diamond, and the dashed line indicates the decomposed phase boundary of C3N4.)
图 2 粒子群算法原理示意图
Figure 2. Schematic diagram of the particle swarm optimization algorithm
图 3 粒子群算法的迭代误差随迭代次数的变化
Figure 3. Variation of iteration error with iteration times in particle swarm optimization algorithm
图 4 标定的常温压缩线与实验结果的对比
Figure 4. Comparison of calculated compression lines with experimental results under room temperature
图 6 g-C3N4和O-C3N4的相边界计算结果（误差棒对应的Gibbs能误差上下限为0.50%）
Figure 6. Calculated phase boundary between g-C3N4 and O-C3N4 (The corresponding Gibbs energy error limits for the error bars are 0.50%.)
图 7 TKX-50产物的Hugoniot线：(a) D-p曲线，(b) 1 mol TKX-50炸药产物中C3N4的物质的量的变化
Figure 7. Hugoniot lines of TKX-50 detonation products: (a) D-p curves; (b) change of the molar amount of C3N4 in the products of 1 mol TKX-50 explosive
表 1 g-C3N4和O-C3N4的热化学状态方程参数
Table 1. Thermochemical equation of state parameters of g-C3N4 and O-C3N4
Material B0/GPa B1 $ {V_{{\text{0\,K}}}} $/(cm3·g−1) Eref/(kJ·mol−1) Sref/(kJ·mol−1·K−1) c1/(mm·s−1) c2/(mm·s−1) α/(cm3·g−1·K−1) g-C3N4 163.62 5.40 0.449 89.86 3.40×10−2 1.39 −1.07 4.41×10−6 O-C3N4 244.12 4.08 0.401 111.85 8.76×10−2 1.15 −0.47 4.19×10−6 
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表 2 实验和计算得到TKX-50炸药的CJ爆轰参数
Table 2. CJ parameters of TKX-50 explosives obtained by experiments and calculations
Method ρ0/(g·cm−3) DCJ/(km·s−1) pCJ/GPa TCJ/K Exp. (detonation test)[48] 1.877 9.432 Exp. (damage test)[49] 1.86 9.037 26.40 Exp. (DRZ test)[50] 1.85 9.050 35.04 Calc. ($ {V_{{\text{0\,K}}}} $) 1.85 9.783 38.20 3161.9 Calc. (95.3%$ {V_{{\text{0\,K}}}} $) 1.85 9.735 33.30 3030.9 Calc. (94.8%$ {V_{{\text{0\,K}}}} $) 1.85 9.525 32.50 2953.9 Calc. (Explo 5.05)[44] 1.877 9.698 42.40 3954 Calc. (CHEETAH 8.0)[48] 1.877 9.735 42.40 2845 Calc. (empirical code)[51] 1.877 9.650 41.90 3724
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