Influence of Ammonium Formate Content on Rheological and Thermal Decomposition Properties of On-Site Mixed Emulsion Matrix
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摘要: 为提高现场混装乳化炸药的耐高温性能，制备了4种不同甲酸铵含量的现场混装乳化炸药基质样品。采用旋转流变仪和同步热分析仪研究了4种样品的流动性、黏弹性、黏温及其热分解性能。结果表明：加入甲酸铵可以提高现场混装乳胶基质的黏度，且随着甲酸铵质量分数的增加，样品的黏度出现先增大后减小的趋势；与未添加甲酸铵的样品相比，加入甲酸铵的样品的弹性模量增大，稳定性增强；当甲酸铵的质量分数不大于9%时，在50 ℃左右的温度下，乳胶基质的黏度均能够满足泵送要求；甲酸铵的加入对乳胶基质的热分解过程没有明显影响；随着甲酸铵质量分数的增加，其外推起始分解温度、活化能、热爆炸临界温度和自加速分解温度均有所增加，现场混装乳胶基质的热稳定性和热安全性得到提升。
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关键词:
- 现场混装乳化炸药基质 /
- 甲酸铵 /
- 流变性能 /
- 热分解性能
Abstract: To enhance the heat-resistant performance of on-site mixed emulsion explosives, four kinds of on-site mixed emulsion explosive matrix samples were prepared by adding ammonium formate with different concentrations into corresponding aqueous phase system, respectively. The fluidity, viscoelasticity, viscosity-temperature, and thermal decomposition properties of the four kinds of samples were investigated through rotational rheometer and synchronous thermal analyzer. The results revealed that the addition of ammonium formate increases the viscosity of the on-site mixed emulsion matrix, and the viscosity of the four kinds of samples exhibits a trend of first increase and then decrease with the increase of ammonium formate mass fraction. Compared with the sample without ammonium formate, the addition of ammonium formate improve the elastic modulus of the emulsion matrix and enhances its stability. When the mass fraction of ammonium formate is not greater than 9%, the viscosity of the emulsion matrix at around 50 ℃ meets the pumping requirements. The addition of ammonium formate shows no significant influence on the thermal decomposition process of the emulsion matrix. However, as ammonium formate mass fraction increases, the extrapolated initial decomposition temperature, activation energy, thermal explosion critical temperature, as well as self-accelerating decomposition temperature all increase, leading to improved thermal stability and thermal safety of the on-site mixed emulsion matrix. -
表 1 乳胶基质配方
Table 1. Formulation of emulsion matrix
Samples Mass fraction/% AN SN Water Ammonium formate Engine oil Diesel Span-80 1 72 5 16 0 2.5 2.5 2 2 69 5 16 3 2.5 2.5 2 3 66 5 16 6 2.5 2.5 2 4 63 5 16 9 2.5 2.5 2 
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表 2 乳胶基质的$G'_{\mathrm{m}} $、$\gamma_{\mathrm{cr}} $与内聚力
Table 2. Emulsion matrix $G'_{\mathrm{m}} $,$\gamma_{\mathrm{cr}} $ and cohesion
Samples $G'_{\mathrm{m}} $/Pa $\gamma_{\mathrm{cr}} $/% Cohesion/Pa 1 815 4.59 37.41 2 861 4.36 37.53 3 984 4.26 41.92 4 1 010 3.94 39.79
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表 3 4种样品的热分解特征温度
Table 3. Thermal decomposition characteristic temperatures of the four kinds of samples
Samples Tonset/℃ Tp/℃ Te/℃ 1 238.36 264.83 278.35 2 245.41 266.24 285.73 3 251.76 282.42 295.08 4 256.65 282.71 296.10
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表 4 Kissger法计算得到的$E_\text{a}$和${\mathrm{lg}}\;A_{\mathrm{k}} $
Table 4. $E_\text{a} $ and ${\mathrm{lg}}\;A_{\mathrm{k}} $ calculated through Kissinger method
Samples $E_\text{a} $/(kJ·mol−1) lg Ak/(kJ·mol−1) R2 1 103.61 6.69 0.984 2 2 124.33 8.75 0.995 9 3 151.42 10.97 0.989 0 4 178.06 13.58 0.995 0
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表 5 4种样品的$T_{\mathrm{b}} $和$T_{{\mathrm{SADT}}} $
Table 5. $T_{\mathrm{b}} $ and $T_{{\mathrm{SADT}}} $ of four kinds of samples
Samples Tb/℃ TSADT/℃ 1 229.52 188.96 2 261.12 222.94 3 268.01 240.67 4 282.67 248.81
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表 6 4种样品的$\Delta {H^ \ne } $、$\Delta {S^ \ne } $和$\Delta {G^ \ne } $
Table 6. $\Delta {H^ \ne } $、 $\Delta {S^ \ne } $ and $\Delta {G^ \ne } $ of four kinds of samples
Samples ΔH≠/(kJ·mol−1) ∆S≠/(J·mol−1·K−1) ∆G≠/(kJ·mol−1) 1 99.60 −63.47 130.21 2 120.04 −24.45 132.65 3 146.94 17.63 137.44 4 173.67 67.74 137.94
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