Influence of physical properties of ammonium nitrate on the detonation behaviour of ANFO

In order to obtain a better understanding of the non-ideal detonation behaviour of ammonium nitrate based explosives, detonation velocities of ANFO (ammonium nitrate and fuel oil) prepared with different kinds of ammonium nitrate (AN) were measured in steel tubes. In this series of test six kinds of AN were used and the influence of the pore diameter, the pore volume and the particle diameter of the AN particle on the detonation velocity of ANFO was investigated.

It was found that the pore diameter and the pore volume had a strong influence on the detonation velocities of ANFO. In the case of ANFO samples which were prepared with AN that had the same pore diameter and the pore volume, when tested the highest detonation velocity (3.85 km/s) was observed when the smallest particle diameter (<0.85 mm) was used. This value corresponded to 75% of the ideal detonation velocity, which was theoretically predicted by the CHEETAH code with the JCZ3-EOS.

The 12 months aging showed the change of the detonation velocities of ANFO and the reaction of ANFO was influenced both by the physical and the chemical properties of AN particles and oil during the storage period.     

农用改性硝酸铵拒爆机理及工业化可行性研究

对农用硝铵作改性处理,通过筛选和优化实验确定了改性硝酸铵配方。结果表明,当硝酸铵中添加3%的改性剂GXJ1,10%的改性剂GXJ2时,产品在1mm铁皮管约束下的雷管感度试验条件下具有拒爆特性。改性硝酸铵总养分与普通硝酸铵相当,并且颗粒强度高,不易粉化、结块和吸潮,具有优良的肥料品质。同时还利用X射线衍射分析、扫描电子显微镜分析对改性硝铵的拒爆机理作初步探讨。最终,建立了改性硝酸铵的脱水性能、流动性能、凝固性能、颗粒强度的评价方法,并进行了工业化可行性研究。     

Detonation characteristics of ammonium nitrate and activated carbon mixtures

To better understand the detonation characteristics of ammonium nitrate (AN) and activated carbon (AC) mixtures, steel tube tests were carried out for AN/AC mixtures of various compositions and different forms of AN (powdered, prilled, phase stabilized and granular), and the detonation velocity was measured. The powdered AN/AC mixtures gave higher detonation velocities than the other AN forms. For all the AN/AC mixtures, the experimentally observed detonation velocities at each loading density were far below the theoretically predicted values calculated by the CHEETAH code based on thermohydrodynamics, exhibiting so-called non-ideal detonation. The lowest detonation velocity of powdered AN/AC mixtures was obtained as D=1.25 km/s for an AC content of 0.1 wt%. This was considered to be close to the critical condition for stable detonation.     

无机酸对硝酸铵热稳定性影响的研究

为了研究硫酸、盐酸两种无机酸对含能材料硝酸铵热稳定性的影响,使用绝热加速量热仪ARC和微量量热仪C80,对纯硝酸铵及硝酸铵和硫酸、盐酸的混合物进行了热分析实验并研究各种样品在恒温以及升温条件下的吸、放热特性。根据化学反应动力学和热力学理论,确定了硝酸铵及其与无机酸的混合物发生放热分解反应的反应动力学参数和热力学参数。基于Semenov热爆炸模型,计算并比较了各样品标准包装的自加速分解反应温度。     

敞开气氛中硝酸铵热分解过程危险特性的实验研究

利用差热分析仪分析和研究了敞开气氛中硝酸铵的热分解过程，通过在硝酸铵样品中加入酸性物质、KCl、有机物等各种杂质，研究硝酸铵热分解过程的影响因素。结果表明，在敞开气氛中，酸性物质和KCl对硝酸铵热分解过程具有催化作用，有机物会降低硝酸铵的热稳定性，研究结论可以为解决硝酸铵的生产、储存和运输过程中的安全问题提供重要参考。     

硝酸及氯离子对高温硝酸铵水溶液热危险性的影响研究

国内外学者对硝酸铵的危险性进行了大量的研究,而对其水溶液的危险性至今开展不多。笔者采用差示扫描量热仪(DSC)及全自动反应量热仪(RC1e)对高温状态下的硝酸铵水溶液的热分解危险性、杂质离子对其稳定性的影响进行了研究。纯硝酸铵和90%硝酸铵水溶液的DSC实验表明,90%硝酸铵溶液和分析纯硝酸铵具有相似的热爆炸危险;90%硝酸铵水溶液在140~180℃之间的RC1e试验表明:硝酸或氯离子单独存在时,对硝酸铵分解都有不同程度的抑制作用,而同时存在时则大大降低体系的热稳定性。该结果对保障硝酸铵在生产、使用过程中的安全具有重要的参考价值。     

Investigation of ammonium nitrate based emulsion ignition characteristic

This paper presents an analysis of the observed ignition behaviors of ammonium nitrate (AN) and emulsion explosives (EE). Pure AN and EE locally ignited by a heat source do not undergo sustained combustion when the pressure is lower than some threshold value usually called the Minimum Burning Pressure (MBP). A reason for pure AN's and EE's incapable of burning was suggested, and the roles of sample water, inorganic salts, oil phase, and sensitizer were discussed. Accelerating rate calorimeter (ARC) was used to study the thermal stability of EE and AN. The results also showed that MBP is of vital importance and useful for the manufacture and application of AN and EE in terms of accident prevention.     

石墨烯对RDX机械感度及爆轰性能的影响

炸药添加剂对改善单质炸药安全与能量特性有重要作用。为研究纳米微颗粒石墨烯(Gr)对黑索今(RDX)热性能、机械感度及爆轰性能的影响，设计不同比例含量的Gr/RDX混合药剂配方，并对其进行差热、撞击感度、摩擦感度、爆速及钢凹深度的测试分析。结果表明:与纯RDX相比，Gr/RDX混合药剂DSC（差示扫描量热）曲线分解峰宽变窄、峰形更尖锐，Gr加速RDX的放热过程；Gr/RDX混合药剂撞击感度与摩擦感度随Gr比例含量的增加呈先降低后升高的趋势，少量Gr可使RDX变得钝感，含量增加时，敏化作用逐渐表现出来；Gr/RDX混合药剂爆速与钢凹深度随Gr比例含量的增加而降低；Gr含量为1%时可显著降低RDX的机械感度，而能量基本不衰减。Gr可作为RDX功能添加剂，在确保能量输出的同时，可降低机械感度、提高安全性。     

提高铵梯炸药生产安全性的技术途径

本采用粗制TNT代替军工TNT应用于工业炸药中,不仅可减少环境的污染,而且可提高生产安全性。实验证明由粗制TNT制成的炸药,其性能可满足使用要求。     

二溴海因危险性试验研究

为评价二溴海因(简称DBDMH)在使用、储运过程中的危险性,采用75℃热稳定性试验对二溴海因在高热条件下的稳定性进行了研究,采用C600微量热法测试了二溴海因的放热起始温度、分解热,并依据《联合国关于危险货物运输的建议书-试验和标准手册》对其爆炸性进行了筛选,通过固体氧化性试验和家兔皮肤刺激性/腐蚀性试验分别对二溴海因的氧化性和皮肤刺激性进行了测试。结果表明:二溴海因在75℃热稳定性试验过程中没有出现着火或爆炸,未出现自加热迹象,不属于太不稳定不能运输的物质;其分解反应只有一步,起始反应温度大约为157℃,分解热为384.8J/g,不属于爆炸品;二溴海因具有氧化性,根据《联合国关于危险货物运输的建议书-规章范本》其包装级别为Ⅱ级;在家兔皮肤刺激性/腐蚀性试验中未见不可逆损伤,对皮肤具有强刺激性。     

HMX基钝感传爆药制备技术

为获得性能更佳的钝感传爆药,以奥克托今(HMX)原料为基础,采用溶剂-非溶剂重结晶技术,并辅以超声喷雾工艺制备细化HMX,同时,通过试验方法制备以丙烯酸酯橡胶(ACM)、F2602和Viton A等3种材料为黏结剂的包覆HMX,并分别测试分析其安全性.结果表明:经过细化后,HMX的热稳定性和热敏感性降低,而撞击安定性则...     

TA-FTIR/MS用于硝酸铵及其混合物的热化学行为研究

为评价物料混合对危险化学品热化学行为的影响,采用热分析-红外/质谱联用技术(TA-FTIR/MS)研究硝酸铵、柠檬酸和蔗糖的混合物的热化学行为。通过对硝酸铵及其混合物的分解温度和分解过程中逸出气体的分析,发现硝酸铵、柠檬酸和蔗糖的混合物热分解温度分别降低至135℃和153℃,而硝酸铵与甲基纤维素的混合物分解温度与硝酸铵基本相同为201℃,且各混合体系的气相分解产物均有氮氧化物(NOX),H2O和CO2。结果表明,混合物受热后其中的硝酸铵首先分解为硝酸和氨气;酸性物质和还原性物质由于对硝酸的分解反应有催化作用,使得混合物的热稳定性下降。     

Effects of typical additives on the thermal stability of ammonium peroxydisulfate

Ammonium peroxydisulfate (APS), one of the most widely used inorganic peroxides in the process industries, is a thermally unstable peroxide and potent oxidizer due to the presence of peroxy bond in the molecule and is incompatible with most substances. To investigate the effect of typical additives on the thermal decomposition of APS, in this paper, diamine phosphate (DAP), monoamine phosphate (MAP), and aluminum hydroxide (AH) were selected as additives; pure APS and samples with 10 wt% and 20 wt% of additives were first tested by differential scanning calorimetry (DSC). The experiments and analysis showed that the samples with 10 wt% of additive had better thermal stability than those with 20 wt% of additive. After screening, the three groups of 10 wt% AH, 10 wt% MAP, and 20 wt% MAP additive conditions could be considered to have a better thermal stability effect on the thermal decomposition of APS. Four groups of samples were, in turn, tested by Phi-Tec II. The adiabatic results showed two discontinuous exothermic processes; 10 wt% AH promoted the weak exothermic effect in the first stage. In contrast, the three groups of additives in the main exothermic stage showed different degrees of inhibition, and the inhibiting effect was ranked as 10 wt% AH, 10 wt% MAP, and 20 wt% MAP in order. Finally, the self-accelerated decomposition temperature (SADT) was calculated under the 25 kg standard package. The adiabatic results, including SADT, were combined to render feasible recommendations for the use of additives, which provides references for the packaging and transportation of additives and their applications.     

铝粉超细化对KClO3/Al/S配方药剂特性的影响

为研究铝粉超细化后对烟火药剂性能的影响,将普通铝粉和纳米铝粉分别与氯酸钾、硫黄粉按照零氧平衡的同一配比(17%Al+63%KClO3+20%S)配制成烟火药剂,分别用0#样品和1#样品表示。用ARC、WL-1型落锤仪和MGY-1型摆式摩擦感度仪等试验装置从热安全性、撞击感度和摩擦感度等方面进行对比试验。结果表明,与含普通铝粉的0#样品相比,含纳米铝粉的1#烟火药剂热分解的初始反应温度明显降低(118.67℃<123.3℃),反应到达最大温升速率所需的时间明显延长(4.94min>0.13 min),反应所能达到的最高压力明显降低(2.77 MPa/g<3.14 MPa/g),反应动力学因子明显降低(361.85 kJ/mol<409.41 kJ/mol),撞击感度明显下降(12%<100%)。这说明铝粉粒径对药剂的性能有一定的影响。纳米铝粉的加入在加速烟火药剂反应进程的同时,可有效降低其反应的激烈程度、压力危险性和撞击危险性,即铝粉超细化后可以有效改善烟火药剂的性能,提高其安全性。     

Ammonium nitrate thermal decomposition with additives

Runaway reactions present a potentially serious threat to the chemical process industry and the community; such reactions occur time and time again often with devastating consequences. The main objective of this research is to study the root causes associated with ammonium nitrate (AN) explosions during storage. The research focuses on AN fertilizers and studies the effects of different types of fertilizer compatible additives on AN thermal decomposition. Reactive Systems Screening Tool (RSST) has been used for reactivity evaluation and to better understand the mechanisms that result in explosion hazards. The results obtained from this tool have been reported in terms of parameters such as “onset” temperature, rate of temperature and pressure rise and maximum temperature. The runaway behavior of AN has been studied as a solid and solution in water. The effect of additives such as sodium sulfate (Na₂SO₄) and potassium chloride (KCl) has also been studied. Multiple tests have been conducted to determine the characteristics of AN decomposition accurately. The results show that the presence of sodium sulfate can increase the “onset” temperature of AN decomposition thus acting as AN thermal decomposition inhibitor, while potassium chloride tends to decrease the “onset” temperature thus acting as AN thermal decomposition promoter.     

UN test O.1 errors in quantifying the behavior of solid oxidizers

The results of the UN test O.1 for oxidizing solids are shown to be incorrect when specimens contain certain inertant additives, illustrated for the case of oxidizers in the ammonium nitrate fertilizer family. Test results for three different AN-based products containing inertants show that two of the three (including calcium ammonium nitrate, CAN, a long-known safer alternative to AN) would be misranked with the O.1 test. An analogy between the heat release rate of substances containing fire retardant (FR) chemicals is established and several ways by which FR behavior can be achieved are demonstrated. It is shown that the O.1 test implicitly adopts only one model of inertant action, and that chemicals which rely on a differing mode of inertant action are liable to be incorrectly treated. It is further shown that the physical basis of the O.1 test—an intimate mixture of finely-comminuted fuel and oxidizer—misrepresents the most common type of accidents involving oxidizers, and that such test results do not correspond to scenarios of a less extreme nature. The new O.3 test improves the analysis method, but does not resolve the problem of excessive commingling of fuel into oxidizer. It is recommended that the intermediate-scale arrangement used by the Bureau of Explosives be adopted for further development and standardization, in preference to the O.1 or O.3 test arrangements.     

硝酸铵水溶液热稳定性研究

采用加速度量热法(ARC)对高温状态下的硝酸铵水溶液的热分解危险性、杂质对其稳定性的影响进行了研究.实验结果表明,硝酸促进硝酸铵的分解,而氯离子对其有抑制作用;当两者同时存在时大大降低系统的稳定性,且硝酸对硝酸铵的影响远大于氯离子.     

Calorimetry studies of ammonium nitrate – Effect of inhibitors,confinement, and heating rate

Ammonium nitrate (AN) has been widely used as a fertilizer for almost a century because it is an excellent nitrogen source. However, AN related explosions continue to occur time and again, despite the fact that AN has been extensively investigated. There have been more than 70 AN-related incidents during the last century, which reemphasize the dire need for further research on AN reactive hazards. This research focuses on the alternatives to make AN safer as a fertilizer by reducing its explosivity, by studying the effect of inhibitors, confinement, and heating rate on AN thermal decomposition using the Reactive Systems Screening Tool (RSST). First, the thermal decomposition of AN in the presence of different types of additives, including sodium bicarbonate, potassium carbonate, and ammonium sulfate, was studied under two concentrations, i.e., 2.8 wt.% and 12.5 wt.%. The results show that they are good inhibitors for AN. Second, the effect of confinement was tested by observing AN decomposition under five different initial pressures, varying from ambient pressure to 187 psig. It is concluded that confinement is dangerous to AN, which should be avoid in AN storage and transportation. Lastly, the effect of heating rate was studied by heating up AN under two heating rates of 0.25 °C min⁻¹ and 2 °C min⁻¹. The lower the heating rate, the lower the “onset” temperature detected.     

Towards the improvement of UN N.5 test method for the characterization of substances which in contact with water emit flammable gases

This paper deals with a sensitivity analysis of main parameters affecting the measurement of the gas flowrate emitted during testing substances for their potential to emit flammables gases in dangerous quantities where in contact with water, according to the UN N.5 test procedure. UN N.5 is described in the Manual of Tests and Criteria of United Nations (part of the Orange Book) (ONU Manual of Test and Criteria, 2008), serving both applications of international transport regulations as well as classifications of dangerous substances according to Globally the Harmonized System (GHS) and the derived regulation applying in the EU known as “CLP” Regulation (Regulation (EC) No 1271/2008). The main reason that justifies the present research is that the measurement of emitted gases is highly critical in the final classification resulting from the interpretation of the test results. Moreover, that idea has been raised to adapt the UN N.5 test protocol for classifying, in the future, substances that by contact with water would emit dangerous quantities of toxic gases.Experiments have been carried out to cover the analysis of the influence of ambient temperature, overall volume of glassware, nature of aqueous media, mass sample and sample-to-liquid mass ratio, since such parameters are not fixed within any defined range in the UN N.5 test procedure. The influence of the flow rate measuring device was also considered. Results confirm that the above mentioned parameters may play a significant role to such an extent as to finally alter the final classification resulting from the testing. Guiding principles have also been derived from our measurements and observations towards an improved and more robust UN test protocol in the future.     

Comparison of calculated data for the flammability and the oxidation potential according to ISO 10156 with experimentally determined values

The classification of flammable gas mixtures is based on either testing or calculation methods proposed by the revised international standard ISO 10156. This standard is used for classification of physical hazards in Chapters 2.2 and 2.4 of the UN Globally Harmonized System of Classification and Labelling of Chemicals (GHS) and in the UN Recommendations on Transport of Dangerous Goods (TDG). The test methods of flammability and oxidizing potential in this standard were developed by BAM. Earlier versions of this standard are not based on triangular diagrams and on the reference combustible substance “ethane”. The old material characteristics, especially in case of oxidizing potential, are based mostly on practical experience without any quantifiable test results. First time it is possible to compare experimental results from the CHEMSAFE database with the newly developed calculation method. In this paper the basic principles of the calculation methods are presented and the methods are validated by examples. A comparison of experimental flammability data with classification results gained by the calculation methods of ISO 10156 is demonstrated.