發(fā)布時間：2018-08-08 11:31

【摘要】：固體推進式滅火技術(shù)(SPGG)憑借其諸多優(yōu)異特性而獲得了廣泛的關(guān)注,諸如惰性氣體生成量大、可常壓貯存、可配合使用液體滅火劑、可按需求定量釋放滅火劑等優(yōu)點,SPGG已成為一種熱門并極具前景的哈龍?zhí)娲鷾缁鸺夹g(shù)。然而,SPGG滅火裝置內(nèi)部的主要成分5-氨基四氮唑/硝酸鍶(5AT/Sr(N03)2)推進劑存在產(chǎn)氣溫度高、燃速受壓力影響變化大等缺陷,削弱了 SPGG滅火裝置的滅火效率,限制其推廣和使用。因此,本文以高氮含能化合物5-氨基四氮唑及其與硝酸鍶組成的推進劑為研究對象,通過添加正負催化劑的方式,深入研究粒徑、催化劑等變量對5AT/Sr(N03)2推進劑燃燒性能的影響,從熱解機理的角度揭示各變量對固體推進劑燃燒性能的影響作用機制,旨在探索一種燃溫低、燃速快、燃速壓力指數(shù)低的新型5AT/Sr(N03)2固體推進劑。首先,本文以高氮含能化合物5AT為研究對象,深入探究5AT的熱解特性及熱解反應(yīng)機制。一方面,制備四種粒徑的5AT樣品,聯(lián)合采用熱重、熱流技術(shù)對不同粒徑的5AT樣品的熱穩(wěn)定性進行對比分析,發(fā)現(xiàn)粒徑越小的5AT對熱的抵抗力越差,借助比表面積和掃描電鏡等測試手段揭示粒徑對5AT熱解的影響機理,推測可能是由于小的顆粒粒徑會形成較高的表面能、更快的傳熱傳質(zhì)速率所導(dǎo)致的,從四種粒徑中選出較容易發(fā)生反應(yīng)、且易實現(xiàn)操作的5AT粒徑范圍,同時預(yù)測5AT樣品熱解反應(yīng)屬于Di擴散模型;另一方面,研究三種不同的納米過渡金屬氧化物(納米氧化鐵、納米氧化銅、納米氧化鎳)催化劑對5AT熱分解的催化機理,借助熱重、熱流、傅里葉紅外、質(zhì)譜、比表面積測試、電鏡掃描等測試手段,發(fā)現(xiàn)過渡金屬氧化物的存在將會加速5AT的熱解速率,這是由于過渡金屬氧化物的添加阻礙了 CN的組合成鍵,而是加速了 CN鍵的斷裂所造成的�？偨Y(jié)來說,粒徑更小、含有過渡金屬氧化物的5AT熱敏感性更強,在生產(chǎn)、運輸、貯存的過程中也需更多安全方面的關(guān)注。其次,本文以5AT/Sr(NO3)2推進劑為研究對象,結(jié)合熱重-質(zhì)譜聯(lián)用技術(shù)探究了推進劑的熱解機理,研究發(fā)現(xiàn)5AT/Sr(NO3)2推進劑的熱解共分為四個階段,第一階段是5AT分解生成疊氮酸、氨基氰和三聚氰胺:第二階段是三聚氰胺分解產(chǎn)生氰化氫及蜜勒胺、蜜白胺等固態(tài)產(chǎn)物;第三階段中蜜勒胺繼續(xù)分解生成氨基氰、疊氮酸、氰化氫等,同時與尚未分解的硝酸鍶之間發(fā)生了氧化還原反應(yīng)生成甲醛、二氧化碳;第四階段硝酸鍶發(fā)生分解最終生成氧化鍶和氮氧化物。最后,本文借助TG-DSC測試、燃溫測試、燃速測試、導(dǎo)熱系數(shù)測量、掃描電鏡等測試手段,分別研究了負催化劑(20%碳酸鈣冷卻劑)、正催化劑(1%納米氧化鐵、1%納米氧化銅、1%納米氧化鎳、2%微米氧化鐵、2%納米氧化鐵)對5AT/Sr(NO3)2推進劑燃燒性能的調(diào)節(jié)作用。添加了 20%碳酸鈣的推進劑在反應(yīng)初期的熱解溫度和活化能均減小,燃速升高,這是由于碳酸鈣調(diào)節(jié)了固相區(qū)的反應(yīng),增大了固相區(qū)的反應(yīng)表面積所引起的,而在反應(yīng)末期其熱解溫度和活化能均變大而燃速大幅度降低,這是由于碳酸鈣分解產(chǎn)生的CO2引發(fā)了氣相區(qū)反應(yīng)的團聚效應(yīng)造成的�？梢钥吹奖M管添加了碳酸鈣之后,推進劑出現(xiàn)了麥撒效應(yīng)并大大降低了燃燒溫度,但是燃速同時大幅度降低,不利于SPGG滅火裝置快速推出滅火介質(zhì)。添加了過渡金屬氧化物(TMO)的5AT/Sr(NO3)2推進劑燃速大大提高,同時燃溫也有不同程度的降低,并且燃速、燃溫改變幅度與TMO的導(dǎo)熱系數(shù)大小規(guī)律保持一致。研究作用機理發(fā)現(xiàn),TMO可以調(diào)節(jié)熱量傳遞和反應(yīng)的表面積以實現(xiàn)對固相區(qū)反應(yīng)的控制,還可以改變氣相區(qū)反應(yīng)的吸熱/放熱量,實現(xiàn)協(xié)同控制固相區(qū)反應(yīng)和氣相區(qū)反應(yīng)的作用。添加了 2%微米氧化鐵的推進劑比添加了 2%納米氧化鐵的推進劑燃速更快,發(fā)現(xiàn)了納米氧化鐵分散在推進劑中所存在的團聚效應(yīng)、顆粒覆蓋效應(yīng),指出將納米顆粒應(yīng)用作燃速調(diào)節(jié)劑時應(yīng)提前采用電化學(xué)溶解等手段進行表面改性處理。通過本文對5AT/Sr(NO3)2推進劑的研究,設(shè)計出一種安全、可擴展、成本低廉、性能優(yōu)良的新型推進劑配方,實現(xiàn)了對傳統(tǒng)5AT/Sr(NO3)2推進劑燃燒性能的優(yōu)化,滿足了在降低燃燒溫度的同時提高燃速、降低燃速壓力指數(shù)的要求,提高5AT/Sr(NO3)2推進劑在SPGG滅火裝置中的滅火效率,進一步推動了新型SPGG滅火技術(shù)的市場應(yīng)用和推廣,促進哈龍?zhí)娲鷾缁鸺夹g(shù)的發(fā)展。
[Abstract]:Solid propelled fire extinguishing technology (SPGG) has received extensive attention for its excellent characteristics, such as large amount of inert gas, storage at normal pressure, and the use of liquid fire extinguishing agent to release fire extinguishing agent according to demand. SPGG has become a hot and promising alternative fire extinguishing technology for Halon. However, SPGG fire extinguishing assembly The main components, 5- amino tetrazolium / strontium nitrate (5AT/Sr (N03) 2) propellant, have high gas production temperature and high burning rate affected by pressure, which weaken the fire extinguishing efficiency of the SPGG fire extinguisher and restrict its popularization and use. Therefore, the propellant composed of 5- amino tetrazolium and its strontium nitrate with high nitrogen energetic compound and the propellant composed of strontium nitrate are studied in this paper. The effect of particle size, catalyst and other variables on the combustion performance of 5AT/Sr (N03) 2 propellant was investigated by adding positive and negative catalysts. The effect mechanism of various variables on the combustion performance of solid propellants was revealed from the point of view of pyrolysis mechanism. A new type of 5AT/Sr (N03) with low combustion temperature, fast burning rate and low burning rate pressure index was explored. ) 2 solid propellant. First, in this paper, a high nitrogen energetic compound 5AT was used as the research object to explore the pyrolysis characteristics of 5AT and the mechanism of pyrolysis reaction. On the one hand, the 5AT samples of four kinds of particle sizes were prepared. The thermal stability of 5AT samples with different particle sizes was analyzed by thermogravimetry and heat flow technique, and the resistance of 5AT to heat was found with smaller particle size. The worse the force, the influence mechanism of particle size on 5AT pyrolysis is revealed by means of specific surface area and scanning electron microscope. It is presumed that it may be caused by the formation of higher surface energy and faster heat and mass transfer rate by the small particle size. It is possible to choose the 5AT particle size range easily and easily to be operated from four kinds of particle sizes. The pyrolysis of 5AT samples belongs to the Di diffusion model. On the other hand, the catalytic mechanism of three different nano transition metal oxides (nanoscale iron oxide, nano cuprous oxide, nanoscale oxide) catalyst for the thermal decomposition of 5AT is studied, and the transition from thermogravimetry, heat flow, Fourier infrared, mass spectrum, specific surface area test and electron microscope scanning are found. The presence of metal oxides will accelerate the pyrolysis rate of 5AT because the addition of transition metal oxides hinders the combination of CN, but accelerates the fracture of the CN bond. In summary, the particle size is smaller, and the 5AT with transition metal oxide is more sensitive, and more safety is needed in the process of production, transportation and storage. Secondly, using 5AT/Sr (NO3) 2 propellant as the research object, the pyrolysis mechanism of propellant was investigated by TG mass spectrometry combined with TG mass spectrometry. The pyrolysis of 5AT/Sr (NO3) 2 propellants was divided into four stages. The first phase was 5AT decomposition of azido, cyanamide and melamine: the second stage was melamine decomposition production. Hydrogen cyanide and melalamines, melamine and other solid products; the third stage melalamines continue to decompose cyanide, azido, hydrogen cyanide and so on. At the same time, the oxidation-reduction reaction of the unresolved strontium nitrate is formed to produce formaldehyde and carbon dioxide; the fourth stage of strontium nitrate decomposition finally produces strontium oxide and nitrogen oxide. Finally, this is the result of the formation of strontium oxide and nitrogen oxide. With the help of TG-DSC test, combustion temperature test, burning rate test, thermal conductivity measurement, scanning electron microscope and other testing means, the combustion performance of 5AT/Sr (NO3) 2 propellant is regulated by negative catalyst (20% calcium carbonate coolant), positive catalyst (1% nanometer iron oxide, 1% nano copper oxide, 1% nano nickel oxide, 2% micron iron oxide, 2% nanometer iron oxide). The pyrolysis temperature and activation energy of the propellant with 20% calcium carbonate were reduced and the burning rate increased. This is due to the effect of calcium carbonate on the reaction of the solid state and the increase of the surface area of the solid state, while the pyrolysis temperature and activation energy of the solid state are all larger and the burning rate is greatly reduced at the end of the reaction, which is due to the carbonation. The CO2 produced by calcium decomposition causes the agglomeration effect of the gas phase reaction. It can be seen that, after adding calcium carbonate, the propellant appears the mesa effect and greatly reduces the combustion temperature, but the burning rate decreases greatly at the same time, which is not conducive to the rapid release of the fire extinguishing medium by the SPGG extinguisher. The 5AT of the transition metal oxide (TMO) is added. The burning rate of /Sr (NO3) 2 propellant is greatly increased and the combustion temperature is reduced in varying degrees, and the burning rate is consistent with the law of the thermal conductivity of TMO. It is found that TMO can adjust the surface area of heat transfer and reaction to control the reaction of the solid phase region, and can also change the reaction of the gas phase region. Heat absorption / heat discharge is used to control solid state reaction and gas phase reaction in synergistic control. The propellant added with 2% micron iron oxide is faster than the propellant adding 2% nanometer iron oxide. The agglomeration effect of nano iron oxide dispersed in the propellant, the effect of particle covering, and the application of nano particles to the burning rate are found. Through the study of 5AT/Sr (NO3) 2 propellant, a new propellant formula with safety, expansibility, low cost and excellent performance has been designed through the study of 5AT/Sr (NO3) propellant in this paper. The combustion performance of the traditional 5AT/Sr (NO3) 2 propellant is optimized and the combustion temperature is reduced. At the same time, improving the burning rate and reducing the burning rate pressure index, improving the fire extinguishing efficiency of 5AT/Sr (NO3) 2 propellant in SPGG fire extinguishing device, further promoting the market application and popularization of new SPGG fire extinguishing technology, and promoting the development of Halon alternative fire extinguishing technology.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：V512

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