Enhanced friction and shock sensitivities of hexachlorodisilane hydrolyzed deposit mixed with KOH

In this work, the effects of potassium hydroxide (KOH) on friction and shock sensitivity of the hexachlorodisialne hydrolysis products were studied. A wide range of KOH content, from 0.02 to 21.5 wt%, in the mixture of KOH and HCDS hydrolyzed deposit was prepared by mixing the deposit with aqueous KOH solution and dried in glovebox. The lowest impact energy (LIE) and lowest friction force (LFF) were determined by BAM fall-hammer and friction test apparatus, respectively. It was found that both shock and friction sensitivities increased with an increase in the KOH content in the HCDS hydrolyzed deposit. In particular, the LIE and LFF decrease from 6 J to 326 N of the original deposit to less than 0.125 J and 7 N for deposit with 0.03 and 0.3 wt% KOH. Differential scanning calorimetry studies showed that a new exothermic peak was observed between 80 °C and 150 °C which is also accompanied by evolution of hydrogen. It is proposed that, the presence of KOH results in the formation of Si–Si–OK groups leading to the weakening of the neighboring Si–Si bonds. Any mechanical impact or friction will lead to the cleavage of the unstable Si–Si bonds and subsequently initiate a fast chain oxidation of adjacent Si–Si and Si–OH bonds to form more Si–O–Si groups, releasing H₂ gas and heat. Recommendations were given for handling and disposing of these explosive deposits.     

Characterization and control of energetic deposits from hexachlorodisilane in process tool exhaust lines

This work aims to characterize and develop a disposal method for a gel-like deposit generated in a vacuum foreline of an atomic layer deposition (ALD) tool that is using hexachlorodisilane (Si₂Cl₆, HCDS) as a precursor. This ALD foreline gel was reproduced by replicating the ALD tool process conditions by using a benchtop system that was a 1/85 scale down of one user's process. All samples were tested for shock sensitivity using the Fall hammer apparatus. Extensive infrared studies were done for unhydrolyzed and hydrolyzed gel. Dissolution tests were conducted to develop a method for removing and disposing the gel off-site. Many different solutions such as solvent based solutions, water based alkaline solutions and alcohol based alkaline solutions were tested. It was found that alcohol based alkaline solutions produced only hydrogen as a byproduct and were considered satisfactory for off-site abatement of gel. Furthermore, in-situ cleaning gel of the foreline using a fluorine/N₂ mixture with a concentration of 1–10vol% was done. They were all effective in cleaning/removing the gel under the condition of ambient temperature and reduced pressure. Finally, recommended procedures were given for removing as well as disposing the ALD gel.     

固体微粒气溶胶灭火剂的改性研究

固体微粒气溶胶灭火剂作为一种新型灭火剂具有优越的抑制火灾的性能,但其应用和推广的关键在于降低灭火气溶胶形成时的温度.本文利用TG方法分析了灭火剂的热分解过程,并通过测定固体微粒气溶胶灭火剂的释放速度、释放区温度分布及灭火性能,研究了固体微粒气溶胶灭火剂的降温消焰技术.同时对气溶胶的成分和固体粒子粒度分布进行了分析.     

Sensitivity of dimethyl amino ethyl azide (DMAZ) as a non-carcinogenic and high performance fuel to some external stimuli

Hydrazine and its derivatives have been used extensively in space programs as liquid propellants. Since they are carcinogen, dimethyl amino ethyl azide (DMAZ) has been introduced as a non-carcinogenic fuel with high performance as compared to the best available fuels. DMAZ contains energetic group –N₃, which may be sensitive to some external stimuli. Thus, it is important to study various aspects of sensitivity of DMAZ in addition to its performance criteria. Various conventional tests as well as computer codes were used to investigate sensitivity of DMAZ to external stimuli such as impact, shock wave, Koenen, burning and electrostatic discharge. The results showed that DMAZ is not sensitive to impact, direct flame and shock wave. Meanwhile, it has moderate and high sensitivity to heat in confined volume and electrostatic discharge, respectively.     

Research on thermal decomposition characteristics of H foaming agent with different moisture contents

N, N-Dinitroso pentamethylene tetramine, also known as H foaming agent, is a self-reactive chemical substance commonly used in the rubber industry. Decomposition, explosion and combustion may be caused by the presence of fire or high temperature. As a high-risk chemical that is strictly regulated in China, H foaming agent has ever triggered multiple accidents. During the study of the decomposition thermal process of H foaming agent, it was found that the presence of moisture content at different levels had a significant effect on its thermal stability. The thermal characteristics of H foaming agent under different moisture contents was studied through the test means such as adiabatic calorimetry and high-pressure differential scanning calorimetry. Through isothermal calorimetry experiment, it was found that the decomposition of H foaming agent had obvious auto-catalytic characteristics. In the moisture content within the range of 0–40%, with the increase of moisture content, the initial exothermic temperature T_onset of the mixture system of H foaming agent and water decreased, while the time from initial heat release to rapid temperature rise of the reaction system (induction period) was gradually prolonged, and the temperature increment of the reaction system was increased gradually. As the proportion of moisture content in the system increased, the adiabatic temperature rise ΔT_ad of the mixture system of H foaming agent and water gradually decreased, meanwhile the time to maximum rate under adiabatic condition (TMR_ad) gradually decreased. The research results have guiding significance for finding the reasonable moisture content of H foaming agent in the drying process and determining the upper temperature limit during storage and transportation.     

Experimental investigation of the flow characteristics of jettisoning in a CO2 carrier

This experimental study was performed to investigate the flow characteristics in the jettisoning flow line of a liquid CO₂ carrier. When a pressurized liquid CO₂ container loses mechanical integrity, possibly by material or mechanical defects, the liquid inventory should be drained out rapidly for safety reasons using the so-called jettisoning process. In the course of jettisoning, the liquid CO₂ undergoes two phase change stages, from liquid to liquid + vapor and from liquid + vapor to solid + vapor. Consequently, the jettisoning release rate is affected by the characteristics of these phase changes. In this study, liquid CO₂ was discharged through a small tube, representing a jettisoning flow line. The temperature and pressure were measured along the tube, and the locations of the phase changes were inferred from the measured data. The experimental results showed that active nucleation occurred near the tube tip and that the phase change into solid and vapor occurred just after leaving the pipe, irrespective of the tube length in this study.     

Vapor flammability above aqueous solutions of flammable liquids

The flammability of vapors above aqueous solutions of ethanol and acetonitrile was studied experimentally in a 20-L combustion apparatus. No liquid was present in the apparatus, but the vapor concentrations were adjusted to correspond to the vapor in equilibrium with a specified aqueous solution. The experimental results for these two systems show that

• As water is added to the vapor, the lower boundary of the flammability zone decreases. For ethanol, the lower flammability limits (LFL) decreases from 3.7% for pure vapor to 3.2% with saturated water vapor. For acetonitrile, the decrease is from 4.2% to 3.8%. Thus, to a good approximation, the water vapor can be treated as an inert, enabling the data to be displayed on a single flammability triangle diagram. This provides a very simplified method for estimating the flammable behavior for aqueous solutions.

• The upper boundary of the flammability zone is unchanged with the addition of water.

• The limiting oxygen concentration (LOC) is essentially constant for all concentrations of aqueous solutions. The LOC for the pure solvent may be used as a universal LOC for all solvent concentrations.

• The vapor mixture above the aqueous solution is not flammable below a certain liquid mol fraction of flammable. The flammable concentration at which this occurs can be called the maximum safe solvent concentration (MSSC). A method is presented to determine the MSSC from experimental flammability data.

• The oxygen concentration defining the flammable boundary for the vapor decreases rapidly from the MSSC and then increases as the liquid solvent concentration increases.

The calculated adiabatic flame temperature (CAFT) method qualitatively predicts the same behavior as the experimental data.     

Coupling effects of the explosion shock wave and heat radiation on the dynamic response of a fixed-roof tank

The occurrence of leakage in large tank farms or oil deposits can lead to fire or explosion accidents. Coupling effects of fire and explosion loadings can cause considerably more damage to adjacent tanks or buildings than either loading individually does. In this study, the combined loadings of the explosion shock wave and heat radiation from a pool fire on a neighboring empty fixed-roof tank were numerically investigated. The effects of the explosion shock wave intensity and relative height of the explosion center [the ratio of the height of the explosion center to the height of the tank (h_r)] were analyzed. The results indicate that tanks damaged by explosion shock waves have decreased fire resistance and critical buckling temperature. Moreover, the thermal buckling deformation of the predamaged tank largely depends on the explosion shock wave. With an increase in the explosion shock wave intensity or a decrease in h_r, the explosion shock wave has greater influence on the fire resistance of the tank, and the critical buckling temperature decreases. This paper can provide an understanding of the dynamics of a tank under explosion shock wave loading, and of the critical failure criterion and failure modes of a target tank under the coupled loading of the explosion shock wave and an adjacent pool fire.     

Development of heat transfer and evaporation model of LNG covered by Hi-Ex foam

Natural gas is a kind of clean, efficient green energy source, which is used widely. Liquefied natural gas (LNG) is produced by cooling natural gas to −161 °C, at which it becomes the liquid. Once LNG was released, fire or explosion would happen when ignition source existed nearby. The high expansion foam (Hi-Ex foam) is believed to quickly blanket on the top of LNG spillage pool and warm the LNG vapor to lower the vapor cloud density at the ground level and raising vapor buoyancy. To identify the physical structure after it contacted with LN₂ and to develop heat transfer model, the small-scale field test with liquid nitrogen (LN₂) was designed. In experiment, three layers including frozen ice layer, frozen Hi-Ex layer and soft layer of Hi-Ex foam were observed at the steady state. By characterizing physical structure of the foam, formulas for calculating the surface of single foam bubble and counting foam film thickness were deduced. The micro heat transfer and evaporation model between cryogenic liquid and Hi-Ex foam was established. Indicating the physical structure of the frozen ice layer, there were a certain number of icicles below it. The heat transfer and evaporation mathematical model between the frozen ice layer and LNG was derived. Combining models above with the heat transfer between LNG, ground and cofferdam, the heat transfer and evaporation mathematical model of LNG covered by Hi-Ex foam was developed eventually. Finally, LN₂ evaporation rate calculated by this model was compared with the measured evaporation rate. The calculated results are 1.2–2.1 times of experimental results, which were acceptable in engineering and proved the model was reliable.     

潮湿巷道风流温度及湿度计算方法研究

对计算潮湿巷道中风流温度和湿度的方法进行改进,提出将饱和空气含湿量与温度的关系拟合为二次曲线计算巷道壁面水分蒸发的方法,编制模拟潮湿巷道中风流与围岩热交换和巷道壁面水分蒸发的计算机程序,解算出风流温度及湿度的变化规律。并将解算结果与将饱和空气含湿量与温度的关系拟合为线形曲线时的解算结果进行分析对比,将饱和空气含湿量和温度之间的关系简单拟合为线性,风流温度的误差在通风时间较短时相对误差较大。随通风距离增长风流温度和相对湿度的误差增加。     

Preparation and performance of novel APP/NaY–Fe suppressant for coal dust explosion

Coal dust explosion occurs easily in the coal chemical industry. To ensure safety in industrial production, NaY zeolite was used as carrier modified with Fe ions and combined with ammonium polyphosphate (APP) to prepare a novel composite suppressant for coal dust explosion. The explosion suppression performance of novel APP/NaY–Fe suppressant was investigated by flame propagation inhibition experiments. The results show that Fe ion modification can effectively improve the explosion suppression performance. By increasing content, the explosion suppression performance of the explosion suppressant increases. The maximum explosion pressure P_max of coal dust drops to 0.13 MPa when 50 wt% explosion suppressants were added, and the coal dust explosion cannot continue to expand. Complete suppression of explosion could be achieved by adding 66 wt% explosion suppressants. Combined with XRD, SEM and TG results, the explosion suppression mechanism was proposed. The novel explosion suppressant has high thermal stability, good dispersity and its explosion suppression components distribute uniformly. It shows good explosion suppression performance by the synergistic effect among explosion-suppression components.     

Investigation on the suppression effect of high momentum C6F12O (Novec-1230) flow on hydrogen jet flame

This work investigates the suppression effect of Novec-1230 on H₂ jet flame. The suppressants are motivated by N₂ flow to get higher momentum and approach the reaction kernel at flame base. The flame area with Novec-1230 is always smaller than that with water mist at the same condition. Novec-1230 exhibits better suppression effect on reaction kernel. The higher-momentum jet flame is more difficult to be suppressed. This is because that the higher-momentum flame makes the suppressant approach the reaction kernel more difficult. In addition, the high N₂ flow rate containing suppressant could destroy flame temperature structure and decrease it. Results inferred that the temperature of flame with Novec-1230 is higher than that with water mist. Moreover, the lower minimum extinguishing time indicates that the suppression efficiency of Novec-1230 is better than that of water mist. The jet flame is extinguished only when H₂ flow rate is low and N₂ flow rate is high. There are two reasons: one is that the higher-momentum jet flame prevents suppressants to enter flame core. The other one is that the burner nozzle is heated to as igniting source during suppression progress. Furthermore, the burning velocity, adiabatic flame temperature, heat production and free radicals are investigated theoretically at Φ = 1.6, 1.0, 0.8 and 0.6. Results indicate that the burning velocity with Novec-1230 is much lower than that with water mist. The adiabatic flame temperature, heat production and free radicals increase firstly and then decrease with Novec-1230 addition at lean flame.     

高倍泡沫加速泄漏LNG扩散的有效性模拟试验

泡沫灭火剂在扑灭液体火灾中起到重要作用,关于低温液体蒸气云扩散控制的研究也逐渐得到应用。通过小尺寸模拟试验验证高倍泡沫加速泄漏LNG扩散的有效性,设计并进行了低温液体自然蒸发和高倍泡沫覆盖低温液体两个对照试验,测量了竖直方向上10个高度处的温度及装置整体质量,从而获取了低温液体蒸气到达泡沫层顶端时温度及蒸发速率的变化情况。结果表明,与未添加泡沫的情况对比,高倍泡沫的覆盖使泄漏低温液体在1 800 s内的蒸发量减少了6.4%,如果时间更长则减少的比例更多,且蒸发出的低温液体穿过泡沫层后蒸气温度可达0℃左右,而未添加泡沫时同等高度处蒸气温度为-75℃左右。0℃时,LNG蒸气密度已明显小于空气密度,此温度下LNG蒸气会迅速向上扩散,而不至在地表积聚,由此证明高倍泡沫能够加速泄漏低温液体蒸气向上扩散,减小了低温液体蒸气在地面积聚并引发火灾爆炸事故的可能性,从而证实了高倍泡沫加速泄漏LNG扩散的有效性。     

纳米氢氧化铝三相泡沫制备研究*

为更好地解决煤矿采空区煤炭自燃问题,以十二烷基硫酸钠为主体进行发泡剂复配,通过泡沫性能测试实验,研制出高性能发泡剂。以纳米氢氧化铝作为固相颗粒,制备出发泡倍数高、稳定性强的纳米氢氧化铝三相泡沫,使用锥形量热仪研究其高温阻燃能力和消烟性能。实验结果表明:当纳米氢氧化铝的质量分数从0提高到1%时,泡沫体积从500 mL增长至830 mL;当质量分数从3%提高到4%时,泡沫析液半衰期由15 min提升至42 min,且能在完全析液后保留三维网状结构。在高温阻燃和消烟能力方面,纳米氢氧化铝三相泡沫的加入将点燃时间从24 s延长至87 s,持续燃烧时间从835 s缩短至325 s,热释放速率高峰值从97.2 kW/m2降低至49.8 kW/m2,烟气生成速率峰值从0.064 m2/s降低至0.012 m2/s,对CO,CO2释放速率也有一定抑制作用。     

不同pH值下含铁矿物对硫酸侵蚀混凝土的影响研究

硫酸侵蚀为混凝土耐久性损伤的一个重要方面.在硫酸盐侵蚀过程中,含铁矿物等侵蚀产物不断形成,导致混凝土材料形成不同程度的腐蚀.为研究不同pH值环境下含铁矿物对混凝土结构腐蚀的影响,在实验室配置了pH值为2.0、3.0和4.0的稀硫酸溶液,结合不同洗刷作用方式来模拟酸雨环境,采用室内长期浸泡试验方法对混凝土试件进行不同程度...     

开敞空间可燃气云爆炸冲击波超压及灾害动力响应研究评述

为了进一步梳理和分析开敞空间可燃云爆炸冲击波超压传播规律及灾害动力响应方面的各项研究成果,推进可燃气体爆炸安全防控,减少人员伤亡和经济损失。在分析现有研究的基础上,总结开敞空间可燃气云爆炸冲击波超压传播规律及灾害动力响应研究等方面存在的不足,提出开敞空间多元混合气体爆炸冲击波超压传播规律研究、多影响参数下可燃气云爆炸冲击波超压传播规律定量分析、基于可燃气云爆炸冲击波超压作用下的承载体动力响应等未来研究的关键技术问题。     

二元混合液体闪点的计算

以混合溶液纯组分易燃液体闪点的饱和蒸气压为基础,应用乌拉尔定律、双液系的气-液相平衡理论,运用Le Chatelier方程和安托因方程导出二元混合液的闪点计算方法。并例举易燃液体与易燃液体组成的理想混合液、易燃液体与易燃液体组成的非理想混合液、易燃液体与不燃液体组成的非理想混合液的计算过程。乙醇溶液闪点的计算结果与现有的文献资料比较,误差在允许范围内。计算数据用Excel处理,快捷准确,用于确定二元混合液体的火灾危险性。     

Removal of VOCs emitted from p-xylene liquid storage tanks by a full-scale compost biofilter

A full-scale compost biofilter system (CBS) was built to treat vapor losses emitted from three analogous vertical fixed roof p-xylene (p-X) liquid storage tanks of 7500 m³ total working volume. The CBS showed a stable and efficient treatment of standing loss (L_S) and working loss (L_W) with an average removal efficiency of 95.4% through 18-month standing storage and filling operation of the tanks. The weight of activated carbon employed in the concentration buffer influences the CBS performance for L_W treatment under high organic loads. The daily average pressure drops across biofilter bed displayed very low with a maximum of 7.6 mm-H₂O. This reflects that the CBS can be operated without stress and compression of biofilter bed and thus reduce maintenance frequency. No additional inputs of chemicals and fuels along with low electricity and water usage helped in its prolonged operation and increased its cost effectiveness. These advantages make the CSB become a promising control technology of vapor losses emitted from fixed roof organic liquid storage tanks.     

泄漏孔高度对液氯槽罐车泄漏后果的影响研究

为研究液氯槽罐车在道路运输过程中,罐体泄漏孔高度对液氯泄漏扩散过程的影响,本文基于计算流体力学软件Fluent,建立不同高度泄漏孔对应的罐体气相、液相空间泄漏的理论模型,计算不同泄漏模型的泄漏量,研究不同风向、风速、泄漏孔径对氯气泄漏扩散过程的影响。结果表明:风向对2种泄漏模式的扩散范围影响不显著;风速较小时,气相空间泄漏的致命范围大于液相泄漏;风速较大时,液相空间泄漏的致命范围远远大于气相空间;同时,两者受风速的影响具有相似点,风速越大泄漏扩散相对稳定后的氯气浓度值越低;气相、液相泄漏模式的致命范围均随泄漏孔径的增大而增大。研究成果可为液氯槽罐车泄漏事故应急救援、应急处置提供依据。     

高能-钝感复合装药结构冲击波感度数值模拟

为得到复合装药结构对冲击波感度的响应情况,采用显式有限元程序AUTODYN对高能炸药和钝感炸药的复合结构进行隔板试验的数值模拟。分析被发药柱内部的压力时程曲线,并据此判定是否发生爆轰,继而得到反映冲击波感度的隔板值。模拟结果显示复合结构尺寸与冲击波感度的非线性关系,拟合得到的公式可为工程中装药结构设计提供参考依据。这种结构用于战斗部装填设计,能够提高战斗部在冲击波载荷下的安全性。