Imidazolium based ionic liquids affecting functional groups and oxidation properties of bituminous coal

Low temperature oxidation of coal will result in coal spontaneous combustion in mined-out areas. We proposed to use ionic liquids to inhibit the coal spontaneous combustion in this paper. In order to study the inhibiting effect of ionic liquid (IL) on coal oxidation, we successfully dissolved bituminous coal samples in six kinds of imidazolium based ionic liquids, [AOEmim][BF₄], [HOEmim][BF₄], [Amim][Cl], [Emim][AC], [Bmim][AC] and [Bmim][OTf]. The functional groups in the coal samples pre-treated by different ILs were detected by Fourier Transform Infrared Spectroscopy (FTIR) in detail. It is found that the ILs are capable of breaking the associated hydroxyls into dissociated hydroxyls. And during the interaction between coal and ILs, the carboxyl groups have been created. Thermo Gravimetric experiment results show that the weight loss ratios of the IL-treated coals were less during 20–400 °C stage, compared with the IL-untreated coal, which indicates that most of the easily reductive groups effectively dissolved in the ionic liquids. According to the exothermic rate curves and the computed activation energy values, it is demonstrated that the [Bmim][OTf] and [Bmim][AC] make better effect than the other ILs for depressing the oxidation rate of bituminous coal.     

Thermal hazard and decomposition kinetics of 1-butyl-2,3-dimethylimidazolium nitrate via TGA/DSC and FTIR

1-Butyl-2,3-dimethylimidazolium nitrate ([Bmmim][NO₃]), a kind of versatile and novel ionic liquids, is widely applied in the modern petrochemical industry. Nevertheless, its thermal hazard safety data at high temperature or thermal disturbance conditions are currently unavailable. Therefore, this study aimed to characterize the thermal risk of [Bmmim][NO₃] through auto-ignition temperature measurements, flash point analysis, thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC), TGA-Fourier transform infrared spectroscopy (TGA-FTIR) and thermal decomposition kinetics analysis. Additionally, [Bmmim][NO₃] was examined using isothermal thermogravimetric analysis at different temperatures (220, 230, 240, 250, 260 and 270 °C). The experimental results show that the flash point of [Bmmim][NO₃] is 305.70 ± 9.30 °C and the auto-ignition temperature is 341.00 ± 21.60 °C with an ignition delay time of 8.6 s. In addition, using the nitrogen atmosphere TGA data to calculate the activation energy according to the Friedman, Kissinger and Flynn-Wall-Ozawa methods, roughly the same results were obtained. Finally, TGA-FTIR results show that [Bmmim][NO₃] produced acetylene, butane, butanol and carbon dioxide during the thermal decomposition process. This study could provide data support and some guidance for the thermal hazard assessment and safety control of [Bmmim][NO₃] during its use and storage.     

Suppression effects of ammonium dihydrogen phosphate dry powder and melamine pyrophosphate powder on an aluminium dust cloud explosion

Selecting a suitable flame-retardant powder is essential for preventing or reducing the risk of aluminium dust cloud explosions. Two types of retardant materials were studied, namely ABC powder (a flame-retardant powder mainly composed of ammonium dihydrogen phosphate dry powder) and melamine pyrophosphate powder (MPP). A specially designed rectangular pipe was used to examine the influences and mass fractions of the aforementioned flame retardants and the effects of compounds on maximum explosion pressure and maximum explosion pressure rate of increase. The results showed that the explosion-suppression effects of MPP powder were superior to those of ABC powder. Furthermore, the suppression effects of combining ABC and MPP to form compounds in various ratios were explored. The explosion-suppression effects of the single flame-retardant powders and flame-retardant powder compound were compared, which revealed that the effects of the flame-retardant compound were intermediate to those of ABC and MPP used separately. No synergistic effect was observed in the compound retardant. However, component mass fractions influenced the retardant properties of the compound. The suppression mechanism was investigated through thermal analysis, which revealed that the decomposition of the two flame-retardant powders was an endothermic process that generated inert gas. The addition of flame-retardant powder delayed the time required by aluminium to break through its oxide film. However, the thermal analysis curve of the compound overlapped those of the two single powders, and no new chemical reaction occurred. Thus, no change was observed in the efficacy of the flame-retardant properties.     

Effect of superfine KHCO3 and ABC powder on ignition sensitivity of PMMA dust layer

In order to evaluate the flame-retardant capacity of KHCO₃ and ABC on the ignition of PMMA dust layer accumulation on hot surfaces, the ignition time and critical heating temperature of PMMA/KHCO₃ and PMMA/ABC dust layer were experimentally investigated. The thermal stability of the mixed dust, the condensed phase products and gas phase products of the mixed dust combustion were analyzed to reveal the flame-retardant mechanism. The ignition time of 30 μm PMMA was obviously longer than that of 5 μm PMMA, and the critical heating temperature was close to that of 5 μm PMMA. KHCO₃ and ABC could greatly extend the ignition time of the PMMA dust layer and increase the critical heating temperature of the dust layer. ABC was more effective than KHCO₃. The decomposition of KHCO₃ and ABC absorbed the heat and inhibits the pyrolysis of PMMA. The HPO₃ and P₂O₅ generated by the decomposition of ABC would cover the surface of PMMA aggregates or particles and act as a physical barrier. The main light combustible gas produced by PMMA pyrolysis were CO and C₂H₄. The CO₂ generated during the decomposition of KHCO₃ could dilute the combustible gas in the ambient to inhibit the combustion of PMMA.     

中空玻璃微珠/氮化硼填充硅橡胶复合材料的介电、导热和阻燃性能研究

为满足5G电子封装材料的性能需求,将一定量的改性中空玻璃微珠(f-HGM)和氮化硼(f-BN)添加进加成型液体硅橡胶中制备了低介电、高导热且阻燃的硅橡胶复合材料。测试结果表明,添加了10份f-HGM和15份f-BN的复合材料的介电常数为2.68,介电损耗为0.008 16,显著低于纯硅橡胶,热导率为0.518 W/m·K,是纯硅橡胶的2.25倍。此外,复合材料的热稳定性得到了提升,pHRR和THR分别下降了55.3%和37.7%。通过气相和凝聚相分析发现,复合材料的气相热解产物浓度大幅降低,残炭的致密性和连续性得到显著提升。     

Evaluation of thermal properties and process hazard of three ionic liquids through thermodynamic calculations and equilibrium methods

Industrial and new energy applications of ionic liquids (ILs) may have to be used at high temperatures conditions, such as in batteries and fuel applications, which may cause thermal hazards. However, there are few studies on the thermal hazards of ILs. To ensure the thermal safety of ILs processes, three commonly used ILs were selected for analysis: 1-butyl-3-methylimidazolium nitrate ([Bmim]NO₃), 1-butyl-2,3-dimethylimidazolium nitrate ([Bmmim]NO₃), and 1,3-dimethylimidazolium nitrate ([Mmim]NO₃). The process hazards under adiabatic conditions demonstrated that [Bmmim]NO₃ and [Mmim]NO₃ have extensive explosion hazards. The self-reaction characteristics determined by the isothermal test indicated that the ILs are nth reactions, and the thermal decomposition features were also determined by thermogravimetric analysis. The data were obtained with a nonlinear thermodynamic model and used to establish the basic thermal hazards of the three ILs. In addition, based on the thermal equilibrium theory, the critical safety parameters can be inferred. The effects of heat transfer in 25.0 g and 50.0 g containers were discussed. The results show that [Mmim]NO₃ will produce a thermal runaway reaction at a lower temperature (<100 °C) and has the shortest reaction time (<1 day), which means [Mmim]NO₃ is considered to be the most hazardous material among the three ILs studied.     

Flammability estimation of 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

Ionic liquids (ILs) are known as room temperature molten salts, which are considered green replacement to traditional organic solvents. The fire hazards of traditional organic solvents mainly depend on the combustibility of their vapors, thus ILs are generally regarded as nonflammable owing to their low volatility. However, recent studies show that ILs may combust due to the potential hazards of thermal decomposition, indicating the issue of fire and explosion of ILs are eager to be evaluated during the applications. In this study, the fire and explosion hazards of IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C₆mim][NTf₂]) are explored in different aspects. The traditional definition of the flammability for the common organic solvent is not thoroughly applicable to [C₆mim][NTf₂] due to the low volatility. Furthermore, the common definition of reactivity for traditional organic solvents also fails to apply, because the decomposition reaction is indeed an endothermic reaction. However, the auto-ignition of some decomposition products will result in fire and explosion hazards for [C₆mim][NTf₂]. Therefore the application of such data in safety purposes should be very careful.     

Determination of heterogeneous reaction mechanisms: A key milestone in dust explosion modelling

Reaction kinetics is fundamental for modelling the thermal oxidation of a solid phase, in processes such as dust explosions, combustion or gasification. The methodology followed in this study consists in i) the experimental identification of the reaction mechanisms involved in the explosion of organic powders, ii) the proposal of simplified mechanisms of pyrolysis and oxidation, iii) the implementation of the model to assess the explosion severity of organic dusts. Flash pyrolysis and combustion experiments were carried out on starch (22 μm) and cellulose (53 μm) at temperatures ranging from 973 K to 1173 K. The gases generated were collected and analyzed by gas chromatography. In this paper, a semi-global pyrolysis model was developed for reactive systems with low Damköhler number. It is in good agreement with the experimental data and shows that both carbon monoxide and hydrogen are mainly generated during the pyrolysis of the solid, the generation of the latter compound being greatly promoted at high temperature. A simplified combustion model was also proposed by adding two oxidation reactions of the pyrolysis products. In parallel, flame propagation tests were performed in a semi open tube in order to assess the burning velocity of such compounds. The laminar burning velocity of cellulose was determined to be 21 cm s⁻¹. Finally, this model will be integrated to a predictive model of dust explosions and its validation will be based on experimental data obtained using the 20 L explosion sphere. The explosion severity of cellulose was determined and will be used to develop and adjust the predictive model.     

阻燃电解液改善钛酸锂电池体系热稳定性研究

为了提高锂离子电池安全性,将碳酸亚乙烯酯、亚硫酸丙烯酯与二甲基乙酰胺加入到1.0mol/L LiPF_6/碳酸乙烯酯+碳酸二乙酯(1∶1wt%)的基准电解液中,配制成阻燃电解液。运用C80微量量热仪对钛酸锂负极(放电至1.0V)与基准电解液共存体系、钛酸锂负极(放电至1.0V)与阻燃电解液共存体系进行热稳定性测试,并计算得到热力学参数。对Li/基准电解液/Li_4Ti_5O_(12)和Li/阻燃电解液/Li_4Ti_5O_(12)半电池进行充放电循环测试、循环伏安测试与SEM扫描电镜测试。实验结果表明,钛酸锂负极与阻燃电解液体系反应放出的热量较钛酸锂负极与基准电解液体系减少了35.4%,且具有更高的活化能,提高了钛酸锂电池体系的热稳定性;同时电化学测试结果表明,阻燃电解液与钛酸锂负极有良好的相容性,可以应用到钛酸锂电池体系。     

新型膨胀型阻燃剂的合成及其在聚丙烯(PP)中的应用

以氨基三甲叉磷酸（ATMP）、尿素为原料采用热缩合法合成新型膨胀型阻燃剂一ATU。用傅里叶红外光谱及元素分析表征ATU的结构及组成。将ATU与常见碳源季戊四醇进行复配,应用于PP材料的阻燃。研究发现ATU集气源酸源于一身,对于PP阻燃效果明显,甚至好于同比例的APP。极限氧指数仪和垂直燃烧仪测试材料燃烧等级;微型燃烧量热仪（MCC）研究了材料燃烧过程中热释放情况;热重分析（TGA）和扫描电镜（SEM）分别从材料的热降解及成炭原理方面上对ATU的阻燃机理进行了研究。     

化学改性空心微珠阻燃热塑性聚氨酯弹性体的研究

为了提高热塑性聚氨酯弹性体的阻燃性，以四氟硼酸盐离子液体对空心微珠进行化学改性，获得新型阻燃热塑性聚氨酯弹性体复合材料。采用锥形量热仪和烟密度测试仪测定分析新型阻燃热塑性聚氨酯弹性体复合材料的阻燃、抑烟性能；探究化学改性后的空心微珠对热塑性聚氨酯弹性体的阻燃与抑烟效果的影响，以及不同组分含量的改性空微珠对热塑性聚氨酯弹性体的阻燃抑烟性能的影响。结果表明:采用四氟硼酸盐离子液体进行化学改性的空心微珠能够明显改善热塑性聚氨酯弹性体的阻燃性能；添加以四氟硼酸盐离子液体进行化学改性的空心微珠的热塑性聚氨酯弹性体复合材料具有一定的抑烟效果，其抑烟性能虽不如添加单一空心微珠的热塑性聚氨酯弹性体复合材料，但优于纯热塑性聚氨酯弹性体材料；相比于添加单一空心微珠的热塑性聚氨酯弹性体复合材料，添加化学改性空心微珠的热塑性聚氨酯弹性体复合材料的抑烟效果下降幅度低于阻燃效果的增强幅度，改性后的复合材料阻燃抑烟总体效果强于未改性的复合材料，改性空心微珠含量越高，总体效果越好。     

Making hybrid mixture explosions a common case

Explosions of gas-dust hybrid mixtures have long been considered as particular cases encountered in specific industrial contexts. However, it should be reminded that during the explosion of an organic powder, the presence of a hybrid mixture composed of the dust itself and its pyrolysis gases is compulsory. On these premises, an experimental study to determine the role of cellulose pyrolysis products (gaseous, condensable and solid) on the global phenomenon is presented. Hybrid mixture explosion tests were exploited to carry out the investigation. The G-G furnace and the 20 L sphere were employed. Several experimental strategies were chosen to demonstrate the impact of pyrolysis reaction on the explosion of organic powders: i) the fuel equivalence ratio of the reactive mixture (case 1), or ii) the mass of reactants (case 2) were respectively kept constant, iii) the effects of water vapor, char and tar were tested. They were next compared to identify the most suitable one. The two first experimental approaches lead to significantly different results: only case 2 keeps the maximum explosion pressure almost constant, but maximum rate of pressure rises and deflagration index greatly decrease when the pyrolysis gases concentration decreases, which highlights the importance of the pyrolysis reaction on the explosion kinetics. It should also be stressed that the maximum explosion severity is not obtained for the pure gases but when a small dust content is added. The same evolution is observed when a small amount of char is introduced to pyrolysis gases, which underlines the influence of the radiative transfer. Adding small amounts of tar to cellulose tends to increase its explosion severity. However, this impact is less than that generated by the addition of pyrolysis gases.     

典型硼化合物与磷酸二氢铵协效阻燃松木的燃烧性能及热解动力学研究

利用木垛法和热重分析法比较研究了硼酸、硼砂与磷酸二氢铵复配阻燃松木的燃烧性能、热解特性及热解反应动力学。结果表明,单种阻燃剂使用时,磷酸二氢铵的阻燃效果优于硼酸和硼砂;两两复配使用具有明显的协效作用,其中阻燃效果:磷酸二氢铵/硼酸＞磷酸二氢铵/硼砂＞硼酸/硼砂,而硼酸与磷酸二氢铵在质量比为2:3时,协效阻燃效果最好。与未处理松木相比,阻燃剂的加入降低了松木在热解阶段的初始分解温度和峰值分解温度,缩短了热解区间,并降低了松木在主要热解阶段的表观活化能,其中热解阶段活化能越低的阻燃松木在燃烧过程中成炭效果和阻燃性能越好。     

高压开关柜阻燃绝缘件在役老化诱发着火事故的综合分析

高压开关柜长期连续运行在高温高湿环境下,内部的阻燃绝缘件会老化而导致性能劣化,进而引起电弧击穿乃至着火事故。为揭示绝缘件样品老化对其击穿与引燃特性的影响机制,针对已在役运行12年开关柜内老化阻燃固封极柱样品和同配方新样品,开展了微观形貌、热重-差示扫描量热、热重-红外光谱和微量燃烧特性综合分析。结果表明:开关柜内的长期电热应力易使环氧树脂绝缘材料的微观结构产生破坏,内部易产生孔洞和裂纹,导致其绝缘性能下降;开关柜内的高温环境易使绝缘材料内部分子链缓慢断裂,导致老化样品更易受热分解;同时,柜内高温高湿环境既可使其材料内部孔隙吸湿而降低绝缘性能,还易导致磷系阻燃剂吸潮氧化,降低其阻燃性能;最后,与新样品相比,12年老化样品在升温初期的燃烧释热更高,一旦形成击穿电弧,更易着火燃烧。研究结果为高压开关柜因绝缘件老化失效而形成击穿起火事故提供了分析要点,并可作为未来更高性能阻燃绝缘件的优化设计依据。     

Thermal hazard analysis of 1-((cyano-1-methylethyl) azo) formamide and effect of incompatible substances on its thermal decomposition

1-((cyano-1-methylethyl) azo) formamide (CABN) is an azo compound that exhibits high thermal sensitivity and self-reactivity. Because of incorrect operation, incompatible substances and other dangerous conditions, thermal explosion accidents may occur during the manufacturing, storage, and transportation of CABN. The pyrolysis characteristics of CABN and its mixture for various heating rates were assessed using differential scanning calorimetry. The results showed that incompatible substances increased the risk of CABN. Moreover, the thermal runaway of CABN under an adiabatic condition was studied using an adiabatic rate calorimeter to obtain the parameters under adiabatic condition. Based on the experimental data, the kinetic parameters of CABN and its mixtures were obtained. In addition, a thermal decomposition kinetic model of CABN was created using Thermal Safety Series. All experiments have shown that the conditions and parameters of CABN must be strictly controlled.     

异戊醇低压热解的同步辐射真空紫外光电离质谱研究

作为新兴生物燃料,大分子醇类燃料在低压下的火灾安全基础迫切需要得到深入研究。热解过程作为火灾过程的初始阶段直接控制着火过程,火灾中碳烟颗粒的产生也依赖于热解反应,因此可燃物的低压热解研究在其低压火灾基础研究中具有重要意义。利用同步辐射真空紫外光电离质谱方法研究了异戊醇在0.2atm下的流动反应器热解,探测到了20余种热解产物,包括烯丙基自由基和C_4H_8O、C_5H_8、C_6H_6等同分异构体,并测量了其摩尔分数。基于实验结果,对燃料分解路径和主要产物的生成及消耗路径进行了探讨。与本组之前正戊醇热解实验的对比表明,由于存在支链结构,异戊醇在热解中比正戊醇更容易产生戊烯、丁烯和丙烯,但更少地产生乙烯。此外,异戊醇在热解中能够生成更多的丙炔和丙二烯等环状化合物前驱体,令其苯和1,3-环戊二烯的生成量更高,表明异戊醇比正戊醇更易于生成多环芳烃和碳烟。     

相变调温防护服用织物的阻燃性能研究*

为提高相变调温防护服的阻燃性能,以保障工作人员的生命安全,系统开展阻燃型相变微胶囊涂层织物的制备与阻燃性能研究。选取2种相变温度的相变微胶囊、2种阻燃基布,利用干法涂层工艺制备相变微胶囊涂层织物;选取2种阻燃剂,以45%和75%的比例涂覆在相变微胶囊涂层的表面,制成16种阻燃型相变微胶囊涂层织物。基于锥形量热仪进行涂层织物阻燃性能测试,分析阻燃剂对涂层织物阻燃性能的影响。结果表明:与未进行阻燃整理的涂层织物相比,有机硅阻燃剂涂层织物的总热释放量平均下降42.22%,磷氮型阻燃剂涂层织物的总热释放量平均下降25.07%,并且随着阻燃剂含量的增加,总热释放量呈下降趋势。另外,有机硅型阻燃剂明显降低了热释放速率与总热释放量,而磷氮型阻燃剂有效地延长了织物开始释放热量的时间和热释放速率达到峰值的时间。因此,2种阻燃剂从不同角度优化了相变微胶囊涂层织物的阻燃性能,提高了相变调温防护服的使用安全性。     

景区典型树种的热解特性及动力学研究

为了研究山林或景区中不同植物的热稳定性,选取了景区种植数量较多的6种典型树种:女贞、枇杷、竹子、松树、柏树和法桐的枝干和叶作为样品。借助同步热分析仪,在温升速率20℃/min的条件下,对未经干燥处理的样品进行热解特性及热解反应动力学研究。通过TG、DTG以及DSC曲线分析各样品的热解过程,并采用分阶段一级反应动力学模型Coats-Redfern法求得相应参数。研究结果表明:所取样品的热解过程都出现4个明显的热解阶段,即脱水阶段、综纤维素热解阶段、木质素热分解阶段、炭化阶段。根据6个树种的主要热解阶段和动力学分析,6种树种的热稳定性从低到高顺序依次为竹子、女贞、枇杷、法桐、柏树、松树。     

基于桶式环形加热的阻燃电缆细观竖直燃烧特性研究实验平台的设计

针对阻燃电缆等难燃材料,为研究其在外界热源条件下的火灾性能与蔓延燃烧特性,研制了基于环形加热的阻燃电缆细观燃烧特性诊断实验平台。该平台主要包括三个部分,即:半封闭环形桶式加热与燃烧腔室、样品竖直固定模块和数据采集系统。实验参数的标定及典型阻燃电缆受热与燃烧实验结果表明,常规条件下无法点燃的阻燃电缆,当置于实验平台的加热炉内被加热一段时间后,底部小火源可将其点燃并呈现猛烈的燃烧与蔓延过程。该加热模块能够详细、准确地研究各种阻燃电缆在环形加热条件下的膨胀、引燃及蔓延燃烧的细观特性,而不同的加热模式有助于深入研究阻燃材料在各种热环境下的火灾特性,为阻燃材料的引燃机理及火蔓延模型研究提供了必要的研究平台。     

煤低温氧化热解的热分析实验研究

在热分析动力学的基础上,对阳泉煤样运用同步热分析仪进行150℃下的氧化以及热解实验,得出该煤样相应的TG-DSC曲线。通过两者的TG-DSC曲线,对比分析煤样的热量释放情况,并结合曲线设定多项式形式的机理函数以分析其动力学特性。实验研究得出:该煤的低温氧化过程较之热解过程是个明显的氧化放热过程;该煤低温氧化和热解过程的最佳机理函数都为多项式,并且相应过程中的TG曲线和DSC曲线适用于同一个机理函数,这与一般所定义的机理函数不同;热解过程较之氧化过程所需的表观活化能较大,相同条件下较易发生煤的氧化自燃。