着床后引燃对电弧迸溅熔珠组织特征的影响*

为探究迸溅熔珠着床后的热交换过程对其组织特征的影响,建立基于着床后高温迸溅熔珠的动态测温方法,从而揭示迸溅熔珠着床后引燃与否对其组织特征形成的影响规律。研究结果表明:引燃可燃物的熔珠受火焰热反馈和铜氧化放热的共同作用,着床后其温度出现反复波动,延长迸溅熔珠的冷却凝固时间,组织呈等轴状;无法引燃可燃物的熔珠在可测范围内,短暂升温后降温速率持续上升,组织更易呈现树枝状或胞状。研究结果可为准确认定电气故障电弧迸溅熔珠引发火灾提供技术支持。     

Analysis of the chosen thermal and flammability parameters of dried sewage dust

The hazardous sludge disposal process in the form of landfills requires the determination inter alia of the flammable and explosion properties of dried sewage sludge dust, which has the ability to ignite and spontaneously combust when stored in silos. At a constant furnace surface temperature, the minimum ignition temperature of the sludge dust layer with a layer thickness of 5 mm is 270 °C, and for a layer thickness of 12.5 mm it is 250 °C. Two selected fire extinguishing powders for Class A, B, C and D fires were used in the study to determine the possibility of reducing the susceptibility of dried wastewater to ignition from heated surface, self-ignition and explosion parameters. The most effective extinguishing powder was ABC Favorit, which increased the value of the minimum ignition temperature of the layer (5 mm thick) to 360 °C and the spontaneous ignition temperature of the sludge with this powder increased by 22 °C at 169.6 cm³ in comparison to the sludge without extinguishing powder, respectively. The lowest self-ignition temperature of 136 °C was recorded for the largest tested volume (169.6 cm³) for dried sewage dust without any fire extinguishing powders. The biggest values of p_max and (dp/dt)_max dried sewage dust were recorded 4.8 bar and 113 bar/s respectively. By analysing the obtained test results, it can be assumed that dried sewage dust is a combustible material with properties similar to biomass.     

Modelling breakdown of industrial thermal insulation during fire exposure

The aging of many of the installations in the oil and gas industry may increase the likelihood of loss of containment of flammable substances, which could lead to major accidents. Flame temperatures in a typical hydrocarbon fire may reach 1100–1200 °C, which are associated with heat flux levels between 250 and 350 kW/m². To limit or delay the escalation of an initial fire, passive fire protection (PFP) can be an effective barrier. Additionally, both equipment and piping may require thermal insulation for heat or cold conservation. Previous studies have investigated whether thermal insulation alone may protect the equipment for a required time period, e.g., until adequate depressurization is achieved. The present study entails the development of a numerical model for predicting the heat transport through a multi-layer wall of a distillation column exposed to fire. The outer surface is covered by stainless-steel weather protective cladding, followed by PFP, thermal insulation, and finally an inner column of carbon steel of variable thicknesses. The model for the breakdown of thermal insulation is based on observed dimensional changes and independent measurements of the thermal conductivity of the insulation after heat treatment. The calculated temperature profiles of thermally insulated carbon steel during fire exposure are compared to fire test results for carbon steel with thicknesses of 16, 12, 6 and 3 mm. The model's predictions agree reasonably well with the experiments. The degradation of the thermal insulation at temperatures above 1100 °C limits its applicability as fire protection, especially for low carbon-steel thickness. However, the model predicts that adding a 10-mm layer of more heat-resistant insulation (PFP) inside the fire-exposed cladding may considerably extend the time to breakdown of the thermal insulation.     

Case study on prevention of fire hazards in coating epoxy-based FRP work with illumination

In this study, we investigated and analyzed the causes of fire hazards on the basis of actual accidents that occurred during epoxy resin fiberglass-coating operations. Results of this study showed that during this process, two major factors could cause a fire. One factor was related to the heat produced during the mixing of the epoxy resin and a polyamide curing agent. From the results of thermal analysis, it was found that the T_onset of the epoxy resin and the polyamide curing agent was 52.8 °C by DSC and T_d10 was 58.9 °C by DT/TGA, causing an exothermic hazard. Further, the results of a pseudo-adiabatic analysis performed in a Dewar vessel showed that the temperature increased from 23.5 °C to 177 °C.The other factor that could increase fire hazard was the illumination source used during the coating operation. Depending on the type of illumination source used, the temperature could increase above 350 °C. The decomposition temperature (T_d10) of PVC was 276.3 °C. The experiments involving epoxy resin fiberglass coating using an illumination source showed serious burn marks, and the polyvinyl chloride (PVC) electrical cable emitted small flames. Therefore, it can be concluded that fire was caused by the combination of two factors—the exothermic reaction between epoxy resin and the polyamide curing agent and the effect of prolonged illumination, both of which caused an increase in temperature leading to auto-ignition of the PVC electric cable.     

Effects of environmental temperature on the thermal runaway of lithium-ion batteries during charging process

Lithium-ion batteries with relatively narrow operating temperature range have provoked concerns regarding the safety of LIBs. In this work, a series of experiments were conducted to explore the thermal runaway (TR) behaviors of charging batteries in a high/low temperature test chamber. The effects of charging rates (0.5 C, 1 C, 2 C, and 3 C), and ambient temperature (2 °C, 32 °C and 56 °C) are comprehensively investigated.The results indicate that the cell exhibited greater thermal hazard at the high charging rate and ambient temperature conditions. As the charging rate increased from 0.5 C to 3 C, more lithium intercalated in the anode prompt the TR triggered in advance, the TR onset temperature decreased from 297.5 °C to 264.7 °C. In addition, the charging time decreased with the elevated ambient temperature, resulting in a relatively higher TR onset temperature and lower maximum temperature, and the average TR critical time declined by 115–143 s. Finally, the TR required less heat accumulation with increasing of charging rate and ambient temperature, and the heat generation of side reaction played a substantial role that accounted for approximately 54%∼63%. These results provide an insight into the charging cell thermal runaway behaviors in complex operation environments and deliver valuable guidance for improving the safety of cell operation.     

Thermal effects of a sonic jet fire impingement on a pipe

Although the effects of jet fires are often limited to rather short distances, if their flames impinge on a pipe or a vessel collapse can occur in very short times. In such cases, the heat flux on the affected equipment is very high and wall temperature can increase very rapidly. This can happen in parallel pipelines, if a release occurs and impinges on another one. Nevertheless, jet fire impingement has been scarcely studied. In this communication the results obtained from an experimental set-up are presented. Sonic jet fires impinged on a pipe containing stagnant air or water. The temperatures of the flames impinging on it were measured for the worst case (flame front-bright zone), as well as the evolution with time of the pipe wall temperature at different locations. Initial temperature increases up to around twenty °C/s were registered for the air inside, with maximum values of up to 600 °C reached in 2.5 min, and 800 °C in approximately 9 min. In the case of pipe containing water, in the zone of the wall in contact with the liquid the heating rates were much lower, the maximum temperature reached being up to approximately 150 °C. From the temperatures of the jet flames and of the pipe, the heat fluxes reaching the pipe and the corresponding heat transfer coefficients were obtained. The results obtained emphasized that safe distances are essential in pipelines, together with fire proofing and other safety measures.     

Full-scale experimental studies for backdraft using solid materials

The backdraft experiments involved three full-scale room fire tests that used solid furnishing, loveseats. From experimental data, a backdraft caused two temperature peaks. The first one was below 600 °C. Then, an abrupt opening of the front door led to a supply of a large amount of fresh air, followed by an indication of sudden temperature rise. The second peak temperature was over 600 °C. Meanwhile, the deflagration resulted in the gases heating and expanding within the fire space, thus forcing unburned gases out of the vent ahead of the flame front. Comparing both cases with natural gas and solid loveseat as the fuel in backdraft, the former can achieve pre-mixture state and readily create an instant explosion wave phenomenon; however, this wave disappeared immediately. On the other hand, the solid loveseat used as the fuel in this study produced backdraft within 30–50 s after opening of the door. After the occurrence of backdraft, fire maintained a period of fully developed stage, which was consistent with the conditions in actual fires.     

Effect of particle size and dust layer size on ignition characteristics of PMMA dust layer on hot surface

Deposition of combustible dust on a hot surface is a hidden danger of fire. In this work, polymethylmethacrylate (PMMA) dust was selected to analyse the influence of dust layer diameter, dust particle size and dust layer thickness on the ignition characteristics of PMMA dust layer. Critical heating temperatures and ignition time had been measured. The STA-GC/MS-FTIR analysis was used to determine that the main products of PMMA pyrolysis were MMA, CO, CO₂, and C₂H₄, of which CO and C₂H₄ were transported to the ambient to cause gas phase combustion on the surface of the dust layer. For 10 mm thick dust layer, the critical heating temperatures of 5 μm PMMA, 100 nm PMMA, and 30 μm PMMA were 300 °C, 330 °C, and 320 °C. As the thickness of the dust layer increased, the gas transport path became longer, the critical heating temperature and ignition time increased. The characteristic particle size (D [3,2]) was utilized to represent the true particle size, and the ignition time increased with the increase of the characteristic particle size. The increase in the diameter of the dust layer had a slight effect on the temperature history and ignition time of the dust layer.     

Experimental research in the fire resistance of the double-frame container

During the road transportation of hazardous materials (hazmat), container was usually used to protect the inner package from accidents. The conventional container is a sandwich-framed construction. When it was subjected to car fire, the combustible materials such as poly-foam interlayer would burn up in few minutes. Once the hazmat leaked out, it could result in the great loss of the public and environment. In this paper, a double-frame container mechanism was firstly proposed for loss prevention. In order to investigate the heat conduction pattern and the effect of interlayer thickness, the two-dimensional (2D) Finite Element (FE) model was developed. Based on the numerical results, the interlayer thickness was defined as 155 mm considering the ignorance of sealing. Furthermore, two small-scale containers whose interlayer were ceramic fiber and phenolic foam separately were manufactured. Pool fire experiments were carried out to evaluate the fire resistance of the mechanism and compare the insulation of the interlayer. Results show that the construction of the container remained complete after about 30-min fire exposure. The maximum temperature inside was below 100 °C during the burning process. When the fire burnt down, the temperature inside increased to 110 °C and then declined gradually during the 1000-min cooling process. Additionally, although the thermal insulation of the container with phenolic foam is relatively better, the ceramic fiber is much more suitable for the interlayer considering the sealing of the container and the stability in heat. In summary, the double-frame container could protect the product inside from car fire. It could be beneficial for the fire-resistant design of much bigger containers, which might be widely used for loss prevention in hazmat transport.     

不同受热温度下一次短路熔珠显微特征分析

为考查冷却条件对导线一次短路熔珠显微组织的影响,实验模拟室内火灾的热环境,对一次短路熔珠进行加热处理,观察温度、加热时间对不同线径铜导线一次短路熔珠金相组织的影响.实验结果表明:温度及加热时问对铜导线一次短路熔珠的金相组织有较大影响,随着温度的升高,时间的增加,在达到某一温度后,细小的柱状晶逐渐长大,一次短路熔珠的细小晶粒变成粗大的柱状晶或胞状晶,有的甚至表现为等轴晶,与铜导线的火烧熔珠的金相组织特征有些相似.     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

Metallurgical analysis of the ‘cause’ arc beads pattern characteristics under different short-circuit currents

Electric arc beads commonly cause large fire and explosion accidents, especially during the powder process industries. During such fires, the original equipment is often severely burned, rendering electrical fire investigation impossible. Therefore, identifying the beads caused by electrical faults through metallurgical investigation is crucial. This study focused on the ‘cause’ of arc beads and determined their pattern characteristics through metallurgical analysis of copper wires with short-circuit currents of 100, 160, 200, and 240 A. According to microstructure characteristics and metallographic knowledge, bead pattern characteristics were divided into six types: hypereutectic (A), dendritic eutectic (B), chilled layer (C), cellular crystal (D), dendritic (E), and coarse columnar crystal (F). Oxide levels of each category were A (4.5%–7.6%) > C (2.0%–3.8%) > B (1.1%–2.4%) > D (1.0%–2.1%) > E (0.6%–1.9%) > F (0.1%–0.7%). When the short-circuit currents were the same, there were a greater number of small particle beads than large ones. As the current increased, the number of distributed beads with a particle size d < 1 mm decreased, with 1 mm ≤ d < 2 mm increased, and with d ≥ 2 mm were stable. Bead size and distribution had a negative linear correlation at 200 A. When the current increased, the proportion of beads with A and C structures gradually decreased, and those with D structures increased to more than 50%. Oxygen content and arc temperature determined the oxide form. These results are vital for electrical fire investigations and provide theoretical support for fire material evidence extraction and cause identification.     

Research on the critical temperature of thermal decomposition for large cartridge emulsion explosives

Emulsion explosives are one type of main industrial explosives. The emergence of the large cartridge emulsion explosives has brought new security incidents. The differential scanning calorimeter (DSC) and the accelerating rate calorimeter (ARC) were selected for the preliminary investigation of the thermal stability of emulsion explosives. The results showed that the initial thermal decomposition temperatures were in the range of 232–239 °C in nitrogen atmosphere (220–232 °C in oxygen atmosphere) in DSC measurements and 216 °C in ARC measurements. The slow cook-off experiments were carried out to investigate the critical temperature of the thermal decomposition (T_c) of the large cartridge emulsion explosives. The results indicated that the larger the diameter of the emulsion explosives, the smaller the T_c is. For the large cartridge emulsion explosives with diameter of 70 mm, the T_c was 170 °C at the heating rate of 3 °C h⁻¹. It is a dangerous temperature for the production of the large cartridge emulsion explosives and it should cause our attention.     

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.     

Thermal characterization of fly ash from one municipal solid waste incinerator (MSWI) in Shanghai

This study aims to develop a methodology for the thermal characterization of MSWI fly ash. We performed TGA–DTA and component variation analysis, microstructure transfer of sintered fly ash, as well as leaching toxicity, volatilization ratio and specification transformation of heavy metals as a function of temperature. It is found that content of crystal phases first increases between room temperature and 800 °C and then decreases between 800 °C and 1200 °C, while that of glass phases registers a reverse trend. Fly ash registers a SiO₂–Al₂O₃–metal oxides system and its content of glass phases is around 57%. Increase of sintering temperature between 600 °C and 1200 °C is conducive to the reduction of soluble As, Cd, Cu, Hg, Pb, Ni and Zn, while content of soluble Cr increases as temperature rises from 800 °C to 1200 °C.     

Thermal decomposition mechanism of 65% lysine sulfate powder and its thermal stability based on thermal analysis

Lysine is widely used in the fields of food, medicine and feed, which generally appears in the form of lysine sulfate or lysine hydrochloride dust because of the high instability of the free L-lysine. The L-lysine Sulfate is in high risk of decomposition, spontaneous ignition and even the dust explosion, because the control temperature in its production process is high up to 90 °C. Thus, the thermal behaviors and its thermal stability of 65% lysine sulfate are experimentally explored in Air and Nitrogen using the simultaneous TG-DSC measurements. Results show: (1) the decomposition of 65% lysine sulfate can be divided into three stages both in the atmospheres of air and nitrogen, and most of the weight loss occurred in the first two stages, which are related with the decarboxylation and deamination process. (2) The effects of atmosphere on the decomposition of 65% lysine sulfate mainly occur at the third stage. In this stage, the weight loss in nitrogen is only 14.2%, which is much lower than that in air (34.3%), which is related to the oxidative degradation at high temperature. Besides, the active energy is slightly increased in nitrogen compared to that in air. (3) The initial temperatures of the decomposition of the 65% lysine sulfate are 145 °C and 155 °C, for the air and nitrogen atmosphere, respectively, which are much lower than that (260 °C) of the pure lysine.     

玻化微珠保温砂浆在隧道防火设计中的应用研究

针对当前多发的隧道火灾,探讨玻化微珠保温砂浆在隧道防火设计中的可行性。通过有限元计算分析,对设置玻化微珠保温砂浆隔热层的隧道衬砌结构防火性能进行研究,同时对不同火灾规模下隧道温度场的影响进行了分析。研究结果表明玻化微珠保温砂浆可以很好地阻止热量的入侵,初步验证了其在隧道防火应用的可行性,可为后续隧道防火设计及相关研究提供参考。     

Thermal safety assessment for solid organic peroxides

The thermal hazards of dicumyl peroxide (DCP) and benzoyl peroxide (BPO), self-reactive chemicals are identified and characterized using high-pressuredifferential scanning calorimeter, and simultaneous thermogravimetric analyzer, a C80 micro-calorimeter is used. The apparent exothermic onset temperature of DCP is found to be between the range of 112–122 °C for different heating rates in DSC tests. There are two coupled peaks of BPO around 105 °C at both the heating rates of 4.0 and 8.0 °C/min while no endothermic peak showed at lower heating rates. Furthermore, another endothermic peak appears immediately after the exothermic peak at about 211 °C of DCP under high-pressure conditions. For BPO, the endothermic peak before the exothermic peak disappears as the pressure increases to 1.0 and 1.5 MPa. The average values of apparent activation energy calculated by Flynn-Wall-Ozawa and Kissinger-Akahira-Sunose methods during the conversion rate between 15 and 75% of DCP are 80.69 and 74.05 kJ/mol, and that of BPO are 119.96 and 112.93 kJ/mol, respectively. According to the isothermal tests, the thermal decomposition of DCP behaviors is an n-th order reaction while BPO conforms to the laws of autocatalytic reaction.     

Autoignition temperature data and scaling for amide solvents

Autoignition temperature tests using the ASTM E659 test method have been conducted for N,N-dimethylacetamide (DMAC) and N,N-dimethylformamide (DMF) in test vessels with volumes of 0.5 l, 5 l, and 12 l. Tests were conducted at three different laboratories yielded good agreement (standard deviation with 5 °C) in all cases except for DMAC in the 0.5 l test vessel (standard deviation of 23 °C). Scaling correlations have been developed for the decrease of autoignition temperature with increasing volume and for increasing values of the vessel volume to surface area ratio. The variations for DMAC are steeper than the literature values for almost all other combustible liquids. Cool flames were observed for DMAC at temperatures as much as 44 °C below the autoignition temperature and for DMF at temperatures as much as 171 °C below its autoignition temperature. The DMF cool flame temperatures in the 5-l and 12-l test vessels are approximately equal to the DMF autoignition temperature in a closed 12-l test vessel. Gas samples taken after the cool flame and hot flame tests reveal the presence of high concentrations of diamines and dimethylamino acetonitrile, and small concentrations of many other partial decomposition/oxidation components.