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Evaluation on thermal explosion induced by slightly exothermic interface reaction.

An asphalt-salt mixture (ASM), which once caused a fire and explosion in a reprocessing plant, was prepared by imitating the real bituminization process of waste on a lab scale to evaluate its actual thermal hazards. Heat flux reaction calorimeters were used to measure the release of heat for the simulated ASM at a constant heating rate and at a constant temperature, respectively. Experimental results show that the reaction in the ASM below about 250 degrees C is a slightly exothermic interface reaction between the asphalt and the salt particles contained in the asphalt, and that the heat release rate increases sharply above about 250 degrees C due to melting of the salt particles. The reaction rates were formulated on the basis of an assumed reaction model, and the kinetic parameters were determined. Using the model with the kinetic parameters, temperature changes with time and drum-radius axes for the ASM-filled drum were numerically simulated assuming a one-dimensional infinite cylinder system, where the drum was being cooled at an ambient temperature of 50 degrees C. The minimum filling temperature, at which the runaway reaction (MFTRR) can occur for the simulated ASM in the drum is about 194 degrees C. Furthermore, a very good linear correlation exists between this MFTRR and the initial radius of salt particles formed in the bituminization product. The critical filling temperature to the runaway reaction is about 162 degrees C for the asphalt-salt mixture, containing zero-size salt particles, filled in the same drum at an ambient temperature of 50 degrees C. Thus, the runaway reaction will never occur in the drum filled with the asphalt-salt mixture under the conditions of the filling temperature below 162 degrees C and a constant ambient temperature of 50 degrees C. As a consequence, the ASM explosion occurred in the reprocessing plant likely was due to a slightly exothermically reaction and self heating.

Explosions↗

Social and political amplification of technological hazards. The case of the PEPCON explosion.

Using an industrial explosion in Henderson, Nevada, as a case study, this paper examines three main issues: the efficacy of a technological hazard event in amplifying otherwise latent issues, the extent to which the hazard event can serve as a focusing event for substantive local and state policy initiatives, and the effect of fragmentation of political authority in managing technological hazards. The findings indicate that the explosion amplified several public safety issues and galvanized the public into pressing for major policy initiatives. However, notwithstanding the amplification of several otherwise latent issues, and the flurry of activities by the state and local governments, the hazard event did not seem to be an effective focusing event or trigger mechanism for substantive state and local policy initiatives. In addition, the study provides evidence of the need for a stronger nexus between political authority, land-use planning and technological hazard management.

Accidents, Occupational↗

Flammability limits and explosion characteristics of toluene-nitrous oxide mixtures.

Flammability limits and explosion characteristics of toluene-nitrous oxide mixtures are experimentally determined in an 8l spherical vessel, and are compared with corresponding values of toluene-air mixtures. The experiments, performed at atmospheric pressure and at an initial temperature of 70 degrees C, show that the flammable range of toluene in nitrous oxide (0.25-22.5 mol%) is about three times as wide as the corresponding range of toluene in air (1.3-7.1 mol%). Maximum values of the explosion pressure ratio and the deflagration index, K(G), are clearly higher when nitrous oxide is applied as an oxidizer. This can be attributed to the increased flame temperature and burning velocity of toluene-nitrous oxide flames. Moreover, extremely high values of K(G) for near-stoichiometric mixtures in combination with strong acoustic oscillations in the pressure signals of these mixtures indicate the existence of a flame accelerating mechanism. These phenomena are enhanced when an initial pressure of 6 bara is applied. Finally, when evaluating the lower flammability limit, it was found that pure nitrous oxide decomposes at pressures above 4.5 bara when applying an ignition energy of about 10 J.

Atmospheric Pressure↗

Explosive properties of 1-hydroxybenzotriazoles.

1-hydroxybenzotriazole and its derivatives are widely used as peptide coupling reagents. However, people are often not aware that such compounds show explosive properties when heated under defined confinement or when subjected to mechanical stimulus. 1-Hydroxybenzotriazole (HOBt) is able to propagate a detonation when a stronger booster is used. Sometimes explosive substances are desensitized to suppress their hazardous properties, yet depending on the amount and nature of desensitizer, the result is often not quite satisfactory. During the last years, some 1-hydroxybenzotriazoles were tested at BAM. The results are presented in this paper.

Borates↗

Crystal structure, thermal decomposition mechanism and explosive properties of [Na(H2TNPG)(H2O)2]n.

The new coordination polymer of sodium trinitrophloroglucinate, [Na(H2TNPG)(H2O)2]n, was synthesized by reacting trinitrophloroglucinol (H3TNPG) with NaHCO3 in aqueous solution and [Na(H2TNPG)(H2O)2]n was recrystallized to be yellow single crystal. The title compound was characterized by using elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystalline belongs to monoclinic system and C2/c space group. Each Na+ ion is six-coordinated to one H2TNPG- anion and four water molecules in which the oxygen atoms in the water molecules act as bridging atoms. Coordination bonds, electrostatic interaction and intermolecular hydrogen bonds assemble the ions into network structures. The thermal decomposition mechanism of the complex was studied by using differential scanning calorimetry (DSC), thermogravimetry/derivative thermogravimetry (TG/DTG) and FT-IR techniques. Under nitrogen atmosphere with a heating rate of 10 degrees C/min the thermal decomposition of the complex contained one endothermic and five exothermic processes. Two intense exothermic decomposition processes were observed in the range of 173-228 degrees C suggesting its energetic nature and the solid decomposition residue at 500 degrees C was sodium isonitrile. Explosive properties revealed that the compound is sensitive to mechanical stimuli. All properties data observed show that the title compound has explosive properties and can act as components of ecologically clean initiating compositions.

Calorimetry, Differential Scanning↗

Characteristic overpressure-impulse-distance curves for vapour cloud explosions using the TNO Multi-Energy model.

A number of models have been proposed to calculate overpressure and impulse from accidental industrial explosions. When the blast is produced by ignition of a vapour cloud, the TNO Multi-Energy model is widely used. From the curves given by this model, data are fitted to obtain equations showing the relationship between overpressure, impulse and distance. These equations, referred herein as characteristic curves, can be fitted by means of power equations, which depend on explosion energy and charge strength. Characteristic curves allow the determination of overpressure and impulse at each distance.

Accidents, Occupational↗

Velocity of detonation at any initial density without using heat of formation of explosives.

The simplest method is introduced for reliable estimating the detonation velocity of large class of CHNO explosives based elemental composition and specific structural groups. There is no need to use heat of formation and the other experimental data for calculation of detonation velocity in the new procedure. Only elemental composition and the number of special structural groups without using heat of formation of explosive is sufficient for reliable desk calculation of detonation velocity. The results show good agreement with experimental values with respect to computed results obtained by complex computer code using BKWS and BKWR equations of state. Predicted velocities of detonation have root-mean-square (rms) percent deviation of 2.2, 5.9 and 5.3 from experimental data for new method, BKWS and BKWR equations of state, respectively.

Explosions↗

Development of a miniature calorimeter for identification and detection of explosives and other energetic compounds.

The development of versatile systems capable of providing rapid, portable, and inexpensive detection of explosives and energetic compounds are critically needed to offer enhanced levels of protection against current and future threats to homeland security, as well as satisfying a wide range of applications in the fields of forensic analysis, emergency response, and industrial hazards analysis. Calorimetric techniques have been largely overlooked in efforts to develop advanced chemical analysis technology, largely because of limitations associated with the physical size of the instruments and the relatively long timescales (>30 min) required to obtain a result. This miniaturized calorimeter circumvents these limitations, thereby creating a first-of-its-kind system allowing thermal analysis to be performed in a portable format that can be configured for use in a variety of field operations with a significantly reduced response time (approximately 2 min). Unlike current explosives detectors, this system is based on calorimetric techniques that are inherently capable of providing direct measurements of energy release potential and therefore do not depend on prior knowledge of familiar compounds.

Calorimetry↗

Preparation and thermal studies on tetranitrodibenzo tetraazapentalene (TACOT): a thermally stable high explosive.

Thermally stable high explosive, tetranitro-2,3,5,6-dibenzo-1,3a,4,6a-tetraazapentalene (TACOT) was synthesized and characterized during this work. Thermo analytical techniques (TG and DSC) were applied to study the thermal decomposition behaviour of TACOT in comparison with benchmark thermally stable high explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB). Kinetic parameters such as reaction order, activation energy and pre-exponential factors were computed from the thermal data. The activation energy for TACOT (292 kJ/mol) was found 1.5 times to that of TATB (200 kJ/mol), which can account for its higher thermal stability and can be attributed to pentalene moiety in the former.

Aza Compounds↗

Microscale solid-phase extraction system for explosives.

A simple, semi-automated, microcolumn solid-phase extraction (SPE) system is optimized for the extraction, preconcentration and HPLC analysis of seven different explosives and explosive derivatives contaminating seawater, river water and well water samples. The microcolumns were constructed from 1/16 in. O.D. PTFE tubing (1 in.=2.54 cm) packed with 0.5-1.5 mg of SPE material. LiChrolut EN or Porapak R. The extraction system consisted of two syringe pumps and several solenoid valves. Optimal detection limits were realized when the sample water flow-rate was maximally increased within the limits of the pump, 5-10 ml/min (despite exceeding the breakthrough threshold of the SPE microcolumn), and when the eluate volume collected from the column was minimized, <5 microl (despite very low recovery percentages).

Automation↗

Trace detection of explosives using a membrane-based displacement immunoassay.

A compact membrane-based displacement immunoassay has been designed for rapid detection of explosive compounds 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at high femtomole levels. The system consists of activated porous membranes, onto which either TNT or RDX antibodies are immobilized, that are inserted into microreactor columns, incorporated into a flow system. The assay is prepared by saturating the immobilized antibody binding sites with labeled antigen. Target analyte is introduced upstream of the microreactor, while the displacement of labeled antigen is monitored downstream using a fluorometer. The concentration of displaced labeled antigen detected is proportional to the concentration of the target analyte introduced into the system. This system provides a reusable and reagentless sensor, suitable for continuous monitoring of explosives, with an operating lifetime of over 50 positive samples. Multiple assays were performed in approximately 5 min at different flow rates, using membranes saturated with varying antibody concentrations. The membrane-based format exhibited a detection limit of approximately 450 fmol for TNT and RDX (100 microl of 1 ng/ml solution) in laboratory samples.

Antibodies, Monoclonal↗

The effect of particle size reduction by grinding on subsampling variance for explosives residues in soil.

Efforts to characterize the surface soil contamination on military training ranges have been compromised by the inability to obtain representative subsamples of soils submitted to analytical laboratories for determination of explosives residues. Two factors affecting subsampling error for explosives residues were examined using soils collected from hand grenade and anti-tank ranges. These factors were increased subsample size and particle size reduction prior to subsampling of soils. Increasing the subsample size from 2 to 50 g did not reduce the soil subsampling error because of the extreme heterogeneous distribution of the solid contaminants. Alternatively, particle size reduction by machine grinding on a ring mill reduced subsampling error to less than 10% relative standard deviation for replicate analyses using 10-g subsamples.

Environmental Monitoring↗

Potentially explosive colonic concentrations of hydrogen after bowel preparation with mannitol.

Hydrogen (H2) concentrations were measured in undiluted samples of intracolonic gas and in expired air in twenty patients undergoing colonoscopy after preparation with either mannitol or castor oil. Potentially explosive intracolonic H2 concentrations were present in six out of ten patients given mannitol, but in none given castor oil. This has important implications for colonoscopic, as well as for surgical, electrosurgery. H2 concentrations in expired air sampled preoperatively did not identify patients with potentially explosive intracolonic hydrogen levels.

Adult↗

Injuries from tire and wheel explosions during servicing.

STUDY OBJECTIVE: To evaluate injuries from tire and wheel explosions that occur during servicing. DESIGN: Retrospective analysis of all injury reports from the National Highway Traffic Safety Administration, the Occupational Safety and Health Administration, and the Insurance Institute for Highway Safety. RESULTS: For the period of 1978 through 1987, there were 694 reported injuries from explosions during tire servicing; 143 of them were fatal, resulting mainly from truck tires. Because the three data sources used different methods for case finding and covered different time periods, the actual number of such injuries was probably greater. Head injuries accounted for 78% of the deaths and 24% of nonfatal injuries. The proportion of injuries occurring during tire inflation declined from 51% in 1978 to 33% in 1987 (P less than .05). Fatal injuries involving single-piece rim wheels increased during the 1980s as multipiece rim wheels were phased out by the trucking industry. CONCLUSIONS: Exploding truck tires and wheel rims cause serious injuries. The use of safety cages during inflation as required by a 1980 Occupational Safety and Health Administration standard appears to have reduced injuries during truck tire inflation. The use of helmets during servicing may further reduce serious injuries.

Accidents↗

Eardrum perforation in explosion survivors: is it a marker of pulmonary blast injury?

STUDY OBJECTIVES: To determine whether isolated eardrum perforation is a marker for concealed blast lung injury in survivors of terrorist bombings. METHODS: Survivors who arrived at hospitals after 11 terrorist bombings in Israel between April 6, 1994, and March 4, 1996, were examined otoscopically by ear, nose, and throat specialists. All patients with eardrum perforation underwent chest radiography and were hospitalized for at least 24 hours for observation. The clinical course and final outcome of patients with isolated perforation of the eardrums and of those with other blast injuries were surveyed. RESULTS: A total of 647 survivors were examined; 193 (29.8%) of them sustained primary blast injuries, including 142 with isolated eardrum perforation and 51 with other forms of blast injuries (18 with isolated pulmonary blast injury, 31 with combined otic and pulmonary injuries, and 2 with intestinal blast injury). Blast lung injury was promptly diagnosed on admission by physical examination and chest radiography. No patient presenting with isolated eardrum perforation developed later signs of pulmonary or intestinal blast injury (mean 0%; 95% confidence interval, 0% to 2.7%). CONCLUSION: Isolated eardrum perforation in survivors of explosions does not appear to be a marker of concealed pulmonary blast injury nor of a poor prognosis. Therefore, in a mass casualty event, persons who have sustained isolated eardrum perforation from explosions may safely be discharged from the emergency department after chest radiography and a brief observation period.

Adolescent↗

Explosion injuries of the hand. Spatial relationship and injury pattern.

Twenty-six hands in 25 male patients were treated for peace-time explosion injuries of the palmar aspect. All patients were examined after a mean interval of 7 (1-17) years. In order to establish a regional pattern for each injury the palmar surface of the hand was divided in 21 fields. For each field a score depending on the extent of injury was calculated. Comparing this regional score with the spatial relation between hand and exploding object resulted in six typical patterns depending on the grip during explosion. With knowledge of the three-dimensional relation between the hand and exploding object, the hand surgeon is prepared for potential problems during operation.

Adolescent↗

Some aromatic nitrate esters: synthesis, structural aspects, thermal and explosive properties.

1-(2-Nitroxyethylnitramino)-2,4,6-trinitrobenzene (I-A), 1, 3-bis(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene (II-A) and 1,3, 5-tris(2-nitroxyethylnitramino)-2,4,6-trinitrobenzene (III-A) have been prepared by condensing picryl chloride, styphnyl chloride and 1, 3,5-trichloro-2,4,6-trinitrobenzene with ethanol amine, respectively, followed by nitration. These compounds have been characterized by infrared spectrum (IR), the elemental analysis and 1H NMR. Further, these compounds have been studied for their thermal and explosive properties. The activation energy of thermal decomposition of these compounds has also been determined using the Ozawa and the Kissinger methods. The data on explosive properties indicate that the impact, friction and velocity of detonation (VOD) increase with an increase in the number of nitrate ester groups.

Esters↗

Assessment of technologies for disposing explosive waste.

The environmental impact and safety aspects are assessed for six different techniques for disposing decommissioned ammunition. These are open burning and open detonation (OD), closed detonation (CD), fluidised bed combustion (FBC), rotary kiln (RK) Incineration, and Mobile furnace (MF) Incineration. The assessment is performed in the form of a multi-criteria decision analysis (MCDA). Objectives for minimising environmental impact and risk are defined to enable selection of the "best" technology. A framework for comparing emissions of different air pollutants is proposed. Environmental impacts are described, especially air pollutants. The environmental impacts of traditional OB and OD can be drastically reduced using controlled incineration techniques in combination with high-pressure water washout. This enables the explosive contents to be separated from the casing, and simultaneously the explosive is transformed to a desensitised water-based slurry.

Air Pollutants↗