TATP模拟物的设计及安全性评估

三过氧化三丙酮（TATP）直接用于安检培训具有危险性高、安全隐患多的问题。设计出可代替TATP在X光机、CT机等高通量安检仪中成像的模拟物。物质组成为m(葡萄糖)∶m(十六醇)∶m(蔗糖)=25.77∶9.68∶14.55，与TATP具有相似的外观及有效原子序数，元素质量分数相差小于0.020%，堆积密度相差0.012 g/cm³。为确保模拟物在红外、拉曼等高灵敏性安检仪中亦存在特征信号，在混合物中加入适量TATP。结果表明，当TATP的加入量为20%（质量分数）时，可有效地表征出混合物中TATP的红外、拉曼特征峰；同时，体系相容性较好，机械感度低，且不具有爆炸性。优化后的配方为:m(葡萄糖)∶m(十六醇)∶m(蔗糖)∶m(TATP）=20.62∶7.74∶11.64∶10.00。该模拟物与TATP的相似度高、安全性好，可直接用于安检人员培训。     

Application of selected-ion flow tube mass spectrometry to the real-time detection of triacetone triperoxide

A fast, efficient, real-time method for the quantitative analysis of the peroxide explosive, TATP, is described. The method utilizes rapid ion-molecule reactions of chemical reagent ions with the vapor above solid TATP. The reactions of three reagent ions (H3O+, O2+, NO+) were examined. Although all three ions exhibited a near-collision-rate reaction with TATP, only NO+ showed product ions that provide unequivocal evidence for a TATP-based explosive. The limit of detection of TATP in the gas phase is 10 ppb (4 x 10(-10) mol L(-1)).     

Power of TATP based explosives

The power of various explosive mixtures based on triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexoxonane, TATP), ammonimum nitrate (AN), urea nitrate (UrN) and water (W), namely TATP/AN, oil/AN, TATP/UrN, TATP/W and TATP/AN/W, was studied using the ballistic mortar test. The ternary mixtures of TATP/AN/W have relatively high power in case of the low water contents. Their power decrease significantly with increasing the water content in the mixture to more than 30%.     

Characterization of triacetone triperoxide by ion mobility spectrometry and mass spectrometry following atmospheric pressure chemical ionization

The atmospheric pressure chemical ionization of triacetone triperoxide (TATP) with subsequent separation and detection by ion mobility spectrometry has been studied. Positive ionization with hydronium reactant ions produced only fragments of the TATP molecule, with m/z 91 ion being the most predominant species. Ionization with ammonium reactant ions produced a molecular adduct at m/z 240. The reduced mobility value of this ion was constant at 1.36 cm(2)V(-1)s(-1) across the temperature range from 60 to 140 °C. The stability of this ion was temperature dependent and did not exist at temperatures above 140 °C, where only fragment ions were observed. The introduction of ammonia vapors with TATP resulted in the formation of m/z 58 ion. As the concentration of ammonia increased, this smaller ion appeared to dominate the spectra and the TATP-ammonium adduct decreased in intensity. The ion at m/z 58 has been noted by several research groups upon using ammonia reagents in chemical ionization, but the identity was unknown. Evidence presented here supports the formation of protonated 2-propanimine. A proposed mechanism involves the addition of ammonia to the TATP-ammonium adduct followed by an elimination reaction. A similar mechanism involving the chemical ionization of acetone with excess ammonia also showed the formation of m/z 58 ion. TATP vapors from a solid sample were detected with a hand-held ion mobility spectrometer operated at room temperature. The TATP-ammonium molecular adduct was observed in the presence of ammonia and TATP vapors with this spectrometer.     

In situ trace detection of peroxide explosives by desorption electrospray ionization and desorption atmospheric pressure chemical ionization

Desorption electrospray ionization (DESI) mass spectrometry is used for the rapid (<5 s), selective, and sensitive detection of trace amounts of the peroxide-based explosives, hexamethylene triperoxide diamine (HMTD), tetracetone tetraperoxide (TrATrP), and triacetone triperoxide (TATP), directly from ambient surfaces without any sample preparation. The analytes are observed as the alkali metal ion complexes. Remarkably, collision-induced dissociation (CID) of the HMTD, TATP, and TrATrP complexes with Na(+), K(+), and Li(+) occurs with retention of the metal, a process triggered by an unusual homolytic cleavage of the peroxide bond, forming a distonic ion. This is followed by elimination of a fragment of 30 mass units, shown to be the expected neutral molecule, formaldehyde, in the case of HMTD, but shown by isotopic labeling experiments to be ethane in the cases of TATP and TrATrP. Density functional theory (DFT) calculations support the suggested fragmentation mechanisms for the complexes. Binding energies of Na+ of 40.2 and 33.1 kcal/mol were calculated for TATP-Na(+) and HMTD-Na(+) complexes, suggesting a strong interaction between the peroxide groups and the sodium ion. Increased selectivity is obtained either by MS/MS or by doping the spray solvent with additives that produce the lithium and potassium complexes of TATP, HMTD, and TrATrP. Addition of dopants into the solvent spray increased the signal intensity by an order of magnitude. When pure alcohol or aqueous hydrogen peroxide was used as the spray solvent, the (HMTD + Na)+ complex was able to bind a molecule of alcohol (methanol or ethanol) or hydrogen peroxide, providing additional characteristic ions to increase the selectivity of analysis. DESI also allowed the rapid detection of peroxide explosives in complex matrixes such as diesel fuel and lubricants using single or multiple cation additives (Na(+), K(+), and Li(+), and NH4(+)) in the spray solvent. Low-nanogram detection limits were achieved for HMTD, TrATrP, and TATP in these complex matrixes. The DESI response was linear over 3 orders of magnitude for HMTD and TATP on paper surfaces (1-5000 ng), and quantification of both peroxide explosives from paper gave precisions (RSD) of less than 3%. The use of pure water and compressed air as the DESI spray solution and nebulizing gas, respectively, showed similar ionization efficiencies to those obtained using methanol/water mixtures and nitrogen gas (the typical choices). An alternative ambient method, desorption atmospheric pressure chemical ionization (DAPCI), was also used to detect trace amounts of HMTD and TATP in air by complexation with gas-phase ammonium ions (NH4(+)) generated by atmospheric pressure ammonia ionization.     

Development of SRM 2907 trace terrorist explosives simulants for the detection of Semtex and triacetone triperoxide

Effective and accurate detection of trace explosives is crucial in the effort to thwart terrorist explosives attacks. A National Institute of Standards and Technology (NIST) standard reference material (SRM) has been developed for the evaluation of trace explosives detectors that sample by collection of residue particles using swiping or air filtration. SRM 2907 Trace Terrorist Explosives Simulants consists of two materials individually simulating the residues of the plastic explosive Semtex [for pentaerytritol tetranitrate (PETN)] and the improvised explosive triacetone triperoxide (TATP). Unique challenges were encountered in the development of these materials, including the selection of suitable inert substrates, material preparation, thermal stability testing, and analytical method development. Two independent analytical methods based on liquid chromatography with ultraviolet absorbance and mass spectrometric detection, LC-UV and LC/MS, respectively, were developed and used to certify the mass fractions of PETN and TATP. These materials were further evaluated for their suitability on a field swipe-sampled trace explosives detectors based on ion mobility spectrometry (IMS).     

Some properties of explosive mixtures containing peroxides Part I. Relative performance and detonation of mixtures with triacetone triperoxide

This study concerns mixtures of triacetone triperoxide (3,3,6,6,9,9-hexamethyl-1,2,4,5,7,8-hexoxonane, TATP) and ammonium nitrate (AN) with added water (W), as the case may be, and dry mixtures of TATP with urea nitrate (UN). Relative performances (RP) of the mixtures and their individual components, relative to TNT, were determined by means of ballistic mortar. The detonation energies, E0, and detonation velocities, D, were calculated for the mixtures studied by means of the thermodynamic code CHEETAH. Relationships have been found and are discussed between the RP and the E0 values related to unit volume of gaseous products of detonation of these mixtures. These relationships together with those between RP and oxygen balance values of the mixtures studied indicate different types of participation of AN and UN in the explosive decomposition of the respective mixtures. Dry TATP/UN mixtures exhibit lower RP than analogous mixtures TATP/AN containing up to 25% of water. Depending on the water content, the TATP/AN mixtures possess higher detonability values than the ANFO explosives. A semi-logarithmic relationship between the D values and oxygen coefficients has been derived for all the mixtures studied at the charge density of 1000 kg m(-3). Among the mixtures studied, this relationship distinguishes several samples of the type of "tertiary explosives" as well as samples that approach "high explosives" in their performances and detonation velocities.     

Thermal reactive hazards of HMX with contaminants

In the past, many unexpected runaway accidents occurred in manufacturing processes, involving volatile chemical and explosive storage and transportation. Incompatible product reactions of high explosives must be carefully considered using loss prevention strategies for thermal hazards risk analysis. High explosive reactions vary via environmental changes, contact materials, or process situations, such as onset temperature and shifts in reaction type when high explosives are in contact with contaminants. Therefore, the manufacture and handling of high explosives require the utmost in safety and loss prevention. HMX (cyclotetramethyene tetranitramine) is one kind of high explosive widely used around the world which is stable with high detonation strength properties. In this study, the influences of contaminants on HMX are investigated. The studied contaminants include ferrous chloride tetrahydrate, ferric chloride hexahydrate, acetone solution, acetic acid, and nitric acid. DSC thermal curves and incompatible reaction kinetic evaluations were preformed using iron, chlorine and acid. Organic acetone solution has lesser effects on HMX. Hopefully, this study will lead to improved thermal hazards risk analysis and reduce accidents.     

Laboratory-scale techniques for the measurement of a material response to an explosive blast

Laboratory-scale experiments were performed to measure the deformation of thin plates in response to varying explosive impulse. Experiments were conducted with a known explosive mass suspended in air at a known distance from an aluminum witness plate clamped in a “shock-hole” fixture. Through the use of well-characterized PETN and TATP explosive charges, the explosive impulse applied to each witness plate was determined a priori. The witness-plate response was measured using high-speed digital cameras to determine time-resolved, three-dimensional surface motion and maximum plate deformation. The results show that the maximum dynamic plate deformation is a straightforward function of applied explosive impulse, as determined from the explosive characterization. The experimental trend is the same despite the two different explosives used, highlighting that explosive impulse, determined through a blast characterization, is the controlling parameter in material blast response. A new experimental technique is used here to measure the dynamic blast response and the experimental errors are documented. Ultimately, applications of laboratory-scale explosive testing to computational code validation, material response scaling, and high-speed material property definition are discussed.     

混装乳化炸药车装药控制系统关键问题的研究

为解决现场混装乳化车的炸药质量稳定性和单孔装药量的准确性,对其装药控制系统的生产炸药质量控制问题、主要元器件质量问题、装药量计量问题、制药安全控制问题等关键技术做了深入分析,提出了采用高精度的极高粘度胶体测量仪表解决混装车炸药的准确计量问题和开发使用配套的信息控制管理系统等改进建议.     

关于推广现场混装炸药车技术的一些思考

我国是工业炸药的生产和使用大国,连续多年的产量都超过了400万t,同时工业炸药作为典型的危险物品,与公共安全息息相关,是社会治安管理的重点监管对象。工业炸药现场混装车技术彻底改变了传统商品炸药的生产、供营和使用模式,本质安全性高是其最突出的特点。大力推广应用现场混装车技术无论是对于提高工业炸药的安全生产管理水平,还是对于提升社会治安管理水平,都具有重要意义,因此受到国家法规政策的鼓励。分析了工业炸药现场混装技术的优势,尤其是对于公共安全的有利作用,研究了现行管理模式存在的弊端,提出为促进工业炸药现场混装技术在我国顺利推广,贯彻创新驱动发展战略,通过体制机制创新,建立由公安机关对工业炸药现场混装技术进行统一管理的更有利的监管模式。鼓励有条件的爆破公司购买和使用现场混装车,大幅度减少工业炸药固定生产点、库房和成品炸药运输等危险源。     

Determination of peroxide-based explosives using liquid chromatography with on-line infrared detection

A nondestructive analytical method for peroxide-based explosives determination in solid samples is described. Reversed-phase high-performance liquid chromatography in combination with on-line Fourier transform infrared (FT-IR) detection is used for the analysis of triacetonetriperoxide (TATP) and hexamethylenetriperoxide diamine (HMTD). In contrast to other liquid chromatographic methods with optical detection, no derivatization or decomposition of the peroxides is required. The peroxides are identified and quantified via their characteristic absorption spectra in the mid-infrared range of the electromagnetic spectrum. The detection limit of 0.5 mmol L-1 for HMTD and 1 mmol L-1 for TATP allows the identification of the explosives in complex matrixes.     

The escape of blast from fragmenting munitions casings

Researchers in the fields of explosives safety or effects often need to estimate the impulse delivered by blast escaping from the fragmenting casings of exploding munitions, relative to the blast impulse from the same explosive charge uncased. Even for free-field conditions, researchers currently depend for such estimates on formulae which either are not soundly derived (e.g. that of Fisher), or are simply fits to available experimental data. This paper will show that a sound analytical formula can be derived, using as a basis the physical assumptions of R.W. Gurney, which are already the basis for other well-known and useful approximations in this field. Furthermore, this new formula can be extended in application to the common situation where the casing fragments before it reaches a high radius of expansion, thus allowing more blast impulse to escape. Drawing on recent work by A.B. Crowley, this can be achieved by including a dependency on the ratio of casing yield stress and explosive product gases internal pressure. An extended set of formulae incorporating this sensitivity to explosive and casing properties are shown to be consistent, at least qualitatively, with recent experimental data from researchers at BAE Systems.     

Trace analysis of peroxide-based explosives

The first method for quantitative trace analysis of peroxide-based explosives is described. A reversed-phase high-performance liquid chromatography method with post-column UV irradiation and fluorescence detection for the analysis of triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) has been developed. After separation, the analytes are degraded photochemically to hydrogen peroxide, which is subsequently determined on the basis of the peroxidase-catalyzed oxidation of p-hydroxyphenylacetic acid to the fluorescent dimer. This two-step reaction scheme in combination with the respective blanks (photochemical reactor switched off) provides for high selectivity. The limits of detection were 2 x 10(-6) mol/L for both TATP and HMTD, respectively. The method has been applied to the analysis of real samples.     

硝酸铵溶液的爆炸危险性及储运安全条件研究

为确定硝酸铵溶液的爆炸危险性及温度、浓度等储运安全条件,采用克南试验、绝热量热试验、联合国隔板试验及析晶特性试验等研究了热分解和殉爆两种情况下硝酸铵溶液的爆炸危险性及安全控制条件。结果表明:140 ℃时,硝酸铵溶液含水质量分数小于4%,为爆炸物;含水质量分数为4%-10%时,则具有爆炸性;含水质量分数大于10%时,不具有爆炸性。硝酸铵质量分数为90%以上时,硝酸铵溶液的起始放热温度在210～230 ℃范围内,T_D24最低为151 ℃。110～140 ℃区间内,高温硝酸铵溶液的冲击波感度与溶液析晶状态有关,大量析晶会发生殉爆。因此,硝酸铵溶液中硝酸铵的质量分数应控制在93%以内;温度上限应控制在140 ℃以内;温度控制下限应根据硝酸铵溶液的析晶温度确定。     

民用爆炸物品使用现场的安全管理

加强民用爆炸物品使用现场的安全管理 ,有利于维护政治稳定、治安稳定 ,有效预防和杜绝涉爆违法、违规案件和事故的发生。本文从加强领导的安全意识和管理职能、落实安全生产责任制、加强从业人员的安全教育和综合素质培养、健全施工现场爆炸物品管理制度、完善施工现场的监督和检查机制、必要的安全管理资金和设施的投入等六个方面论述了加强用民爆炸物品使用现场安全管理的必要性。     

民用爆炸物品使用现场的安全管理

加强民用爆炸物品使用现场的安全管理 ,有利于维护政治稳定、治安稳定 ,有效预防和杜绝涉爆违法、违规案件和事故的发生。本文从加强领导的安全意识和管理职能、落实安全生产责任制、加强从业人员的安全教育和综合素质培养、健全施工现场爆炸物品管理制度、完善施工现场的监督和检查机制、必要的安全管理资金和设施的投入等六个方面论述了加强用民爆炸物品使用现场安全管理的必要性。     

Quantitative analysis of metabolic gases by multichannel Raman spectroscopy: use of a newly designed elliptic-spherical integration type of cell holder

We describe the quantitative analysis of some metabolic gases bymultichannel Raman spectroscopy. Raman spectra were measured forair, acetone, ammonia, carbon dioxide, and mixed gas consisting ofacetone, ammonia, and air. We designed a new elliptic-sphericalintegration type of cell holder to obtain the Raman spectra of gaseswith a high signal-to-noise ratio. Concentrations of acetone, ammonia, and carbon dioxide were determined by the peak intensities ofRaman bands at 2940, 3228, and 1385 cm(-1), respectively. To compensate for the fluctuations of Ramanintensities caused by several factors, such as the fluctuations oflaser power, the peak intensity of a band at 2324 cm(-1) dueto nitrogen gas was used as an internal intensity standard. Thecorrelation coefficient between the corrected Raman intensity at 2940cm(-1) and the concentration of acetone was calculated to be0.984 for a concentration range of 2-12 ppm. The detection limitof acetone gas was found to be 2 ppm.     

Factors affecting high-pressure solvent extraction (accelerated solvent extraction) of additives from polymers

Irganox 1010 (pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)] propionate) is successfully extracted from polypropylene using solvents at high temperatures and pressures in a homemade accelerated solvent extraction system. For example, using freeze-ground polymer, 90% extraction is possible within 5 min with 2-propanol at 150 °C. Extraction curves for 2-propanol and acetone fit well to the "hot ball" model, previously developed for supercritical fluid extraction. Diffusion coefficients are determined for extractions with 2-propanol, acetone, and cyclohexane over a range of temperatures, and the activation energies for the diffusion are 134, 107, and 61 kJ mol(-)(1), respectively. The lower figure for acetone and cyclohexane indicates that these solvents swell the polymer more than does 2-propanol. The polymer dissolves in the solvent at too high a temperature, which causes blockage of the transfer lines. For maximum extraction rates, the highest temperature for each solvent that avoids dissolution of the polymer should be used. The use of mixed solvents is investigated and shows advantages in some cases, with the aim of producing a solvent that will swell the polymer but not dissolve it.     

Rapid nondestructive spectrometric measurement of temperature-dependent gas-liquid solubility equilibria

Gas-liquid solubility equilibria (Henry's Law behavior) are of basic interest to many different areas. Temperature-dependent aqueous solubilities of various organic compounds are of fundamental importance in many branches of environmental science. In a number of situations, the gas/dissolved solute of interest has characteristic spectroscopic absorption that is distinct from that of the solvent. For such cases, we report facile nondestructive rapid measurement of the temperature-dependent Henry's law constant (K(H)) in a static sealed spectrometric cell. Combined with a special cell design, multiwavelength measurement permits a large range of K(H) to be spanned. It is possible to derive the K(H) values from the absorbance measured in the gas phase only, the liquid phase only (preferred), and both phases. Underlying principles are developed, and all three approaches are illustrated for a solute like acetone in water. A thermostatic spectrophotometer cell compartment, widely used and available, facilitates rapid temperature changes and allows rapid temperature-dependent equilibrium measurements. Applicability is shown for both acetone and methyl isobutyl ketone. Very little sample is required for the measurement; the K(H) for 4-hydroxynonenal, a marker for oxidative stress, is measured to be 56.9 ± 2.6 M/atm (n = 3) at 37.4 °C with 1 mg of the material available.