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.     

硝酸羟胺的热稳定性评估及热分解机理研究

为评估氧化剂硝酸羟胺的热稳定性,使用标准液体铝皿于3K/min、4K/min、5K/min加热速率下进行热分析。借助非等温DSC曲线的参数值,应用Kissinger法和Ozawa法求得热分解反应的表观活化能和指前因子,根据Zhang-Hu-Xie-Li公式、Hu-Yang-Liang-Xie公式、Hu-Zhao-Gao公式以及Zhao-Hu-Gao公式,计算硝酸羟胺的自加速分解温度和热爆炸临界温度,并对热分解机理函数进行了研究。设计了7条热分解反应路径,采用密度泛函理论B3LYP/6-311++G(d,p)方法对硝酸羟胺的热分解进行了动力学和热力学计算。计算结果表明,硝酸羟胺热分解的自加速分解温度TSADT=370.05K,热爆炸临界温度Tbe0=388.68K,Tbp0=397.54K,热分解最可几机理函数的微分形式为f(α)=17×(1-α)18/17。硝酸羟胺热分解各路径中,动力学优先支持路径Path 6、Path 5、Path 4和Path 1生成NO和NO_2,其次是Path 2、Path 7和Path 3生成N2和N_2O。温度在373K以下时,Path 1′反应无法自发进行,硝酸羟胺无法进行自发的热分解。从热力学的角度来看,硝酸羟胺在370.05K以下储存是安全的。     

Synthesis, growth and thermal and Fourier transform infrared spectral characterization of tetraethylammonium tetrachloro manganate (II) monohydrate crystals

Single crystals of a novel tetraethylammonium tetrachloro manganate (II) monohydrate (TEATC-Mn) were grown by slow evaporation solution technique at room temperature. These crystals belong to a class of interesting ferroelectric materials. The grown crystals were characterized through powder X-ray diffraction (XRD), thermogravimetry, differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC) studies and Fourier transform infrared (FTIR) spectra. While the results of the elemental analysis of the compound agree with the stoichiometry, its crystallinity is confirmed by the powder X-ray diffraction pattern. The weight losses observed were suitably explained based on the formulated decomposition pattern. The differential thermal analysis of the compound conforms to the thermogravimetric study. The endothermic peak observed in the high temperature differential scanning calorimetry suggests the occurrence of a phase transition in the compound between 300 and 370 °C while the corresponding low temperature study shows thermal anomalies at −41.7, −51.7 and at −52.4 °C. This suggests the occurrence of both first and second order phase transitions. The characteristic absorptions in the FTIR spectrum further characterize the compound. Further investigations on the ferroelectric behaviour of the compound at low temperatures are in progress.     

Estimation of the critical rate of temperature rise for thermal explosion of first-order autocatalytic decomposition reaction systems using non-isothermal DSC

A method of estimating the critical rate of temperature rise for thermal explosion of first-order autocatalytic decomposition reaction systems using non-isothermal DSC is presented. Information is obtained on the increasing rate of temperature in highly nitrated nitrocellulose containing 14.14% of nitrogen when the first-order autocatalytic decomposition converts into thermal explosion.     

复合乳化剂制备重铵油炸药的热稳定性分析

为了了解复合乳化剂对重铵油炸药热稳定性影响,使用C80微量量热仪分析了单一乳化剂和复合乳化剂制备的重铵油炸药在恒定升温速率1 K/min下的热分解特性,并计算在此过程中的动力学和热力学参数。结果表明:复合乳化剂的加入抑制了重铵油炸药的热分解,提升了重铵油炸药的反应起始温度以及峰值温度。同时,活化能的增加说明使用复合乳化剂制备的重铵油炸药热稳定和热安全性均高于使用单一乳化剂,并随着复合乳化剂比例的不同稳定性提升程度也有所不同,在乳化剂配比为SP-80∶T-152=1∶2时稳定性最高。     

Effects of heating rate, temperature and iron catalysis on the thermal behaviour and decomposition of 2-nitrobenzoyl chloride

Runaway reactions arising from the decomposition of thermally unstable materials are a concern in industry due to the potentially devastating effects that they yield. Studies into the occurrence of thermal runaway incidents have shown the most likely cause to be a result of an inadequate investigation of the process prior to its operation on a large-scale. The chlorination of ortho-nitrated carboxylic acids is an industrially important reaction in the fine and agrochemical industries. The products of these reactions, ortho-nitrated acid chlorides, have been involved in runaway incidents that have resulted in violent explosions; hence, their thermal stability must be studied. Previous studies [S.D. Lever, M. Papadaki, Study of condition-dependent decomposition reactions: the thermal behaviour and decomposition of 2-nitrobenzoyl chloride, Part I, J. Hazard. Mater. 115 (2004) 91-100] showed that the decomposition of the parent molecule, 2-nitrobenzoyl chloride, is highly condition-dependent with the sample heating rate and temperature of decomposition playing a preponderant role in the course of the decomposition. Here, we present the results of studies of the decomposition of 2-nitrobenzoyl chloride, when the sample is subjected to various heating treatments, temperatures and in the presence of iron. As the temperature of decomposition was increased from 150 to 162 degrees C, the heat of decomposition was reduced from -215 to -90 kJ/mol. As the heat up rate applied in bringing the sample to the decomposition temperature increased, the heat of decomposition also increased. An increase in the heat up rate from 2 to 7.5 degrees C/min resulted in an increase in the heat of decomposition from -90 to -215 kJ/mol. The presence of iron and silver was observed to lower the heat of decomposition from -185 to -160 and -110 kJ/mol, respectively. Under most conditions investigated, the temperature at which gas flow was initiated was 147-150 degrees C. The presence of iron reduced this temperature to 140 degrees C. Decomposition was observed to take place over two stages, where the sample was heated directly from 40 degrees C at the required heat up rate. Where the sample was heated in stages and where calibrations had been carried out preceding decomposition, the decomposition took place in one stage alone.     

MEMS-SPMT用推进剂的热稳定性和能量特性研究

以斯蒂芬酸铅作为推进剂的主要组分,硝化棉为粘接剂,通过添加高氯酸铵、细铝粉,得到了可用于MEMS-SPMT的推进剂。采用DSC研究了高氯酸铵、铝粉、硝化棉对斯蒂芬酸铅热稳定性的影响,研究了4种推进剂配方的热解特性,并利用CEA软件进行热力计算,研究了2种喷管扩张比(面积比)下4种推进剂配方的能量特性。结果表明,高氯酸铵和铝对斯蒂芬酸铅的热稳定性无明显影响,硝化棉能降低斯蒂芬酸铅的热稳定性。硝化棉与高氯酸铵质量比大的推进剂热稳定性较低。增加硝化棉、高氯酸铵的质量含量和增大喷管扩张比均能提高推进剂比冲。     

非爆炸且不可还原农用硝酸铵的热稳定性评估

绍了一种测试含能材料热稳定性的新方法——加速度量热仪，并用此法研究了硝酸铵和非爆炸且不可还原农用硝酸铵的热分解过程，得到了绝热分解温度与压力随时间的变化、自加热速率与分解压力随温度的变化曲线，计算了分解动力学参数表观活化能和指前因子，讨论了放热反应系统的热惰性因子对测试结果的影响，表明非爆炸且不可还原农用硝酸铵具有良好的热稳定性、安全性及其热稳定性的提高是爆炸特性得以消除的原因。     

Thermal behaviour kinetic study of dihydroglyoxime and dichloroglyoxime

Glyoxime derivatives have increasingly gained attention because of their potential for generation of energetic materials. In this paper, the thermal behaviours of dihydroglyoxime (DHG) and dichloroglyoxime (DCG) in a nitrogen atmosphere were studied under non-isothermal conditions by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. The results showed that the decomposition of DCG occurs in two continuous steps, in the 160-230 °C temperature range. Each thermal degradation stage for DCG results an exothermic peak in the DSC curve. On the other hand, applying TG-DSC techniques indicates that DHG sublimates about 178 °C before it decomposes. Also, the influence of the different heating rates such as 5, 10, 15 and 20 °C min^− 1 on the thermal behaviour of both compounds was investigated. The results of DSC experiments indicate that the peak temperature of DCG decomposition and sublimation temperature for DHG were increased, as the heating rate was increased. The kinetic parameters such as activation energy and pre-exponential factor for each compound were found by means of the Kissinger method and were verified by the Ozawa-Flynn-Wall method. Based on the values of activation energy obtained by the Kissinger method, the first stage of DCG decomposition has an activation energy about 100 kJ mol^− 1 and the sublimation process for DHG has an activation energy about 259 kJ mol^− 1. Finally, the thermodynamic parameters (ΔG^#, ΔH^# and ΔS^#) for decomposition of DCG and sublimation of DAG were determined.     

Synthesis, characterization, thermal and explosive properties of potassium salts of trinitrophloroglucinol

Three different substituted potassium salts of trinitrophloroglucinol (H(3)TNPG) were prepared and characterized. The salts are all hydrates, and thermogravimetric analysis (TG) and elemental analysis confirmed that these salts contain crystal H2O and that the amount crystal H2O in potassium salts of H3TNPG is 1.0 hydrate for mono-substituted potassium salts of H3TNPG [K(H2TNPG)] and di-substituted potassium salt of H3TNPG [K2(HTNPG)], and 2.0 hydrate for tri-substituted potassium salt of H3TNPG [K3(TNPG)]. Their thermal decomposition mechanisms and kinetic parameters from 50 to 500 degrees C were studied under a linear heating rate by differential scanning calorimetry (DSC). Their thermal decomposition mechanisms undergo dehydration stage and intensive exothermic decomposition stage. FT-IR and TG studies verify that their final residua of decomposition are potassium cyanide or potassium carbonate. According to the onset temperature of the first exothermic decomposition process of dehydrated salts, the order of the thermal stability from low to high is from K(H2TNPG) and K2(HTNPG) to K3(TNPG), which is conform to the results of apparent activation energy calculated by Kissinger's and Ozawa-Doyle's method. Sensitivity test results showed that potassium salts of H3TNPG demonstrated higher sensitivity properties and had greater explosive probabilities.     

AKTS模拟分析硝酸铵的热稳定性

为了研究了硝酸铵(AN)的热危险性,采用差示扫描量热仪(DSC)对AN进行扫描测试,获得了AN在不同升温速率下的热分解规律。运用热动力学分析软件AKTS计算得到AN的热力学和动力学参数,采用风险矩阵法评估了AN热分解的危险性。结果表明:AN起始分解温度为228~250℃,放热量为2 340~2 650 J/g,分解反应活化能为100~175 k J/mol,模拟并计算了AN在绝热条件下反应体系达到最大反应速率所需要的时间为24 h的温度T_(D24)=137.2℃。利用风险矩阵法评估了AN的危险等级为Ⅱ级。针对此危险等级,提出了降低AN储存风险的措施。     

Effect of malonyl malonanilide dimers on the thermal stability of nitrocellulose

Three malonanilide dimers (MA2-MA4) were prepared by the reaction of ethyl malonate with malonanilide derivatives (M2-M4). These dimers were investigated as new stabilizers for nitrocellulose. The evaluation process has been performed through Bergman-Junk (BJ) test, thermal analysis measurements (TGA and DSC) and kinetic parameters calculations (E(a)). The comparative study between mass spectra and thermal analysis of the new dimers helped in resolving the thermal decomposition mechanisms for the new dimers. It was found that the new dimers especially (MA2 and MA4) showed better stabilizing effect for the nitrocellulose than the centralite 1 (C1) which is the common stabilizer.     

A new high-nitrogen compound [Mn(ATZ)(H2O)4] x 2H2O: synthesis and characterization

A new high-nitrogen compound [Mn(ATZ)(H(2)O)(4)] x 2H(2)O (ATZ=5,5-azotetrazolate) was synthesized. Crystal structure and elemental, IR and thermal analyses were investigated in the present work. It crystallized in triclinic space group P-1 with lattice parameters a=6.304(2)A, b=7.004(2)A, c=7.921(3)A, alpha=76.114(5) degrees , beta=74.023(5) degrees , gamma=69.254(4) degrees . TG-DTG and DSC measurements are employed to postulate the thermal decomposition mechanism. The thermal decomposition kinetics of the main exothermic reaction was investigated by non-isothermal method and obtained its enthalpy of decomposition and the probable kinetic mechanism. An attempt was made to incorporate the relation between thermal stability and the structure.     

Synthesis of BaZrO3 by a solid-state reaction technique using nitrate precursors

High phase purity barium metazirconate powders have been synthesized from a modified solid-state reaction. Reactive powders consisting of submicron particles and narrow particle size distribution were obtained by heating a 1:1 molar mixture of barium nitrate and zirconyl nitrate at 800°C up to 8 h. Simultaneous thermal analysis (TG-DTA) assisted in elucidating the probable reaction pathways leading to the formation of the target compound in the BaO-ZrO₂ system. Systematic structural and microstructural characterization on the green powders and the compacts sintered up to 1700°C were carried out. A two-stage sintering schedule consisting of a 6 h soak at 1600°C followed by slow heating up to 1700°C with no dwell, led to highly dense microstructural features.     

Studies on three-dimensional coordination polymer [Cd2(N2H4)2(N3)4]n: crystal structure, thermal decomposition mechanism and explosive properties

A 3D coordination polymer of cadmium(II) hydrazine azide, [Cd2(N2H4)2(N3)4]n, was synthesized and characterized by elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic, P2(1)/c space group, a=12.555(2)A, b=11.724(2)A, c=7.842(1)A, beta=94.56(2) degrees and Z=4. The crystal contains two crystallographically independent sets of distorted octahedral Cd(II) atoms and dimeric units of Cd2N2, Cd2(NNN)2, Cd2(NN)2 through double micro-1, 1 azide bridges, micro-1, 3 azide bridges and bidentate bridging hydrazine ligands, respectively, and thus generating a 3D network structure. 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 two intense exothermic decomposition processes in the range of 150-304 degrees C in the DSC curve, and the final decomposed residue at 500 degrees C was Cd. Sensitivity tests revealed that the title complex is very insensitive to external stimuli.     

Synthesis, characterization and properties of nitrogen-rich salts of trinitrophloroglucinol

Five different nitrogen-rich salts of trinitrophloroglucinol (H(3)TNPG) have been prepared by the reaction of ammonia, aminoguanidine (AG), carbohydrazide (CHZ), semicarbazide (SCZ) and 5-aminotetrazo (ATZ) with trinitrophloroglucinol in aqueous solution through the heating method of water bath, with the yield up to 80%. These salts were characterized by elemental analysis, FT-IR, DSC and TG-DTG techniques. Their melting temperature is consistent with the thermal decomposition temperature. Their thermal decomposition process and kinetic parameters from 323 to 673K were investigated under a linear heating rate by DSC. The thermal decomposition of these salts undergoes an intensive exothermic decomposition stage to evolve abundant gas products and the enthalpies of exothermic decomposition reaction are high. The tests of sensitivity properties show these salts are insensitivity. All the properties of five nitrogen-rich salts appeared to depend on molecule structures and interconnection. It can be concluded that the five compounds are worthy of further in-depth studies as the gas-generating composition, emission reagents and propellants.     

木粉与硝酸铵混合物热分解动力学分析

用DSC和TG,在不同的线性升温速率下,通过对比DSC和TG曲线及热特征温度,考察了分析纯硝酸铵(AN)、工业AN以及木粉与分析纯AN混合物的热分解行为,推断出了分解反应最概然机理函数和动力学方程.结果表明:AN中加入少量的木粉使热安定性显著降低.     

Synthesis, characterization and thermal studies on furazan- and tetrazine-based high energy materials

This paper reports the synthesis of high energy materials (HEMs) viz. 3,3'-diamino-4,4'-azoxyfurazan (DAAF), 3,3s'-azobis(6-amino-1,2,4,5-tetrazine) [DAAT] and 1,4-dihydrazino tetrazine (DHTz). The products obtained were characterized by IR, 1H NMR, 13C NMR and mass spectra. Thermolysis of these compounds carried out by applying TG-DTA and DSC techniques indicated that the thermal stability of DAAF and DAAT was in the temperature range of 230-250 degrees C, whereas that of DHTz was up to approximately 140 degrees C. TG-FTIR of gaseous products of these compounds suggests the evolution of NH2CN/NH3 and HCN as major decomposition products. The impact and friction sensitivity data revealed that DAAF is insensitive to mechanical stimuli whereas DAAT and DHTz are vulnerable to impact stimuli. The cyclic voltammetric studies brought out that, DAAF, DAAT and DHTz are electroactive compounds and thereby can be detected at even low concentration at pH 7 and 13. The theoretical predictions of explosive power of DAAF, DAAT and DHTz alone and their combinations with well-known insensitive high explosives using Becker-Kistiakowsky Wilson (BKW) code as well as that of propellants based on them by NASA-CEC-71 suggest their potential in specific systems.     

Thermal and crystallization behavior of zirconia precursor used in the solution precursor plasma spray process

Yttria stabilized zirconia (7YSZ) solution precursor has been successfully used in the deposition of high durability thermal barrier coatings. In this paper, the thermal and crystallization behaviors of 7YSZ precursor were investigated by TG-DTA, FTIR and XRD. The results show that the precursor decomposition and crystallization temperatures greatly depend on heating rate e. g. 74°C for the crystallization temperature when tripping the heating rate. With a 10 °C/min heating rate, the weight loss due to precursor pyrolysis occurs predominantly at temperatures below 500 °C. A small weight loss due to the oxidation of residual carbon is detected from 800 °C to 950 °C. The complete crystallization of the tetragonal phase was determined to be around 500 °C by DTA and XRD analyses with a 10 °C/min heating rate. The crystallization kinetics and the activation energy of amorphous 7YSZ precursor were investigated by variable heating rate DTA. The calculated activation energy is 66.2 kJ/mol. The Avrami parameter value was determined to be 2.68, which indicates that crystallization nucleation and growth is diffusion-controlled. The crystalline phase of 7YSZ coatings deposited by the Solution Precursor Plasma Spray process was identified by XRD and Raman spectrum. The average YSZ grain size in the SPPS coating was determined to be 61 nm.     

Evaluation of danger from fermentation-induced spontaneous ignition of wood chips

Recently we conducted investigations in biological wastes because large pile-up storage of waste wood chips and others caused many fires in Japan. This paper shows the experimental results on wood chips with thermal analysis, by using a Thermogravimetry-differential thermal analysis (TG-DTA) and micro calorimeters, and as well with spontaneous ignition measurements, such as a UN wire mesh cube tester and a spontaneous ignition tester (SIT). Exothermic reaction of wood chips was observed during 45-60 degrees C only by the high sensitive microcalorimeters, TAM and MS 80. This reaction is far apart from the second major reaction by oxidation and is not easy to be recognized by the conventional detectors, like the TG-DTA and the wire mesh cube tester, because their sensitivity cannot meet the strict requirement. Correspondingly, experimental results under the adiabatic condition in the SIT confirmed this theory, in which the onset temperature of spontaneous ignition of wood chips was measured as 50-80 degrees C. This implies that the weak initial reaction at ambient temperatures mainly results from microbial fermentation in the presence of its inherent moisture and possibly gives rise to the further intense combustion sustained by a chemical reaction if the heat cannot be removed from the large scale storage of wood chips.