
Nikita V MuravyevRussian Academy of Sciences | RAS · N. N. Semenov Institute of Chemical Physics
Nikita V Muravyev
PhD
thermal analysis, kinetics & energetic materials
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Publications (85)
In this Correspondence, a question is raised on how confident are the computed detonation performance values. Consideration of the energetic materials in a recent Research Article in this journal and some other newly synthesized promising compounds shows that the variation between the available methods of calculation is surprisingly high.
During the development of novel energetic materials first analysis of synthesized compound includes both physico-chemical characterization and energetic potential evaluation. Evaluation of energetic performance includes determination of the detonation parameters, which is most often calculated rather than experimentally determined. To accelerate de...
In this review article, the Kinetics Committee of the International Confederation for Thermal Analysis and Calorimetry (ICTAC) delivers a collection of recommendations for the kinetic analysis of thermal decomposition processes. These recommendations specifically focus on the thermal decomposition processes in inorganic, organic, and polymeric mate...
Organic derivatives of hydroxylamine are important reagents in modern chemistry, but their thermal stability and related hazards have not yet been systematically studied. In the present study, we report a detailed thermal analysis of N-hydroxysuccinimide (NHS), N-hydroxyphthalimide (NHPI), 1,4-piperazine diol (PipzDiol), 1,3,5-trihydroxy-1,3,5-tria...
Novel energetic materials (EM) often combine two intrinsically counter trends, viz., a high energy density and mediocre safety parameters, like thermal stability and sensitivity toward mechanical stimuli. A rational design of promising EMs requires a proper understanding of their thermal stability at both macroscopic and molecular levels. In the pr...
Mechanical stress is an important trigger of reactions in chemicals. Historically, the standard testing protocols for impact and friction sensitivity have been developed mainly for energetic materials and explosives. As a result, the structure− mechanical safety data is available for common explosives and is constantly reported for newly synthesize...
Energetic materials are important class of functional compounds that combine the beauty of extreme high-energy chemistry with rigorous constraints on safety and performance. As a result, the development of energetic materials is a challenging process that require the best of computational, chemical synthesis, and material design techniques. This re...
Pyrazine 1,4-dioxide (PZDO) is a chemical frequently employed as a coformer in cocrystal design. It has two N-oxide fragments that signify potential hazards, but we found no information about it in prior literature. Therefore, we investigate the thermal behavior, thermochemical properties, and mechanical sensitivity of the title compound. We demons...
Energetic ionic liquids (EILs) have drawn considerable attention as potential liquid propellant components. However, most known EILs are oxygen-deficient and can be used only with external oxidizer. Herein, we report the first example of energetic mesoionic liquid, 3-methylazasydnone, that can function both as a monopropellant and in bipropellant s...
Tetrazino-tetrazine 1,3,6,8-Tetraoxide (TTTO) is one of the most powerful energetic materials synthesized to date. Its thermal decomposition of [1,2,3,4]tetrazino[5,6-e][1,2,3,4]tetrazine 1,3,6,8-tetraoxide (TTTO) has been investigated for the first time. The obtained formal kinetic model of thermolysis includes the two-dimensional nucleation-growt...
The development of liquid energetic fuels with improved properties is an important topic in space propulsion technologies. In this manuscript, a series of energetic ionic liquids incorporating a 1,2,5‐oxadiazole ring and nitrate, dicyanamide or dinitramide anion was synthesized and their physicochemical properties were evaluated. The synthesized co...
Vaporization is an important aspect of the performance and detection of energetic materials. While the traditional techniques concentrate on bulk property changes during sublimation, atomic force microscopy (AFM) offers the possibility to track particle volume changes under heating. Ideally, this will enable the investigation of chemicals that are...
Nitro derivatives of benzotriazoles are safe energetic materials with remarkable thermal stability. In the present study, we report on the kinetics and mechanism of thermal decomposition for 5,7-dinitrobenzotriazole (DBT) and 4-amino-5,7-dinitrobenzotriazole (ADBT). The pressure differential scanning calorimetry was employed to study the decomposit...
A number of new high-performing energetic materials combines the explosophoric functionalities, high nitrogen content, and relies on fused heterocyclic blocks. Two representatives of this design approach have been synthesized recently, namely, 1,2,9,10-tetranitrodipyrazolo[1,5-d:5ʹ,1ʹ-f][1,2,3,4]-tetrazine (1), and 2,9-dinitrobis([1,2,4]triazolo)[1...
Attention is called to numerous publications that have recently appeared in Biomass Conversion and Biorefinery and reported on the application of single heating rate methods to pyrolysis data. Emphasis is laid on the fact that these methods generally fail to determine trustworthy kinetics triplets, i.e., the reaction model, activation energy, and p...
The energetic materials are actually not used as a single chemical but rather as ingredients in formulations resulted various interface existed. The intimacy of mixing and particle size are well known governing characteristics for energetic formulations. Today, two different approaches for design of energetic materials have evolved as a result of t...
When linearly heating trehalose dihydrate (TH-DH) at a relatively high heating rate (β ≥ 1.5 K min–1), the thermal dehydration begins in the solid state and transitions to the liquid state at the melting point of TH-DH (∼370 K). The complex mass loss and phase change characteristics observed during the thermal dehydration is due to the contributory...
There is an urgent demand for novel energetic materials with improved performance to serve as oxygen suppliers (oxidizers) and high-energy additives. Synthesis and characterization of compound that combines both of the above roles, bis-(2-difluoroamino-2,2-dinitroethyl)nitramine (1), is reported. 1 was synthesized by difluor-oamination of bis(2,2-d...
This paper is a literature survey that focuses on the present development of thermokinetic publications. It demonstrates that in recent years pyrolysis kinetics has turned into a major application of the thermokinetics. Analysis of the respective publications suggests that too often their quality leaves much to be desired because of the poor choice...
Cocrystal design is an important and well-developed approach in the pharmaceutical industry. Energetic materials can be thought of as unique and challenging objects for cocrystal engineering since abundant explosophoric functionalities prevent exploiting common supramolecular synthons. Screening of cocrystal formation using thermal analysis methods...
The standard enthalpies of formation of nitro-NNO-azoxy compounds including nitro-NNO-azoxybenzene (2), 3-nitro-4-{[4-(nitro-NNO-azoxy)furazan-3-yl]-NNO-azoxy}-furazan (4), and bis-4,4′-(nitro-NNO-azoxy)-3,3′-azofurazan (6), as well as those of nitro compounds including 3-nitro-4-[(4-nitrofurazan-3-yl)-NNO-azoxy]furazan (3) and 4,4′-dinitro-3,3′-az...
Performance of several neural network architectures (convolutional neural network CNN, multilayer perceptron MLP, CNN/MLP hybrid CDD) was evaluated for kinetic analysis of complex processes with overlapping independent reaction mechanisms based on the nucleation-growth Johnson-Mehl-Avrami (JMA) model. Theoretically simulated data used for the testi...
A reliable kinetic description of the thermal stability of energetic materials (EM) is very important for safety and storage-related problems. Among other related issues, autocatalysis very often complicates the decomposition kinetics of EM. In the present study, the kinetics and decomposition mechanism of a promising energetic compound, 5-amino-3,...
Modern trends in the development of energetic materials include the various methods of particle surface modification and the widespread use of nanosized powders. Atomic force micros-copy (AFM) is a useful, but often overlooked advanced tool for the investigation of surface, subsurface, and interface properties of energetic compounds. This review hi...
The initiation of energetic materials by mechanical stimuli is a critical stage of their functioning, but remains poorly understood. Using atomic force microscopy (AFM) we explore the microscopic initiation behavior of four prototypical energetic materials: 3,4-dinitropyrazole, \epsilon-CL-20, \alpha-PETN and picric acid. Along with the various che...
Thus, a selective method has been developed for the synthesis of regioisomeric N-unsubstituted di(nitropyrazolyl)-1,2,4-oxadiazoles – potential thermally stable energetic materials. All studied isomers were shown to be superior to hexanitrostilbene by their energetic performance, thermal stability, and sensitivity to mechanical stimuli. Regiochemic...
The continuous need for energetic materials with increased performance and improved safety characteristics stimulates synthetic efforts as well as physical modification of existing compounds. The present study reports the fabrication of 1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (HMX)-based composites with common commercial polymers , polymethyl acryl...
In this study, we investigated the mechanistic features and kinetics of the thermal decomposition of solids accompanied by liquefaction as exemplified by the thermal dehydration reactions of monosodium L-glutamate monohydrate (MSG-MH). The thermal dehydration of MSG-MH occurs via two mass-loss processes comprising the elimination of crystalline wat...
Analysis of thermal behavior of liquids is often accompanied by vaporization. In an extreme case, the calorimetric (DSC) experiment reveals the only endothermic evaporation instead of the more valuable thermal decomposition. 3-Methylfuroxan (MMF) is an energetic monosubstituted 1,2,5-oxadiazole N-oxide that shows the above behavior. We investigate...
The effect of polymer binders on the thermal behavior, combustion, and composition of condensed gasification products of model boron-containing compositions was studied to determine the optimal fuel composition for the gas generator of a ducted rocket engine. The physicochemical transformations of boron particles during combustion wave propagation...
Mechanical and thermal hazards are critical for chemical compounds. Foremost, the design of novel energetic materials that are stable, insensitive, but have a detonation performance superior to in-service materials is of great interest. However, a single source of safety data for hazardous materials with explosophoric functionalities is still missi...
A series of highly energetic nitrogen-rich salts comprised of a 5-(trinitromethyl)tetrazolate anion and high-nitrogen cations was synthesized by simple and efficient chemical routes from readily available commercial reagents. These energetic materials were fully characterized by IR and multinuclear NMR (1H, 13C, 14N) spectroscopy, elemental analysi...
The standard state enthalpy of formation and the enthalpy of sublimation are essential thermochemical parameters determining the performance and application prospects of energetic materials. Direct experimental measurements of these properties are complicated by low volatility and high heat release in bomb calorimetry experiments. As a result, the...
Artificial neural networks (ANNs) are a method of machine learning (ML) that is now widely used in physics, chemistry, and material science. ANN can learn from data to identify non-linear trends and give accurate predictions. ML methods, and ANNs in particular, have already demonstrated their worth in solving various chemical engineering problems,...
Thermal decomposition of solids is often accompanied by autocatalysis, one of the possible causes of which is the formation of a liquid phase. The kinetic model considering the liquefaction of solid reactant under isothermal conditions was proposed by Bawn in the 1950s. Present study reports the application of the Bawn model to the thermolysis of 3...
Thermal decomposition of cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (Bicyclo-HMX) both in solid state and in solution has been studied with a set of thermal analysis methods. Differential scanning calorimetry data obtained at several heating rates were analyzed using the model-fitting kinetic technique using the free open-source THINKS...
In the present work, we studied in detail the thermochemistry, thermal stability, mechanical sensitivity, and detonation performance for 20 nitro-, cyano-, and methyl derivatives of 1,2,5-oxadiazole-2-oxide (furoxan), along with their bis-derivatives. For all species studied, we also determined the reliable values of the gas-phase formation enthalp...
Thermal decomposition of 1,3,5-triazines with azido, trinitroethyl, and nitramino groups, the three important energetic functionalities, has been studied with a range of thermal analysis tools. The involved compounds melt under heating with the following mass loss and heat and gas release in the course of thermal decomposition. Model-fitting kineti...
Energetic compounds 1–6, consisting of one or two furazan rings linked by azo or azoxy bridges and one or two nitro‐NNO‐azoxy substituents, were synthesized by nitration of the corresponding tert‐butyl‐NNO‐azoxy precursors with NO2BF4. Novel methods for the synthesis of 3,4‐bis(tert‐butyl‐NNO‐azoxy)furazan (7) and bis‐4,4′‐(tert‐butyl‐NNO‐azoxy)‐3,...
A smooth synthesis of 4H-[1,2,3]triazolo[4,5-c][1,2,5]oxadiazole 5-oxide 1 and its energetic salts (ammonium, hydroxylammonium, guanidinium, triaminoguanidinium) is reported. The compounds synthesized were characterized by multinuclear nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy, mass spectrometry, elemental analysis, differenti...
A computer simulation of cocrystal structures of [1,2,5]oxadiazolo[3,4-e][1,2,3,4]tetrazine-4,6-dioxide (FTDO) with benzotrifuroxan (BTF) in ratios of (1 : 1), (2 : 1) and (3 : 1) was performed, and their thermodynamic stability and physical–chemical characteristics were calculated. According to calculations, the (3 : 1) cocrystal is thermodynamica...
Several energy-rich bifuroxans incorporating nitro and azido functionalities have been synthesized and thoroughly characterized by IR and multinuclear NMR spectroscopy, elemental analysis, single-crystal X-ray diffraction and differential scanning calorimetry. N-oxide regiochemistry was employed to design the tunable azido(nitro)bifuroxans with dif...
The problem of the space debris is an important aspect of the on-ground casualty risk reduction. Some articles, like fuel tanks made of titanium alloy, survive during the atmospheric post-mission re-entry and impact the Earth's surface, thus posing a serious hazard. A pyrotechnic device is proposed to bring an additional heating of space debris at...
Physicochemical changes occurring in an oxide shell of boron particles during heating are extremely important for the oxidation and combustion of boron, including those in solid propellant compositions. The Al2O3, MgO, MgF2, Al, and Mg impurities were experimentally discovered in an oxide layer on boron particles obtained by various methods. The go...
A supercritical antisolvent process has been applied to obtain the nitrocellulose nanoparticles with an average size of 190 nm from the nitrocellulose fibers of 20 μm in diameter. Compared to the micron-sized powder, nano-nitrocellulose is characterized with a slightly lower decomposition onset, however, the friction sensitivity has been improved s...
The kinetic parameters of thermal decomposition of furazano-1,2,3,4-tetrazine-1,3-dioxide (FTDO) and the (75/25) FTDO/dinitrazapentane (DNP) system were experimentally investigated by differential scanning calorimetry. Kissinger kinetic analysis was performed using differential scanning calorimetry data obtained at heating rates of 0.1–5.0 K/min. T...
Thermal decomposition of solids often includes simultaneous occurrence of the overlapping processes with unequal contributions in a specific physical quantity variation during the overall reaction (e.g., the opposite effects of decomposition and evaporation on the caloric signal). Kinetic analysis for such reactions is not a straightforward, while...
7‐Nitro‐3‐(nitro‐NNO‐azoxy)[1,2,4]triazolo[5,1‐c][1,2,4]‐triazin‐4‐amine (4) is the first high‐melting compound bearing adjacent nitro‐NNO‐azoxy and amino groups. It was synthesized by nitration of 7‐nitro‐3‐(tert‐butyl‐NNO‐azoxy)[1,2,4]triazolo[5,1‐c][1,2,4]triazin‐4‐amine (3) with NO2BF4. Compound 4 is a rather thermally stable (decomposition ons...
Crystallization of different biological targets and pharmaceuticals from ionic liquids (ILs) could result in previously unknown polymorph modifications. Crystallization of high energy materials (HEMs) from ILs has not been studied so far. This paper is devoted to the first attempts to crystallize a highly energetic compound – 2,4,6,8,10,12-hexanitr...
A series of highly energetic organic salts comprising a tetrazolylfuroxan anion, explosophoric azido or azo functionalities, and nitrogen‐rich cations were synthesized by simple, efficient, and scalable chemical routes. These energetic materials were fully characterized by IR and multinuclear NMR (¹H, ¹³C, ¹⁴N, ¹⁵N) spectroscopy, elemental analysis...
Combustion of thermite composition Mg/Fe2O3 with micron-and nano-sized components was studied in pyrotechnic heater setup. Pressed charges were burned out in hermetic steel tubes with simultaneous pressure and temperature registration. Advanced system of thermocouples connections allows drawing thermal maps of the steel case heating with high spati...
Thermal stability of energetic materials, being of the utmost importance for safety issues, is often considered in terms of kinetics, e.g., the Arrhenius parameters of the decomposition rate constant. The latter, in turn, are commonly determined using conventional thermoanalytical procedures with the use of simple Kissinger or Ozawa methods for kin...
The discovery of novel explosophoric building blocks for the construction of energetic compounds is extremely rare. Here, based on the comparative experimental properties and computational analysis of compounds where nitroaryl backbone bonded with various nitrogen/oxygen-rich groups, it is shown that those compounds that have azasydnone group, poss...
Проведено исследование порошков бора и его соединений, полученных различными методами - металлотермическим, электролитическим и крекингом бороводородов. Детально исследованы кристаллическое состояние, размер и микроструктура частиц, наличие и состав примесей, а также химический состав оксидного слоя частиц бора. Проведен анализ влияния указанных ха...
This paper describes a study of boron powders and powder compounds, obtained by various methods, including metallothermal, electrolytic, and borane cracking methods. The crystal state, particle size and microstructure, presence and composition of impurities, and chemical composition of the oxide layer of boron particles are profoundly investigated....
Oxidation of nanosized titanium (nano-Ti), a promising component of energetic compounds, was studied using thermogravimetry and differential scanning calorimetry. To obtain more comprehensive insight into the kinetics and mechanism of oxidation, a variety of complementary non-isothermal and isothermal thermoanalytical experiments were performed. In...
High‐nitrogen‐content compounds have attracted great scientific interest and technological importance because of their unique energy content, and they find diverse applications in many fields of science and technology. Understanding of structure–property relationship trends and how to modify them is of paramount importance for their further improve...
A complete series of complexes of lanthanides and yttrium (except radioactive Pm) with BT2- ligand were synthesized from sodium5,5'-bitetrazolate and available REE salts. Eight new complexes were structurally characterized by single-crystal XRD. [M(BT)(H2O)7]2[BT]·6H2O, (M=Pr (1), Gd (2)) complexes are isomorphous and consist of [M(BT)(H2O)7]+ ions...
The design of novel energetic materials with improved performance, optimized parameters, and environmental compatibility remains a challenging task. In this study, new high‐energy materials based on isomeric dinitrobi‐1,2,5‐oxadiazole structures comprising nitrofurazan and nitrofuroxan subunits were synthesized. Due to planarity and strong noncoval...
The key steps of the synthesis of two high energy compounds, namely, 4-(2,2,2-trinitroethyl)-2,6,8,10,12-pentanitrohexaazaisowurtzitane and 4,10-bis(2,2,2-trinitroethyl)-2,6,8,12-tetranitrohexaazaisowurtzitane, were optimized. Their enthalpy of formation, density, impact and friction sensitivity, and thermal stability were experimentally determined...
Thermal behavior of two principally different wax materials (viz., paraffin Russian grade P-2 and microcrystalline Sasol 0907) has been investigated using thermogravimetry and differential scanning calorimetry at atmospheric and elevated pressure. The variation of experimental conditions during thermoanalytical studies highly affects the kinetics a...
The safety properties of hazardous materials, viz., thermal stability and sensitivity to mechanical stimuli (typically, to impact and friction) are of utmost importance for industrial applications. Direct experimental measurements of these values are demanding in terms of both methodology and experimental effort necessary to meet existing standards...
This study focused on kinetic modeling of a specific type of multistep heterogeneous reaction comprising exothermic and endothermic reaction steps, as exemplified by the practical kinetic analysis of the experimental kinetic curves for the thermal decomposition of molten ammonium dinitramide (ADN). It is known that the thermal decomposition of ADN...
FOX-7, first synthesized two decades ago, is a promising insensitive energetic compound. Enthalpy of formation is among the most important parameters that influence, e.g., the detonation velocity, a crucial performance indicator of an energetic material. Very surprisingly, despite the fact that FOX-7 has been known for almost 20 years, its accurate...
Thermal decomposition of a novel promising high-performance explosive dihydroxylammonium 5,5’-bistetrazole-1,1’-diolate (TKX-50) was studied using a number of thermal analysis techniques (thermogravimetry, differential scanning calorimetry, and accelerating rate calorimetry, ARC). To obtain more comprehensive insight into kinetics and mechanism of...
The thermal decomposition and combustion of binary mixture of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) and ammonium perchlorate (AP) are investigated at various concentrations. Thermal stability was investigated by thermal analysis techniques, i.e., DSC/TGA, combined with FTIR spectrometry, and accelerating rate calorimetry (ARC). Two...
The nitrogen-rich energetic compound 5-amino-3,4-dinitropyrazole (5-ADP) was investigated using complementary experimental techniques. X-ray diffraction indicates the strong intermolecular hydrogen bonding in 5-ADP crystals. Compound exhibits low impact sensitivity (23 J) and insensitivity to friction. The activation energy of thermolysis determine...
Inspired by the recent victory of the computer program Alpha Go [D.Silver et al, Nature, 2016] over the world strongest human Go player and by the ability of this program based on artificial neural networks(ANN) for self-learning, we present the attempt to perform the thermokinetic analysis using ANN models. Various virtual combinations of kinetic...
High pressure differential scanning calorimetry (HP-DSC) has been used to study thermal decomposition of energetic materials, i.e., trinitrotoluene, cyclotrimethylenetrinitramine, and ammonium dinitramide. HP-DSC runs have been performed in the range of 0.1–14 MPa both in inert and oxidative environments to determine the effect of pressure on vapor...
The influence of nanosized oxides of Ti, Al, Fe, and Si on the HMX thermolysis and combustion is reported. The following order of their catalytic efficiency in HMX thermolysis was obtained: TiO2 > Fe2O3zAl2O3 > SiO2. The catalytic performance was analyzed and the key factors were shown to be specific surface area, content, and the acid/base propert...