CrystEngComm, Год журнала: 2022, Номер 24(16), С. 2948 - 2953
Опубликована: Янв. 1, 2022
Two novel low melting-point cocrystals with high performances were obtained by cocrystallizing TNB 1,4-DNI and DNMT, namely TNB/1,4-DNI (1) TNB/DNMT (2).
Язык: Английский
Crystal Growth & Design, Год журнала: 2024, Номер 24(17), С. 7361 - 7388
Опубликована: Авг. 19, 2024
In 2011, cocrystallization of energetic materials became a hot topic and pathway to overcome the energy−safety contradiction; especially for commercially attractive nitramines, it first preference researchers. The present review focuses on energetic−energetic four CL20, HMX, BCHMX, RDX, structural aspects these cocrystals, their influence thermochemical detonation properties. Cocrystallization has proven be crystal engineering technique achieve safety morphological suitability cocrystals (EECCs). Overall, in most cases, impact sensitivities EECCs are decreased, this is phenomenal change; however, needed adjust with properties slightly, negligible if coformer (EMs) properly chosen. There other notable variations morphologies packing crystals, including key such as relatively high density melting point. These changes occur due binding energy, trigger bond length, cohesive energy during cocrystallization. Researchers highly focused nitramines; earlier reported methods lacking selectivity scalability. When comes adoption industrial scale production EECCs, more difficult. We conducted thorough literature survey. Also we discussed about recently developed VPSZ coagglomeration method, which provides huge opportunity tune performance existing easy up level.
Язык: Английский
Процитировано
6
CrystEngComm, Год журнала: 2019, Номер 22(1), С. 61 - 67
Опубликована: Ноя. 14, 2019
Solvent and heat induced self-assembly to CL-20/HMX co-crystals has been investigated. The mechanism towards such process could be concluded nanoparticle inducing, oriented aggregation, surface integration assembly.
Язык: Английский
Процитировано
36
Crystal Growth & Design, Год журнала: 2020, Номер 20(6), С. 3826 - 3833
Опубликована: Апрель 20, 2020
A new 1:3 CL-20 (2,4,6,8,10,12-hexanitrohexaazaisowurtzitane)/4,5-MDNI (1-methyl-4,5-dinitroimidazole) cocrystal (1) in combination with the previously reported 1:1 CL-20/4,5-MDNI (2) together have been first realized different stoichiometric ratios based on and 4,5-MDNI energetic–energetic cocrystals. Subtle differences intermolecular interactions packing motifs may lead to formations of cocrystals 1 2 by structure comparisons. Moreover, properties (e.g., density, thermal properties, sensitivity, detonation performances) varied significantly under crystal structures. For instance, comprehensive performances (ρ: 1.813 g/cm3; D: 8604 m/s, P: 34.45 GPa; IS: 16 J) were less excellent than those 2, whereas exhibited a velocity superior that LLM-105 (2,6-diamino-3,5-dinitropyrazine-l-oxide, relatively insensitive explosive) low impact sensitivity close LLM-105; thus, act as high-energy explosive. findings offer insights into design preparation energetic other cocrystals, enrich better understanding for provide smart strategy tune performances.
Язык: Английский
Процитировано
35
Crystal Growth & Design, Год журнала: 2020, Номер 20(8), С. 5526 - 5537
Опубликована: Июль 7, 2020
On the basis of literature analysis, we have built a database containing fusion temperatures two-component molecular cocrystals and individual compounds (1947 cocrystals/salts). In order to estimate thermodynamics formation crystals, created on values reported in from 1900 until 2019 inclusive. The includes enthalpies Gibbs energy crystals obtained by various methods. A new algorithm for estimating sublimation energies has been developed based their only. divides into clusters including structurally related compounds. Using this approach, calculated 269 whose were calorimetric method. thermodynamic functions process 509 analyzed. diagram method used analyze parameters under study. An analysis experimental data distribution sectors shown that number with enthalpy-driven processes cocrystal corresponds 70.8%, whereas those entropy-driven correspond 29.2%. detailed comparative carried out different monotropic polymorphic forms, same composition stoichiometries, racemate enantiomers.
Язык: Английский
Процитировано
35
Molecules, Год журнала: 2022, Номер 27(12), С. 3755 - 3755
Опубликована: Июнь 10, 2022
The crystal and molecular structures, intermolecular interactions, energy of CL-20, HATO, FOX-7 were comparatively predicted based on dynamic (MD) simulations. By comparison, the 2D fingerprint plot, Hirshfeld surface, reduced density gradient isosurface, electrostatic potential surface studied to detect interactions. Meanwhile, effects vacuum different solvents habit by AE MAE model, respectively. calculation was also analysed equilibrium structures these models MD Our results would provide fundamental insights for engineering energetic materials.
Язык: Английский
Процитировано
20
FirePhysChem, Год журнала: 2023, Номер 4(1), С. 21 - 33
Опубликована: Май 25, 2023
In order to discover of high-energy materials with characteristics that surpass modern benchmarks, it is necessary study the widest range potential structures. The design energetic compounds using high-nitrogen cage scaffolds provides new opportunities. One promising representatives polycyclic multinitragen cages hexaazaisowurtzitane, since most powerful explosive CL-20 based on it. recent years, synthesis analogues has been actively developed. This review presents progress in synthesis, performance and structure-property relationship for polynitro hexaazaisowurtzitanes over past decade.
Язык: Английский
Процитировано
11
Small, Год журнала: 2024, Номер unknown
Опубликована: Май 27, 2024
Abstract The fabrication of materials with hierarchical structures has garnered great interest, owing to the potential for significantly enhancing their functions. Herein, a strategy coupling molecular solvation and crystal growth is presented fabricate porous spherulites 2,4,6,8,10,12‐hexanitro‐2,4,6,8,10,12‐hexaazaisowurtzitane (CL‐20), an important energetic material. With addition polyvinylpyrrolidone in antisolvent crystallization, metastable solvate CL‐20 formed grows spherulitically, spontaneously desolvates obtain spherulite when filtration, which characteristic peak nitro group shifts detected by situ micro‐confocal Raman spectroscopy. effect thought induce CL‐20, confirmed density functional theory calculations, meanwhile acting on (020) face trigger spherulitic growth, demonstrated through infrared spectroscopy Rietveld refinement powder X‐ray diffraction. Moreover, compared common crystals, exhibit enhanced combustion increases 6.24% pressure, 40.21% pressurization rate, 9.63% pressure duration effect, indicating capability boost energy release crystals. This work demonstrates new route via solvation‐growth construct organic crystals provides insight into structure‐property relations material design.
Язык: Английский
Процитировано
4
FirePhysChem, Год журнала: 2024, Номер 5(1), С. 68 - 73
Опубликована: Июнь 1, 2024
The literature widely reported information about apparent high impact sensitivities of both the pure 2,4,6-trinitrotoluene (TNT; i.e. 14 - 16 J) and ɛ-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ɛ-CL20; 2 4.4 J), which mostly correspond to BAM method determination. This brief overview discusses reasons these error data. physical organic chemistry approach this problem has confirmed Beijing Inst. Technology value 13.2 J for ɛ-CL20 LANL 39.2 TNT. morphological instability ɛ-CL20, when in contact with polar binders or plasticizers, might not have much influence on its application propellants. stabilization ɛ- β-CL20 upon entry into a cocrystal coformer having character polynitro compound (especially nitramines) could be practical importance. sensitivity TNT is important handling processing safety related specific samples. However, they cannot used molecular-structural analyses predictions as comparative standard, currently widespread literature.
Язык: Английский
Процитировано
4
The Journal of Physical Chemistry C, Год журнала: 2019, Номер 123(27), С. 16565 - 16576
Опубликована: Июнь 19, 2019
Polymorphism is universal in organic crystals like conventional energetic materials (EMs), and it may cause a difference thermal stability, one of the most important properties EMs. Nevertheless, deep insights into differences polymorphic EMs are lacking. 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) powerful EM commercialized already possesses three polymorphs stabilized at common condition, which exhibit many performances. However, underlying mechanism responsible for these remains unclear. In this work, self-consistent charge density functional tight binding scheme molecular dynamics simulations combined to reveal decay CL-20, with considerations an extreme volume constraint two heating types. The lower activity ε-CL-20 distinguished from β- γ-CL-20 relatively low temperature 1000 K, as only does not decompose time scale simulation 20 ps. partly its impact sensitivity. Two high temperatures 1500 2000 K cannot differentiate their activities. Moreover, unimolecular N–N breakage governs first steps all polymorphs. Five types bond cleavages, including NO2 partitions 5- 6-membered rings, cleavage C–N bonds C–C breakage, observed decay. Interestingly, five ignitions be any case. Besides, we find that disfavors formation stable products N2 CO2. These results expected give complicated sensitivity
Язык: Английский
Процитировано
33
Crystal Growth & Design, Год журнала: 2019, Номер 19(5), С. 2779 - 2784
Опубликована: Апрель 10, 2019
Cocrystallization of energetic compounds has recently been considered as an effective method to adjust the properties through selection coformers, particularly improve detonation and reduce mechanical sensitivity CL-20. In this research, a reliable promising design strategy synthesize CL-20-based cocrystals was presented, where (i) coformer should show local structural similarity CL-20, i.e., five- or six-membered symmetric heterocycles, (ii) molecular structure contain electron-donating groups. order verify adaptability strategy, pyrazine, 2,6-dimethoxy-3,5-dinitropyrazine, 2,5-dimethylpyrazine were selected templates symmetrical N-heterocyclic for cocrystallization with Fortunately, on basis results experiments crystal analysis, three successfully cocrystallized Moreover, two same components different stoichiometric ratios formed by pyrazine addition, designed cocrystals, including thermal stability, properties, sensitivities, also studied in detail. CL-20 aforementioned coformers demonstrates appropriateness coformers. light finding, safety can be modulated employing suitable
Язык: Английский
Процитировано
31