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CL-20
Small · 2026 · IF 11.8

Pseudomorphic Replacement Driven Construction of Hierarchical Homostructured CL-20 Core-Shell Architectures for Safety Improvement

Yujie Song,Ya Guo,Ruibing Lv,Nan Wu,Xiaoqing Zhou,Shilong Hao,Hongzhen Li,Qi Zhang

Hierarchical homostructured core-shell architectures (HHCS) integrate the advantages of maintaining high energy density and enhancing interfacial stability. However, their rational design and controllable construction remain significantly challenging. Herein, we propose a self-limiting surface pseudomorphic replacement strategy mediated by localized solvation regulation, enabling the precise construction of HHCS of ε-2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (ε-CL-20). Specifically, a γ-butyrolactone (γ-BL)/H 2 O mixed solvent system induces a selective surface dissolution—recrystallization process on ε-CL-20 crystals, forming a stable CL-20∙γ-BL solvate (S γ-BL ) layer. This layer undergoes interfacially induced nucleation on the crystal surface and exhibits self-limiting growth while preserving the morphology of the parent crystal, thereby enabling a morphology-preserving pseudomorphic replacement process. Upon thermal treatment, solvent removal and solid-state rearrangement facilitate the conversion of the outer solvate shell into the CL-20 phase, yielding a homogeneous shell with hierarchical nanoporous features. The resulting HHCS of CL-20 exhibits a remarkable enhancement in safety performance: its impact sensitivity value increases from 2.5 to 12 J, while the packing density decreases by only 4.85%. Importantly, the core-shell structure consists solely of ε-CL-20, with no heterogeneous materials. This work presents an interfacial-engineering strategy that provides new theoretical and methodological insights for the safety-oriented design and structural regulation of high-energy molecular crystals.

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CHEMICAL ENGINEERING JOURNAL · 2026 · IF 12.5

Fabrication and investigation of ignition and combustion characteristics of CL-20/CDs composite energetic micro-units

Jiechao Wang,Jiangdong Xu,Wangjian Cheng,Lei Gao,Yutong Wang,Huaiqian Liu,Qianqian He,Chongwei An,Chuanhao Xu

Introducing “0D” CDs as photosensitizers to enhance the laser responsiveness • Constructing photothermal conversion interface micro-units using hydrogen bonding • CDs regulate the pore size distribution of porous micro-units • Establishment of the ignition-combustion model and mechanistic elucidation Composite energetic micro-units are integrated energetic systems in which synergistic components and structural design enable functional coupling and controllable energy release, offering a crucial assembly strategy for efficient laser ignition of high-energy explosives. A key scientific challenge lies in constructing photosensitive micro-units with stable photothermal conversion interfaces and effective energy transfer pathways. In this work, CL-20 is used as the primary energy releasing component, while carbon dots (CDs) are innovatively introduced as photosensitive materials. Sodium alginate (SA) and polyvinyl alcohol (PVA) form the network framework to construct spherical composite energetic micro-units with a three-dimensional porous architecture. Characterization of chemical composition, morphology, and pore size distribution reveals that CDs induce the formation of intermolecular hydrogen bonds and the rearrangement of the hydrogen-bonding network between SA and PVA, which anchoring the boundaries of the 3D network, suppressing the formation of large pores (>50 μm), and enabling controlled regulation of pore size distribution. Laser ignition tests demonstrate that both ignition threshold and ignition delay decrease with increasing CDs content, reaching minima of 166.66 W·cm −2 and 35.4 ms, respectively, confirming the high photothermal conversion efficiency. Furthermore, increasing CDs content (1–9%) induces a pore-migration effect, where large pores gradually disappear and small pores (<50 μm) become dominant. This small porous structure shortens heat and mass transfer distances during combustion and enhances energy release efficiency. For instance, the combustion duration of sample C 7 (7% CDs) is 3.37 times shorter than that of C 1 (1% CDs). These findings provide valuable guidance and data support for the photosensitized design of composite energetic micro-units and for advancing the understanding of their laser ignition and combustion propagation characteristics in high-energy explosive systems.

CAS / MDL: 10125-13-0 9005-38-3
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ACS Omega · 2022 · IF 4.132

Tuning the Energetic Performance of CL-20 by Surface Modification Using Tannic Acid and Energetic Coordination Polymers

Bin Yuan,Yu Zhang,Ke-xin Wang,Tian-ping Wang,Yan Li,Shun-guan Zhu,Lin Zhang,Zhen-xin Yi,Hua Guan,Chen-guang Zhu

The energetic performance of hexanitrohexaazaisowurtzitane (CL-20) was modulated with two energetic coordination polymers (ECPs), [Cu(ANQ)2(NO3)2] and [Ni(CHZ)3](ClO4)2, in this study by a two-step method. First, tannic acid polymerized in situ on the surface of CL-20 crystals. Then, [Cu(ANQ)2(NO3)2] and [Ni(CHZ)3](ClO4)2 were hydrothermally formed on the surface of CL-20/TA, respectively. Explosion performance tests show that the impact sensitivity of the coated structure CL-20/TA/[Cu(ANQ)2(NO3)2] is 58% less than that of CL-20 with no energy decrease. On the other hand, CL-20/TA/[Ni(CHZ)3](ClO4)2 can be initiated by a low laser energy of 107.3 mJ (Nd:YAG, 1064 nm, 6.5 ns pulse width), whereas CL-20 cannot be initiated by even 4000 mJ laser energy. This study shows that it is feasible to modify the performance of CL-20 by introducing energetic CPs with certain properties, like high energy insensitive, laser-sensitive, etc., which could be a prospective method for designing high energy insensitive energetic materials in the future.

研究领域: 含能材料 · 材料化学 · 火炸药工程
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Defence Technology · 2025 · IF 5.9

Interfacial stability effect of PDA@PVDF dual-coating on CL-20: Synergistically suppressed polymorphic transition and solubility

Hao Wang,Chenming Li,Enjie Zhang,Yapeng Ou,Xiaoxia Ma

Hexanitrohexaazaisowurtzitane (CL-20) is a high-energy explosive widely used in composite explosives and propellants, but its application is severely limited by thermally induced ε-to-γ polymorphic transition and high solubility in nitrate ester solvents. The transition reduces energy density and increasing sensitivity, and the solubility causes dissolution-recrystallization defects (e.g., voids, compositional inhomogeneities) during long-term storage. To address these issues while preserving its high energetic performance, this study developed a polydopamine@polyvinylidene fluoride (PDA@PVDF) dual-coating strategy, fabricating CL-20 composite particles with a core-shell structure. In-situ X-ray diffraction (XRD) results confirmed that the ε-to-γ phase transition temperature of CL-20 increased from 110 °C (pristine CL-20) to 140 °C. Meanwhile, the CL-20@PDA@9%PVDF sample exhibited the lowest solubility and the best solvent resistance, and the solubility of CL-20 in nitrate ester solvents was drastically reduced from 0.229 g/100 g to 0.026 g/100 g, an 88.6% decrease, effectively enhancing its structural and solvent resistance stability. For energetic performance, when mixed with aluminum powder at a 7:3 mass ratio, the CL-20@PDA@9%PVDF/Al composite achieved a combustion heat of 8275 J/g, 8.7% higher than that of the unmodified Al/CL-20 system (7611 J/g). Combustion pressure tests showed that although the modified system exhibited slightly lower initial peak pressure and pressure rise rate due to dilute CL-20 content from inert coatings, it presented a unique "delayed enhancement" effect, with pressure gradually surpassing and ultimately exceeding that of the unmodified system in the middle and late combustion stages, enabling more sustained high-pressure output. This work realizes the synergistic optimization of CL-20’s polymorphic/solvent stability and energetic performance, providing a feasible and scalable approach for the practical application of CL-20 in advanced energetic systems.

CAS / MDL: 1185-53-1 62-31-7
研究领域: 含能材料 · 材料科学 · 应用化学 · 热稳定性工程
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FUEL · 2023 · IF 7.4

Significantly different inhibition mechanisms of graphene oxide in laser-ignited combustion of micro and nano CL-20

Jiaxin Su,Yan Hu,Bin Zhou,Lizhi Wu,Yinghua Ye,Ruiqi Shen

Because of its high energy density, hexanitrohexaazaisowurtzitane(CL-20) has been widely used in propellants in place of conventional oxidizers. The adjustable burning rate of the CL-20 is a key factor in adapting the propellant to various environments. In this work, the effects of graphene oxide(GO) content on the thermal release, ignition and combustion characteristics of micro and nano CL-20 were thoroughly conducted based on the differential scanning calorimetry measurements (DSC), laser ignition, burning rate test and condensed combustion products collection. The results show GO has a positive effect on micro and nano CL-20 in ignition performance and a negative effect on combustion rate. Owing to the addition of GO, the original flameless combustion of CL-20 changes to flaming combustion. With increasing GO content, the burning rates of micro and nano CL-20 show completely different descending laws. Furthermore, the combustion mechanism of nano and micro CL-20/GO has been studied in detail. The burning rate of micro CL-20/GO is primarily determined by the condensed phase, and that of nano composite is controlled by both of the condensed and gas phases. This work provides a deeply insight into the influence mechanism of GO on the properties of nano and micro CL-20.

CAS / MDL: 110-54-3
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Defence Technology · 2025 · IF 5.9

Enhanced hydrophobicity and photosensitivity of DATNBI/alginate films via ionic cross-linking for near-infrared laser ignition

Ping Ye,Weimiao Wang,Xiaodong Li,Zhiqiang Qiao,Changping Guo,Jinjin He,Xu Zhou,Rui Li,Guangcheng Yang,Guoqing Lv

Based on the characteristics of laser-induced surface ignition, energetic photosensitive films show promising potential to meet the ignition requirements of various energetic materials (EMs). In this study, DATNBI/ferric alginate (DI/FeA), DI/cobalt alginate (DI/CoA), and DI/nickel alginate (DI/NiA) films are fabricated by employing sodium alginate (SA) with a three-dimensional network structure as the film matrix, via ionic cross-linking of SA with Fe 3+ , Co 2+ , and Ni 2+ ions. The study demonstrates that the ionic cross-linking enhances the hydrophobic performance of the films, with the water contact angle increasing from 82.1° to 123.5°. Concurrently, the films’ near-infrared (NIR) light absorption improved. Furthermore, transition metal ions facilitate accelerated electron transfer, thereby catalyzing the thermal decomposition of DATNBI. Under 1064 nm laser irradiation, the DI/FeA film exhibits exceptional combustion performance, with an ignition delay time as low as 76 ms. It successfully acts as an NIR laser ignition medium to initiate the self-sustained combustion of CL-20. This study demonstrates the synergistic realization of enhanced hydrophobicity, improved photosensitivity, and promoted catalytic decomposition through microstructural design of the material, providing new insights for the design of additive-free EMs in laser ignition applications.

研究领域: 材料科学 · 化学工程 · 光学 · 物理化学 · 激光技术
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2025 · IF 2.1

Determination and Correlation of Solubility of 2,4,6,8,10,12-Hexacyclopropyl-2,4,6,8,10,12-hexaazaisowurtzitane in 12 Pure Solvents at Temperatures Ranging from 278.15K to 318.15K

Jianhui Du,Yunlu Li,Guoliang Jin,Jianlong Wang,Lizhen Chen

2,4,6,8,10,12-Hexacyclopropyl-2,4,6,8,10,12-hexaazaisowurtzitane (HCPIW) is a novel nitration precursor used in the synthesis of CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane). Investigating the solubility of HCPIW is of significant importance for optimizing its synthesis and crystallization processes, as well as for advancing the development of the CL-20 synthetic route. However, to the best of our knowledge, no studies have been reported on the solubility of HCPIW. To support downstream processing, its solubility in 12 pure solvents (dichloromethane, chloroform, carbon tetrachloride, 1,1,2-trichloroethane, 1,2-dichloroethane, n-hexane, cyclohexane, ethyl acetate, acetone, methanol, ethanol, and acetonitrile) was determined by the gravimetric method over the temperature range of 278.15 to 318.15 K. The experimental solubility data were correlated using the Apelblat equation, Yaws model, van’t Hoff equation, and a polynomial empirical model. All four models exhibited excellent agreement with the experimental data, with correlation coefficients (R2) exceeding 0.99 and root-mean-square deviations (RMSD) approaching zero. These models are thus suitable for accurately describing the solubility behavior of HCPIW. This study provides essential thermodynamic data to support further research and process development involving HCPIW.

CAS / MDL: 61-90-5
研究领域: 化学工程 · 热力学 · 材料科学 · 有机合成 · 工艺优化
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FirePhysChem · 2026 · IF 3.6

3D Printing and Performance Study of CL-20-based Composite Energetic Materials with PVA/PAA/M-PTW Networks

Handong Shi,Shijiao Li,Chuanhao Xu,Kai Han,Fan Liao,Yanpeng Lv,Guoqiang He,Wenxuan Liang,Chongwei An

This work presents a molecular-to-structural strategy for fabricating high-performance CL-20-based composite energetic materials using direct ink writing (DIW). A poly(vinyl alcohol)/poly(acrylic acid)/modified potassium titanate whisker (PVA/PAA/ M-PTW) interpenetrating polymer network (IPN) was designed to simultaneously enhance mechanical strength and reduce mechanical sensitivity. The hydrogen bonding–covalent crosslinking–filler reinforcement mechanism ensured uniform dispersion of CL-20 crystals and strong interfacial adhesion within the polymer matrix. Surface modification of PTW with 5 wt% KH-550 improved compatibility with the IPN, yielding printed structures with excellent form accuracy and adhesion to aluminum substrates (0.961 MPa). The optimized composite exhibited high compressive strength (16.77 MPa) and reduced impact and friction sensitivities compared with ε-CL-20 and submicron CL-20 samples. It achieved stable detonation wave transmission within a 90°-160° corner range in a 1.2 × 1.2mm charge slot, with the critical detonation size reaching 0.3m × 0.3mm. The measured detonation velocity of 7267.9m/s (83.2% of theoretical). These results demonstrate that the DIW-based PVA/PAA/M-PTW system enables the precise construction of high-strength, low-sensitivity energetic composites with reliable detonation performance, providing a promising pathway for advanced micro-scale energetic devices.

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APPLIED SURFACE SCIENCE · 2021 · IF 6.707

Fabrication and characterization of CL-20/PEI/GO composites with enhanced thermal stability and desensitization via electrostatic self-assembly

Xiaomin Song,Qi Huang,Bo Jin,Rufang Peng

To improve the encapsulation of GO to CL-20, PEI was utilized as a linker bridge to self-assemble into composite CL-20/PEI/GO in this study. The self-assembly was in-depth characterized, including Zeta potential, SEM, DLS, XPS, Raman spectra, HPLC and power-XRD. The possible self-assembled mechanism was also proposed, which indicates the electrostatic interaction introduced by PEI should be responsible for the self-assembly. The performance of a self-assembled composite was characterized by BAM and DSC analysis. And the results indicate the enhanced interaction promotes GO more efficiently encapsulate CL-20 and improve the safety of the energetic material. Therefore, this work demonstrates a novel and facile method to solve the deprived interaction and corresponding weak desensitization between desensitizer and energetic material.

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Defence Technology · 2026 · IF 6.4

Simple and controllable preparation of high-energy insensitive CL-20/DAAF composite microspheres with enhanced combustion and mechanical properties

Yanpeng Lyu,Fan Liao,Ligang Zhang,Handong Shi,Guoqiang He,Xintong Han,Jiaoyang Liu,Chuanhao Xu,Chongwei An

High energy and low sensitivity are generally mutually exclusive in energetic materials, and precise regulation of the microstructure is an effective strategy to balance these properties. In this study, CL-20/DAAF composite microspheres with various microstructures—including core-shell, hollow, porous, and irregular hollow structures—were fabricated using a tubular continuous-flow device combined with the principles of phase separation and recrystallization. The influence of the binder on the morphology and properties was also investigated. The results demonstrated that, compared with raw CL-20, the composite microspheres exhibited significantly reduced sensitivity and improved mechanical properties. Specifically, the impact energy increased from 1.75 J to 7.50 J, and the friction sensitivity threshold increased from 108 N to 168 N. The average compressive stress and compressive strain of the PBX charges were enhanced by 22.89%–108.19% and 25.75%–50.28%, respectively, with the 2.5% NC + 2.5% F 2602 composite binder delivering the optimal mechanical performance. In ignition experiments, hollow microspheres showed the highest combustion efficiency, while core-shell microspheres released energy more steadily, achieving a maximum combustion duration of 2175 ms. Theoretical calculations indicated that this composite binder system possesses a higher theoretical detonation velocity. The study confirms that adjusting the microstructure can effectively enhance the combustion and mechanical properties of composite microspheres, thereby balancing high energy with low sensitivity. The tubular continuous-flow self-assembly technology, integrated with phase separation and recrystallization principles, provides a feasible pathway for the controllable construction of composite microsphere architectures and offers a reference for the design and fabrication of other energetic composite microspheres.

CAS / MDL: 9002-89-5
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NEW JOURNAL OF CHEMISTRY · 2016 ·Vol. 41 ·期 3 ·1129-1136 · IF 3.277

Simultaneous selective extraction of nitramine explosives using molecularly imprinted polymer hollow spheres from post blast samples

Jian Wang,Zihui Meng,Min Xue,Lili Qiu,Xiao Dong,Zhibin Xu,Xuan He,Xueyong Liu,Jinshan Li

Molecularly imprinted polymer hollow spheres (MIHSs) were produced by using hexanitrohexaazaisowurtzitane (HNIW or CL-20) as a template, silica nanospheres as a sacrificial matrix, acrylamide as a functional monomer, ethylene glycol dimethacrylate as a cross-linker and acetonitrile as a porogen at 4 °C under UV irradiation. This sorbent was applied to the selective solid-phase extraction (SPE) of several explosives simultaneously by using a newly-developed SPE procedure. For the first time, 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and CL-20 were selectively extracted and determined simultaneously from simulated post-blast samples prepared from motor oil and vacuum pump oil. The matrix effects were successfully eliminated and accurate quantization was achieved. When the loading amounts of HMX, RDX, TNT and CL-20 were, respectively, below 10, 2, 5 and 20 nmol for 100 mg of MIHS, these explosives were almost retrieved completely (above 98%). For the MIHSs and non-imprinted polymer hollow spheres (NIHSs), in acetonitrile and methanol, the imprinting factors (IFs) of CL-20 and tetraacetyldibenzylhexaazaisowurtzitane (TADB, a structural analogue of CL-20) changed dramatically, from 7.75 to 1.57 and 0.88 to 2.39, respectively. It highlighted the significant effect of solvents on imprinted sites.

CAS / MDL: 2530-85-0 78-10-4
研究领域: 分析化学 · 材料科学 · 环境科学
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