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Defence Technology（防务技术） 2024年第8期38卷 75-88页

作者： Xinru Yang Yushi Wen Congmei Lin Feiyan Gong Zhijian Yang Fude Nie Institute of Chemical materials China Academy of Engineering PhysicsMianyang 621900China

The practical application of energetic materials, particularly 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20), is frequently impeded by phase transition challenges. In this study, we propose a novel strategy to enhance the stability of CL-20 by employing a thermo-sensitive polymer,poly(N-isopropylacrylamide)(PNIPAM), to modulate its phase transitions. Our approach involves the use of an in-situ polymerized polydopamine(PDA) shell as a platform for surface grafting through atom transfer radical polymerization, yielding a core-shell structured CL-20@PDA-PNIPAM. Through comprehensive characterization, the successful grafting of PNIPAM is confirmed, significantly enhanced the phase stability of CL-20. Notably, our core-shell structure exhibits a 13℃ increase in phase transition temperature compared to raw CL-20, thereby delaying the ε→a phase transition by over 80 min under combined thermal and solvent conditions. The enhanced stability is attributed to the hydrophobic nature of PNIPAM above its low critical solution temperature in water, which effectively shields the CL-20 crystal. These findings provide new insights into enhancing the stability and safety of energetic materials in complex environments, highlighting the potential of our molecular switch mechanism.

关键词： 2,4,6,8,10,12-Hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane(CL-20) Phase stability Polydopamine(PDA) Poly-N-Isopropylacrylamide(PNIPAM) Thermal and solvent effects

Negative enthalpy alloys and local chemical ordering:a concept and route leading to synergy of strength and ductility

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National Science Review 2024年第4期11卷 172-184页

作者： Zibing An Tao Yang Caijuan Shi Shengcheng Mao Lihua Wang Ang Li Wei Li Xianmeng Xue Ming Sun Yifan Bai Yapeng He Fuzeng Ren Zhouguang Lu Ming Yan Yang Ren Chain-Tsuan Liu Ze Zhang Xiaodong Han Beijing Key Lab of Microstructure and Property of Advanced materials College of Materials Science &Engineering Beijing University of Technology Department of materials Science and engineering City University of Hong Kong Key Laboratory of Partial Acceleration physics& Technology Institute of High Energy PhysicsChinese Academy of Sciences Department of materials Science &engineering Southern University of Science and Technology Department of physics City University of Hong Kong State Key Laboratory of Silicon materials Department of Materials Science and Engineering Zhejiang University

Solid solutions are ubiquitous in metals and alloys. Local chemical ordering(LCO) is a fundamental sub-nano/nanoscale process that occurs in many solid solutions and can be used as a microstructure to optimize strength and ductility. However, the formation of LCO has not been fully elucidated, let alone how to provide efficient routes for designing LCO to achieve synergistic effects on both superb strength and ductility. Herein, we propose the formation and control of LCO in negative enthalpy alloys. With engineering negative enthalpy in solid solutions, genetic LCO components are formed in negative enthalpy refractory high-entropy alloys(RHEAs). In contrast to conventional ‘trial-and-error' approaches, the control of LCO by using engineering negative enthalpy in RHEAs is instructive and results in superior strength(1160 MPa) and uniform ductility(24.5%) under tension at ambient temperature, which are among the best reported so far. LCO can promote dislocation cross-slip, enhancing the interaction between dislocations and their accumulation at large tensile strains; sustainable strain hardening can thereby be attained to ensure high ductility of the alloy. This work paves the way for new research fields on negative enthalpy solid solutions and alloys for the synergy of strength and ductility as well as new functions.

关键词： negative enthalpy alloys local chemical ordering strength ductility dislocation

Microstructure and magnetocaloric properties of melt-extracted SmGdDyCoAl high-entropy amorphous microwires

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Rare Metals 2024年第3期43卷 1234-1242页

作者： Shi-Jie Wei Hong-Xian Shen Lun-Yong Zhang Lin Luo Xin-Xing Tang Jian-Fei Sun Xiao-Qing Li School of materials Science and engineering Harbin Institute of TechnologyHarbin150001China Applied materials physics Department of Materials Science and EngineeringKTH-Royal Institute of Technology10044StockholmSweden

This paper presents a systematic investigation of the microstructure and magnetocaloric properties of melt-extracted Sm_(20)Gd_(20)Dy_(20)Co_(20)Al_(20)high-entropy *** fabricated wires exhibited an amorphous structure,and the temperature interval of the undercooled liquid AT was 45 *** microwires underwent a second-order magnetic transition from a ferromagnetic to a paramagnetic state near the Curie temperature(T_(C)=52 K),The maximum magnetic entropy change(-ΔS_M^(max)),the relative cooling power and the refrigeration capacity reached 6.34 J·kg^(-1)·K^(-1).422.09 J·kg^(-1)and 332.94 J·kg^(-1),respectively,under a magnetic field change of 5 *** addition,the temperature-averaged entropy changes with two temperature lifts(3 and 10 K)were 6.32 and 6.27 J·kg^(-1)·K^(-1),*** good magnetocalorie performance highlights the significant potential for the Sm_(20)Gd_(20)Dy_(20)Co_(20)Al_(20)microwires to be used as magnetic refrigerant materials in low-temperature region *** work will serve as a valuable reference for future investigations on low-temperature high-entropy magnetocaloric materials.

关键词： Melt-extraction High-entropy amorphous microwires Magnetocaloric effect Magnetic refrigeration

Surface engineering on MnO2 nanorods by La single atoms to accelerate oxygen reduction kinetics

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Rare Metals 2024年第9期43卷 4302-4311页

作者： Zhang-Long He Liu-Qi Wang Min Jiang Jia-Nan Xie Shan Liu Jin-Can Ren Rui Sun Wen-Bin Lv Wei-Bin Guo Yu-Ling Liu Bing Li Qi Liu Hao He School of materials Science and engineering Changsha University of Science and Technology School of materials Science and engineering NanjingUniversity of Science and Technology School of materials Science and engineering Shanghai JiaoTong University Department of physics City University of Hong Kong

Surface engineering,which modulates the electronic structure and adsorption/desorption properties of electrocatalysts,is one of the key strategies for improving the catalytic ***,we demonstrate a facile solid-phase reaction for surface engineering of MnO2to boost the oxygen reduction *** reaction with surface hydroxy groups,La single atoms with loading amount up to 2.7 wt%are anchored onto *** surface engineering,the oxygen reduction reaction （ORR） kinetics is significantly improved with the half-wave potential from 0.70 to 0.84 V,the number of transferred electrons from 2.5 to 3.9 and the limiting current density from 4.8 to 6.0 mA·*** addition,the catalyst delivers superior discharge performance in both alkaline and neutral metal–air *** functional theory （DFT） calculations reveal that atomic La modulates the surface electronic configuration of MnO2,reduces its d-band center and thus lowers the OOH*and O*reaction energy *** work provides a new route for rational design of highly active electrocatalyst and holds great potential for application in various catalytic reactions.

关键词： Electron injection Metal–air batteries Oxygen reduction reaction Single atoms Surface engineering

Anisotropic Mechanical Response of Nacre to Heat Treatment Under Indentation:Effect of Structural Orientation

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Journal of Bionic engineering 2024年第3期21卷 1453-1464页

作者： Simin Liang Yingying Li Hongmei Ji Xiaowu Li Department of materials physics and Chemistry School of Materials Science and EngineeringKey Laboratory for Anisotropy and Texture of MaterialsMinistry of EducationNortheastern UniversityShenyang110819China

It is generally considered that heat treatments have a negative impact on the mechanical properties of nacre due to thermal decomposition of the organic ***,the present work investigated the microindentation behavior on fresh and heat-treated nacres from two orthogonal directions,and the results demonstrate that both hardness value and damage tolerance can remain almost unchanged on the cross-section with the organic matrix degeneration,despite a significant deterioration on the platelet *** analyses suggest that the anisotropic response of indentation behavior to heat treatment in nacre is primarily caused by its structural ***,compared with a single layer of irregular interplatelet interfaces in cross-sectional specimens,the multiple layers of parallel interlamellar interfaces in in-plane specimens exhibit a much greater ability to impede indenter-triggered destruction,and heat treatments would reduce the in-plane hardness but nearly have no effect on the cross-sectional ***,the deeper embedding of platelets in cross-sectional specimens enhances their resistance to interface cracking caused by organic matrix degradation at high temperatures,leading to a reduced sensitivity to ***,the indentation behavior of nacre shows different tendencies in response to variations in the organic matrix state along normal and parallel directions.

关键词： Nacre Structural orientation Heat treatment Indentation behavior Organic matrix

Significantly enhanced thermal stability of HMX by phase-transition lysozyme coating

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Defence Technology（防务技术） 2024年第5期35卷 60-68页

作者： Jiahui Liu Congmei Lin Jianhu Zhang Chengcheng Zeng Zhijian Yang Fude Nie Institute of Chemical materials China Academy of Engineering Physics(CAEP)Mianyang 621900China Graduate School China Academy of Engineering Physics(CAEP)Mianyang 621900China

A new robust bio-inspired route by using lysozyme aqueous solution for surface modification on 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)was described in this *** crystals were coated by in situ phase transition of lysozyme(PTL)*** HMX decorated by PTL was characterized by SEM,XRD,FTIR and XPS,demonstrating a dense core-shell coating *** coverage of lysozyme on HMX crystal was calculated by the ratio of sulfur *** surface coverage increased from 60.5% to 93.5% when the content of PTL was changed from 0.5 wt% to 2.0 wt%,indicating efficient *** thermal stability of HMX was investigated by in situ XRD and *** thermal phase transition temperature of HMX(β to δ phase)was delayed by 42℃ with 2.0 wt% PTL coating,which prevented HMX from thermal damage and sensitivity by the effect of PTL *** heating at 215℃,large cracks appeared in the naked HMX crystal,while the PTL coated HMX still maintained intact,with the impact energy of HMX dropped dramatically from 5 J to 2 ***,the impact energy of HMX with 1.0 wt% and 2.0 wt% coating content(HMX@PTL-1.0 and HMX@PTL-2.0)was unchanged(5 J).Present results potentially enable large-scale fabrication of polymorphic energetic materials with outstanding thermal stability by novel lysozyme coating.

关键词： HMX Lysozyme Phase transition Thermal stability Sensitivity

Retaining the self-released chalcogenate at reconstructed cobalt sites by self-transformed carbonate regulation for boosted oxygen evolution

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Journal of Energy Chemistry 2024年第10期97卷 46-54页

作者： Jingxuan Zhao Zhe Xue Qing Wang Xiangyang Li Shoujie Liu Xu Zhao School of Chemical engineering and Technology Xi'an Jiaotong University Key Laboratory of materials physics Institute of Solid State Physics Hefei Institutes of Physical Science (HFIPS) Chinese Academy of Sciences School of materials Science and engineering Anhui University

The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction（OER） ***,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER ***,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER *** selftransformed CO32-can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeOx2-for enhanced SeOx2-retention,which can accelerate the rate-limiting step for*OOH formation during *** to CoOOH-SeOx2-with limited SeOx2-residues,CoOOH-CO32-/SeOx2-with elevated SeOx2-retention by CO32-regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards *** strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.

关键词： Carbonate regulation Chalcogenate retention Electrochemical reconstruction Orbital hybridization Oxygen evolution reaction

A lithium–tin fluoride anode enabled by ionic/electronic conductive paths for garnet-based solid-state lithium metal batteries

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Rare Metals 2024年第2期43卷 575-587页

作者： Lei Zhang Qian-Kun Meng Xiang-Ping Feng Ming Shen Yu-Qing Zhang Quan-Chao Zhuang Run-Guo Zheng Zhi-Yuan Wang Yan-Hua Cui Hong-Yu Sun Yan-Guo Liu School of materials Science and engineering Northeastern UniversityShenyang110819China School of Resources and materials Northeastern University at QinhuangdaoQinhuangdao066004China School of materials and physics China University of Mining&TechnologyXuzhou221116China Institute of Electronic engineering China Academy of Engineering PhysicsMianyang621900China

The high energy density and stability of solid-state lithium metal batteries(SSLMBs)have garnered great ***-type oxides,especially Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO),with high ionic conductivity,wide electrochemical window,and stability to Li metal anode,are promising solid-state electrolyte(SSEs)materials for ***,Li/LLZTO interface issues including high interface resistance,inhomogeneous Li deposition,and Li dendrite growth have hindered the practical application of ***,a multi-functional Li–SnF_(2) composite anode with Li,LiF,and Li-Sn alloy was specifically designed and *** composite anode improves the wettability to LLZTO,constructing an intimate contact interface between it and ***,ionic/electronic conductive paths in situ formed at the interface can effectively uniform Li deposition and suppress Li *** solid-state symmetric cell exhibits low interface resistance(11Ω·cm^(2)) and high critical current density(1.3 mA·cm^(−2))at 25℃.The full SSLMB based on LiFePO_(4) or LiNi_(0.5)Co_(0.2)Mn_(0.3)O_(2) cathode also shows stable cycling performance and high rate *** work provides a new composite anode strategy for achieving high-energy density and high-safety SSLMBs.

关键词： Solid-state lithium metal batteries(SSLMBs) Lithium-tin fluoride anode Ionic/electronic conductive Interface resistance Lithium dendrite

New Strategy for Boosting Cathodic Performance of Protonic Ceramic Fuel Cells Through Incorporating a Superior Hydronation Second Phase

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Energy & Environmental materials 2024年第4期7卷 83-92页

作者： Chuan Zhou Xixi Wang Dongliang Liu Meijuan Fei Jie Dai Daqin Guan Zhiwei Hu Linjuan Zhang Yu Wang Wei Wang Ryan O'Hayre San Ping Jiang Wei Zhou Meilin Liu Zongping Shao State Key Laboratory of materials-Oriented Chemical engineering College of Chemical Engineering Nanjing Tech University Max Planck Institute for Chemical physics of Solids Key Laboratory of Interfacial physics and Technology Shanghai Institute of Applied Physics Chinese Academy of Sciences Department of Metallurgical and materials engineering Colorado School of Mines WA School of Mines: Minerals Energy and Chemical Engineering (WASM-MECE) Curtin University Suzhou Laboratory School of materials Science and engineering Georgia Institute of Technology

For protonic ceramic fuel cells,it is key to develop material with high intrinsic activity for oxygen activation and bulk proton conductivity enabling water formation at entire electrode ***,a higher water content which benefitting for the increasing proton conductivity will not only dilute the oxygen in the gas,but also suppress the O2adsorption on the electrode surface.

关键词： cathode high-hydrating capability proton conductivity protonic ceramic fuel cells

Cathodic corrosion as a facile and universal method for scalable preparation of powdery single atom electrocatalysts

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Nano Research 2024年第6期17卷 4943-4950页

作者： Rui Li Xiayan Yan Meng Liu Qingkai Zhao Jie Du Xinxin Tan Jingwen Ba Rongguang Zeng Wenhua Luo Jingsong Xu Institute of materials China Academy of Engineering PhysicsJiangyou 621907China Science and Technology on Surface physics and Chemistry Laboratory Jiangyou 621908China

Top-down strategy has been widely applied for synthesis of metal single atom catalysts(SACs)via converting metal nanoparticles or bulk metals into atomically dispersed ***,we report a simple electrochemical atomic migration strategy for top-down synthesis of SACs via a facile cathodic corrosion process without involving high temperature or harsh *** of metal nanoparticles on cathode are firstly disbanded under high negative voltage,and emitted into the electrolyte in the form of atomic metal anions in Zintl *** escaped atomically dispersed metal species are then oxidized by water molecules and captured by the defects on the pre-added nitrogen doped carbon carriers in the *** cathodic corrosion strategy is confirmed to be suitable for scalable synthesis of kinds of metal SACs(e.g.,Pt,Pd,and Ir)on doped carbon ***,the as-prepared nitrogen doped carbon powder supported Pt SACs exhibit superior catalytic activity toward hydrogen evolution reaction(HER)with a low overpotential of 0.024 V at 10 mA·cm^(−2)and a low Tafel slope of 29.7 mV·dec^(−1)as well as a long-term durability.

关键词： cathodic corrosion top-down strategy powdery single atom catalysts hydrogen evolution reaction scalable synthesis