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Ultra-fast amorphization of crystalline alloys by ultrasonic vibrations

Journal of Materials Science & Technology 2023年第11期142卷 76-88页

作者： Luyao Li Guo-Jian Lyu Hongzhen Li Caitao Fan Wenxin Wen Hongji Lin Bo Huang Sajad Sohrabi Shuai Ren Xiong Liang Yun-Jiang Wang Jiang Ma Weihua Wang Guangdong Key Laboratory of Electromagnetic Control and Intelligent Robots Shenzhen UniversityShenzhen 518060China State Key Laboratory of Nonlinear Mechanics Institute of MechanicsChinese Academy of SciencesBeijing 100190China National Engineering Research Center of Near-net-shape Forming for Metallic Materials South China University of TechnologyGuangzhou 510640China Institute of Materials School of Materials Science and EngineeringShanghai UniversityShanghai 200444China School of Engineering Science University of Chinese Academy of SciencesBeijing 101408China Songshan Lake Materials Laboratory Dongguan 523808China Institute of Physics Chinese Academy of SciencesBeijing 100190China

The amorphization of alloys is of both broad scientific interests and engineering significance.Despite considered as an efficient strategy to regulate and even achieve record-breaking properties of metallic materials,a facile and rapid method to trigger solid-state amorphization is still being pursued.Here we report such a method to utilize ultrasonic vibration to trigger amorphization of intermetallic compound.The ultrasonic vibrations can cause tunable amorphization at room temperature and low stress(2 MPa)conveniently.Remarkably,the ultrasonic-induced amorphization could be achieved in 60 s,which is 360 times faster than the ball milling(2.16×10^(4) s)with the similar proportion of amorphization.The elements redistribute uniformly and rapidly via the activated short-circuit diffusion.Both experimental evidences and simulations show that the amorphous phase initiates and expands at nanograin boundaries,owing to the induction of lattice instability.This work provides a groundbreaking strategy for developing novel materials with tunable structures and properties.

关键词： amorphization Ultrasonic vibration Lattice instability Elemental diffusion

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Promoting amorphization of commercial TiO_(2) upon sodiation to boost the sodium storage performance

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Journal of Energy Chemistry 2023年第6期81卷 379-388,I0009页

作者： Tao Li Ling-Yun Kong Xue Bai Yan-Xiang Wang Yong-Xin Qi Key Laboratory of Liquid-Solid Structural Evolution and Processing of Materials of Ministry of Education State Key Laboratory of Crystal MaterialsShandong UniversityJinan 250061ShandongChina School of Materials Science and Engineering Shandong University of Science and TechnologyQingdao 266590ShandongChina

Anatase TiO_(2) is a promising anode material for sodium-ion batteries,yet the low electronic and ionic conductivities are the main obstacles for its practical application.Even though the amorphization of TiO_(2) upon sodiation has already been observed,its underneath mechanisms are not fully elucidated.Herein,a low-cost nitrogen-containing carbon source of polyacrylonitrile is adopted to modify commercial anatase TiO_(2) by a convenient and nontoxic ball-milling technique combined with subsequent annealing treatment.In particular,the employment of a nitrogen-doping approach accompanied by nitrogendoped carbon coating,results in a greatly improved conductivity,overall leading to a high reversible capacity of about 260 m A h g^(-1)at 25 m A g^(-1),superior rate capabilities,and an ultra-stable capacity of about 186 m A h g^(-1)after 1600 cycles at 500 m A g^(-1).Detailed characterizations denote that the improved conductivity as well as the small size of the synthesized TiO_(2) grains play a key role in the TiO_(2) amorphization upon sodiation,with the TiO_(2)/C nanocomposite undergoing a complete amorphization in just few cycles.Finally,the irreversible amorphization of TiO_(2) is confirmed to be a crucial ingredient facilitating the Na+diffusion kinetics and pseudocapacitive behavior,thus boosting the sodium storage performance.

关键词： Commercial TiO_(2) Anode material amorphization Nitrogen doping Sodium-ion battery

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amorphization activated FeB_(2) porous nanosheets enable efficient electrocatalytic N_(2) fixation

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Journal of Energy Chemistry 2021年第2期30卷 82-89,I0004页

作者： Ke Chu Weicong Gu Qingqing Li Yaping Liu Ye Tian Wuming Liu School of Materials Science and Engineering Lanzhou Jiaotong UniversityLanzhou 730070GansuChina Department of Physics College of ScienceHebei North UniversityZhangjiakou 075000HebeiChina Institute of Physics Chinese Academy of SciencesBeijing 100190China

Designing active,robust and cost-effective catalysts for the nitrogen reduction reaction(NRR) is of paramount significance for sustainable electrochemical NH3 synthesis.Transition-metal diborides(TMB_2)have been recently theoretically predicted to be a new class of potential NRR catalysts,but direct experimental evidence is still lacking.Herein,we present the first experimental demonstration that amorphous FeB_2 porous nanosheets(a-FeB_2 PNSs) could be a highly efficient NRR catalyst,which exhibited an NH3 yield of 39.8 μg h^(-1) mg^(-1)(-0.3 V) and a Faradaic efficiency of 16.7%(-0.2 V),significantly outperforming their crystalline counterpart and most of existing NRR catalysts.First-principle calculations unveiled that the amorphization could induce the upraised d-band center of a-FeB_2 to boost d-2π~* coupling between the active Fe site and ~*N_2 H intermediate,resulting in enhanced ~*N_2 H stabilization and reduced reaction barrier.Out study may facilitate the development and understanding of earth-abundant TMB_2-based catalysts for electrocatalytic N_2 fixation.

关键词： Electrocatalytic nitrogen fixation Transition-metal diborides amorphization Density functional theory

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amorphization IN Nb-M (M=Fe, Co, Ni) BINARY METAL SYSTEMS INDUCED BY ION BEAM ASSISTED DEPOSITION (IBAD)

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Acta Metallurgica Sinica(English Letters) 2002年第2期15卷 160-166页

作者： F.Pan, F. Zeng and B. Zhao Laboratory of Advanced Materials, Department of Materials and Engineering, Tsinghua University, Beijing 100084, China Lab. of Adv. Mat. Dept. of Mat. and Eng. Tsinghua Univ. Beijing 100084 China

Ion beam assisted deposition technique (IBAD) was utilized to systematically study amorphization in binary metal systems of Nb-magnetic element, i.e., Nb-M (M=Fe, Co or Ni). The glass forming range termed as Nb fraction of Nb-Fe system was about 34at.% to 56at.%, that of Nb-Co system was about 32at.% to 72at.% and that of Nb-Ni about 20at. % to 80at. %. Similar percolation patterns were found in amorphous alloy films. The fractal dimensions of the percolation patterns approach to 2, which indicates 2-D layer growth for amorphous phases. It is regarded that the assisted Ar+ ion beam during the deposition process plays important role for the 2-D layer growth. Some metastable crystalline phases were obtained in these three systems by IBAD, e.g., bcc supersaturated solid solutions in Nb-Fe and Nb-Co systems, fcc and hcp phases in Nb-Co and Nb-Ni systems. The formation and competing between the amorphous and the metastable crystalline phases were determined by both the phases' thermodynamic states in binary metal systems and kinetics during IBAD process.

关键词： amorphization ion beam assisted deposition glass forming range metastable phase

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In Situ HRTEM Observation of Electron-Irradiation-Induced amorphization and Dissolution of the E(Al_(18)Cr_2Mg_3) Phase in 7475 Al Alloy

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Acta Metallurgica Sinica(English Letters) 2015年第2期28卷 147-151页

作者： Mao-Hua Li Yan-Qing Yang Bin Huang Xian Luo Wei Zhang Yan-Xia Chen Ming Han Ji-Gang Ru State Key Laboratory of Solidification Processing Northwestern Polytechnical University Beijing Institute of Aeronautical Materials

Electron irradiation effects on phase stability of the E （Al18Cr2Mg3） phase have been investigated by high- angle annular dark-field scanning transmission electron microscopy and high-resolution transmission electron microscopy （HRTEM）. The in situ HRTEM observations show that the Ala8Cr2Mg3 particles with different thickness undergo amorphization and dissolution under 300 keV electron irradiation at 25 ℃. The results indicate that the intermetallic compound Al18Cr2Mg3 is unstable under electron irradiation, and structural changes mainly depend on the thickness of particles. amorphization in the thick particles is caused by a combination of chemical disordering and an increase in point defect concentration. Dissolution after amorphization in the thin particles is attributed to the diffusion of point defect towards the Al matrix.

关键词： Intermetallic compound Al18Cr2Mg3 Irradiation effects amorphization Dissolution

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Hot-melt extrusion promotes dissolution,extends“spring-parachute”process and inhibits crystallization in supersaturating microparticle systems

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Particuology 2023年第7期78卷 35-48页

作者： Yanfei Zhang Huifeng Zhang Huan Yu Yinghui Ma Chengyi Hao Xiaoying Lin Yong Zhang Zhengqiang Li Xianrong Qi Jia Zeng Nianqiu Shi School of Pharmacy jilin Medical University Jilin132013jilin ProvinceChina Collge of Life Science Jilin UniversityChangchun130012jilin ProvinceChina Department of Pharmaceutics School of Pharmaceutical SciencePeking UniversityBeijing100191China College of Pharmaceutical Sciences Yanbian UniversityYanji133002jilin ProvinceChina

Despite the potential advantages of amorphism-induced supersaturation,the merit of new amorphiza-tion formation methods on the properties of the amorphous drug including the stability of the amor-phous state,dissolution/solubility,supersaturation,and"spring-parachute"process is still poorly understood,particularly for certain amorphous supersaturating drug delivery systems(aSDDS).The present work aimed to explore the detailed merit of current attractive amorphization manufacturing methods(i.g.,hot-melt extrusion(HME)technique)on the property improvement of aSDDS in form of amorphous solid dispersion microparticles by employing a model Bcs II drug nitrendipine and a polyvinylpyrrolidone-based model polymer copovidone.Many asDDS systems were developed by various methods,and their physicochemical properties were characterized by SEM,PXRD and DSC.HME-triggered amorphization induced superior supersaturation by the observation of the highest dissolution and solubility.HME induced the optimal supersaturation duration by the observed greatest extension of"spring-parachute"process(e.g,maximum AUCspring-parachute).HME technique is comparable with other techniques for the stabilization of amorphous state during storage.All aSDDS systems by HME and other methods showed improved long-term stability of the amorphous state in comparison to the pure amorphous drug.Fourier transformation infrared spectroscopy,Noyes-Whitney equation,nucleation theory and Gibbs free energy of transfer(△G)were used to analyze the underlying mechanisms.Mo-lecular mechanism studies indicated that HME caused a stronger crystallization inhibition effect in the asDDS systems than other methods,but molecular interaction is not a dominant mechanism for property enhancement caused by HME.For the mechanism associated with the polymer itself(PVPVA64),it could inhibit the drug recrystallization,solubilize the drug spontaneously and cause the improved molecular interactions in all aSDDS systems.This study provided a deep insight into detailed advantage of HME-t

关键词： Hot-melt extrusion-triggered amorphization Extensionof"spring-parachute"process Promotion of dissolution/solubility Inhibition of crystallization from a supersaturated state Amorphism-based supersaturating drug microparticle systems

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In-situ study for the elastic structure evolutions of threedimensional Ir-O framework during the oxygen evolution reaction in acid

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Nano Research 2023年第7期16卷 9022-9030页

作者： Jun Qi Xinyu Zhong Huiyan Zeng Chao Wang Zhongfei Liu Jiajun Chen Long Gu Enna Hong Mengxian Li Jiong Li Chunzhen Yang School of Materials Shenzhen Campus of Sun Yat-Sen UniversityShenzhen 518107China Shanghai Institute of Applied Physics Chinese Academy of SciencesShanghai 201204China University of Chinese Academy of Sciences Beijing 100049China Shanghai Advanced Research Institute Chinese Academy of SciencesShanghai 201210China

Understanding the dynamic structural and chemical evolutions at the catalyst-electrolyte interfaces is crucial for the development of active and stable electrocatalysts.In this work,β-Li_(2)IrO_(3)is employed as a model catalyst for the oxygen evolution reaction(OER).Its elastic three-dimensional Ir-O framework enables us to investigate the Li^(+)cation dissolution-induced structure evolutions and the formation mechanism of amorphous IrO_(x)species.Electrochemical measurements by rotating ring disk electrode(RRDE)reveal that up to 60%of the measured OER current can be ascribed to catalyst degradation.A series of in-situ X-ray diffraction spectroscopy(XRD),X-ray absorption spectroscopy(XAS),and Raman spectroscopy are conducted.Structure vibration is observed with oxidation states of Ir being reduced abnormally during OER at high potentials.It’s hypothesized that the reversible proton intercalations are responsible for the Ir turn-over mechanism.Results of this work demonstrate a stable and elastic iridate structure and reveal the initial catalyst degradation behaviors during OER in acid media.

关键词： oxygen evolution reaction structure evolution amorphization acid media catalyst degradation

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Roadmap of amorphous metal-organic framework for electrochemical energy conversion and storage

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Nano Research 2023年第3期16卷 4107-4118页

作者： Hang Wang Qi Yang Nan Zheng Xingwu Zhai Tao Xu Zhixin Sun Liang Wu Min Zhou Hefei National Laboratory for Physical Sciences at the Microscale School of Chemistry and Materials ScienceUniversity of Science and Technology of ChinaHefei 230026China

Metal-organic frameworks(MOFs),a well-known coordination network involving potential voids,have attracted attention for energy conversion and storage.As far as is known,MOFs are not only believed to be crystalline.Emerging amorphous MOFs(aMOFs)are starting as supplementary to crystalline MOF(cMOF)in various electrochemical energy fields owing to intrinsic superiorities over crystalline states,greater ease of processing,and distinct physical and chemical properties.aMOFs retain the basic skeletons and connectivity of building units but without any long-range order.Such structural features over long range possess the isotropy without grain boundaries,resulting in fast ions flux and uniform distribution.Simultaneously,distinct shortrange characteristics provide diverse pore confined environment and abundant active sites,and thus accelerate mass transport and charge transfer during electrochemical reactions.Deep understandings and controllable design of aMOF may broaden the opportunities for both scientific researches beyond crystalline materials and practical applications.To date,comprehensive reviews about aMOFs in the fields of energy conversion and storage remain woefully underrepresented.Herein,we summarize the roadmap of aMOF from the development,structural design,opportunity,application,bottleneck,and perspective.In-depth structure-activity relationships with aMOF chemistry are highlighted in the typical electrochemical energy conversion like water oxidation and energy storage,including supercapacitor and battery.The combination of disordered nature at long range and short range,alongside the dynamic structural changes,is promising to reinforce cognition of aMOF domains with MOF versatility,shedding light on the design for efficient electrochemical energy applications via amorphization.

关键词： metal-organic frameworks amorphization energy conversion energy storage

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High-Pressure Irreversible amorphization of La<sub>1/3</sub>NbO<sub>3</sub>

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Journal of Modern Physics 2011年第5期2卷 323-334页

作者： Itzhak Halevy Amir Hen Amir Broide Mike L. Winterrose Shimon Zalkind Zhiqiang Chen 不详

The crystallographic structure of La1/3NbO3 perovskite was studied at high pressures using a diamond-anvil cell and synchrotron radiation. High-pressure energy dispersive (EDS) x-ray diffraction and high-pressure angle dispersive (ADS) x-ray diffraction revealed an irreversible amorphization at ~10 GPa. A large change in the bulk modulus accompanied the high-pressure amorphization.

关键词： La1/3NbO3 High-Pressure amorphization Perovskites

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The Mechanism of High Pressure amorphization

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Progress in Natural Science:Materials International 1993年第3期 276-279页

作者：李冬剑王景唐丁炳哲秦志成 Beijing 100080 Institute of Physics Shenyang 110015.PRC State Key Lab.for RSA Institute of Metal Research Academia Sinica

1 IntroductionHigh pressure amorphization is to heat crystalline alloys under high pressure to atemperature below the melting point for some time,and then quench them to the liquidnitrogen temperature.After pressure-quenching treatment,the high pressure is removed andthe temperature rises to the room temperature,and the crystalline alloys are transformedto amorphous state spontaneously.

关键词： high pressure amorphization metastable phase transformation volume change during phase transformation

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