| 777 | 2 | 489 |
| 下载次数 | 被引频次 | 阅读次数 |
高熵氧化物陶瓷因其独特的性质被认为是潜在的高性能吸波材料。采用简单的固相反应烧结法成功合成出尖晶石/岩盐型复相结构的(Fe0.2Co0.2Ni0.2Cu0.2Zn0.2)Cox Oy高熵陶瓷。全面分析了其晶体结构、微观结构、元素含量及价态，并测定其电磁波吸收性能，探究了该高熵复相陶瓷的吸波性能随烧结温度的变化规律。结果表明，烧结温度为900℃时所得样品具有最多的氧空位以及最大的介电常数，在匹配厚度为3.0 mm，频率为9.37 GHz时，可获得–36.14 dB的最小反射损耗，有效吸收带宽为2.86 GHz，表现出最佳的电磁波吸收性能。
Abstract：Introduction With the rapid development of wireless communication technology,electromagnetic waves are regarded as a main medium for energy and information transmission.Absorbing materials,as a focus of scientific research in recent years,play a key role in effectively reducing electromagnetic radiation pollution in the environment,thereby reducing the negative effect of electromagnetic waves.The design of absorbing materials follows the principles of"thin,light,wide,and strong"to meet practical applications.At present,there are various types of absorbing materials,mainly including magnetic metals,polymer based composite materials,ferrites,and carbon-based materials.However,all the materials have their limitations.For instance,magnetic materials have a superior performance,but they have a poor oxidation resistance,which are prone to eddy current losses,thus affecting the absorption efficiency.The preparation cost of polymer-based composite materials is high,and their application fields are limited.Ferrite materials have an insufficient temperature stability and a high surface density.In addition,carbon-based materials suffer from poor impedance matching and narrow absorption frequency bands.These inherent limitations hinder a widespread applicability of absorbing materials in diverse application scenarios.Therefore,developing novel absorbing materials with superior oxidation resistance and high-temperature stability has an important practical significance.Methods High-entropy multiphase oxide ceramics was prepared by a solid-state reaction method.In the preparation process,FeO,Co O,NiO,CuO,ZnO and Co_2O3 as raw materials in a molar ratio of 1:1:1:1:1:5 were ground with anhydrous ethanol in a mill at 200r/min for 8 h,and then dried at 80℃to obtain a mixed powder.Subsequently,8 g of the mixed powder was pressed into a round billet with a diameter of 30 mm at 10 MPa.The obtained round billet was then heated and reacted in a model BR-12N muffle furnace at different temperatures (i.e.,800,900,1000℃ and 1100℃) for 6 h to obtain the samples of (Fe0.2Co0.2Ni0.2Cu0.2Zn0.2)Cox Oy high-entropy ceramics (HEO),which were named samples HEO-800,HEO-900,HEO-1000,and HEO-1100,respectively.Results and discussion The results show that the obtained samples HEO-800,HEO-900,HEO-1000,and HEO-1100 all exhibit spinel and rock salt phases,as well as pore structures and irregular blocks.The degree of crystallization gradually increases with increasing temperature,which can be attributed to the accelerated diffusion of atoms at the interface and the gradual increase in grain size due to the presence of oxygen vacancies.The XPS analysis indicates that the high-entropy multiphase oxide ceramics sintered at different temperatures all have oxygen vacancies,and the maximum oxygen vacancies occur at 900℃.The conductivity test shows that the sample HEO-900 has the maximum conductivity.The electromagnetic wave absorption test results reveal that the RLmin values of the samples HEO-800,HEO-900,HEO-1000,and HEO-1100 are–9.85,–36.14,–13.73 dB,and–4.61 d B,respectively.The sample HEO-900 obtained via sintering at 900℃ has the optimum absorbing property.Except for the sample HEO-900,the reflection loss of other samples is not high mainly due to the weak dielectric loss caused by low oxygen vacancy,while the magnetic loss is opposite to the dielectric loss.The magnetic loss and dielectric loss synergistically promote the improvement of absorption performance of the material.In addition,the impedance matching area also firstly increases and then decreases as the temperature increases.The impedance area of the sample HEO-900 is relatively large,indicating that there are more electromagnetic waves incident on the interior of the material and the absorption efficiency increases.Conclusions The results indicated that oxygen vacancies were easily generated in (Fe0.2Co0.2Ni0.2Cu0.2Zn0.2)Cox Oy high-entropy ceramics due to the multivalent state and multiple transformations of element Co,which was conducive to electron transfer.The presence of multiphase structure and oxygen vacancies increased the dielectric loss of the material and the interface polarization and defect polarization of the system,thus significantly improving the absorption capacity of electromagnetic waves.This study found that the sample HEO-900 sintered at 900℃ had the optimum absorption performance (i.e.,the RLmin value of–36.14 d B and an optimal bandwidth of 2.86 GHz at a matching thickness of 3.0 mm and a frequency of 9.37 GHz).
[1] ZENG X J, CHENG X Y, YU R H, et al. Electromagnetic microwave absorption theory and recent achievements in microwave absorbers[J].Carbon, 2020, 168:606–623.
[2] ZHAO B, DENG J S, ZHAO C X, et al. Achieving wideband microwave absorption properties in PVDF nanocomposite foams with an ultra-low MWCNT content by introducing a microcellular structure[J]. J Mater Chem C, 2020, 8(1):58–70.
[3] REN Y M, LI P C, QIN Z, et al. Homodispersed MoS2/Co9S8heterostructure nanoparticles confined in rGO aerogels via Kirkendall effect for efficient electromagnetic interference shielding[J]. J Alloys Compd, 2024, 989:174310.
[4] ZHANG F, WU L J, SUN K, et al. Microwave absorption properties and mechanism analyses of core–shell structured high-entropy oxides coated with PPy[J]. J Alloys Compd, 2024, 988:174151.
[5]国洪晨.(Mg、Co、Ni、Cu、Zn)O基高熵氧化物制备及性能研究[D].济南:齐鲁工业大学, 2022.GUO Hongchen. Preparation and properties of(Mg, Co, Ni, Cu,Zn)O-based high entropy oxides[D]. Jinan:Qilu University of Technology, 2022.
[6] DAI G H, DENG R X, YOU X, et al. Entropy-driven phase regulation of high-entropy transition metal oxide and its enhanced high-temperature microwave absorption by in situ dual phases[J]. J Mater Sci Technol, 2022, 116:11–21.
[7] BAI L, CHANG N, ZHAO M Y, et al. Broadband absorption performance of 3D-printed polyetheretherketone-based electromagnetic wave-absorbing composites[J]. Chin J Aeronaut, 2024, 37(8):547–558.
[8] YE Z W, WANG K J, LI X Q, et al. Preparation and characterization of ferrite/carbon aerogel composites for electromagnetic wave absorbing materials[J]. J Alloys Compd, 2022, 893:162396.
[9] KIM S H, LEE S Y, ZHANG Y L, et al. Carbon-based radar absorbing materials toward stealth technologies[J]. Adv Sci, 2023, 10(32):e2303104.
[10] XU H, DENG J S, BAI Z Y, et al. Natural magnetite/coke composite:A novel promising microwave absorption material[J]. J Alloys Compd,2023, 931:167497.
[11]魏玉鹏,朱俊志,蔺景鹏,等.碳微/纳米纤维复合微波吸收材料的研究进展[J].材料导报, 2021, 35(15):15205–15211.WEl Yupeng, ZHU Junzhi, LIN Jingpeng, et al. Mater Rep, 2021,35(15):15205–15211.
[12] QIN M, ZHANG L M, ZHAO X R, et al. Defect induced polarization loss in multi-shelled spinel hollow spheres for electromagnetic wave absorption application[J]. Adv Sci, 2021, 8(8):2004640.
[13] XIANG H M, XING Y, DAI F Z, et al. High-entropy ceramics:Present status, challenges, and a look forward[J]. J Adv Ceram, 2021, 10(3):385–441.
[14] AAMLID S S, OUDAH M, ROTTLER J, et al. Understanding the role of entropy in high entropy oxides[J]. J Am Chem Soc, 2023, 145(11):5991–6006.
[15]颜邓伊,许文举,吉利,等.高熵陶瓷材料的研究进展[J].材料保护, 2023, 56(8):35–49.YAN Dengyi, XU Wenju, JI Li, et al. Mater Prot, 2023, 56(8):35–49.
[16] ROST C M, SACHET E, BORMAN T, et al. Entropy-stabilized oxides[J]. Nat Commun, 2015, 6:8485.
[17]张扬,邹芹,李艳国,等.高熵氧化物的研究进展与展望[J].金刚石与磨料磨具工程, 2022, 42(1):30–41.ZHANG Yang, ZOU Qin, LI Yanguo, et al. Diam Abr Eng, 2022, 42(1):30–41.
[18] ZHOU L, LI F, LIU J X, et al. High-entropy A2B2O7-type oxide ceramics:A potential immobilising matrix for high-level radioactive waste[J]. J Hazard Mater, 2021, 415:125596.
[19] KRYSKO E, MIN L J, WANG Y, et al. Studies on the structure and the magnetic properties of high-entropy spinel oxide(MgMnFeCoNi)Al2O4[J]. APL Mater, 2023, 11(10):101123.
[20] MCCORMACK S J, NAVROTSKY A. Thermodynamics of high entropy oxides[J]. Acta Mater, 2021, 202:1–21.
[21] JIAO Y T, DAI J, FAN Z H, et al. Overview of high-entropy oxide ceramics[J]. Mater Today, 2024, 77:92–117.
[22]张伟明,向会敏,戴付志,等.高熵陶瓷:吸波材料设计新策略[J].宇航材料工艺, 2022, 52(2):13–25.ZHANG Weiming, XIANG Huimin, DAI Fuzhi, et al. Aerosp Mater Technol, 2022, 52(2):13–25.
[23] ZHOU Y B, SHEN X W, QIAN T, et al. A review on the rational design and fabrication of nanosized high-entropy materials[J]. Nano Res, 2023, 16(5):7874–7905.
[24] YAO Y G, DONG Q, BROZENA A, et al. High-entropy nanoparticles:Synthesis–structure–property relationships and data-driven discovery[J].Science, 2022, 376(6589):eabn3103.
[25] CHANG X, DUAN Z W, WANG D S, et al. High-entropy spinel ferrites with broadband wave absorption synthesized by simple solid-phase reaction[J]. Molecules, 2023, 28(8):3468.
[26] RADO?A, HAWE?EK?,?UKOWIEC D, et al. Dielectric and electromagnetic interference shielding properties of high entropy(Zn,Fe, Ni, Mg, Cd)Fe2O4 ferrite[J]. Sci Rep, 2019, 9(1):20078.
[27]李德鹏,严智楷,赵彪,等.(Fe, Co, Ni, Cu, Zn)CrxOy高熵复相陶瓷的制备及其吸波性能[J]. J Chin Ceram Soc, 2022, 50(6):1489–1498.LI Depeng, YAN Zhikai, BIAO Zhao, et al. J Chin Ceram Soc, 2022,50(06):1489–1498.
[28] YAN Z K, LI D P, ZHANG X, et al. Dual-phase high-entropy(FeCoNiZn)xV2Oy oxides with promising microwave absorption properties[J]. Ceram Int, 2022, 48(24):36871–36879.
[29]范冰冰,邱洪辰,李梦茹,等.高熵陶瓷吸波材料研究进展[J].硅酸盐学报, 2023, 51(12):3204–3214.FAN Bingbing, QIU Hongchen, LI Mengru, et al. J Chin Ceram Soc,2023, 51(12):3204–3214.
[30] ZHAO J, WANG D, JIN X, et al. Highly electro-conductive B4C–TiB2composites with three-dimensional interconnected intergranular TiB2network[J]. J Adv Ceram, 2023, 12(1):182–195.
[31] ZHAO B, FAN B B, SHAO G, et al. Facile synthesis of novel heterostructure based on SnO2 nanorods grown on submicron Ni walnut with tunable electromagnetic wave absorption capabilities[J]. ACS Appl Mater Interfaces, 2015, 7(33):18815–18823.
[32] SHI R, ZHANG Y Y, WANG Z H. Facile synthesis of a ZnCo2O4electrocatalyst with three-dimensional architecture for methanol oxidation[J]. J Alloys Compd, 2019, 810:151879.
[33] ZHANG Y C, SHEN Y Q, DANG M M, et al. In situ synthesis hydrophobic Co/CoO/C nanofibers with enhanced microwave absorption[J]. Ceram Int, 2021, 47(7):9178–9187.
[34] REEVES-MCLAREN N, SHARP J, BELTRáN-MIR H, et al.Spinel-rock salt transformation in LiCoMnO4–δ[J]. Proc Math Phys Eng Sci, 2016, 472(2185):20140991.
[35] WINDISCH C F Jr, EXARHOS G J, OWINGS R R. Vibrational spectroscopic study of the site occupancy distribution of cations in nickel cobalt oxides[J]. J Appl Phys, 2004, 95(10):5435–5442.
[36] ZHONG W L, PENG Q, TANG X K, et al. Mn-regulated CuFe2O4spinel based active component continuous exsolution catalyst for long-term degradation of tetracycline[J]. Sep Purif Technol, 2024, 343:127104.
[37] ZHOU X M, ZHANG X Y, WANG G Y, et al. Preparation of(Zr Ti Co Ni Nb)Ox high-entropy oxide powders by microwave heating with thermal field modulation[J]. Ceram Int, 2023, 49(22):35544–35551.
[38] LIU X Y, TIAN F Y, SHENG J, et al. High-entropy porous spinel ferrite@amorphous carbon nanocomposites with abundant structural defects for wide-band electromagnetic wave absorption[J]. Chem Eng J,2024, 490:151848.
[39] HE X Y, ZHAO Y H, CHEN R R, et al. Hierarchical FeCo2O4@polypyrrole core/shell nanowires on carbon cloth for high-performance flexible all-solid-state asymmetric supercapacitors[J].ACS Sustainable Chem Eng, 2018, 6(11):14945–14954.
[40] LI Y, DUAN F, LIU S L, et al. Hierarchical flower-like Ni3V2O8/Co3V2O8 composites as advanced anode materials for lithium-ion batteries[J]. Funct Mater Lett, 2020, 13(3):2050014.
[41] QIAN J J, DU B, HE C, et al. Morphology-controlled preparation and tunable electromagnetic wave absorption performance of manganese dioxide nanostructures[J]. J Am Ceram Soc, 2022, 105(5):3339–3352.
[42] LI X L, BAO J, SHADIKE Z, et al. Stabilizing transition metal vacancy induced oxygen redox by Co2+/Co3+redox and sodium-site doping for layered cathode materials[J]. Angew Chem Int Ed Engl, 2021, 60(40):22026–22034.
[43] ZOU Y H, ZHANG W, CHEN N, et al. Generating oxygen vacancies in MnO hexagonal sheets for ultralong life lithium storage with high capacity[J]. ACS Nano, 2019, 13(2):2062–2071.
[44]高雨毅,李千慧,韩擎之,等.高温雷达吸波涂层研究进展[J].航空发动机, 2024, 50(3):17–32.GAO Yuyi, LI Qianhui, HAN Qingzhi, et al. Aeroengine, 2024, 50(3):17–32.
[45] GAO L, ZHANG R D, WEI C K, et al. The dielectric and microwave absorption properties variation with temperature of La0.5Sr0.5CoO3ceramics and improved microwave absorption by FSS[J]. Ceram Int,2021, 47(18):26430–26437.
[46] CHEN H, ZHAO B, ZHAO Z F, et al. Achieving strong microwave absorption capability and wide absorption bandwidth through a combination of high entropy rare earth silicide carbides/rare earth oxides[J]. J Mater Sci Technol, 2020, 47:216–222.
[47] WANG J, LIU W, LUO G, et al. Synergistic effect of well-defined dual sites boosting the oxygen reduction reaction[J]. Energy Environ Sci,2018, 11(12):3375–3379.
[48] GUAN P F, ZHANG X F, GUO J J. Assembled Fe3O4 nanoparticles on graphene for enhanced electromagnetic wave losses[J]. Appl Phys Lett,2012, 101(15):153108.
[49]李天天,夏龙,黄小萧,等.介电损耗型微波吸收材料的研究进展[J].材料工程, 2021, 49(6):1–13.LI Tiantian, XIA Long, HUANG Xiaoxiao, et al. J Mater Eng, 2021,49(6):1–13.
[50] PU Y P, ZHANG Q W, LI R, et al. Dielectric properties and electrocaloric effect of high-entropy(Na0.2Bi0.2Ba0.2Sr0.2Ca0.2)TiO3ceramic[J]. Appl Phys Lett, 2019, 115(22):223901.
[51] ZHOU S Y, PU Y P, ZHANG Q W, et al. Microstructure and dielectric properties of high entropy Ba(Zr0.2Ti0.2Sn0.2Hf0.2Me0.2)O3 perovskite oxides[J]. Ceram Int, 2020, 46(6):7430–7437.
[52] XU Z, DU Y C, LIU D W, et al. Pea-like Fe/Fe3C nanoparticles embedded in nitrogen-doped carbon nanotubes with tunable dielectric/magnetic loss and efficient electromagnetic absorption[J].ACS Appl Mater Interfaces, 2019, 11(4):4268–4277.
基本信息:
DOI：10.14062/j.issn.0454-5648.20240607
中图分类号:TQ174.1
引用信息:
[1]王中义,任玉美,杨帅,等.尖晶石/岩盐型(Fe_(0.2)Co_(0.2)Ni_(0.2)Cu_(0.2)Zn_(0.2))Co_x O_y高熵陶瓷的制备与吸波性能[J].硅酸盐学报,2025,53(03):647-657.DOI:10.14062/j.issn.0454-5648.20240607.
基金信息:
国家自然科学基金项目(U21A2064); 河南省自然科学基金重点项目(242300421188); 河南省航空材料与技术重点实验室开放基金(ZHKF-240104/05); 河南省高等学校重点科研项目(24A150045)资助
2024-12-27
2024-12-27
2024-12-27