热处理升温速率对钡铁氧体空心微珠形貌与吸波性能的影响
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摘要
采用将火焰热喷涂技术、自蔓延高温合成技术及快速冷却凝固技术结合在一起的自反应淬熄法,制备了以尖晶石型钡铁氧体为主的空心微珠,然后分别以3,7和15℃·min-13种升温速率将其加热到1100℃、保温4 h后再冷却至室温,通过扫描电镜(SEM),X射线衍射(XRD)和矢量网络分析仪等手段,研究了3种升温速率下空心微珠形貌和吸波性能的变化。结果表明:未热处理时,空心微珠主要由Al2O3,Fe2O3,Fe3O4,BaFe2O4组成,表面无明显晶粒出现,最低反射率为-2 dB;3℃·min-1慢速升温条件下,空心微珠物相主要由Fe2O3,BaFe12O19,BaAl12O19和Al2O3组成,表面出现了典型的六角晶型,反射率有3个极值,最低反射率为-16.5 dB,低于-10 dB的吸收带宽为2.2GHz;7℃·min-1中速升温条件下,物相组成为Fe2O3,BaFe12O19,BaAl12O19,Al2O3和Fe3O4,微珠表面以片状晶为主,最低反射率为-6.5dB;15℃·min-1快速升温条件下,由于晶体生长和受扩散控制的固相反应不充分,物相组成中出现了Ba0.83Fe11O17.33和BaFe13.2O20.8中间相,空心微珠表面主要为等轴晶,最低反射率为-3.9 dB。慢速升温时钡铁氧体空心微珠吸波性能优于中速和快速升温条件。
Hollow ceramic microspheres containing barium ferrites with spinel structure were synthesized by self-reactive quenching technology based on flame hot spraying technology,self-propagating high-temperature synthesis( SHS) technology and rapid solidification technology. The samples were calcined to 1100 ℃ with different heating rates of 3,7 and 15 ℃·min- 1,and were kept at 1100 ℃ for 4 h,and then cooled to room temperature. Effects of there heating rates on the morphology and microwave absorption properties were tested by scanning electron microscopy( SEM),X-ray diffraction( XRD) and vector network analyzer. The results showed that,when hollow microsphers were not heated,the phases were mainly made up of Al2O3,Fe2O3,Fe3O4and BaFe2O4. There was no obvious crystal on the surface,and the minimum value of reflection loss was- 2 dB. When heated with 3 ℃·min- 1slow heating rate,the phase components of hollow microspheres were Fe2O3,BaFe12O19,BaAl12O19,Al2O3,and the surface took on classical hexagonal crystals. The reflection loss had three extremas,with the minimum value of- 16. 5 dB,and the frequency bandwidth for lower than- 10 dB was 2. 2 GHz. When heated with 7 ℃·min- 1medium heating rate,the phase components were Fe2O3,BaFe12O19,BaAl12O19,Al2O3and Fe3O4. The surfaces were mainly made up of plate crystals,and the minimum value of reflection loss was- 6. 5 dB. When heated with 15 ℃·min- 1fast heating rate,intermediate phases of Ba0. 83 Fe11O17. 33and BaFe13. 2O20. 8were obtained,because the crystal growth was insufficient and solid phase reaction controlled by diffusion was insufficient,too. The crystals on the surface of hollow microspheres were mostly isometric crystals,and the mimimum value of reflection loss was- 3. 9 dB. The microwave absorption properties with slow heating rate were better than those with medium and fast heating rates.
Hollow ceramic microspheres containing barium ferrites with spinel structure were synthesized by self-reactive quenching technology based on flame hot spraying technology,self-propagating high-temperature synthesis( SHS) technology and rapid solidification technology. The samples were calcined to 1100 ℃ with different heating rates of 3,7 and 15 ℃·min- 1,and were kept at 1100 ℃ for 4 h,and then cooled to room temperature. Effects of there heating rates on the morphology and microwave absorption properties were tested by scanning electron microscopy( SEM),X-ray diffraction( XRD) and vector network analyzer. The results showed that,when hollow microsphers were not heated,the phases were mainly made up of Al2O3,Fe2O3,Fe3O4and BaFe2O4. There was no obvious crystal on the surface,and the minimum value of reflection loss was- 2 dB. When heated with 3 ℃·min- 1slow heating rate,the phase components of hollow microspheres were Fe2O3,BaFe12O19,BaAl12O19,Al2O3,and the surface took on classical hexagonal crystals. The reflection loss had three extremas,with the minimum value of- 16. 5 dB,and the frequency bandwidth for lower than- 10 dB was 2. 2 GHz. When heated with 7 ℃·min- 1medium heating rate,the phase components were Fe2O3,BaFe12O19,BaAl12O19,Al2O3and Fe3O4. The surfaces were mainly made up of plate crystals,and the minimum value of reflection loss was- 6. 5 dB. When heated with 15 ℃·min- 1fast heating rate,intermediate phases of Ba0. 83 Fe11O17. 33and BaFe13. 2O20. 8were obtained,because the crystal growth was insufficient and solid phase reaction controlled by diffusion was insufficient,too. The crystals on the surface of hollow microspheres were mostly isometric crystals,and the mimimum value of reflection loss was- 3. 9 dB. The microwave absorption properties with slow heating rate were better than those with medium and fast heating rates.
引文
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[11]Wei L,Zhang H,Li S S,Ma Y,Gong S K.Influence of heat treatments on microstructure of single crystal Ni3Al-base superalloy[J].Chinese Journal of Rare Metals,2012,36(2):178.(魏丽,张恒,李树索,马岳,宫声凯.热处理对一种Ni3Al基单晶合金组织的影响[J].稀有金属,2012,36(2):178.)
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[13]Lei J,Dai H L,Mao E L,Xiao F,Li S P.Preparation and surface modification of spherical nano-BaFe12O19[J].J.Chin.Cera.Soc.,2010,38(12):2289.(雷军,戴红莲,毛恩亮,肖峰,李世普.球形纳米BaFe12O19的制备及表面改性[J].硅酸盐学报,2010,38(12):2289.)
[14]Chen M,Cheng X D,Mao F.Effects of heat treatment on structure and static magnetic properties of barium ferrite hollow microspheres[J].The Chinese Journal of Process Engineering,2008,8(5):1018.(陈明,程旭东,毛昉.热处理对钡铁氧体空心微球结构和静磁性能的影响[J].过程工程学报,2008,8(5):1018.)
[15]Yan L,Huang Y,Wang Y L,Li Y Q.Influence of roasting on the phase composition and magnetic properties of BaFe12O19nanoparticles prepared by sol-gel selfpropagation high-temperature synthesis[J].J.Magn.Mater.Devices,2007,38(4):37.(闫梨,黄英,王艳丽,李玉青.焙烧对溶胶凝胶自蔓延燃烧法制备的钡铁氧体粉体相成分与磁性能的影响[J].磁性材料及器件,2007,38(4):37.)
[16]Chen X D,Wang G Q,Duan Y P,Li W P,Liu S H.Synthesis of compound ceramic with shell-core structure and its electromagnetic characters[J].Journal of Inorganic Materials,2007,22(3):456.(陈晓东,王桂芹,段玉平,李伟平,刘顺华.壳-芯型复合陶瓷材料的制备及其电磁特性[J].无机材料学报,2007,22(3):456.)
[17]Zhang Y G.Ferromagnetic Materials[M].Chengdu:Chengdu Telecommunication Engineering College Press,1988.84.(张有纲.磁性材料[M].成都:成都电讯工程学院出版社,1988.84.)
[2]Shi X,Pu Y P,Liu D.Preparation of magnetic barium ferrite powders by microwave hydrothermal method[J].Journal of Synthetic Crystals,2013,33(6):70.(石轩,蒲永平,刘丹.微波水热法合成BaFe12O19磁性粉体[J].人工晶体学报,2013,42(1):134.)
[3]Topal U,Ozkan H,Topal K G.Improved properties of BaFe12O19prepared by ammonium nitrate melt technique and washed in HCl[J].J.Alloy Compd.,2006,422(1-2):276.
[4]Zuo J Z,Jiang J H,Ma A B,Wang Z H,Lin P H.Co-Ni-P chemical plating of ash hollow microspheres and microwave properties of coatings[J].Material Protection,2011,44(4):15.(左锦中,江静华,马爱斌,王泽华,林萍华.粉煤灰空心微珠的Co-Ni-P化学镀及镀层的吸波性能[J].材料保护,2011,44(4):15.)
[5]Geleil A S,Hall M M,Shelby J E.Hollow glass microspheres for use in radiation shielding[J].Non-Crystalline Solids,2006,35(2):620.
[6]Schmitt M L,Shelby J E,Hall M M.Preparation of hollow glass microspheres from sol-gel derived glass for application in hydrogen gas storage[J].Journal of NonCrystalline Solids,2006,(352):626.
[7]Xu L Q,Zhang W Q,Yang Q,Ding Y W,Yu W C,Qian Y T.A novel route to hollow and solid carbon spheres[J].Carbon,2005,43(5):1090.
[8]Wang Z L,Yin J S.Graphitic hollow carbon calabashes[J].Chem.Phys.Lett.,1998,289(1-2):189.
[9]Oda Y,Fukuyama K,Nishikawa K,Namba S,Yoshitake H,Tatsumi T.Mesocellular foam carbons:aggregates of hollow carbon spheres with open and closed wall structures[J].Chemistry of Materials,2004,16(20):3860.
[10]Yuan H P,Li Z N,Zhao X S,Wang S M,Liu X P,Jiang L J.Effect of heat treatment on structure and properties of Nd-Mg-Ni-System hydrogen storage electrode alloys[J].Chinese Journal of Rare Metals,2013,37(3):341.(苑慧萍,李志念,赵旭山,王树茂,刘晓鹏,蒋利军.热处理对Nd-Mg-Ni储氢合金结构和性能的影响[J].稀有金属,2013,37(3):341.)
[11]Wei L,Zhang H,Li S S,Ma Y,Gong S K.Influence of heat treatments on microstructure of single crystal Ni3Al-base superalloy[J].Chinese Journal of Rare Metals,2012,36(2):178.(魏丽,张恒,李树索,马岳,宫声凯.热处理对一种Ni3Al基单晶合金组织的影响[J].稀有金属,2012,36(2):178.)
[12]Lan Y H,Gao X X,Qiao Y,Gao J,Bao X Q.Study on self-propagating high-temperature synthesizing BaFe12O19[J].Material Review,2007,21(SpecialⅧ):333.(兰银辉,高学绪,乔袆,高静,包小倩.自蔓延高温合成钡铁氧体的研究[J].材料导报,2007,21(专辑Ⅷ):333.)
[13]Lei J,Dai H L,Mao E L,Xiao F,Li S P.Preparation and surface modification of spherical nano-BaFe12O19[J].J.Chin.Cera.Soc.,2010,38(12):2289.(雷军,戴红莲,毛恩亮,肖峰,李世普.球形纳米BaFe12O19的制备及表面改性[J].硅酸盐学报,2010,38(12):2289.)
[14]Chen M,Cheng X D,Mao F.Effects of heat treatment on structure and static magnetic properties of barium ferrite hollow microspheres[J].The Chinese Journal of Process Engineering,2008,8(5):1018.(陈明,程旭东,毛昉.热处理对钡铁氧体空心微球结构和静磁性能的影响[J].过程工程学报,2008,8(5):1018.)
[15]Yan L,Huang Y,Wang Y L,Li Y Q.Influence of roasting on the phase composition and magnetic properties of BaFe12O19nanoparticles prepared by sol-gel selfpropagation high-temperature synthesis[J].J.Magn.Mater.Devices,2007,38(4):37.(闫梨,黄英,王艳丽,李玉青.焙烧对溶胶凝胶自蔓延燃烧法制备的钡铁氧体粉体相成分与磁性能的影响[J].磁性材料及器件,2007,38(4):37.)
[16]Chen X D,Wang G Q,Duan Y P,Li W P,Liu S H.Synthesis of compound ceramic with shell-core structure and its electromagnetic characters[J].Journal of Inorganic Materials,2007,22(3):456.(陈晓东,王桂芹,段玉平,李伟平,刘顺华.壳-芯型复合陶瓷材料的制备及其电磁特性[J].无机材料学报,2007,22(3):456.)
[17]Zhang Y G.Ferromagnetic Materials[M].Chengdu:Chengdu Telecommunication Engineering College Press,1988.84.(张有纲.磁性材料[M].成都:成都电讯工程学院出版社,1988.84.)