粉煤灰磁珠Fe含量和研磨粒径对Fe<sub>3</sub>C@C-CNTs复合材料结构和吸波性能的影响

朱培; 张晓民; 俞洁; 杨爽; 陈天星; 贺攀阳

doi:10.13801/j.cnki.fhclxb.20220307.001

粉煤灰磁珠Fe含量和研磨粒径对Fe₃C@C-CNTs复合材料结构和吸波性能的影响

doi: 10.13801/j.cnki.fhclxb.20220307.001

朱培¹,
张晓民^1, ,,
俞洁²,
杨爽³,
陈天星¹,
贺攀阳¹

1.
西安建筑科技大学　资源工程学院，西安 710055
2.
中国科学院固体物理研究所　安徽省纳米材料与纳米安全研究所，合肥 230031
3.
哈尔滨工业大学　复合材料与结构研究中心，哈尔滨 150080

基金项目: 咸阳市科技局资助的研发项目：基于粉煤灰的先进吸附材料的开发(2021ZDYF-GY-0034)；酒钢集团科技研发项目资助项目(4500618489)

详细信息

通讯作者:
张晓民，博士，教授，博士生导师，研究方向为矿物材料、固废资源化利用　E-mail：xmzhang@xauat.edu.cn

中图分类号: TB333
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出版历程
- 收稿日期: 2021-12-30
- 修回日期: 2022-02-06
- 录用日期: 2022-02-17
- 网络出版日期: 2022-03-08
- 刊出日期: 2023-01-15

Impact of Fe content of coal fly ash magnetospheres and the grinding size upon microstructure and microwave absorption properties of Fe₃C@C-CNTs nanocomposites

1.
School of Resource Engineering, Xi'an University of Architecture and Technology, Xi'an 710055, China
2.
Anhui Institute of Nanomaterials and Nanosafety, Institute of Solid Physics, Chinese Academy of Sciences, Hefei 230031, China
3.
Research Center for Composite Materials and Structures, Harbin Institute of Technology, Harbin 150080, China

Funds: R&D Program Funded by the Science and Technology Bureau of Xianyang City: Development of Advanced Adsorbing Materials Based on Coal Fly Ash (2021ZDYF-GY-0034); Jiujiang Steel Group Science and Technology R&D Project Funding Project (4500618489)

摘要

摘要: 以粉煤灰磁珠作为原料，采用化学气相沉积(CVD)方法制备纳米结构铁/碳复合材料。该复合材料呈现良好的吸波性能，但存在磁珠性质不均一、结构调控难等问题。本文采用摇床方法对磁珠进行分选，并进行研磨处理，考察了磁珠Fe含量和研磨粒径对CVD生成产物的影响。结果表明，富铁磁珠CVD生成产物为碳包覆磁性颗粒与碳纳米管组成的复合材料(Fe₃C@C-CNTs)，该复合材料呈现多孔团簇球形结构。磁珠Fe含量增加，复合材料的相对碳沉积量(C/Fe值)减小，石墨化程度降低(D峰和G峰面积比I_D/I_G值升高)，导致材料阻抗匹配值升高，吸波性能获得提升。磁珠Fe含量为71.43wt%时，复合材料有效吸收频带达到4.5 GHz，最小反射损耗(RL_min)达到−16.1 dB。对磁珠进行研磨后，CVD生成产物的C/Fe值不变，但碳沉积速率增大，I_D/I_G值升高，电磁波衰减常数下降，但阻抗匹配明显提高，吸波性能大幅度提升。研磨粒径为18.23 μm时，复合材料有效吸收频带达到4.8 GHz，RL_min可达到−34.7 dB。分析表明，复合材料优异的吸波性能得益于CNTs和Fe₃C@C对电磁波的协同吸收作用；独特的多孔团簇结构增强了电磁波在材料中多次反射，促进了界面极化。
- 粉煤灰磁珠 /
- 碳包覆 /
- 碳纳米管 /
- 衰减常数 /
- 阻抗匹配 /
- 吸波性能
Abstract: Nano-structured iron/carbon composites can be prepared by chemical vapor deposition (CVD) using coal fly ash magnetospheres as raw materials, showing good microwave absorption properties. However, there are problems such as uneven properties of magnetospheres and difficulty in structural regulation. In this paper, the magnetospheres were separated by the shaking bed method, and then were grinded. The effects of the magnetospheres Fe content and the grinding particle size on the CVD products were investigated. The results show that the CVD product of Fe-rich magnetospheres is Fe₃C@C-CNTs, and the composite exhibits a porous cluster spherical structure. With the increase of magnetic bead Fe content, the relative carbon deposition (C/Fe value) of the composite decreases, and the graphitization degree decreases (Higher D/G peak intensity ratio I_D/I_G value increases), resulting in the increase of impedance matching value and the improvement of wave absorption performance. When the Fe content is 71.43wt%, the effective absorption band of the composite reaches 4.5 GHz, and the minimum reflection loss (RL_min) reaches −16.1 dB. After grinding the magnetospheres, the C/Fe value of CVD products is unchanged, but the carbon deposition rate increases, the I_D/I_G value increases, and the electromagnetic wave attenuation constant decreases, but the impedance matching is significantly improved, and the microwave absorption performance is greatly improved. When the grinding particle size is 18.23 μm, the effective absorption band of the composite is 4.8 GHz, and the RL_min can reach −34.7 dB. The excellent microwave absorption properties of the composites benefit from the synergistic absorption of CNTs and Fe₃C@C. Multiple reflections of microwave are supposed to be enhances in the porous cluster aggregated spheres, and the promoted interface polarization is also attributed to the excellent microwave absorption properties.
- coal fly ash Magnetospheres (MSs) /
- carbon coating /
- carbon nanotubes (CNTs) /
- attenuation constant /
- impedance matching /
- microwave absorption properties

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图 1 MSs与纳米铁/碳-碳纳米管(Fe₃C@C-CNTs)复合材料的XRD图谱

Figure 1. XRD patterns of MSs and nano-structured iron/carbon-carbon nanotubes (Fe₃C@C-CNTs) composites

1—Magnetite; 2—Maghemite; 3—Magnesioferrite; 4—Hematite; 5—Quartz; 6—Fe₃C; 7—Graphite

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图 2 Fe₃C@C-CNTs复合材料的SEM图像 (a) 和TEM图像 (b)

Figure 2. SEM image (a) and TEM image (b) of Fe₃C@C-CNTs composites

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图 3 摇床分选产物磁珠剖面SEM图像：(a) 1^#；(b) 2^#；(c) 3^#；摇床分选产物制备的Fe₃C@C-CNTs复合材料SEM图像：(d) S1-1；(e) S1-2；(f) S1-3

Figure 3. SEM images of magnetospheress section of specific gravity product: (a ) 1^#; (b) 2^#; (c) 3^#; SEM images of Fe₃C@C-CNTs composites prepared by shaker separation products: (d) S1-1; (e) S1-2; (f) S1-3

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图 4 摇床分选产物制备的Fe₃C@C-CNTs复合材料拉曼光谱

Figure 4. Raman spectra of Fe₃C@C-CNTs composite prepared by shaker separation products

D—D peak; G—G peak; I_D—D peak intensity; I_G—G peak intensity

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图 5 摇床分选产物制备的Fe₃C@C-CNTs复合材料介电常数和磁导率

Figure 5. Permittivity and permeability of Fe₃C@C-CNTs composite prepared by shaker separation products

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图 6 摇床分选产物制备Fe₃C@C-CNTs复合材料的衰减常数(α) (a)和阻抗匹配值(Z) (b)

Figure 6. Attenuation constant (α) (a) and impedance matching value (Z) (b) of Fe₃C@C-CNTs composite prepared by shaker separation products

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图 7 摇床分选产物制备的Fe₃C@C-CNTs复合材料反射损耗图：(a) S1-1；(b) S1-2；((c)、(d)) S1-3

Figure 7. Reflective loss diagram of Fe₃C@C-CNTs composites by shaker separation products: (a) S1-1; (b) S1-2; ((c), (d)) S1-3

RL—Reflection loss

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图 8 研磨产物1 (a) 和产物2 (b) 的SEM图像；研磨产物制备的Fe₃C@C-CNTs复合材料SEM图像：(c) S2-1；(d) S2-2

Figure 8. SEM images of grinding product 1 (a) and product 2 (b); SEM images of Fe₃C@C-CNTs composites prepared by grinding products: (c) S2-1; (d) S2-2

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图 9 研磨产物制备的Fe₃C@C-CNTs复合材料拉曼光谱

Figure 9. Raman spectra analysis results of Fe₃C@C-CNTs composites prepared by grinding products

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图 10 研磨产物制备的Fe₃C@C-CNTs复合材料的C/Fe值随制备时间的变化图

Figure 10. Plot of C/Fe values of Fe₃C@C-CNTs composites prepared by grinding products with preparation time

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图 11 研磨产物制备的Fe₃C@C-CNTs复合材料介电常数和磁导率

Figure 11. Permittivity and permeability of Fe₃C@C-CNTs composites prepared by grinding products

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图 12 研磨产物制备的Fe₃C@C-CNTs复合材料衰减常数(a)和阻抗匹配(b)

Figure 12. Attenuation constant (a) and impedance matching (b) of Fe₃C@C-CNTs composites prepared by grinding products

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图 13 研磨产物制备的Fe₃C@C-CNTs复合材料反射损耗图：(a) S2-1；((b)、(c)) S2-2

Figure 13. Reflective loss diagram of Fe₃C@C-CNTs composites prepared by grinding products: (a) S2-1; ((b), (c)) S2-2

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表 1 −38 μm磁珠(MSs) EDX结果

Table 1. −38 μm magnetospheres (MSs) EDX results

Element	Mass fraction/wt%
O	32.3
Fe	52.4
Si	5.7
Al	2.6
Ca	3.3
Mg	2.5
Mn	0.9
Ti	0.3

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表 2 MSs摇床分选产物1^#、2^#、3^#的产率、密度、Fe含量

Table 2. Yield, density, and Fe content of MSs shaker separation products 1^#, 2^#, 3^#

Shaker separation products	Yield/%	Density/(g·cm⁻³)	Fe/wt%
1^#	49.08	4.07	47.49
2^#	31.42	4.44	64.36
3^#	17.96	5.01	71.43

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表 3 Fe₃C@C-CNTs复合材料的C/Fe值

Table 3. C/Fe value of Fe₃C@C-CNTs composites

Sample	C/Fe value
S1-1	8.06
S1-2	6.71
S1-3	6.34
Note：C/Fe value—Mass ratio of C to Fe.

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表 4 磁珠研磨产物的粒径变化

Table 4. Particle size change of grinding products of magnetospheres

Grinding products	D_av/μm
No grinding magnetospheres	28.82
Product 1	22.62
Product 2	18.23
Note: D_av—Average grain diameter.

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表 5 碳基吸波材料的性能对比

Table 5. Performance comparison of carbon-based absorbing materials

Sample	Mass fraction /wt%	Bandwith/GHz	RL_min/dB	Ref.
3D Fe₃O₄/CNTs	50	3.9	−51.0	[4]
Fe@RC	45	5.3	−47.1	[10]
MCNO /MWCNT	—	4.3	−25.6	[11]
C@Fe@Fe₃O₄	50	5.2	−40.0	[34]
Fe/C nanofibers	30	4.0	−20.2	[38]
Fe₃O₄/C	29	2.5	−29.4	[39]
Fe@CNCs	30	3.0	−22.5	[40]
S1-3	15	4.5	−16.1	This work
S2-2	15	4.8	−34.7	This work
Notes: RC—Residual carbon; MCNO—Magnetic carbon nano-onion matrix; MWCNT—Multi-walled carbon nanotubes; CNCs—Cored carbon nanocapsules; RL_min—Minimum reflection loss.

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