硅酸盐学报

热处理温度对Fe₃O₄纳米微晶玻璃显微形貌和吸波性能的影响

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崔世宁 ¹ , 阮健 ¹^,²^,³ , 胡巨臣 ¹ , 田晨 ²^,⁴ , 韩建军 ²^,³^,⁴ , 刘超 ²^,³^,⁴

硅酸盐学报 | 先进玻璃材料技术与产业发展专题—研究论文 2025,53(10): 2820-2829

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硅酸盐学报 |先进玻璃材料技术与产业发展专题—研究论文 2025 , 53 (10) : 2820 -2829

热处理温度对Fe₃O₄纳米微晶玻璃显微形貌和吸波性能的影响

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崔世宁¹, 阮健¹^,²^,³, 胡巨臣¹, 田晨²^,⁴, 韩建军²^,³^,⁴, 刘超²^,³^,⁴

作者信息

^1．先进玻璃材料全国重点实验室，武汉 430070

^2．武汉理工大学硅酸盐材料工程研究中心，武汉 430070

^3．湖北省特种玻璃工程技术研究中心，武汉 430070

^4．硅酸盐科学与先进建材全国重点实验室，武汉 430070

通讯作者:

阮健（1982—），男，博士，副研究员。

作者简介:

崔世宁（1999—），男，硕士研究生。

Effect of Heat Treatment Temperature on the Microstructure and Electromagnetic Wave Absorption Properties of Glass-Ceramics Containing Fe₃O₄ Nanocrystallines

Shining CUI¹, Jian RUAN¹^,²^,³, Juchen HU¹, Chen TIAN²^,⁴, Jianjun HAN²^,³^,⁴, Chao LIU²^,³^,⁴

Affiliations

^1.State Key Laboratory of Advanced Glass Materials, Wuhan 430070, China

^2.Research Center of Silicate Materials Engineering, Wuhan University of Technology, Wuhan 430070, China

^3.Specialty Glass Engineering Technology Research Center of Hubei Province, Wuhan 430070, China

^4.State Key Laboratory of Silicate Materials for Architectures, Wuhan 430070, China

Corresponding Author:

RUAN Jian (1982-), male, Ph.D., Associate Professor. E-mail: jian_ruan@whut.edu.cn

CUI Shining (1999-), male, Master candidate. E-mail: 1598116323@qq.com

出版时间: 2025-10-20 doi: 10.14062/j.issn.0454-5648.20250304

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摘要

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采用熔体-淬冷法和热处理制备了含有花状Fe₃O₄纳米晶的硅酸盐微晶玻璃，并研究了热处理温度（620~740 ℃）对显微结构、电磁参数和吸波性能的影响。结果表明：随着温度升高，Fe₃O₄晶粒逐渐增多，而它们聚集形成的花状结构尺寸先增大，后减小。饱和磁化强度M_s逐渐由5.2增至9.5 emu/g，但回波损耗先增强，后降低。其中，当热处理温度为700 ℃时，Fe₃O₄花状结构尺寸最大，吸波性能较佳。当材料厚度为7 mm时，回波损耗最低达-18 dB，有效带宽为2 GHz（14~16 GHz）。根据经典Debye方程和Cole-Cole图像分析，较大的花状纳米结构加强了电磁波在微晶玻璃中传输时的反射和散射，引起介电损耗增加并形成更好的阻抗匹配，从而使材料表现出更佳的吸波性能。

关键词

微晶玻璃 / 四氧化三铁纳米晶 / 显微形貌 / 回波损耗 / 吸波材料

Abstract

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Introduction

In recent years, microwave-absorbing composites that are both cost-effective and high-performance are developed to address the electromagnetic radiation issues like interference, pollution, and health risks. Spinel ferrite glass-ceramics as all-inorganic composites have attracted wide attention. They combine the magnetic properties of ferrite crystals with the advantages of glass, i.e., high temperature resistance, oxidation resistance, ease of formability, cost-effectiveness, and adjustable dielectric constant. Fe₃O₄ is widely used as an electromagnetic wave absorber due to its high saturation magnetization, strong spin-polarization, half-metallic properties, and low cost. Fe₃O₄ can also utilize industrial solid wastes like iron tailings as raw materials to achieve resource recycling. In this paper, silicate glass-ceramics containing flower-like Fe₃O₄ nanocrystals were prepared based on SiO₂-Al₂O₃-K₂O-Na₂O-P₂O₅-B₂O₃-Fe₂O₃ system via appropriate heat treatment. The special structure could enable the glass-ceramics to exhibit a higher reflection loss. A thorough examination of the mechanism of reflection loss was conducted, elucidating the key factors affecting dielectric loss and impedance matching on the microwave-absorbing performance of Fe₃O₄ glass-ceramics.

Methods

Raw materials (Sinopharm Chemical Reagent Co., Ltd. China) were weighed in a nominal composition of the glasses with approximately 30 g of each. Then, they were thoroughly mixed to ensure uniformity, and melted in a corundum crucible in an electric furnace at 1 580 ℃ for 2 h. Afterwards, the melt was poured into a mold for shaping. The as-quenched glasses were annealed at 500 ℃ for 1 h. Finally, the glasses were heat-treated at 620-740 ℃ with a heating rate of 10 ℃/min for 2 h. The samples were groundinto powders or cut and polished into small pieces for subsequent characterizations.

The crystalline phases of the samples were determined by X-ray diffraction (XRD). The crystallinity was determined via calculating the I_a/I_b value, where I_a is the crystalline phase intensity and I_b is the total intensity of the sample. The microstructures of the glass-ceramics were characterized by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopy (EDS). The coercive field (H_c), initial magnetic permeability (µ_i), and magnetic saturation (M_s) of the samples at room temperature were determined by vibrating sample magnetometry (VSM). The glass powder was heated and thoroughly mixed with paraffin at a ratio of 4∶1, then pressed into a ring-shape with an outer diameter of 7 mm, an inner diameter of 3.04 mm, and a thickness of 2 mm in a mold. In the frequency range of 2-18 GHz, the electromagnetic parameters were measured by a vector network analyzer (VNA), and the reflection loss values of the samples were obtained based on the transmission line theory.

Results and discussion

The results of scanning electron microscopy (SEM), vibrating sample magnetometry (VSM), and vector network analysis (VNA) reveal that an increase in temperature results in a gradual increase in the number of Fe₃O₄ grains, while the size of the flower-like structures formed by their aggregation initially increases and subsequently decreases. Also, the saturation magnetization (M_s) increases from 5.2 to 9.5 emu·g^-1 although the reflection loss exhibits an initial increase and a subsequent decline. When heat-treated at 700 ℃, the samples exhibit the most significant enhancement in Fe₃O₄ flower-like structures and the most optimal microwave absorption performance. The interfaces of the polyphase structure in the glass-ceramics generate polarization and relaxation, which enhance the dielectric loss. The mutual migration of electrons between Fe²⁺ and Fe³⁺ ions at octahedral sites induces a loss of conductivity. Meanwhile, electron hopping triggers a resonance, leading to an enhanced dielectric loss. The enhancement of crystallinity in the glass matrix promotes the magnetism, thereby leading to an improvement in magnetic loss. As the value of dielectric loss is close to that of the magnetic loss, the glass attains an effective impedance matching, thereby enhancing its reflection loss. This allows for enhanced penetration of electromagnetic waves into the material, leading to optimal reflection loss and effective absorption bandwidth at a thickness of 7 mm.

Conclusions

Silicate glass-ceramics containing flower-like Fe₃O₄ were prepared. The size of the flower-like structure was adjusted via heat-treatment temperature. At 700 ℃, the size of the flower-like structure was the largest. For a thickness of 7 mm, the reflectivity reached -18 dB, and the effective absorption bandwidth was approximately 2 GHz. Based on the analysis of the Debye equation and Cole-Cole plots, the larger flower-like nanostructures enhanced the reflection and scattering of electromagnetic waves during their transmission in the glass-ceramics. This led to an increase in dielectric loss and the formation of better impedance matching, revealing a multiple conduction-reflection-electromagnetic wave absorption mechanism.

Key words

glass-ceramics / ferroferric oxide nanocrystalline / microscopic morphology / reflection loss / electromagnetic wave absorbing materials

引用本文

崔世宁, 阮健, 胡巨臣, 田晨, 韩建军, 刘超. 热处理温度对Fe₃O₄纳米微晶玻璃显微形貌和吸波性能的影响. 硅酸盐学报, 2025 , 53 (10) : 2820 -2829 . DOI: 10.14062/j.issn.0454-5648.20250304

Shining CUI, Jian RUAN, Juchen HU, Chen TIAN, Jianjun HAN, Chao LIU. Effect of Heat Treatment Temperature on the Microstructure and Electromagnetic Wave Absorption Properties of Glass-Ceramics Containing Fe₃O₄ Nanocrystallines[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (10) : 2820 -2829 . DOI: 10.14062/j.issn.0454-5648.20250304

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湖北省重点研发计划项目(2021BAA062)

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2025年第53卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250304

接收时间：2025-04-28
首发时间：2026-10-21
出版时间：2025-10-20

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收稿日期：2025-04-28
修回日期：2025-05-15

基金

湖北省重点研发计划项目(2021BAA062)

作者信息

^1．先进玻璃材料全国重点实验室，武汉 430070

^2．武汉理工大学硅酸盐材料工程研究中心，武汉 430070

^3．湖北省特种玻璃工程技术研究中心，武汉 430070

^4．硅酸盐科学与先进建材全国重点实验室，武汉 430070

通讯作者:

阮健（1982—），男，博士，副研究员。

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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