聚合物转化SiHfCN陶瓷的制备及其吸波性能

doi:10.15541/jim20230546

无机材料学报 ›› 2024, Vol. 39 ›› Issue (6): 681-690.DOI: 10.15541/jim20230546

聚合物转化SiHfCN陶瓷的制备及其吸波性能

张育育(), 吴轶城, 孙佳(), 付前刚()

西北工业大学超高温结构复合材料重点实验室, 陕西省纤维增强轻质复合材料重点实验室, 西安 710072

收稿日期:2023-11-29 修回日期:2023-12-29 出版日期:2024-06-20 网络出版日期:2024-01-08
通讯作者: 孙佳, 副教授. E-mail: j.sun@nwpu.edu.cn;
付前刚, 教授. E-mail: fuqiangang@nwpu.edu.cn
作者简介:张育育(1997-), 女, 博士研究生. E-mail: Zhangyuyu@mail.nwpu.edu.cn
基金资助:
国家重点研发计划(2022YFB3708600);国家重点研发计划(2021YFA0715802);国家自然科学基金(52101098);航空科学基金(2022Z055053004)

Preparation and Wave-absorbing Properties of Polymer-derived SiHfCN Ceramics

ZHANG Yuyu(), WU Yicheng, SUN Jia(), FU Qiangang()

State Key Laboratory of Ultra High Temperature Composite Materials, Shaanxi Key Laboratory of Fiber Reinforced Light Composite Materials, Northwestern Polytechnical University, Xi’an 710072, China

Received:2023-11-29 Revised:2023-12-29 Published:2024-06-20 Online:2024-01-08
Contact: SUN Jia, associate professor. E-mail: j.sun@nwpu.edu.cn;
FU Qiangang, professor. E-mail: fuqiangang@nwpu.edu.cn
About author:ZHANG Yuyu (1997-), female, PhD candidate. E-mail: Zhangyuyu@mail.nwpu.edu.cn
Supported by:
National Key R&D Program of China(2022YFB3708600);National Key R&D Program of China(2021YFA0715802);National Natural Science Foundation of China(52101098);Aeronautical Science Foundation of China(2022Z055053004)

摘要/Abstract

摘要：

聚合物转化SiCN陶瓷得益于质量轻和热膨胀系数低等优势, 在电磁波吸收领域受到广泛关注。由于电磁损耗机制单一及耐温性不足, SiCN陶瓷的吸波性能有待进一步提高, 借助多组元协同作用增强吸波性能是可行的途径之一。本工作对聚氮硅烷结合不同化合物进行单源化改性得到SiHfCN、SiHfCN-C、SiHfCN-B和SiHfCN-N等四种纳米陶瓷。结果表明：SiHfCN中由于Hf源的含氧量高达13.5%(质量分数), 生成HfO₂和SiO₂, 使其最低反射损耗(Reflection loss, RL_min)仅为-13.8 dB, 有效吸收带宽(Effective absorption bandwidth, EAB)仅为0.42 GHz。相比于SiHfCN, 含Hf聚合物分别与C源、B源和N源共改性增加了聚合物转化陶瓷的界面和导电相, SiHfCN-C、SiHfCN-B和SiHfCN-N的介电常数实部和虚部分别提高了1.4~1.8和2.7~3.9倍, RL_min分别为-50.6、-57.3和-63.5 dB, EAB分别为3.53、3.99和4.01 GHz, 吸波性能得到了显著改善。SiHfCN-C中大量的自由碳抑制了HfO₂的生成, 增强了电导损耗。SiHfCN-B中生成了B-N和B-C键, 且析出的纳米棒状HfSiO₄提供了更多的异质界面, 增强了极化损耗。SiHfCN-N中因引入大量N使N-C键数量增加, 强化了偶极子极化损耗, 同时生成纳米碳片, 不仅可以增强电导损耗, 而且提供大量界面, 改善了阻抗匹配并增强了界面极化, 因而SiHfCN-N具有最佳的吸波性能。

关键词: 聚合物转化陶瓷, 聚氮硅烷, 超高温陶瓷, 吸波性能

Abstract:

Polymer-derived SiCN ceramics benefiting from advantages of light mass and low coefficient of thermal expansion, have received wide attention in electromagnetic wave absorption field. However, the wave absorptive performance of SiCN ceramics needs to be further improved due to its monomer loss mechanism and insufficient temperature resistance. Enhancing their wave absorptive performance with the aid of multicomponent synergy is a feasible way, but still facing some challenges in preparation and wave absorption. In this work, four types of nanoceramics, SiHfCN, SiHfCN-C, SiHfCN-B, and SiHfCN-N were obtained by single-source modification of polysilazane combining different compounds. The results showed that SiHfCN generated HfO₂ and SiO₂ for up to 13.5% (in mass) oxygen content in the Hf source, resulting in the minimum reflection loss (RL_min) of only -13.8 dB and the effective absorption bandwidth (EAB) of only 0.42 GHz. Compared to SiHfCN, the co-modification of the Hf-containing polymer with C, B and N sources increased the interface and conductive phases of polymer-derived ceramics, real and imaginary parts of SiHfCN-C, SiHfCN-B, and SiHfCN-N gave rise to 1.4-1.8 and 2.7-3.9 times higher, respectively, with RL_min of -50.6, -57.3 and -63.5 dB, and EAB of 3.53, 3.99 and 4.01 GHz, showing a significant improvement in their wave absorptive properties. The SiHfCN-C inhibited the generation of HfO₂ for massive free carbon, which could enhance the conductivity loss. The SiHfCN-B generated B-N and B-C bonds, and precipitated nanorods of HfSiO₄ to provide more heterogeneous interfaces, increasing the polarization loss. The SiHfCN-N increased the content of N-C bond due to the introduction of abundant N, enhancing the dipole polarization loss, while the generated carbon nanosheets not only enhanced the conductivity loss but also provided rich interfaces, which improved the impedance matching and amplified the polarization loss, thus exhibiting excellent wave absorptive performance.

Key words: polymer-derived ceramic, polysilazane, ultra-high temperature ceramic, wave-absorbing property

中图分类号:

TB332

张育育, 吴轶城, 孙佳, 付前刚. 聚合物转化SiHfCN陶瓷的制备及其吸波性能[J]. 无机材料学报, 2024, 39(6): 681-690.

ZHANG Yuyu, WU Yicheng, SUN Jia, FU Qiangang. Preparation and Wave-absorbing Properties of Polymer-derived SiHfCN Ceramics[J]. Journal of Inorganic Materials, 2024, 39(6): 681-690.

图/表 11

表1 不同样品的原料比例(%, 质量分数)

Table 1 Raw material proportions (%, in mass) of different samples

SSPs	PDCs	PSN	Hf isopropoxide isopropanol complex	DVB	Melamine	Dimethylamino borane
P7Hf3	SiHfCN	7	3	-	-	-
P7Hf3-C	SiHfCN-C	7	3	6	-	-
P7Hf3-N	SiHfCN-N	7	3	-	6	-
P7Hf3-B	SiHfCN-B	7	3	-	-	6

图1 合成的SSPs的表征

Fig. 1 Characterization of the synthesized SSPs (a) FT-IR spectra; (b) TG curves

图2 PDCs的XRD谱图

Fig. 2 XRD patterns of the PDCs (a) Pyrolyzed at 1000 ℃; (b) Annealed at 1500 ℃

表2 PDCs的元素含量(%, 质量分数)和经验化学式

Table 2 Elemental contents (%, in mass) and empirical chemical compositions of the PDCs

Element	SiHfCN	SiHfCN-C	SiHfCN-N	SiHfCN-B
Si	35.5	42.3	40.8	33.8
Hf	22.5	18.6	20.4	13.5
C	13.6	24	8.2	13.3
N	22.8	9.4	55.5	29.8
O	5.6	5.7	7.1	5.3
Empirical formula	SiHf_0.10C_0.90N_1.29O_0.28	SiHf_0.07C_1.33N_0.45O_0.24	SiHf_0.08C_0.47N_2.73O_0.31	SiHf_0.06C_0.92N_1.77O_0.28B_0.33

图3 PDCs的Raman分析

Fig. 3 Raman analysis of the PDCs (a) Raman spectra; (b) Computed free carbon size

图4 PDCs的XPS高分辨谱图

Fig. 4 XPS high-resolution spectra of the PDCs (a) C1s; (b) O1s; (c) N1s; (d) Hf4f; (e) Si2p; (f) B1s

图5 PDCs的SEM照片及EDS分析

Fig. 5 SEM images and EDS analyses of the PDCs (a) SiHfCN; (b) SiHfCN-C; (c) SiHfCN-N; (d) SiHfCN-B; (e) Elemental contents (%, in atom) of spots in (a-d)

图6 SiHfCN和SiHfCN-C的TEM照片

Fig. 6 TEM images of SiHfCN and SiHfCN-C (a-d) SiHfCN; (e-h) SiHfCN-C; (a, e) Bright field images; (b, c, f, g) HRTEM images with corresponding SAED inserted; (d, h) EDS mappings

图7 SiHfCN-N和SiHfCN-B的TEM照片

Fig. 7 TEM images of SiHfCN-N and SiHfCN-B (a-d) SiHfCN-N; (e-h) SiHfCN-B; (a, e) Bright field images; (b, c, f, g) HRTEM images with corresponding SAED inserted; (d, h) EDS mappings

图8 PDCs的电磁参数

Fig. 8 Electromagnetic parameters of the PDCs (a) Real part; (b) Imaginary part; (c) Loss tangent; (d) Attenuation coefficient; (e, f) Cole-Cole curves; Colorful figures are available on website

图9 PDCs的RL图和阻抗匹配图

Fig. 9 RL patterns and impedance matching maps of the PDCs (a-h) RL patterns; (i-l) Impedance matching maps; (a, b, i) SiHfCN; (c, d, j) SiHfCN-C; (e, f, k) SiHfCN-N; (g, h, l) SiHfCN-B

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聚合物转化SiHfCN陶瓷的制备及其吸波性能

Preparation and Wave-absorbing Properties of Polymer-derived SiHfCN Ceramics

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