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

doi:10.15541/jim20230546

Abstract

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

CLC Number:

TB332

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.

Figures/Tables 11

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

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

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

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

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

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

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)

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

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

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

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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