Hollow-structured ceramic fibers with multiple components are ideal as lightweight insulation materials. In this study, tetraethyl orthosilicate, boric acid, and zirconia octahydrate were used as raw materials for fabricating SiZrBOC hollow ceramic fibers through coaxial electrospinning. These ceramic fibers exhibit a low thermal conductivity and an excellent temperature resistance. The electrospun SiZrBOC hollow ceramic fibers display a clean and compact morphology with internal folds. Fourier-transform infrared spectroscopy and thermogravimetric analysis (TGA) were used to assess the transformation process and thermal behavior of the hollow ceramic fibers. The results suggest that the incorporation of B promotes the formation of Si–O–B bonds within the system, leading to a maximum yield of 75.49 wt% for the production of the SiZrBOC hollow ceramic fibers. The phase composition and microstructure of the SiZrBOC hollow ceramic fibers were analyzed via X-ray diffraction (XRD) measurements. The pyrolysis at 1000 °C resulted in the appearance of diffraction peaks corresponding to SiO2 and SiC in the XRD patterns of the SiZrBOC hollow ceramic fibers. Laser thermal conductivity measurements reveal that the SiZrBOC hollow ceramic fibers exhibit a thermal conductivity of only 0.06 W‧m−1K−1 at 25 °C and 0.124 W‧m−1K−1 at 500 °C, indicating a significantly superior thermal insulation performance compared with conventional solid SiZrBOC ceramic fibers.
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