由聚钛碳硅烷制备高结晶近化学计量比SiC(Ti)纤维

doi:10.15541/jim20240243

无机材料学报 ›› 2024, Vol. 39 ›› Issue (12): 1377-1383.DOI: 10.15541/jim20240243 CSTR: 32189.14.10.15541/jim20240243

所属专题：【结构材料】超高温结构陶瓷(202412)

由聚钛碳硅烷制备高结晶近化学计量比SiC(Ti)纤维

苟燕子(), 康伟峰, 张庆雨

国防科技大学空天科学学院, 新型陶瓷纤维及其复合材料重点实验室, 长沙 410073

收稿日期:2024-05-14 修回日期:2024-06-26 出版日期:2024-07-03 网络出版日期:2024-07-03
作者简介:苟燕子(1984-), 副研究员. E-mail: y.gou2012@hotmail.com
基金资助:
国家自然科学基金(52272100);湖南省自然科学基金(2022JJ30662);新型陶瓷纤维及其复合材料重点实验室基金(WDZC20215250507)

Preparation of Nearly Stoichiometric SiC(Ti) Fibers with Highly Crystalline Microstructure from Polytitanocarbosilane

GOU Yanzi(), KANG Weifeng, ZHANG Qingyu

Science and Technology on Advanced Ceramic Fibers and Composites Laboratory, College of Aerospace Science and Engineering, National University of Defense Technology, Changsha 410073, China

Received:2024-05-14 Revised:2024-06-26 Published:2024-07-03 Online:2024-07-03
About author:GOU Yanzi (1984-), associate professor. E-mail: y.gou2012@hotmail.com
Supported by:
National Natural Science Foundation of China(52272100);Natural Science Foundation of Hunan Province(2022JJ30662);Fund of Science and Technology on Advanced Ceramic Fibers and Composites Laboratory(WDZC20215250507)

摘要/Abstract

摘要：

SiC纤维具有高强度、耐高温、抗氧化等优良性能, 可应用于航空航天及高技术装备等重要领域。然而, 当前国产含钛SiC纤维的制备温度较低, 纤维中仍富含多余的杂质氧和游离碳, 这严重影响了其耐高温性能。本工作以低软化点聚碳硅烷(LPCS)和钛酸四丁酯(Ti(OBu)₄)为原料合成了聚钛碳硅烷(PTCS)先驱体, 所得PTCS的钛质量分数为0.36%~1.81%。然后经过PTCS熔融纺丝、空气不熔化、热解无机化和高温烧结, 制备了高结晶近化学计量比的SiC(Ti)纤维, 该纤维的C、O元素的质量分数分别为30.45%和<1.0%, C/Si比约为1.05, β-SiC晶粒尺寸为100~200 nm。纤维中的Ti元素主要以TiC相的形式存在, 从而有助于纤维的高温烧结致密化。SiC(Ti)纤维表面光滑致密, 纤维芯部呈现明显的穿晶断裂特征, 平均单丝拉伸强度为2.04 GPa, 杨氏模量为308 GPa。本研究为研制高性能连续SiC纤维提供了重要的参考价值。

关键词: 聚钛碳硅烷, 熔融纺丝, SiC纤维, 先驱体陶瓷, 高温烧结

Abstract:

Due to high tensile strength, excellent high-temperature and oxidation resistance, SiC fibers could be applied in many important fields such as aerospace and high-tech equipment. However, the current preparation temperature of domestically produced titanium-containing SiC fibers is relatively low, while the fibers are still full of excess oxygen and free carbon, which seriously affects their high-temperature resistance. In this work, the polytitanocarbosilane (PTCS) precursor was synthesized by using low-softening-point polycarbosilane (LPCS) and tetrabutyl titanate (Ti(OBu)₄). Mass fraction of titaniumin in the precursor was in the range of 0.36%-1.81%. The nearly stoichiometric polycrystalline SiC(Ti) fibers were successfully prepared through PTCS melt spinning, air curing, pyrolysis, and high-temperature sintering. Mass fractions of carbon and oxygen in SiC(Ti) fibers were 30.45% and <1.0%, respectively, with a C/Si ratio of approximately 1.05 and β-SiC grain size of 100-200 nm. The titanium element in SiC(Ti) fibers mainly existed in the form of TiC phase, which was beneficial to densification of the fibers during the sintering process. The SiC(Ti) fibers showed smooth and dense surface, exhibiting obvious transgranular fracture. Average tensile strength of the SiC(Ti) fibers was 2.04 GPa, and elastic modulus was 308 GPa. All results of this work provide important reference for the development of high-performance continuous SiC fibers.

Key words: polytitanocarbosilane, melt spinning, SiC fiber, precursor-derived ceramic, high-temperature sintering

中图分类号:

TQ343

苟燕子, 康伟峰, 张庆雨. 由聚钛碳硅烷制备高结晶近化学计量比SiC(Ti)纤维[J]. 无机材料学报, 2024, 39(12): 1377-1383.

GOU Yanzi, KANG Weifeng, ZHANG Qingyu. Preparation of Nearly Stoichiometric SiC(Ti) Fibers with Highly Crystalline Microstructure from Polytitanocarbosilane[J]. Journal of Inorganic Materials, 2024, 39(12): 1377-1383.

图/表 7

图1 LPCS*、PTCS*先驱体(a)和PTCS*-AC纤维(b)的FT-IR谱图[4]

Fig. 1 FT-IR spectra of LPCS*, PTCS* precursors (a) and PTCS*-AC fibers (b)[4]

表1 LPCS*、PTCS-2*、PTCS-6*和PTCS-10*的分析结果

Table 1 Analytic results of LPCS*, PTCS-2*, PTCS-6*, and PTCS-10*

Polymer	LPCS*	PTCS-2*	PTCS-6*	PTCS-10*
A₂₁₀₀/A₁₂₅₀	1.01	0.98	0.95	0.85
Silicon content/ (%, in mass)	43.34	43.78	43.48	42.07
Carbon content/ (%, in mass)	40.44	40.71	41.28	40.87
Oxygen content/ (%, in mass)	1.32	1.58	2.52	3.11
Titanium content/ (%, in mass)	-	0.36	1.00	1.81
M_n	1126	1152	1249	1140
PDI	2.32	2.33	2.25	2.21
Ceramic yield/ (%, in mass)	49.9	61.6	64.2	67.5

图2 LPCS*、PTCS*先驱体(a)和PTCS*-AC纤维(b)的TG曲线[4]

Fig. 2 TG curves of LPCS*, PTCS* precursors (a) and PTCS*-AC fibers (b)[4]

图3 Si-C-Ti-O纤维表面(a, b)和截面(c, d)的SEM照片

Fig. 3 SEM images of surface (a, b) and cross section (c, d) of Si-C-Ti-O fibers

图4 Si-C-Ti-O纤维(a)和SiC(Ti)纤维(b)的XRD谱图

Fig. 4 XRD patterns of Si-C-Ti-O fibers (a) and SiC(Ti) fibers (b)

图5 Si-C-Ti中间纤维表面(a, b)和截面(c, d)的SEM照片

Fig. 5 SEM images of surface (a, b) and cross section (c, d) of Si-C-Ti intermediate fibers

图6 SiC(Ti)纤维表面(a, b)和截面(c, d)的SEM照片

Fig. 6 SEM images of surface (a, b) and cross section (c, d) of SiC(Ti) fibers

参考文献 26

[1]	BUNSELL A R, PIANT A. A review of the development of three generations of small diameter silicon carbide fibres. Journal of Materials Science, 2006, 41(3): 823.
[2]	WANG P, LIU F, WANG H, et al. A review of third generation SiC fibers and SiC_f/SiC composites. Journal of Materials Science and Technology, 2019, 35(12): 2743.
[3]	SCHAWALLER D, CLAUSS B, BUCHMEISER M R. Ceramic filament fibers — a review. Macromolecular Materials and Engineering, 2012, 297(6): 502.
[4]	ZHANG Q, CHEN T, KANG W, et al. Synthesis of polytitanocarbosilane and preparation of Si-C-Ti-B fibers. Processes, 2023, 11: 1189.
[5]	KANG W, ZHANG Q, GOU Y. Fabrication of highly crystalline titanium-containing SiC fibers with different boron contents exhibiting excellent electromagnetic wave absorption. Journal of Materials Science, 2024, 59(7): 2739.
[6]	WU S, GOU Y, WANG Y, et al. Effect of heat treatment on composition, microstructure and mechanical property of domestic KD-SA SiC fibers. Journal of Inorganic Materials, 2023, 38(5): 569. DOI
[7]	XIANG Y, WU S, YU J, et al. Long-time oxidation behavior of the nearly stoichiometric polycrystalline SiC fibers under air atmosphere at different temperatures. Journal of the European Ceramic Society, 2024, 44(6): 3569.
[8]	KANG W, CHEN J, ZHANG Y, et al. SiC fibers with different diameters exhibiting excellent high-temperature resistance and oxidation resistance. Journal of Materials Research and Technology, 2023, 23: 1559.
[9]	ISHIKAWA T, KOHTOKU Y, KUMAGAWA K, et al. High- strength alkali-resistant sintered SiC fibre stable to 2200 ℃. Nature, 1998, 391(6669): 773.
[10]	TAKEDA M, SAEKI A, SAKAMOTO J I, et al. Effect of hydrogen atmosphere on pyrolysis of cured polycarbosilane fibers. Journal of the American Ceramic Society, 2000, 83(5): 1063.
[11]	BHATT R, SOLA F, EVANS L, et al. Microstructural, strength, and creep characterization of Sylramic™, Sylramic™-iBN and super Sylramic™-iBN SiC fibers. Journal of the European Ceramic Society, 2021, 41(9): 4697.
[12]	CHOLLON G, ALDACOURROU B, CAPES L, et al. Thermal behaviour of a polytitanocarbosilane-derived fibre with a low oxygen content: the Tyranno Lox-E fibre. Journal of Materials Science, 1998, 33(4): 901.
[13]	LIPOWITZ J, RABE J A, ZANGVIL A, et al. Structure and properties of Sylramic^TM silicon carbide fiber -- a polycarbosilane, stoichiometric β-SiC composition. Ceramic Engineering and Science Proceedings, 1997, 18(3): 147.
[14]	JONES R E, PETRAK D, RABE J, et al. Sylramic^TM SiC fibers for CMC reinforcement. Journal of Nuclear Materials, 2000, 283: 556.
[15]	宋永才, 冯春祥, 陆逸, 等. 聚钛碳硅烷的新合成法及其研究. 国防科技大学学报, 1991, (1): 31.
[16]	宋永才. 高含钛量碳化硅纤维的研制. 国防科技大学学报, 1989(2): 101.
[17]	杨一明, 冯春祥, 陆逸, 等. 聚钛碳硅烷及含钛碳化硅纤维的制备. 宇航材料工艺, 1991(3): 20.
[18]	王亦菲, 赵鹏, 宋永才, 等. 富碳的含钛碳化硅纤维先驱体的合成. 宇航材料工艺, 2001(2): 24.
[19]	WANG P, GOU Y, WANG H. Third generation SiC fibers for nuclear applications. Journal of Inorganic Materials, 2020, 35(5): 525. DOI
[20]	SONG L, FAN B, CHEN Y, et al. Ultralight and hyperelastic SiC nanofiber aerogel spring for personal thermal energy regulation. Journal of Advanced Ceramics, 2022, 11(8): 1235.
[21]	WANG P, GOU Y, WANG H, et al. Revealing the formation mechanism of the skin-core structure in nearly stoichiometric polycrystalline SiC fibers. Journal of the European Ceramic Society, 2020, 40(6): 2295.
[22]	CHEN J, ZHANG Y, YAN D, et al. Flexible ultrafine nearly stoichiometric polycrystalline SiC fibers with excellent oxidation resistance and superior thermal stability up to 1900 ℃. Journal of the European Ceramic Society, 2022, 42(5): 1938.
[23]	YAN D, CHEN J, ZHANG Y, et al. B₄C/SiC ceramic hollow microspheres prepared by slurry-coating and precursor conversion method. Journal of the European Ceramic Society, 2022, 42(2): 392.
[24]	ZHANG Y, CHEN J, YAN D, et al. Conversion of silicon carbide fibers to continuous graphene fibers by vacuum annealing. Carbon, 2021, 182: 435.
[25]	ZHANG Y, WANG Y, CHEN J, et al. Effects of PyC coating on SiC fibers after ultra-high temperature annealing. Ceramics International, 2022, 48(5): 6826.
[26]	ZHANG Y, CHEN T, CHEN J, et al. The effects of annealing atmosphere and intrinsic component on high temperature evolution behaviors of SiC fibers. Materials Science and Engineering: A, 2022, 848: 143363.

由聚钛碳硅烷制备高结晶近化学计量比SiC(Ti)纤维

Preparation of Nearly Stoichiometric SiC(Ti) Fibers with Highly Crystalline Microstructure from Polytitanocarbosilane

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吴爽, 苟燕子, 王永寿, 宋曲之, 张庆雨, 王应德. 高温热处理对国产KD-SA型SiC纤维组成结构与力学性能的影响[J]. 无机材料学报, 2023, 38(5): 569-576.
[2]	王袁杰, 裴学良, 李好义, 徐鑫, 何流, 黄政仁, 黄庆. 自由基引发活性聚碳硅烷交联及其在制备SiC纤维中的应用[J]. 无机材料学报, 2021, 36(9): 967-973.
[3]	王西,王克杰,柏辉,宋卓林,王波,张程煜. 化学气相渗透2D-SiC_f/SiC复合材料的蠕变性能及损伤机理[J]. 无机材料学报, 2020, 35(7): 817-821.
[4]	王堋人, 苟燕子, 王浩. 第三代SiC纤维及其在核能领域的应用现状[J]. 无机材料学报, 2020, 35(5): 525-531.
[5]	余汉青, 董志军, 袁观明, 丛野, 李轩科, 罗永明. B-C掺杂SiC纤维的制备及其性能研究[J]. 无机材料学报, 2019, 34(5): 493-501.
[6]	王国栋, 宋永才. 熔融纺丝过程优化制备细直径碳化硅纤维及其对力学性能的影响[J]. 无机材料学报, 2018, 33(7): 721-727.
[7]	穆阳, 邓佳欣, 李皓, 周万城. 两种连续SiC纤维的高温介电及吸波性能对比[J]. 无机材料学报, 2018, 33(4): 427-433.
[8]	左亚卓, 李红, 王少雷, 杨敏, 任慕苏, 孙晋良. (C-SiC)_f/C复合材料的烧蚀性能[J]. 无机材料学报, 2017, 32(11): 1141-1146.
[9]	曹适意, 王军, 王浩, 王小宙. 自由碳的脱除对SiC纤维微观结构和性能的影响[J]. 无机材料学报, 2016, 31(5): 529-534.
[10]	袁钦, 宋永才. 连续SiC纤维和SiC_f/SiC复合材料的研究进展[J]. 无机材料学报, 2016, 31(11): 1157-1165.
[11]	袁文玉, 成来飞, 武恒, 刘永胜. 硅源对植物纤维制备SiC纤维的影响[J]. 无机材料学报, 2015, 30(2): 159-164.
[12]	王得印, 宋永才, 简科. 组成和结构对连续SiC纤维电阻率的影响[J]. 无机材料学报, 2012, 27(2): 162-168.
[13]	张荣军, 杨延清, 沈文涛. 三级化学气相沉积法制备SiC纤维及拉伸性能测试[J]. 无机材料学报, 2010, 25(8): 840-844.
[14]	刘旭光,王应德,王磊,薛金根,蓝新艳. 十字形碳化硅纤维的制备与微波电磁特性[J]. 无机材料学报, 2010, 25(4): 441-444.
[15]	张荣军, 杨延清, 王晨, 沈文涛, 罗贤. 三级化学气相沉积法制备SiC纤维的微观组织结构[J]. 无机材料学报, 2010, 25(12): 1281-1285.