B-C掺杂SiC纤维的制备及其性能研究

doi:10.15541/jim20180218

无机材料学报 ›› 2019, Vol. 34 ›› Issue (5): 493-501.DOI: 10.15541/jim20180218 CSTR: 32189.14.10.15541/jim20180218

B-C掺杂SiC纤维的制备及其性能研究

余汉青^1,²,董志军^1,²(),袁观明^1,²,丛野^1,²,李轩科³(),罗永明⁴

^1. 武汉科技大学省部共建耐火材料与冶金国家重点实验室, 武汉 430081
^2. 武汉科技大学湖北省煤转化与新型炭材料重点实验室, 武汉 430081
^3. 湖南大学先进炭材料及应用技术湖南省重点实验室, 长沙 410082
^4. 中国科学院化学研究所, 北京 100190

收稿日期:2018-05-04 修回日期:2018-12-17 出版日期:2019-05-20 网络出版日期:2019-05-14
作者简介:余汉青(1991-), 男, 硕士研究生. E-mail:HQYusmile1207@163.com
基金资助:
国家自然科学基金项目(51352001);国家自然科学基金项目(91016003)

Boron-carbon doped Silicon Carbide Fibers: Preparation and Property

Han-Qing YU^1,²,Zhi-Jun DONG^1,²(),Guan-Ming YUAN^1,²,Ye CONG^1,²,Xuan-Ke LI³(),Yong-Ming LUO⁴

^1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China
^2. The Hubei Province Key Laboratory of Coal Conversion & New Carbon Materials, Wuhan University of Science and Technology, Wuhan 430081, China;
^3. Hunan Province Key Laboratory for Advanced Carbon Materials and Applied Technology, Hunan University, Changsha 410082, China
^4. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2018-05-04 Revised:2018-12-17 Published:2019-05-20 Online:2019-05-14
Supported by:
National Natural Science Foundation of China 51352001, 91016003(51352001);National Natural Science Foundation of China 51352001, 91016003(91016003)

摘要/Abstract

摘要：

以聚碳硅烷、聚硼硅氮烷和二甲苯可溶沥青为原料通过低温共混得到了一种B-C掺杂SiC前驱体, 再经熔融纺丝、预氧化以及高温热处理制得B-C掺杂SiC纤维。采用红外光谱(IR)、X射线衍射(XRD)、扫描电镜(SEM)等手段对B-C掺杂SiC前驱体及其纤维的组成和微观结构进行了分析和表征, 主要研究了热处理温度对纤维组成、结构、力学性能和抗氧化性能的影响。结果表明: 硼的引入有效地抑制了高温热处理过程中SiC晶粒的长大, 提高了C掺杂SiC纤维的稳定性; B-C掺杂碳化硅纤维经1600 ℃处理后主要由β-SiC组成, 并含有少量的O、B和N。B-C掺杂SiC纤维抗氧化性能优于C掺杂SiC纤维, 这主要归因于掺杂纤维在高温氧化过程中形成的硼硅酸盐玻璃膜对其内部的沥青炭起到了很好的氧化防护作用。

关键词: 聚碳硅烷, 聚硼硅氮烷, 掺杂, SiC纤维, 抗氧化

Abstract:

The B-C doped SiC precursor was obtained by blending of polycarbosilane, polyborosilicate and xylene soluble pitch at low temperature. The resulted precursor was melt-spun into precursor fibers. The B-C doped silicon carbide fibers were finally obtained by pre-oxidation and high temperature heat-treatment of the precursor fibers successively. The composition and microstructure of B-C doped SiC precursor and its fibers were characterized by IR, XRD and SEM. Effect of the heat-treatment temperature on the composition, structure, mechanic property and oxidation resistance was studied. The results show that the introduction of boron in SiC fibers restrains the growth of SiC grains at high temperature treatment effectively, and simaltaneously improves the thermal stability of the C-doped SiC fibers. B-C doped silicon carbide fibers obtained by heating the pre-oxidized fibers at 1600 ℃ were mainly composed of β-SiC and a small amount of O, B and N. B-C doped SiC fibers ownse better oxidation resistance than the C-doped SiC fibers, which can be attributed to the formation of borosilicate film during the high-temperature oxidation of the B-C doped SiC fibers. This film plays a role effectively in preventing the pith carbon in the doped fibers from oxidation.

Key words: polycarbosilance, polyborosilazane, doping, SiC fiber, anti-oxidation

中图分类号:

TQ343

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.

Han-Qing YU, Zhi-Jun DONG, Guan-Ming YUAN, Ye CONG, Xuan-Ke LI, Yong-Ming LUO. Boron-carbon doped Silicon Carbide Fibers: Preparation and Property[J]. Journal of Inorganic Materials, 2019, 34(5): 493-501.

图/表 11

图1 原料及B-C掺杂SiC前驱体的FT-IR谱图(a)及B-C掺杂SiC前驱体的11B NMR谱图(b)

Fig. 1 FT-IR spectra of raw materials and B-C-doped SiC precursor (a) and 11B NMR spectra of B-C-doped SiC precursor (b)

图2 不同温度热处理得到的C掺杂SiC纤维(a)、B-C掺杂SiC纤维(b)的XRD谱图及热处理温度对掺杂SiC纤维晶粒尺寸的影响(c)

Fig. 2 XRD patterns of C doped SiC fibers (a) and B-C doped SiC fibers (b), dependence of grain size on the heat-treatment temperature for the doped SiC fibers (c)

图3 不同温度热处理得到的C掺杂SiC纤维的SEM照片及EDS图谱 Figure (b) is line scanning for sample in (a), and insets in (c, d) are the corresponding EDS patterns

Fig. 3 SEM images and EDS patterns of C doped SiC fibers after heat treatment at (a, b) 1300,(c) 1400, (d) 1500, and (e) 1600 ℃

图4 不同温度热处理得到的B-C掺杂SiC纤维的SEM照片(a,c~f)、EDS图谱(b)及EDS面扫描元素分布图(g~k) (a, b) 1300 ℃; (c) 1400 ℃; (d) 1500 ℃; (e-k) 1600 ℃

Fig. 4 SEM image s(a, c-f), EDS patterns (b) and EDS mapping (g~k) of B-C doped SiC fibers after heat-treatment at different temperatures

图5 C掺杂及B-C掺杂SiC纤维的拉伸强度随热处理温度变化的关系曲线

Fig. 5 Dependence of tensile strength on the heat-treatment temperature for C doped and B-C doped SiC fibers

表1 不同温度热处理得到的C掺杂SiC纤维的组成

Table 1 Chemical composition of C doped SiC fibers after heat-treatment at different temperatures

Composition/wt%	900 ℃	1300 ℃	1400 ℃	1500 ℃
Si	42.68	51.82	54.98	64.54
C	36.46	31.76	30.87	25.75
O	20.68	16.42	14.15	9.71

表2 不同温度热处理得到的B-C掺杂SiC纤维的组成

Table 2 Chemical composition of B-C doped SiC fibers after heat-treatment at different temperatures

Composition/wt%	900 ℃	1300 ℃	1400 ℃	1500 ℃
Si	47.94	58.73	61.90	71.43
C	34.75	30.32	28.36	23.48
O	16.95	12.58	9.34	4.80
B	0.21	0.22	0.22	0.23
N	0.15	0.15	0.16	0.16

图6 C掺杂(a)、B-C掺杂(b)SiC纤维在空气中1000、1200、1400 ℃等温氧化1 h后的XRD图谱

Fig. 6 XRD patterns of C doped (a) and B-C doped (b) SiC fibers after isothermal oxidation at 1000, 1200 and 1400 ℃ in air for 1 h

图7 C掺杂SiC纤维在空气中1000 (a)、1200 (b)、1400 ℃ (c)等温氧化1 h后的SEM照片及EDS图谱

Fig. 7 SEM images, EDS patterns of C doped SiC fibers after isothermal oxidation at 1000 ℃ (a), 1200 ℃ (b), and 1400 ℃ (c) in air for 1 h

图8 B-C掺杂SiC纤维在1000 (a)、1200 (b)、1400 ℃ (c, d)等温氧化1 h后的SEM照片

Fig. 8 SEM images of B-C doped SiC fibers after isothermal oxidation at 1000 (a), 1200 (b), 1400 ℃ (c, d) in air for 1 h

图9 1200 ℃氧化1 h后的B-C掺杂SiC纤维XPS宽扫描谱图(a)及Si2p(b)和B1s(c)的高分辨率谱图

Fig. 9 XPS wide scan spectra (a) and high resolution XPS spectra for B1s (b) and Si2p (c) region of the B-C doped SiC fibers after oxidation at 1200 ℃ for 1 h

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B-C掺杂SiC纤维的制备及其性能研究

Boron-carbon doped Silicon Carbide Fibers: Preparation and Property

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