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

参考文献 20

[1]	杨连, 黎阳, 洪流 , 等. 功能化碳化硅纤维研究进展. 人工晶体学报, 2016,45(5):1397-1403.
[2]	班国东, 刘朝辉, 叶圣天 , 等. 新型涂覆型雷达吸波材料的研究进展. 表面技术, 2016,45(6):140-146. DOI URL
[3]	宋永才, 王娟, 冯春祥 . 由PDMS与PVC共热解聚碳硅烷制备SiC-C纤维. 材料研究学报, 2004,18(3):295-300. DOI URL
[4]	ZUO X, DONG Z, LI W , et al. Oxidation behavior of carbon-silicon and carbon-boron-silicon alloys derived from solvent-soluble silicon and boron-silicon-doped coal-tar pitches. Materials and Technology, 2014,48(1):59-66.
[5]	BERNARD S, MAJOULET O, SANDRA F , et al. Direct synthesis of periodic mesoporous silicoboron carbonitride frameworks via the nanocasting from ordered mesoporous silica with boron-modified polycarbosilazane. Advanced Engineering Materials, 2013,15(3):134-140. DOI URL
[6]	HANG S X, HAO S C, ZHU Y . Preparation and properties of pinacolborane modified polycarbosilane as SiC fiber precursor. Journal of Inorganic & Organometallic Polymers & Materials, 2015,25(6):1-5. DOI URL
[7]	XU X H, MAO Y, CHEN F , et al. Effects of oxidation cross-linking and sintering additives (TiN, B) on the formation and heat-resistant performance of polymer-derived SiC (Ti, B) films. Ceramics International, 2016,42(7):8636-8644. DOI URL
[8]	LEE J, BUTT D P, BANEY R H , et al. Synthesis and pyrolysis of novel polysilazane to SiBCN ceramic. Journal of Non-Crystalline Solids, 2005,351(37):2995-3005. DOI URL
[9]	GUO A, ROSO M, MODESTI M , et al. Characterization of porosity, structure, and mechanical properties of electrospun SiOC fiber mats. Journal of Materials Science, 2015,50(12):4221-4231. DOI URL
[10]	TANG Y, WANG J, LI X D , et al. Preceramic polymer for SiBNC fiber via one-step condensation of silane, BCl₃, and silazane. Journal of Applied Polymer Science, 2010,110(2):921-928. DOI URL
[11]	FU Q, LI H, S HI X , et al. Microstructure and growth mechanism of SiC_w hiskers on carbon/carbon composites prepared by CVD. Materials Letters, 2005,59(19/20):2593-2597. DOI URL
[12]	HEMIDA A T, TENAILLEAU H, BARDEAU L , et al. A quasi-stoic hiometric SiC-based experimental fibre obtained from a boron- doped polycarbosilane precursor. Journal of Materials Science, 1997,32(21):5791-5796.
[13]	CAO F, LI X D, KIM D P . Efficient curing of polymet hylsilane by borazine and reaction mechanism study. Journal of Organometallic Chemistry, 2003,688(1):125-131. DOI URL
[14]	YUAN QIN, SONG YONG-CAI . Effect of SiC_xO_y decompositim on densification of SiCO(Al) fibers during sintering process. Journal of Inorganic Materials, 2016,31(12):1320-1326. DOI URL
[15]	CHOLLON G, CZERNIAK M, PAILLER R , et al. A model SiC- based fibre with a low oxygen content prepared from a polycarbosilane precursor. Journal of Materials Science, 1997,32(4):893-911. DOI URL
[16]	CINIBULK M K, PART HASARAT HY T A . Characterization of oxidized polymer-derived SiBCN fibers. Journal of the American Ceramic Society, 2001,84(10):2197-2202. DOI URL
[17]	MULLER A, ZERN A, GERSTEL P , et al. Boron-modified poly (propenylsilazane)-derived Si-B-C-N ceramics: preparation and high temperature properties. Journal of the European Ceramic Society, 2002,22(9/10):1631-1643. DOI URL
[18]	LIPOWITZ J . Structure and properties of ceramic fibers prepared from organosilicon polymers. Journal of Inorganic & Organometallic Polymers, 1991,1(3):277-297. DOI URL
[19]	KOBAYAS HI K, MAEDA K, SANO H , et al. Formation and oxidation resistance of the coating formed on carbon material composed of B₄C-SiC powders. Carbon, 1995,33(4):397-403. DOI URL
[20]	WU H, ZHANG W . Fabrication and properties of ZrB₂-SiC-BN machinable ceramics. Journal of the European Ceramic Society, 2010,30(4):1035-1042. DOI URL

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	沈浩, 陈倩倩, 周渤翔, 唐晓东, 张媛媛. A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化[J]. 无机材料学报, 2024, 39(9): 1022-1028.
[2]	程俊, 张家伟, 仇鹏飞, 陈立东, 史迅. P掺杂β-FeSi₂材料的制备与热电输运性能[J]. 无机材料学报, 2024, 39(8): 895-902.
[3]	赵志翰, 郭鹏, 魏菁, 崔丽, 刘山泽, 张文龙, 陈仁德, 汪爱英. Ti-DLC薄膜压阻性能及载流子输运行为研究[J]. 无机材料学报, 2024, 39(8): 879-886.
[4]	李家琪, 李小松, 李煊赫, 朱晓兵, 朱爱民. 暖等离子体合成过渡金属掺杂氧化锰析氧电催化剂[J]. 无机材料学报, 2024, 39(7): 835-844.
[5]	蔡飞燕, 倪德伟, 董绍明. 高熵碳化物超高温陶瓷的研究进展[J]. 无机材料学报, 2024, 39(6): 591-608.
[6]	刘国昂, 王海龙, 方成, 黄飞龙, 杨欢. B₄C含量对(Ti_0.25Zr_0.25Hf_0.25Ta_0.25)B₂-B₄C陶瓷力学性能及抗氧化性能的影响[J]. 无机材料学报, 2024, 39(6): 697-706.
[7]	郑斌, 康凯, 张青, 叶昉, 解静, 贾研, 孙国栋, 成来飞. 前驱体转化陶瓷法制备Ti₃SiC₂陶瓷及其热稳定性研究[J]. 无机材料学报, 2024, 39(6): 733-740.
[8]	张幸红, 王义铭, 程源, 董顺, 胡平. 超高温陶瓷复合材料研究进展[J]. 无机材料学报, 2024, 39(6): 571-590.
[9]	TAM YU Puy Mang, 徐愉, 高泉浩, 周海琼, 张振, 尹浩, 李真, 吕启涛, 陈振强, 马凤凯, 苏良碧. 掺铒CaF₂、SrF₂、PbF₂晶体的光谱性能与团簇结构研究[J]. 无机材料学报, 2024, 39(3): 330-336.
[10]	周云凯, 刁亚琪, 王明磊, 张宴会, 王利民. 聚苯胺改性Ti₃C₂(OH)₂抗氧化性的第一性原理计算研究[J]. 无机材料学报, 2024, 39(10): 1151-1158.
[11]	李秋实, 殷广明, 吕伟超, 王怀尧, 李婧琳, 杨红光, 关芳芳. Na⁺/g-C₃N₄材料的制备及光催化降解亚甲基蓝机理[J]. 无机材料学报, 2024, 39(10): 1143-1150.
[12]	戴乐, 刘洋, 高轩, 王书豪, 宋雅婷, 唐明猛, 刘丽莎, 汪尧进. 浓度梯度掺杂实现BiFeO₃薄膜自极化[J]. 无机材料学报, 2024, 39(1): 99-106.
[13]	苏楠, 邱介山, 王治宇. 高容量氟掺杂碳包覆纳米硅负极材料: 气相氟化法制备及其储锂性能[J]. 无机材料学报, 2023, 38(8): 947-953.
[14]	王新玲, 周娜, 田亚文, 周明冉, 韩静茹, 申远升, 胡执一, 李昱. SnS₂/ZIF-8衍生二维多孔氮掺杂碳纳米片复合材料的锂硫电池性能研究[J]. 无机材料学报, 2023, 38(8): 938-946.
[15]	李光兰, 王天宇, 刘一辰, 路中发. 片状NiFeCo-LDH-Ti₆C_3.75复合催化剂的制备及电催化析氧性能[J]. 无机材料学报, 2023, 38(7): 823-829.