陶瓷前驱体配比对Si-Zr-B掺杂沥青基炭材料抗氧化性能的影响

doi:10.15541/jim20150647

无机材料学报 ›› 2016, Vol. 31 ›› Issue (12): 1311-1319.DOI: 10.15541/jim20150647

陶瓷前驱体配比对Si-Zr-B掺杂沥青基炭材料抗氧化性能的影响

张旭^1,2, 董志军^1,2, 袁观明^1,2, 丛野^1,2, 李轩科^1,2,3

(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中心, 长沙 410082)

收稿日期:2015-12-22 修回日期:2016-02-04 出版日期:2016-12-16 网络出版日期:2016-11-23
作者简介:张旭(1991–), 男, 硕士研究生. E-mail: 15827071494@sina.cn
基金资助:
国家自然科学基金(91016003, 51352001, 51372177)

Effects of Ceramic Precursor Ratio on Antioxidation Properties of Pitch-based Carbon Materials Doped with Si-Zr-B

ZHANG Xu^1,2, DONG Zhi-Jun^1,2, YUAN Guan-Ming^1,2, CONG Ye^1,2, LI Xuan-Ke^1,2,3

(1. The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and Technology, Wuhan 430081, China; 2. Hubei Province Key Laboratory of Coal Conversion & New Carbon Materials, Wuhan University of Science and Technology, Wuhan 430081, China; 3. The Research Center for Advanced Carbon Materials, Hunan Unirersity, Changsha 410082, China)

Received:2015-12-22 Revised:2016-02-04 Published:2016-12-16 Online:2016-11-23
About author:ZHANG Xu. E-mail: 15827071494@sina.cn
Supported by:
National Natural Science Foundations of China(91016003, 51352001, 51372177)

摘要/Abstract

摘要：

以SiC、ZrC、ZrB₂前驱体和二甲苯可溶煤沥青为原料共裂解制备了Si-Zr-B掺杂沥青, 掺杂沥青经共炭化、冷压成型以及高温热处理得到了Si-Zr-B掺杂沥青基炭材料。采用XRD、SEM、EDS等手段分析了掺杂沥青基炭材料的组成和微观形貌, 并研究了其在1500℃静态空气环境中的氧化行为。结果表明, 随着SiC前驱体含量的降低, Si-Zr-B掺杂沥青基炭材料的失重率呈现先减少后增大的趋势, 当原料中SiC、ZrC和ZrB₂前驱体质量比为1:2:1时, 所制备的样品具有较好的抗氧化性能, 它在1500℃氧化4 h, 失重为27.5wt%, 氧化深度为0.7 mm。在Si-Zr-B掺杂沥青基炭材料表面氧化形成的致密的SiO₂-ZrO₂-B₂O₃玻璃态阻氧层可以有效降低氧化性气氛向材料内部扩散的速率, 提高其抗氧化性能。

关键词: Si-Zr-B, 掺杂, 沥青基炭材料, 抗氧化性能

Abstract:

The Si-Zr-B doped coal-tar pitch was synthesized by co-pyrolysis of xylene soluble pitch, silicon carbide precursor, zirconium boride precursor, and zirconium carbide precursor. The pitch-based carbon materials doped with Si-Zr-B were prepared through co-carbonization, cold moulding and followed by high temperature heat treatment from the obtained Si-Zr-B doped coal-tar pitch. The phase composition and microstructure of the carbon materials were characterized by XRD, SEM and EDS. The oxidation behavior of specimens was tested at 1500℃ in static air. The results show that weight loss of the doped carbon materials is increased firstly and then decreased with the decrease of content of silicon carbide precursor in Si-Zr-B doped coal-tar pitch. The doped carbon materials obtained from Si-Zr-B doped coal-tar pitch, with a mass ratio of the polycarbosilane, zirconium carbide precursor and zirconium boride precursor at 1:2:1, shows an excellent oxidant resistance. After oxidation in air at 1500℃ for 4 h, its weight loss and oxidation depth is 27.5wt% and 0.7 mm, respectively. A dense SiO₂-ZrO₂-B₂O₃ glassy oxide layer which formed during oxidation in air can effectively reduce the rate of oxygen diffusion and thus improve the oxidation resistance of the carbon materials derived from the doped coal-tar pitch.

Key words: Si-Zr-B, doping, pitch-based carbon material, antioxidation properties

中图分类号:

TB332

张旭, 董志军, 袁观明, 丛野, 李轩科. 陶瓷前驱体配比对Si-Zr-B掺杂沥青基炭材料抗氧化性能的影响[J]. 无机材料学报, 2016, 31(12): 1311-1319.

ZHANG Xu, DONG Zhi-Jun, YUAN Guan-Ming, CONG Ye, LI Xuan-Ke. Effects of Ceramic Precursor Ratio on Antioxidation Properties of Pitch-based Carbon Materials Doped with Si-Zr-B[J]. Journal of Inorganic Materials, 2016, 31(12): 1311-1319.

图/表 11

表1 Si-Zr-B掺杂沥青基炭材料的元素组成

Table 1 Element contents of Si-Zr-B doped pitch-based carbon materials

Sample	C/wt%	Si/wt%	Zr/wt%	B/wt%
SZB0	100	0	0	0
SZB411	66.3	25.2	7.6	0.9
SZB211	66.9	19.8	11.9	1.4
SZB121	63.5	9.9	23.9	2.7
SZB141	57.8	6.3	30.4	3.5

图1 不同温度后续热处理得到的掺杂沥青基炭材料的XRD图谱

Fig. 1 XRD patterns of the doped coal-pitch based carbon materials after heat-treatment at different temperatures

图2 Si-Zr-B掺杂沥青基炭材料的XRD谱图

Fig. 2 XRD patterns of pitch-based carbon materials doped with Si-Zr-B

图3 1600℃热处理得到的试样SZB211的表面元素分布

Fig. 3 Elemental analysis results of the specimen SZB211 after heat-treatment at 1600℃^(a) SEM image of SZB211; (b) Boron, (c) Carbon; (d) Sillion; (e) Zirconium

图4 1600℃热处理得到的Si-Zr-B掺杂沥青基炭材料的SEM照片

Fig. 4 Typical SEM images of pitch-based carbon materials doped with Si-Zr-B after heat-treatment at 1600℃^(a) SZB0; (b,c) SZB411; (d) SZB211; (e,f) SZB121; (g,h) SZB141

图5 Si-Zr-B掺杂沥青基炭材料在1500℃空气中氧化4 h后的光学照片

Fig. 5 Optical pictures of pitch-based carbon materials doped with Si-Zr-B after oxidation at 1500℃ for 4 h in air

图6 Si-Zr-B掺杂沥青基炭材料在1500℃空气中氧化4 h后的截面光学照片

Fig. 6 Optical pictures of the transverse section of pitch- based carbon materials doped with Si-Zr-B after oxidation at 1500℃ for 4 h in air

图7 Si-Zr-B掺杂沥青基炭材料在1500℃空气中的氧化失重曲线

Fig. 7 Oxidation weight loss curves of pitch-based carbon materials doped with Si-Zr-B after oxidation at 1500℃ in air

图8 Si-Zr-B掺杂沥青基炭材料在1500℃空气中氧化4 h后样品表面的XRD图谱

Fig. 8 XRD patterns of pitch-based carbon materials doped with Si-Zr-B after oxidation at 1500℃ for 4 h in air

图9 Si-Zr-B掺杂沥青基炭材料在1500℃空气中氧化4 h后表面的SEM照片

Fig. 9 Typical SEM images of pitch-based carbon materials doped with Si-Zr-B after oxidation at 1500℃ in air for 4 h^(a) SZB411; (b) SZB211; (c) SZB121; (d) SZB14

图10 Si-Zr-B掺杂沥青基炭材料在1500℃空气中氧化4 h后的截面线扫描EDS谱图

Fig. 10 Cross section linear EDS analysis of pitch-based carbon materials doped with Si-Zr-B after oxidation at 1500℃ for 4 h in air^(a) SZB411; (b) SZB211; (c) SZB121; (d) SZB141

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陶瓷前驱体配比对Si-Zr-B掺杂沥青基炭材料抗氧化性能的影响

Effects of Ceramic Precursor Ratio on Antioxidation Properties of Pitch-based Carbon Materials Doped with Si-Zr-B

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