聚硅氮烷原位功能化碳纤维设计及其高温抗氧化性能

邓紫怡; 赵新星; 张建; 余木火; 王刚; 孙泽玉

doi:10.13801/j.cnki.fhclxb.20230418.001

聚硅氮烷原位功能化碳纤维设计及其高温抗氧化性能

doi: 10.13801/j.cnki.fhclxb.20230418.001

东华大学　纤维材料改性国家重点实验室，上海市轻质结构复合材料重点实验室，上海市高性能纤维复合材料省部共建协同创新中心，上海 201020

基金项目: 纤维材料改性国家重点实验室开放课题 (KF2203)，氢能专项；上海市“科技创新行动计划”高新技术领域项目(19511106703)；中央高校基本科研业务费专项资金(2232020G-12)

详细信息

通讯作者:
孙泽玉，博士，讲师，硕士生导师，研究方向为高性能纤维及复合材料　E-mail: sunzeyu@dhu.edu.cn

中图分类号: TQ34；TB332
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出版历程
- 收稿日期: 2022-12-22
- 修回日期: 2023-03-24
- 录用日期: 2023-04-09
- 网络出版日期: 2023-04-18
- 刊出日期: 2023-11-01

In-situ polysilazane modified carbon fiber for high temperature anti-oxidation

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, Shanghai Key Laboratory of Lightweight Structural Composites, Center for Civil Aviation Composites, Donghua University, Shanghai 201620, China

Funds: State Key Laboratory for Modification of Chemical Fibers and Polymer Materials Open Topic (KF2203), Hydrogen Energy Special Project; High-tech Field Projects of Action Plan for Science and Technology Innovation of Shanghai (19511106703); Special Funds for the Basic Scientific Research Expenses of Central Government Universities (2232020G-12)

摘要

摘要: 由于碳纤维在高温含氧的环境下易被氧化，且与基体发生强界面反应而导致其性能劣化，影响了其在复合材料领域的应用。本文通过在碳纤维表面构筑聚丙烯腈(PAN)过渡层及有机聚硅氮烷(OPSZ)陶瓷前驱体层，经低温固化与高温裂解后形成C-Si₃N₄保护涂层，制备了具有高温抗氧化效能的PAN-OPSZ/碳纤维。扫描电镜与能谱仪的结果表明：PAN层的涂覆有助于Si元素在碳纤维表面附着，将PAN溶液的浓度从1%提高到3%，Si元素的相对含量随即从2.81%提高到了8.26%。采用PAN与OPSZ浓度为3wt%制备的PAN-OPSZ/碳纤维的拉伸强度仅比未涂层碳纤维降低了2.08%，表明其未对碳纤维力学性能造成明显降低。制备的PAN-OPSZ/碳纤维的抗氧化能力得到了显著提高，在700℃的空气气氛下失重率低于8wt%，而未涂层碳纤维的失重率高达70wt%。以上结果说明，PAN-OPSZ涂层能有效提高碳纤维的高温抗氧化性，在碳纤维增强复合材料领域具有十分广阔的应用前景。
- 碳纤维表面涂层 /
- 抗氧化性 /
- 聚合物转化陶瓷 /
- 聚硅氮烷 /
- 聚丙烯腈
Abstract: Carbon fiber is easily oxidized in a high-temperature oxygen-containing environment. The strong interfacial reactions with the matrix result in deterioration of their performance, which limits their use in carbon fiber-reinforced composites. In this paper, a C-Si₃N₄ protective coating which has high-temperature anti-oxidation performance was formed by constructing a polyacrylonitrile (PAN) layer and an organopolysilazane (OPSZ) layer on the surface of carbon fibers with curing at low-temperature and cracking at high-temperature. The results of scanning electron microscope and energy dispersive spectrometer show that the coating of PAN layer is helpful for Si element to adhere to the surface of carbon fiber. Increasing the concentration of the PAN solution from 1% to 3%, the relative content of the Si element increased from 2.81% to 8.26%. The tensile strength of PAN-OPSZ/carbon fiber prepared with PAN and OPSZ concentration of 3wt% was only 2.08% lower than that of uncoated carbon fiber, indicating that it did not cause obvious damage to the mechanical properties of carbon fiber. The oxidation resistance of the as-prepared PAN-OPSZ/carbon fibers was significantly improved, with a mass loss of less than 8wt% in an air atmosphere at 700℃, while the mass loss of uncoated carbon fibers was as high as 70wt%. The above results show that the PAN-OPSZ coating can effectively improve the high temperature oxidation resistance of carbon fibers, and has a very broad application prospect in the field of reinforced composites.
- coating of carbon fiber /
- oxidation resistance /
- polymer derived ceramics /
- polysilazane /
- polyacrylonitrile

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图 1 聚丙烯腈(PAN)-有机聚硅氮烷(OPSZ)/碳纤维的制备过程

CFs—Carbon fibers

Figure 1. Process of the preparation of polyacrylonitrile (PAN)-organopolysilazane (OPSZ)/carbon fiber

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图 2 不同热处理温度下的碳纤维单丝拉伸性能

Figure 2. Single-filament tensile properties of carbon fibers at different heat treatment temperatures

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图 3 涂层碳纤维在氮气下1200℃烧结后的SEM图像

Figure 3. SEM images of coated carbon fiber under N₂ up to 1200°C

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图 4 不同裂解温度的PAN-OPSZ/碳纤维的SEM图像：(a) 1200℃；(b) 1450℃；((c), (d)) 1600℃

Figure 4. SEM images of PAN-OPSZ/carbon fiber at various pyrolysis temperature: (a) 1200℃; (b) 1450℃; ((c), (d)) 1600℃

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图 5 涂层碳纤维的面分析：(a) SEM图像； (b) Si元素面分布

Figure 5. EDS analysis of coated carbon fiber: (a) SEM image; (b) Si element surface distribution

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图 6 对比不同碳纤维的XRD图谱：(a) 不同浓度；(b) 不同烧结温度

Figure 6. Comparisons of XRD patterns of carbon fibers: (a) Different concentrations; (b) Various pyrolysis temperature

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图 7 3%PAN涂覆组1450℃烧结后涂层纤维的TG (a)和DTG (b)

dm/dt—Mass change rate of samples per unit time

Figure 7. TG (a) and DTG (b) analyses of 3%PAN-OPSZ/carbon fibers after sintering at 1450℃

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图 8 1450℃烧结后涂层碳纤维的900℃ TG-DTG曲线

Figure 8. 900℃ TG-DTG curves of coated carbon fibers after sintering at 1450℃

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图 9 无涂层和有涂层CF的单丝拉伸强度：(a)不同OPSZ浓度；(b)不同PAN浓度

Figure 9. Single silk tensile strength of uncoated and coated CF: (a) Different OPSZ concentrations; (b) Different PAN concentrations

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表 1 样品名释义

Table 1. Interpretation of samples

Sample	Coating	Heat treatment
Raw CF	—	—
1200℃-CF	—	1200℃ for 2 h
1450℃-CF	—	1450℃ for 2 h
1600℃-CF	—	1600℃ for 2 h
Uncoated CF	—	400℃ for 0.5 h
0%PAN-9%OPSZ/CF	9%OPSZ	—
2%PAN-9%OPSZ/CF	2%PAN and 9%OPSZ	—
0%PAN-3%OPSZ/CF	3%OPSZ	—
1%PAN-3%OPSZ/CF	1%PAN and 3%OPSZ	—
2%PAN-3%OPSZ/CF	2%PAN and 3%OPSZ	—
3%PAN-3%OPSZ/CF	3%PAN and 3%OPSZ	—
3%PAN-5%OPSZ/CF	3%PAN and 5%OPSZ	—
3%PAN-7%OPSZ/CF	3%PAN and 7%OPSZ	—
3%PAN-9%OPSZ/CF	3%PAN and 9%OPSZ	—
1200℃-uncoated CF	—	1200℃ for 2 h
1450℃-uncoated CF	—	1450℃ for 2 h
1200℃-coated CF	3%PAN and 9%OPSZ	1200℃ for 2 h
1450℃-coated CF	3%PAN and 9%OPSZ	1450℃ for 2 h
1600℃-coated CF	3%PAN and 9%OPSZ,	1600℃ for 2 h

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表 2 涂层碳纤维的EDS面分析

Table 2. EDS analysis data of coated CF

Sample	Coating	T/℃	Element	Element/wt%	Atom/at%
1	1%PAN-3%OPSZ/CF	1200	C	85.36	88.97
			Si	2.81	1.25
			O	7.15	5.59
			N	4.69	4.19
2	3%PAN-3%OPSZ/CF	1200	C	74.75	81.74
			Si	8.26	3.86
			O	13.16	10.80
			N	3.83	3.59
3	1%PAN-9%OPSZ/CF	1200	C	82.49	86.92
			Si	3.87	1.75
			O	8.76	6.93
			N	4.87	4.40
4	1%PAN-3%OPSZ/CF	1450	C	80.30	86.74
			Si	7.04	3.26
			O	6.93	4.53
			N	5.73	5.47
5	3%PAN-3%OPSZ/CF	1450	C	70.11	78.29
			Si	11.76	5.61
			O	3.49	2.92
			N	12.79	12.25
6	1%PAN-9%OPSZ/CF	1450	C	71.97	79.04
			Si	7.80	3.66
			O	2.83	2.33
			N	14.25	13.42
Note: T—Temperature.

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表 3 3%PAN涂覆组1450℃烧结后涂层纤维在700℃的热重分析数据

Table 3. Thermogravinmetric analysis data at 700℃ of 3%PAN/carbon fibers after sintering at 1450℃

Sample	T₁/℃	T₂/℃	W₁/wt%	W₂/wt%
Uncoated CF	510	630	15.8	70.4
3%PAN-3%OPSZ/CF	700	700	0.1	7.5
3%PAN-5%OPSZ/CF	700	700	0.8	7.9
3%PAN-7%OPSZ/CF	700	700	0.9	8.2
3%PAN-9%OPSZ/CF	700	700	1.0	6.4
Notes: T₁—Initial decomposition temperature; T₂—Maximum decomposition temperature in the first stage; W₁—Mass loss fraction at 700℃; W₂—Total mass loss fraction.

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表 4 1450℃烧结后的涂层碳纤维在900℃的热重分析数据

Table 4. Thermogravinmetric analysis data at 900℃ of 1450℃-coated carbon fiber

Sample	T₁/℃	W₁/wt%	W₂/wt%	Total weight-lessness time/min
Uncoated CF	705	58.8	100.0	4.50
3%PAN-3%OPSZ/CF	735	30.8	92.6	8.00
3%PAN-5%OPSZ/CF	739	28.4	84.2	8.50
3%PAN-7%OPSZ/CF	750	22.5	87.3	14.25
3%PAN-9%OPSZ/CF	780	13.8	82.0	15.00

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表 5 无涂层和有涂层CF的单丝拉伸性能

Table 5. Single silk tensile performance of uncoated and coated CF

Sample	Tensile strength/ MPa	Standard deviation of tensile strength/MPa	Coefficient of variation (CV) for tensile strength value/%	Relative loss value of tensile strength/%
1450℃-CF	2444	293	11.98	—
1450℃-3%OPSZ/CF	2099	237	11.30	14.11
1450℃-1%PAN-3%OPSZ/CF	2179	305	13.99	10.84
1450℃-2%PAN-3%OPSZ/CF	2278	290	12.74	6.78
1450℃-3%PAN-3%OPSZ/CF	2393	246	11.23	2.08
1450℃-3%PAN-5%OPSZ/CF	2002	189	9.44	18.08
1450℃-3%PAN-7%OPSZ/CF	1496	175	11.69	38.78
1450℃-4%PAN-3%OPSZ/CF	1842	239	12.99	24.63

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