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

doi:10.15541/jim20200695

无机材料学报 ›› 2021, Vol. 36 ›› Issue (9): 967-973.DOI: 10.15541/jim20200695 CSTR: 32189.14.10.15541/jim20200695

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

王袁杰¹^,²(), 裴学良¹(), 李好义³, 徐鑫², 何流¹, 黄政仁¹, 黄庆¹

1.中国科学院宁波材料技术与工程研究所, 先进能源材料工程实验室, 宁波 315201
2.中国科学技术大学纳米科学技术学院, 苏州 215123
3.北京化工大学机电工程学院, 北京 100029

收稿日期:2020-12-03 修回日期:2021-01-25 出版日期:2021-09-20 网络出版日期:2021-03-01
通讯作者: 裴学良, 副研究员. E-mail: peixueliang@nimte.ac.cn
作者简介:王袁杰(1996-), 男, 硕士研究生. E-mail: wangyuanjie@nimte.ac.cn
基金资助:
宁波市科技创新2025重大专项(2019B10091);宁波“3315计划”创新团队项目(2018A-03-A)

Crosslinking of Active Polycarbosilane Initiated by Free Radical and Its Application in the Preparation of SiC Fibers

WANG Yuanjie¹^,²(), PEI Xueliang¹(), LI Haoyi³, XU Xin², HE Liu¹, HUANG Zhengren¹, HUANG Qing¹

1. Engineering Laboratory of Advanced Energy Materials, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
2. Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China
3. College of Mechanical and Electrical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2020-12-03 Revised:2021-01-25 Published:2021-09-20 Online:2021-03-01
Contact: PEI Xueliang, associate professor. E-mail: peixueliang@nimte.ac.cn
About author:WANG Yuanjie(1996-), male, Master candidate. E-mail: wangyuanjie@nimte.ac.cn
Supported by:
Ningbo 2025 Science and Technology Innovation Major Project(2019B10091);Ningbo “3315 Plan” Innovation Team Project(2018A-03-A)

摘要/Abstract

摘要：

在基于先驱体聚碳硅烷转化制备SiC陶瓷纤维过程中, 交联过程是保持纤维形貌和提高陶瓷产率的必要条件。本研究以含丙烯酸酯基的聚碳硅烷(A-PCS)为原料, 通过引入自由基热引发剂在热解升温过程中实现原料的交联成型。采用红外光谱仪(FT-IR)和差示扫描量热仪(DSC)研究了引发剂含量对A-PCS交联程度、交联速率以及热降解速率的影响规律; 采用热失重(TG)、元素分析仪和X射线衍射仪(XRD)分析了陶瓷产率、陶瓷产物组成以及无定形态随温度的变化。研究结果表明: 加入自由基热引发剂可提高A-PCS中的丙烯酸酯基的交联速率, 减少交联阶段的热失重; 将质量百分比为1%自由基热引发剂的A-PCS以5 ℃/min升至250 ℃时, 丙烯酸酯基反应完全, 1500 ℃的陶瓷产率为69.5%; 通过静电纺丝加工工艺可获得直径介于2~5 μm的A-PCS原丝, 并通过后续升温热解转化为SiC纤维; 所得SiC纤维形貌规整、无熔并现象, 且随着热解温度的升高从无定形态向结晶形态转变。

关键词: 活性聚碳硅烷, 静电纺丝, 快速热交联, SiC纤维

Abstract:

In the preparation of SiC ceramic fibers based on precursor polycarbosilane, the crosslinking treatment is a neccessary process to maintain the fiber morphology and improve the ceramic yield. In this study, polycarbosilane containing acrylate group (A-PCS) was used as raw material, and the thermal free radical initiator was introduced to realize the crosslinking formation during the pyrolysis process. FT-IR and DSC were used to analyze the influence of initiator content on crosslinking degree, crosslinking rate and thermal degradation rate of A-PCS; TG, elemental analysis and XRD were used to analyze the evolution of ceramic yield, composition and amorphous change with temperature. The introduction of free radical thermal initiator can improve the crosslinking rate of acrylate group in A-PCS and reduce the thermal weight loss at the crosslinking stage. When free radical thermal initiator (weight percent 1%) was added, the acrylate group was consumed completely after heating to 250 ℃ at 5 ℃/min and the ceramic yield at 1500 ℃ was 69.5%. A-PCS fibers with diameter of 2-5 μm were obtained by electrospinning process, and then transformed into SiC fibers by subsequent pyrolysis. The morphology of the SiC fibers was regular with no fusion phenomenon. In addition, with the increase of pyrolysis temperature, the amorphous SiC fiber can be transformed into crystalline structure.

Key words: active polycarbosilane, electrostatic spinning, rapid thermal crosslinking, SiC fiber

中图分类号:

TQ174

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.

WANG Yuanjie, PEI Xueliang, LI Haoyi, XU Xin, HE Liu, HUANG Zhengren, HUANG Qing. Crosslinking of Active Polycarbosilane Initiated by Free Radical and Its Application in the Preparation of SiC Fibers[J]. Journal of Inorganic Materials, 2021, 36(9): 967-973.

图/表 8

图1 A-PCS自由基交联机理[28]

Fig. 1 Free radical cross-linking mechanism of A-PCS[28]

图2 不同温度下A-PCS-0(a)、A-PCS-0.5(b)、A-PCS-1(c)和A-PCS-2(d)的红外光谱图

Fig. 2 FT-IR spectra of A-PCS-0 (a), A-PCS-0.5 (b), A-PCS-1 (c), and A-PCS-2 (d) at different temperatures

图3 不同温度下A-PCS-0、A-PCS-0.5、A-PCS-1和A-PCS-2中丙烯酸酯基团的反应程度

Fig. 3 Reaction degrees of the acrylate groups of the A-PCS-0, A-PCS-0.5, A-PCS-1, and A-PCS-2 at different temperatures

图4 A-PCS-0、A-PCS-0.5、A-PCS-1和A-PCS-2的DSC(a)和TG(b)曲线

Fig. 4 DSC (a) and TG (b) curves of A-PCS-0, A-PCS-0.5, A-PCS-1, and A-PCS-2

图5 A-PCS-1纤维经不同升温速率加热至250 ℃或1100 ℃后的SEM照片

Fig. 5 Morphologies of A-PCS-1 fiber after being heated to 250 ℃ or 1100 ℃ at different heating rates

图6 PCS、air cured-PCS和A-PCS-1的TG曲线

Fig. 6 TG curves of PCS, air cured-PCS and A-PCS-1

表1 A-PCS-1和air cured-PCS经不同热处理后的元素分析结果

Table 1 Element composition of the A-PCS-1 and air cured-PCS after different thermal treatments

Sample	Pyrolysis temperature/℃	Weight percent /%					Chemical formula
Sample	Pyrolysis temperature/℃	Si	C	O	H	Cl	Chemical formula
A-PCS-1	-	41.78	42.60	6.87	8.75	0.22	SiC_2.43O_0.29H_5.98Cl_0.04
	1100	56.44	36.70	6.86	0	0	SiC_1.52O_0.21
	1500	59.59	36.90	3.52	0	0	SiC_1.45O_0.10
Air cured-PCS	-	45.84	39.00	7.86	7.30	0	SiC_1.99O_0.30H_4.47
	1100	58.58	32.50	8.92	0	0	SiC_1.30O_0.27
	1500	65.12	33.00	1.88	0	0	SiC_1.19O_0.05

图7 (a)A-PCS-1纤维经1500 ℃热解后的形貌; (b)由A-PCS-1转化所得SiC纤维的XRD图谱

Fig. 7 (a) Morphology of A-PCS-1 fiber after being heated to 1500 ℃; (b) XRD patterns of SiC fiber derived from A-PCS-1

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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

Crosslinking of Active Polycarbosilane Initiated by Free Radical and Its Application in the Preparation of SiC Fibers

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