聚醚酰亚胺耐热大分子偶联剂增强增韧石英纤维/含硅芳炔复合材料

doi:10.7503/cjcu20170149

摘要/Abstract

摘要：

设计并制备了一种新型乙炔基封端聚醚酰亚胺大分子偶联剂(BDA-K), 探究了其对石英纤维(QF)/含硅芳炔(PSA)复合材料界面增强增韧的效果. 在常温下, 加入大分子偶联剂的复合材料层间剪切强度、弯曲强度和缺口冲击强度分别提高了54.1%, 59.0%和23.8%; 在250 ℃时, 层间剪切强度和弯曲强度保留率分别达到89.0%和89.6%, 500 ℃时保留率分别达到63.3%和67.9%. 傅里叶变换红外光谱和X光电子能谱分析结果表明, BDA-K参与PSA的交联固化, 与QF发生有效化学键合; 热重分析(TGA)结果表明, 由于BDA-K的分子结构中引入耐热官能团酰亚胺环等, 使其大分子偶联剂的T_d5达到489 ℃; 扫描电子显微镜(SEM)结果表明, 柔软的大分子层提供了适中的界面结合, 使强度和韧性都得到提高.

关键词: 石英纤维, 含硅芳炔, 聚醚酰亚胺, 大分子偶联剂, 界面增强增韧

Abstract:

A novel acetylene-terminated polyetherimide macromolecular coupling agent(BDA-K) was designed and synthesized, and its effects on the interfacial reinforcement and toughness of the quartz fiber(QF) reinforced silicon-containing aryl-alkyne(PSA) matrix composites were investigated. The interlaminar shear strength(ILSS), flexural strength and notched impact strength increased by 54.1%, 59.0% and 23.8% compared with those of untreated at room temperature. The retention of ILSS and flexural strength reached 89.0% and 89.6% at 250 ℃ and 63.3% and 67.9% at 500 ℃, respectively. The FTIR and XPS spectra indicate that BDA-K takes part in PSA curing and effective chemical bonds form between BDA-K and QF. Owing to the introduction of heat-proof groups i.e. the imide rings to BDA-K backbone, TGA results reveal that the value of T_d5 is up to 489 ℃. The interphase morphologies by SEM show that soft and moderate macromolecule layers constructed between the matrix and the fiber treated with BDA-K, which improves the mechanical strength and toughness of the QF/PSA composites.

Key words: School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China)

中图分类号:

O631.1⁺1

TrendMD:

顾渊博, 扈艳红, 杜磊, 邓诗峰, 周燕, 汝凌傲. 聚醚酰亚胺耐热大分子偶联剂增强增韧石英纤维/含硅芳炔复合材料. 高等学校化学学报, 2017, 38(9): 1670.

GU Yuanbo, HU Yanhong, DU Lei, DENG Shifeng, ZHOU Yan, RU Lingao. Reinforcement and Tougheness of Quartz Fiber/Silicon-containing Arylacetylene with Heat-resistant Polyetherimide Macromolecular Coupling Agent^†. Chem. J. Chinese Universities, 2017, 38(9): 1670.

图/表 10

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Temperature/℃	ILSS/MPa		Retention rate of ILSS		Flexural strength/MPa		Retention rate of flexural strength
Temperature/℃	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K
r. t.	15.9	24.5			197.9	314.6
250	14.1	21.8	88.7	89.0	181.6	281.8	91.8	89.6
500	8.6	15.5	54.1	63.3	121.7	213.5	61.5	67.9

Temperature/℃	ILSS/MPa		Retention rate of ILSS		Flexural strength/MPa		Retention rate of flexural strength
Temperature/℃	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K	Untreated	3.5%BDA-K
r. t.	15.9	24.5			197.9	314.6
250	14.1	21.8	88.7	89.0	181.6	281.8	91.8	89.6
500	8.6	15.5	54.1	63.3	121.7	213.5	61.5	67.9

Sample	Element distribution(%)
Sample	C_1s	N_1s	O_1s	Si_2p
QF	56.26	9.31	21.83	12.60
QF-BDA-K	69.22	6.30	16.87	7.61

Sample	Element distribution(%)
Sample	C_1s	N_1s	O_1s	Si_2p
QF	56.26	9.31	21.83	12.60
QF-BDA-K	69.22	6.30	16.87	7.61

Binding energy/eV	Functional group	QF content(%)	QF-BDA-K content(%)
284.6	—C—C—(C₁_s peak)	56.12	64.81
286.1	—C—N—(C₁_s peak)	15.33	18.13
286.5	—C—OH(C₁_s peak)	21.56	13.23
288.2	—C=O(C₁_s peak)	6.99	3.83
398.3	—N= in a cyclic structure(N₁_s peak)	20.66	5.11
399.7	—NH—CO—(N₁_s peak)	79.34	62.85
400.4	Imide ring(N₁_s peak)		32.04
531.6	—C=O(O₁_s peak)	16.61	14.32
531.9	—Si—O—(O₁_s peak)	35.46	46.90
532.6	—C—OH(O₁_s peak)	5.13	3.79
532.7	SiO₂(O₁_s peak)	42.80	29.13
533.6	C—O—C(O₁_s peak)		5.86
101.5	—Si—O—Si—(Si₂_p peak)		21.46
102.3	—Si—OH(Si₂_p peak)	31.35	27.80
103.3	SiO₂(Si₂_p peak)	68.65	50.74