低密度碳粘接碳纤维复合材料(CBCF)抗氧化改性研究

doi:10.15541/jim20170445

摘要/Abstract

摘要：

以全氢聚硅氮烷(PHPS)为原料, 采用浸渍-热转化方法, 在低密度碳粘接碳纤维复合材料(CBCF)中短切碳纤维表面成功包覆硅氧氮(SiON)涂层。采用扫描电子显微镜(SEM)、能量色散X射线光谱(EDS)等分析测试手段对碳纤维表面的SiON涂层进行了形貌和物相分析, 结果表明: 涂层主要由Si、O、N元素组成, 在PHPS浓度为3wt%和5wt%条件下制备的涂层均匀、致密, 随着PHPS浓度的提高, 涂层厚度增加, 但易发生结块。当PHPS浓度为10wt%和20wt%时, 制备的SiON涂层出现结块并且存在裂纹。采用热重分析和等温氧化实验对纯CBCF和SiON涂层改性的CBCF复合材料抗氧化性能进行考核, 结果显示碳纤维表面包覆SiON涂层能够显著提高CBCF复合材料的抗氧化性, 随着PHPS浓度增大, 低密度CBCF复合材料抗氧化性能显著提高。

关键词: 全氢聚硅氮烷, 碳粘接碳纤维复合材料, 浸渍-热转化法, SiON涂层, 抗氧化

Abstract:

Perhydropolysilazane (PHPS) derived SiON coatings were deposited on surface of chopped carbon fiber in carbon-bonded carbon fiber (CBCF) composite by precursor infiltration-thermal (PIT) conversion method. Morphology and elemental analysis of SiON coating were investigated by SEM and EDS. The results show that the coatings are uniform, dense and mainly composed of Si, O and N elements. Meanwhile, the coating gets thicker with the increasing concentration of PHPS, but tends to agglomerate in the opening pores, especially when the concentration of PHPS reaches 10wt% and 20wt%, obvious agglomeration emerges in the opening pores. Meanwhile, cracks appear in the coating on the carbon fibre surface. Finally, oxidation resistance of CBCF composites treated by SiON coating was studied by TGA analysis and isothermal oxidation assessment. The results show that SiON coatings deposited on the carbon fiber surface in CBCF composite can remarkably enhance the oxidation resistance of CBCF, and the oxidation resistance increases with the increasing concentration of PHPS.

Key words: perhydropolysilazane, carbon-bonded carbon fiber (CBCF), precursor infiltration thermal conversion (PIT), SiON coating, oxidation resistance

中图分类号:

TQ174

师建军, 张宗波, 冯志海, 张大海, 王筠, 徐彩虹. 低密度碳粘接碳纤维复合材料(CBCF)抗氧化改性研究[J]. 无机材料学报, 2018, 33(7): 728-734.

SHI Jian-Jun, ZHANG Zong-Bo, FENG Zhi-Hai, ZHANG Da-Hai, WANG Yun, XU Cai-Hong. Modification of Oxidation Resistance for Low Density Carbon-bonded Carbon Fiber (CBCF) Composite[J]. Journal of Inorganic Materials, 2018, 33(7): 728-734.

图/表 13

图1 高孔隙率碳粘接碳纤维复合材料(CBCF)外观照片(a)和SEM照片(b)

Fig. 1 Optical picture (a) and SEM micrograph (b) of high porosity carbon-bonded carbon fiber (CBCF) composite

图2 PHPS前驱体在空气中的转化过程

Fig. 2 Conversion process of PHPS precursor in air

图3 未固化和100℃固化1 h后PHPS涂层的红外谱图

Fig. 3 FT-IR spectra of PHPS uncured and cured at 100℃ for 1 h

图4 不同PHPS浓度下制备SiON涂层的EDS图谱

Fig. 4 EDS spectra of SiON coatings prepared at different PHPS concentrations

表1 CBCF中碳纤维表面各元素含量

Table 1 Contents of elements on the surface of uncoated and coated carbon fiber

Samples	Contents of elements/wt%(at%)
Samples	Si	O	N	C
CBCF	0.72(0.32)	5.76(4.41)	0.73(0.64)	92.79(94.64)
PHPS3	13.65(6.47)	5.81(4.83)	2.97(2.82)	77.56(85.88)
PHPS5	13.76(6.64)	13.15(11.14)	1.67(1.62)	71.41(80.60)
PHPS10	13.51(6.41)	6.56(5.45)	2.59(2.46)	77.34(85.65)
PHPS20	13.72(6.65)	5.71(4.78)	2.51(2.43)	78.06(86.15)

图5 不同PHPS浓度下CBCF中碳纤维表面涂层的SEM照片

Fig. 5 SEM images of the coatings on carbon fiber surface in cured CBCF composite at different concentrations of PHPS (a) PHPS3; (b) PHPS5; (c) PHPS10; (d) PHPS20

表2 不同PHPS浓度制备的涂层厚度和CBCF复合材料密度

Table 2 Coating thickness and volume densities of the CBCFs prepared at different concentrations of PHPS

Samples	CBCF	PHPS3	PHPS5	PHPS10	PHPS20
Density/(g•cm^-3)	0.22	0.23	0.25	0.29	0.33
Coating thickness/µm	0	0.26	0.32	0.33	0.41

图6 SiON涂层包覆的CBCF复合材料在空气中的热失重(TGA)曲线

Fig. 6 Weight loss curves of CBCF composites coated with SiON coatings

表3 不同PHPS浓度下制备的SiON涂层包覆CBCF复合材料在空气中的热失重数据

Table 3 TGA data of CBCF composites coated by SiON coatings prepared with different PHPS concentrations at air

Samples	CBCF	PHPS3	PHPS5	PHPS10	PHPS20	PHPS100
W ^*/%	0	6.0	14.5	26.2	57.6	-
T_d5/℃	442	644	649	650	653	-
T_d10/℃	506	656	659	660	667	-
Residue/ (1000℃, %)	0	8.6	17.8	30.8	52.5	105.4

图7 在不同温度下PHPS改性的CBCF复合材料等温氧化质量变化曲线

Fig. 7 Mass changes of CBCF composites modified by PHPS after isothermal oxidation tests at different temperatures

图8 PHPS20试样经550℃等温氧化实验后XPS元素分析结果

Fig. 8 XPS plots of PHPS20 after isothermal oxidation assessments

图9 经620℃等温氧化实验后CBCF复合材料的光学照片

Fig. 9 Optical images of CBCF composites after isothermal oxidation tests at 620℃(a) CBCF; (b) PHPS20

图10 经620℃等温氧化实验后PHPS20试样的XRD图谱

Fig. 10 XRD pattern of PHPS20 after isothermal-oxidation test at 620℃

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