SiC/SiC复合材料基体硼改性方法及其力学性能研究

doi:10.15541/jim20240457

摘要/Abstract

摘要：

SiC/SiC复合材料已成为高超音速飞行器和高推重比航空发动机的核心热结构材料之一。设计含硼陶瓷前驱体结构及组分, 利用其作为前驱体浸渍裂解(PIP)工艺的浸渍剂, 并将一定量的自愈合组元引入基体, 是提升SiC/SiC复合材料抗氧化性能的技术途径之一。本研究采用硼烷吡啶或硼烷三乙胺作为硼源, 与固态聚碳硅烷(PCS)二甲苯溶液复配, 制备得到硼改性PCS溶液。以此作为PIP工艺浸渍剂, 分别制备了不同基体硼改性SiC/PyC(热解碳)/SiC复合材料, 并研究了硼改性PCS衍生陶瓷的理化性质以及基体硼改性前后SiC/PyC/SiC复合材料的物理及力学性能。研究结果表明, 适量的硼烷吡啶及硼烷三乙胺作为硼源加入固态PCS溶液中, 可在其衍生陶瓷中有效引入硼异质元素。与未改性PCS相比, 硼改性PCS(BP-1和BP-2)的陶瓷产率更高, 衍生陶瓷均呈半结晶β-SiC结构, 其中硼异质元素引入量分别为1.7%和2.2%(质量分数)。与未改性复合材料相比, 基体改性SiC/SiC复合材料密度、显气孔率以及断裂韧性等变化不大, 但弯曲模量从116 GPa提升至132 GPa。另外, 单独采用硼烷吡啶作为硼源所制备的改性复合材料弯曲强度为658 MPa, 与未改性复合材料弯曲强度(643 MPa)相近且离散系数更低。这些结果为基体硼改性SiC/SiC复合材料的制备及高性能SiC/SiC复合材料热端部件的研制提供了重要参考。

关键词: SiC/SiC复合材料, 硼烷, 固态聚碳硅烷, 基体硼改性, 力学性能

Abstract:

SiC/SiC composites have emerged as essential thermal structure materials for development of hypersonic vehicles and high thrust-to-weight ratio aero-engines. Design and utilization of boron-containing ceramic precursors as impregnation agents for precursor infiltration and pyrolysis (PIP) to introduce self-healing components into matrix represent a key strategy for enhancing the antioxidant properties of SiC/SiC composites. Here, borane pyridine or borane triethylamine were utilized as boron sources and subsequently mixed with a solid polycarbosilane (PCS) xylene solution to prepare different boron-modified PCS solutions. These solutions were used as PIP impregnation agents to fabricate various boron-modified SiC/PyC (pyrolytic carbon)/SiC composites. The physicochemical properties of boron-modified PCS-derived ceramics, along with the physical and mechanical properties of SiC/PyC/SiC composites before and after matrix boron modification, were investigated. Results demonstrated that addition of appropriate amounts of borane pyridine and borane triethylamine as boron sources in solid PCS solutions effectively introduced boron as a heterogeneous element into the derived SiC ceramics. Compared to PCS, the boron-modified PCS solutions (BP-1 and BP-2) exhibited increased ceramic yields. The derived ceramics exhibited a semi-crystalline β-SiC structure, with boron element contents of 1.7% and 2.2% (in mass), respectively. In contrast to unmodified composite, the boron-modified SiC/SiC composites exhibited negligible changes in density, apparent porosity, and fracture toughness. However, the flexural modulus increased from 116 GPa to 132 GPa. Furthermore, the flexural strength of the modified composite using borane pyridine alone as boron source was 658 MPa, comparable to the unmodified composite's strength of 643 MPa, but with a reduced dispersion coefficient. All above data demonstrate that borane pyridine can be used as boron source for preparation of boron-modified SiC/SiC composites, providing valuable insights for developing high-performance SiC/SiC composite hot-end components.

Key words: SiC/SiC composite, borane, polycarbosilane, matrix boron modification, mechanical property

中图分类号:

TQ174

陈义, 邱海鹏, 陈明伟, 徐昊, 崔恒. SiC/SiC复合材料基体硼改性方法及其力学性能研究[J]. 无机材料学报, 2025, 40(5): 504-510.

CHEN Yi, QIU Haipeng, CHEN Mingwei, XU Hao, CUI Heng. SiC/SiC Composite: Matrix Boron Modification and Mechanical Properties[J]. Journal of Inorganic Materials, 2025, 40(5): 504-510.

图/表 12

表1 SiC/SiC复合材料编号及其浸渍剂类型

Table 1 SiC/SiC composite numbers and their impregnating agent types

Entry	Impregnating agent type	Composite label
1	PCS 50% xylene solution	C0
2	BP-1 solution	C1
3	BP-2 solution	C2

图1 SiC/SiC复合材料制备流程图

Fig. 1 Flow chart of SiC/SiC composite preparation

表2 陶瓷前驱体类型及其管式炉裂解转化陶瓷产率

Table 2 Types of ceramic precursor and their tube furnace ceramic yields

Entry	Precursor type	Ceramic yield/%
1	PCS 50% xylene solution	68
2	BP-1 solution	79
3	BP-2 solution	81
4	Borane pyridine	49
5	Borane pyridine 10% xylene solution	18

图2 典型PCS分子结构(a)及其与硼烷吡啶、硼烷三乙胺可能的交联网络示意图(b)

Fig. 2 Typical PCS molecular structure (a) and its possible crosslinked network with borane pyridine and borane triethylamine (b)

图3 硼烷吡啶、PCS、BP-1和BP-2衍生陶瓷的XRD谱图

Fig. 3 XRD patterns of borane pyridine, PCS, BP-1 and BP-2 derived ceramics

表3 陶瓷前驱体类型及其衍生陶瓷元素含量(质量分数)

Table 3 Types of ceramic precursor and element contents (in mass) of derived ceramic

Entry	Precursor type	O/%	C/%	Si/%	B/%	N/%
1	PCS	1.1	39.9	59.0	0	0
2	BP-1	1.5	42.1	53.3	1.7	1.4
3	BP-2	1.2	32.8	61.0	2.2	2.8

图4 PCS、BP-1和BP-2制备SiC/SiC复合材料过程中的增重率

Fig. 4 Weight gain rates during the preparation of SiC/SiC composites using PCS, BP-1 and BP-2

表4 SiC/SiC复合材料的表观密度及显气孔率

Table 4 Apparent density and porosity of SiC/SiC composites

Entry	SiC/SiC composite	Density/ (g·cm^-3)	Porosity/%
1	C0	2.37±0.01	7.80±0.72
2	C1	2.35±0.02	8.40±1.02
3	C2	2.38±0.03	6.27±0.88

图5 SiC/SiC复合材料C0~C2断口纤维直径及PyC界面层厚度

Fig. 5 Fiber diameter and PyC interphase thickness of SiC/SiC composites C0-C2

图6 SiC/SiC复合材料C0~C2室温弯曲应力-应变曲线

Fig. 6 Flexural stress-strain curves of SiC/SiC composites C0-C2 at room temperature

图7 SiC/SiC复合材料C0~C2的室温弯曲强度(a)、弯曲模量(b)及断裂韧性(c)

Fig. 7 (a) Flexural strength, (b) flexural modulus and (c) fracture toughness of SiC/SiC composites C0-C2 at room temperature

图8 SiC/SiC复合材料C0~C2的断口形貌

Fig. 8 Fracture morphologies of SiC/SiC composites C0-C2

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