SiCf/SiC复合材料耐高温氟熔盐腐蚀性能研究

doi:10.15541/jim20170010

无机材料学报 ›› 2017, Vol. 32 ›› Issue (11): 1133-1140.DOI: 10.15541/jim20170010

SiC_f/SiC复合材料耐高温氟熔盐腐蚀性能研究

王洪达^1,2,3, 周海军^1,2, 董绍明^1,2, 王震^1,2, 胡建宝^1,2, 冯倩⁴

1. 中国科学院上海硅酸盐研究所, 结构陶瓷与复合材料工程研究中心, 上海 200050;
2. 中国科学院高性能陶瓷和超微结构国家重点实验室, 上海 200050;
3. 中国科学院大学研究生院, 北京 100049;
4. 东华大学, 分析测试中心, 上海 201600

收稿日期:2017-01-05 修回日期:2017-02-22 出版日期:2017-11-20 网络出版日期:2017-10-20
作者简介:王洪达(1989-), 男, 博士研究生. E-mail: whd19890819@163.com
基金资助:
中国科学院战略性先导科技专项(XDA02040203);上海市自然科学基金(14ZR1445800);Strategic Priority Research Programme of the Chinese Academy of Sciences (XDA02040203);Natural Science Foundation of Shanghai, China (14ZR1445800)

Corrosion Behavior of SiC_f/SiC Composites in High Temperature Fluoride Salt Environment

WANG Hong-Da^1,2,3, ZHOU Hai-Jun^1,2, DONG Shao-Ming^1,2, WANG Zhen^1,2, HU Jian-Bao^1,2, FENG Qian⁴

1. Structural Ceramics and Composites Engineering Research Center, Shanghai Institute of Ceramics Chinese Academy of Sciences, Shanghai 200050, China;
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics Chinese Academy of Sciences, Shanghai 200050, China;
3. School of Graduate, University of Chinese Academy of Sciences, Beijing 100049, China;
4. Analysis and Testing Center, Donghua University, Shanghai 201600, China

Received:2017-01-05 Revised:2017-02-22 Published:2017-11-20 Online:2017-10-20

摘要/Abstract

摘要：

实验研究了熔渗(MI)工艺、浸渍-裂解(PIP)工艺和化学气相渗透(CVI)工艺制备SiC_f/SiC复合材料在800℃的氟熔盐(46.5mol% LiF-11.5mol% NaF-42.0mol% KF)中的腐蚀行为, 通过X射线衍射仪、扫描电镜以及能谱仪等表征手段, 对腐蚀前后样品的物相组成和微观结构进行了分析。实验结果表明, 不同工艺获得的SiC基体与高温氟熔盐的相容性与基体组成有关; MI-SiC中的游离Si相以及PIP-SiC和CVI-SiC中的富氧相是SiC基体中的两种腐蚀弱区, 易被熔盐选择性腐蚀; MI-SiC_f/SiC复合材料以纤维束间游离Si基体腐蚀为主, PIP-SiC_f/SiC复合材料基体腐蚀损伤集中在网络状富氧带, CVI-SiC_f/SiC复合材料的腐蚀损伤主要是沉积层间的含氧边界以及由此造成的基体层状剥离。与MI和PIP样品相比, CVI基体纯度高, 结晶度好, 表观腐蚀速率仅为0.0445 μg/(mm²·h), 具有更好的耐氟熔盐腐蚀性能。

关键词: SiC_f/SiC复合材料, 制备工艺, 氟熔盐, 腐蚀行为

Abstract:

Corrosion behavior of SiC_f/SiC composites, which were prepared via molten infiltration(MI), polymer impregnation and pyrolysis(PIP), and chemical vapor infiltration process(CVI), respectively, was studied by immersion in 46.5mol% LiF-11.5mol% NaF- 42.0mol% KF eutectic salt at 800℃. The evolution of phase composition and microstructure was characterized by X-ray diffraction and scanning electron microscope with energy dispersive spectrometer. The SiC matrix of SiC_f/SiC composites, derived from different preparation process, has different compositions and microstructures, leading to various compatibility with fluoride salt at high temperature. Residual free Si in MI-SiC matrix and O-contained phase in PIP-SiC matrix are the weak area with worse corrosion resistance in liquid fluoride salt and will be corroded preferentially in terms of thermodynamic. Due to the higher purity and better crystallinity over the MI-SiC matrix and PIP-SiC matrix, CVI-SiC matrix shows more excellent compatibility with fluoride salt at high temperature and has the smallest corrosion rate of 0.0445 μg/(mm²·h). Least weak area confined to the O-rich boundaries between deposited layers may account for the good corrosion resistance of CVI SiC matrix.

Key words: SiC_f/SiC composites, preparation processing, molten fluoride salt, corrosion behavior

中图分类号:

TQ174

王洪达, 周海军, 董绍明, 王震, 胡建宝, 冯倩. SiC_f/SiC复合材料耐高温氟熔盐腐蚀性能研究[J]. 无机材料学报, 2017, 32(11): 1133-1140.

WANG Hong-Da, ZHOU Hai-Jun, DONG Shao-Ming, WANG Zhen, HU Jian-Bao, FENG Qian. Corrosion Behavior of SiC_f/SiC Composites in High Temperature Fluoride Salt Environment[J]. Journal of Inorganic Materials, 2017, 32(11): 1133-1140.

图/表 9

表1 不同工艺制备的SiCf/SiC复合材料

Table 1 SiCf/SiC composites prepared by different processes

Process	MI	PIP	CVI
Raw materials	Si + Resin	PCS	MTS
Architecture	3D braid	Plain woven	Plain woven
Interphase	~100 nm PyC	~100 nm PyC	~100 nm PyC
Fiber volume fraction	~42%	~35%	~40%

表2 FLiNaK共晶熔盐中杂质种类及含量

Table 2 Impurities of molten salts FLiNaK

Impurities	Metal cations						Acid ions and chloride ions
Impurities	Mg	Ca	Al	Cr	Fe	Ni	Cl^-	NO^2-	NO^3-	PO₄^3-	SO₄^2-
Content/×10^-6	12	13	8	7	13	17	8.1	≤5.0	25.8	≤5.0	7.7

图1 MI、PIP和CVI样品在800℃氟熔盐中腐蚀100 h后的质量损失率和腐蚀速率

Fig. 1 Mass loss ratio and apparent mass loss rate of MI, PIP and CVI samples after corrosion in molten fluoride salt at 800℃ for 100 h

图2 (a)MI、(b)PIP和(c)CVI样品腐蚀前后的XRD图谱

Fig. 2 XRD patterns of samples (a) MI, (b) PIP and (c) CVI before and after corrosion

表3 MI-SiC基体不同物相区域元素组成/at%

Table 3 Element composition of points in MI-SiC matrix/at%

Point	1	2	3	4	5
C	-	54.87	57.59	-	54.07
Si	100	45.13	42.41	100	45.93

图3 MI样品腐蚀前(a)表面和(b)截面以及经800℃氟熔盐腐蚀100 h后(c)表面和(d)截面SEM照片

Fig. 3 Surface and cross-section microstructures of MI samples (a,b) before and (c,d) after corrosion

图4 不同温度下Si和SiC与1 mol F2可能发生反应所对应的标准吉布斯自由能变

Fig. 4 Standard Gibbs free energy of formation per molecule of F2 for the salt constituents and the silicofluoride formed from Si and SiC in the tested MI-SiC matrix at 850℃

图5 PIP样品腐蚀前(a)表面及(c)截面和800℃氟熔盐腐蚀100 h后(b)表面和(e)截面的微观结构, (d)为深灰色带状区域能谱线扫描结果, (f)为龟裂腐蚀区放大图

Fig. 5 Microstructure evolution of PIP samples: surface (a) before and (b) after corrosion, corrosion section (c) before and (e, f) after corrosion, and (d) EDS linerscan analysis results of dark gray area

图6 CVI样品形貌：腐蚀前(a)表面和(b)截面形貌以及腐蚀后(c,e)表面和(d,f)截面形貌

Fig. 6 Microstructure evolution of CVI samples: surface (a) before and (c,e) after corrosion, corrosion section (b) before and (d,f) after corrosion.

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SiC_f/SiC复合材料耐高温氟熔盐腐蚀性能研究

Corrosion Behavior of SiC_f/SiC Composites in High Temperature Fluoride Salt Environment

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SiCf/SiC复合材料耐高温氟熔盐腐蚀性能研究

Corrosion Behavior of SiCf/SiC Composites in High Temperature Fluoride Salt Environment

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SiC_f/SiC复合材料耐高温氟熔盐腐蚀性能研究

Corrosion Behavior of SiC_f/SiC Composites in High Temperature Fluoride Salt Environment