聚碳硅烷基复合涂层PCS裂解行为及其抗激光烧蚀性能

doi:10.15541/jim20230143

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1271-1280.DOI: 10.15541/jim20230143

所属专题：【结构材料】热障与环境障涂层(202312)

聚碳硅烷基复合涂层PCS裂解行为及其抗激光烧蚀性能

蔡佳¹^,²(), 赵芳霞¹(), 范栋¹^,², 黄利平², 牛亚然²(), 郑学斌², 张振忠¹

1.南京工业大学材料科学与工程学院, 南京 211816
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2023-03-21 修回日期:2023-06-07 出版日期:2023-07-17 网络出版日期:2023-07-17
通讯作者: 赵芳霞, 教授. E-mail: fangxiazhao@126.com;
牛亚然, 研究员. E-mail: yrniu@mail.sic.ac.cn
作者简介:蔡佳(1998-), 女, 硕士研究生. E-mail: cj15850730899@163.com
基金资助:
上海市科学技术委员会科学基金项目(20ZR1465700)

Pyrolysis Behavior and Laser Ablation Resistance of PCS in Polycarbosilane Composite Coatings

CAI Jia¹^,²(), ZHAO Fangxia¹(), FAN Dong¹^,², HUANG Liping², NIU Yaran²(), ZHENG Xuebin², ZHANG Zhenzhong¹

1. College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2023-03-21 Revised:2023-06-07 Published:2023-07-17 Online:2023-07-17
Contact: ZHAO Fangxia, professor. E-mail: fangxiazhao@126.com;
NIU Yaran, professor. E-mail: yrniu@mail.sic.ac.cn
About author:CAI Jia(1998-), female, Master candidate. E-mail: cj15850730899@163.com
Supported by:
Natural Science Foundation of Shanghai(20ZR1465700)

摘要/Abstract

摘要：

针对高性能激光防护涂层的开发问题, 根据聚碳硅烷(PCS)裂解时会消耗大量激光能量, 并产生高温陶瓷保护相的特点, 本研究创新性地提出在传统氧化钇稳定氧化锆(YSZ)隔热涂层表面再复合PCS烧蚀型涂层的防护思路, 采用料浆法结合大气等离子喷涂技术(APS)在Ni基合金表面分别制备了NiCrAlY/YSZ/PCS-TiO₂(YPT)和NiCrAlY/YSZ/PCS-Y₂O₃(YPY)涂层。在研究TiO₂和Y₂O₃添加相对PCS裂解行为影响的基础上, 系统研究了YPT和YPY复合涂层对10.6 μm CO₂激光器的抗激光烧蚀性能, 并与单层YSZ涂层进行比较。结果表明, YPY和YPT复合涂层比传统YSZ涂层的激光防护效果更好, 这是因为在激光烧蚀初期, 涂层表面的PCS裂解会消耗激光能量, 且烧蚀后残余的Y₂SiO₅、SiC和SiO₂相会沉积在YSZ涂层上, 形成致密的保护层, 继续对YSZ涂层进行激光防护。YPY比YPT涂层激光防护性能更好, 这是因为Y₂O₃具有高热导率和低热膨胀系数, YPY涂层产生的温度梯度更小, 从而缓解热应力, 且Y₂O₃参与PCS的裂解生成了Y₂SiO₅相, 比TiO₂更能抑制PCS裂解引起的体积膨胀。此外YPY涂层中心烧蚀温度更高, 生成PCS裂解产物SiC和SiO₂相的速度更快, 能及时保护下方涂层, 表现出更好的抗激光烧蚀性能。该研究有望为新型抗激光复合涂层的设计提供研究思路。

关键词: 聚碳硅烷, 添加相, 复合涂层, 裂解, 抗激光烧蚀性能

Abstract:

For the development of high-performance laser protective coatings, this work innovatively proposes the idea of recombining PCS ablative coatings on the surface of traditional yttrium stabilized zirconia (YSZ) thermal insulation coatings. Based on characteristics of the consumption of large amount laser energy through decomposition of polycarbosilane (PCS) and production of high-temperature ceramic protective phases, NiCrAlY/YSZ/PCS-TiO₂(YPT) and NiCrAlY/YSZ/PCS-Y₂O₃(YPY) coatings were prepared on the surface of Ni-based alloy by slurry method combined with atmospheric plasma spraying (APS). Based on the effect of TiO₂ and Y₂O₃ addition on the pyrolysis behavior of PCS, the laser ablation resistance of YPT and YPY composite coatings on 10.6 μm CO₂ laser were systematically studied and compared with that of single layer YSZ coating. The results show that YPY and YPT composite coatings have better laser protection effect than traditional YSZ coating, because in the early stage of laser ablation, the PCS decomposition on the coating surface can consume laser energy, and the residual Y₂SiO₅, SiC and SiO₂ phases after ablation can be deposited on the YSZ coating, forming a dense protective layer, which can continue to play a role in laser protection of the YSZ coating. YPY coating has better laser protection performance than YPT coating, because Y₂O₃ has higher thermal conductivity and lower coefficient of thermal expansion. Smaller temperature gradient can be produced in YPY coating, which can alleviate thermal stress. Moreover, Y₂O₃ participates in the pyrolysis of PCS to generate Y₂SiO₅ phase, which inhibits more volume expansion in PCS pyrolysis than that in TiO₂. In addition, the core ablation temperature of YPY coating is higher, and the formation of PCS pyrolysis products SiC and SiO₂ phase is faster, which can timely protect the lower coating, showing better laser ablation resistance. This study is expected to provide a new idea for the design of novel laser resistant composite coatings.

Key words: polycarbosilane, addition, composite coating, pyrolysis, laser ablation resistance

中图分类号:

TQ174

蔡佳, 赵芳霞, 范栋, 黄利平, 牛亚然, 郑学斌, 张振忠. 聚碳硅烷基复合涂层PCS裂解行为及其抗激光烧蚀性能[J]. 无机材料学报, 2023, 38(11): 1271-1280.

CAI Jia, ZHAO Fangxia, FAN Dong, HUANG Liping, NIU Yaran, ZHENG Xuebin, ZHANG Zhenzhong. Pyrolysis Behavior and Laser Ablation Resistance of PCS in Polycarbosilane Composite Coatings[J]. Journal of Inorganic Materials, 2023, 38(11): 1271-1280.

图/表 15

表1 YSZ和NiCrAlY涂层喷涂参数[18]

Table 1 Spray parameters of YSZ and NiCrAlY coatings[18]

Coatings	YSZ	NiCrAlY
Ar/slpm	30−40	30−40
H₂/slpm	5−15	5−15
Spray distance/mm	90−130	200−300
Feed rate/(r·min^-1)	15−30	15−30
Power/kW	38−48	30−40

图1 10.6 μm CO2激光考核装置示意图

Fig. 1 Schematic of 10.6 μm CO2 laser examination device

图2 PT (a)和PY (b)涂层的XRD图谱

Fig. 2 XRD patterns of PT (a) and PY (b) coatings

图3 不同温度下PT (a)和PY (b)涂层裂解产物的红外光谱图

Fig. 3 Infrared spectra of products pyrolyzed from PT (a) and PY (b) coatings at different temperatures

图4 PT、PY、PCS的TG (a)和DSC (b)曲线

Fig. 4 TG (a) and DSC (b) curves of PT, PY and PCS

图5 PT (a)和PY (b)涂层在空气中不同温度热处理2 h后的XRD谱图

Fig. 5 XRD patterns of PT (a) and PY (b) coatings after heat-treated at different temperatures in air for 2 h

图6 YPT和YPY涂层经425 W/cm2激光烧蚀不同时间的宏观形貌

Fig. 6 Morphologies of YPT and YPY coatings ablated by 425 W/cm2 laser for different periods

图7 YPT (a)和YPY (b)涂层经425 W/cm2激光烧蚀不同时间的温度曲线

Fig. 7 Temperature curves of YPT (a) and YPY (b) coatings ablated by 425 W/cm2 laser for different periods

图8 YPT (a)和YPY (b)涂层经425 W/cm2激光烧蚀不同时间的XRD图谱

Fig. 8 XRD patterns of YPT (a) and YPY (b) coatings after 425 W/cm2 laser ablation for different periods

图9 YPT和YPY涂层经425 W/cm2激光烧蚀5 s的SEM表面形貌

Fig. 9 Surface SEM morphologies of YPT and YPY coatings after 425 W/cm2, 5 s laser ablation (a, d) Original morphologies; (b, e) Central ablative zone; (c, f) Transition zone; (g) EDS results of A1, A2 and P1 points

图10 YPT和YPY原始涂层(a, d)和经425 W/cm2激光烧蚀5 s的SEM截面形貌(b, c, e, f)及EDS结果(g, h)

Fig. 10 Cross-sectional original SEM morphologies (a, d), cross-sectional morphologies (b, c, e, f) and EDS results (g, h) of YPT and YPY coatings after 425 W/cm2, 5 s laser ablation

图11 YSZ、YPT和YPY涂层经2123和4246 W/cm2激光分别烧蚀5和10 s的(a)表面形貌和(b)背面形貌

Fig. 11 Surface morphologies (a) and back surface morphologies (b) of YSZ, YPT and YPY coatings ablated by 2123 and 4246 W/cm2 laser for 5 and 10 s, respectively

图12 YPT (a)和YPY (b)涂层经4246 W/cm2激光烧蚀10 s的XRD图谱

Fig. 12 XRD patterns of YPT (a) and YPY (b) coatings after 4246 W/cm2, 10 s laser ablation

图13 YSZ、YPT和YPY原始涂层经4246 W/cm2激光烧蚀10 s的SEM表面形貌和EDS分析结果

Fig. 13 SEM surface morphologies and EDS analyses of YSZ, YPT and YPY coatingsafter 4246 W/cm2, 10 s laser ablation (a, e, i) Original coatings; (b, f, j) High magnification of central ablation areas; (c, g, k) Low magnification of central ablation areas; (d, h, l) Transition areas; (m) EDS results; (n) YPT element mappings ; (o) YPY element mappings

图14 YSZ (a)、YPT (b)和YPY (c)涂层经4246 W/cm2激光烧蚀10 s中心烧蚀区域的SEM截面形貌及其对应的元素分布图

Fig. 14 Cross-sectional SEM morphologies and corresponding elements mapping of the central ablation area of YSZ (a), YPT (b) and YPY (c) coatings after 4246 W/cm2, 10 s laser ablation

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聚碳硅烷基复合涂层PCS裂解行为及其抗激光烧蚀性能

Pyrolysis Behavior and Laser Ablation Resistance of PCS in Polycarbosilane Composite Coatings

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