RE2Ti2O7陶瓷在V2O5和Na2SO4+V2O5熔盐中的热腐蚀行为与机理

doi:10.15541/jim20260081

无机材料学报 ›› 2026, Vol. 41 ›› Issue (10): 1533-1540.DOI: 10.15541/jim20260081

• 研究快报 • 上一篇

RE₂Ti₂O₇陶瓷在V₂O₅和Na₂SO₄+V₂O₅熔盐中的热腐蚀行为与机理

高智欣¹^,²(), 付帅¹^,², 包亦望¹^,², 吕奎霖¹^,²(), 刘小根¹^,²()

¹ 中国建筑材料科学研究总院绿色建筑材料全国重点实验室, 北京 100024
² 中国国检测试控股集团股份有限公司, 北京 100024

收稿日期:2026-02-27 修回日期:2026-04-30 出版日期:2026-10-20 网络出版日期:2026-05-08
通讯作者: 吕奎霖, 高级工程师. E-mail: lvkuilin@ctc.ac.cn;
刘小根, 教授级高工. E-mail: xtlxg88@163.com
作者简介:高智欣(1998-), 女, 博士. E-mail: gaozhixin0705@foxmail.com

Thermal Corrosion Behavior and Mechanism of RE₂Ti₂O₇ Ceramics in V₂O₅ and Na₂SO₄+V₂O₅ Molten Salts

GAO Zhixin¹^,²(), FU Shuai¹^,², BAO Yiwang¹^,², LÜ Kuilin¹^,²(), LIU Xiaogen¹^,²()

¹ State Key Laboratory of Green Building Materials, China Building Materials Academy, Beijing 100024, China
² China Testing & Certification International Group Co., Ltd., Beijing 100024, China

Received:2026-02-27 Revised:2026-04-30 Published:2026-10-20 Online:2026-05-08
Contact: Lü Kuilin, senior engineer. E-mail: lvkuilin@ctc.ac.cn;
LIU Xiaogen, professor. E-mail: xtlxg88@163.com
About author:GAO Zhixin (1998-), female, PhD. E-mail: gaozhixin0705@foxmail.com
Supported by:
Beijing Nova Program(20250484762);Wu Zhongwei Youth Science and Technology Award Project

摘要/Abstract

摘要：

在追求高推重比航空发动机的应用背景下, 热障涂层材料在具备优异隔热性能的同时, 还必须具有能够抵抗高温燃气中熔融盐(如V₂O₅和硫酸盐)“热腐蚀”的能力。本研究通过固相烧结法合成了RE₂Ti₂O₇ (RE=Dy, Yb)陶瓷, 并通过热重-差示扫描量热(TG-DSC)分析检测了其相稳定性和分解行为, 并系统研究了该陶瓷在900、1000和1100 ℃下在V₂O₅及Na₂SO₄+V₂O₅熔盐中的腐蚀行为。TG-DSC结果显示, RE₂Ti₂O₇在1100 ℃下未出现明显分解峰, 表现出良好的热稳定性。在纯V₂O₅熔盐环境中, 陶瓷表面生成颗粒状的稀土钒酸盐(REVO₄), 并伴随柱状TiO₂析出; 腐蚀产物呈致密层状分布, 有效限制了腐蚀介质的进一步侵蚀。引入Na₂SO₄后, 体系中形成的NaVO₃降低了局部熔体黏度, 显著提高离子迁移率, 从而加速了稀土元素和钛元素的溶出与再沉淀过程, 使腐蚀产物以柱状REVO₄和TiO₂为主。基于相图分析与吉布斯自由能(ΔG)计算, 提出了V₂O₅与RE₂Ti₂O₇之间的反应以氧化还原和离子交换为主, 并运用路易斯酸碱理论解释了加入Na⁺对溶剂化与络合行为的影响机制, 进而揭示了整体腐蚀动力学机制。综上, RE₂Ti₂O₇陶瓷表现出优异的高温熔盐耐腐蚀性, 具备作为热障涂层候选材料的应用潜力。

关键词: 热障涂层, RE₂Ti₂O₇陶瓷, Na₂SO₄+V₂O₅熔盐, 反应机理, 热腐蚀

Abstract:

In the context of developing aircraft engines with high thrust-to-weight ratio, thermal barrier coating (TBC) materials must possess excellent thermal insulation properties and be capable of withstanding the thermal corrosion caused by molten salts (such as V₂O₅ and sulfates) in high-temperature combustion gases. In this study, RE₂Ti₂O₇ (RE=Dy and Yb) ceramics were synthesized via a solid-state sintering method. The phase stability and decomposition behavior were examined through thermogravimetric-differential scanning calorimetry (TG-DSC) analysis. The corrosion behavior of RE₂Ti₂O₇ upon exposure to V₂O₅ and Na₂SO₄+V₂O₅ molten salts at 900, 1000, and 1100 ℃ was analyzed. TG-DSC results show that RE₂Ti₂O₇ retains good thermal stability at 1100 ℃, with no obvious decomposition peaks. In a pure V₂O₅ molten salt environment, granular rare earth vanadates (REVO₄) form on the surface, accompanied by columnar TiO₂ precipitation. The corrosion products were distributed in a dense layered structure, which would limit further deep corrosion. Upon the introduction of Na₂SO₄, the NaVO₃ formed in the system reduced the local melt viscosity and significantly increased ionic mobility, thereby accelerating the dissolution and reprecipitation of rare earths and titanium. This resulted in corrosion products dominated by columnar REVO₄ and TiO₂. Based on phase diagrams and Gibbs free energy (ΔG) calculations, a reaction pathway dominated by redox reactions and ion exchange between V₂O₅ and RE₂Ti₂O₇ was proposed. Furthermore, Lewis acid-base theory was employed to explain how the addition of Na⁺ alters solvation and complexation behavior, thereby influencing the overall corrosion kinetics. In summary, RE₂Ti₂O₇ ceramics exhibit excellent corrosion resistance in high-temperature molten salts, demonstrating their potential as candidate materials for thermal barrier coatings.

Key words: thermal barrier coating, RE₂Ti₂O₇ ceramic, Na₂SO₄+V₂O₅ salt, reaction mechanism, thermal corrosion

中图分类号:

TQ174

高智欣, 付帅, 包亦望, 吕奎霖, 刘小根. RE₂Ti₂O₇陶瓷在V₂O₅和Na₂SO₄+V₂O₅熔盐中的热腐蚀行为与机理[J]. 无机材料学报, 2026, 41(10): 1533-1540.

GAO Zhixin, FU Shuai, BAO Yiwang, LÜ Kuilin, LIU Xiaogen. Thermal Corrosion Behavior and Mechanism of RE₂Ti₂O₇ Ceramics in V₂O₅ and Na₂SO₄+V₂O₅ Molten Salts[J]. Journal of Inorganic Materials, 2026, 41(10): 1533-1540.

图/表 12

Fig. 1 (a) DSC and (b) TG curves of RE2Ti2O7 samples in the temperature range of 100-1300 ℃

Fig. 2 XRD patterns of V2O5 salt and RE2Ti2O7 samples after 10 h exposure at 900, 1000, and 1100 ℃ (a) Dy2Ti2O7; (b) Yb2Ti2O7

Fig. 3 (a-c, e-g) SEM images and corresponding (d, h) elemental distributions at marked points of RE2Ti2O7+V2O5 after 10 h exposure at 900, 1000, and 1100 ℃ (a-d) Dy2Ti2O7; (e-h) Yb2Ti2O7

Fig. 4 SEM cross-sectional images of RE2Ti2O7+V2O5 after 10 h exposure at 900, 1000, and 1100 ℃ (a-c) Dy2Ti2O7; (d-f) Yb2Ti2O7

Fig. 5 XRD patterns of 50% Na2SO4 + 50% V2O5 and RE2Ti2O7 ceramics after 10 h exposure at different temperatures (a) Dy2Ti2O7; (b) Yb2Ti2O7

Fig. 6 (a-f) SEM images and elemental distributions of Dy2Ti2O7 reacting with 50% V2O5+50% Na2SO4 salt for 10 h at different temperatures; (g-l) SEM images and elemental distributions of Yb2Ti2O7 reacting with 50% V2O5+50% Na2SO4 salt for 10 h at different temperatures (a, b, g, h) 900 ℃; (c, d, i, j) 1000 ℃; (e, f, k, l) 1100 ℃

Fig. 7 SEM cross-sectional images and elemental distributions of RE2Ti2O7 and 50% Na2SO4+50% V2O5 reacted for 10 h at 900, 1000, and 1100 ℃ (a-c) Dy2Ti2O7; (d-f) Yb2Ti2O7

Fig. 8 (a) Gibbs free energy between various compounds; (b) Schematic diagram of the reaction between RE2Ti2O7 and V2O5/50% Na2SO4+50% V2O5

Fig. S1 XRD patterns of RE2Ti2O7 samples (a) Dy2Ti2O7; (b) Yb2Ti2O7

Fig. S2 Phase diagram of TiO2 and V2O5 at high temperatures[22]

Table S1 Elemental mapping of SEM image marked points showing the reaction between Dy2Ti2O7 and 50% V2O5+50% Na2SO4 salt at different temperatures in Fig. 6(b, d, f)

Temperature/℃	Point	Product	Composition/(%, in atom)
Temperature/℃	Point	Product	O	S	Na	V	Ti	Dy
900	1	Na salt	57.16±0.15	0.36±0.05	24.12±0.11	13.56±0.05	4.65±0.12	0.15±0.01
	2	DyVO₄	51.69±0.13	0.83±0.02	3.80±0.10	22.90±0.25	1.90±0.13	19.59±0.31
	3	TiO₂	57.65±0.16	0.68±0.04	8.69±0.10	1.91±0.11	30.85±0.28	0.23±0.08
1000	4	Na salt	62.02±0.12	0.32±0.06	25.63±0.19	6.39±0.13	1.16±0.02	4.48±0.11
	5	DyVO₄	59.64±0.11	/	1.70±0.02	20.71±0.14	0.79±0.06	17.15±0.12
	6	TiO₂	64.12±0.13	0.63±0.05	0.14±0.01	0.58±0.08	34.16±0.23	0.37±0.04
1100	7	Na salt	62.02±0.14	0.41±0.07	23.18±0.25	7.48±0.11	3.46±0.09	3.45±0.11
	8	DyVO₄	58.41±0.04	0.43±0.05	/	23.25±0.21	0.38±0.03	17.54±0.12
	9	TiO₂	52.49±0.05	0.20±0.01	0.29±0.01	1.99±0.03	33.45±0.25	1.16±0.04

Table S2 Elemental mapping of SEM image marked points showing the reaction between Yb2Ti2O7 and 50% V2O5+50% Na2SO4 salt at different temperatures in Fig. 6(h, j, l)

Temperature/℃	Point	Product	Composition/(%, in atom)
Temperature/℃	Point	Product	O	S	Na	V	Ti	Yb
900	10	Na salt	61.89±0.36	0.31±0.02	23.64±0.15	13.97±0.16	0.19±0.02	/
	11	YbVO₄	56.97±0.23	0.52±0.08	1.16±0.15	24.50±0.14	0.80±0.05	16.05±0.15
	12	TiO₂	63.68±0.33	0.40±0.03	2.67±0.13	3.55±0.11	28.21±0.23	1.48±0.09
1000	13	Na salt	59.42±0.35	0.89±0.07	17.24±0.14	16.05±0.22	2.23±0.09	4.17±0.14
	14	YbVO₄	50.18±0.28	0.92±0.09	2.75±0.12	21.12±0.16	2.40±0.07	19.46±0.22
	15	TiO₂	63.11±0.31	0.69±0.04	2.59±0.08	3.57±0.10	28.24±0.24	1.84±0.21
1100	16	Na salt	68.34±0.36	0.43±0.05	15.71±0.21	4.78±0.23	6.66±0.14	4.02±0.17
	17	YbVO₄	69.69±0.38	0.65±0.01	/	14.91±0.18	0.69±0.03	14.06±0.20
	18	TiO₂	66.53±0.34	0.44±0.03	2.12±0.10	1.51±0.12	25.23±0.24	1.36±0.08

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RE₂Ti₂O₇陶瓷在V₂O₅和Na₂SO₄+V₂O₅熔盐中的热腐蚀行为与机理

Thermal Corrosion Behavior and Mechanism of RE₂Ti₂O₇ Ceramics in V₂O₅ and Na₂SO₄+V₂O₅ Molten Salts

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