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

doi:10.15541/jim20260081

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的隔热性能的同时,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和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之间以氧化还原和离子交换为主的反应路径,并运用路易斯酸碱理论解释了Na⁺的加入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-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 °C, 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 will 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, RE₂Ti₂O₇ceramics, Na₂SO₄ +V₂O₅salts, 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, DOI: 10.15541/jim20260081.

GAO Zhixin, FU Shuai, BAO Yiwang, LV Kuilin, LIU Xiaogen. Thermal Corrosion Behavior and Mechanism of RE₂Ti₂O₇ Ceramics in V₂O₅ and Na₂SO₄+V₂O₅ Molten Salts[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260081.

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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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