硅酸盐学报

纳米t-ZrO₂增强钛合金表面陶瓷膜层低温力学性能

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钱伟峰 ¹ , 宁炳坤 ¹ , 谢天祥 ¹ , 李帅康 ¹ , 杨泽慧 ² , 张震 ³ , 陈永楠 ¹

硅酸盐学报 | 研究论文 2026,54(1): 225-234

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硅酸盐学报 |研究论文 2026 , 54 (1) : 225 -234

纳米t-ZrO₂增强钛合金表面陶瓷膜层低温力学性能

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钱伟峰¹, 宁炳坤¹, 谢天祥¹, 李帅康¹, 杨泽慧², 张震³, 陈永楠¹

作者信息

^1．长安大学材料科学与工程学院，西安 710064

^2．西部钛业有限责任公司，西安 710064

^3．西北有色金属研究院，西安 710016

通讯作者:

陈永楠（1981—），男，博士，教授。

作者简介:

钱伟峰（1997—），男，博士研究生。

Low-Temperature Mechanical Properties of Ceramic Coatings on Titanium Alloy Surface Enhanced by Nano-t-ZrO₂

Weifeng QIAN¹, Bingkun NING¹, Tianxiang XIE¹, Shuaikang LI¹, Zehui YANG², Zhen ZHANG³, Yongnan CHEN¹

Affiliations

^1.School of Materials Science and Engineering, Chang'an University, Xi'an 710064, China

^2.Western Titanium Industry Co., Ltd., Xi'an 710064, China

^3.Northwest Institute for Nonferrous Metal Research, Xi'an 710064, China

Corresponding Author:

CHEN Yongnan (1981-), male, Ph.D., Professor. E-mail: frank_cyn@163.com

QIAN Weifeng (1997-), male, Doctoral candidate. E-mail: langyaqwf@163.com

出版时间: 2026-01-20 doi: 10.14062/j.issn.0454-5648.20250206

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摘要

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通过调控脉冲频率优化等离子体电解氧化（PEO）工艺，制备了不同晶粒直径的复合陶瓷膜层，并研究了原位纳米四方相氧化锆（t-ZrO₂）对钛合金表面PEO陶瓷膜层低温力学性能的影响机制。纳米压痕和动态热机械分析结果表明，随着t-ZrO₂晶粒直径的减小，其马氏体相变温度（M_s）降低，当服役温度处于M_s附近时膜层的塑性变形能力及低温抗振性能显著增强。通过膜层纳米结构表征结合分子动力学模拟发现小直径的晶粒通过更高的界面能抑制了马氏体相变，从而降低了M_s；且具有更小晶粒直径的膜层可以通过晶间滑移和晶内塑性变形提高低温下的阻尼性能。本工作为提升钛合金表面膜层在低温下服役可靠性提供了一种可行方法和思路。

关键词

陶瓷膜层 / 氧化锆相变 / 低温振动 / 纳米晶

Abstract

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Introduction

Titanium alloys are indispensable in aerospace and military fields for manufacturing precision components owing to their exceptional specific strength and stiffness—properties that enable weight reduction while maintaining structural integrity under high mechanical loads. However, in harsh low-temperature service environments, titanium alloys suffer from insufficient wear and corrosion resistance, necessitating surface modification. Ceramic coatings, renowned for their high hardness, excellent chemical stability, and resistance to extreme environments, are commonly applied to address this issue. Among various coating technologies, Plasma Electrolytic Oxidation (PEO) stands out due to its advantages of strong film-substrate adhesion and the ability to tailor coating composition for functionalization. Nevertheless, ceramic coatings—primarily composed of ionic or covalent bonds—exhibit inherent brittleness, which is exacerbated at low temperatures. This brittleness severely limits the service reliability and lifespan of titanium alloy components in low-temperature environments. Tetragonal zirconia (t-ZrO₂) has emerged as a promising toughening agent for ceramics by undergoing a martensitic transformation to monoclinic zirconia (m-ZrO₂) under external stress or temperature changes, accompanied by a 3%-5% volume expansion. This expansion generates a compressive stress field that inhibits crack propagation, thereby improving the coating's toughness. Critical to this effect is the martensitic transformation start temperature (M_s) of t-ZrO₂, which is strongly dependent on grain size. Optimizing the grain size of in-situ formed nano t-ZrO₂ to match specific low-temperature service windows thus becomes a key strategy for enhancing the low-temperature mechanical performance of PEO ceramic coatings.

Methods

This study aimed to systematically investigate the influence mechanism of in-situ nano t-ZrO₂ grain size on the low-temperature static and dynamic mechanical properties of Ti6Al4V-based PEO ceramic coatings, and to develop a practical process for improving the coatings' service reliability in cryogenic environments. To achieve this, the PEO process was optimized by adjusting the pulse frequency ranging from 500 Hz to 2000 Hz to prepare four sets of TiO₂/t-ZrO₂ composite ceramic coatings denoted as D1, D2, D3, and D4 samples with distinct average t-ZrO₂ grain diameters, alongside a reference sample (RS) without t-ZrO₂. The Ti6A14V substrates were first machined into two standard sizes: 10 mm × 10 mm × 1 mm for static mechanical testing and 60 mm × 6 mm × 1 mm for dynamic testing. Prior to PEO treatment, the substrates were sequentially grounded, cleaned with ethanol, and dried. The zirconium salt electrolyte used for D1-D4 samples consisted of 15 g/L K₂ZrF₆, 5 g/L (NaPO₃)₆, 5 g/L NaH₂PO₄, 10 g/L NH₄HF₂, and 1 L distilled water, and the phosphate electrolyte for RS contained 10 g/L (NaPO₃)₆, 10 g/L NaH₂PO₄, and 15 g/L NH₄HF₂. All PEO treatments were performed using a single-pulse DC power supply (MAO-20D) under constant current mode (0.2 A/cm²), a fixed duty cycle of 20%, and a treatment time of 20 min.

Results and discussion

The t-ZrO₂ grain diameter decreased significantly with increasing PEO pulse frequency: D1 samples (500 Hz) had an average grain diameter of ~40 nm, D2 sample (1000 Hz) ~30 nm, D3 sample (1500 Hz) ~22 nm, and D4 sample (2000 Hz) ~17 nm. This trend was attributed to shorter single-pulse times at higher frequencies, which restricted t-ZrO₂ nanocrystal growth during PEO. XRD analysis revealed that all composite coatings consisted of t-ZrO₂, TiO₂, and a small amount of m-ZrO₂, with the t-ZrO₂ characteristic peak at 30.2° showing increased full width at half maximum and decreased intensity with higher pulse frequency—consistent with Scherrer formula calculations for reduced grain size. The M_s temperature of t-ZrO₂ decreased with decreasing grain diameter. XRD-derived t-ZrO₂ volume fraction (V_t) showed that V_t of D1 sample exhibited a sharp drop from 68% to 26% at 250 K, D2 sample and D3 sample at 200 K, while D4 sample showed no significant V_t change down to 150 K. This was explained by higher interfacial energy in smaller grains, which increased the martensitic nucleation energy barrier. When service temperatures were near M_s, the coatings' plastic deformation ability was significantly enhanced. Nanoindentation tests showed that D1-D4 samples had higher H and E than RS samples, with stepwise H³/E² increases corresponding to stress-induced martensitic transformation. Dynamic mechanical properties were markedly improved by t-ZrO₂ and smaller grain sizes. Dynamic Mechanical Analysis (DMA) results showed that D1-D4 samples had higher loss modulus and tanθ than RS samples across all temperatures. D1 sample peaked at 300 K, D2 sample at 250 K, D3 sample at 200 K, and D4 sample at 150 K, aligning with their M_s temperatures. Smaller grains exhibited superior damping due to increased grain boundary area, which promoted energy dissipation via grain boundary sliding and intragranular dislocation motion. MD simulations confirmed inhomogeneous strain distribution concentrated at t-ZrO₂/TiO₂ interfaces and t-ZrO₂ grains, and an inverse Hall-Petch effect in small grains. D4 sample sacrificed ~29% tensile strength compared to D1 sample to achieve a ~60% higher strain rate, enhancing ductility.

Conclusions

This work demonstrates that adjusting PEO pulse frequency to control t-ZrO₂ grain diameter is an effective strategy to optimize the low-temperature mechanical properties of ceramic coatings. The mechanism involving M_s temperature regulation, interfacial energy enhancement, and grain boundary sliding provides theoretical and experimental basis for the design of low-temperature vibration-resistant coatings on titanium alloys, which is of great significance for improving the service life of titanium alloy components in low-temperature aerospace environments.

Key words

ceramic coatings / zirconia phase transformation / low-temperature vibration / nanocrystals

引用本文

钱伟峰, 宁炳坤, 谢天祥, 李帅康, 杨泽慧, 张震, 陈永楠. 纳米t-ZrO₂增强钛合金表面陶瓷膜层低温力学性能. 硅酸盐学报, 2026 , 54 (1) : 225 -234 . DOI: 10.14062/j.issn.0454-5648.20250206

Weifeng QIAN, Bingkun NING, Tianxiang XIE, Shuaikang LI, Zehui YANG, Zhen ZHANG, Yongnan CHEN. Low-Temperature Mechanical Properties of Ceramic Coatings on Titanium Alloy Surface Enhanced by Nano-t-ZrO₂[J]. Journal of the Chinese Ceramic Society, 2026 , 54 (1) : 225 -234 . DOI: 10.14062/j.issn.0454-5648.20250206

基金

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国家自然科学基金面上项目(52271051)
陕西省技术创新引导专项“三项改革”项目(2024ZC-YYDP-109)
陕西省秦创原“科学家+工程师”队伍建设(2023KXJ-272)

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2026年第54卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20250206

接收时间：2025-03-26
首发时间：2026-10-27
出版时间：2026-01-20

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出版历史

收稿日期：2025-03-26
修回日期：2025-05-11

基金

国家自然科学基金面上项目(52271051)

陕西省技术创新引导专项“三项改革”项目(2024ZC-YYDP-109)

陕西省秦创原“科学家+工程师”队伍建设(2023KXJ-272)

作者信息

^1．长安大学材料科学与工程学院，西安 710064

^2．西部钛业有限责任公司，西安 710064

^3．西北有色金属研究院，西安 710016

通讯作者:

陈永楠（1981—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20250206

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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