使役环境涡轮叶片EB-PVD热障涂层失效机制

运用场发射扫描电镜、能量色散光谱仪和金相显微镜等测试表征手段,详细检查退役高温发动机涡轮叶片表面涂层残存状况,发现带气膜孔的高温发动机涡轮叶片经服役2000 h后,表面各部位EB-PVD涂层承受CMAS攻击、硬质物撞击和冷热应力冲击程度各异,导致退役叶片表面共存多种损伤.通过对这些损伤现象的分析,了解使役环境下叶片各部位的失效模式和失效机理.研究结果表明:叶棱为受CMAS攻击最严重处,同时也是受硬质点撞击最密集处,存在大面积涂层脱落;气膜孔周围的TBCs涂层受CMAS攻击发生本质性固化,受交变热应力和机械应力共同作用而呈规律性脱落;叶棱周围气膜孔表面(无论是叶背或是叶盆)均存在硬质物碾压划过叶片表面而压实CMAS,引起表面TBCs脱落的现象,同时在气膜孔内发现飞落的TBCs柱和CMAS块,从侧面反应对叶片表面造成实质性伤害的硬质物可能为脱落的TBCs柱或固化的CMAS块.     

大气等离子喷涂YSZ 涂层中CMAS 渗透行为分析

目的 建立大气等离子制备的热障涂层的结构特征与高温环境中CMAS渗透速率之间的定量关系,分析微裂纹、孔洞等缺陷对渗透行为的影响。方法 利用大气等离子喷涂方法制备ZrO2-8％Y2O3（YSZ）涂层。用摩尔比为45SiO2︰33CaO︰13AlO1.5︰9MgO的CMAS涂覆涂层表面,在1 200 ℃条件下进行CMAS渗透试验。通过SEM、EDS、XRD对涂层微观结构和物相进行测试,并通过图像分析处理软件计算涂层的孔隙率,分析孔径的分布规律。测量CMAS渗透速率,分析涂层结构对渗透速率的影响,改进CMAS理论渗透速率计算方法。结果 熔融态的CMAS能够快速渗透涂层,使得涂层的孔隙率由12.8%降至4%。YSZ涂层中直径大于3 μm的孔隙不易被填充。把有效孔隙率引入到CMAS渗透速率的计算中,可以将计算结果与实测结果之间的偏差降至5%以内。CMAS渗透后30 min内,YSZ未发生明显的相变,40 min后发现涂层出现腐蚀现象。结论 大气等离子喷涂YSZ涂层中微裂纹的直径尺寸影响CMAS渗透速率,而曲折程度对渗透速率的影响较小。直径较小的裂纹能够加速渗透,直径较大的孔洞可以阻碍CMAS的渗透。由于大气等离子喷涂YSZ中存在大量直径较小的微裂纹,使得高温环境中CMAS能够在较短时间内渗透YSZ涂层,使涂层出现致密化。     

CMAS corrosion resistance characteristics of RE50TaxZr50-xO175+0.5x thermal barrier oxides in RE2Zr2O7-RETaO4 systems

The corrosion resistance characteristics of RE-rich RE₅₀Ta_xZr_50-xO_175+0.5x oxides in RE₂Zr₂O₇-RETaO₄ systems to calcium-magnesium-alumino-silicate (CMAS) at 1300 °C, and the influence of RE³⁺ and Ta⁵⁺ on chemical reactions and reactive crystallization of CMAS melts were investigated. The results show that following the thermochemical reactions, apatite, pyrochlore, reprecipitated fluorite and residual Yb(Y)TaO₄ phases were the predominant reaction products. Formation abilities of apatite and pyrochlore were found to be proportional to the ionic radius of RE³⁺. The increase of Ta⁵⁺ amount can decrease the number of available RE³⁺ to form apatite. Moreover, the resistance characteristic to CMAS corrosion in RE₅₀Ta_xZr_50-xO_175+0.5x systems was decided by the combined action of apatite and pyrochlore phases. The cohesive mixture of apatite and pyrochlore phases can generate a dense layer near the reaction front, which had a positive effect on suppressing CMAS infiltration. The ability of the fluorite + RETaO₄ two-phase field was determined to be sufficient to mitigate CMAS corrosion.     

Experimental and mathematical modelling of corrosion behaviour of CMAS coated oxide/oxide CMCs

CMAS corrosion of turbine blades is a crucial failure in turbine engines and their components. In this study, oxide/oxide CMCs (AS-N610), which are candidates for gas turbine (GT) applications, are investigated for its corrosion behaviour at different temperatures and time in presence of CMAS. The corrosion studies using CMAS coating of the CMCs reveal that CMCs had a weight gain of ～6% owing to formation of α-Al₂O₃ at 1000 °C. The SE image indicated the penetration of CMAS into the porous CMC. At 1000 °C, CMAS degraded to form a black glassy substance (Calcium alumino silicate) with traces of Mg which led to corrosion of the matrix. Indentation fracture toughness of the oxide/oxide CMCs was 7.78 ± 0.5 MPa m^0.5 which degraded by ～12% at 1000 °C after 10 h in the presence of CMAS. A mathematical model derived through diffusion equation indicated weight gain of ～0.3 g which was closer to experimental data.     

Excellent CMAS resistance of a newly developed equiatomic high entropy (Dy1/4Ho1/4Tm1/4Yb1/4)2Si2O7 ceramic pyrosilicate

In this work, novel equiatomic high entropy (Dy_1/4Ho_1/4Tm_1/4Yb_1/4)₂Si₂O₇ or (4RE_1/4)₂Si₂O₇ ceramic pyrosilicate was fabricated through a single solid solution method to use as environmental barrier coating. The SEM analysis of high entropy powders shows the homogenous mixing and XRD proves the formation of single β-phase after milling and sintering. The coefficient of thermal expansion was reported as (2.3–4.8 × 10⁻⁶ K⁻¹) from 400 K⁻¹ to 1723 K⁻¹. The ultra-low thermal diffusivity (0.4 mm² s⁻¹) and thermal conductivity (0.8 W/m°C) were reported at 1500 °C for this novel HE ceramic disilicate. The as fabricated (4RE_1/4)₂Si₂O₇ pyrosilicate shows an excellent CMAS resistant for even up to 48 h and negligible amount of Ca is able to penetrate in the substrate. Rare earth disilicate species with intermediate radii such as Tm³⁺ helps in maintaining phase stability along with passive element Yb³⁺ of smaller radii which also protect the interface from severe CMAS attack. However, the rare earth species with larger radii such as Dy³⁺ and Ho³⁺ actively take part in apatite formation leading to reduced corrosion activity of CMAS melt by changing its composition. This result confirms the application of (4RE_1/4)₂Si₂O₇ as a potential candidate to be used as protecting coating material in harsh combustion environments.     

Interaction of Gd2Si2O7 with CMAS melts for environmental barrier coatings

Environmental barrier coatings (EBCs) prevent the oxidation of ceramic matrix composites (CMC), which are used as components in gas turbines. However, EBCs deteriorate more rapidly in real environments, molten silicate deposits accelerate the deterioration of EBCs. In this study, high-temperature behavior sintered Gd₂Si₂O₇ with calcia-magnesia-alumina-silica (CMAS) melt at 1400 °C for 0.5, 2, 12, 48, and 100 h was investigated. HT-XRD results showed that at 1300 °C, CMAS and Gd₂Si₂O₇ chemically reacted to form Ca₂Gd₈(SiO₄)₆O₂ (apatite). The reaction layer became thicker as the heat-treatment time increased, and the thickness of the reaction layer has increased following a parabolic curve. With the extension of the reaction time from 0.5 to 100 h, the thickness of the reaction layer increased from approximately 98 to 315 µm. It was confirmed that Ca₂Gd₈(SiO₄)₆O₂ grew vertically on the Gd₂Si₂O₇ surface. Vertical and horizontal cracks were found after reacting at 1400 °C for 100 h, but no interfacial delamination occurred in this study. In addition, the effects of CaO:SiO₂ molar ratios, monosilicates (RE₂SiO₅) and disilicates (RE₂Si₂O₇), heat-treatment time, and cation size were determined and compared with the results of previous studies (Gd₂SiO_5, Yb₂SiO_5, and Er₂Si₂O₇).     

The CMAS corrosion behavior of high-entropy (Y0.2Dy0.2Er0.2Tm0.2Yb0.2)4Hf3O12 hafnate material prepared by ultrafast high-temperature sintering (UHS)

High-temperature molten calcium-magnesium-alumina-silicate (CMAS) corrosion has become a fatal factor for the failure of aero-engine thermal barrier coatings. In this study, a promising entropy-stabilized (Y_0.2Dy_0.2Er_0.2Tm_0.2Yb_0.2)₄Hf₃O₁₂ (5YH) hafnate was prepared by the emerging ultrafast high-temperature sintering (UHS), and its corrosion and wetting behavior of molten CMAS were investigated. For the corrosion mechanism, the precipitation of the high-entropy apatite phase promotes the formation of the HfO₂ phase, and it can improve the density and stability of the slow-growing reaction layer, hindering the further penetration of molten CMAS. At 1300 ℃, a reaction layer with a three-layered morphology is generated, resulting from the decreased viscosity of the molten CMAS. Moreover, computational analysis shows that molten CMAS on the 5YH surface has a larger contact angle (17°) than traditional YSZ (13°), and the spreading area is about 90 % of traditional YSZ, which benefits for its good CMAS corrosion resistance.     

Anti-CMAS corrosion mechanism of Al2O3 pore sealing and laser remelting on thermal barrier coatings

The sol-dip-coating method and surface laser remelting technology are applied to form an Al₂O₃ layer on a YSZ coating surface to effectively block the environmental sediment CMAS. The behaviour and mechanism for CMAS corrosion of the coating are investigated, and the interfacial reliability of the coating and matrix is calculated by using the Monte Carlo method. The bonding force between the Al₂O₃ sol and YSZ coating can be effectively improved by laser surface treatment. Samples subjected to a laser pretreatment and posttreatment (YL-AL) of the YSZ coating are found to show the best interfacial bonding strength between Al₂O₃ and YSZ. Furthermore, the YL-AL sample shows a higher CMAS resistance than the laser posttreatment (Y-AL) samples, which effectively combines the chemical resistance of Al₂O₃ to CMAS and the physical resistance of the laser re-melted densification layer against CMAS penetration.     

Quantifying the efficiency of reactions between silicate melts and rare earth aluminate-zirconate T/EBC materials

The durability of thermal and environmental barrier coatings (T/EBCs) exposed to molten calcium magnesium aluminosilicate (CMAS) deposits depends on the nature of reactions between the coatings and deposits. These reactions consume the melt, and the crystallization products can block porosity that otherwise facilitates melt infiltration. The ideal reactions rapidly crystallize the melt with a small amount of dissolved T/EBC. This work compares the relative efficiency of reaction products reported in the literature to those formed on four prospective T/EBC materials based on multi-phase combinations of Gd- or Y-zirconates with GdAlO₃, YAlO₃, Gd₄Al₂O₉, or Y₄Al₂O₉. The results show that adding the aluminates to the zirconate materials promotes Gd- or Y-based aluminosilicates garnet and cuspidine crystallization, in addition to apatite. These phases effectively crystallize the melt, but the reaction efficiency is reduced compared to reactions with single phase zirconates. The implications for integration of these multiphase materials into T/EBC architectures are discussed.     

CMAS环境下PS-PVD 7YSZ涂层的抗热冲击性能及失效机制

采用等离子喷涂-物理气相沉积（PS-PVD）工艺制备柱状7YSZ热障涂层,同时在7YSZ涂层表面沉积CMAS熔盐,研究在1250 ℃高温下,CMAS对柱状PS-PVD 7YSZ涂层抗热冲击性能的影响。采用SEM、EDS、XRD等检测方法分析热障涂层微观结构、元素分布和物相组成。结果表明：沉积CMAS熔盐的7YSZ涂层在热循环240次发生层离剥落失效,而未沉积CAMS的涂层无明显剥落,其热循环寿命明显优于沉积CMAS熔盐的7YSZ涂层。在CMAS和循环热冲击的耦合作用下,PS-PVD 7YSZ涂层失效机制为：在热冲击过程中,CMAS熔盐渗入并填充7YSZ涂层,引起渗透区和未渗透区热膨胀系数不均衡,从而产生热不匹配应力;此外,热冲击过程中由于温度梯度的存在也会引起温度梯度热应力,在这两种热应力的耦合作用下,引起涂层内部横向裂纹的产生,并随着热冲击次数的增加,横向裂纹发生扩展,最终导致涂层出现层离剥落失效。