电子束物理气相沉积LaZrCeO热障涂层微结构与热循环性能

热障涂层(thermal barrier coatings,TBCs)是一种由金属黏结层、热生长氧化物层和陶瓷面层组成的金属-陶瓷复合系统,在先进的航空发动机领域上引起了广泛的关注,但目前先进热障涂层的热循环寿命提升和失效行为研究仍然是一个难点。本研究采用电子束物理气相沉积技术(electron beam physical vapour deposition,EB-PVD)制备LaZrCeO/YSZ双陶瓷层热障涂层,研究热障涂层的相结构、显微组织和失效行为。结果表明:LaZrCeO/YSZ涂层为烧绿石与萤石结构组成的复合涂层材料,LaZrCeO/YSZ涂层的微观结构由羽毛状纳米结构和柱内孔隙组成;在1100℃热循环条件下,LaZrCeO/YSZ双陶瓷层热障涂层展现了良好的热循环寿命;热循环实验后,由于应力累积的作用裂纹在热生长氧化层(TGO)中萌生并扩展,包括水平裂纹和垂直裂纹两大类,进而引起整个涂层体系的不稳定,最终导致涂层失效。     

High-temperature oxidation behavior and analysis of impedance spectroscopy of 7YSZ thermal barrier coating prepared by plasma spray-physical vapor deposition

Quasi-columnar structure 7YSZ(yttria stabilized zirconia) thermal barrier coatings(TBCs) are prepared by plasma spray-physical vapor deposition(PS-PVD) onto pretreated and un-pretreated bond coating, respectively. An isothermal oxidation experiment of 7YSZ TBCs is carried out in the atmosphere of 950 °C in order to simulate the high-temperature oxidation process of engine blades. The isothermal oxidation process of 7YSZ thermal barrier coatings is investigated systematically by impedance spectroscopy. The electrochemical physical model and equivalent circuit of columnar 7YSZ coatings are established. Results show that the isothermal oxidation kinetic curve of columnar 7YSZ thermal barrier coatings appears to follow the parabolic law. A pretreatment of bond coating can reduce the growth rate of the thermally grown oxide(TGO) layer, restraining the initiation and propagation of microcracks between YSZ and TGO layers. The oxidation rate constants of 7YSZ coatings with pretreated and un-pretreated bond coating are 0.101×10~(-12) cm~2·s~(-1) and 0.115 × 10~(-13) cm~2 ·s~(-1), respectively. Impedance analysis shows that the content of oxygen vacancies decreases and the density increases after the TGO layer is oxidized for 150 h. In addition, shrinkage microcracks formed by sintering during the oxidation process is the main reason for an increase of the capacitance and a decrease of the resistance in the grain boundary of YSZ.     

交流阻抗谱法在热障涂层失效研究中的应用

介绍了交流阻抗谱法作为无损检测方法在热障涂层失效分析中的应用。通过对热循环、静态氧化过程中热障涂层体系的阻抗谱分析,利用交流阻抗谱对热障涂层进行拟合,得到了服役过程中D_M以及TGO电阻R拟合的结果与氧化时间呈抛物线关系;并根据阻抗的变化确定了粘结层的氧化过程中氧化物成分从Al₂O₃变化到混合氧化物的过程;对陶瓷层电阻的拟合结果表明,陶瓷层在热循环250~350次之间的电阻变化与陶瓷层内微观结构以及应力的变化有关。     

航空发动机热障涂层材料体系的研究

介绍了热障涂层的结构、陶瓷表层材料和中间粘结层的材料发展趋势。热障涂层的结构已由经典的双层结构向成分、结构连续变化的梯度结构发展,涂层的寿命有明显的提高。制备方法中电子束物理气相沉积技术具有明显优势。热障涂层表层材料的最佳成分是(质量百分数6%～8%)Y2O3部分稳定的ZrO2陶瓷材料。粘结层体系发展的一个重要趋势是能同时保证力学性能和抗氧化性能的低Al含量NiCoCrAlY。     

电子束物理气相沉积YSZ热障涂层热循环性能

考察了YSZ热障涂层的抗热循环性能;分别利用SEM、XRD分析了热循环前后涂层的显微结构和相组成。经分析可知,YSZ热障涂层具有典型的柱状晶结构,沉积态时YSZ涂层为t/t′相,经过600次热循环后,YSZ涂层未发现脱落。     

Failure of EB-PVD Thermal Barrier Coatings Subjected to Thermo-Mechanical Loading

Thermal barrier coatings (TBCs) were developed to protect metallic blades and vanes working in turbo-engines. The two-layered structure TBCs, consisting of NiCoCrAlY bond coat and yttria stabilized zirconia (YSZ), were deposited on a cylinder of superalloy substrate by the electron beam-physical vapor deposition (EB-PVD). The failure mechanism of the TBCs was investigated with a thermo-mechanical fatigue testing system under the service condition similar to that for turbine blades. Non-destructive evaluation of the coated specimens was conducted through the impedance spectroscopy. It is found that the crack initiation mainly takes place on the top coat at the edge of the heated zones.     

Hot Corrosion Behavior of Double-ceramic-layer LaTi2 Al9O19/YSZ Thermal Barrier Coatings

LaTi 2 Al 9 O 19 (LTA) exhibits promising potential as a new kind of thermal barrier coating (TBC) material, due to its excellent high-temperature capability and low thermal conductivity. In this paper, LTA/yttria stabilized zirconia (YSZ) TBCs are produced by atmospheric plasma spraying. Hot corrosion behavior and the related failure mechanism of the coating are investigated. Decomposition of LTA does not occur even after 1 458 hot corrosion cycles at 1 373 K, revealing good chemical stability in molten salt of Na 2 SO 4 and NaCl. However, the molten salt infiltrates to the bond coat, causing dissolving of the thermally grown oxide (TGO) in the molten salt and hot corrosion of the bond coat. As a result, cracking of the TBC occurs within the oxide layer. In conclusion, the ceramic materials LTA and YSZ reveal good chemical stability in molten salts of Na 2 SO 4 and NaCl, and the bond coat plays a significant role in providing protection for the component against hot corrosion in the LTA/YSZ TBCs. LTA exhibits very promising potential as a novel TBC material.     

梯度热障涂层的设计

 采用电子束物理气相沉积方法 (EB PVD)制备了梯度热障涂层,其结构设计为NiCoCrAlY粘结层 /Al₂O₃ YSZ过渡层 /YSZ陶瓷层。YSZ陶瓷层的结构为柱状晶结构,Al₂O₃ YSZ梯度过渡层为梯度微孔结构。采用有限元方法对梯度热障涂层进行热应力分析,优化了Al₂O₃ YSZ梯度过渡层的组成。计算结果表明,梯度涂层的内应力显著降低,而且界面及其附近应力和应变变化较平缓。过渡层厚度的增加有利于降低涂层内应力和缓和涂层界面处的应力集中。     

热障涂层杨氏模量和泊松比的测试

为了降低航空发动机热端部件的温度,空气等离子喷涂已被广泛地应用。为确定热障涂层的残余应力、结合力、断裂韧性、疲劳裂纹扩展速率等性能和特性,需要知道其杨氏模量和泊松比。因为涂层厚度非常薄且使用时是结合在基体上的,所以需要一个能够在原处测量涂层的杨氏模量和泊松比的方法。采用等离子喷涂工艺在GH150高温合金上喷涂了MCrAIY和陶瓷层,利用一种改进的悬臂梁方法测量了热障涂层的杨氏模量和泊松比。这种无损测试方法为测定其他薄膜材料的杨氏模量和泊松比提供了借鉴。     

纳米结构热障涂层的制备与性能研究

为充分发掘氧化锆(YSZ:ZrO2-6wt%Y2O3)基热障涂层的潜力,利用纳米级的YSZ粉末作为陶瓷涂层原材料,分别对采用等离子喷涂(APS)和电子束物理气相沉积(EB-PVD)沉积具有纳米结构陶瓷涂层的工艺过程进行全面研究.对比性试验结果表明,涂层中引入纳米结构使热障涂层具有更高的隔热效果,更高的硬度以及更高的抗剥落能力.并对纳米结构陶瓷涂层微观结构的高温稳定性进行研究分析.     

Influence of Gd2O3 and Yb2O3 Co-doping on Phase Stability,Thermo-physical Properties and Sintering of 8YSZ

The role of multicomponent rare earth oxides in phase stability, thermophysical properties and sintering for ZrO2-based thermal barrier coatings (TBCs) materials is investigated. 8YSZ codoped with 3 mol% Gd2O3 and 3 mol% Yb2O3 (GYb-YSZ) powders are synthesized by solid state reaction for 24 h at various temperatures. As temperature increases, stabilizers are dissolved into zirconia matrix gradually. Synthesized at 1 500 °C, GYb-YSZ is basically composed of cubic phase. GYb-YSZ exhibits excellent phase stability and sinters lower than 8YSZ by nearly three times. The thermal conductivity of GYb-YSZ is much lower than that of 8YSZ, and the thermal expansion coefficient of GYb-YSZ is comparable to that of 8YSZ. The influence of Gd2O3 and Yb2O3 co-doping on phase stability, thermal conductivity and sintering of 8YSZ is discussed.     

等离子喷涂工艺参数对GdPO4热障涂层组织结构和结合强度的影响

随着航空发动机涡轮进口温度提升,目前最广泛使用的Y₂O₃部分稳定ZrO₂(YSZ)热障涂层(TBCs)已难以满足需求,亟须发展新一代超高温TBCs。GdPO₄是一种极具应用前景的TBCs材料。本工作采用等离子喷涂方法制备GdPO₄/YSZ双陶瓷层结构TBCs,研究喷涂工艺参数特别是喷涂功率对GdPO₄陶瓷涂层相组成、表面形貌、微观结构以及结合强度的影响。结果表明:等离子喷涂GdPO₄过程中会有元素P损耗,得到的涂层除了GdPO₄外,还有一些Gd₃PO₇相;随着喷涂功率降低,Gd₃PO₇相含量减少;GdPO₄陶瓷涂层的主体结构由充分熔融的喷涂粒子堆垛构成,其中镶嵌有未熔化粒子构成的微区;随着喷涂功率降低,未熔化微区增多,涂层厚度降低;GdPO₄/YSZ TBCs的结合强度随喷涂功率降低而减小,主要是由于未熔化微区增多降低了涂层的内聚力;因此,低喷涂功率不利于涂层的结合强度。     

大气等离子喷涂热障涂层高温氧化行为研究

采用等离子喷涂工艺在GH4099合金基体上制备了热障涂层,并进行了1050℃恒温氧化试验,综合利用X射线衍射仪、扫描电子显微镜、能谱分析仪等检测手段,分析了涂层的显微结构及高温氧化行为。结果表明：等离子喷涂（APS）热障涂层在高温氧化过程中,黏结层被氧化生成热生长氧化物（TGO）。但长时间氧化后,在与TGO毗邻的金属黏结层中产生了范围较窄但浓度变化较大的贫Al带,TGO层出现保护性Al2O3向非保护性混合氧化物转变的现象,导致致密Al2O3层的连续性被破坏,TGO厚度快速增加。     

Effect of Sintering on Thermal Conductivity and Thermal Barrier Effects of Thermal Barrier Coatings

Thermal barrier coatings (TBCs) are mostly applied to hot components of advanced turbine engines to insulate the components from hot gas. The effect of sintering on thermal conductivity and thermal barrier effects of conventional plasma sprayed and nanostructured yttria stabilized zirconia (YSZ) thermal barrier coatings (TBCs) are investigated. Remarkable increase in thermal conductivity occurs to both typical coatings after heat treatment. The change of porosity is just the opposite. The grain size of the nanostructured zirconia coating increases more drastically with annealing time compared to that of the conventional plasma sprayed coating, which indicates that coating sintering makes more contributions to the thermal conductivity of the nanostructured coating than that of the conventional coating. Thermal barrier effect tests using temperature difference technique are performed on both coatings. The thermal barrier effects decrease with the increase of thermal conductivity after heat treatment and the decline seems more drastic in low thermal conductivity range. The decline in thermal barrier effects is about 80 °C for nanostructured coating after 100 h heat treatment, while the conventional coating reduces by less than 60 °C compared to the as-sprayed coating.     

EB-PVD热障涂层对IC10合金力学性能的影响

采用电弧离子镀技术在IC20合金基体上制备NiCrAlYSi粘结层,利用电子束物理气相沉积（EB—PVD）技术在粘结层上制备YSZ陶瓷面层。研究了YSZ热障涂层对IC10合金拉伸、持久、疲劳性能的影响。结果表明：IC10合金沉积YSZ热障涂层后,980℃／200MPa高温持久寿命与IC10合金相当;900℃高温抗拉强度σb、屈服强度σ0.2、伸长率占和断面收缩率砂与基体相比,基本保持不变;室温抗拉强度σb。屈服强度σ0.2：与基体相比稍有下降;800℃／447MPa疲劳寿命与基体合金相当。因此,IC10合金沉积TBCs涂层后,对IC10合金力学性能无明显影响,不影响合金的实际使用。     

表面处理对热障涂层界面微结构的影响

采用真空电弧离子镀技术在单晶高温合金DD32上制备HY5金属粘结层,通过振动光饰、吹砂2种不同的表面处理方法改变粘结层表面状态,再在粘结层表面利用电子束物理气相沉积技术制备陶瓷层。研究了不同处理方法对粘结层表面状态的影响;测试了不同表面处理方法下制备的热障涂层的高温氧化性能并对比分析了它们的变化规律。此外,探讨了不同表面处理方法对界面元素成分及失效特征的影响。研究结果表明,通过表面处理可以去除粘结层表面较大的凸起,提高表面平整度,提高热障涂层抗氧化性能。与粗糙界面相比,光滑界面形成的TGO层均匀致密,Al含量高。经长时间的高温氧化后,粗糙界面的TGO层出现明显皱曲现象,陶瓷层开裂剥落。     

热障涂层表面裂纹水浸超声检测

为有效检测热障涂层(TBCs)表面裂纹,进行了热障涂层表面裂纹水浸超声检测技术的应用研究。以常用的大气等离子喷涂(APS)热障涂层作为试验材料,采用水浸超声检测回波声程差和C扫描图像对不同深度、宽度和长度的热障涂层表面裂纹进行了表征。结果表明:热障涂层基体材料对热障涂层表面裂纹的检测效果无明显影响;通过优化检测参数和合理选用仪器探头,利用水浸超声方法可实现对热障涂层表面深度为0.1 mm、长度为2 mm裂纹的有效检测;水浸超声检测技术可以获得裂纹的长度、深度参数,是解决热障涂层表面裂纹检测问题的有效方法。      

等离子喷涂LaTi2Al9O19热障涂层的微观组织结构及热物理性能

 第一代热障涂层(TBCs)由氧化钇部分稳定的氧化锆(YSZ)陶瓷隔热层和金属粘结层组成,该涂层长期使用温度低于1 200℃。随着先进航空发动机向着高推重比发展,迫切要求发展新一代超高温、高隔热热障涂层材料。LaTi₂Al₉O₁₉(LTA)在1 500℃长期保持相稳定,是一种非常有前景的超高温热障涂层候选材料。本文采用大气等离子喷涂(APS)制备了LTA涂层,研究了喷涂工艺对涂层微观组织结构和热物理性能的影响。结果表明沉积态涂层中含少量的非晶态,在860℃和1 130℃出现晶化峰。等离子喷涂过程中La₂O₃挥发量较多,导致沉积态涂层中La元素与原始粉末相比含量偏低,而其他组分的化学成分随喷涂功率变化不大。LTA涂层的热扩散系数在1 400℃下为0.3~0.4 mm²·s^-1,热导率为1.1~1.6 W·m^-1·K^-1。1 050℃经过20小时热处理后,得到晶化的涂层在晶化温度范围内的热扩散系数和热导率值均增大。随着喷涂功率减小,涂层孔隙率增加,热导率减小。     

APS热障涂层氧化动力方程适用性实验

使用实验的方法研究了大气等离子喷涂(APS)热障涂层在4种不同高温环境下的氧化层生长规律, 并且使用目前常见的两种氧化层生长动力学曲线方程拟合了涂层氧化的实验数据, 分别得到了相应的方程特征参数值.研究结果表明:APS热障涂层在所研究的4种温度下的动力学曲线形式上是一致的;抛物线形式的动力学方程只能描述较高温度下的氧化层生长规律, 而幂函数形式的动力学方程对氧化温度的适应能力比较强, 能很好的描述在所研究的4种温度下APS热障涂层的生长规律.      

小孔喷丸强化工艺试验研究

依托试验研究,对航空零件喷丸强化技术的应用范围做出了有限的扩大。试验过程中,采用了遮蔽试片的方法,解决了小于试片尺寸的小孔表面喷丸强化的测定难题,通过大量的工艺试验,获得了合理的工艺参数,为零构件小孔的喷丸强化提供了基础。该试验的成功使得零件加工过程中将小孔喷丸应用范围扩大至Ф14．2,进一步拓展了喷丸工艺应用范围,为以后产品加工中小孔喷丸强化工艺的选取打下了基础。