粘结层中Co与Ni元素含量对热障涂层组织及寿命的影响

高温服役过程中热障涂层的MCrAlY粘结层形成致密的氧化铝层,从而提高了涂层和基体的抗氧化性能。利用等离子喷涂制备的热障涂层,其粘结层中的Co与Ni的含量和界面微观结构是影响氧化的重要因素。通过在Ni基高温合金基体上利用低压等离子喷涂(LPPS)分别制备粘结层为CoNiCrAlY和NiCoCrAlY的热障涂层进行高温循环氧化实验,比较研究了这两种热障涂层在1 050℃下的循环氧化寿命和失效特征。研究表明粘结层表面形貌对氧化物的生长具有重要影响,其中CoNiCrAlY粘结层更易在TGO层中形成尖晶石氧化物,最终无法形成连续的Al_2O_3层,导致涂层失效,而NiCoCrAlY粘结层表现出不同的失效方式。同时,粘结层和基体中Ni、Co等元素在氧化过程中存在强烈的互扩散,Co与Ni含量对两种涂层BC/基体界面处宏观空洞的生长产生了不同影响。     

热循环条件下NiCrAlYSi/YSZ热障涂层层间损伤及元素扩散行为研究

采用真空电弧镀设备制备热障涂层(TBCs)中的NiCrAlYSi金属粘结层,采用电子束物理气相沉积工艺(EB-PVD)制备YSZ陶瓷层,利用带能谱仪的扫描电子显微镜对沉积态和热循环损伤后的热障涂层试样的形貌、组织结构以及元素成分进行分析,研究热障涂层从热循环初期到失效的过程中层间损伤及元素扩散行为。结果表明,随着热循环时间的延长,NiCrAlYSi/YSZ涂层先后经历快速氧化和氧化速率很低的阶段,1100h后由于陶瓷层脱落,粘结层继续氧化导致涂层增重突然增大。热循环初期,Zr、O向内扩散,Ni、Cr、Al向外扩散,TGO层中的Al元素供应充足,主要发生Al的选择性氧化;1100h后,TGO层中Al元素供应不足,Cr、Ni开始氧化,生成Al_(1.92)Cr_(0.08)O_3和镍铝氧化物。这种不均匀的氧化使局部涂层体积膨胀,裂纹萌生于TGO层,随着裂纹的增殖、生长,最终贯穿等轴晶区和TGO层,导致热障涂层失效。     

YZrHf热障涂层的制备及热震性能分析

目的 研究喷涂态YZrHf热障涂层的微观组织及其抵抗高温热冲击的性能,探讨高温条件下热生长氧化物(TGO)对陶瓷层的影响。方法 采用大气等离子喷涂(APS)技术制备厚度约为300μm的YZrHf热障涂层,并将涂层在950℃下保温15 min后进行水冷循环热震实验,直至涂层剥落失效,使用SEM、EDS、X射线衍射仪对制备态及热震实验后的热障涂层微观组织进行分析。结果 涂层表面粗糙不平且分布有十几到几十微米长度的网状裂纹,这些相互贯通的裂纹为氧气的进入提供了通道。经过101次循环热震实验后,涂层部分区域剥落失效,SEM结果显示,在陶瓷层/黏结层界面处、黏结层内部均出现了热生长氧化物,且在陶瓷层中分布有横向、纵向的贯通性裂纹,而在TGO生长区域,也出现了一些小裂纹,但涂层并未剥落。经测定分析可知,TGO的主要成分为Al₂O₃、Cr₂O₃、NiO以及尖晶石氧化物组成的混合物(CSN)。结论 热震实验后TGO层中Al元素贫化,Ni、Cr等元素向界面处迁移参与反应,同时尖晶石氧化物以α-Al₂     

热障涂层失效机理研究进展

热障涂层(TBCs)具有良好的隔热性能,是航空发动机和燃气轮机高温部件的关键材料.在高温服役状态,涂层的剥落会导致严重的问题,因此涂层的失效机理是热障涂层研究中急需解决的关键问题.除了受到热应力的影响以外,涂层的失效还受到热生长氧化物(TGO)的生成和长大的影响,本文介绍了粘结层的氧化、TGO的生成和长大以及微裂纹的产生、扩展、直到剥离脱落的整个失效过程;探讨了影响热障涂层失效的若干因素,并对其进行的各种改性研究进行了概述,分析总结了热障涂层失效相关研究的发展趋势.     

HVOF和APS喷涂制备掺杂超细Al2O3颗粒复合CoNiCrAlY涂层研究

在MCrACY中添加一定量Al2O3可提高其高温磨损性能.为此,将CoNiCrAlY和微米级Al2O3粉末颗粒按比例混合后在密封球磨机里球磨,筛分后得到复合CoNiCrAlY/Al2O3粉末颗粒.分别采用超音速火焰(HVOF)喷涂和大气等离子(APS)喷涂制备复合CoNiCrAlY/Al2O3涂层,并对喷涂粉末及2种涂层的形貌及性能进行了分析表征.SEM分析显示粉末颗粒内部含弥散分布的超细Al2O3颗粒.2种方式制备的涂层都含有弥散分布的超细Al2O3颗粒.HVOF制备的涂层中保留超细Al2O3颗粒较好.APS制备的涂层中超细Al2O3颗粒有所减少,涂层层间形成大量层状氧化物.2种方式制备的涂层中,HVOF制备的涂层硬度、结合强度高.     

热障涂层材料的研究进展

热障涂层技术广泛用于航空涡轮发动机等尖端领域,相关的研究涉及新型热障涂层材料的开发、粘结层成分和表面结构的优化、高温氧化后热生长氧化物(TGO)或TGO/粘结层(BC)界面处残余应力水平的检测、新型涂层制备工艺的开发等诸多方面.主要阐述了时7-8YSZ热障涂层材料的改良、烧绿石结构材料的开发、超音速微粒轰击粘结层表面细...     

EB-PVD 热障涂层TGO中氧化物混合区的形成及其影响

研究了电子束物理气相沉积热障涂层在1150～30℃之间的循环氧化行为;分析了TGO中YSZ-Al2O3混合区的形成过程及其对TGO的生长与TBCs失效的影响.TGO的向外生长和TBC沉积时形成的YSZ细晶区是形成YSZ-Al2O3混合区的两个重要条件.YSZ-Al2O3混合区对TBCs失效的影响表现在加速TGO的生长和裂纹易在该混合区形成两方面.     

火焰喷涂Al2O3/TiO2-NiCrBSi梯度热障涂层的微观组织

采用金相显微镜,SEM,EDAX,XRD等手段研究了1Cr18Ni9Ti基体上氧乙炔火焰喷涂制备的AI2O3／TiO2-NiCrBSi梯度热障涂层的微观结构。结果表明,涂层沿厚度方向陶瓷与合金组元较均匀过渡,二者之间结合良好。涂层制备过程中,陶瓷－合金组元之间没有发生化学反应,无新相生成。当两组元含量相差较大,涂层形成以高组元为基体相,低组元为第二相弥散分布的复合结构;当两组元含量相近时,则以带状分布。     

超音速微粒轰击粘结层对热障涂层抗氧化性能的影响

较长时间高温氧化,会使金属粘结层与热生长氧化物界面处贫铝,造成热喷涂陶瓷层失效.对金属粘结层进行超音速微粒轰击,可以增加铝扩散的浓度梯度,提高热障涂层的抗氧化能力.采用等离子喷涂(APS)在镍基高温合金GH99上制备了热障涂层,并对粘结层进行了超音速微粒轰击处理,研究了该处理工艺对粘结层显微结构及高温氧化行为的影响.结果表明:APS热障涂层经1 050 ℃、96 h氧化后.热生长氧化物层产生大量非保护性混合氧化物;超音速微粒轰击工艺使粘结层表层区域产生大量位错等缺陷,涂层经1 050 ℃、3 h氧化后进入稳态氧化期,同时出现Al在粘结层表层的富集,经1 050 ℃、196 h氧化后粘结层无加速氧化趋势,热障涂层的抗高温氧化性能得到提高.     

溅射Ni11Co26Cr6Al0.5Y涂层对镍基合金在1000 ℃氧化行为的影响

通过对有/无Ni11Co26Cr6Al0.5Y涂层镍基合金在1000℃进行氧化动力学曲线测定,及组织结构观察,研究了Ni11Co26Cr6Al0.5Y涂层对镍基合金高温氧化行为的影响。结果表明:高温氧化期间,合金发生外氧化和内氧化,外氧化层由NiO、NiCrO_4、CoWO_4构成,中间氧化物由TiO_2、Al_2O_3、NiWO_4构成,中间层氧化物层抑制了基体中Al元素向外扩散,形成平直连续的Al_2O_3内氧化物层;合金氧化动力学曲线呈现起伏波动的特征。镍基合金经溅射Ni11Co26Cr6Al0.5Y涂层,可有效改善合金的抗氧化性能;涂层的氧化动力学曲线仅在氧化初期有轻微增重而后趋于平稳,遵循抛物线规律,其形成的Al_2O_3氧化膜未发生明显剥落,仅在涂层内及近涂层/基体界面区域存在少量Al_2O_3内氧化物。     

Influence of Water Vapor on the Isothermal Oxidation Behavior of Thermal Barrier Coatings

The oxidation of specimens with thermal barrier coating (TBC) consisted of nickel-base superalloy, low-pressure plasma sprayed Ni-28Cr-6AI-0.4Y (wt pct) bond coating and electron beam physical vapor deposited 7.5 wt pct yttria stabilized zirconia (YSZ) top coating was studied at 1050℃ respectively in flows of 02, and mixture of O2 and 5%H2O under atmospheric pressure. The thermal barrier coating has relatively low oxidation rate at 1050℃ in pure O2. Oxidation rate of thermal barrier coating in the atmosphere of O% and 5%H2O is increased The oxidation kinetics obeys almost linear law after long exposure time in the presence of 5% water vapor. Oxide formed along the interface between bond coat and top coat after oxidation at 1050℃ in pure O2 consisted of Al2O3, whereas interfacial scales formed after oxidation at 1050℃ in a mixture of O2 and 5%H2O were mainly composed of Ni(AI,Cr)2O4,NiO and AI2O3. It is suggested that the effect of water vapor on the oxidation of the NiCrAlY coating may be attributed     

Einfluss einer PVD‐Al‐Zwischenschicht auf die Eigenschaften eines thermisch gespritzten Wärmedämmschichtsystems nach Temperaturwechselbelastung

Thermal barrier coatings (TBC) generally consist of a metallic bond coat (BC) and a ceramic top coat (TC). Co–Ni–Cr–Al–Y metallic super alloys and Yttria stabilised zirconia (YSZ) have been widely used as bond coat and top coat for thermal barrier coatings systems, respectively. As a result of long‐term exposure of thermal barrier coatings systems to oxygen‐containing atmospheres at high temperatures, a diffusion of oxygen through the porous ceramic layer occurs and consequently an oxidation zone is formed in the interface between ceramic top coat and metallic bond coat. Alloying components of the BC layer create a so‐called thermally grown oxides layer (TGO). One included oxide type is α‐Al₂O₃. α‐Al₂O₃ lowers oxygen diffusion and thus slows down the oxidation process of the bond coat and consequently affects the service life of the coating system positively. The distribution of the alloying elements in the bond coat layer, however, generally causes the formation of mixed oxide phases. The different oxide phases have different growth rates, which cause local stresses, micro‐cracking and, finally, delamination and failure of the ceramic top coat layer. In the present study, a thin Al inter‐layer was deposited by DC‐Magnetron Sputtering on top of the Co–Ni–Cr–Al–Y metallic bond coat, followed by thermal spraying of yttria‐stabilised zirconia (YSZ) as a top coat layer. The deposited Al inter‐layer is meant to transform under operating conditions into a closed layer with high share of α‐Al₂O₃ that slows down the growth rate of the resulting thermally grown oxides layer. Surface morphology and microstructure characteristics as well as thermal cycling behaviour were investigated to study the effect of the intermediate Al layer on the oxidation of the bond coat compared to standard system. The system with Al inter‐layer shows a smaller thermally grown oxides layer thickness compared to standard system after thermal cycling under same conditions.     

镀铝表面改性7YSZ纳米热障涂层热震性能分

为提高7YSZ纳米热障涂层的热震性能, 实验中采用超音速火焰喷涂(HVOF)在涡轮叶片模拟工件上制备了粘结层NiCrCrAlYTa, 再使用大气等离子喷涂(APS)在粘结层上制备了7YSZ纳米陶瓷层。采用磁控溅射在7YSZ热障涂层样品表面镀铝, 并在不同压力下(200、250、300 Pa)对镀铝样品进行热处理表面改性。对喷涂态样品和镀铝改性后样品进行水淬热震实验, 1050℃保温10 min+水冷5 min为一个热循环, 观察热障涂层镀铝改性前后样品在水淬热循环过程中形貌和结构演变。实验结果表明, 镀铝改性后样品表面存在铝薄膜蒸发、凝固后形成的疏松纳米Al晶粒表层以及由Al和ZrO₂原位反应形成的致密α-Al₂O₃底层。在镀铝样品热处理过程中, 随着压力升高, 疏松层致密度逐渐增加。不同热处理压力下镀铝表面改性后样品经过73次水淬热循环后剥落面积均小于喷涂态样品, 显示出良好的抗热震性。     

等离子喷涂与溶胶-凝胶法组合制备中高温太阳能选择性吸收复合涂层

为了制备出高效的非真空、中高温太阳能选择性吸收涂层,先在光亮Cu片上等离子喷涂Cr—Al2O3金属陶瓷吸收层,再用溶胶-凝胶法在其上制备了SnO2选择性透过膜,对复合涂层的相结构、表面形貌、光学性能进行了研究。结果表明：金属陶瓷吸收层由金属颗粒Cr与Al2O3组成,物相稳定,表面凹凸不平,气孔较多,发射率较高;覆盖Sn...     

Microstructure and thermal behaviour of plasma sprayed zirconia/alumina composite coating

In thermal barrier coatings (TBC), failure occurs near or at the interface between the metallic bondcoat and topcoat. On high temperature conditions, an oxide scale which is named thermally grown oxide (TGO) occurs along the bond/topcoat interface. For diminishing the creation of TGO, a dense coating with low residual stress and thermal stress buffer layer was preferable. High hardness ceramic coatings could be obtained by gas tunnel type plasma spraying, and the deposited coating had superior property in comparison with those deposited by conventional type plasma spray method. In this study, the gas tunnel type plasma spraying system was utilized to produce a zirconia/alumina functionally graded thermal barrier coating and discussed its physical and mechanical properties, thermal behavior and high temperature oxidation resistance of the coating are discussed. Consequently, the proposed system exhibited superior mechanical properties and oxidation resistance at the expenses of a slightly lower thermal insulating effect. This interlayer is preferred in order to minimize the detrimental effect of the phase transformation of gamma-Al2O3 to alpha-Al2O3.     

电弧喷涂Al,45CT及其复合涂层的抗高温氧化性能与机理

为获得抗氧化性能优良的涂层,采用电弧喷涂方法制备了Al,45CT及其复合涂层,探讨了3种涂层过渡层的形貌、物相及其相应的作用,分析了3种涂层的组织结构、抗氧化性能与机理。结果表明:Al涂层和复合涂层高温氧化后表面氧化膜有剥落现象,涂层中的抗氧化元素Cr含量很低;45CT涂层中的抗氧化元素Cr含量仍然很高,涂层的自我修复能力很强,表面生成的Cr2O3氧化膜具有优异的抗氧化性能;在涂层与基体结合处有一层过渡层,不仅增强了涂层与基体的结合力,还能进一步阻止氧化性气体向基体入侵,起到二次保护作用。     

冷喷涂制备TiAl_3-Al复合层及其抗高温氧化性能

为了提高γ-TiAl合金的抗高温氧化性能,采用冷喷涂技术在γ-TiAl合金基体上喷涂纯Al层后进行热扩散处理,制备了厚约250μm的TiAl3-Al复合涂层,研究了该涂层在950℃下的长时间高温氧化行为,用X射线衍射仪(XRD)分析了复合涂层的相组成,用场发射电子显微镜研究了其形貌,用电子探针分析了其成分。结果表明:冷喷涂纯Al层致密,存在少量微裂纹和微气孔;TiAl3-Al复合涂层和基体之间生成了TiAl3相,TiAl3与Al的界面有空洞;γ-TiAl合金高温氧化70 h即失重,氧化产物为TiO2和Al2O3的混合物;TiAl3-Al复合涂层进入稳态氧化阶段后,增重缓慢,遵循近抛物线规律,高温氧化1 000 h后涂层仍完好,氧化产物主要为Al2O3相,还有微量的TiO2及钛氮化合物;TiAl3-Al复合涂层提高了γ-TiAl合金的抗高温氧化性能。     

大气等离子体喷涂Sm2Zr2O7涂层的结构和性能

稀土锆酸盐材料具有比Y2O3部分稳定ZrO2陶瓷低的热导率,是新型热障涂层的潜在候选材料之一.利用大气等离子体喷涂技术以喷雾造粒的Sm2Zr2O7粉体制备涂层,并在相同条件下沉积8wt%Y2O3稳定ZrO2涂层.对比评价了两种涂层的结构、热物理性能和力学性能.X射线衍射结果表明,制备态Sm2Zr2O7涂层为缺陷萤石结构.扫描电镜分析显示,Sm2Zr2O7和8wt%Y2O3稳定ZrO2涂层为典型的层状结构,内部有很多气孔、裂纹等缺陷.800℃测得的Sm2Zr2O7涂层的热导率为0.44 W/(m.K),比相同条件下测得的8wt%Y2O3稳定ZrO2涂层的热导率低~40%,两者的热膨胀系数相似.力学测试结果显示,Sm2Zr2O7涂层的抗折强度、硬度和弹性模量均低于8wt%Y2O3稳定ZrO2涂层.     

The effect of bond coat oxidation on the microstructure and endurance of a thermal barrier coating system

Abstract

Isothermal oxidation tests have been carried out on a thermal barrier coating (TBC) system consisting of a nickel-based superalloy, CoNiCrAlY bond coat applied by HVOF and yttria-stabilised zirconia (YSZ) top coat applied by EB-PVD. Bond coat microstructure, coating cracking and failure were characterised using high resolution scanning electron microscopy complemented with compositional analyses using energy dispersive X-ray spectrometry. A protective alumina layer formed during the deposition of the YSZ top coat and this grew with sub-parabolic kinetics during subsequent isothermal oxidation at temperatures in the range 950 to 1150°C. After short exposures at 1050°C and final cooling, small sub-critical cracks were found to exist within the YSZ but adjacent to bond coat protuberances. Their formation is related to the development of local tensile strains associated with the growth of an alumina layer (TGO) on the non-planar bond coat surface. However, for the specimens examined, these cracks did not propagate, in contrast to other TBC systems, and final spallation was always found to have occurred at the bond coat/TGO interface. This shows that the strain energy within the TGO layer made a significant contribution to the delamination process.