La2(Zr0.7Ce0.3)2O7——新型高温热障涂层

采用电子束物理气相沉积技术(EB-PVD)制备了新型La2(Zr0.7Ce0.3)2O7 (LZ7C3)热障涂层.研究了涂层的组分、显微结构、表面和横截面形貌以及恒温氧化行为.结果表明:涂层中La2O3/ZrO2/CeO2的相对含量偏离了化学计量比,但X 射线衍射(XRD)相结构与靶材非常相似.通过CeO2 掺杂后,LZ7C3体材料的热膨胀系数比La2Zr2O7 (LZ)大;在1100℃恒温氧化890h的条件下,LZ7C3涂层的抗氧化增重性能明显优于传统的Y2O3部分稳定化的ZrO2(8YSZ)涂层.此外,热膨胀不匹配、黏结层氧化和陶瓷涂层内部微观裂纹的出现可能是导致LZ7C3涂层恒温氧化失效的主要原因.     

Microstructure behaviour and influence on thermally grown oxide formation of double‐ceramic‐layer EB‐PVD thermal barrier coatings annealed at 1,300 °C under ambient isothermal conditions

To resist high thermal loads in turbines effectively, turbine blades are protected by thermal barrier coatings in combination with additional air cooling. State‐of‐the‐art yttria stabilised zirconia top coats do not operate at temperatures higher than 1,200 °C. Promising candidates for alternative top coats are pyrochlores, lanthanum zirconate and gadolinium zirconate. But lifetime of pyrochlores is short because of spallation. However, combinations of yttria stabilised zirconia and lanthanum zirconate or gadolinium zirconate as multilayer systems are promising top layers operating at higher temperatures than yttria stabilised zirconia. Such thermal barrier coatings top coats as double‐ceramic‐layer systems consisting of 7 wt.% yttria stabilised zirconia and lanthanum zirconate or gadolinium zirconate were deposited by Electron Beam‐Physical Vapour Deposition. The focus of the work was set on the influence of the coating design and the microstructure variation generated at different rotating speeds on the adhesion and thermally grown oxide behaviour after isothermal oxidation at 1,300 °C. Phase formation of the thermal barrier coatings top coats was obtained using X‐ray diffraction. After isothermal oxidation tests for 50 h at 1,300 °C, both, microstructure change and the formation of the thermally grown oxide were investigated. While the pyrochlore single‐ceramic‐layer are completely spalled off, microstructure of the double‐ceramic‐layer reveals only crack initiation. The thermally grown oxide thickness was determined by means of scanning electron microscopy. A high aluminum and oxygen content in the thermally grown oxide is found using X‐ray spectroscopy. Existence of α‐phase in Al₂O₃ was proved by X‐ray diffraction. After isothermal testing, no phase transformation can be detected regarding the double‐ceramic‐layer coatings.     

Evaluation of mixed oxide formation and sintering behavior in thermal barrier coatings on nickel‐based superalloy

Thermal barrier coatings are widely used in aircraft turbines to protect nickel‐based superalloys from the effect of high temperature oxidation and hot corrosion. In this study, both NiCrAlY bond coat and yttria‐stabilized zirconia top coat were deposited using atmospheric plasma spray technique. After coating production, specimens were exposed to oxidation in air atmosphere at 900 °C, 1000 °C and 1100 °C for different periods of time up to 50 h. Microstructural transformations in the ceramic top coat and growth behavior of the thermally grown oxide layer were examined using scanning electron microscopy, porosity calculation, elemental mapping and hardness measurement. Formation of different types of oxides in the thermally grown oxide layer shows that this process strongly depends on deposition technique as well as on oxidation time and temperature. Hardness values of the top coat increased with a decrease in the porosity of the top coat. Uniformity and homogeneity of the thermally grown oxide layer and densification of the top coat were evaluated in terms of the structural durability of thermal barrier coating systems.     

Phases in Plasma Sprayed Thermal Barrier Coatings from Yttria Partially Stabilized Zirconia

The application of thermal barrier coatings (TBC) is increasing in aeroengines. Surface temperatures up to 1450°C require the application of ceramic TBCs because the temperature capability of metallic substrate materials is not high enough. The service life of turbine components could be improved by the use of yttria partially stabilized zirconia top coatings. The most successfull TBCs are made from 7–9 wt‐% yttria partially stabilized zirconia. One of the most discussed reasons of damages of such TBCs is the transformation between monoclinic and tetragonal phase in zirconia in connection with a dramatic change in volume. Thus in this work resulting phases of plasma sprayed zirconia coatings were investigated. It was found that no monoclinic phase could be detected after heat treatments at 1300, 1400 and 1466°C with cooling rates > 2°/min. Only with cooling rates < 2°/min monoclinic phases occured. It can be concluded that the metastable tetragonal high temperature configuration of yttria partially stabilized zirconia is “very stable”. The conditions in aeroengines with cooling rates > 2°C prevent the formation of the monoclinic phase in zirconia.     

Modification of NiCoCrAlY with Pt: Part Ⅱ. Application in TBC with pure metastable tetragonal(t’) phase YSZ and thermal cycling behavior

A thermal barrier coating system comprising Pt-modified NiCoCrAlY bond coating and nanostructured 4mol.% yttria stabilized zirconia(4YSZ, hereafter) top coat was fabricated on a second generation Ni-base superalloy. Thermal cycling behavior of NiCoCrAlY-4 YSZ thermal barrier coatings(TBCs) with and without Pt modification was evaluated in ambient air at 1100?C up to 1000 cycles, aiming to investigate the effect of Pt on formation of thermally grown oxide(TGO) and oxidation resistance. Results indicated that a dual layered TGO, which consisted of top(Ni,Co)(Cr,Al)_2O_4 spinel and underlying α-Al_2O_3, was formed at the NiCoCrAlY/4 YSZ interface with thickness of 8.4μm, accompanying with visible cracks at the interface. In contrast, a single-layer and adherent α-Al_2O_3 scale with thickness of 5.6μm was formed at the interface of Pt-modified NiCoCrAlY and 4 YSZ top coating. The modification of Pt on NiCoCrAlY favored the exclusive formation of α-Al_2O_3 and the reduction of TGO growth rate, and thus could effectively improve overall oxidation performance and extend service life of TBCs. Oxidation and degradation mechanisms of the TBCs with/without Pt-modification were discussed.     

Oxidation behaviour of an intermetallic Ti–Al–Cr–Zr bond coat on a γ–TiAl based TNB alloy with 7YSZ thermal barrier coating

Abstract

Intermetallic titanium aluminide alloys are attractive light-weight materials for high temperature applications in automotive and aero engines. The development of γ-TiAl alloys over the past decades has led to their successful commercial application as low pressure turbine blades. The operating temperatures of γ-TiAl based alloys are limited by deterioration in strength and creep resistance at elevated temperatures as well as poor oxidation behaviour above 800 °C. Since improvement in oxidation behaviour of γ-TiAl based alloys without impairing their mechanical properties represents a major challenge, intermetallic protective coatings have aroused increasing interest in the last years.

In this work, a 10 μm thick intermetallic Ti–46Al–36Cr–4Zr (in at.-%) coating was applied on a TNB alloy using magnetron sputtering. This layer provided excellent oxidation protection up to 1000 °C. Microstructural changes in this coating during the high temperature exposure were extensively investigated using scanning and transmission electron microscopy. The coating developed a three-phase microstructure consisting of the hexagonal Laves-phase Ti(Cr,Al)₂, the tetragonal Cr₂Al phase and the cubic τ-TiAl₃ phase. After long-term exposure the three-phase microstructure changed to a two-phase microstructure of the hexagonal α₂-Ti₃Al phase and an orthorhombic body-centred phase, whose crystal structure has not yet been definitely identified. On the coating, a thin protective alumina scale formed. Applying this intermetallic layer as bond coat, thermal barrier coatings (TBCs) of yttria partially stabilized zirconia were deposited on γ-TiAl based TNB samples using electron-beam physical vapour deposition. The results of cyclic oxidation testing (1 h at elevated temperature, 10 min. cooling at ambient temperature) revealed a TBC lifetime of more than 1000 h of cyclic exposure to air at 1000 °C. The ceramic topcoat exhibited an excellent adhesion to the thermally grown alumina scale which contained fine ZrO₂ precipitates.     

Entwicklung von Oxid – Keramik zur Anwendung als Wärmedämmschichten

Development of Oxide Ceramics for an Application as TBC The standard thermal barrier coating material yttria stabilised zirconia (YSZ) is limited in long term operation to a maximum temperature of about 1200°C. As a result further increase of the gas inlet temperature and hence the efficiency of gas turbines are hardly to achieve with YSZ coatings. In a screening procedure especially perowskite (ABO₃, A = Sr,Ba, B = Zr) and pyrochlore (A₂B₂O₇, e.g. A = La and other rare earth elements, B = e.g. Zr) materials have been identified as possible candidates for thermal barrier coatings. Basic physical properties (e.g. thermal expansion coefficient, thermal diffusivity and conductivity) of several candidates have been determined using sintered, dense samples. The possibility of optimization of the properties by using specific compositions will be discussed. From promising materials powders which are suitable for plasma‐spraying have been produced by spray‐drying. New TBC systems consisting of new materials (BaZrO₃, La₂Zr₂O₇) deposited by atmospheric plasma spraying and vacuum plasma sprayed MCrAlY bondcoats were tested in a gas burner facility. Especially La₂Zr₂O₇ coatings gave promising results. A further improvements could be achieved by the use of layered or graded coatings with a YSZ coating at the bondcoat interface and on top a layer of the new TBC material. First results of thermal cycling tests with 1250 and 1350°C surface temperature will be presented.     

Thermally grown oxide scales on γ-TiAl coated with thermal protection systems

Abstract

Thermal barrier coatings (TBCs) of yttria partially stabilized zirconia were deposited on gamma TiAl samples using electron-beam physical vapour deposition. The specimens were coated with intermetallic Ti –Al – Cr layers and CrAlYN/CrN nanoscale multilayer coatings. The lifetime of the TBC systems was determined performing cyclic oxidation tests in air at temperatures between 850 and 950–C. The TBC systems with Ti –Al – Cr and CrAlYN/CrN layers did not fail at 850 and 900–C during the maximum exposure time period of 1000 cycles of 1 h dwell time at high temperature. No spallation of the thermal barrier coatings was observed. As revealed by post-oxidation microstructural analysis, the protective coatings were severely degraded when exposed at 900–C, resulting in growth of mixed oxides on the substrate. Underneath the thermal barrier coating an outer oxide scale with a columnar structure was observed, consisting of rutile and α-Al₂O₃. Energy-dispersive X-ray spectroscopy analysis revealed zirconia and chromia being dissolved in the outer oxide scale. The columnar structure and the presence of zirconia indicated an effect of the TBC on the morphology of the outer oxide scale. The zirconia top coat exhibited an excellent adherence to this oxide scale formed on the protective layers when degraded, and at defects like cracks. When thermally cycled at 950–C, the TBC system on specimens coated with Ti –Al – Cr failed by spallation of the thermally grown mixed oxides, whereas the thermal barrier coating was well adherent to the outer oxide scale at this temperature, too.     

Coatings on graphite crucibles used in melting uranium

Standard coatings for graphite crucibles used for melting uranium have generally been zirconia based and have been applied as a paint or by flame spraying. These coatings do not provide adequate protection at the temperatures normally required for melting uranium alloys. Yttria provides superior protection above 1300°C but becomes less satisfactory above 1450°C when applied directly on graphite. The utilization of a protective niobium/zirconia bilayer coating between the yttria and the graphite results in improved performance at 1500°C. Yttria has been satisfactorily applied both by plasma spraying and by brush applying a stable suspension. When the protective niobium layer is used, coating adherence after melting is excellent and multiple use of coatings is practical. The coatings adhere to graphite with a high coefficient of thermal expansion (CTE) (≈7 μm m^-1 °C^-1) much better than to standard crucible grade graphite (≈4μm m^-1 °C^-1). A single Nb/Y₂O₃-coated high CTE graphite crucible has been used for seven melts at 1450°C without repair or increased carbon contamination.The yttria paint coating is cost effective when compared with flame- or plasma-sprayed zirconia.     

Adhesive strength of new thermal barrier coatings of rare earth zirconates

La₂Zr₂O₇ (LZ) and La₂(Zr_0.7Ce_0.3)₂O₇ (LZ7C3) as novel candidate materials for thermal barrier coatings (TBCs) were prepared by electron beam-physical vapor deposition (EB-PVD). The adhesive strength of the as-deposited LZ and LZ7C3 coatings were evaluated by transverse scratch test. Meanwhile, the factors affecting the critical load value were also investigated. The critical load value of LZ7C3 coating is larger than that of LZ coating, whereas both values of these two coatings are lower than that of the traditional coating material, i.e. 8 wt% yttria stabilized zirconia (8YSZ). The micro-cracks formed in the scratch channel can partially release the stress in the coating and then enhance the adhesive strength of the coating. The width of the scratch channel and the surface spallation after transverse scratch test are effective factors to evaluate the adhesive strength of LZ and LZ7C3 coatings.     

Calcia-doped yttria-stabilized zirconia for thermal barrier coatings: synthesis and characterization

Doping with other oxides has been a stabilization method of ZrO₂ for thermal barrier coating applications. Such a stabilized system is 7–8 mol% YO_1.5-doped zirconia (7YSZ), which has been in use for around 20 years. In this study, calcia (CaO) and yttria (Y₂O₃) have been used for doping ZrO₂ to produce a stable single-phase cubic calcia-doped yttria-stabilized zirconia (CaYSZ). This has been synthesized using wet chemical synthesis as well as by solid-state synthesis. Unlike partially stabilized zirconia where 5 mol% CaO is doped into ZrO₂, CaYSZ has been found to be stable up to 1600 °C. Detailed CaYSZ synthesis steps and phase characterization are presented. Wet chemical synthesis resulted in a stable single-phase CaYSZ just after 4 h treatment at 1400 °C, whereas a 36 h annealing at 1600 °C is required for CaYSZ synthesis during solid-state processing. The CaYSZ has been found stable even for 600 h at 1250 °C. Coefficient of thermal expansion and sintering temperature of CaYSZ was found to be 11 × 10⁻⁶ K⁻¹ and 1220 °C, respectively, which are comparable to 7YSZ. An increase in sintering rate with increasing dopant concentration has also been observed.     

Oxide layer development under thermal cycling and its role on damage evolution and spallation in TBC system

The nature and cause of failure of thermal barrier coatings (TBCs) consisting of physical vapor deposited (PVD) yttria stabilized zirconia (YSZ, 8 wt.% Y₂O₃) and a diffusion aluminide bond coat (Pt-Al) were investigated after oxidative thermal cycling and isothermal heat treatment at 1177 °C in air. Experiments were conducted for 45 and 10-minute hold times and for isothermal condition for disk specimens with and without TBC. It is found that microcracks starts in the oxide scales at the bond coat grain boundary protrusions. Total number of thermal cycles affect the density of microcracks within the TGO layer. Evidence is presented that higher density of microcracks in the 10-min hold-time experiments tend to separate the TBC from the TGO layer via extensive coating micro-decohesion and promotes 'complete' TBC separation as opposed to traditional 'partial' spallation of TBC from the substrate as in the 45-min hold-time and isothermal experiments.     

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.     

Thermal barrier coatings produced by laser cladding

A 2kW C0₂ laser has been used to clad a mild steel substrate with two different ceramic coatings, namely yttria partially stabilized zirconia (8 wt% YPSZ) or a mixture of YPSZ and pure alumina powder. A range of laser processing parameters has been investigated. Results have been obtained showing the possibility of using the laser beam for producing a clad layer of thermal barrier coating with different topography depending on the processing conditions.On leave from Scientific Research Council, Baghdad, Iraq.     

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.     

Thermal and crystallization behavior of zirconia precursor used in the solution precursor plasma spray process

Yttria stabilized zirconia (7YSZ) solution precursor has been successfully used in the deposition of high durability thermal barrier coatings. In this paper, the thermal and crystallization behaviors of 7YSZ precursor were investigated by TG-DTA, FTIR and XRD. The results show that the precursor decomposition and crystallization temperatures greatly depend on heating rate e. g. 74°C for the crystallization temperature when tripping the heating rate. With a 10 °C/min heating rate, the weight loss due to precursor pyrolysis occurs predominantly at temperatures below 500 °C. A small weight loss due to the oxidation of residual carbon is detected from 800 °C to 950 °C. The complete crystallization of the tetragonal phase was determined to be around 500 °C by DTA and XRD analyses with a 10 °C/min heating rate. The crystallization kinetics and the activation energy of amorphous 7YSZ precursor were investigated by variable heating rate DTA. The calculated activation energy is 66.2 kJ/mol. The Avrami parameter value was determined to be 2.68, which indicates that crystallization nucleation and growth is diffusion-controlled. The crystalline phase of 7YSZ coatings deposited by the Solution Precursor Plasma Spray process was identified by XRD and Raman spectrum. The average YSZ grain size in the SPPS coating was determined to be 61 nm.     

Thermal barrier coatings for jet engine improvement

The aim of these investigations is to develop thermal barrier coatings (TBCs) with improved resistance against thermal cycling to prevent problems of over-heating in the hot section of jet engines. Plasma-sprayed TBCs consisting of an Ni-Cr-Al bond coat and zirconia overlayers stabilized with different materials (CaO, MgO or Y₂O₃) were tested in a burner rig under thermocyclic conditions, in a hot gas centrifugal rig and in a modern jet engine. These tests demonstrate good correlation between the failure mode of the coatings in the thermocyclic tests and in engine tests. The best performance in all tests was shown by zirconia partially stabilized with yttria according to microanalytical investigations of the unstressed and stressed TBCs. Furthermore, heat treatments as well as ongoing optimization of the spraying parameters of the TBCs demonstrate potential improvement.     

Study of YSZ-based electrochemical sensors with oxide electrodes for high temperature applications

Potentiometric sensors based on yttria stabilized zirconia (YSZ) with WO₃ as sensing electrode were fabricated using either Pt or Au electrodes. The sensors were studied in the temperature range 550–700°C in the presence of different concentrations (300-1000 ppm) of NO₂ and CO in air. The response to NO₂ was very stable with fast response time (20-40 s). The best sensitivity (18.8 mV/decade) using Pt electrodes was observed at 600°C. At the same temperature a cross-sensitivity (-15 mV/decade) to CO gas was also noticed. The response to CO was decreased (-4 mV/decade) using Au electrode. The role played by WO₃ on the sensing electrode was discussed.     

Mechanical behaviour of as sprayed and sintered air plasma sprayed partially stabilised zirconia

Abstract

The mechanical behaviour of free standing air plasma sprayed (APS) partially yttria stabilised zirconia (P-YSZ) thermal barrier coatings (TBC) at room temperature and at elevated temperatures up to 1050°C have been investigated. Creep tests under constant compressive load have been conducted as well as cyclic measurements of compressive stress – strain hysteresis loops with increasing maximum load, yielding Young's moduli of the porous partially yttria stabilised zirconia. Both mechanical parameters are needed for accurate modelling of the local stress fields of, for example, airfoils to identify critical regions where damage or even failure of the component may occur. Specimens in the as sprayed and sintered state were tested. The microstructural changes caused by sintering and mechanical loading at high temperature of the thermal barrier coatings have been characterised by porosity measurements made from metallographic cross-sections.     

Influence of the Thermal Barrier Coatings Design on the Oxidation Behavior

The properties of two different types of thermal barrier coatings(TBCs) were compared to improve the surface characteristics on high temperature components.These TBCs consisted of a duplex TBC and a five-layered functionally graded TBC.NiCrAlY bond coats were deposited on a number of Inconel-738LC specimens using high velocity oxy-fuel spraying(HVOF) technique.For duplex coating,a group of these specimens were coated with yttria stabilized zirconia(YSZ) using plasma spray technique.Functionally graded NiCrA...