Furnace cyclic oxidation behavior of multicomponent low conductivity thermal barrier coatings

Ceramic thermal barrier coatings (TBCs) will play an increasingly important role in advanced gas turbine engines due to their ability to further increase engine operating temperatures and reduce cooling, thus helping achieve future engine low emission, high efficiency, and improved reliability goals. Advanced multicomponent zirconia (ZrO₂)-based TBCs are being developed using an oxide defect clustering design approach to achieve the required coating low thermal conductivity and high-temperature stability. Although the new composition coatings were not yet optimized for cyclic durability, an initial durability screening of the candidate coating materials was conducted using conventional furnace cyclic oxidation tests. In this paper, furnace cyclic oxidation behavior of plasma-sprayed ZrO₂-based defect cluster TBCs was investigated at 1163°C using 45 min hot-time cycles. The ceramic coating failure mechanisms were studied using scanning electron microscopy (SEM) combined with x-ray diffraction (XRD) phase analysis after the furnace tests. The coating cyclic lifetime is also discussed in relation to coating processing, phase structures, dopant concentration, and other thermo-physical properties.     

COSP: A computer model of cyclic oxidation

A computer model useful in predicting the cyclic oxidation behavior of alloys is presented. The model considers the oxygen uptake due to scale formation during the heating cycle and the loss of oxide due to spalling during the cooling cycle. The balance between scale formation and scale loss is modeled and used to predict weight change and metal loss kinetics. A simple uniform spalling model is compared to a more complex random spall site model. In nearly all cases, the simpler uniform spall model gave predictions as accurate as the more complex model. The model has been applied to several nickel-base alloys which, depending upon composition, form Al₂O₃ or Cr₂O₃ during oxidation. The model has been validated by several experimental approaches. Versions of the model that run on a personal computer are available.     

Investigation on the oxidation behaviour of gamma titanium aluminides coated with thermal barrier coatings

In the present study, the applicability of thermal barrier coatings (TBCs) on γ‐TiAl alloys was investigated. Two alloys with the chemical compositions of Ti‐45Al‐8Nb‐0.2B‐0.15C and Ti‐45Al‐1Cr‐6Nb‐0.4W‐0.2B‐0.5C‐0.2Si were used. Before TBC deposition, the specimens were pre‐oxidised in laboratory air or low partial pressure oxygen atmosphere. Yttria partially stabilised zirconia top coats were then deposited using electron‐beam physical vapour deposition (EB‐PVD). The oxidation behaviour of the γ‐TiAl specimens with TBC was studied by cyclic oxidation testing in air at 850 and 900 °C. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (EDS). No spallation of the TBC was observed for pre‐oxidised specimens of both alloys when exposed to air at 850 °C for 1100 cycles of 1 h dwell time at high temperature. SEM micrographs of the thermally grown oxide scale revealed outer mixed TiO₂/Al₂O₃ protrusions with a columnar structure. The protrusions contained small particles of zirconia and a low amount of about 0.5 at% zirconium was measured by EDS analysis throughout this outer oxide mixture. The TBCs exhibited excellent adherence on the oxide scale. Intercolumnar gaps and pores in the root area of the TBC were filled with titania and alumina. Below the outer columnar oxide scale, a broad porous zone of predominant titania was observed. The transition region between the oxide scale and substrate consisted of a discontinuous nitride layer intermixed with alumina particles and intermetallic phases rich in niobium formed at the nitride layer/substrate interface. When thermally cycled at 900 °C, the oxide scales on the alloy Ti‐45Al‐8Nb‐0.2B‐0.15C pre‐oxidised in low partial pressure oxygen spalled off after 540 cycles. For the sample with TBC, spallation was observed after 810 cycles. Failure occurred in the thermally grown oxide near the oxide/nitride layer interface. Microstructural examinations revealed again oxide scales with columnar structure beneath the zirconia top coat and good adherence of the TBC on the thermally grown oxides formed at 900 °C.     

Mechanical properties testing and results for thermal barrier coatings

Mechanical test data for thermal barrier coatings, including modulus, static strength, and fatigue strength data, are reviewed in support of the development of durability models for heat engine applica-tions. The materials include 7 and 8 wt % yttria partially stabilized zirconia (PSZ) as well as a cermet ma-terial (PSZ +10 wt % NiCoCrAlY). Both air plasma sprayed and electron beam physical vapor deposited coatings were tested. The data indicate the basic trends in the mechanical properties of the coatings over a wide range of isothermal conditions. Some of the trends are correlated with material density.     

Interface fracture toughness and fracture mechanisms of thermal barrier coatings investigated by indentation test and acoustic emission technique

Interface fracture toughness and fracture mechanisms of plasma-/sprayed thermal barrier coatings (TBCs) were investigated by interfacial indentation test (IIT) in combination with acoustic emission (AE) measurement. Critical load and AE energy were employed to calculate interface fracture toughness. The critical point at which crack appears at the interface was determined by the IIT. AE signals produced during total indentation test not only are used to investigate the interface cracking behavior by Fast Fourier Transform (FFT) and wavelet transforms but also supply the mechanical information. The result shows that the AE signals associated with coating plastic deformation during indentation are of a more continuous type with a lower characteristic frequency content (30-60 kHz), whereas the instantaneous relaxation associated with interface crack initiation produces burst type AE signals with a characteristic frequency in the range 70-200 kHz. The AE signals energy is concentrated on different scales for the coating plastic deformation, interface crack initiation and interface crack propagation. Interface fracture toughness calculated by AE energy was 1.19 MPam_1/2 close to 1.58 MPam_1/2 calculated by critical load. It indicates that the acoustic emission energy is suitable to reflect the interface fracture toughness.     

Formation and behavior of thermal barrier coatings on nickel-base superalloys

Plasma-sprayed thermal barrier coatings (TBCs) have been used to extend the life of combustors. Electron beam physical vapor deposited (EB-PVD) ceramic coating has been developed for more demanding rotating as well as stationary turbine components. Here 3 kW RF magnetron sputtering equipment was used to gain zirconia ceramic coatings on hollow turbine blades and vanes, which had been deposited NiCrAIY by cathodic arc deposition. NiCrAlY coating surface was treated by shot peening; the effects of shot peening on the residual stress are presented. The results show that RF sputtered TBCs are columnar ceramics, strongly bonded to metal substrates. NiCrAlY bond coat is made of β, γ‘ and Cr phases, ZrO2 ceramic layer consists of t‘ and c phases. No degradation occurs to RF ceramic coatings after 100 h high temperature oxidation at 1150℃ and 500 thermal cycles at 1150℃ for 2 min, air-cooling.     

Determination of cracking resistance of thermal spray coatings during four-point bend testing using an acoustic emission technique

An acoustic emission (AE) technique was used for the determination of the onset of cracking of thermal spray self-fluxing NiCrFeBSi coatings under tensile loading using a 4-point bend testing apparatus. These coatings were flame sprayed on 42CrMoS4 cylinders having different diameters. Two different post-treatment fusing processes, induction, and flame fusing, were used. Along with the investigations of the effect of cylinder diameters and fusing processes onto the cracking resistance of the coatings, the effect of the same two parameters on the residual stresses was also investigated. Results show that, independently of the diameter of the cylinder, the flame-fused coatings possess a higher cracking resistance than their induction-fused counterparts, i.e., that the strain to fracture is higher for the flame-fused coatings. A correlation between the strain to fracture and the residual strain in the coatings has been established. This study points out that the combination of an AE technique with a bending test apparatus shows some major benefits to obtain important information on the relative ductility of thermal spray coatings.     

Isothermal and cyclic oxidation resistance of boron-modified and germanium-doped silicide coatings for titanium alloys

Since titanium alloys with an adequate balance of mechanical properties and high-temperature oxidation resistance have not been developed, protective coatings are required. In our previous paper, B-modified and Ge-doped silicide diffusion coatings grown on CP Ti, Ti–24Al–11Nb, Ti–22Al–27Nb, and Ti–20Al–22Nb by the halide-activated, pack-cementation method were described. In this study, isothermal and cyclic oxidation were used to evaluate the oxidation performance of these coatings in comparison to uncoated substrates. The rate-controlling mechanism for isothermal oxidation at high temperature was solid-state diffusion through a SiO₂ scale, while the mechanism for low-temperature oxidation involved grain-boundary diffusion through TiO₂. Both isothermal and cyclic oxidation rates for the B-modified and Ge-doped silicide coatings were much slower than for pure TiSi₂. Oxygen contamination was not detected by microhardness measurements in the coated substrates after 200 oxidation cycles at 500–1000°C for the Ti–Al–Nb alloys, or at 500–875°C for CP Ti. The excellent oxidation resistance for the optimum coating compositions is discussed.     

Influence of the mode of introduction of a reactive element on the high temperature oxidation behavior of an alumina‐forming alloy. Part I: Isothermal oxidation tests

Different modes of introduction of yttrium have been tested with regard to the influence on the high temperature oxidation behavior of a FeCral alloy. Y₂O₃ sol‐gel coatings, Y₂O₃ metal‐organic chemical vapor deposition (MOCVD) coatings, implanted yttrium ions and yttrium as alloying element (0.1 wt.%) in the same Fe‐20Cr‐5Al alloy were oxidized at 1100°C in air under atmospheric pressure. Whatever the mode of introduction of the reactive element, the oxidation rates were not decreased compared to the oxidation rate of the blank specimen. The observation of the oxidized surface indicated that the alumina scale largely spalled from the blank alloy. Spallation was reduced for the Y₂O₃ sol‐gel coated, the Y₂O₃ MOCVD coated alloys and the yttrium ion implanted steels. The Y‐containing alloy did not exhibit any detachment of the oxide scale, indicating the best high temperature oxidation behavior, at least from the viewpoint of scale adherence.     

Effect of surface preparation on the durability of NiCoCrAlY coatings for oxidation protection and bond coats for thermal barrier coatings

A principal concern with alumina‐forming coatings for high‐temperature oxidation protection and bond coats (BCs) for ceramic thermal barrier coatings (TBCs) used in gas turbines is the spalling of the alumina scales during service. This paper describes the effects of BC surface preparation on the durability of NiCoCrAlY coatings exposed under thermal cycling conditions. State‐of‐the‐art TBC systems deposited by electron beam physical vapor deposition (EBPVD) with NiCoCrAlY overlay BCs were found to fail as the result of defects which included transient oxides, defects in the BC surface, defects in the as‐deposited microstructure of the TBC, and excessive oxidation of reactive element additions. In some instances, the TBC life was greatly extended by surface treatments, such as fine polishing. The oxidation behavior of NiCoCrAlY coatings, absent a TBC, was found to be sensitive to Y content and to surface preparation. This paper describes how a variety of surface treatments affected coating lives and failure mechanisms.     

Influence of cycling parameter variation on thermal cyclic oxidation testing of high temperature materials (COTEST)

The effect of cycling parameter variation (i.e. oxidation temperature, upper and lower dwell time, humidity in test gas) of the oxidation/spallation kinetics on four alloys was investigated within the framework of an EC funded research project (COTEST). For this purpose, specimens of AISI 441, Alloy 800H, CM 247 and P91 were subjected to thermocyclic testing in dry or humidified air. It was found that a minimum of 300 h accumulated hot dwell time is required for meaningful test results. Detailed characterisation of the corrosion products was performed using OM, SEM/EDX and XRD. The net weight change curves were evaluated with regards to the characteristic quantitative parameters describing oxide growth rate, time to onset of spallation/breakaway and weight of spalled oxide. Analysis of these values was made by the ANOVA method, which allows assessment of the significance of the roles of different test parameters and parameter variations on the oxidation/spallation kinetics from a limited number of experiments.     

Processing, repairing and cyclic oxidation behaviour of sol–gel thermal barrier coatings

Sol–gel Thermal Barriers Coatings (TBCs) are manufactured using the dip-coating technique optimised in terms of process parameters including sol formulation, rate of withdrawing and heat treatment. The specific mechanisms of sol–gel TBCs, deposited on either NiAl or NiPtAl bond-coated superalloy substrates, are described. The possibility to reinforce and stabilise the crack network formed during the heat treatment or the first oxidation cycles using supplementary dip-coatings and appropriate process parameters is investigated. It is shown that implementing this technique that can be further regarded as an attractive way for repairing TBCs, significantly improves the cyclic oxidation behaviour of the multi-materials systems.     

热障涂层双层黏结层的高温氧化行为

采用箱式电阻炉研究了具有梯度热膨胀系数的（孔隙层+氧化层）双层黏结层结构热障涂层的高温氧化行为。采用气罩等离子喷涂在Inconel 738合金基材上制备60μm厚的孔隙层,通过超音速火焰喷涂（HVOF）在孔隙层上制备120μm厚的氧化层。在1000℃下对黏结层进行不同时间的高温氧化试验。结果表明,黏结层由孔隙层和氧化层组成;喷涂态孔隙层具有典型的层状结构,未出现明显氧化;喷涂态氧化层较为致密,内部弥散分布着细小的α-Al₂O₃颗粒;具有梯度热膨胀系数黏结层表面的热生长氧化物（TGO）生长速率显著低于传统黏结层,且不再遵循抛物线生长规律,而是以对数规律生长;由于生长速率缓慢,尽管在制备过程中消耗了部分Al元素,但在500 h范围内TGO仍然以α-Al₂O₃为主。      

Influence of the mode of introduction of a reactive element on the high temperature oxidation behavior of an alumina‐forming alloy. Part II: Cyclic oxidation tests

Several routes of yttrium introduction were applied to test the high temperature oxidation performance of a FeCrAl alloy. Isothermal oxidation tests were described in a previous paper (Part I of this paper in this journal, 2004, 55, 352). Cyclic oxidation tests were performed in air under atmospheric pressure on blank specimens, Y₂O₃ sol‐gel coated‐, Y₂O₃ metal‐organic chemical vapor deposited (MOCVD)‐, yttrium ion implanted‐alloys, as well as on a steel containing 0.1 wt. % of yttrium as an alloying element. For the 20 hours cycles, all the samples, except FeCrAl‐0.1Y, exhibit weight losses after a few cycles, indicating drastic spallation of the oxide scales. The MOCVD coated specimen has the highest weight loss. The oxidation kinetics of the FeCrAl‐0.1Y alloy obey a parabolic law, indicating that the alumina scale formed on its surface is protective even after more than 1200 hours of oxidation (> 50 cycles). The 100 hours cycle oxidation tests give similar results. The FeCrAl‐0.1Y alloy exhibits the best oxidation behavior with very little spallation after more than 2000 hours (85 days) of oxidation at 1100°C (20 cycles). Most of the other samples exhibit severe oxide scale spallation followed by an increase of their oxidation rate related to the formation of non‐protective iron oxides.     

Effect of nano‐particulate sol–gel coatings on the oxidation resistance of high‐strength steel alloys during the press‐hardening process

The need for lighter constructional materials in automotive industries has increased the use of high‐strength steel alloys. To enhance passenger's safety press hardening may be applied to steel parts. However, as the steel parts are heated up to 950 °C during this process they have to be protected by some kind of coating against the intense oxide formation usually taking place. As the coating systems used so far all have certain disadvantages in this work the ability of nano‐particulate thin coatings obtained by the sol–gel process to improve the oxidation resistance of 22MnB5 steel is investigated. The coatings obtained from three sols containing lithium aluminum silicate and potassium aluminum silicate showed the best performance against oxidation. The structural properties of the coating materials were characterized using different methods like XRD and differential thermal analysis. Comparison of the oxidation rate constants proved the ability of the coatings to protect against oxidation at temperatures up to 800 °C. Press‐hardening experiments in combination with investigations on the thermal shock resistance of the coated samples also showed the ability of the coatings to stay intact during press hardening with only slight spalling of the coatings in the bending areas. The absence of any secondary intermetallic phases and layer residues during laser beam welding experiments on coated samples proves the suitability of the nano‐particulate coatings for further industrial processing.     

High-temperature oxidation and hot corrosion behavior of two kinds of thermal barrier coating systems for advanced gas turbines

High-temperature oxidation and hot corrosion tests were conducted at 800 to 1100 °C under isothermal and thermal-cycle conditions for two kinds of thermal barrier coating (TBC) systems with different compositions of ceramic top coat: Y₂O₃-stabiIized zirconia (YSZ) and CaO-SiO₂-ZrO₂ (C₂S-CZ). Qualitative and quantitative failure analyses were carried out to clarify the failure mechanisms of TBC systems. In high-temperature oxidation up to 1100 °C, the YSZ-TBC system was subjected more easily to spalling of the ceramic top coat. This is attributed to the localized oxidation along the ceramic top coat/metallic (NiCrAlY) bond coat interface, as compared with the case of the C₂S-CZ-TBC system. Thus, the most significant oxidation damage resulted in the YSZ system under the thermal-cycle condition. On the other hand, for hot corrosion by Na₂SO₄-NaCI molten salt up to 1000 °C, the C₂S-CZ system was more reactive with the molten salt to form a new phase layer composed of both the metallic bond coat constituents, such as aluminum and chromium, and corrosive species such as oxygen at the inner region of the ceramic top coat. Furthermore, effects of both the heat treatment, in particular the atmosphere after plasma spraying, and the chromium content of the bond coat were investigated for each coating system.     

Evaluation of aluminide diffusion coatings for thermal cyclic oxidation protection of a nickel‐base superalloy

Active element modified aluminide diffusion coatings on IN738 substrates were produced by a new route using continuously cast, aluminum alloy wires consisting of Al‐Y, Al‐Ce, Al‐La and Al‐Si‐Y. The cast wires were used as evaporation sources for ion‐vapour deposition followed by diffusion heat treatments to form nickel aluminide coatings. In order to examine the oxidation resistance of these coatings at elevated temperatures, thermal cyclic oxidation experiments were carried out in air at 1050°C. While all coatings were found to provide significant protection, the Al‐La modified coatings provided the greatest resistance to cyclic oxidation. On the other hand, with coatings based on Al‐Si‐Y alloys, while silicon has a strong ability to reduce the outward diffusion of aluminum, the adverse effect of silicon on mechanical properties of the coating, together with the formation of volatile silicon monoxide, led to catastrophic localized oxidation of the protective coatings.     

The role of alloying elements in commercial alloys for corrosion resistance in oxidizing‐chloridizing atmospheres. Part II: Experimental investigations

In an extensive study the role of the alloying elements in commercial alloys for corrosion resistance was studied in air without and with 0.1 and 2 vol.% Cl₂, respectively. In the first part of this paper [1] the thermodynamic fundamentals were discussed on the basis of the new concept of the quasi‐stability diagrams. The second part which is presented here reports the results from investigations at 650, 800 and 1000°C and testing times up to 1000 hrs where 14 commercial alloys were tested with regard to their corrosion behavior. The materials were selected so that the role of the alloying elements Mo, C, Si, Al, N, Fe, Ni and Cr would be evident from the results. The exposure tests were followed by extensive microstructural analyses of the corrosion scales and the metal subsurface zones so that type, mechanism and extent of corrosion could be characterized in great detail. At the end a ranking was possible of the different materials and with regard to the detrimental or beneficial role of the different alloying elements. The present results thus provide a much deeper insight into materials resistance in oxidizing‐chloridizing environments at high temperatures.