Thermal conductivity investigation of zirconia co-doped with yttria and niobia EB-PVD TBCs

A technique used to improve the life cycle and/or the working temperature of the turbine blades uses ceramic coatings over metallic material applied by electron beam-physical vapor deposition (EB-PVD). The most usual material for this application is yttria doped zirconia. Addition of niobia, as a co-dopant in the Y₂O₃–ZrO₂ system, can reduce thermal conductivity. The purpose of this work is to evaluate the influence of the addition of niobia on the microstructure and thermal properties of the ceramic coatings. This new formulation will, in the future, be able to become an alternative to the composition currently used by the aerospace field in EB-PVD thermal barrier coatings (TBC). A significant reduction of the thermal conductivity, measured by laser flash technique, in the zirconia ceramic coatings co-doped with yttria and niobia when compared with zirconia–yttria coatings was observed.     

Review Nano and macro-structured component fabrication by electron beam-physical vapor deposition (EB-PVD)

The objective of this paper is to demonstrate the versatility of electron beam-physical vapor deposition (EB-PVD) technology in engineering new materials with controlled microstructure and microchemistry in the form of coatings. EB-PVD technology is being explored in forming net-shaped components for many applications including space, turbine, optical, biomedical and auto industry. Coatings are often applied on components to extend their performance and life under severe environmental conditions including thermal, corrosion, wear, and oxidation. In addition, coatings have been used in designing and developing sensors. Performance and properties of the coatings depend upon its composition, microstructure and deposition condition. This paper presents recent results of various materials including ceramic, metallic, and functionally graded coatings produced by EB-PVD. Simultaneous co-evaporation of multiple ingots of different compositions in the high energy EB-PVD chamber has brought considerable interest in the architecture of functional graded coatings, nano-laminated coatings and designing of new structural materials that could not be produced economically by conventional methods. In addition, high evaporation and condensate rate allowed fabricating precision net-shaped components with nanograined microstructure for various applications. This paper will also present the results of various metallic and ceramic coatings including chromium, titanium carbide (TiC), hafnium carbide (HfC), tantalum carbide (TaC), hafnium nitride (HfN), titanium-boron-carbonitride (TiBCN), and partially yttria stabilized zirconia (YSZ), and HfO₂-based TBC coatings deposited by EB-PVD for various applications.     

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.     

Fabrication of TBC-armored rocket combustion chambers by EB-PVD methods and TLP assembling

A thermal barrier coating (TBC) system for rocket chambers made of Cu-based high strength alloys has been developed in a pilot project in line with EB-PVD (electron-beam physical vapor deposition) technology aiming at TBC application on Cu-based walls of real rocket combustion chambers. The TBC system consists of a metallic bond coating compatible with Cu-based material and an yttria partially stabilized zirconia TBC. The TBC overlayer is a distinctive ceramic structure designed for an exceptionally low Young’s modulus to withstand the extreme mismatch stresses between the internally LN-cooled high thermal expansion Cu metal base and the low thermal expansion hot ceramic shell. The TBC system has been qualified under close-to-service conditions on cylindrical LH₂-cooled combustion chamber segments, where they have performed superior.

As EB-PVD technology is a line-of-sight process that is rather able to coat internal cavities, a transient liquid phase (TLP) joining technique for fully coated parts has been developed, that allows to assemble complete components out of vapor-accessible fully coated parts. It is capable, e.g. to incorporate sinuous cooling passages in the throat areas of combustion chambers, and/or to assemble oversized parts out of smaller components by maintaining parent metal properties. A manufacturing process is outlined for making internal TBC armored combustion chambers.     

Synthesis and properties of zirconia thin films

Thin films of zirconia have been synthesized using reactive DC magnetron sputtering. It has been found that films with good optical constants, high refractive index (1·9 at 600 nm) and low extinction coefficient can be prepared at ambient temperatures. The optical constants and band gap and hence the composition are dependent on the deposition parameters such as target power, rate of deposition and oxygen background pressure. Thermal annealing of the films revealed that the films showed optical and crystalline inhomogeneity and also large variations in optical constants.     

Electrophoretic deposition and its use to synthesize ZrO2/Al2O3 micro-laminate ceramic/ceramic composites

Electrophoretic deposition has been employed to synthesize yttria-stabilized zirconia (YSZ)/alumina, laminar microcomposites with a total of 80 layers, >2mm. 10 wt% solids, ethanol suspensions of YSZ or Al₂O₃ powders were deposited layer by layer. The deposited samples had a green density, ~60% theoretical. The deposition process was characterized by the rate-of-deposition as a function of voltage and the microstructure of the sintered, theoretically dense samples was characterized by optical and electron microscopy. Microindentation was used to explore the mechanical properties of the laminates.     

A study of titanium thin films in transmission laser micro-joining of titanium-coated glass to polyimide

Electron beam evaporation (EB-PVD) and cathodic arc physical vapor deposition (CA-PVD) techniques were used for the preparation of titanium (Ti) thin films onto Pyrex borosilicate 7740 glass wafers and the deposited films were characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques. The microstructure and surface morphology of the films were studied as a function of the film deposition techniques. Film properties such as, adherence, microstructure and roughness were interconnected to the laser joint strength between Ti coated glass wafers and polyimide films. Ti thin films on glass had a natural oxide layer on the surface as found from XPS. AFM study showed the formation of a uniform Ti coating consisted of packed crystallites with average size of 35 nm by EB-PVD. The root-mean-square surface roughness of the films was 1-2 nm. Whereas, films prepared by CA-PVD had crystallites with an average size of 120 nm and defects in the form of macro-particles which is a common attribute of this deposition system. The surface roughness of the film was 125 nm. The laser joint strength was found to be influenced by the Ti film quality on the glass substrate.     

溶胶浸渗处理对EB-PVD 制备的YSZ电解质涂层的影响

为探索溶胶浸渗处理对电子束物理气相沉积(EB-PVD)制备8%摩尔比的氧化钇稳定氧化锆(8YSZ)涂层微观结构及性能的影响,采用EB-PVD工艺在沉积速率1μm/min的条件下制备了8YSZ电解质涂层.制备态涂层的断面表现为疏松的柱状晶结构,导致涂层的气密性差,因此对涂层进行了溶胶浸渗处理,即首先在负压下将涂层浸渗在钇锆的溶胶内,再进行550℃保温2 h的热处理.SEM分析表明,溶胶分解产物可以堵塞柱状晶间的孔隙,其渗入涂层的深度可达3μm.浸渗处理后,涂层的气体扩散系数由未处理态的6.78×10-5cm4/(N.s)降低至8次浸渗处理后的6.54×10-6cm4/(N.s).8次溶胶浸渗处理后涂层的电导率相比处理前提高不超过10%.     

Numerical study on modification of ceramic coatings by high-intensity pulsed ion beam

ZrO₂ ceramic coatings, which often call thermal barrier coatings (TBCs), fabricated by electron beam physical vapor deposition (EB-PVD), are widely used in high-temperature environment of aircraft and industry gas-turbine engines, because of the excellent strain tolerance imparted by the columnar structure. However, channels separating the columnar grains in EB-PVD TBCs provide paths for oxygen or other aggressive species from ambient atmosphere into the bond coat, resulting in the premature spallation-failure during high-temperature service. In our previous study, high-intensity pulsed ion beam (HIPIB) technique has been proposed to modify the EB-PVD TBCs, where a melted, densified top layer can be produced as a result of extremely thermal effect induced by the HIPIB irradiation. In this paper, HIPIB melting process is investigated numerically using a physical model based on experimental data, taking into account the surface morphology of HIPIB-melted TBCs to explore the mechanism of interaction between HIPIB and the coatings. Deposition process of the beam energy in TBCs was simulated by Monte Carlo method, and the non-linear equations describing the thermal conducting process were solved numerically based on the deposited energy to obtain the evolution of the temperature field of TBCs. The calculated melting depth of irradiated EB-PVD TBCs is consistent with results obtained in the HIPIB irradiation experiments.     

工艺参数对EB-PVD制备YSZ涂层的影响

为探讨电子束物理气相沉积(EB-PVD)制备8 mol.%氧化钇稳定氧化锆(8YSZ)涂层过程中工艺参数对涂层致密性、表面粗糙度和晶粒择优取向生长的影响,利用扫描电镜、原子力显微镜和X射线衍射技术对涂层的上述性能进行了分析.分析结果表明,随沉积速率由750 nm/min下降至20 nm/min,YSZ涂层的晶粒逐渐聚合长大,晶粒之间的孔隙减少,涂层的气体扩散系数相应地由2.41×10-4cm4/(N·s)下降至6.56×10-5cm4/(N·s).YSZ涂层的表面粗糙度随靶基距的提高逐渐降低,涂层的晶体学取向随蒸汽粒子入射角的改变而改变,入射角为30°时(111)晶面具有平行于涂层表面排列的趋势,入射角为45°时(311)和(420)晶面具有平行于表面排列的趋势,而入射角为60°时(220)和(331)晶面具有平行于表面排列的趋势.     

Evolutions of residual stress and microstructure in ZrO2 thin films deposited at different temperatures and rates

The residual stress in ZrO₂ thin films prepared by electron beam evaporation was measured by viewing the substrate deformation using an optical interferometer. The influences of deposition temperature and deposition rate on the residual stress have been studied. The results show that residual stress in ZrO₂ thin films varies from tensile to compressive depending on deposition temperature and deposition rate, respectively. The value of compressive stress increases with the increasing of deposition temperature and deposition rate. At the same time, X-ray diffraction measurement was carried out in order to examine the crystallization behavior of the ZrO₂ thin films as a function of deposition temperature and deposition rate. The relationship between the residual stress and the microstructure has also been discussed.     

高温防护涂层研究进展

高温防护涂层在防止航空涡轮发动机抗高温腐蚀以及延长发动机寿命方面起着越来越重要的作用。电子束物理气相沉积和等离子喷涂是目前制备高温涂层的两种最重要方法。本文综述了高温涂层国内外研究的进展,介绍了几种新型高温防护涂层,讨论了涂层使用的局限性及其发展前景。     

Structural and optical properties of CdS thin films grown by chemical bath deposition

Cubic cadmium sulphide (CdS) thin films with (111) preferential orientation were prepared by chemical bath deposition (CBD) technique, using the reaction between NH₄OH, CdSO₄ and CS(NH₂)₂. The films properties have been investigated as a function of bath temperature and deposition time. Structural properties of the obtained films were studied by X-ray diffraction analysis. The structural parameters such as crystallite size have been evaluated. The transmission spectra, recorded in the UV visible range reveal a relatively high transmission coefficient (70%) in the obtained films. The transmittance data analysis indicates that the optical band gap is closely related to the deposition conditions, a direct band gap ranging from 2.0 eV to 2.34 eV was deduced. The electrical characterization shows that CdS films' dark conductivities can be controlled either by the deposition time or the bath temperature.     

Analytical electron microscopy of the mixed zone in NiCoCrAlY-based EB-PVD thermal barrier coatings: as-coated condition versus late stages of TBC lifetime

Abstract

The microstructural evolution of the alumina-zirconia mixed zone in a NiCoCrAlY-based electron beam physical vapor deposited (EB-PVD) yttria partially stabilized zirconia (Y-PSZ) thermal barrier coating (TBC) system from the as-coated condition into the advanced stages of TBC lifetime is monitored by analytical transmission electron microscopy (TEM). In the as-coated condition yttria-rich islands at the thermally-grown oxide (TGO)/TBC interface locally impede zirconia uptake of the scale during TBC deposition and give rise to the formation of an “off-plane” alumina-zirconia mixed zone textured perpendicular to the TGO/TBC interface. During prolonged isothermal/cyclic oxidation an increased chromium diffusion through the TGO scale turns the mixed zone into a reaction zone introducing a morphological instability of the mixed zone/TBC interface due to solutioning of the bottom TBC layer.

This microstructural pattern is corroborated by a triple-stage growth model for the mixed zone during three successive stages in TBC lifetime: (i) during TBC deposition, the thickness of the mixed zone increases due to predominant outward aluminum diffusion and uptake of zirconia. No columnar alumina zone (CAZ) has formed at this stage, (ii) upon completion of the transition alumina-to-corundum phase transformation the thickness of the mixed zone remains constant while the change in diffusion mechanism for an inward oxygen diffusion process now initiates parabolic growth of the columnar alumina sublayer of the TGO scale, (iii) in the late stage of TBC lifetime an marked outward chromium diffusion from the bond coat causes the mixed zone to resume growth due to TBC destabilization and the formation of a (Al, Cr)₂O₃ mixed oxide matrix phase.

A transient YCrO₃ phase is proposed for driving the destabilization of yttria-rich sections of the bottom TBC layer.     

Nano-grained Net-Shaped Fabrication of Re Components by EB-PVD

Cost-effective net-shaped forming components have brought considerable interest into the Department of Defense, the National Aeronautics & Space Administration, and the Department of Energy. Electron beam-physical vapor deposition (EB-PVD) offers flexibility in forming net-shaped components with tailored microstructure and chemistry. High-purity rhenium components, including rhenium-coated graphite balls and rhenium plates and tubes, have been successfully manufactured by EB-PVD. EB-PVD rhenium components exhibited submicron and nano-size microstructure with high hardness and strength as compared with chemical vapor deposition (CVD). It is estimated that the cost of rhenium components manufactured by EB-PVD would be less than the current CVD and powder-high-temperature isostatic pressure technologies.     

High-speed oxide coating by laser chemical vapor deposition and their nano-structure

Oxide thick films, partially yttria-stabilized zirconia (YSZ) and titania (TiO₂), were prepared by laser chemical vapor deposition (LCVD). The assistance of laser tremendously increased the deposition rate for YSZ and TiO₂ films up to 660 and 2500 μm/h, respectively. The increase in the deposition rate was accompanied by plasma formation around the deposition zone, and the plasma was observed over critical values of laser power and substrate pre-heating temperature. A wide variety of morphologies of films from feather-like columnar to dense microstructures were obtained depending on deposition conditions. The columnar structure contained a large amount of nano-pores at columnar boundary and inside grains. These columnar structure and nano-pores were advantageous for applying YSZ films to thermal barrier coatings.     

Phases in copper-stabilized zirconia solid oxide fuel cells anode material

Solid oxide fuel cells (SOFC) are emerging as an alternate source of energy. Anodes form one of the components of the fuel cells. Ni/Yttrium stabilized zirconia is a classic anode material for SOFC when hydrogen is used as the fuel source, but it is not that effective when methane is used as fuel source due to carbon deposition on the anode. Recently, copper stabilized zirconia has been investigated as anode material for SOFC for its self-cleaning properties. We have tried to investigate phases in copper stabilized zirconia for better understanding of its properties. Copper stabilized zirconia (CSZ) with different CuO loading was prepared by the solid-state reaction method. X-ray diffraction studies on these samples reveal only monoclinic zirconia phase in those samples loaded with less than 5 mol% of CuO. Traces of monoclinic CuO along with monoclinic ZrO₂ is observed in the samples when loading of CuO is between 5 and 20 mol%. Orthorhombic copper zirconium oxide and monoclinic zirconia phases were observed when CuO loading was greater than 20 mol%. Scanning and back-scattered electron micrographs reveal a clear two-phase structure only in the samples with greater than 20 mol% of CuO loading. Atomic force microscopy carried out on 33 mol% loaded zirconia shows a three-phase structure with flattened seven-fold-coordination of Zr⁴⁺ with oxygen.     

Nanostructured thin films of indium oxide nanocrystals confined in alumina matrixes

Nanocrystals of indium oxide (In₂O₃) with sizes below 10 nm were prepared in alumina matrixes by using a co-pulverization method. The used substrates such as borosilicate glasses or (100) silicon as well as the substrate temperatures during the deposition process were modified and their effects characterized on the structural and physical properties of alumina-In₂O₃ films. Complementary investigation methods including X-ray diffraction, optical transmittance in the range 250-1100 nm and transmission electron microscopy were used to analyze the nanostructured films. The crystalline order, morphology and optical responses were monitored as function of the deposition parameters and the post-synthesis annealing. The optimal conditions were found and allow realizing suitable nanostructured films with a major crystalline order of cubic phase for the In₂O₃ nanocrystals. The optical properties of the films were analyzed and the key parameters such as direct and indirect band gaps were evaluated as function of the synthesis conditions and the crystalline quality of the films.     

Overview on the Development of Nanostructured Thermal Barrier Coatings

Thermal barrier coatings （TBCs） have successfully been used in gas turbine engines for increasing operation temperature and improving engine efficiency. Over the past thirty years, a variety of TBC materials and TBC deposition techniques have been developed. Recently, nanostructured TBCs emerge with the potential of commercial applications in various industries. In this paper, TBC materials and TBC deposition techniques such as air plasma spray （APS）, electron beam physical vapor deposition （EB-PVD）, laser assisted chemical vapor deposition （LACVD） are briefly reviewed. Nanostructured 7-8 wt pct yttria stabilized zirconia （7-8YSZ）TBC by air plasma spraying of powder and new TBC with novel structure deposited by solution precursor plasma spray （SPPS） are compared. Plasma spray conditions, coating forming mechanisms, microstructures,phase compositions, thermal conductivities, and thermal cycling lives of the APS nanostructured TBC and the SPPS nanostructured TBC are discussed. Research opportunities and challenges of nanostructured TBCs deposited by air plasma spray are prospected.     

Distribution and structures of nanopores in YSZ-TBC deposited by EB-PVD

Distribution and arrangement of nanopores in an YSZ (7 wt% Y₂O₃–ZrO₂)-thermal barrier coating (TBC) deposited by an electron beam-physical vapor deposition (EB-PVD) have been investigated by means of transmission electron microscopy. The YSZ-TBC deposited by the EB-PVD showed a typical columnar structure normal to the bond coat surface on the substrate. It has been generally believed that one column is a single crystal and grows continuously from the substrate. In the present study, however, it was found that each column consisted of a number of subcolumns with different misorientations and contained nanopores at the subcolumn boundaries. In addition to the nanopores at the subcolumn boundaries, nanopores with smaller size were observed within subcolumns, and were arranged periodically perpendicular to the growth direction of the subcolumns. Such arrangement and distribution of nanopores may be due to the misorientation of YSZ plate-like grains in the formation and coalescence processes of the YSZ subcolumns.