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.     

High-growth rate YSZ thermal barrier coatings deposited by MOCVD demonstrate high thermal cycling lifetime

Yttria-stabilized zirconia (YSZ) thermal barrier coatings (TBC) were prepared by metalorganic chemical vapor deposition (MOCVD) using Y(OButⁿ)₃, Zr(OButⁿ)₄ precursors and O₂ carrier gas. A thermodynamic analysis guided experiments by optimizing elemental molar (n) stoichiometric ratios for the (Zr-Y-O-C-H system). This analysis showed single-phase YSZ was favored at 950 °C, 1 kPa, n_O/(n_Y + n_Zr) > 30, n_Y/(n_Y + n_Zr) = 0.06-0.10 (fixed n_C, n_H). Experimental YSZ growth had multiple phases (fcc, monoclinic), had a relatively high growth rate (43 μm/h, 1005 °C), had an Arrhenius dependence (845-950 °C, E_a = 53.8 ± 7.9 kJ/mol), had columnar grains (SEM analysis), and had a coating through-thickness n_Y/(n_Y + n_Zr) = 0.04 (EPMA analysis). Doubling the inlet yttrium precursor mole fraction resulted in fcc YSZ growth with a coating through-thickness n_Y/(n_Y + n_Zr) = 0.07. Hot-insertion thermal cycling of YSZ coatings on FeCrAlY bond coats showed >1000 h lifetime, matching current standards for EB-PVD YSZ coatings.     

Oxidation and Hot Corrosion of Gadient Thermal Barrier Coatings Prepared by EB—PVD

The performances of gradient thermal barrier coatings (GTBCs)produced by EB-PVD were evaluated by isothermal oxidation and cyclic hot corrosion(HTHC) tests.Compared with conventional two-layered TBCs, the GTBCs exhibite better resistance to not only oxidation but also hot-corrosion.Adense Al2O3 layer in the GTBCs effectively prohibites inward diffusion of Oand S and outward diffusion of Al and Cr during the tests.On the other hand ,an “inlaid“ interface ,resulting from oxidation of the Al along the columnar grains of the bond coat,enhances the adherence of Al2O3 layer.Failure of the GTBC finally occurred by cracking at the interface between the bond coat and Al2O3 layer, due to the combined effect of sulfidation of the bond coat and thermal cycling.     

Microstructure and texture of EB-PVD TBCs grown under different rotation modes

The role of vapor incidence pattern (VIP) on the microstructure and texture of thermal barrier coatings (TBCs) produced by electron-beam physical vapor deposition (EB-PVD) is examined. Two distinct VIPs are induced by proper design of the substrate rotation mode. One is the sunrise–sunset pattern typical of conventional deposition on the curved face of a rotating cylinder (mode A), and the other is a conical pattern resulting when deposition is done on the cylinder base at an offset distance from the plume axis (mode P). These geometries afford fundamental insight on the processes of microstructure and texture evolution and also have practical implications to the variability of properties that may be expected between the body and platform regions of a turbine airfoil. Comparable deposition rates and thickness uniformity can be achieved by proper selection of the experimental geometry. Both coatings exhibit the typical 100 texture normal to the substrate, but mode A also yields a preferred in-plane orientation which is absent in mode P. The ensuing differences in column packing and tip shadowing yield lower densities and larger pipe-like inter-columnar voids in mode P. The absence of an in-plane evolutionary selection mechanism in the latter also leads to narrower columns than in mode A.     

Oxidation and Hot Corrosion of Gradient Thermal Barrier Coatings Prepared by EB-PVD

The performances of gradient thermal barrier coatings (GTBCs) produced by EB-PVD were evaluated by isothermal oxidation and cyclic hot corrosion (HTHC) tests. Compared with conventional two-layered TBCs, the GTBCs exhibite better resistance to not only oxidation but also hot-corrosion. A dense Al2O3 layer in the GTBCs effectively prohibites inward diffusion of O and S and outward diffusion of Al and Cr during the tests. On the other hand, an "inlaid" interface, resulting from oxidation of the Al along the columnar grains of the bond coat, enhances the adherence of AI2O3 layer. Failure of the GTBC finally occurred by cracking at the interface between the bond coat and AI2O3 layer, due to the combined effect of sulfidation of the bond coat and thermal cvcling.     

EB-PVD process and thermal properties of hafnia-based thermal barrier coating

Thermal barrier coatings (TBCs) are being developed for the key technology of gas turbine and diesel engine applications. In general, 8 mass% Y₂O₃–ZrO₂ (8YSZ) coating materials are used as the top coating of TBCs. The development of hafnia-based TBC was started in order to realize the high reliability and durability in comparison with 8YSZ, and the 7.5 mass% Y₂O₃–HfO₂ (7.5YSH) was selected for coating material. By the investigation of electron-beam physical vapor deposition (EB-PVD) process using 7.5YSH ceramic ingot, 7.5YSH top coating with about 200 µm thickness could be formed. The microstructure of the 7.5YSH coated at coating temperature of 850 °C showed columnars of laminated thin crystals. On the other hand, the structure of the 7.5YSH coated at coating temperature of 950 °C showed solid columnars. From the result of sintering behavior obtained by heating test of 7.5YSH coating, it was recognized that the thermal durability of 7.5YSH coating was improved up to about 100 °C in comparison with 8YSZ coating. This tendency was confirmed by the experimental result of the thermal expansion characteristics of sintered 7.5YSH and 8YSZ.

©2003 Elsevier Science Ltd. All rights reserved.     

等离子体激活电子束物理气相沉积NiCoCrAlY涂层的制备及微观组织结构研究

针对传统电子束物理气相沉积(EB-PVD)制备的柱状晶结构MCrAlY涂层存在线性缺陷的问题,本文建立了等离子体激活EB-PVD(PA EB-PVD)设备,并采用PA EB-PVD技术制备出了具有等轴晶结构的新型NiCoCrAlY涂层。结果表明,增大电弧放电电压和基板偏压均可以提高沉积粒子的能量。随着沉积粒子能量增强,涂层逐渐由柱状晶结构转变为致密等轴晶结构,晶粒尺寸增大;另一方面,涂层成份离析效应增强,主要体现在Al含量降低和Cr含量升高。     

EB-PVD工艺制备SiC/ZrO_2涂层的微观组织结构研究

本文利用EB-PVD工艺在高温合金表面制备SiC/ZrO2防热涂层,对制备态和不同温度晶化处理后的涂层进行了微观组织结构分析。结果表明,随退火温度升高,SiC结晶程度提高,Ramam光谱出现了SiC的TO带和LO带;SiC层中分散的sp2杂化碳团簇产生了急剧的聚集,形成了大的团簇结构。退火处理后SiC表层发生钝性氧化,涂层表面C元素含量大幅度减少,而O元素含量迅速增加;XPSC1s和Si2p谱峰的中心向高结合能方向发生了偏移;表层中C-C键的含量减少,Si-O键的含量逐渐增加。     

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.     

Substrate Effects on the High-Temperature Oxidation Behavior of Thermal Barrier Coatings

The high-temperature oxidation behaviors of the NiCrAlYSi/P-YSZ thermal barrier coatings (TBCs) produced by electron beam-physical vapor deposition (EB-PVD) on directionally solidified (DS) and single crystalline (SC) Ni-based superalloy substrates were investigated. The cross-sectional microstructure investigation, isothermal and cyclic oxidation tests were conducted for the comparison of oxidation behaviors of TBCs on different substrates. Although TBC on DS substrate has a relatively higher oxidation rat...     

EB-PVD 热障涂层的热循环失效机理

采用电子束物理气相沉积方法(EB—PVD)在NiCrAlY粘结层上沉积Y2O3部分稳定的ZrO2陶瓷层。对样品进行了1050C的热循环实验。结果表明，沉积态陶瓷层表面比较致密．其柱状晶粒簇拥成团，晶粒簇间存在间隙。随着热循环不断进行，陶瓷层表面变得疏松，晶粒簇间距增大，相邻较大的间隙互相连接成微裂纹。并逐渐横向及纵向扩展。1050C循环200次，粘结层氧化物是均匀连续的—薄层，主要由Al2O3组成；循环300次后,出现了NiO、尖晶石等氧化物。根据显微结构观察和EDS、XRD分析结果，提出了EB—PVD热障涂层热循环的失效机理。     

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.     

EB-PVD在热障涂层中的研究及应用

EB-PVD是以高能电子束为热源的一种蒸发镀膜技术.在真空的环境下,高能离子束轰击靶材(金属,陶瓷等),使其融化、升华、蒸发,最后沉积在基片上.由于EB-PVD技术具有蒸发和沉积速率高,涂层致密,化学成分易于精确控制,可得到柱状晶组织,无污染,热效率高,基片与薄膜之间有较强的结合力等诸多优点,已被广泛应用于国防和民用领域.本文介绍了EB-PVD技术在制备热障涂层时优势、不足与改进措施.     

Improved oxidation resistance and diffusion barrier behaviors of gradient oxide dispersed NiCoCrAlY coatings on superalloy

NiCoCrAlY has been used as the bond coat material in thermal barrier coating (TBC) to protect the superalloy substrate from oxidation and hot-corrosion. Inter-diffusion of elements between the coating and substrate could degrade the oxidation resistance of the coating and the mechanical properties of the superalloy. In this work, a gradient oxide dispersed (OD) NiCoCrAlY coating was produced onto DZ125 superalloy using electron beam-physical vapor deposition (EB-PVD). For comparison, conventional NiCoCrAlY (OD free) coated specimens were also produced by EB-PVD. The oxidation and inter-diffusion behaviors of the coated specimens at 1373 K were investigated. As compared to OD free coating, the OD coating exhibits not only a lower oxidation rate but also an improved oxide scale adherence because outward diffusion of the elements such as Ta, W and Hf from the superalloy was effectively blocked by the OD zone. Meanwhile, the presence of minor Hf in the OD coating contributes to the improved oxide scale adherence by reactive element mechanism.     

Thermal barrier coatings produced by chemical vapor deposition

Yttria stabilized zirconia (YSZ) can be employed as thermal barrier coatings (TBCs) on Ni-based super alloys in gas turbines and aircraft engines. The YSZ coatings have been fabricated by atmospheric plasma spraying or electron-beam physical vapor deposition. The increase in operation temperature of gas turbines demands another fabrication process to obtain high quality TBCs. Chemical vapor deposition (CVD) can be an alternative route to prepare TBCs due to excellent conformal coverage and columnar microstructure. This paper reviews the fabrication of YSZ films by conventional thermal CVD and plasma CVD intended for TBCs. A new laser CVD developed by our group with a high deposition rate of 660 µμh^-1 was also briefly introduced.     

Thermoelectric properties of SiC thick films deposited by thermal plasma physical vapor deposition

SiC thick films of about 300 µm could be prepared with a deposition rate above 300 nm/s by thermal plasma physical vapor deposition (TPPVD) using ultrafine SiC powder as a starting material. The thermoelectric properties were investigated as a function of composition and doping content. The nondoped films showed n-type conduction. Although the Seebeck coefficient reached as high as -480 µV/K, the power factor was only around 1.6 × 10^-4 Wm^-1 K^-2 at 973 K due to the relatively high electrical resistivity. In order to reduce the electrical resistivity and to deposit layers with n-type and p-type conduction, N₂, B and B₄C were selected as the dopants. Nitrogen-doped samples exhibit n-type characterization, B and B₄C-doped samples exhibit p-type characterization, and the electrical resistivity decreased from 10^-2–10^-3 to 10^-4–10^-5 Ωm after doping. The maximum power factor of the nitrogen-doped SiC and the thick films deposited with B₄C powder reached 1.0 × 10^-3 and 6.4 × 10^-4 Wm^-1 K^-2 at 973 K, respectively.

© 2003 Elsevier Science Ltd. All rights reserved.     

石英晶体监控法镀制高精度光学薄膜

讨论了石英晶体监控法在光学薄膜镀制过程中的应用原理。通过与常规的光学监控法镀制的膜层相比较．证实了石英晶体监控法有助于提高光学薄膜的光学品质。试验表明所镀膜层的光学性能优异，在光通信和激光器等领域具有广阔的应用前景。     

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     

CVD法与PCVD法TiN薄膜研究

用等离子增强化学气相沉积（ＰＣＶＤ）法和化学气相沉积（ＣＶＤ）法分别制备ＴiV系薄膜。采用扫描电镜、Ｘ射线衍射仪和连续加载压入仪研究分析薄膜的微观结构、相结构和薄膜的力学性能,并采用电极电位法测定了薄膜的耐腐蚀性能,研究表明,PCVD法ＴiN系薄膜的微观组织形态明显优于同类的ＣＶＤ法薄膜,ＰＣＶＤ法薄膜晶粒尺寸细小,均匀,形态圆整,组织致密;ＣＶＤ法薄膜晶粒形态为多边形,尺寸较粗大、不均匀,组织致密性差,ＰＣＶＤ法ＴiN系薄膜的声望生和结合力等力学性能可达或优于同类ＣＶＤ法薄膜,虽然ＰＣＶＤ法薄膜的氯含量（约为２％）远主ＣＶＤ法薄膜（约为０．５％）,但ＰＣＶＤ法薄膜的耐蚀性能却明显优于ＣＶＤ法薄膜,还研究分析了ＰＣＶＤ法和ＣＶＤ法成膜模式对薄膜微观结构和性能的影响机理。     

Effects of different acetylene/nitrogen ratios on characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition

The effects of C₂H₂/(C₂H₂ + N₂) ratios on the characteristics of carbon coatings on optical fibers prepared by thermal chemical vapor deposition are investigated. The C₂H₂/(C₂H₂ + N₂) ratios are set to 60, 70, 80, 90, and 100%. Additionally, the deposition temperature, working pressure, and mass flow rate are 1003 K, 133 kPa, and 40 sccm, respectively. The deposition rate, microstructure, and electrical resistivity of carbon coatings are measured. The low-temperature surface morphology of carbon-coated optical fibers is elucidated. Experimental results indicate that the deposition rate increases with increasing the C₂H₂/(C₂H₂ + N₂) ratio, and the deposition process is located at a surface controlled regime. As the deposition rate increases, the electrical resistivity of carbon coatings increases, while the ordered degree, nano-crystallite size, and sp² carbon atoms of the carbon coatings decrease. Additionally, the low-temperature surface morphology of the carbon coatings shows that if the carbon coating thickness is not smaller than 289 nm, decreasing the deposition rate is good for producing hermetic optical fiber coatings.