钨涂层及氧化镧合金面对等离子体材料研究

介绍了等离子体喷涂钨涂层和粉末冶金钨氧化镧合金面对等离子体材料的制备,并对其进行了性能分析,主要包括微观结构、杂质含量、气孔大小及气孔率分布、结合强度、热导率以及热负荷疲劳性能和承受能力。结果表明:真空等离子体喷涂钨涂层性能比大气喷涂钨涂层性能优越,是更为合适的钨涂层制备技术。真空喷涂钨涂层具有较低的气孔率、较高的热导率、较低的杂质含量和较优异的热负荷性能,能够承受10 MW/m²、100周次疲劳测试。氧化镧弥散掺杂相具有钉扎作用,能够抑制钨烧结过程中的长大,有效提高钨材料强度,改善热负荷性能,W-1%La₂O₃(质量分数)材料能够承受6MW/m²的热负荷。     

Thermal Performance and Microstructure of Vacuum Plasma Sprayed Tungsten Coatings under Cyclic Heat Load

采用真空等离子喷涂技术在铜基体表面制备了钨涂层,分别通过NiCrAl和W75Cu25涂层作为中间层。5 MW/m2, 2 s的高热负荷电子束实验表明NiCrAl中间层提高了涂层的热导率并降低了热应力和残余应力值。W75Cu25涂层作为中间层则表现出较差的热疲劳性能。高热负荷电子束真空等离子喷涂钨涂层表现出侵蚀和微裂纹。因热应力导致涂层发生塑性变形,在高温情况下裂纹起源于熔融的钨颗粒,但是,裂纹被钨涂层塑性变形和孔洞所抑制     

Characterization Studies of Mullite Coatings on Cast Aluminum

Thermal barrier coating of mullite was plasma sprayed on cast aluminum A 356.0, in the T6 condition (solution treated, quenched and artificially aged) for use in internal combustion engine applications. This study pertains to the mechanical, thermal, wear, corrosion and micro structural characterization of the coating. An average coating tensile strength of 50 MPa and average adhesive bond strength of 20 MPa was measured in the mechanical tests. A wear factor of 0.7 × 10⁻³ mg/Nm was measured in the wear studies using a pin on disk apparatus. An average value of 0.151 W/m K was measured in the thermal conductivity test. The coating withstood 100 cycles in the thermal shock test, without any sign of spallation. Corrosion tests showed no signs of corrosion even after 500 h. The microstructural and porosity studies were conducted using an optical microscope and scanning electron microscope with an energy dispersive spectroscopy (EDS) attachment. The studies revealed a crystalline microstructure of the substrate, which correspond to the splat structure of the coating. The porosity of the coated layers ranged from 6 to 21% by volume, at an average of 12-16%. EDS studies showed the elements present in the coating. X-ray diffraction patterns taken on coated specimens, showed the phases present in the coating, and indicated a crystalline structure of the coating along with some amorphous matter.     

Non-contact sensing of TBC/BC interface temperature in a thermal gradient

Luminescence lifetimes of rare-earth ions in yttria-stabilized zirconia have been shown to exhibit temperature sensitivity from 500-1150 °C [Gentleman, M.M. and Clarke, D.R. (2005) Surface and Coatings Technology 200, 1264; Gentleman, M.M. and Clarke, D.R. (2004) Surface and Coatings Technology 188-189, 93.]. These doped zirconias can be deposited along with standard thermal barrier coatings to create thin temperature sensing layers within the coating. Of particular interest is the temperature at the coating/bond coat interface as the oxidation life of a TBC system is exponentially dependent on this temperature. In this study, thin (∼ 10 μm) layers of europia-doped yttria-stabilized zirconia were deposited by EB-PVD onto bond-coated CMSX-4 superalloy buttons to achieve sensor layers located next to the TBC/BC interface. These coatings were then used to measure the interface temperature in a thermal gradient. Combined with pyrometric measurements of the coating-surface temperature and metal-surface temperature, the thermal conductivity of the coating (1.5 W/mK) and heat flux (∼ 1 MW/m²) in the tests were calculated.     

Cracking investigation of W and W(C) films deposited by physical vapor deposition on steel substrates

This paper presents the investigation of the cracking of coatings deposited on steel substrates. The coating on substrate systems consisted on pure tungsten films (W) and films of solid solutions of carbon in tungsten [W(C)], which were deposited by direct current reactive magnetron sputtering on stainless steel substrates. The systems were strained uniaxially with a microtensile device adapted to a scanning electron microscope. The mechanical response was analyzed from the experimental results: the straining of the samples showed an evolution of the density of cracks in the coating, which was described trough an empirical equation based on the Weibull distribution function. The density of cracks, which corresponds to the crack saturation of the coating, appeared to vary inversely with coating thickness. Critical parameters relative to their mechanical stability were also determined from the experimental results: the strain energy release rate for crack extension through the film, G^f_c, and the fracture toughness, K^f_Ic, of the coatings. These values are included between 0.2 and 14 J m⁻², and between 0.1 and 2.5 MPa m^−1/2. The fracture resistance of W and W(C) coatings was found to be correlated to their thickness and microstructure.     

表面接枝含氟树脂改性HGB的制备及性能研究

目的对中空玻璃微珠(HGB)进行表面接枝含氟树脂改性,以其为填料制备含氟树脂涂料,并进行性能研究。方法将中空玻璃微珠分别经NaOH溶液、硅烷偶联剂KH550、HDI三聚体、含氟树脂处理,并通过FTIR、SEM、EDS等表征手段对接枝情况进行验证。以制备的表面接枝含氟树脂HGB(F-HGB)为填料,制备了含氟树脂隔热涂料,研究了HGB改性温度、时间对F-HGB接触角的影响,以及HGB粒径、添加量、改性、涂层厚度对涂料的疏水性能、隔热性能、拉伸强度的影响。结果成功制备出F-HGB,50℃下接枝含氟树脂反应8h,F-HGB与纯水的静态接触角为149.21°。与HGB/含氟树脂涂料相比,F-HGB/含氟树脂涂料的疏水性能、隔热性能、拉伸强度均有较大幅度的提高和改善。当F-IM16K添加量为20 phr时,F-HGB/含氟树脂涂层与水的接触角为100°,模拟曝晒实验涂层试板温差为7.4℃,拉伸强度为10.39 MPa。当F-K1添加量为20 phr时,F-HGB/含氟树脂涂层的导热系数为0.0701 W/(m·K),同时涂层隔热性能随HGB粒径、添加量的增大而增强,拉伸强度随之降低,但表面改性能有效减小涂料拉伸强度的降低幅度。结论 F-HGB具有疏水、隔热、与含氟树脂相容性好的特点,可作为功能填料制备疏水、隔热、力学性能优良的多功能涂料。     

Thermal cycling resistance of modified thick thermal barrier coatings

The thermal cycling properties of several modified thick thermal barrier coatings (TTBC) were studied in three test series in which the maximum coating temperature was fixed to 1000, 1150 and 1300 °C. The modified coating structures were all segmentation-cracked coatings and some of these coatings were surface-sealed. The segmentation-cracked coatings were produced by laser glazing or by using appropriate plasma spray parameters. The sealing treatments were made by using aluminium phosphate or sol–gel-based sealant. In this paper, it was demonstrated that regardless of whether the segmentation-cracked TTBCs were made by using specific plasma spray parameters or by laser glazing, the strain tolerance of the coating improved significantly. Instead, both sealing treatments reduced the thermal cycling resistance of the TTBCs to some degree, especially in the case of aluminium phosphate sealing. Coating microstructures, their mechanical and elastic properties and residual stresses were taken into consideration when estimating the thermal cycling properties and failure modes of the coatings.     

Mechanical Properties of LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript> and Thermal Cycling Behaviors of Plasma-Sprayed LaTi<Subscript>2</Subscript>Al<Subscript>9</Subscript>O<Subscript>19</Subscript>/YSZ Thermal Barrier Coatings

Recently, extensive efforts have been made to develop new thermal barrier coating (TBC) materials which can operate at temperatures above 1523 K over a long term. In this article, LaTi₂Al₉O₁₉ (LTA) was synthesized by solid-state reaction at 1773 K, and the mechanical properties of the LTA bulk were evaluated. The microhardness is about 14 GPa, comparable to that of YSZ bulk, whereas the Young’s modulus is about 44 GPa, lower than the value of YSZ. However, the fracture toughness of 0.8-1 MPa m^1/2 is much lower than that of bulk YSZ. A double-ceramic-layer LTA/YSZ TBC structure was proposed and the TBC sprayed by plasma spraying. Thermal cycling tests of the TBC specimens were performed at 1373 K with a dwell time of 10 min. The LTA remained good stability with ZrO₂ and Al₂O₃. However, the single layer LTA TBC was cracked at the LTA/bond coat interface after about 300 cycles, due to its poor thermal shock resistance, while the YSZ TBC yielded a lifetime of about 1000 cycles. The LTA/YSZ TBC remained intact even after 3000 cycles, exhibiting a promising potential as new TBC materials.     

Thermal shock behavior of nanostructured and conventional Al2O3/13 wt%TiO2 coatings fabricated by plasma spraying

The thermal shock behavior of three kinds of Al₂O₃/13 wt%TiO₂ coatings fabricated by plasma spraying was studied in this paper. One kind of those coatings was derived from conventional fused and crushed feedstock powder available commercially; the other two kinds of coatings were derived from nanostructured agglomerated feedstock powders. These two nano coatings possess moderate pores and pre-existing microcracks, they were composed of fused structure and three-dimensional net or skeleton-like structure. For conventional coatings, the pores and pre-existing cracks were bigger, sharp-point and mostly distributed between splats. Thermal shock tests for the three coatings were performed by water quenching method. Testing result showed the two kinds of nano coatings had much higher thermal shock resistance than the conventional coatings. The improved thermal shock resistance for nano coatings could attribute to their improved microstructure and crack propagation mode. The damage evolution and failure mechanism of coatings was quite different at thermal shock temperature of 650 °C and 850 °C, which was explained by a simple model. Different crack propagating modes in nanostructured and conventional coatings during thermal shock tests were due to their different microstructures in these two kinds coatings. The stress state of coating surfaces during the thermal cycles was also discussed in this paper.     

Mullite-rich plasma electrolytic oxide coatings for thermal barrier applications

A study has been undertaken of the characteristics exhibited by mullite-rich plasma electrolytic oxide coatings grown on aluminium alloys by using silicate-rich electrolytes. It is found that they can be grown at a higher rate, and to a greater thickness, than alumina PEO coatings on aluminium. The thermal conductivity of these coatings has been measured using a steady-state method. It is shown to be of the order of 0.5 W m^− 1 K^− 1, which may be compared with ∼ 1.5 W m^− 1 K^− 1 for pure alumina PEO coatings and ∼ 10-15 W m^− 1 K^− 1 for dense polycrystalline mullite. Coupled with excellent substrate adhesion and good mechanical properties, this relatively low conductivity makes these coatings attractive for thermal barrier applications. Furthermore, they are shown to exhibit a relatively low global stiffness (∼ 40 GPa), which will reduce the magnitude of thermally-induced stresses and improve the resistance to spallation during temperature changes.     

合金钢热障涂层等离子喷涂及高温力学特性研究

目的研究等离子喷涂热障涂层微观组织与高温力学性能,为热障涂层在合金钢的应用及其失效机制提供理论支撑。方法采用等离子喷涂技术在30Cr Mn Si A钢基体上制备Ni Co Cr Al Y/YSZ热障涂层,利用扫描电镜显微观察、物相分析、热震试验、拉伸试验等技术方法,考察涂层在高温条件下的失效行为。结果合金钢等离子喷涂热障涂层为典型双层层片状结构,YSZ涂层仅含有稳定四方相。800℃时,涂层试样拉伸试验后的断裂载荷与无涂层试样相比高10%。热障涂层的抗热震性良好,经900℃热震循环试验10次后,涂层完好;经1000℃热震循环6次后,涂层剥落失效,剥落面位于粘结层与基体之间。热震循环过程中,钢基体被氧化甚至腐蚀。涂层试样边缘产生应力集中,随着热震次数的增加,裂纹逐渐扩展,最终导致涂层成块剥落。温度由700℃升至900℃,Ni Co Cr Al Y涂层硬度下降幅度大于YSZ涂层和30Cr Mn Si基体。结论粘结层与钢合金基体的热膨胀不匹配是导致热震试验涂层剥落的主要原因。热障涂层的隔热作用使涂层试样的基体温度较低,导致其断裂载荷与无涂层试样相比较高。     

Characterization of modified thick thermal barrier coatings

In gas turbines and diesel engines, there is a demand for thick thermal barrier coatings (TTBCs) due to the increased process combustion temperatures. Unfortunately, the increased thickness of plasma-sprayed thermal barrier coatings (TBCs) normally leads to a reduced coating lifetime. For that reason, the coating structures have to be modified. When modifying the structure of TTBCs, the focus is normally on elastic modulus reduction of the thick coating to improve the coating strain tolerance. On the other hand, coating structural modification procedures, such as sealing treatments, can be performed when increased hot-corrosion resistance or better mechanical properties are needed. In this article, several modified zirconia-based TTBC structures with specific microstructural properties are discussed. Coating surface sealing procedures such as phosphate sealing, laser glazing, and sol-gel impregnation were studied as potential methods for increasing the hot-corrosion and erosion resistance of TTBCs. Some microstructural modifications also were made by introducing segmentation cracks into the coating structures by laser glazing and by using special spraying parameters. These last two methods were studied to increase the strain tolerance of TTBCs. The coating microstructures were characterized by optical microscopy, a scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and x-ray diffraction (XRD). The effect of sealing procedures on the basic thermal and mechanical properties of the coatings was studied. In addition, some correlations between the coating properties and microstructures are also presented, and the advantages and drawbacks of each modification procedure are discussed.     

Thermal conductivity and elastic modulus evolution of thermal barrier coatings under high heat flux conditions

Laser high heat flux test approaches have been established to obtain critical properties of ceramic thermal barrier coatings (TBCs) under near-realistic temperature and thermal gradients that may be encountered in advanced engine systems. Thermal conductivity change kinetics of a thin ceramic coating were continuously monitored in real time at various test temperatures. A significant thermal conductivity increase was observed during the laser-simulated engine heat flux tests. For a 0.25 mm thick ZrO₂-8% Y₂O₃ coating system, the overall thermal conductivity increased from the initial value of 1.0 W/m K to 1.15, 1.19, and 1.5 W/m K after 30 h of testing at surface temperatures of 990, 1100, and 1320 °C, respectively, Hardness and elastic modulus gradients across a 1.5 mm thick TBC system were also determined as a function of laser testing time using the laser sintering/creep and microindentation techniques. The coating Knoop hardness values increased from the initial hardness value of 4 GPa to 5 GPa near the ceramic/bond coat interface and to 7.5 GPa at the ceramic coating surface after 120 h of testing. The ceramic surface modulus increased from an initial value of about 70 GPa to a final value of 125 GPa. The increase in thermal conductivity and the evolution of significant hardness and modulus gradients in the TBC systems are attributed to sintering-induced microporosity gradients under the laser-imposed high thermal gradient conditions. The test techniques provide a viable means for obtaining coating data for use in design, development, stress modeling, and life prediction for various TBC applications.     

SiC/SiC–YAG–YSZ oxidation protective coatings for carbon/carbon composites

SiC/SiC–YAG–YSZ coatings were prepared by pack cementation, chemical vapor deposition and slurry painting on carbon/carbon (C/C) composites. The microstructures and oxidation behavior of coatings were investigated. The results show that the coatings displayed good oxidation and thermal shock resistance due to a dense glassy layer with silicates formed on the coating of SiC–YAG–YSZ. The weight gain rate of coated C/C composites was 1.77% after oxidation for 150 h at 1773 K. SiC in outer coating can promote the formation of oxygen diffusion barrier and lead to the optimum oxidation resistance for the coatings, compared with YSZ and YAG.     

Protecting the infrastructure with thermal spray coatings—Technical note

Thermal sprayed aluminum and zinc provide long-term (> 20 years to first maintenance) corrosion control coatings. However, this application is usually more expensive than painting or galvanizing if thermal spraying (metallizing) is not integrated into the design and fabrication phases of new construction and repair projects. Aluminum and zinc metallized coatings are tough enough to withstand fabrication, transportation, and assembly operations. The improved capabilities and productivity of metallizing equipment for aluminum and zinc spraying are a major factor in their current cost competitiveness. The net result is that the cost difference between metallizing, paint, and galvanizing is getting closer every day. Even though the initial application cost of metallizing may be higher, the life cycle cost (LCC) and average equivalent annual costs (AEAC) are lower than paint coating systems. Metallizing LCCs, when properly engineered into the construction schedule, are equal to or less than paint coating LCCs. This article summarizes some metallizing considerations for installing improved corrosion control coating systems in new construction and in maintenance and repair of infrastructure. Editor’s Note: The following constants have been used to convert between English and Metric dimensions: 1ft²-0.0929 m²; 1lb/ft²-4.89 kg/m²; 1 mil=0.025mm. Presented at the 5th National Thermal Spray Conference (NTSC-93), Infrastructure Maintenance and Repair Session, 10 June 1993, Anaheim, CA.     

Effect of Thermal Aging on Microstructure and Functional Properties of Zirconia-Base Thermal Barrier Coatings

Thermal barrier coating (TBCs) systems made of plasma sprayed zirconia are commonly used in gas turbine engines to lower metal components surface temperature and allow higher combustion temperature that results in higher fuel efficiency and environmentally cleaner emissions. Low thermal conductivity and long service life are the most important properties of these coatings. The objective of this work was to study the influence of a long-term heat treatment (i.e., 1200 °C/2000 h) on different characteristics of atmospheric plasma sprayed TBCs. Two zirconia feedstock materials were evaluated, namely, yttria partially stabilized zirconia and dysprosia partially stabilized zirconia. Several spray conditions were designed and employed to achieve different coating morphologies. Microstructure analyses revealed that the coating microstructure was significantly dependent on both operating conditions and heat treatment conditions. Significant changes in coatings porosity occurred during heat treatment. The lowest thermal conductivity was reached with the dysprosia partially stabilized zirconia material. Heat treatment affected TBCs adhesion strength as well.     

Evaluation of thermal sprayed coating using ultrasonic inspection by means of bottom echo back reflection

Thermal spraying technique is widely used in various mechanical parts as a surface reforming technique. However, as demand to maintain superior mechanical performance in harsh operating environment increases, the need for non-destructive evaluation method for thermal spray coating becomes more important. For this purpose, we thinned the thickness of the thermal sprayed coating by abrasion with blasting and used ultrasonic inspection by means of bottom echo reflection for effective measurement of abrasion quantity in thermal sprayed coating. The results obtained are summarized as follows. When the thickness of thermal sprayed coating becomes thin, the echo height increases. This is because thermal sprayed coatings absorb ultrasonic energy. Ultrasonic energy absorbed by Al₂O₃ is smaller compared with Fe-13Cr coating. Thermal sprayed coatings submerged in water have a lower echo height compared with air. As mentioned above, the thermal sprayed coating thickness can be estimated using ultrasonic inspection by means of bottom echo back reflection.     

金刚石粒径及含量对超音速激光沉积金刚石/Cu复合涂层微观结构及性能的影响

目的研究不同金刚石粒径及含量对超音速激光沉积金刚石/Cu复合涂层微观结构及性能的影响。方法利用超音速激光沉积技术制备金刚石/Cu复合涂层。采用扫描电镜和摩擦磨损测试对涂层的显微组织结构和磨损性能进行了分析,用激光闪烁法测量复合涂层的热导率。结果金刚石均匀分布在复合涂层中,原始粉末中金刚石体积分数从30%增加到50%时,复合涂层中金刚石颗粒的面积占比仅从14.01%升至16.79%,远低于金刚石颗粒在原始粉末中的含量。400目金刚石/Cu复合涂层的平均热导率为296 W/(m·K),摩擦系数为0.551;800目金刚石/Cu复合涂层的平均热导率为238 W/(m·K),摩擦系数为0.545。结论原始粉末中金刚石配比的增加并未对复合涂层中金刚石含量的提升有显著作用。金刚石/Cu复合涂层的热导率随着增强相颗粒含量的增加而降低,随着增强相颗粒粒径的增大而提高。不同粒径金刚石颗粒的添加能显著降低Cu涂层的摩擦系数,且小粒径金刚石颗粒的添加使复合涂层的摩擦系数更低和更稳定,从而使其具有更小的磨损量和磨痕宽度,表现出较优的耐磨损性能。     

面向等离子体材料钨厚涂层的制备及表征

等离子体喷涂技术在面向等离子体材料钨涂层的制备中占据主导地位,本实验采用CuMo/MoW作为涂层的中间过渡层,分别以结晶钨粉和羰基钨粉为原料,用大气等离子体喷涂技术在CuCrZr合金基体(110 mm×130mm)上制备了3-4 mm厚的3种钨涂层.对钨涂层微观组织、力学性能和热学性能研究表明,羰基钨粉制备的钨涂层的综合性能优于结晶钨粉,且薄涂层的结合强度优于厚涂层.优化喷涂工艺后,金相法测得钨涂层孔隙率＜2％,涂层的结合强度最大值为10 MPa,EDS测得氧含量为6％左右,纯钨层热导率最大值为12.52 W/(m.K),涂层氧含量过高导致涂层热导率显著降低.研究表明采用大气等离子体喷涂技术在铜合金上制备3～4mm厚的钨涂层是可行的,该技术可为下一步低成本、高性能厚钨涂层的制备奠定基础.     

Cyclic oxidation and mechanical behaviour of slurry aluminide coatings for steam turbine components

The excellent steam oxidation resistance of iron aluminide coatings on ferritic steels at 650 °C has been demonstrated both by laboratory tests and field exposure. These coatings are formed by the application of an Al slurry followed by diffusion heat treatment at 700 °C for 10 h. The resulting microstructure is mostly composed of Fe₂Al₅ on top of a much thinner FeAl layer. This coating exhibits perpendicular cracks due to thermal expansion mismatch between coating and substrate. However, these stress relieving cracks do not seem to have an effect on the mechanical properties of the substrate. Cyclic oxidation, creep resistance and TMF testing of these coatings at 650 °C indicate excellent performance.